WO2019187670A1 - Entry sheet for drilling, and drilling method employing same - Google Patents

Entry sheet for drilling, and drilling method employing same Download PDF

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Publication number
WO2019187670A1
WO2019187670A1 PCT/JP2019/004295 JP2019004295W WO2019187670A1 WO 2019187670 A1 WO2019187670 A1 WO 2019187670A1 JP 2019004295 W JP2019004295 W JP 2019004295W WO 2019187670 A1 WO2019187670 A1 WO 2019187670A1
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WO
WIPO (PCT)
Prior art keywords
resin composition
drilling
entry sheet
composition layer
drill bit
Prior art date
Application number
PCT/JP2019/004295
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French (fr)
Japanese (ja)
Inventor
孝幸 亀井
洋介 松山
賢二 石蔵
Original Assignee
三菱瓦斯化学株式会社
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Application filed by 三菱瓦斯化学株式会社 filed Critical 三菱瓦斯化学株式会社
Priority to KR1020207025533A priority Critical patent/KR102582789B1/en
Priority to CN201980022283.0A priority patent/CN111918752B/en
Priority to JP2020510356A priority patent/JP7129030B2/en
Publication of WO2019187670A1 publication Critical patent/WO2019187670A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B35/00—Methods for boring or drilling, or for working essentially requiring the use of boring or drilling machines; Use of auxiliary equipment in connection with such methods
    • 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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to an entry sheet for drilling and a drilling method using the same.
  • a drilling method for a laminated board or multilayer board used as a printed wiring board material generally one or a plurality of laminated boards or multilayer boards are stacked, and an aluminum foil alone or A method is employed in which a sheet in which a layer of a resin composition is formed on the surface of an aluminum foil (hereinafter, this “sheet” is referred to as “drill drilling entry sheet”) is drilled. .
  • Patent Document 1 discloses a water-soluble resin layer on an aluminum foil on which a thermosetting resin thin film is formed in order to meet the demands for reducing the inner wall roughness and improving the hole position accuracy at the time of drilling.
  • An entry sheet for drilling is disclosed.
  • Patent Document 2 discloses a lubricant sheet for drilling in which a non-halogen colorant is blended in a resin composition.
  • Patent Document 3 discloses a drilling auxiliary plate comprising a lubricating layer, a composite material including a nanostructured powder such as tungsten disulfide and a solid wear-resistant lubricating layer that is a high heat transfer compound, and a support.
  • Patent Document 4 discloses a drill hole entry sheet including a layer of a resin composition in which a water-soluble resin, a water-soluble lubricant and carbon powder are mixed.
  • Patent Document 5 discloses a heat-dissipating lubricated aluminum cover for drilling that contains graphite as an inorganic filler in a composite material.
  • the use range of the drill bit diameter in mass production is mostly from 0.5 mm to 0.105 mm. Specific examples include 0.5 mm, 0.45 mm, 0.4 mm, 0.35 mm, 0.3 mm, 0.25 mm, 0.2 mm, 0.15 mm, and 0.105 mm. Further, the minimum drill bit diameter is also shifting from 0.105 mm to 0.075 mm, and a small portion of 0.05 mm drilling has been attempted against the laser drilling technology. In addition, there is a strong demand for improving the hole position accuracy in printed wiring board processing with a drill bit diameter of 0.2 mm and 0.15 mm. Furthermore, because of the competition from globalization and the demand of emerging countries, demands for productivity improvement and cost reduction are also unknown.
  • the frictional heat between the drill bit and the laminate or multilayer board melts the resin composition containing the water-soluble resin around the drill bit, resulting in lubricity. Is expressed.
  • the effect of the lubricity of the resin composition layer is not always sufficient, and it does not sufficiently meet the demand for improving the hole position accuracy. In other words, it is desired to develop an entry sheet for drilling that meets the demand for higher hole position accuracy.
  • the present invention has been made in view of the above problems, and even when a drill having a small drill bit diameter is used, it has excellent resistance to breakage of the drill bit and hole position accuracy, and is free from scraps derived from an entry sheet for drilling.
  • An object of the present invention is to provide an entry sheet for drilling with less winding and a drilling method using the same.
  • the present invention is as follows.
  • [1] A metal foil, and a resin composition layer formed on at least one side of the metal foil,
  • the resin composition layer further satisfies a relationship represented by the following formula (iii): The entry sheet for drilling according to [1]. 0.005 ⁇ 10 5 ⁇ G ′ (70) ⁇ 80 ⁇ 10 5 (iii) (In the above formula, G ′ (70) represents the shear storage modulus (unit: Pa) of the resin composition at 70 ° C.)
  • the resin composition contains a water-soluble resin (A). The entry sheet for drilling according to [1] or [2].
  • the resin composition contains a filler (B), The entry sheet for drilling according to any one of [1] to [3].
  • the filler (B) is talc and / or molybdenum disulfide.
  • the water-soluble resin (A) is polyethylene oxide, polypropylene oxide, polytetramethylene glycol, polyethylene glycol, polypropylene glycol, polyoxyethylene monoether compound, polyoxyethylene monostearate, polyoxyethylene sorbitan monostearate, poly One or more selected from the group consisting of a glycerin monostearate compound and a polyoxyethylene propylene copolymer, [3] The entry sheet for drilling according to any one of [5] to [5]. [7]
  • the resin composition layer has a thickness in the range of 0.02 to 0.3 mm; The entry sheet for drilling according to any one of [1] to [6].
  • the metal foil has a thickness in the range of 0.05 to 0.5 mm;
  • the drill bit entry sheet has excellent resistance to breakage of the drill bit and hole position accuracy, and has little wrapping of debris derived from the drill hole entry sheet. And a drilling method using the same can be provided.
  • the present embodiment a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
  • the present invention is not limited to this, and various modifications can be made without departing from the gist thereof. Is possible.
  • the drill hole entry sheet of the present embodiment (hereinafter, also simply referred to as “entry sheet”) has a metal foil and a resin composition layer formed on at least one surface of the metal foil,
  • the shear storage modulus (unit: Pa) at 56 ° C. and 62 ° C. is shown.)
  • the resin composition layer may be formed on one side of the metal foil, or may be formed on both sides.
  • the composition of the resin composition of the layer may be the same or different.
  • the resin composition layer in this embodiment is a layer in which the shear storage modulus satisfies the relationship represented by the above formulas (i) and (ii).
  • the entry sheet of the present embodiment has a drill bit breakage resistance by imparting lubricity and reducing excessive load on the cutting tool at the part where the cutting part of the workpiece and the cutting tool come into contact with each other during cutting. It is expected that functions such as improvement and improvement of hole position accuracy by improvement of machinability are expected, and it is desirable that the scrap of the resin composition layer does not wind around the cutting tool.
  • the cutting process in which the entry sheet functions is a dynamic process, and the resin composition layer is in contact with the blade of a drill that rotates at high speed during use.
  • the shear storage elastic modulus is defined among the storage elastic moduli.
  • the resin composition layer changes from a solid state to a gel state, and the resin composition layer in the gel state contributes to the functions of the entry sheet.
  • the temperature at which the gel state is too high, a load is applied to the cutting tool before exerting the lubricity of the entry sheet, and in continuous processing, it affects the hole position accuracy and drill bit breakage. it is conceivable that.
  • ⁇ G ′ in the formula (i) is the common logarithm (log 10 (G ′ (62))) of the shear storage modulus (G ′ (62)) at 62 ° C. and the shear storage modulus (G ′ ( 56)) is a difference from the common logarithm (log 10 (G ′ (56))), and formula (i) defines the range of ⁇ G ′.
  • the shear storage elastic modulus shows a tendency to decrease with increasing temperature, but the equation (i) shows the shear storage elasticity depending on the difference between log 10 (G ′ (62)) and (log 10 (G ′ (56))). It prescribes that the rate shows a predetermined tendency.
  • ⁇ G ′ is ⁇ 3.0 to ⁇ 1.0, preferably ⁇ 2.8 to ⁇ 1.0, more preferably ⁇ 2.6 to ⁇ 1.0, and even more preferably ⁇ It is 2.4 to -1.0, and particularly preferably -2.2 to -1.0.
  • ⁇ G ′ is ⁇ 3.0 or more, winding of the resin composition layer scrap around the cutting tool is further suppressed. Further, when ⁇ G ′ is ⁇ 1.0 or less, the drill bit breakage resistance and the hole position accuracy are further improved.
  • Formula (ii) shows the range of G ′ (56).
  • G ′ (56) is 4.5 ⁇ 10 5 to 100 ⁇ 10 5 , preferably 20 ⁇ 10 5 to 100 ⁇ 10 5 , more preferably 30 ⁇ 10 5 to 100 ⁇ 10 5 , More preferably, it is 35 ⁇ 10 5 to 100 ⁇ 10 5 , and particularly preferably 40 ⁇ 10 5 to 100 ⁇ 10 5 .
  • G ′ (56) is 4.5 ⁇ 10 5 or more, the wrapping of the scraps of the resin composition layer around the cutting tool is further suppressed. Further, when G ′ (56) is 100 ⁇ 10 5 or less, the drill bit breakage resistance and the hole position accuracy are further improved.
  • G ′ (62) is preferably 0.010 ⁇ 10 5 to 4.4 ⁇ 10 5 , more preferably 0.10 ⁇ 10 5 to 4.4 ⁇ 10 5 , and even more preferably 0. 20 ⁇ 10 5 to 4.4 ⁇ 10 5 , particularly preferably 0.40 ⁇ 10 5 to 4.4 ⁇ 10 5 .
  • G ′ (62) is 0.010 ⁇ 10 5 or more, the winding of the resin composition layer scrap around the cutting tool tends to be further suppressed.
  • G ′ (62) is 4.4 ⁇ 10 5 or less, the drill bit breakage resistance and the hole position accuracy tend to be further improved.
  • the resin composition layer further satisfies the relationship represented by the following formula (iii). 0.005 ⁇ 10 5 ⁇ G ′ (70) ⁇ 80 ⁇ 10 5 (iii) (In the above formula, G ′ (70) represents the shear storage modulus (unit: Pa) of the resin composition at 70 ° C.)
  • Formula (iii) shows the range of G ′ (70).
  • G ′ (70) is preferably 0.005 ⁇ 10 5 to 80 ⁇ 10 5 , more preferably 0.020 ⁇ 10 5 to 40 ⁇ 10 5 , and still more preferably 0.150 ⁇ 10 5 to 10 ⁇ 10 5 .
  • G ′ (70) is 0.005 ⁇ 10 5 or more, the winding of the resin composition layer scrap around the cutting tool tends to be further suppressed.
  • G ′ (70) is 80 ⁇ 10 5 or less, the drill bit breakage resistance and the hole position accuracy tend to be improved.
  • the value of ⁇ G ′ can be adjusted by controlling the values of G ′ (56) and G ′ (62).
  • G ′ (56), G ′ (62), and G ′ (70) can be adjusted according to the type and content of the resin used and the type and content of the filler. For example, when the filler is included and the case where the filler is not included, the shear storage elastic modulus is improved as a whole by including the filler. Further, as the filler content increases, the overall shear storage modulus increases, but in particular, the increase rate of the shear storage modulus on the high temperature side tends to increase. Also, if the particle size is reduced without changing the filler content, the overall shear storage modulus is lower than when the particle size is large, but the rate of decrease is higher on the high temperature side. Tend to be.
  • the shear storage modulus can be measured by the method described in the examples.
  • composition of resin composition layer As a component which comprises a resin composition layer, water-soluble resin (A) is preferable and a filler (B) may be contained as needed.
  • A water-soluble resin
  • B filler
  • Water-soluble resin (A) As the water-soluble resin (A), a polymer water-soluble resin having a weight average molecular weight of 1.0 ⁇ 10 5 to 2.0 ⁇ 10 6 , and a weight average molecular weight of 3.0 ⁇ 10 6 due to the difference in molecular weight. These can be classified into medium-molecular water-soluble resins having a molecular weight of 3 to 7.0 ⁇ 10 4 and low-molecular water-soluble resins having a weight average molecular weight of 1.0 ⁇ 10 2 to 2.5 ⁇ 10 3 .
  • the polymer water-soluble resin contributes to the overall improvement of the moldability of the resin composition layer and the shear storage modulus, and can contribute to the improvement of the adhesion to the workpiece and the improvement of the hole position accuracy thereby.
  • the medium-molecular water-soluble resin and the low-molecular water-soluble resin can contribute to improvement of lubricity, cutting waste discharging property, and hole position accuracy.
  • water-soluble means a property of dissolving 1 g or more in 100 g of water at 25 ° C. and 1 atm.
  • the water-soluble resin (A) is not particularly limited.
  • polyethylene oxide, polypropylene oxide, polytetramethylene glycol, polyethylene glycol, polypropylene glycol, polyoxyethylene monoether compound, polyoxyethylene monostearate, polyoxy One type or two or more types selected from the group consisting of ethylene sorbitan monostearate, polyglycerin monostearate compound, and polyoxyethylene propylene copolymer may be mentioned.
  • the polymer water-soluble resin (a-1) is not particularly limited, and examples thereof include polyethylene oxide and polypropylene oxide.
  • the polymer water-soluble resin (a-1) may be used alone or in combination of two or more.
  • the weight average molecular weight of the polymer water-soluble resin (a-1) is 1.0 ⁇ 10 5 to 2.0 ⁇ 10 6 , preferably 1.0 ⁇ 10 5 to 1.0 ⁇ 10 6 , More preferably, it is 1.0 ⁇ 10 5 to 6.0 ⁇ 10 5 .
  • the weight average molecular weight of the polymer water-soluble resin (a-1) is within the above range, the drill bit breakage resistance and the hole position accuracy are further improved, and winding tends to be suppressed.
  • the content of the polymer water-soluble resin (a-1) is preferably 3 to 15 parts by mass, more preferably 5 to 12 parts by mass with respect to 100 parts by mass of the total amount of the resin components in the resin composition. More preferably 7 to 10 parts by mass.
  • the content of the polymer water-soluble resin (a-1) is within the above range, the film forming property and the hole position accuracy of the resin composition layer tend to be further improved.
  • the medium-molecule water-soluble resin (a-2) is not particularly limited, and examples thereof include glycol compounds such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; polyoxyethylene oleyl ether, polyoxyethylene cetyl ether, polyoxyethylene Polyoxyethylene monoether compounds such as stearyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether; polyoxyethylene monostearate, polyoxyethylene sorbitan monostearate, polyglycerin mono A stearate compound, a polyoxyethylene propylene copolymer, etc. are mentioned. Among these, polytetramethylene glycol, polyethylene glycol, and polypropylene glycol are preferable.
  • the medium molecular water-soluble resin (a-2) may be used alone or in combination of two or more.
  • the weight average molecular weight of the medium molecular water-soluble resin (a-2) is 3.0 ⁇ 10 3 to 7.0 ⁇ 10 4 , preferably 3.0 ⁇ 10 3 to 3.0 ⁇ 10 4 , More preferably, it is 3.0 ⁇ 10 3 to 1.0 ⁇ 10 4 .
  • the weight average molecular weight of the medium-molecule water-soluble resin (a-2) is within the above range, the drill bit breakage resistance and the hole position accuracy are further improved, and winding tends to be suppressed.
  • the content of the medium molecular water-soluble resin (a-2) is preferably 40 to 85 parts by mass, more preferably 55 to 85 parts by mass with respect to 100 parts by mass of the total amount of the resin components in the resin composition. More preferably, it is 65 to 80 parts by mass.
  • the content of the medium molecular water-soluble resin (a-2) is within the above range, the accuracy of the resin composition layer and the hole position tends to be further improved.
  • the low-molecular water-soluble resin (a-3) is not particularly limited, and examples thereof include glycol compounds such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; polyoxyethylene oleyl ether, polyoxyethylene cetyl ether, polyoxyethylene Polyoxyethylene monoether compounds such as stearyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether; polyoxyethylene monostearate, polyoxyethylene sorbitan monostearate, polyglycerin mono A stearate compound, a polyoxyethylene propylene copolymer, etc. are mentioned.
  • glycol compounds such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol
  • polyoxyethylene oleyl ether polyoxyethylene cetyl ether
  • polyoxyethylene Polyoxyethylene monoether compounds such as stearyl ether, polyoxyethylene lauryl ether, polyoxyethylene non
  • polyoxyethylene monoether compounds polyoxyethylene monostearate, polyoxyethylene sorbitan monostearate, polyglycerin monostearate compounds, and polyoxyethylene propylene copolymers are preferred.
  • the low molecular weight water-soluble resin (a-3) may be used alone or in combination of two or more.
  • the content of the low molecular weight water-soluble resin (a-3) is preferably 3 to 25 parts by mass, more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the total amount of the resin components in the resin composition. More preferably, it is 10 to 20 parts by mass.
  • the content of the low-molecular water-soluble resin (a-3) is within the above range, the lubricity and the hole position accuracy of the resin composition layer tend to be further improved.
  • the filler (B) is not particularly limited, and examples thereof include silica, talc, kaolin, mica, boehmite, and molybdenum compounds (molybdenum disulfide, molybdenum oxide, and zinc molybdate). Of these, talc and / or molybdenum disulfide are preferable. By using such a filler, the drill bit breakage resistance and the hole position accuracy are further improved, and the winding tends to be suppressed.
  • the median diameter (average particle diameter) of the filler (B) is preferably 0.3 ⁇ m or more and 10 ⁇ m or less, more preferably 0.3 ⁇ m or more and 8 ⁇ m or less, and further preferably 0.5 ⁇ m or more and 6 ⁇ m or less.
  • the median diameter is, for example, a particle diameter (D50) having a height of 50% in a cumulative particle diameter distribution curve (number basis) measured by a particle diameter measuring method such as a laser diffraction method. It is.
  • the content of the filler (B) is preferably 10 to 150 parts by mass, more preferably 30 to 125 parts by mass, and still more preferably with respect to 100 parts by mass of the total amount of the resin components in the resin composition. 50 to 100 parts by mass.
  • the content of the filler (B) is within the above range, the drill bit breakage resistance and the hole position accuracy are further improved, and winding tends to be suppressed.
  • the shape of the filler (B) is not particularly limited, but is preferably, for example, a plate shape. Compared with what has a substantially spherical shape such as silicone resin powder, the plate-like filler (B) has a greater resistance during shearing. Therefore, by setting the content of the filler (B) within the above range, ⁇ G ′ and the like can be adjusted within the range of the present embodiment. On the other hand, the closer the shape of the filler (B) is to a sphere, the smaller the resistance during shearing, and the more difficult it is to adjust ⁇ G ′ and the like.
  • the filler (B) talc and / or molybdenum disulfide having a plate shape is preferable, and by making these contents in the above range, the resistance to breakage of the drill bit tends to be further improved. is there.
  • the resin composition layer may contain an additive as necessary.
  • the type of additive is not particularly limited, but for example, surface conditioner, leveling agent, antistatic agent, emulsifier, antifoaming agent, wax additive, coupling agent, rheology control agent, antiseptic, antifungal agent, oxidation Examples include inhibitors, light stabilizers, nucleating agents such as sodium formate, heat stabilizers, and colorants.
  • the thickness of the resin composition layer is appropriately selected depending on the diameter of the drill bit used for drilling and the configuration of the drilled object to be processed (for example, a printed wiring board material such as a laminate or multilayer board). Is done. Among these, the thickness of the resin composition layer is preferably 0.02 to 0.3 mm, more preferably 0.02 to 0.2 mm, and still more preferably 0.02 to 0.1 mm. . When the thickness of the resin composition layer is 0.02 mm or more, a sufficient lubrication effect is obtained and the load on the drill bit is reduced, so that the breakage of the drill bit tends to be further suppressed. is there. Moreover, it exists in the tendency which can suppress the winding of the resin composition to a drill bit because the thickness of a resin composition layer is 0.3 mm or less.
  • the metal foil used for the drill hole entry sheet of the present 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.
  • a metal seed species of metal foil, aluminum is mentioned from a viewpoint of availability, cost, and workability, for example.
  • the material of the aluminum foil aluminum having a purity of 95% or more is preferable. Examples of such aluminum foil include 5052, 3004, 3003, 1N30, 1N99, 1050, 1070, 1085, as defined in JIS-H4160. 8021.
  • the impact of the drill bit is reduced and the biting property with the tip of the drill bit is improved, combined with the lubricating effect of the drill bit by the resin composition.
  • the hole position accuracy of the processed hole can be further increased.
  • the thickness of the metal foil is preferably 0.05 to 0.5 mm, more preferably 0.05 to 0.3 mm, and still more preferably 0.05 to 0.2 mm.
  • the thickness of the metal foil is 0.05 mm or more, the occurrence of burrs on the drilling object (for example, a laminate) during drilling tends to be further suppressed.
  • the thickness of the metal foil is 0.5 mm or less, the discharge of chips generated during drilling tends to be easier.
  • each layer constituting the drill hole entry sheet of the present embodiment is measured as follows. First, using a cross section polisher (manufactured by JEOL Datum Co., Ltd., trade name “CROSS-SECTIONPOLISHERSM-09010”) or ultramicrotome (manufactured by Leica, product number “EMUC7”), the entry sheet is placed in the stacking direction of each layer. Disconnect. Then, using a SEM (Scanning Electron Microscope, KEYENCE product number “VE-7800”), the section formed by observing the section from a direction perpendicular to the section that has been cut and formed, for example, The thickness of the metal foil and the resin composition layer is measured. The thickness of five places is measured for one visual field, and the average value is taken as the thickness of each layer.
  • a cross section polisher manufactured by JEOL Datum Co., Ltd., trade name “CROSS-SECTIONPOLISHERSM-09010”
  • ultramicrotome manufactured by Leica, product number “EMUC7
  • the manufacturing method of the entry sheet for drilling of this embodiment is not specifically limited, For example, it forms and forms a resin composition layer on the at least single side
  • the method for forming the resin composition layer on the metal foil is not particularly limited, and a known method can be used. As such a method, for example, a solution of a resin composition in which a resin or the like is dissolved or dispersed in a solvent is coated on a metal foil by a method such as a coating method, and further dried and / or cooled and solidified. The method of letting it be mentioned.
  • the solvent used for the resin composition solution has a lower boiling point than water and water.
  • a mixed solution composed of a solvent is preferable.
  • Use of a mixed solution composed of water and a solvent having a boiling point lower than that of water contributes to reduction of residual bubbles in the resin composition layer.
  • the kind of solvent whose boiling point is lower than water is not specifically limited, For example, alcohol compounds, such as ethanol, methanol, and isopropyl alcohol, are mentioned, Low boiling solvents, such as methyl ethyl ketone and acetone, can also be used.
  • As another solvent it is possible to use a solvent obtained by partially mixing tetrahydrofuran or acetonitrile having high compatibility with the resin composition in water or an alcohol compound.
  • the drill drilling method of the present embodiment includes a hole forming step of forming a hole in the laminated plate or the multilayer plate using the drill hole entry sheet.
  • the diameter (drill bit diameter) of the drill bit used for the drilling process is preferably 0.10 mm ⁇ or less, and more preferably 0.080 mm ⁇ or less. Since such a drill bit is thin, it is particularly easy to break, and the hole position accuracy is also required.
  • the entry sheet of the present embodiment in particular, the drill bit breakage resistance and hole position accuracy, and the effect of suppressing the winding of the resin composition layer debris around the cutting tool are more effective. Demonstrated. It should be noted that there is no problem even if the drill hole entry sheet of this embodiment is adopted for drilling using a drill bit having a diameter of more than 0.30 mm ⁇ .
  • the entry sheet for drilling according to the present embodiment can be suitably used for drilling a printed wiring board material, more specifically, a laminated board or a multilayer board.
  • an entry sheet for drilling is arranged 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 foil side is in contact with the printed wiring board material Then, drilling can be performed from the upper surface (resin composition layer side) of the entry sheet.
  • ⁇ Shear storage modulus> The shear storage elastic modulus of the resin composition layers in Examples and Comparative Examples was measured using a dynamic viscoelasticity measuring device “DISCOVER HR-2” manufactured by TA Instruments. The method for preparing the measurement sample is described below. The entry sheet for drilling prepared by the method described in Example 1 was softened at 170 ° C. and only the resin composition layer was taken out and then cooled and solidified as a measurement sample. . In addition, as a pre-measurement preparation method of the dynamic viscoelasticity measuring device, a measurement sample is set on the measurement stand of the dynamic viscoelasticity measuring device, the measurement stand is heated to 170 ° C., and then the dynamic viscoelasticity measuring device is attached.
  • the resin composition layer was sandwiched between a parallel plate and a measuring table having a diameter of 20 mm until the gap between the parallel plate and the measuring table was 0.2 mm, and the measuring table was cooled to 30 ° C. and the temperature was stabilized. Measurement was performed under the following measurement conditions.
  • a copper-clad laminate (trade name: HL832NS-L, copper foil thickness 5 ⁇ m, double-sided board, manufactured by Mitsubishi Gas Chemical Co., Ltd.) having a thickness of 0.04 mm is stacked on the upper surface of the copper-clad laminate, and examples and The drill hole entry sheet prepared in the comparative example is arranged so that the resin composition layer side is the upper surface, and a 1.5 mm thick patch plate on the back surface (lower surface) of the stacked copper-clad laminate (Paper phenol laminate PS1160-G, manufactured by Risho Co., Ltd.) was placed.
  • the drill hole entry sheet prepared in the comparative example is arranged so that the resin composition layer side is the upper surface, and a 1.5 mm thick patch plate on the back surface (lower surface) of the stacked copper-clad laminate (Paper phenol laminate SPB-W, manufactured by Nippon Decorac Co., Ltd.) was placed.
  • the collected drill bit was observed with a microscope having a magnification of 100 times.
  • the maximum diameter with the processing scrap wound was obtained, and the winding was evaluated according to the following criteria.
  • Table 1 shows raw materials used for manufacturing the drilling entry sheets of Examples and Comparative Examples.
  • Example 1 As the polymer water-soluble resin (a-1), 8 parts by mass of polyethylene oxide having a weight average molecular weight of 560,000 (manufactured by Meisei Chemical Industry Co., Ltd., Alcox E-45) and the medium-molecule water-soluble resin (a-2) 77 parts by mass of polyethylene glycol having a weight average molecular weight of 3,300 (manufactured by Sanyo Chemical Industries Co., Ltd., PEG4000S) and polyethylene glycol monostearic acid having a weight average molecular weight of 1,540 as a low molecular weight water-soluble resin (a-3) 15 parts by mass of ester (manufactured by NOF Corporation, Nonion S15.4) was dissolved in a water / methanol mixed solvent so that the solid content concentration of the resin composition solution was 30%.
  • the mixing ratio of the water / methanol mixed solvent was 50/50.
  • the resin composition solution was dried on one side of an aluminum foil (used aluminum foil: JIS-A1100H, thickness 0.07 mm, manufactured by Mitsubishi Aluminum Co., Ltd.) using a bar coater to determine the thickness of the resin composition layer. It applied so that it might become 50 micrometers, it dried at 90 degreeC for 5 minute (s) with the dryer, and it cooled to normal temperature, and produced the entry sheet for drilling.
  • Examples 2 to 6 Comparative Examples 1 to 4> An entry sheet for drilling was prepared in the same manner as in Example 1 except that the raw materials used were changed as shown in Table 2.
  • FIG. 1 shows the measurement results of the shear storage modulus of Examples 2, 3, and 5 and Comparative Examples 1, 2, and 3.
  • the present invention has industrial applicability as an entry sheet for drilling used for drilling a laminated plate or multilayer board.
  • the hole position accuracy is excellent, the drill breakage due to peeling between the metal foil and the resin composition layer is less, and the conventionally required adhesive layer is Because it is unnecessary, it can provide an entry sheet for drilling with excellent economic efficiency.

Abstract

This entry sheet for drilling includes a metal foil, and a resin composition layer formed on at least one surface of the metal foil, wherein the shear storage modulus of the resin composition layer satisfies relationships expressed by formulas (i) and (ii). (i) -3.0≤ΔG'≤-1.0 (ii) 4.5×105 ≤ G'(56)≤100×105 (In the formulas, ΔG'=log10(G'(62))-log10(G'(56)), and G'(56) and G'(62) represent the storage elastic modulus (unit: Pa) of the resin composition at 56°C and 62°C respectively.)

Description

ドリル孔あけ用エントリーシート及びそれを用いたドリル孔あけ加工方法Entry sheet for drilling and drilling method using the same
　本発明は、ドリル孔あけ用エントリーシート及びそれを用いたドリル孔あけ加工方法に関する。 The present invention relates to an entry sheet for drilling and a drilling method using the same.
　プリント配線板材料に使用される積層板や多層板のドリル孔あけ加工方法としては、一般的に積層板又は多層板を１枚又は複数枚重ねて、その最上部に当て板としてアルミニウム箔単体又はアルミニウム箔表面に樹脂組成物の層を形成したシート（以下、本明細書ではこの「シート」を「ドリル孔あけ用エントリーシート」という）を配置して孔あけ加工を行う方法が採用されている。 As a drilling method for a laminated board or multilayer board used as a printed wiring board material, generally one or a plurality of laminated boards or multilayer boards are stacked, and an aluminum foil alone or A method is employed in which a sheet in which a layer of a resin composition is formed on the surface of an aluminum foil (hereinafter, this “sheet” is referred to as “drill drilling entry sheet”) is drilled. .
　近年、プリント配線板に対する信頼性向上の要求や高密度化の進展に伴い、積層板又は多層板のドリル孔あけ加工に対して、ドリル孔あけ加工時の内壁粗さの低減や孔位置精度の向上など、高品質なドリル孔あけ加工が要求されている。 In recent years, with the demand for improved reliability of printed wiring boards and the progress of higher density, the drilling of laminated boards or multilayer boards has been performed with reduced inner wall roughness and improved hole position accuracy during drilling. There is a demand for high-quality drilling such as improvement.
　上述したドリル孔あけ加工時の内壁粗さの低減や孔位置精度の向上などの要求に対応すべく、例えば、特許文献１には、熱硬化性樹脂薄膜を形成したアルミニウム箔に水溶性樹脂層を形成したドリル孔あけ用エントリーシートが開示されている。また、特許文献２には、樹脂組成物にノンハロゲンの着色剤を配合した孔あけ用滑剤シートが開示されている。 For example, Patent Document 1 discloses a water-soluble resin layer on an aluminum foil on which a thermosetting resin thin film is formed in order to meet the demands for reducing the inner wall roughness and improving the hole position accuracy at the time of drilling. An entry sheet for drilling is disclosed. Patent Document 2 discloses a lubricant sheet for drilling in which a non-halogen colorant is blended in a resin composition.
　更に、固体潤滑剤を使用したドリル孔あけ用エントリーシートも開示されている。例えば、特許文献３には、潤滑層と、二硫化タングステンなどのナノ構造粉と高伝熱化合物である固体の耐摩耗潤滑層が含まれる複合材と、支持体とからなる孔あけ用補助板が開示されている。また、特許文献４には、水溶性樹脂、水溶性滑剤と炭素粉とを混合した樹脂組成物の層を含むドリル孔あけ用エントリーシートが開示されている。さらに、特許文献５には、複合材中に無機充填剤としてグラファイトを含む穿孔用放熱潤滑アルミニウムカバーが開示されている。 Furthermore, an entry sheet for drilling using a solid lubricant is also disclosed. For example, Patent Document 3 discloses a drilling auxiliary plate comprising a lubricating layer, a composite material including a nanostructured powder such as tungsten disulfide and a solid wear-resistant lubricating layer that is a high heat transfer compound, and a support. Is disclosed. Patent Document 4 discloses a drill hole entry sheet including a layer of a resin composition in which a water-soluble resin, a water-soluble lubricant and carbon powder are mixed. Further, Patent Document 5 discloses a heat-dissipating lubricated aluminum cover for drilling that contains graphite as an inorganic filler in a composite material.
特開２００３－１３６４８５号公報JP 2003-136485 A 特開２００４－２３０４７０号公報JP 2004-230470 A 特開２００７－２８１４０４号公報JP 2007-281404 A 特開２００８－２２２７６２号公報JP 2008-222762 A 特開２００６－３４６９１２号公報JP 2006-346912 A
　ところで、半導体技術の進展にともなって、プリント配線板に対する高密度化及び信頼性向上の要求は、益々高度化している。量産におけるドリルビット径の使用範囲は、０．５ｍｍから０．１０５ｍｍが多くを占めている。具体的には０．５ｍｍ、０．４５ｍｍ、０．４ｍｍ、０．３５ｍｍ、０．３ｍｍ、０．２５ｍｍ、０．２ｍｍ、０．１５ｍｍ、０．１０５ｍｍなどがある。また最小ドリルビット径も０．１０５ｍｍから０．０７５ｍｍに移行しつつあり、レーザー孔あけ技術に対抗して、ごく一部では、０．０５ｍｍのドリル孔あけが試みられている。また、０．２ｍｍ、０．１５ｍｍのドリルビット径でのプリント配線板加工においても、孔位置精度の向上への要求が強い。更には、グローバル化による競争と新興国需要の取り込みの為、生産性向上及びコスト低減要求もまた、とどまることを知らない。 By the way, with the progress of semiconductor technology, the demand for higher density and higher reliability for printed wiring boards is becoming increasingly sophisticated. The use range of the drill bit diameter in mass production is mostly from 0.5 mm to 0.105 mm. Specific examples include 0.5 mm, 0.45 mm, 0.4 mm, 0.35 mm, 0.3 mm, 0.25 mm, 0.2 mm, 0.15 mm, and 0.105 mm. Further, the minimum drill bit diameter is also shifting from 0.105 mm to 0.075 mm, and a small portion of 0.05 mm drilling has been attempted against the laser drilling technology. In addition, there is a strong demand for improving the hole position accuracy in printed wiring board processing with a drill bit diameter of 0.2 mm and 0.15 mm. Furthermore, because of the competition from globalization and the demand of emerging countries, demands for productivity improvement and cost reduction are also unknown.
　従来のドリル孔あけ用エントリーシートを用いた加工においては、ドリルビットと積層板又は多層板との摩擦熱によって、ドリルビット周囲の水溶性樹脂などを含む樹脂組成物が溶融することで、潤滑性が発現する。しかし、従来のドリル孔あけ用エントリーシートにおいては、樹脂組成物の層の潤滑性の効果は必ずしも十分でなく、孔位置精度の向上への要求に十分に応えられていない。すなわち、より高度な孔位置精度の要求に応えるドリル孔あけ用エントリーシートの開発が望まれている。 In processing using a conventional drill hole entry sheet, the frictional heat between the drill bit and the laminate or multilayer board melts the resin composition containing the water-soluble resin around the drill bit, resulting in lubricity. Is expressed. However, in the conventional entry sheet for drilling, the effect of the lubricity of the resin composition layer is not always sufficient, and it does not sufficiently meet the demand for improving the hole position accuracy. In other words, it is desired to develop an entry sheet for drilling that meets the demand for higher hole position accuracy.
　また一方で、生産性向上及びコスト低減要求の観点からは、上記のとおり、ドリルビット径が小さいドリルを用いた場合においても、耐ドリルビット折損性に優れることが求められ、その他、ドリルビットに対してドリル孔あけ用エントリーシート由来の屑が付着しにくいことも求められる。 On the other hand, from the viewpoint of productivity improvement and cost reduction requirements, as described above, even when a drill with a small drill bit diameter is used, it is required to have excellent drill bit breakage resistance. On the other hand, it is also required that scraps derived from the entry sheet for drilling do not adhere easily.
　本発明は上記問題点に鑑みてなされたものであり、ドリルビット径が小さいドリルを用いた場合においても、耐ドリルビット折損性及び孔位置精度に優れ、ドリル孔あけ用エントリーシート由来の屑の巻き付きが少ないドリル孔あけ用エントリーシート、及びそれを用いたドリル孔あけ加工方法を提供することを目的とする。 The present invention has been made in view of the above problems, and even when a drill having a small drill bit diameter is used, it has excellent resistance to breakage of the drill bit and hole position accuracy, and is free from scraps derived from an entry sheet for drilling. An object of the present invention is to provide an entry sheet for drilling with less winding and a drilling method using the same.
　本発明者らは、上記の課題を解決するため種々の検討を行った結果、樹脂組成物層のせん断貯蔵弾性率を調整することにより、上記課題を解決し得ることを見出し、本発明を完成するに至った。 As a result of various studies to solve the above problems, the present inventors have found that the above problems can be solved by adjusting the shear storage elastic modulus of the resin composition layer, and the present invention has been completed. It came to do.
　すなわち、本発明は以下のとおりである。
〔１〕
　金属箔と、該金属箔上の少なくとも片面に形成された樹脂組成物層と、を有し、
　該樹脂組成物層のせん断貯蔵弾性率が、下記式（ｉ）、（ｉｉ）で表される関係を満たす、
　ドリル孔あけ用エントリーシート。
　　　－３．０≦△Ｇ’≦－１．０…（ｉ）
　　　４．５×１０５≦Ｇ’（５６）≦１００×１０５…（ｉｉ）
（上記式中、△Ｇ’＝ｌｏｇ１０（Ｇ’（６２））－ｌｏｇ１０（Ｇ’（５６））であり、Ｇ’（５６）、Ｇ’（６２）は、それぞれ、前記樹脂組成物の５６℃、６２℃におけるせん断貯蔵弾性率（単位：Ｐａ）を示す。）
〔２〕
　前記樹脂組成物層が、下記式（ｉｉｉ）で表される関係をさらに満たす、
　〔１〕に記載のドリル孔あけ用エントリーシート。
　　　０．００５×１０５≦Ｇ’（７０）≦８０×１０５…（ｉｉｉ）
（上記式中、Ｇ’（７０）は前記樹脂組成物の７０℃におけるせん断貯蔵弾性率（単位：Ｐａ）を示す。）
〔３〕
　前記樹脂組成物が、水溶性樹脂（Ａ）を含有する、
　〔１〕又は〔２〕に記載のドリル孔あけ用エントリーシート。
〔４〕
　前記樹脂組成物が、充填材（Ｂ）を含有する、
　〔１〕～〔３〕のいずれか一項に記載のドリル孔あけ用エントリーシート。
〔５〕
　前記充填材（Ｂ）が、タルク及び／又は二硫化モリブデンである、
　〔４〕に記載のドリル孔あけ用エントリーシート。
〔６〕
　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、ポリテトラメチレングリコール、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化合物、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化合物、及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種類又は２種類以上である、
　〔３〕～〔５〕のいずれか一項に記載のドリル孔あけ用エントリーシート。
〔７〕
　前記樹脂組成物層が、０．０２～０．３ｍｍの範囲の厚さを有する、
　〔１〕～〔６〕のいずれか一項に記載のドリル孔あけ用エントリーシート。
〔８〕
　前記金属箔が、０．０５～０．５ｍｍの範囲の厚さを有する、
　〔１〕～〔７〕のいずれか一項に記載のドリル孔あけ用エントリーシート。
〔９〕
　〔１〕～〔８〕のいずれか一項に記載のドリル孔あけ用エントリーシートを用いて、積層板又は多層板に孔を形成する孔形成工程を有する、
　ドリル孔あけ加工方法。 That is, the present invention is as follows.
[1]
A metal foil, and a resin composition layer formed on at least one side of the metal foil,
The shear storage elastic modulus of the resin composition layer satisfies the relationship represented by the following formulas (i) and (ii).
Entry sheet for drilling.
−3.0 ≦ ΔG ′ ≦ −1.0 (i)
4.5 × 10 5 ≦ G ′ (56) ≦ 100 × 10 5 (ii)
(In the above formula, ΔG ′ = log 10 (G ′ (62)) − log 10 (G ′ (56))), and G ′ (56) and G ′ (62) are the resin composition, respectively. The shear storage modulus (unit: Pa) at 56 ° C. and 62 ° C. is shown.)
[2]
The resin composition layer further satisfies a relationship represented by the following formula (iii):
The entry sheet for drilling according to [1].
0.005 × 10 5 ≦ G ′ (70) ≦ 80 × 10 5 (iii)
(In the above formula, G ′ (70) represents the shear storage modulus (unit: Pa) of the resin composition at 70 ° C.)
[3]
The resin composition contains a water-soluble resin (A).
The entry sheet for drilling according to [1] or [2].
[4]
The resin composition contains a filler (B),
The entry sheet for drilling according to any one of [1] to [3].
[5]
The filler (B) is talc and / or molybdenum disulfide.
The entry sheet for drilling according to [4].
[6]
The water-soluble resin (A) is polyethylene oxide, polypropylene oxide, polytetramethylene glycol, polyethylene glycol, polypropylene glycol, polyoxyethylene monoether compound, polyoxyethylene monostearate, polyoxyethylene sorbitan monostearate, poly One or more selected from the group consisting of a glycerin monostearate compound and a polyoxyethylene propylene copolymer,
[3] The entry sheet for drilling according to any one of [5] to [5].
[7]
The resin composition layer has a thickness in the range of 0.02 to 0.3 mm;
The entry sheet for drilling according to any one of [1] to [6].
[8]
The metal foil has a thickness in the range of 0.05 to 0.5 mm;
The entry sheet for drilling according to any one of [1] to [7].
[9]
[1] to [8], using a drill hole entry sheet according to any one of the above, having a hole forming step of forming a hole in the laminate or multilayer board,
Drilling method.
　本発明によれば、ドリルビット径が小さいドリルを用いた場合においても、耐ドリルビット折損性及び孔位置精度に優れ、ドリル孔あけ用エントリーシート由来の屑の巻き付きが少ないドリル孔あけ用エントリーシート、及びそれを用いたドリル孔あけ加工方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, even when a drill with a small drill bit diameter is used, the drill bit entry sheet has excellent resistance to breakage of the drill bit and hole position accuracy, and has little wrapping of debris derived from the drill hole entry sheet. And a drilling method using the same can be provided.
実施例２、３及び５、並びに、比較例１、２、及び３のせん断貯蔵弾性率の測定結果を示す。The measurement result of the shear storage elastic modulus of Examples 2, 3, and 5 and Comparative Examples 1, 2, and 3 is shown.
　以下、本発明を実施するための形態（以下、「本実施形態」という。）について詳細に説明するが、本発明はこれに限定されるものではなく、その要旨を逸脱しない範囲で様々な変形が可能である。 DESCRIPTION OF EMBODIMENTS Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. However, the present invention is not limited to this, and various modifications can be made without departing from the gist thereof. Is possible.
［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、金属箔と、該金属箔上の少なくとも片面に形成された樹脂組成物層と、を有し、該樹脂組成物層のせん断貯蔵弾性率が、下記式（ｉ）、（ｉｉ）で表される関係を満たすものである。
　　　－３．０≦△Ｇ’≦－１．０…（ｉ）
　　　４．５×１０５≦Ｇ’（５６）≦１００×１０５…（ｉｉ）
（上記式中、△Ｇ’＝ｌｏｇ１０（Ｇ’（６２））－ｌｏｇ１０（Ｇ’（５６））であり、Ｇ’（５６）、Ｇ’（６２）は、それぞれ、前記樹脂組成物の５６℃、６２℃におけるせん断貯蔵弾性率（単位：Ｐａ）を示す。） [Entry sheet for drilling holes]
The drill hole entry sheet of the present embodiment (hereinafter, also simply referred to as “entry sheet”) has a metal foil and a resin composition layer formed on at least one surface of the metal foil, The shear storage elastic modulus of the resin composition layer satisfies the relationship represented by the following formulas (i) and (ii).
−3.0 ≦ ΔG ′ ≦ −1.0 (i)
4.5 × 10 5 ≦ G ′ (56) ≦ 100 × 10 5 (ii)
(In the above formula, ΔG ′ = log 10 (G ′ (62)) − log 10 (G ′ (56))), and G ′ (56) and G ′ (62) are the resin composition, respectively. The shear storage modulus (unit: Pa) at 56 ° C. and 62 ° C. is shown.)
　樹脂組成物層は、金属箔の片面に形成された形態であってよく、両面に形成された形態であってもよい。両面に樹脂組成物層を形成する場合、層の樹脂組成物の組成は同じであっても異なっていてもよい。 The resin composition layer may be formed on one side of the metal foil, or may be formed on both sides. When forming a resin composition layer on both surfaces, the composition of the resin composition of the layer may be the same or different.
［樹脂組成物層］
　本実施形態における樹脂組成物層は、せん断貯蔵弾性率が、上記式（ｉ）、（ｉｉ）で表される関係を満たす層である。本実施形態のエントリーシートは、切削の際に被加工物の切削部分と切削工具とが接触する部分において、潤滑性の付与や、切削工具への過度な負担の軽減による耐ドリルビット折損性の向上、切削性の向上による孔位置精度の向上といったような機能を果たすことが期待され、また、樹脂組成物層の屑が切削工具に巻き付かないことが望ましい。エントリーシートが機能する切削加工は動的なプロセスであり、使用時において樹脂組成物層は高速回転するドリルの刃に接触している状態である。このような状態において諸機能が発揮される構成を特定する観点から、本実施形態においては、貯蔵弾性率の中でも、せん断貯蔵弾性率を規定する。特に、温度を上げた際に貯蔵弾性率が急降下するところでは、樹脂組成物層が固体状態からゲル状態となり、ゲル状態の樹脂組成物層がエントリーシートの諸機能の発揮に寄与しているものと考えられる。この際に、ゲル状態になる温度が高すぎる場合には、エントリーシートの潤滑性の発揮の前に、切削工具に負荷がかかり、連続加工においては孔位置精度、ドリルビット折損にも影響するものと考えられる。また、ゲル状態になったとしても、ゲル状態時の貯蔵弾性率が高ければ潤滑性が乏しくなり、ゲル状態時の貯蔵弾性率が低すぎれば潤滑膜が形成され難くなり、いずれの場合も潤滑性や、ドリルビット折損などをもたらす切削工具の負担、及び孔位置精度の観点から好ましくないものと考えられる。また、固体状態時の貯蔵弾性率が低いほど樹脂組成物層の屑が切削工具に巻きつきやすくなるものと考えられる。但し、作用機序については上記観点に制限されるものではない。 [Resin composition layer]
The resin composition layer in this embodiment is a layer in which the shear storage modulus satisfies the relationship represented by the above formulas (i) and (ii). The entry sheet of the present embodiment has a drill bit breakage resistance by imparting lubricity and reducing excessive load on the cutting tool at the part where the cutting part of the workpiece and the cutting tool come into contact with each other during cutting. It is expected that functions such as improvement and improvement of hole position accuracy by improvement of machinability are expected, and it is desirable that the scrap of the resin composition layer does not wind around the cutting tool. The cutting process in which the entry sheet functions is a dynamic process, and the resin composition layer is in contact with the blade of a drill that rotates at high speed during use. From the viewpoint of specifying a configuration in which various functions are exhibited in such a state, in this embodiment, the shear storage elastic modulus is defined among the storage elastic moduli. In particular, where the storage modulus suddenly drops when the temperature is raised, the resin composition layer changes from a solid state to a gel state, and the resin composition layer in the gel state contributes to the functions of the entry sheet. it is conceivable that. In this case, if the temperature at which the gel state is too high, a load is applied to the cutting tool before exerting the lubricity of the entry sheet, and in continuous processing, it affects the hole position accuracy and drill bit breakage. it is conceivable that. Even in the gel state, if the storage elastic modulus in the gel state is high, the lubricity is poor, and if the storage elastic modulus in the gel state is too low, it is difficult to form a lubricating film. From the viewpoint of the cutting performance, the load of the cutting tool that causes breakage of the drill bit, and the hole position accuracy, it is considered to be undesirable. Moreover, it is considered that the lower the storage elastic modulus in the solid state, the more easily the scraps of the resin composition layer are wound around the cutting tool. However, the mechanism of action is not limited to the above viewpoint.
　式（ｉ）における△Ｇ’は、６２℃におけるせん断貯蔵弾性率（Ｇ’（６２））の常用対数（ｌｏｇ１０（Ｇ’（６２）））と５６℃におけるせん断貯蔵弾性率（Ｇ’（５６））の常用対数（ｌｏｇ１０（Ｇ’（５６）））との差を示すものであり、式（ｉ）は△Ｇ’の範囲を規定するものである。一般に、せん断貯蔵弾性率は、温度上昇とともに減少する傾向を示すが、式（ｉ）は、ｌｏｇ１０（Ｇ’（６２））と（ｌｏｇ１０（Ｇ’（５６））の差によりせん断貯蔵弾性率が所定の傾向を示すことを規定するものである。 ΔG ′ in the formula (i) is the common logarithm (log 10 (G ′ (62))) of the shear storage modulus (G ′ (62)) at 62 ° C. and the shear storage modulus (G ′ ( 56)) is a difference from the common logarithm (log 10 (G ′ (56))), and formula (i) defines the range of ΔG ′. In general, the shear storage elastic modulus shows a tendency to decrease with increasing temperature, but the equation (i) shows the shear storage elasticity depending on the difference between log 10 (G ′ (62)) and (log 10 (G ′ (56))). It prescribes that the rate shows a predetermined tendency.
　△Ｇ’は、－３．０～－１．０であり、好ましくは－２．８～－１．０であり、より好ましくは－２．６～－１．０であり、さらに好ましくは－２．４～－１．０であり、特に好ましくは－２．２～－１．０である。△Ｇ’が－３．０以上であることにより、樹脂組成物層の屑の切削工具への巻き付きがより抑制される。また、△Ｇ’が－１．０以下であることにより、耐ドリルビット折損性及び孔位置精度がより向上する。 ΔG ′ is −3.0 to −1.0, preferably −2.8 to −1.0, more preferably −2.6 to −1.0, and even more preferably − It is 2.4 to -1.0, and particularly preferably -2.2 to -1.0. When ΔG ′ is −3.0 or more, winding of the resin composition layer scrap around the cutting tool is further suppressed. Further, when ΔG ′ is −1.0 or less, the drill bit breakage resistance and the hole position accuracy are further improved.
　式（ｉｉ）はＧ’（５６）の範囲を示すものである。Ｇ’（５６）は、４．５×１０５～１００×１０５であり、好ましくは２０×１０５～１００×１０５であり、より好ましくは３０×１０５～１００×１０５であり、さらに好ましくは３５×１０５～１００×１０５であり、特に好ましくは４０×１０５～１００×１０５である。Ｇ’（５６）が４．５×１０５以上であることにより、樹脂組成物層の屑の切削工具への巻き付きがより抑制される。また、Ｇ’（５６）が１００×１０５以下であることにより、耐ドリルビット折損性及び孔位置精度がより向上する。 Formula (ii) shows the range of G ′ (56). G ′ (56) is 4.5 × 10 5 to 100 × 10 5 , preferably 20 × 10 5 to 100 × 10 5 , more preferably 30 × 10 5 to 100 × 10 5 , More preferably, it is 35 × 10 5 to 100 × 10 5 , and particularly preferably 40 × 10 5 to 100 × 10 5 . When G ′ (56) is 4.5 × 10 5 or more, the wrapping of the scraps of the resin composition layer around the cutting tool is further suppressed. Further, when G ′ (56) is 100 × 10 5 or less, the drill bit breakage resistance and the hole position accuracy are further improved.
　また、Ｇ’（６２）は、好ましくは０．０１０×１０５～４．４×１０５であり、より好ましくは０．１０×１０５～４．４×１０５であり、さらに好ましくは０．２０×１０５～４．４×１０５であり、特に好ましくは０．４０×１０５～４．４×１０５である。Ｇ’（６２）が０．０１０×１０５以上であることにより、樹脂組成物層の屑の切削工具への巻き付きがより抑制される傾向にある。また、Ｇ’（６２）が４．４×１０５以下であることにより、耐ドリルビット折損性及び孔位置精度がより向上する傾向にある。 G ′ (62) is preferably 0.010 × 10 5 to 4.4 × 10 5 , more preferably 0.10 × 10 5 to 4.4 × 10 5 , and even more preferably 0. 20 × 10 5 to 4.4 × 10 5 , particularly preferably 0.40 × 10 5 to 4.4 × 10 5 . When G ′ (62) is 0.010 × 10 5 or more, the winding of the resin composition layer scrap around the cutting tool tends to be further suppressed. Moreover, when G ′ (62) is 4.4 × 10 5 or less, the drill bit breakage resistance and the hole position accuracy tend to be further improved.
　樹脂組成物層は、下記式（ｉｉｉ）で表される関係をさらに満たすことが好ましい。
　　　０．００５×１０５≦Ｇ’（７０）≦８０×１０５…（ｉｉｉ）
（上記式中、Ｇ’（７０）は樹脂組成物の７０℃におけるせん断貯蔵弾性率（単位：Ｐａ）を示す。） It is preferable that the resin composition layer further satisfies the relationship represented by the following formula (iii).
0.005 × 10 5 ≦ G ′ (70) ≦ 80 × 10 5 (iii)
(In the above formula, G ′ (70) represents the shear storage modulus (unit: Pa) of the resin composition at 70 ° C.)
　式（ｉｉｉ）はＧ’（７０）の範囲を示すものである。Ｇ’（７０）は、好ましくは０．００５×１０５～８０×１０５であり、より好ましくは０．０２０×１０５～４０×１０５であり、さらに好ましくは０．１５０×１０５～１０×１０５である。Ｇ’（７０）が０．００５×１０５以上であることにより、樹脂組成物層の屑の切削工具への巻き付きがより抑制される傾向にある。また、Ｇ’（７０）が８０×１０５以下であることにより、耐ドリルビット折損性及び孔位置精度より向上する傾向にある。 Formula (iii) shows the range of G ′ (70). G ′ (70) is preferably 0.005 × 10 5 to 80 × 10 5 , more preferably 0.020 × 10 5 to 40 × 10 5 , and still more preferably 0.150 × 10 5 to 10 × 10 5 . When G ′ (70) is 0.005 × 10 5 or more, the winding of the resin composition layer scrap around the cutting tool tends to be further suppressed. Moreover, when G ′ (70) is 80 × 10 5 or less, the drill bit breakage resistance and the hole position accuracy tend to be improved.
　△Ｇ’の値は、Ｇ’（５６）及びＧ’（６２）の値を制御することにより、調整することができる。また、Ｇ’（５６）、Ｇ’（６２）、及びＧ’（７０）は、用いる樹脂の種類及び含有量、並びに、充填材の種類及び含有量により、調整することができる。例えば、充填材を含む場合と含まない場合とで比較すると、充填材を含むことにより、全体的にせん断貯蔵弾性率が向上する。また、充填剤の含有量が多くなるにつれ、全体的にせん断貯蔵弾性率が向上するが、特に、高温側のせん断貯蔵弾性率の上昇率が高くなる傾向にある。また、充填剤の含有量を変えずにその粒子径を小さくすると、粒子径が大きい場合と比較して、全体的にせん断貯蔵弾性率が低くなるが、その低下率は高温側の方が高くなる傾向にある。 The value of ΔG ′ can be adjusted by controlling the values of G ′ (56) and G ′ (62). G ′ (56), G ′ (62), and G ′ (70) can be adjusted according to the type and content of the resin used and the type and content of the filler. For example, when the filler is included and the case where the filler is not included, the shear storage elastic modulus is improved as a whole by including the filler. Further, as the filler content increases, the overall shear storage modulus increases, but in particular, the increase rate of the shear storage modulus on the high temperature side tends to increase. Also, if the particle size is reduced without changing the filler content, the overall shear storage modulus is lower than when the particle size is large, but the rate of decrease is higher on the high temperature side. Tend to be.
　本実施形態においてせん断貯蔵弾性率の測定は、実施例に記載の方法により行うことができる。 In this embodiment, the shear storage modulus can be measured by the method described in the examples.
〔樹脂組成物層の組成〕
　樹脂組成物層を構成する成分としては、水溶性樹脂（Ａ）が好ましく、必要に応じて、充填材（Ｂ）が含まれてもよい。以下、各成分について詳説する。 [Composition of resin composition layer]
As a component which comprises a resin composition layer, water-soluble resin (A) is preferable and a filler (B) may be contained as needed. Hereinafter, each component will be described in detail.
（水溶性樹脂（Ａ））
　水溶性樹脂（Ａ）としては、その分子量の違いによりさらに、重量平均分子量が１．０×１０５～２．０×１０６である高分子水溶性樹脂、重量平均分子量が３．０×１０３～７．０×１０４である中分子水溶性樹脂、及び重量平均分子量が１．０×１０２～２．５×１０３である低分子水溶性樹脂に分類できる。高分子水溶性樹脂は、樹脂組成物層の成形性、せん断貯蔵弾性率の全体的な向上に寄与し、被切削物との密着性の向上と、それによる孔位置精度の向上に寄与し得る。また、中分子水溶性樹脂及び低分子水溶性樹脂は、潤滑性や、切削屑の排出性、孔位置精度の向上に寄与し得る。なお、本実施形態において、「水溶性」とは、２５℃、１気圧において、水１００ｇに対し、１ｇ以上溶解する性質をいう。 (Water-soluble resin (A))
As the water-soluble resin (A), a polymer water-soluble resin having a weight average molecular weight of 1.0 × 10 5 to 2.0 × 10 6 , and a weight average molecular weight of 3.0 × 10 6 due to the difference in molecular weight. These can be classified into medium-molecular water-soluble resins having a molecular weight of 3 to 7.0 × 10 4 and low-molecular water-soluble resins having a weight average molecular weight of 1.0 × 10 2 to 2.5 × 10 3 . The polymer water-soluble resin contributes to the overall improvement of the moldability of the resin composition layer and the shear storage modulus, and can contribute to the improvement of the adhesion to the workpiece and the improvement of the hole position accuracy thereby. . In addition, the medium-molecular water-soluble resin and the low-molecular water-soluble resin can contribute to improvement of lubricity, cutting waste discharging property, and hole position accuracy. In the present embodiment, “water-soluble” means a property of dissolving 1 g or more in 100 g of water at 25 ° C. and 1 atm.
　水溶性樹脂（Ａ）としては、特に制限されないが、例えば、ポリエチレンオキサイド、ポリプロピレンオキサイド、ポリテトラメチレングリコール、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化合物、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化合物、及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種類又は２種類以上が挙げられる。このような水溶性樹脂（Ａ）を用いることにより、耐ドリルビット折損性及び孔位置精度がより向上し、巻き付きが抑制される傾向にある。 The water-soluble resin (A) is not particularly limited. For example, polyethylene oxide, polypropylene oxide, polytetramethylene glycol, polyethylene glycol, polypropylene glycol, polyoxyethylene monoether compound, polyoxyethylene monostearate, polyoxy One type or two or more types selected from the group consisting of ethylene sorbitan monostearate, polyglycerin monostearate compound, and polyoxyethylene propylene copolymer may be mentioned. By using such a water-soluble resin (A), drill bit breakage resistance and hole position accuracy are further improved and winding tends to be suppressed.
（高分子水溶性樹脂（ａ－１））
　高分子水溶性樹脂（ａ－１）としては、特に制限されないが、例えば、ポリエチレンオキサイド、ポリプロピレンオキサイドが挙げられる。高分子水溶性樹脂（ａ－１）は、１種単独で用いてもよく、又は２種類以上を組み合わせて用いてもよい。 (Polymer water-soluble resin (a-1))
The polymer water-soluble resin (a-1) is not particularly limited, and examples thereof include polyethylene oxide and polypropylene oxide. The polymer water-soluble resin (a-1) may be used alone or in combination of two or more.
　高分子水溶性樹脂（ａ－１）の重量平均分子量は、１．０×１０５～２．０×１０６であり、好ましくは１．０×１０５～１．０×１０６であり、より好ましくは１．０×１０５～６．０×１０５である。高分子水溶性樹脂（ａ－１）の重量平均分子量が上記範囲内であることにより、耐ドリルビット折損性及び孔位置精度がより向上し、巻き付きが抑制される傾向にある。 The weight average molecular weight of the polymer water-soluble resin (a-1) is 1.0 × 10 5 to 2.0 × 10 6 , preferably 1.0 × 10 5 to 1.0 × 10 6 , More preferably, it is 1.0 × 10 5 to 6.0 × 10 5 . When the weight average molecular weight of the polymer water-soluble resin (a-1) is within the above range, the drill bit breakage resistance and the hole position accuracy are further improved, and winding tends to be suppressed.
　高分子水溶性樹脂（ａ－１）の含有量は、樹脂組成物中の樹脂成分の総量１００質量部に対して、好ましくは３～１５質量部であり、より好ましくは５～１２質量部であり、さらに好ましくは７～１０質量部である。高分子水溶性樹脂（ａ－１）の含有量が上記範囲内であることにより、樹脂組成物層の製膜性及び孔位置精度がより向上する傾向にある。 The content of the polymer water-soluble resin (a-1) is preferably 3 to 15 parts by mass, more preferably 5 to 12 parts by mass with respect to 100 parts by mass of the total amount of the resin components in the resin composition. More preferably 7 to 10 parts by mass. When the content of the polymer water-soluble resin (a-1) is within the above range, the film forming property and the hole position accuracy of the resin composition layer tend to be further improved.
（中分子水溶性樹脂（ａ－２））
　中分子水溶性樹脂（ａ－２）としては、特に限定されず、例えば、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等のグリコール化合物；ポリオキシエチレンオレイルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテル等のポリオキシエチレンのモノエーテル化合物；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化合物、ポリオキシエチレンプロピレン共重合体などが挙げられる。このなかでも、ポリテトラメチレングリコール、ポリエチレングリコール、ポリプロピレングリコールが好ましい。中分子水溶性樹脂（ａ－２）は、１種単独で用いてもよく、又は２種類以上を組み合わせて用いてもよい。 (Medium water-soluble resin (a-2))
The medium-molecule water-soluble resin (a-2) is not particularly limited, and examples thereof include glycol compounds such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; polyoxyethylene oleyl ether, polyoxyethylene cetyl ether, polyoxyethylene Polyoxyethylene monoether compounds such as stearyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether; polyoxyethylene monostearate, polyoxyethylene sorbitan monostearate, polyglycerin mono A stearate compound, a polyoxyethylene propylene copolymer, etc. are mentioned. Among these, polytetramethylene glycol, polyethylene glycol, and polypropylene glycol are preferable. The medium molecular water-soluble resin (a-2) may be used alone or in combination of two or more.
　中分子水溶性樹脂（ａ－２）の重量平均分子量は、３．０×１０３～７．０×１０４であり、好ましくは３．０×１０３～３．０×１０４であり、より好ましくは３．０×１０３～１．０×１０４である。中分子水溶性樹脂（ａ－２）の重量平均分子量が上記範囲内であることにより、耐ドリルビット折損性及び孔位置精度がより向上し、巻き付きが抑制される傾向にある。 The weight average molecular weight of the medium molecular water-soluble resin (a-2) is 3.0 × 10 3 to 7.0 × 10 4 , preferably 3.0 × 10 3 to 3.0 × 10 4 , More preferably, it is 3.0 × 10 3 to 1.0 × 10 4 . When the weight average molecular weight of the medium-molecule water-soluble resin (a-2) is within the above range, the drill bit breakage resistance and the hole position accuracy are further improved, and winding tends to be suppressed.
　中分子水溶性樹脂（ａ－２）の含有量は、樹脂組成物中の樹脂成分の総量１００質量部に対して、好ましくは４０～８５質量部であり、より好ましくは５５～８５質量部であり、さらに好ましくは６５～８０質量部である。中分子水溶性樹脂（ａ－２）の含有量が上記範囲内であることにより、樹脂組成物層の及び孔位置精度がより向上する傾向にある。 The content of the medium molecular water-soluble resin (a-2) is preferably 40 to 85 parts by mass, more preferably 55 to 85 parts by mass with respect to 100 parts by mass of the total amount of the resin components in the resin composition. More preferably, it is 65 to 80 parts by mass. When the content of the medium molecular water-soluble resin (a-2) is within the above range, the accuracy of the resin composition layer and the hole position tends to be further improved.
（低分子水溶性樹脂（ａ－３））
　低分子水溶性樹脂（ａ－３）としては、特に限定されず、例えば、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等のグリコール化合物；ポリオキシエチレンオレイルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテル等のポリオキシエチレンのモノエーテル化合物；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化合物、ポリオキシエチレンプロピレン共重合体などが挙げられる。このなかでも、ポリオキシエチレンのモノエーテル化合物、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化合物、及びポリオキシエチレンプロピレン共重合体が好ましい。低分子水溶性樹脂（ａ－３）は、１種単独で用いてもよく、又は２種類以上を組み合わせて用いてもよい。 (Low molecular water-soluble resin (a-3))
The low-molecular water-soluble resin (a-3) is not particularly limited, and examples thereof include glycol compounds such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; polyoxyethylene oleyl ether, polyoxyethylene cetyl ether, polyoxyethylene Polyoxyethylene monoether compounds such as stearyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether; polyoxyethylene monostearate, polyoxyethylene sorbitan monostearate, polyglycerin mono A stearate compound, a polyoxyethylene propylene copolymer, etc. are mentioned. Of these, polyoxyethylene monoether compounds, polyoxyethylene monostearate, polyoxyethylene sorbitan monostearate, polyglycerin monostearate compounds, and polyoxyethylene propylene copolymers are preferred. The low molecular weight water-soluble resin (a-3) may be used alone or in combination of two or more.
　低分子水溶性樹脂（ａ－３）の含有量は、樹脂組成物中の樹脂成分の総量１００質量部に対して、好ましくは３～２５質量部であり、より好ましくは５～２０質量部であり、さらに好ましくは１０～２０質量部である。低分子水溶性樹脂（ａ－３）の含有量が上記範囲内であることにより、樹脂組成物層の潤滑性及び孔位置精度がより向上する傾向にある。 The content of the low molecular weight water-soluble resin (a-3) is preferably 3 to 25 parts by mass, more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the total amount of the resin components in the resin composition. More preferably, it is 10 to 20 parts by mass. When the content of the low-molecular water-soluble resin (a-3) is within the above range, the lubricity and the hole position accuracy of the resin composition layer tend to be further improved.
（充填材（Ｂ））
　充填材（Ｂ）としては、特に制限されないが、例えば、シリカ、タルク、カオリン、マイカ、ベーマイト、モリブデン化合物（二硫化モリブデン、酸化モリブデン、モリブデン酸亜鉛）が挙げられる。このなかでも、タルク及び／又は二硫化モリブデンが好ましい。このような充填材を用いることにより、耐ドリルビット折損性及び孔位置精度がより向上し、巻き付きが抑制される傾向にある。 (Filler (B))
The filler (B) is not particularly limited, and examples thereof include silica, talc, kaolin, mica, boehmite, and molybdenum compounds (molybdenum disulfide, molybdenum oxide, and zinc molybdate). Of these, talc and / or molybdenum disulfide are preferable. By using such a filler, the drill bit breakage resistance and the hole position accuracy are further improved, and the winding tends to be suppressed.
　充填材（Ｂ）のメディアン径（平均粒子径）は、好ましくは０．３μｍ以上１０μｍ以下であり、より好ましくは０．３μｍ以上８μｍ以下であり、さらに好ましくは０．５μｍ以上６μｍ以下である。充填材（Ｂ）のメディアン径が上記範囲内であることにより、耐ドリルビット折損性及び孔位置精度がより向上し、巻き付きが抑制される傾向にある。ここで、メディアン径とは、例えば、レーザー回折法などの粒子径の測定方法で測定される、粒子径の累積分布曲線（個数基準）において、５０％の高さとなる粒子直径（Ｄ５０）のことである。 The median diameter (average particle diameter) of the filler (B) is preferably 0.3 μm or more and 10 μm or less, more preferably 0.3 μm or more and 8 μm or less, and further preferably 0.5 μm or more and 6 μm or less. When the median diameter of the filler (B) is within the above range, drill bit breakage resistance and hole position accuracy are further improved, and winding tends to be suppressed. Here, the median diameter is, for example, a particle diameter (D50) having a height of 50% in a cumulative particle diameter distribution curve (number basis) measured by a particle diameter measuring method such as a laser diffraction method. It is.
　充填材（Ｂ）の含有量は、樹脂組成物中の樹脂成分の総量１００質量部に対して、好ましくは１０～１５０質量部であり、より好ましくは３０～１２５質量部であり、さらに好ましくは５０～１００質量部である。充填材（Ｂ）の含有量が上記範囲内であることにより、耐ドリルビット折損性及び孔位置精度がより向上し、巻き付きが抑制される傾向にある。 The content of the filler (B) is preferably 10 to 150 parts by mass, more preferably 30 to 125 parts by mass, and still more preferably with respect to 100 parts by mass of the total amount of the resin components in the resin composition. 50 to 100 parts by mass. When the content of the filler (B) is within the above range, the drill bit breakage resistance and the hole position accuracy are further improved, and winding tends to be suppressed.
　充填材（Ｂ）の形状は、特に制限されないが、例えば、板状であることが好ましい。シリコーンレジンパウダーなどの略球形を有するものと比較して、板状の充填材（Ｂ）は、せん断時の抵抗が大きくなる。そのため、充填剤（Ｂ）の含有量を上記範囲とすることにより、△Ｇ’等を本実施形態の範囲に調整することが可能となる。一方で、充填剤（Ｂ）の形状が球形に近いほど、せん断時の抵抗が小さく、△Ｇ’等を調整しにくい傾向にある。 The shape of the filler (B) is not particularly limited, but is preferably, for example, a plate shape. Compared with what has a substantially spherical shape such as silicone resin powder, the plate-like filler (B) has a greater resistance during shearing. Therefore, by setting the content of the filler (B) within the above range, ΔG ′ and the like can be adjusted within the range of the present embodiment. On the other hand, the closer the shape of the filler (B) is to a sphere, the smaller the resistance during shearing, and the more difficult it is to adjust ΔG ′ and the like.
　このような観点から、充填材（Ｂ）としては板状を有するタルク及び／又は二硫化モリブデンが好ましく、これらの含有量を上記範囲とすることにより、耐ドリルビット折損性がさらに向上する傾向にある。 From such a viewpoint, as the filler (B), talc and / or molybdenum disulfide having a plate shape is preferable, and by making these contents in the above range, the resistance to breakage of the drill bit tends to be further improved. is there.
（その他の成分）
　樹脂組成物層は、必要に応じて、添加剤を含有していてもよい。添加剤の種類は、特に限定されないが、例えば、表面調整剤、レベリング剤、帯電防止剤、乳化剤、消泡剤、ワックス添加剤、カップリング剤、レオロジーコントロール剤、防腐剤、防黴剤、酸化防止剤、光安定剤、ギ酸Ｎａなどの核剤、熱安定化剤、および着色剤が挙げられる (Other ingredients)
The resin composition layer may contain an additive as necessary. The type of additive is not particularly limited, but for example, surface conditioner, leveling agent, antistatic agent, emulsifier, antifoaming agent, wax additive, coupling agent, rheology control agent, antiseptic, antifungal agent, oxidation Examples include inhibitors, light stabilizers, nucleating agents such as sodium formate, heat stabilizers, and colorants.
　樹脂組成物層の厚さは、ドリル孔あけ加工する際に使用するドリルビット径や、加工する孔あけ対象物（例えば、積層板または多層板などのプリント配線板材料）の構成などによって適宜選択される。このなかでも、樹脂組成物層の厚さは、好ましくは０．０２～０．３ｍｍであり、より好ましくは０．０２～０．２ｍｍであり、さらに好ましくは０．０２～０．１ｍｍである。樹脂組成物層の厚さが０．０２ｍｍ以上であることにより、より十分な潤滑効果が得られ、ドリルビットへの負荷が軽減されるので、ドリルビットの折損をさらに抑制することができる傾向にある。また、樹脂組成物層の厚さが０．３ｍｍ以下であることにより、ドリルビットへの樹脂組成物の巻き付きを抑制することができる傾向にある。 The thickness of the resin composition layer is appropriately selected depending on the diameter of the drill bit used for drilling and the configuration of the drilled object to be processed (for example, a printed wiring board material such as a laminate or multilayer board). Is done. Among these, the thickness of the resin composition layer is preferably 0.02 to 0.3 mm, more preferably 0.02 to 0.2 mm, and still more preferably 0.02 to 0.1 mm. . When the thickness of the resin composition layer is 0.02 mm or more, a sufficient lubrication effect is obtained and the load on the drill bit is reduced, so that the breakage of the drill bit tends to be further suppressed. is there. Moreover, it exists in the tendency which can suppress the winding of the resin composition to a drill bit because the thickness of a resin composition layer is 0.3 mm or less.
〔金属箔〕
　本実施形態のドリル孔あけ用エントリーシートに使用される金属箔は、特に限定されないが、上記樹脂組成物層との密着性が高く、ドリルビットによる衝撃に耐え得る金属材料であると好ましい。金属箔の金属種としては、入手性、コストおよび加工性の観点から、例えばアルミニウムが挙げられる。アルミニウム箔の材質としては、純度９５％以上のアルミニウムが好ましい、そのようなアルミニウム箔としては、例えば、ＪＩＳ－Ｈ４１６０に規定される、５０５２、３００４、３００３、１Ｎ３０、１Ｎ９９、１０５０、１０７０、１０８５、８０２１が挙げられる。金属箔にアルミニウム純度９５％以上のアルミニウム箔を用いることによって、ドリルビットによる衝撃の緩和、およびドリルビット先端部との食いつき性が向上し、樹脂組成物によるドリルビットの潤滑効果と相俟って、加工孔の孔位置精度を一層高めることができる。 [Metal foil]
The metal foil used for the drill hole entry sheet of the present 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. As a metal seed | species of metal foil, aluminum is mentioned from a viewpoint of availability, cost, and workability, for example. As the material of the aluminum foil, aluminum having a purity of 95% or more is preferable. Examples of such aluminum foil include 5052, 3004, 3003, 1N30, 1N99, 1050, 1070, 1085, as defined in JIS-H4160. 8021. By using an aluminum foil with an aluminum purity of 95% or more for the metal foil, the impact of the drill bit is reduced and the biting property with the tip of the drill bit is improved, combined with the lubricating effect of the drill bit by the resin composition. The hole position accuracy of the processed hole can be further increased.
　金属箔の厚さは、好ましくは０．０５～０．５ｍｍであり、より好ましくは０．０５～０．３ｍｍであり、さらに好ましくは０．０５～０．２ｍｍである。金属箔の厚さが０．０５ｍｍ以上であることにより、ドリル孔あけ加工時の孔あけ対象物（例えば、積層板）のバリの発生をより抑制することができる傾向にある。また、金属箔の厚さが０．５ｍｍ以下であることにより、ドリル孔あけ加工時に発生する切り粉の排出がより容易になる傾向にある。 The thickness of the metal foil is preferably 0.05 to 0.5 mm, more preferably 0.05 to 0.3 mm, and still more preferably 0.05 to 0.2 mm. When the thickness of the metal foil is 0.05 mm or more, the occurrence of burrs on the drilling object (for example, a laminate) during drilling tends to be further suppressed. Moreover, when the thickness of the metal foil is 0.5 mm or less, the discharge of chips generated during drilling tends to be easier.
　本実施形態のドリル孔あけ用エントリーシートを構成する各層の厚さは、次のようにして測定する。まず、クロスセクションポリッシャー（日本電子データム株式会社製、商品名「ＣＲＯＳＳ-ＳＥＣＴＩＯＮＰＯＬＩＳＨＥＲＳＭ-０９０１０」）、またはウルトラミクロトーム（Ｌｅｉｃａ社製、品番「ＥＭＵＣ７」）を用いて、エントリーシートを、各層の積層方向に切断する。その後、ＳＥＭ（走査型電子顕微鏡（ＳｃａｎｎｉｎｇＥｌｅｃｔｒｏｎＭｉｃｒｏｓｃｏｐｅ）、ＫＥＹＥＮＣＥ社製品番「ＶＥ－７８００」）を用いて、切断して現れた断面に対して垂直方向からその断面を観察し、構成する各層、例えば、金属箔及び樹脂組成物層の厚さを測定する。１視野に対して、５箇所の厚さを測定し、その平均値を各層の厚さとする。 The thickness of each layer constituting the drill hole entry sheet of the present embodiment is measured as follows. First, using a cross section polisher (manufactured by JEOL Datum Co., Ltd., trade name “CROSS-SECTIONPOLISHERSM-09010”) or ultramicrotome (manufactured by Leica, product number “EMUC7”), the entry sheet is placed in the stacking direction of each layer. Disconnect. Then, using a SEM (Scanning Electron Microscope, KEYENCE product number “VE-7800”), the section formed by observing the section from a direction perpendicular to the section that has been cut and formed, for example, The thickness of the metal foil and the resin composition layer is measured. The thickness of five places is measured for one visual field, and the average value is taken as the thickness of each layer.
〔ドリル孔あけ用エントリーシートの製造方法〕
　本実施形態のドリル孔あけ用エントリーシートの製造方法は、特に限定されず、例えば、金属箔の少なくとも片面上に樹脂組成物層を形成して製造される。金属箔上に樹脂組成物層を形成させる方法は特に限定されず、公知の方法が使用できる。そのような方法としては、例えば、樹脂等を溶媒に溶解又は分散させた樹脂組成物の溶液を、コーティング法などの方法で、金属箔上に塗工して、更に乾燥させる及び／又は冷却固化させる方法が挙げられる。 [Method of manufacturing entry sheet for drilling holes]
The manufacturing method of the entry sheet for drilling of this embodiment is not specifically limited, For example, it forms and forms a resin composition layer on the at least single side | surface of metal foil. The method for forming the resin composition layer on the metal foil is not particularly limited, and a known method can be used. As such a method, for example, a solution of a resin composition in which a resin or the like is dissolved or dispersed in a solvent is coated on a metal foil by a method such as a coating method, and further dried and / or cooled and solidified. The method of letting it be mentioned.
　コーティング法などによって、樹脂組成物の溶液を金属箔上に塗工して、乾燥させて樹脂組成物層を形成する場合、樹脂組成物の溶液に用いる溶媒は、水と水よりも沸点が低い溶媒とからなる混合溶液であることが好ましい。水と水よりも沸点が低い溶媒からなる混合溶液を用いることは、樹脂組成物層中の残留気泡の低減に寄与する。水よりも沸点が低い溶媒の種類は、特に限定されないが、例えば、エタノール、メタノールやイソプロピルアルコールなどのアルコール化合物が挙げられ、メチルエチルケトンやアセトンなどの低沸点溶剤も用いることが可能である。その他の溶媒として、水やアルコール化合物に樹脂組成物との相溶性が高いテトラヒドロフランやアセトニトリルを一部混合させた溶媒などを用いることが可能である。 When a resin composition solution is applied to a metal foil by a coating method or the like and dried to form a resin composition layer, the solvent used for the resin composition solution has a lower boiling point than water and water. A mixed solution composed of a solvent is preferable. Use of a mixed solution composed of water and a solvent having a boiling point lower than that of water contributes to reduction of residual bubbles in the resin composition layer. Although the kind of solvent whose boiling point is lower than water is not specifically limited, For example, alcohol compounds, such as ethanol, methanol, and isopropyl alcohol, are mentioned, Low boiling solvents, such as methyl ethyl ketone and acetone, can also be used. As another solvent, it is possible to use a solvent obtained by partially mixing tetrahydrofuran or acetonitrile having high compatibility with the resin composition in water or an alcohol compound.
〔ドリル孔あけ加工方法〕
　本実施形態のドリル孔あけ加工方法は、上記ドリル孔あけ用エントリーシートを用いて、積層板又は多層板に孔を形成する孔形成工程を有する。また、そのドリル孔あけ加工に用いるドリルビットの直径（ドリルビット径）は、好ましくは０．１０ｍｍφ以下であり、より好ましくは０．０８０ｍｍφ以下である。このようなドリルビットは、細いため特に折損しやすく、また、孔位置精度も必要とされる。これに対して、本実施形態のエントリーシートを用いることにより、特に、耐ドリルビット折損性及び孔位置精度、並びに、樹脂組成物層の屑の切削工具への巻き付きの抑制効果がより効果的に発揮される。なお、直径０．３０ｍｍφ超のドリルビットを用いるドリル孔あけ加工に、本実施形態のドリル孔あけ用エントリーシートを採用しても問題ない。 [Drill drilling method]
The drill drilling method of the present embodiment includes a hole forming step of forming a hole in the laminated plate or the multilayer plate using the drill hole entry sheet. Moreover, the diameter (drill bit diameter) of the drill bit used for the drilling process is preferably 0.10 mmφ or less, and more preferably 0.080 mmφ or less. Since such a drill bit is thin, it is particularly easy to break, and the hole position accuracy is also required. On the other hand, by using the entry sheet of the present embodiment, in particular, the drill bit breakage resistance and hole position accuracy, and the effect of suppressing the winding of the resin composition layer debris around the cutting tool are more effective. Demonstrated. It should be noted that there is no problem even if the drill hole entry sheet of this embodiment is adopted for drilling using a drill bit having a diameter of more than 0.30 mmφ.
　本実施形態のドリル孔あけ用エントリーシートは、例えば、プリント配線板材料、より具体的には、積層板又は多層板をドリル孔あけ加工する際に好適に用いることができる。具体的には、積層板又は多層板を１枚又は複数枚重ねたもの（プリント配線板材料）の少なくとも最上面に、金属箔側がプリント配線板材料に接するようにドリル孔あけ用エントリーシートを配置し、そのエントリーシートの上面（樹脂組成物層側）から、ドリル孔あけ加工を行うことができる。 The entry sheet for drilling according to the present embodiment can be suitably used for drilling a printed wiring board material, more specifically, a laminated board or a multilayer board. Specifically, an entry sheet for drilling is arranged 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 foil side is in contact with the printed wiring board material Then, drilling can be performed from the upper surface (resin composition layer side) of the entry sheet.
　以下に、本発明の実施例の効果を、本発明の範囲から外れる比較例と比較して説明する。 Hereinafter, the effects of the examples of the present invention will be described in comparison with comparative examples that are out of the scope of the present invention.
＜せん断貯蔵弾性率＞
　実施例及び比較例における樹脂組成物層のせん断貯蔵弾性率は、ＴＡインスツルメンツ社製の動的粘弾性測定装置「ＤＩＳＣＯＶＥＲ　ＨＲ－２」を用いて測定した。以下に測定試料の準備方法について記載する。実施例1に記載の方法で作製したドリル孔あけ用エントリーシートを、１７０℃で樹脂組成物層を軟化させて樹脂組成物層のみを取り出した後に、冷却し固化させたものを測定試料とした。また動的粘弾性測定装置の測定前準備方法として、前記動的粘弾性測定装置の測定台上に測定試料を設置し、測定台を１７０℃に加温した後、動的粘弾性測定装置付属の直径２０ｍｍパラレルプレートと測定台とで、該パラレルプレートと測定台間のギャップが０．２ｍｍとなるまで樹脂組成物層を挟み込み、測定台を３０℃まで冷却し温度が安定した後に測定した。測定条件として下記測定条件にて測定を行った。 <Shear storage modulus>
The shear storage elastic modulus of the resin composition layers in Examples and Comparative Examples was measured using a dynamic viscoelasticity measuring device “DISCOVER HR-2” manufactured by TA Instruments. The method for preparing the measurement sample is described below. The entry sheet for drilling prepared by the method described in Example 1 was softened at 170 ° C. and only the resin composition layer was taken out and then cooled and solidified as a measurement sample. . In addition, as a pre-measurement preparation method of the dynamic viscoelasticity measuring device, a measurement sample is set on the measurement stand of the dynamic viscoelasticity measuring device, the measurement stand is heated to 170 ° C., and then the dynamic viscoelasticity measuring device is attached. The resin composition layer was sandwiched between a parallel plate and a measuring table having a diameter of 20 mm until the gap between the parallel plate and the measuring table was 0.2 mm, and the measuring table was cooled to 30 ° C. and the temperature was stabilized. Measurement was performed under the following measurement conditions.
〔測定条件〕
　モード　　：せん断モード
　昇温速度　：１０℃／分
　温度範囲　：３０～１５０℃
　周波数　　：１．０Ｈｚ
　歪　　　　：０．０１％ 〔Measurement condition〕
Mode: Shear mode Temperature increase rate: 10 ° C / min Temperature range: 30-150 ° C
Frequency: 1.0Hz
Distortion: 0.01%
〔孔位置精度、平均折損孔数（耐ドリルビット折損性）の評価における加工条件〕
　厚さ０．０４ｍｍの銅張積層板（商品名：ＨＬ８３２ＮＳ－Ｌ、銅箔厚さ５μｍ、両面板、三菱ガス化学株式会社製）を６枚積み重ねた銅張積層板の上面に、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をその樹脂組成物層側が上面になるように配置し、積み重ねた銅張積層板の最下板の裏面（下面）に厚さ１．５ｍｍの当て板（紙フェノール積層板ＰＳ１１６０－Ｇ、利昌株式会社製）を配置した。そして、０．０６０ｍｍφドリルビット（ユニオンツール株式会社製）５本を用いて、下記加工条件でドリルビット１本につき１０，０００孔の設定で、下記の条件で各ドリルビットが折損するまで孔あけ加工を行った。
　回転数　　　　　　　　　　　：３３０，０００ｒｐｍ
　送り速度　　　　　　　　　　：２．９４ｍ／ｍｉｎ
　ドリルビット１本の孔あけ回数：１０，０００孔設定 [Processing conditions for evaluation of hole position accuracy, average number of broken holes (drill bit breakage resistance)]
A copper-clad laminate (trade name: HL832NS-L, copper foil thickness 5 μm, double-sided board, manufactured by Mitsubishi Gas Chemical Co., Ltd.) having a thickness of 0.04 mm is stacked on the upper surface of the copper-clad laminate, and examples and The drill hole entry sheet prepared in the comparative example is arranged so that the resin composition layer side is the upper surface, and a 1.5 mm thick patch plate on the back surface (lower surface) of the stacked copper-clad laminate (Paper phenol laminate PS1160-G, manufactured by Risho Co., Ltd.) was placed. Then, using five 0.060 mmφ drill bits (manufactured by Union Tool Co., Ltd.), set up 10,000 holes per drill bit under the following processing conditions, and drill until each drill bit breaks under the following conditions. Processing was performed.
Number of revolutions: 330,000 rpm
Feeding speed: 2.94 m / min
Number of drill holes for one drill bit: 10,000 holes set
〔孔位置精度の評価方法〕
　ドリル１本分の加工孔につき、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。ドリルビット１本分ごとに、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５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、下記評価基準により孔位置精度を評価した。孔位置精度の算出に用いた式は、下記のとおりである。 [Evaluation method of hole position accuracy]
The difference between the hole position on the back surface (bottom surface) of the bottom plate of the stacked copper-clad laminate and the specified coordinates for the drilled hole for one drill is measured with a hole analyzer (model number: HA-1AM, manufactured by Hitachi Via Mechanics Co., Ltd.). ). For each drill bit, an average value and a standard deviation (σ) were calculated for the deviation, and “average value + 3σ” was calculated. Then, the average value with respect to the value of “average value + 3σ” for each of the five drill bits used was calculated as the hole position accuracy of the entire drilling process, and the hole position accuracy was evaluated according to the following evaluation criteria. The formula used to calculate the hole position accuracy is as follows.
Figure JPOXMLDOC01-appb-M000001
 　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　（３）
（ここで、ｎは使用したドリルビットの本数を示す。）
（評価基準）
　５：孔位置精度が、１５μｍ未満
　４：孔位置精度が、１５μｍ以上１７μｍ未満
　３：孔位置精度が、１７μｍ以上２５μｍ未満
　２：孔位置精度が、２５μｍ以上３５μｍ未満
　１：孔位置精度が、３５μｍ以上
Figure JPOXMLDOC01-appb-M000001
 (3)
(Here, n indicates the number of drill bits used.)
(Evaluation criteria)
5: Hole position accuracy is less than 15 μm 4: Hole position accuracy is not less than 15 μm and less than 17 μm 3: Hole position accuracy is not less than 17 μm and less than 25 μm 2: Hole position accuracy is not less than 25 μm and less than 35 μm 1: Hole position accuracy is 35 μm more than
〔平均折損孔数（耐ドリルビット折損性）の評価方法〕
　前記加工条件にて、各ドリルビットが折損するまでの孔あけ回数をカウントし、５本の平均値を算出し、得られた平均値（平均折損孔数）に基づき、下記基準により耐ドリルビット折損性を評価した。
（評価基準）
　５：平均折損孔数が、８０００以上
　４：平均折損孔数が、７０００以上８０００未満
　３：平均折損孔数が、６０００以上７０００未満
　２：平均折損孔数が、５０００以上６０００未満
　１：平均折損孔数が、５０００未満 [Evaluation method of average number of broken holes (breakage resistance of drill bit)]
Under the above processing conditions, the number of drilling times until each drill bit breaks is counted, the average value of five is calculated, and based on the obtained average value (average number of broken holes), the drill bit resistance according to the following criteria Breakability was evaluated.
(Evaluation criteria)
5: The average number of broken holes is 8000 or more 4: The average number of broken holes is 7000 or more and less than 8000 3: The average number of broken holes is 6000 or more and less than 7000 2: The average number of broken holes is 5000 or more and less than 6000 1: Average breakage The number of holes is less than 5000
〔巻き付き〕
　厚さ０．０６ｍｍの銅張積層板（商品名：ＨＬ８３２ＮＳ－Ｌ、銅箔厚さ３μｍ、両面板、三菱ガス化学株式会社製）を８枚積み重ねた銅張積層板の上面に、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をその樹脂組成物層側が上面になるように配置し、積み重ねた銅張積層板の最下板の裏面（下面）に厚さ１．５ｍｍの当て板（紙フェノール積層板ＳＰＢ－Ｗ、日本デコラック株式会社製）を配置した。そして、０．０８０ｍｍφドリルビット（商品名：ＫＭＷＭ４７６ＥＷＵ、ユニオンツール株式会社製）３本を用いて、下記条件でドリルビット１本につき１０，０００孔、計３０，０００孔のドリル孔あけ加工を行った。
　回転数　　　　　　　　　　　：２８０，０００ｒｐｍ
　送り速度　　　　　　　　　　：１．４ｍ／ｍｉｎ
　ドリルビット１本の孔あけ回数：１０，０００孔 (With winding)
On the upper surface of a copper clad laminate having a stack of eight copper clad laminates (trade name: HL832NS-L, copper foil thickness 3 μm, double-sided board, manufactured by Mitsubishi Gas Chemical Co., Ltd.) having a thickness of 0.06 mm, The drill hole entry sheet prepared in the comparative example is arranged so that the resin composition layer side is the upper surface, and a 1.5 mm thick patch plate on the back surface (lower surface) of the stacked copper-clad laminate (Paper phenol laminate SPB-W, manufactured by Nippon Decorac Co., Ltd.) was placed. Then, using three 0.080 mmφ drill bits (trade name: KMWM476EWU, manufactured by Union Tool Co., Ltd.), 10,000 holes are drilled per drill bit under the following conditions, and a total of 30,000 holes are drilled. It was.
Rotational speed: 280,000 rpm
Feeding speed: 1.4m / min
Number of drills per drill bit: 10,000 holes
　回収したドリルビットを、倍率１００倍の顕微鏡にて観察した。ドリルビットに樹脂組成物層の屑が巻き付いた状態の部分について、ドリルビット径方向で最も大きな径（以下、「加工屑巻き付きの最大径」という。）を求め、下記基準により巻き付きを評価した。
（評価基準）
　３：樹脂組成物層の巻き付きの最大径が、ドリルビット径の１．２倍未満
　２：樹脂組成物層の巻き付きの最大径が、ドリルビット径の１．２倍以上２．０倍未満
　１：樹脂組成物層の巻き付きの最大径が、ドリルビット径の２．０倍以上 The collected drill bit was observed with a microscope having a magnification of 100 times. About the part of the state where the scrap of the resin composition layer was wound around the drill bit, the largest diameter in the drill bit radial direction (hereinafter referred to as “the maximum diameter with the processing scrap wound”) was obtained, and the winding was evaluated according to the following criteria.
(Evaluation criteria)
3: The maximum diameter of the resin composition layer wound is less than 1.2 times the drill bit diameter 2: The maximum diameter of the resin composition layer wound is 1.2 times or more and less than 2.0 times the drill bit diameter 1 : The maximum wound diameter of the resin composition layer is 2.0 times or more the drill bit diameter
＜原材料＞
　表１に、実施例及び比較例のドリル孔あけ用エントリーシートの製造に用いた原材料を示した。 <Raw materials>
Table 1 shows raw materials used for manufacturing the drilling entry sheets of Examples and Comparative Examples.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
〔実施例１〕
　高分子水溶性樹脂（ａ－１）として重量平均分子量５６０，０００のポリエチレンオキサイド（明成化学工業株式会社製、アルコックスＥ－４５）８質量部と、中分子水溶性樹脂（ａ－２）として重量平均分子量３，３００のポリエチレングリコール（三洋化成工業株式会社製、ＰＥＧ４０００Ｓ）７７質量部と、低分子水溶性樹脂（ａ－３）として重量平均分子量１，５４０のポリエチレングリコ－ル－モノステアリン酸エステル（日油株式会社製、ノニオンＳ１５．４）１５質量部とを、樹脂組成物溶液の固形分濃度が３０％となるように水／メタノール混合溶媒に溶解させた。水／メタノール混合溶媒の混合割合は５０／５０とした。この樹脂組成物溶液をアルミニウム箔（使用アルミニウム箔：ＪＩＳ－Ａ１１００Ｈ、厚さ０．０７ｍｍ、三菱アルミニウム株式会社製）の片面に、バーコーターを用いて乾燥後の樹脂組成物の層の厚さが５０μｍとなるように塗布し、乾燥機にて９０℃、５分間乾燥させ、常温まで冷却して、ドリル孔あけ用エントリーシートを作製した。 [Example 1]
As the polymer water-soluble resin (a-1), 8 parts by mass of polyethylene oxide having a weight average molecular weight of 560,000 (manufactured by Meisei Chemical Industry Co., Ltd., Alcox E-45) and the medium-molecule water-soluble resin (a-2) 77 parts by mass of polyethylene glycol having a weight average molecular weight of 3,300 (manufactured by Sanyo Chemical Industries Co., Ltd., PEG4000S) and polyethylene glycol monostearic acid having a weight average molecular weight of 1,540 as a low molecular weight water-soluble resin (a-3) 15 parts by mass of ester (manufactured by NOF Corporation, Nonion S15.4) was dissolved in a water / methanol mixed solvent so that the solid content concentration of the resin composition solution was 30%. The mixing ratio of the water / methanol mixed solvent was 50/50. The resin composition solution was dried on one side of an aluminum foil (used aluminum foil: JIS-A1100H, thickness 0.07 mm, manufactured by Mitsubishi Aluminum Co., Ltd.) using a bar coater to determine the thickness of the resin composition layer. It applied so that it might become 50 micrometers, it dried at 90 degreeC for 5 minute (s) with the dryer, and it cooled to normal temperature, and produced the entry sheet for drilling.
＜実施例２～６、比較例１～４＞
　用いた原料を表２に示す通りに変更したこと以外は、実施例１と同様にして、ドリル孔あけ用エントリーシートを作製した。 <Examples 2 to 6, Comparative Examples 1 to 4>
An entry sheet for drilling was prepared in the same manner as in Example 1 except that the raw materials used were changed as shown in Table 2.
　表２に各評価結果を示し、図１に実施例２、３及び５、並びに、比較例１、２、及び３のせん断貯蔵弾性率の測定結果を示す。 Table 2 shows the evaluation results, and FIG. 1 shows the measurement results of the shear storage modulus of Examples 2, 3, and 5 and Comparative Examples 1, 2, and 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　本出願は、２０１８年３月３０日に日本国特許庁へ出願された日本特許出願（特願２０１８－６９１６９）に基づくものであり、その内容はここに参照として取り込まれる。 This application is based on a Japanese patent application (Japanese Patent Application No. 2018-69169) filed with the Japan Patent Office on March 30, 2018, the contents of which are incorporated herein by reference.
　本発明は、積層板や多層板のドリル孔あけ加工等の際に使用されるドリル孔あけ用エントリーシートとして産業上の利用可能性を有する。特に、本発明によれば、従来のドリル孔あけ用エントリーシートに比べて、孔位置精度に優れ、金属箔と樹脂組成物層との剥離によるドリル折損が少なく、従来必要であった接着層が不要なため経済性にも優れたドリル孔あけ用エントリーシートを提供できる。
  INDUSTRIAL APPLICABILITY The present invention has industrial applicability as an entry sheet for drilling used for drilling a laminated plate or multilayer board. In particular, according to the present invention, compared to a conventional drill hole entry sheet, the hole position accuracy is excellent, the drill breakage due to peeling between the metal foil and the resin composition layer is less, and the conventionally required adhesive layer is Because it is unnecessary, it can provide an entry sheet for drilling with excellent economic efficiency.

Claims (9)

  1. 　金属箔と、該金属箔上の少なくとも片面に形成された樹脂組成物層と、を有し、
    　該樹脂組成物層のせん断貯蔵弾性率が、下記式（ｉ）、（ｉｉ）で表される関係を満たす、
    　ドリル孔あけ用エントリーシート。
    　　　－３．０≦△Ｇ’≦－１．０…（ｉ）
    　　　４．５×１０５≦Ｇ’（５６）≦１００×１０５…（ｉｉ）
    （上記式中、△Ｇ’＝ｌｏｇ１０（Ｇ’（６２））－ｌｏｇ１０（Ｇ’（５６））であり、Ｇ’（５６）、Ｇ’（６２）は、それぞれ、前記樹脂組成物の５６℃、６２℃におけるせん断貯蔵弾性率（単位：Ｐａ）を示す。）     A metal foil, and a resin composition layer formed on at least one side of the metal foil,
    The shear storage elastic modulus of the resin composition layer satisfies the relationship represented by the following formulas (i) and (ii).
    Entry sheet for drilling.
    −3.0 ≦ ΔG ′ ≦ −1.0 (i)
    4.5 × 10 5 ≦ G ′ (56) ≦ 100 × 10 5 (ii)
    (In the above formula, ΔG ′ = log 10 (G ′ (62)) − log 10 (G ′ (56))), and G ′ (56) and G ′ (62) are the resin composition, respectively. The shear storage modulus (unit: Pa) at 56 ° C. and 62 ° C. is shown.)
  2. 　前記樹脂組成物層が、下記式（ｉｉｉ）で表される関係をさらに満たす、
    　請求項１に記載のドリル孔あけ用エントリーシート。
    　　　０．００５×１０５≦Ｇ’（７０）≦８０×１０５…（ｉｉｉ）
    （上記式中、Ｇ’（７０）は前記樹脂組成物の７０℃におけるせん断貯蔵弾性率（単位：Ｐａ）を示す。）     The resin composition layer further satisfies a relationship represented by the following formula (iii):
    The entry sheet for drilling according to claim 1.
    0.005 × 10 5 ≦ G ′ (70) ≦ 80 × 10 5 (iii)
    (In the above formula, G ′ (70) represents the shear storage modulus (unit: Pa) of the resin composition at 70 ° C.)
  3. 　前記樹脂組成物が、水溶性樹脂（Ａ）を含有する、
    　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。     The resin composition contains a water-soluble resin (A).
    An entry sheet for drilling according to claim 1 or 2.
  4. 　前記樹脂組成物が、充填材（Ｂ）を含有する、
    　請求項１～３のいずれか一項に記載のドリル孔あけ用エントリーシート。     The resin composition contains a filler (B),
    The entry sheet for drilling according to any one of claims 1 to 3.
  5. 　前記充填材（Ｂ）が、タルク及び／又は二硫化モリブデンである、
    　請求項４に記載のドリル孔あけ用エントリーシート。     The filler (B) is talc and / or molybdenum disulfide.
    The entry sheet for drilling according to claim 4.
  6. 　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、ポリテトラメチレングリコール、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化合物、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化合物、及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種類又は２種類以上である、
    　請求項３～５のいずれか一項に記載のドリル孔あけ用エントリーシート。     The water-soluble resin (A) is polyethylene oxide, polypropylene oxide, polytetramethylene glycol, polyethylene glycol, polypropylene glycol, polyoxyethylene monoether compound, polyoxyethylene monostearate, polyoxyethylene sorbitan monostearate, poly One or more selected from the group consisting of a glycerin monostearate compound and a polyoxyethylene propylene copolymer,
    The entry sheet for drilling according to any one of claims 3 to 5.
  7. 　前記樹脂組成物層が、０．０２～０．３ｍｍの範囲の厚さを有する、
    　請求項１～６のいずれか一項に記載のドリル孔あけ用エントリーシート。     The resin composition layer has a thickness in the range of 0.02 to 0.3 mm;
    The entry sheet for drilling according to any one of claims 1 to 6.
  8. 　前記金属箔が、０．０５～０．５ｍｍの範囲の厚さを有する、
    　請求項１～７のいずれか一項に記載のドリル孔あけ用エントリーシート。     The metal foil has a thickness in the range of 0.05 to 0.5 mm;
    The entry sheet for drilling according to any one of claims 1 to 7.
  9. 　請求項１～８のいずれか一項に記載のドリル孔あけ用エントリーシートを用いて、積層板又は多層板に孔を形成する孔形成工程を有する、
    　ドリル孔あけ加工方法。
          Using the entry sheet for drilling according to any one of claims 1 to 8, comprising a hole forming step of forming a hole in a laminated board or a multilayer board;
    Drilling method.
PCT/JP2019/004295 2018-03-30 2019-02-06 Entry sheet for drilling, and drilling method employing same WO2019187670A1 (en)

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