WO2013146612A1 - ドリル孔あけ用エントリーシート - Google Patents
ドリル孔あけ用エントリーシート Download PDFInfo
- Publication number
- WO2013146612A1 WO2013146612A1 PCT/JP2013/058376 JP2013058376W WO2013146612A1 WO 2013146612 A1 WO2013146612 A1 WO 2013146612A1 JP 2013058376 W JP2013058376 W JP 2013058376W WO 2013146612 A1 WO2013146612 A1 WO 2013146612A1
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- WIPO (PCT)
- Prior art keywords
- resin
- drilling
- entry sheet
- water
- resin composition
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B26—HAND CUTTING TOOLS; CUTTING; SEVERING
- B26D—CUTTING; DETAILS COMMON TO MACHINES FOR PERFORATING, PUNCHING, CUTTING-OUT, STAMPING-OUT OR SEVERING
- B26D7/00—Details of apparatus for cutting, cutting-out, stamping-out, punching, perforating, or severing by means other than cutting
- B26D7/08—Means for treating work or cutting member to facilitate cutting
- B26D7/088—Means for treating work or cutting member to facilitate cutting by cleaning or lubricating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B41/00—Boring or drilling machines or devices specially adapted for particular work; Accessories specially adapted therefor
- B23B41/14—Boring or drilling machines or devices specially adapted for particular work; Accessories specially adapted therefor for very small holes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B47/00—Constructional features of components specially designed for boring or drilling machines; Accessories therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B26—HAND CUTTING TOOLS; CUTTING; SEVERING
- B26F—PERFORATING; PUNCHING; CUTTING-OUT; STAMPING-OUT; SEVERING BY MEANS OTHER THAN CUTTING
- B26F1/00—Perforating; Punching; Cutting-out; Stamping-out; Apparatus therefor
- B26F1/16—Perforating by tool or tools of the drill type
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0011—Working of insulating substrates or insulating layers
- H05K3/0044—Mechanical working of the substrate, e.g. drilling or punching
- H05K3/0047—Drilling of holes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B2224/00—Materials of tools or workpieces composed of a compound including a metal
- B23B2224/16—Molybdenum disulphide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B2250/00—Compensating adverse effects during turning, boring or drilling
- B23B2250/12—Cooling and lubrication
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/02—Details related to mechanical or acoustic processing, e.g. drilling, punching, cutting, using ultrasound
- H05K2203/0214—Back-up or entry material, e.g. for mechanical drilling
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/12—Using specific substances
- H05K2203/127—Lubricants, e.g. during drilling of holes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
- Y10T428/24967—Absolute thicknesses specified
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/256—Heavy metal or aluminum or compound thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/269—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension including synthetic resin or polymer layer or component
Definitions
- the present invention relates to an entry sheet for drilling holes.
- a drilling method for a laminated board or multilayer board used as a printed wiring board material one or a plurality of laminated boards or multilayer boards are stacked, and a metal foil such as aluminum or the like is used as a backing plate on the uppermost part.
- a sheet having a resin composition layer formed on the surface of the metal foil (hereinafter, this sheet is generally referred to as “entry sheet for drilling” or simply referred to as “entry sheet”) is provided for drilling.
- a method of processing is generally adopted.
- a “copper-clad laminate” is often used as the laminate, but a “laminate” having no copper foil in the outer layer may be used.
- Patent Documents 1 to 3 have not yet fully met the above-mentioned demand.
- the technologies proposed in Patent Documents 4 and 5 it is unclear how nanostructured powder acts on lubricity, wear resistance of drill bits, etc., and the involvement of nanostructured materials in hole position accuracy is also involved. It has not been revealed. Therefore, the development of an entry sheet for drilling with excellent hole position accuracy is desired. Such an entry sheet for drilling is expected to contribute to high density, high reliability, productivity improvement, and cost reduction.
- an object of the present invention is to provide an entry sheet for drilling that is superior in hole position accuracy as compared with a conventional drilling entry sheet.
- molybdenum disulfide as a solid lubricant in the resin composition used for the entry sheet for drilling, and its blending amount.
- the resin composition used for the entry sheet for drilling was optimized to a specific range.
- the drill bit easily bites into the entry sheet, and the hole position accuracy is improved by improving the centering property of the drill bit.
- the solid lubrication action of molybdenum disulfide has been found to increase the lubricity of the entry sheet and facilitate the discharge of chips. This prevents the chips from becoming lumps (coagulation) and falling off, and during drilling (cutting), the chips are formed between the tip of the drill bit and the bottom of the hole formed. It has been found that the problem of breakage of the drill bit caused by being caught in can be prevented.
- centering property refers to straightness in the cutting direction during cutting.
- resin composition layer a layer made of a resin composition
- the cutting edge at the tip of the rotating drill bit slides. However, it bites on the surface of the resin composition layer.
- centering force means an external stress that improves the centering property of the drill bit. Examples of the centripetal force include stress acting on the rotation center when the drill bit rotates.
- a drilling entry sheet comprising a metal support foil and a layer made of a resin composition formed on at least one surface of the metal support foil, the resin composition comprising a resin, 70 parts by mass to 130 parts by mass of molybdenum disulfide as a solid lubricant with respect to 100 parts by mass of the resin, and the layer made of the resin composition has a thickness in the range of 0.02 to 0.3 mm.
- An entry sheet for drilling (2) The entry sheet for drilling according to the above (1), wherein the molybdenum disulfide has an average particle diameter of 1 to 20 ⁇ m.
- the water-soluble resin (A) is polyethylene oxide, polypropylene oxide, sodium polyacrylate, polyacrylamide, polyvinyl pyrrolidone, cellulose derivative, polytetramethylene glycol and polyalkylene glycol polyester, polyethylene glycol, polypropylene glycol, poly One or more selected from the group consisting of monoethers of oxyethylene, polyoxyethylene monostearate, polyoxyethylene sorbitan monostearate, polyglycerin monostearate, and polyoxyethylene propylene copolymer
- the thermoplastic water-insoluble resin is an amide elastomer, butadiene elastomer, ester elastomer, olefin elastomer, urethane elastomer, styrene elastomer, polybutene, low density polyethylene, chlorinated polyethylene, metallocene polyolefin Resin, ethylene / acrylic acid ester / maleic anhydride copolymer, ethylene / glycidyl (meth) acrylate copolymer, ethylene / vinyl acetate copolymer resin, modified ethylene / vinyl acetate copolymer resin, ethylene / (meth) acrylic acid Drill drilling according to (6) above, comprising one or more water-insoluble resins selected from the group consisting of copolymer resins, ionomer resins, and ethylene / (meth) acrylic acid ester copolymer resins Entry sheet.
- the water-insoluble lubricant that is not the solid lubricant is one selected from the group consisting of amide compounds, fatty acid compounds, fatty acid ester compounds, aliphatic hydrocarbon compounds, and higher aliphatic alcohols Or the entry sheet for drilling
- a primer layer that is a resin film is further provided between the metal support foil and the layer made of the resin composition, and the primer layer has a thickness in the range of 0.002 to 0.02 mm.
- the resin contained in the primer layer contains one or more thermosetting resins selected from the group consisting of epoxy resins and cyanate resins.
- the resin contained in the primer layer is selected from the group consisting of urethane polymers, vinyl acetate polymers, vinyl chloride polymers, polyester polymers, acrylic polymers, and their copolymer resistance.
- the resin contained in the primer layer is one or more adhesives selected from the group consisting of melamine resin, urea resin, phenol resin, chloroprene rubber, nitrile rubber, styrene butadiene rubber, and silicone rubber.
- the layer made of the resin composition is formed on the at least one surface of the metal supporting foil by a coating method, and the layer made of the resin composition has a boiling point higher than water and water.
- a solution dissolved or dispersed in a mixed solvent with a low solvent is applied on the at least one surface of the metal supporting foil, and the solvent having a boiling point lower than that of water is alcohol, methyl ethyl ketone, acetone, tetrahydrofuran , And an entry sheet for drilling according to any one of (1) to (16) above, comprising one or more solvents selected from the group consisting of acetonitrile.
- the drill hole entry sheet of the present embodiment (hereinafter, also simply referred to as “entry sheet”) includes a metal support foil and a layer (hereinafter referred to as a resin composition) formed on at least one side of the metal support foil.
- the resin composition contains a resin and 70 parts by mass to 130 parts by mass of molybdenum disulfide as a solid lubricant with respect to 100 parts by mass of the resin,
- the resin composition layer has a thickness in the range of 0.02 to 0.3 mm.
- the solid lubricant is a solid used as a thin film or powder to protect the drill bit and the hole wall surface of the printed wiring board material from damage during relative motion and reduce friction and wear.
- the solid lubricant preferably has a melting point of 300 ° C. or higher, which makes it more thermally stable even in air at a temperature (for example, 200 ° C.) higher than the operating temperature of the entry sheet when drilling. It is difficult to melt and can maintain a solid state.
- the operating temperature of the entry sheet at the time of drilling differs depending on the drill bit diameter, the drill bit rotation speed (rpm), and the workpiece, it is preferably 100 ° C. or more and less than 200 ° C. For example, for a drill bit with an average diameter of 0.9 mm ⁇ , it may be 120 ° C.
- the resin composition of the present embodiment is preferably a composition containing a water-soluble resin (A).
- the water-soluble resin (A) is a concept including a water-soluble lubricant that is not a solid lubricant in addition to a water-soluble resin.
- the “non-solid lubricant” lubricant is a concept including a liquid lubricant and a semi-solid lubricant.
- the resin composition of the present embodiment may include a known thermoplastic water-insoluble resin, a water-insoluble lubricant that is not a solid lubricant, and other additives such as a nucleating agent, a colorant, A heat stabilizer or the like may be included.
- water-insoluble means that the solubility in water at room temperature is 10 mg / dm 3 or less. That is, in this specification, “water-soluble” means that the solubility in water at room temperature exceeds 10 mg / dm 3 .
- Examples of the resin contained in the resin composition of the present embodiment include a water-soluble resin (A), a thermoplastic water-insoluble resin, and a water-insoluble lubricant that is not a solid lubricant.
- the resin contained in the resin composition plays the role of a carrier that moves the solid lubricant toward the drill bit and the printed wiring board material in addition to the original role of the resin in the entry sheet. That is, the resin can be moved toward the drill bit or the printed wiring material by pushing the solid lubricant toward the drill bit or the printed wiring material when drilling with the drill bit.
- the resin composition of this embodiment contains 70 parts by mass to 130 parts by mass and 80 parts by mass to 110 parts by mass of molybdenum disulfide with respect to 100 parts by mass of the resin contained in the resin composition.
- the content is preferably 80 to 100 parts by mass.
- the content ratio of molybdenum disulfide is 70 parts by mass or more, the object of the present invention can be achieved more effectively and reliably.
- the content ratio of molybdenum disulfide is 130 parts by mass or less, the aggregation of molybdenum disulfide can be more effectively and reliably suppressed, and as a result, the hole position accuracy is sufficiently good.
- Molybdenum disulfide (MoS 2 ) has the following characteristics. That is, molybdenum disulfide has a Mohs hardness of 1 to 1.5 and is a soft mineral next to talc. Molybdenum disulfide does not melt even when heated, but gradually oxidizes from 350 ° C. in the atmosphere to molybdenum trioxide (MoO 3 ). When molybdenum disulfide is further heated, it decomposes thermally.
- the characteristic of molybdenum disulfide is that the coefficient of friction ⁇ is smaller than that of graphite, which is a conventional solid lubricant, and in particular in the temperature region of 100 ° C. or more and less than 200 ° C., it is hardly affected by humidity. The friction coefficient ⁇ is stable. On the other hand, graphite is not necessarily so, and the friction coefficient ⁇ increases in the above temperature range.
- the present inventors have a critical content ratio range that expresses an exceptional improvement in hole position accuracy when molybdenum disulfide is used as the solid lubricant to be blended in the drill drilling entry sheet. I found out.
- the inclusion of molybdenum disulfide in a specific ratio in the resin composition can be applied to zinc molybdate, molybdenum trioxide, etc., which have been considered to be good solid lubricants for improving the hole position accuracy.
- the molybdenum disulfide preferably has a friction coefficient ⁇ of 0.2 or less, particularly at a drilling temperature of 100 ° C. or higher and lower than 200 ° C.
- the measuring method of the friction coefficient ⁇ conforms to JIS K7125 (1999).
- the friction coefficient ⁇ is 0.2 or less, the original performance as a solid lubricant can be more effectively and reliably exhibited.
- the purity of molybdenum disulfide is preferably 85% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more.
- the upper limit of the purity of molybdenum disulfide is not specifically limited, 100 mass% may be sufficient and 99 mass% may be sufficient.
- the purity of molybdenum disulfide is measured by the difference method.
- molybdenum oxide, iron, insoluble residue, carbon, water, and oil contained in molybdenum disulfide are impurities, and the value obtained by subtracting the mass of the impurities from the total mass is the molybdenum disulfide mass.
- the mass ratio of molybdenum is defined as its purity.
- ICP Inductively ⁇ Coupled Plasma
- the mechanism of action by the solid lubricant is considered as follows.
- the mechanism of action is not limited to this. That is, at the time of drilling, the drill bit is heated by frictional heat between the drill bit and an object to be drilled (for example, a printed wiring board material such as a laminated board or a multilayer board).
- an object to be drilled for example, a printed wiring board material such as a laminated board or a multilayer board.
- the resin composition around the drill bit has a temperature higher than the melting point of the resin contained therein, the resin melts and exhibits lubricity.
- the drill bit easily slides due to melting or thermal deformation of the resin contained in the resin composition.
- FIGS. 8 and 9 are diagrams schematically showing how the drill bit enters the entry sheet when drilling, and the water-soluble resin (A) that has become a crystal indicated by the symbol B is used as the resin.
- FIG. 9 shows a case where the resin composition contains no solid lubricant
- FIG. 9 shows a case where the resin composition contains molybdenum dioxide as a solid lubricant.
- the tip of the drill bit A enters the resin composition layer and searches for a biting point while skidding. It will be.
- the present inventors have found that molybdenum disulfide is blended as a solid lubricant and the blending amount is optimized.
- molybdenum disulfide which is a solid lubricant, has an appropriate hardness. And even under the temperature at the time of drilling, the solid state of the shape is maintained, and the position is easily fixed.
- the resin composition containing the water-soluble resin (A) B includes molybdenum dioxide E as a solid lubricant as shown in FIG. 9, when the tip of the drill bit A enters the resin composition layer, The solid lubricant E having a fixed shape and position is eaten. As a result, the centripetal force D is increased, and in particular, there is an effect of being excellent in the initial and cumulative 3,000-hits hole position accuracy.
- molybdenum disulfide E which is a solid lubricant, maintains a solid state with a fixed shape even at the drilling temperature, so that the thermal deformation of the resin composition and the skidding of the drill bit A Can be suppressed. Then, the drill bit A can obtain a sufficient centering force D, and the hole position accuracy is improved. As a result, even in the cumulative 6,000 hits in which the wear of the drill bit A has progressed, a remarkable effect of excellent hole position accuracy is exhibited.
- molybdenum disulfide E which is a solid lubricant, adheres to the surface and grooves of the drill bit A and the hole wall of the object to be drilled.
- Molybdenum disulfide E which is a solid lubricant, has a fixed shape because it is solid, so that it is always present between the object to be drilled and the drill bit A to improve lubricity and suppress drill bit wear. It becomes possible to play.
- Molybdenum disulfide which is a solid lubricant, is contained in a resin film (which will be described in detail later, hereinafter also referred to as “primer layer”) that may be provided between the metal support foil and the resin composition layer. Also good. Since the primer layer is in direct contact with the metal support foil (for example, aluminum foil), the inclusion of molybdenum disulfide in the primer layer has the effect of improving the hole position accuracy by molybdenum disulfide even in the immediate vicinity of the metal support foil. Can do. In particular, molybdenum disulfide is further included in the primer layer so that the particles are in contact with each other (by fine packing), thereby further enhancing the effect of improving the hole position accuracy.
- Molybdenum disulfide is preferably contained in an amount of 1 to 50 parts by mass, and more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the composition constituting the primer layer.
- the content ratio of molybdenum disulfide is 1 part by mass or more, the effect of molybdenum disulfide can be more effectively and reliably exhibited.
- the content ratio of molybdenum disulfide is 50 parts by mass or less, the adhesion between the thin primer layer and the metal supporting foil can be maintained higher.
- the resin constituting the primer layer containing molybdenum disulfide may be either a thermosetting resin or a thermoplastic resin, or may be an adhesive resin.
- Molybdenum disulfide is more suitable to select the optimal particle size and content ratio within a specific range according to the specifications of the drilled object, for example, printed wiring board material such as a laminated board or multilayer board. preferable.
- Molybdenum disulfide has a layered structure, has a fixed shape, and is a solid having an appropriate hardness.
- the molybdenum disulfide contained in the resin composition preferably has a particle size in the range of 0.1 to 50 ⁇ m, more preferably in the range of 0.5 to 29 ⁇ m.
- the average particle diameter of molybdenum disulfide is preferably 1 ⁇ m to 20 ⁇ m, more preferably 1 ⁇ m to 15 ⁇ m, still more preferably 1 ⁇ m to 10 ⁇ m, and particularly preferably 3 ⁇ m to 8 ⁇ m. Due to its characteristics, molybdenum disulfide is particularly susceptible to biting in small diameter drill bits where hole position accuracy is important. In addition, since molybdenum disulfide has a layered structure and a thin shape, molybdenum disulfide is easy to be caught in the groove when the drill bit is rotated, and contributes to discharge of chips.
- the average particle diameter of molybdenum disulfide is 1 ⁇ m or more, the position of the solid lubricant whose shape is fixed is more easily fixed, so that the function as the solid lubricant is more effectively and reliably performed.
- the average particle diameter of molybdenum disulfide is 20 ⁇ m or less, the hole position accuracy can be further improved, and the discharge of chips can be further facilitated.
- the average particle size value of the molybdenum disulfide particle size is more important than the maximum particle size value. This is because the overall particle diameter of molybdenum disulfide contained in the resin composition at a high ratio of 70 to 130 parts by mass with respect to 100 parts by mass of the resin is the characteristic of the drilling entry sheet. This is because it has a greater influence on the positional accuracy and lubricity. Therefore, it is more important to manage the average particle size than the maximum particle size of molybdenum disulfide in order to improve the performance of the drill hole entry sheet.
- a sample is dispersed in a solution consisting of a 0.2% hexametaphosphate solution and a few drops of 10% triton, and a laser diffraction particle size distribution analyzer (model number: The maximum length of each projected solid lubricant particle is measured using SALD-2100 (manufactured by Shimadzu Corporation).
- SALD-2100 manufactured by Shimadzu Corporation
- a particle size distribution curve is created from the measurement results.
- the range from the maximum particle size to the minimum particle size indicated by the curve is the range of the particle size of the solid lubricant, and the particle size distribution curve is the average particle size is the particle size having the highest solid lubricant content on a volume basis. To do.
- ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Molybdenum disulfide is non-swellable. For this reason, unlike the swellable solid lubricant, it is not necessary to strictly manage the moisture retention, which is industrially advantageous.
- an aqueous solution in which 10 parts by mass of a solid lubricant is blended in 90 parts by mass of water has a constant inner diameter in the height direction of a beaker or a flask, and has a flat inner bottom surface. Place in a container and stir until well mixed.
- the sedimentation height of the solid lubricant is measured, and the sedimentation height ratio (from the inner bottom surface to the upper surface of the solid lubricant sediment relative to the height from the inner bottom surface of the container to the liquid surface of the aqueous solution) (Height ratio) is less than 50% is defined as non-swelling.
- the case where the sedimentation height ratio is 90% or more is defined as dispersion or swelling, and the case where the sedimentation height ratio is 50% or more and less than 90% is defined as swelling.
- the height from the inner bottom surface to the liquid surface is 68 mm
- the height from the inner bottom surface to the top surface of the molybdenum disulfide sediment is 28 mm
- the sedimentation height ratio is 41.2%
- the resin contained in the resin composition is a water-soluble resin (A), and a solution (dispersion) containing the water-soluble resin (A) and molybdenum disulfide at the time of preparing the entry sheet.
- a water-soluble resin (A) a water-soluble resin (A)
- a solution (dispersion) containing the water-soluble resin (A) and molybdenum disulfide at the time of preparing the entry sheet has the following advantages. First, molybdenum disulfide tends to be uniformly dispersed in the liquid and is less likely to aggregate. As a result, also in the resulting entry sheet, molybdenum disulfide can be favorably dispersed throughout the sheet. Moreover, when molybdenum disulfide remains in a hole after drilling, it becomes easy to wash. However, when manufacturing the solution of water-soluble resin (A), it is preferable to stir sufficiently so that the concentration gradient of molybdenum disulfide does not occur.
- the water-soluble resin (A) is not particularly limited. As described above, the water-soluble resin (A) is a concept including a water-soluble resin and a water-soluble lubricant that is not a solid lubricant.
- the water-soluble resin include one or two selected from the group consisting of polyethylene oxide, polypropylene oxide, sodium polyacrylate, polyacrylamide, polyvinyl pyrrolidone, cellulose derivatives, polytetramethylene glycol, and polyalkylene glycol polyesters. The above is preferable. Polyester of polyalkylene glycol is a condensate obtained by reacting polyalkylene glycol and dibasic acid.
- polyalkylene glycol examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and glycols exemplified by these copolymers.
- dibasic acid examples include partial esters of polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, sebacic acid and pyromellitic acid, and acid anhydrides. These are used singly or in combination of two or more.
- water-soluble lubricants that are not solid lubricants include polyethylene glycol and polypropylene glycol; polyoxyethylene oleyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene lauryl ether, and polyoxyethylene nonyl.
- Polyoxyethylene monoethers exemplified by phenyl ether, polyoxyethylene octylphenyl ether, etc .; polyoxyethylene monostearate, polyoxyethylene sorbitan monostearate; hexaglycerin monostearate, decahexaglycerin monostearate, etc. And polyglycerin monostearates; and polyoxyethylene propylene copolymers. These are used singly or in combination of two or more.
- thermoplastic water-insoluble resin is not particularly limited, and a known substance can be applied.
- thermoplastic water-insoluble resins include amide elastomers, butadiene elastomers, ester elastomers, olefin elastomers, urethane elastomers, styrene elastomers, polybutenes, low density polyethylene, chlorinated polyethylene, and metallocene polyolefin resins.
- Ethylene / acrylic acid ester / maleic anhydride copolymer Ethylene / acrylic acid ester / maleic anhydride copolymer, ethylene / glycidyl (meth) acrylate copolymer, ethylene / vinyl acetate copolymer resin, modified ethylene / vinyl acetate copolymer resin, ethylene / (meth) acrylic acid copolymer
- Polymerized resins, ionomer resins, and ethylene / (meth) acrylic acid ester copolymer resins are exemplified. These are used singly or in combination of two or more.
- the water-insoluble lubricant that is not a solid lubricant is not particularly limited, and a known substance can be applied.
- water-insoluble lubricants that are not solid lubricants include amide compounds exemplified by ethylene bisstearoamide, oleic amide, stearamide, methylene bisstearamide, lauric acid, stearic acid, and palmitic acid.
- Fatty acid compounds exemplified by acid, oleic acid, etc. fatty acid ester compounds exemplified by butyl stearate, butyl oleate, glycol laurate, etc., aliphatic hydrocarbon compounds exemplified by liquid paraffin, polyethylene wax, etc.
- Higher aliphatic alcohols exemplified by olein alcohol and the like. These are used singly or in combination of two or more.
- the thickness of the resin composition layer varies depending on the diameter of the drill bit used for drilling and the structure of the drilling object to be processed (for example, a printed wiring board material such as a laminated board or a multilayer board).
- the thickness of the resin composition layer is preferably in the range of 0.02 to 0.3 mm, and more preferably in the range of 0.02 to 0.2 mm.
- the thickness of the resin composition layer is 0.02 mm or more, a more sufficient lubrication effect is obtained and the load on the drill bit is reduced, so that breakage of the drill bit can be further suppressed.
- the thickness of the resin composition layer is 0.3 mm or less, the wrapping of the resin composition around the drill bit can be suppressed.
- a method for forming the resin composition layer for example, a solution obtained by appropriately melting the resin composition, or a solution obtained by dissolving or dispersing in a solvent, directly or indirectly, on at least one surface of the metal supporting foil.
- resin composition solution a method (coating method) of forming a resin composition by drying, cooling, or solidifying the coating liquid may be mentioned.
- a method (hot melt method) in which a sheet of a resin composition is prepared in advance and bonded to a metal supporting foil may be used. At that time, the fact that the resin film (primer layer) is formed in advance on one side of the metal support foil forming the resin composition layer is because the metal support foil and the resin composition layer are laminated and integrated. preferable. Details will be described later.
- the solvent used is water and water. It is preferable that the mixed solvent contains a solvent having a lower boiling point. Use of a mixed solvent containing water and a solvent having a boiling point lower than that of water contributes to generation of dense spherulites and reduction of residual bubbles in the resin composition.
- the solvent having a boiling point lower than that of water is not particularly limited, and examples thereof include alcohols such as ethanol, methanol and isopropyl alcohol, and low-boiling solvents such as methyl ethyl ketone and acetone can also be used.
- the other solvent examples include a solvent obtained by partially mixing tetrahydrofuran or acetonitrile having high compatibility with the resin composition in water and alcohols.
- the mixing ratio of water and a solvent having a boiling point lower than that of water is preferably in the range of 90/10 to 50/50, more preferably in the range of 80/20 to 50/50 on a mass basis.
- the range of 70/30 to 50/50 is more preferable, and the range of 60/40 to 50/50 is more preferable.
- the mixing ratio of the solvent having a boiling point lower than that of water is 10 or more, when the water-soluble resin (A) is used, the dense spherulites are more easily generated.
- the mixing ratio of the solvent having a boiling point lower than that of water is 50 or less, the entry sheet can be produced more stably industrially.
- the temperature of the entry sheet for drilling is preferably 120 ° C. to 160 ° C.
- the cooling and solidification is preferably normal temperature. After heating and drying, the temperature reaches normal temperature (for example, 10 to 30 ° C.) in 5 to 30 seconds. It is preferable to cool.
- the heating temperature is 160 ° C. or lower, the entry sheet can be produced industrially and more stably.
- the cooling temperature is room temperature, it is possible to suppress the formation of condensation in a subsequent process.
- the metal support foil used for the drill hole entry sheet of this embodiment is not particularly limited, but is preferably a metal material that has high adhesion to the resin composition layer and can withstand the impact of the drill bit.
- the thickness of the metal supporting foil is preferably 0.05 to 0.5 mm, more preferably 0.05 to 0.3 mm. When the thickness of the metal supporting foil is 0.05 mm or more, the occurrence of burrs on the drilling object (for example, a laminated plate) can be suppressed during drilling. Moreover, when the metal support foil has a thickness of 0.5 mm or less, it is easier to discharge chips generated during drilling.
- species of metal support foil aluminum is preferable from a viewpoint of availability, cost, and workability.
- the aluminum foil is preferably aluminum having a purity of 95% or more.
- examples of such an aluminum foil include 5052, 3004, 3003, 1N30, 1N99, 1050, 1070, 1085, and 8021 defined in JIS-H4160.
- the thickness of the primer layer is preferably 0.002 to 0.02 mm, and more preferably 0.002 to 0.01 mm.
- the thickness of the primer layer can be appropriately selected according to the particle size of molybdenum disulfide.
- the resin contained in the primer layer is preferably one that can improve adhesion to the resin composition layer, and may be either a thermoplastic resin or a thermosetting resin, or an adhesive resin. Also good.
- thermoplastic resin examples include urethane polymers, vinyl acetate polymers, vinyl chloride polymers, polyester polymers, acrylic polymers, and copolymers thereof.
- thermosetting resin examples include epoxy resins and cyanate resins.
- adhesive resin that functions as an adhesive examples include synthetic resins such as melamine resin, urea resin, and phenol resin, chloroprene rubber, nitrile rubber, styrene butadiene rubber, and silicone rubber, in addition to the above-described resins. .
- the resin contained in a primer layer is used individually by 1 type or in combination of 2 or more types.
- each layer constituting the drill hole entry sheet is measured as follows. That is, from the surface of the resin composition layer side of the drill hole entry sheet, a cross section polisher (manufactured by JEOL Datum Co., Ltd., trade name “CROSS-SECTION POLISER SM-09010”), or ultra microtome (manufactured by Leica, Using the product name “EM UC7”), the entry sheet for drilling is cut in the stacking direction of each layer.
- a cross section polisher manufactured by JEOL Datum Co., Ltd., trade name “CROSS-SECTION POLISER SM-09010”
- ultra microtome manufactured by Leica, Using the product name “EM UC7”
- the entry sheet for drilling according to the present embodiment is preferable when it is used for drilling a laminated board or a multilayer board because the object of the present invention is more effectively and reliably achieved.
- the drilling process is a drilling process with a diameter (drill bit diameter) of 0.2 mm ⁇ or less, preferably a drilling process with a diameter of 0.05 mm ⁇ or more and 0.2 mm ⁇ or less. Can be achieved more effectively and reliably.
- drill bit breakage when drill bit applications with small diameter of 0.05mm ⁇ or more and 0.15mm ⁇ or less, especially extremely small drill bits of 0.05mm ⁇ or more and 0.105mm ⁇ or less, where hole position accuracy is important Is preferable in that it can be significantly reduced.
- the drill bit diameter of 0.05 mm ⁇ is the lower limit of the available drill bit diameter, and is not limited to the above as long as a drill bit having a smaller diameter becomes available. Moreover, there is no problem even if the entry sheet of this embodiment is adopted for drilling using a drill bit having a diameter of more than 0.2 mm ⁇ .
- the entry sheet for drilling of this embodiment is used, for example, when drilling a printed wiring board material, more specifically, a laminated board or a multilayer board.
- an entry sheet for drilling is provided on at least the uppermost surface of one or a plurality of laminated boards or multilayer boards (printed wiring board material) so that the metal supporting foil side is in contact with the printed wiring board material. It can arrange
- the drill drilling entry sheet of the present embodiment can reduce breakage of the drill bit during drilling due to excellent hole positioning accuracy during drilling and excellent lubricity of the resin composition layer. As a result, it is possible to design a higher density, and to perform drilling with high quality and excellent productivity. Alternatively, it is possible to increase the number of stacked holes to be drilled at a time, contributing to productivity improvement and cost reduction.
- Polyethylene glycol may be abbreviated as “PEG” and “polyethylene oxide” may be abbreviated as “PEO”.
- Example 1 30 parts by mass of polyethylene oxide having a weight average molecular weight of 150,000 (manufactured by Meisei Chemical Co., Ltd., trade name: Altop MG-150) and polyethylene glycol having a weight average molecular weight of 20,000 (trade name, manufactured by Sanyo Chemical Industries, Ltd.) : PEG 20000) was dissolved in a water / MeOH (methanol) mixed solution so that the resin solid content was 30% by mass. The ratio of water and MeOH at this time was 60/40 by mass ratio.
- molybdenum disulfide manufactured by Daizo Co., Ltd., particle size range: 0.5 ⁇ m to 29 ⁇ m, average particle size: 5 ⁇ m, molybdenum disulfide purity: 98%, Friction coefficient ⁇ : 0.4
- Resin composition side of the aluminum foil (usage aluminum foil: 1100, thickness 0.1 mm, manufactured by Mitsubishi Aluminum Co., Ltd.) in which an epoxy resin film having a thickness of 0.01 mm is formed on one surface of the resin composition solution thus obtained.
- the resin composition layer after drying was applied to a thickness of 0.05 mm, dried at 120 ° C. for 5 minutes in a dryer, and then cooled to room temperature.
- An opening entry sheet was prepared.
- a scanning electron micrograph (magnification: 10,000 times) of a part of molybdenum disulfide used in this example is shown in FIG.
- Example 2 In accordance with Example 1, a resin composition solution was prepared with the types and content ratios of the materials shown in Table 1, and the resin composition layer after drying had a thickness of 0.05 mm. Was made.
- n indicates the number of drills used.
- For the hole position accuracy refer to the hole position accuracy of 3,000 hits where the drill bit wear is not relatively advanced and the hole position accuracy of 6,000 hits where the drill bit wear is relatively advanced.
- the determination criteria shown in Table 1 were used. The lower judgment of the cumulative drilling numbers of 3,000 hits and 6,000 hits was regarded as a comprehensive judgment. At this time, “ ⁇ ” indicates that the hole position accuracy is very good, “ ⁇ ” indicates that the hole position accuracy is good, “ ⁇ ” indicates that the hole position accuracy is slightly poor, and “ ⁇ ” indicates that the hole position accuracy is poor. .
- the particle size of the solid lubricant was measured as follows. First, a solid lubricant sample is dispersed in a solution consisting of a 0.2% hexametaphosphoric acid solution and a few drops of 10% Triton, and a laser diffraction particle size distribution analyzer (model number: SALD-2100, manufactured by Shimadzu Corporation) was used to measure the maximum length of each projected solid lubricant particle. Next, a particle size distribution curve was created from the measurement results.
- FIG. 4 shows the particle size distribution curves of molybdenum disulfide, zinc molybdate and molybdenum trioxide.
- the average particle size was ascending in order of zinc molybdate, molybdenum disulfide, and molybdenum trioxide.
- Table 1 shows the results of the hole position accuracy (average value (Ave.) + 3 ⁇ average value) for holes of 1 to 6,000 hits.
- Table 2 shows the results of the hole position accuracy (average value (Ave.) + 3 ⁇ average value) for holes of 1 to 6,000 hits.
- FIG. 5 shows the results of the hole position accuracy of all the examples and comparative examples plotted against the blending amount of the solid lubricant.
- ⁇ is a comparative example in which no solid lubricant is blended
- ⁇ is Examples 1 and 2
- ⁇ is a comparative example using a solid lubricant 2
- ⁇ is a solid lubricant 3.
- the comparative example using “x” and “x” indicate plots of the comparative example using the solid lubricant 4, respectively.
- composition (1) of the water-soluble resin (A) is 30 parts by mass of polyethylene oxide (manufactured by Meisei Chemical Co., Ltd., trade name: Altop MG-150, Mw: 150,000), polyethylene glycol (Sanyo Chemical Industries, Ltd.) Product name: PEG 20000, Mw: 20,000) 70 parts by mass, totaling 100 parts by mass.
- polyethylene oxide manufactured by Meisei Chemical Co., Ltd., trade name: Altop MG-150, Mw: 150,000
- polyethylene glycol Sanyo Chemical Industries, Ltd.
- the type (2) of the solid lubricant is molybdenum disulfide (manufactured by Daizo Co., Ltd., trade name: M-5 powder, particle size range: 0.5 to 29 ⁇ m, average particle size: 5 ⁇ m, molybdenum disulfide purity: 98 %, Layered structure).
- the type (3) of the solid lubricant is zinc molybdate (manufactured by Nippon Inorganic Chemical Industry Co., Ltd., particle size range: 0.4 ⁇ m to 13 ⁇ m, average particle size: 3 ⁇ m, layered structure. Partial scanning of zinc molybdate) Type electron micrograph (magnification: 10,000 times) is shown in FIG.
- the type (3) of the solid lubricant is molybdenum trioxide (manufactured by Nippon Inorganic Chemical Industry Co., Ltd., particle size range: 0.7 ⁇ m to 55 ⁇ m, average particle size: 16 ⁇ m, columnar structure. Partial scanning of molybdenum trioxide. Type electron micrograph (magnification: 10,000 times) is shown in FIG. Moreover, what did not use a solid lubricant was made into the kind (5).
- the solid lubricant is 0 part by weight, 5 parts by weight, 10 parts by weight, 20 parts by weight, 40 parts by weight, 60 parts by weight, 80 parts by weight, 90 parts by weight with respect to 100 parts by weight of the resin contained in the resin composition. , 100 parts by mass and 200 parts by mass.
- Drilling conditions (1) were a drill bit (C-CFU020S manufactured by Tungaloy Co., Ltd., drill bit diameter: 0.2 mm ⁇ ), rotation speed: 200,000 rpm, feed rate: 13 ⁇ m / rev. Ascending speed: 25.4 m / min, and the object to be drilled is a copper clad laminate (Mitsubishi Gas Chemical Co., Ltd., trade name: CCL-HL832, thickness: 0.2 mm, copper foil thickness: 12 ⁇ m) 5 were stacked.
- the present inventors blended molybdenum disulfide as a solid lubricant in a large amount from 70 parts by mass to 130 parts by mass with respect to 100 parts by mass of the resin contained in the resin composition.
- Even a person skilled in the art cannot predict the result of the present invention that achieves such a significant improvement in the hole position accuracy.
- molybdenum disulfide achieves extremely excellent hole position accuracy in any of the cumulative number of holes.
- the drill bit wear was not progressed compared to the samples of Comparative Examples 1 to 22 and the drill bit was not progressed. It was found that the position accuracy was excellent. That is, by optimizing the blending amount of molybdenum disulfide, the molybdenum disulfide of the present invention has a remarkable hole position accuracy as compared with conventionally used solid lubricants such as zinc molybdate and molybdenum trioxide. It was found to be excellent.
- an entry sheet for drilling that has excellent hole position accuracy and reduced breakage of the drill bit as compared to a conventional drilling entry sheet.
- A drill bit
- B crystal of water-soluble resin (A)
- C metal support foil
- D centripetal force
- E molybdenum disulfide
Abstract
Description
(1)金属支持箔と、その金属支持箔の少なくとも片面上に形成された樹脂組成物からなる層と、を備えるドリル孔あけ用エントリーシートであって、前記樹脂組成物は、樹脂と、その樹脂100質量部に対して70質量部~130質量部の固体潤滑剤としての二硫化モリブデンとを含有し、前記樹脂組成物からなる層は、0.02~0.3mmの範囲の厚さを有する、ドリル孔あけ用エントリーシート。
(2)前記二硫化モリブデンは、1~20μmの平均粒径を有する、上記(1)に記載のドリル孔あけ用エントリーシート。
(3)前記二硫化モリブデンの純度が、85質量%以上である、上記(1)又は(2)に記載のドリル孔あけ用エントリーシート。
(4)前記樹脂組成物は、水溶性樹脂(A)を含有する、上記(1)~(3)のいずれかに記載のドリル孔あけ用エントリーシート。
(5)前記水溶性樹脂(A)が、ポリエチレンオキサイド、ポリプロピレンオキサイド、ポリアクリル酸ソーダ、ポリアクリルアミド、ポリビニルピロリドン、セルロース誘導体、ポリテトラメチレングリコール及びポリアルキレングリコールのポリエステル、ポリエチレングリコール、ポリプロピレングリコール、ポリオキシエチレンのモノエーテル類、ポリオキシエチレンモノステアレート、ポリオキシエチレンソルビタンモノステアレート、ポリグリセリンモノステアレート類、およびポリオキシエチレンプロピレン共重合体からなる群より選択される1種または2種以上の水溶性樹脂を含む、上記(4)に記載のドリル孔あけ用エントリーシート。
(6)前記樹脂組成物は、熱可塑性の非水溶性樹脂を含む、上記(1)~(5)のいずれかに記載のドリル孔あけ用エントリーシート。
(7)前記熱可塑性の非水溶性樹脂が、アミド系エラストマー、ブタジエン系エラストマー、エステル系エラストマー、オレフィン系エラストマー、ウレタン系エラストマー、スチレン系エラストマー、ポリブテン、低密度ポリエチレン、塩素化ポリエチレン、メタロセン系ポリオレフィン樹脂、エチレン・アクリル酸エステル・無水マレイン酸共重合体、エチレン・グリシジル(メタ)アクリレート共重合体、エチレン・酢酸ビニル共重合樹脂、変性エチレン・酢酸ビニル共重合樹脂、エチレン・(メタ)アクリル酸共重合樹脂、アイオノマー樹脂、およびエチレン・(メタ)アクリル酸エステル共重合樹脂からなる群より選択される1種または2種以上の非水溶性樹脂を含む、上記(6)に記載のドリル孔あけ用エントリーシート。
(8)前記樹脂組成物は、固体潤滑剤ではない非水溶性潤滑剤を含む、上記(1)~(7)のいずれかに記載のドリル孔あけ用エントリーシート。
(9)前記固体潤滑剤ではない非水溶性潤滑剤が、アマイド系化合物、脂肪酸系化合物、脂肪酸エステル系化合物、脂肪族炭化水素系化合物、および高級脂肪族アルコールからなる群より選択される1種または2種以上の化合物を含む、上記(8)に記載のドリル孔あけ用エントリーシート。
(10)前記金属支持箔は、0.05~0.5mmの範囲の厚さを有する、上記(1)~(9)のいずれかに記載のドリル孔あけ用エントリーシート。
(11)前記金属支持箔と前記樹脂組成物からなる層との間に、樹脂皮膜であるプライマー層を更に備え、該プライマー層は0.002~0.02mmの範囲の厚さを有する、上記(1)~(10)のいずれかに記載のドリル孔あけ用エントリーシート。
(12)前記プライマー層が、二硫化モリブデンを含む固体潤滑剤を含有する、上記(11)に記載のドリル孔あけ用エントリーシート。
(13)前記プライマー層は、前記二硫化モリブデンを、プライマー層を構成する組成物100質量部に対して、1質量部~50質量部含む、上記(12)に記載のドリル孔あけ用エントリーシート。
(14)前記プライマー層に含まれる前記樹脂が、エポキシ系樹脂およびシアネート系樹脂からなる群より選択される1種または2種以上の熱硬化性樹脂を含む、上記(11)~(13)のいずれかに記載のドリル孔あけ用エントリーシート。
(15)前記プライマー層に含まれる前記樹脂が、ウレタン系重合体、酢酸ビニル系重合体、塩化ビニル系重合体、ポリエステル系重合体、およびアクリル系重合体並びにそれらの共重合耐からなる群より選択される1種または2種以上の熱可塑性樹脂を含む、上記(11)~(13)のいずれかに記載のドリル孔あけ用エントリーシート。
(16)前記プライマー層に含まれる前記樹脂が、メラミン樹脂、ユリア樹脂、フェノール樹脂、クロロプレンゴム、ニトリルゴム、スチレンブタジエンゴム、およびシリコーンゴムからなる群より選択される1種または2種以上の接着性樹脂を含む、上記(11)~(13)のいずれかに記載のドリル孔あけ用エントリーシート。
(17)前記樹脂組成物からなる層が、前記金属支持箔の前記少なくとも片面上にコーティング法により形成されるものであって、前記樹脂組成物からなる層は、水と、水よりも沸点の低い溶媒との混合溶媒に溶解または分散させた液を、前記金属支持箔の前記少なくとも片面上に塗布されたものであって、前記水よりも沸点の低い溶媒が、アルコール、メチルエチルケトン、アセトン、テトラヒドロフラン、およびアセトニトリルからなる群より選択される1種または2種以上の溶媒を含む、上記(1)~(16)のいずれかに記載のドリル孔あけ用エントリーシート。
(18)前記混合溶媒に含まれる前記水と、前記水よりも沸点の低い溶媒との配合比が、質量基準で90/10~50/50の範囲である、上記(17)に記載のドリル孔あけ用エントリーシート。
(19)直径0.2mmφ以下のドリルビットによる孔あけ加工に用いられる、上記(1)~(18)のいずれかに記載のドリル孔あけ用エントリーシート。
(20)積層板または多層板のドリル孔あけ加工に用いられる、上記(1)~(19)のいずれかに記載のドリル孔あけ用エントリーシート。
本実施形態のドリル孔あけ用エントリーシート(以下、単に「エントリーシート」ともいう。)は、金属支持箔と、その金属支持箔の少なくとも片面上に形成された樹脂組成物からなる層(以下、「樹脂組成物層」という。)と、を備えるドリル孔あけ用エントリーシートである。本実施形態のドリル孔あけ用エントリーシートにおいて、該樹脂組成物は、樹脂と、その樹脂100質量部に対して70質量部~130質量部の固体潤滑剤としての二硫化モリブデンとを含有し、該樹脂組成物層は、0.02~0.3mmの範囲の厚さを有するものである。
重量平均分子量150,000のポリエチレンオキサイド(明成化学工業株式会社製、商品名:アルトップMG-150)30質量部と、重量平均分子量20,000のポリエチレングリコール(三洋化成工業株式会社製、商品名:PEG20000)70質量部とを、樹脂固形分が30質量%になるように、水/MeOH(メタノール)混合溶液に溶解させた。この時の水とMeOHとの比率を質量比で60/40とした。さらに、この水溶性樹脂組成物の溶液に、固体潤滑剤として二硫化モリブデン(ダイゾー株式会社製、粒径の範囲:0.5μm~29μm、平均粒径:5μm、二硫化モリブデン純度:98%、摩擦係数μ:0.4)を水溶性樹脂組成物に含まれる樹脂100質量部に対して、80質量部配合し、十分に分散させた。こうして得られた樹脂組成物溶液を、片面に厚さ0.01mmのエポキシ樹脂皮膜を形成したアルミニウム箔(使用アルミニウム箔:1100、厚さ0.1mm、三菱アルミニウム株式会社製)の樹脂皮膜面側に、バーコーターを用いて、乾燥後の樹脂組成物層の厚さが0.05mmになるように塗布し、乾燥機にて120℃で5分間乾燥後、常温まで冷却することで、ドリル孔あけ用エントリーシートを作製した。なお、本実施例で用いた二硫化モリブデンの一部の走査型電子顕微鏡写真(倍率:10000倍)を、図1に示す。
実施例1に準じて、表1に示す各材料の種類及び含有割合にて樹脂組成物溶液を調製し、乾燥後の樹脂組成物層の厚さが0.05mmであるドリル孔あけ用エントリーシートを作製した。
実施例1に準じて、表1に示す各材料の種類及び含有割合にて樹脂組成物溶液を調製し、乾燥後の樹脂組成物層の厚さが0.05mmであるドリル孔あけ用エントリーシートを作製した。
実施例及び比較例で作製したドリル孔あけ用エントリーシートの各サンプルについて、以下の評価を行った。
(1)孔位置精度
積み重ねた銅張積層板上に、ドリル孔あけ用エントリーシートをその樹脂組成物層を上にして配置し、ドリル孔あけ加工を行った。ドリルビット1本につき6,000hitsの孔あけ加工し、4本のドリルビットを用いて繰り返した。ドリルビット1本分ごとに、1~1,500hits、1~3,000hits、1~4,500hits、1~6,000hitsの孔につき、積み重ねた銅張積層板の最下板の裏面(下面)における孔位置と指定座標とのズレを、ホールアナライザー(型番:HA-1AM、日立ビアメカニクス株式会社製)を用いて測定した。そのズレについて、平均値及び標準偏差(σ)を計算し、「平均値+3σ」を算出した。その後、ドリル孔あけ加工全体の孔位置精度として、使用した4本のドリルビットについて、それぞれの「平均値+3σ」の値に対する平均値を算出して表記した。用いた式は、下記のとおりである。1~3,000hits、1~6,000hitsの結果を、表1に示す。
固体潤滑剤の粒度は下記のようにして測定した。まず、固体潤滑剤の試料を0.2%ヘキサメタりん酸溶液と10%トリトン数滴とからなる溶液に分散させ、レーザー回折式粒度分布測定装置(型番:SALD-2100、株式会社島津製作所製)を使用して、投影した固体潤滑剤の粒子それぞれの最大長さを測定した。次いで、測定結果から粒度分布曲線を作成した。その曲線の示す最大粒径から最小粒径の範囲を固体潤滑剤の粒径の範囲とし、また、粒度分布曲線において固体潤滑剤の質量基準での含有割合が最も高い粒径を平均粒径とした。図4に、二硫化モリブデン、モリブデン酸亜鉛および三酸化モリブデンの粒度分布曲線を示す。平均粒径は、小さい方から、モリブデン酸亜鉛、二硫化モリブデン、三酸化モリブデンの順であった。
固体潤滑剤の種類(3)は、モリブデン酸亜鉛(日本無機化学工業株式会社製、粒径の範囲:0.4μm~13μm、平均粒径:3μm、層状構造。モリブデン酸亜鉛の一部の走査型電子顕微鏡写真(倍率:10000倍)を図2に示す。)であった。
固体潤滑剤の種類(3)は、三酸化モリブデン(日本無機化学工業株式会社製、粒径の範囲:0.7μm~55μm、平均粒径:16μm、柱状構造。三酸化モリブデンの一部の走査型電子顕微鏡写真(倍率:10000倍)を図3に示す。)であった。
また、固体潤滑剤を用いなかったものを、種類(5)とした。
Claims (20)
- 金属支持箔と、その金属支持箔の少なくとも片面上に形成された樹脂組成物からなる層と、を備えるドリル孔あけ用エントリーシートであって、
前記樹脂組成物は、樹脂と、その樹脂100質量部に対して70質量部~130質量部の固体潤滑剤としての二硫化モリブデンとを含有し、
前記樹脂組成物からなる層は、0.02~0.3mmの範囲の厚さを有する、ドリル孔あけ用エントリーシート。 - 前記二硫化モリブデンは、1~20μmの平均粒径を有する、請求項1に記載のドリル孔あけ用エントリーシート。
- 前記二硫化モリブデンの純度が、85質量%以上である、請求項1又は2に記載のドリル孔あけ用エントリーシート。
- 前記樹脂組成物は、水溶性樹脂(A)を含有する、請求項1~3のいずれか1項に記載のドリル孔あけ用エントリーシート。
- 前記水溶性樹脂(A)が、ポリエチレンオキサイド、ポリプロピレンオキサイド、ポリアクリル酸ソーダ、ポリアクリルアミド、ポリビニルピロリドン、セルロース誘導体、ポリテトラメチレングリコール及びポリアルキレングリコールのポリエステル、ポリエチレングリコール、ポリプロピレングリコール、ポリオキシエチレンのモノエーテル類、ポリオキシエチレンモノステアレート、ポリオキシエチレンソルビタンモノステアレート、ポリグリセリンモノステアレート類、およびポリオキシエチレンプロピレン共重合体からなる群より選択される1種または2種以上の水溶性樹脂を含む、請求項4に記載のドリル孔あけ用エントリーシート。
- 前記樹脂組成物は、熱可塑性の非水溶性樹脂を含む、請求項1~5のいずれか1項に記載のドリル孔あけ用エントリーシート。
- 前記熱可塑性の非水溶性樹脂が、アミド系エラストマー、ブタジエン系エラストマー、エステル系エラストマー、オレフィン系エラストマー、ウレタン系エラストマー、スチレン系エラストマー、ポリブテン、低密度ポリエチレン、塩素化ポリエチレン、メタロセン系ポリオレフィン樹脂、エチレン・アクリル酸エステル・無水マレイン酸共重合体、エチレン・グリシジル(メタ)アクリレート共重合体、エチレン・酢酸ビニル共重合樹脂、変性エチレン・酢酸ビニル共重合樹脂、エチレン・(メタ)アクリル酸共重合樹脂、アイオノマー樹脂、およびエチレン・(メタ)アクリル酸エステル共重合樹脂からなる群より選択される1種または2種以上の非水溶性樹脂を含む、請求項6に記載のドリル孔あけ用エントリーシート。
- 前記樹脂組成物は、固体潤滑剤ではない非水溶性潤滑剤を含む、請求項1~7のいずれか1項に記載のドリル孔あけ用エントリーシート。
- 前記固体潤滑剤ではない非水溶性潤滑剤が、アマイド系化合物、脂肪酸系化合物、脂肪酸エステル系化合物、脂肪族炭化水素系化合物、および高級脂肪族アルコールからなる群より選択される1種または2種以上の化合物を含む、請求項8に記載のドリル孔あけ用エントリーシート。
- 前記金属支持箔は、0.05~0.5mmの範囲の厚さを有する、請求項1~9のいずれか1項に記載のドリル孔あけ用エントリーシート。
- 前記金属支持箔と前記樹脂組成物からなる層との間に、樹脂皮膜であるプライマー層を更に備え、該プライマー層は0.002~0.02mmの範囲の厚さを有する、請求項1~10のいずれか1項に記載のドリル孔あけ用エントリーシート。
- 前記プライマー層が、二硫化モリブデンを含む固体潤滑剤を含有する、請求項11に記載のドリル孔あけ用エントリーシート。
- 前記プライマー層は、前記二硫化モリブデンを、プライマー層を構成する組成物100質量部に対して、1質量部~50質量部含む、請求項12に記載のドリル孔あけ用エントリーシート。
- 前記プライマー層に含まれる前記樹脂が、エポキシ系樹脂およびシアネート系樹脂からなる群より選択される1種または2種以上の熱硬化性樹脂を含む、請求項11~13のいずれか1項に記載のドリル孔あけ用エントリーシート。
- 前記プライマー層に含まれる前記樹脂が、ウレタン系重合体、酢酸ビニル系重合体、塩化ビニル系重合体、ポリエステル系重合体、およびアクリル系重合体並びにそれらの共重合耐からなる群より選択される1種または2種以上の熱可塑性樹脂を含む、請求項11~13のいずれか1項に記載のドリル孔あけ用エントリーシート。
- 前記プライマー層に含まれる前記樹脂が、メラミン樹脂、ユリア樹脂、フェノール樹脂、クロロプレンゴム、ニトリルゴム、スチレンブタジエンゴム、およびシリコーンゴムからなる群より選択される1種または2種以上の接着性樹脂を含む、請求項11~13のいずれか1項に記載のドリル孔あけ用エントリーシート。
- 前記樹脂組成物からなる層が、前記金属支持箔の前記少なくとも片面上にコーティング法により形成されるものであって、前記樹脂組成物からなる層は、水と、水よりも沸点の低い溶媒との混合溶媒に溶解または分散させた液を、前記金属支持箔の前記少なくとも片面上に塗布されたものであって、前記水よりも沸点の低い溶媒が、アルコール、メチルエチルケトン、アセトン、テトラヒドロフラン、およびアセトニトリルからなる群より選択される1種または2種以上の溶媒を含む、請求項1~16のいずれか1項に記載のドリル孔あけ用エントリーシート。
- 前記混合溶媒に含まれる前記水と、前記水よりも沸点の低い溶媒との配合比が、質量基準で90/10~50/50の範囲である、請求項17に記載のドリル孔あけ用エントリーシート。
- 直径0.2mmφ以下のドリルビットによる孔あけ加工に用いられる、請求項1~18のいずれか1項に記載のドリル孔あけ用エントリーシート。
- 積層板または多層板のドリル孔あけ加工に用いられる、請求項1~19のいずれか1項に記載のドリル孔あけ用エントリーシート。
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US10159153B2 (en) | 2012-03-27 | 2018-12-18 | Mitsubishi Gas Chemical Company, Inc. | Entry sheet for drilling |
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JPWO2015152162A1 (ja) * | 2014-03-31 | 2017-04-13 | 三菱瓦斯化学株式会社 | ドリル孔あけ用エントリーシート |
KR102365234B1 (ko) * | 2014-03-31 | 2022-02-18 | 미츠비시 가스 가가쿠 가부시키가이샤 | 드릴 구멍 내기용 엔트리 시트 |
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US11383307B2 (en) | 2015-09-02 | 2022-07-12 | Mitsubishi Gas Chemical Company, Inc. | Entry sheet for drilling and method for drilling processing using same |
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US11819930B2 (en) | 2016-11-14 | 2023-11-21 | Mitsubishi Gas Chemical Company, Inc. | Material for built-up edge formation and built-up edge formation method |
US11225625B2 (en) | 2017-05-25 | 2022-01-18 | Mitsubishi Gas Chemical Company, Inc. | Lubricant material for assisting machining process, lubricant sheet for assisting machining process, and machining method |
JP2020107710A (ja) * | 2018-12-27 | 2020-07-09 | 大智化学産業株式会社 | 孔あけ加工用当て板 |
Also Published As
Publication number | Publication date |
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JPWO2013146612A1 (ja) | 2015-12-14 |
KR102066302B1 (ko) | 2020-01-14 |
PH12014502138A1 (en) | 2014-12-01 |
MY168401A (en) | 2018-11-01 |
RU2603401C2 (ru) | 2016-11-27 |
TWI593330B (zh) | 2017-07-21 |
IN2014DN07967A (ja) | 2015-05-01 |
JP5896345B2 (ja) | 2016-03-30 |
KR20140147092A (ko) | 2014-12-29 |
US20150072122A1 (en) | 2015-03-12 |
CN104321173A (zh) | 2015-01-28 |
TW201404258A (zh) | 2014-01-16 |
RU2014142826A (ru) | 2016-05-20 |
US10159153B2 (en) | 2018-12-18 |
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