Classifications

• • 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
• • 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
  • 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
• • 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
• • 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
• • 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
  • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
  • H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
  • H05K2203/0786—Using an aqueous solution, e.g. for cleaning or during drilling of holes
• • 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

Definitions

• the present invention relates to an entry sheet for drilling used for drilling a copper-clad laminate or multilayer board.
• a drilling method for copper-clad laminates and multilayer boards used as printed wiring board materials one or more copper-clad laminates or multilayer boards are stacked, and aluminum foil alone is used as a backing plate on the top.
• a method in which a sheet having a resin composition layer formed on the surface of an aluminum foil (hereinafter, this “sheet” is usually referred to as “drill drilling entry sheet” in this specification) and drilling is generally used. It has been adopted.
• high-quality drilling such as improved hole location accuracy and reduced hole wall roughness has been demanded.
• a drilling method using a sheet made of a water-soluble resin such as polyethylene glycol for example, see Patent Document 1
• a drilling lubricant sheet in which a water-soluble resin layer is formed on a metal foil for example, Patent Document 1
• a punching entry sheet for example, see Patent Document 3
• a water-soluble resin layer is formed on an aluminum foil on which a thermosetting resin thin film is formed
• the object of the present invention is to reduce the hole wall roughness without reducing the hole position accuracy by reducing the thickness of the water-soluble resin composition layer to reduce the resin wrapping around the drill. To provide an entry sheet.
• the present inventors have found that even if the water-soluble resin composition layer is made thinner than the conventional drill hole entry sheet, a specific water-soluble resin, a specific water-soluble resin, It has been found that an entry sheet for drilling, in which a layer of a water-soluble resin composition composed of polyethylene glycol, a specific water-soluble lubricant resin, and a specific water-soluble substance is formed on the surface of a metal foil, solves the above problems. It was. That is, the present invention is as follows.
• the water-soluble resin composition is Contains 30 to 85 parts by weight of water-soluble resin (A) having a number average molecular weight of 80,000 to 400,000 Contains 10-60 parts by weight of polyethylene glycol (B) having a number average molecular weight of 15,000-25,000, Containing 5 to 50 parts by weight of water-soluble lubricant resin (C), For 100 parts by weight of the water-soluble resin mixture (X) comprising the water-soluble resin (A), the polyethylene glycol (B) and the water-soluble lubricant resin (C), polyhydric alcohols, amino acid derivative alcohols, An entry sheet for drilling, comprising 0.1 to 5 parts by weight of one or more water-soluble substances (Y) selected from the group consisting of organic acids and organic acid salts.
• the water-soluble resin (A) is selected from the group consisting of polyethylene oxide, polypropylene oxide, sodium polyacrylate, polyacrylamide, polyvinyl pyrrolidone, carboxymethyl cellulose, polytetramethylene glycol, and polyalkylene glycol polyester 1
• the entry sheet for drilling according to the above [1] which is a seed or two or more kinds.
• the hole wall roughness is further reduced without decreasing the hole position accuracy even if the thickness of the water-soluble resin composition layer is made thinner than before. Resin wrapping around can be reduced. As a result, drilling with high quality and excellent productivity has become possible.
• the present invention provides an entry sheet for drilling comprising a metal foil and a layer of a water-soluble resin composition laminated and integrated on at least one side of the metal foil, wherein the water-soluble resin composition has a number average molecular weight.
• Polyhydric alcohols and amino acid derivatives with respect to 100 parts by weight of the water-soluble resin mixture (X) comprising the water-soluble resin (A), the polyethylene glycol (B) and the water-soluble lubricant resin (C).
• An entry sheet for drilling characterized by containing 0.1 to 5 parts by weight of one or more water-soluble substances (Y) selected from the group consisting of alcohols, organic acids and organic acid salts, less than Although it can manufacture by the method shown, it is not limited to this.
• Y water-soluble substances
• the water-soluble resin mixture (X) includes a water-soluble resin (A) having a number average molecular weight of 80,000 to 400,000, preferably 80,000 to 150,000, and a polyethylene having a number average molecular weight of 15,000 to 25,000.
• the number average molecular weight of the water-soluble resin (A) is less than 80,000, the pore wall roughness is reduced due to a decrease in pore position accuracy due to the water-soluble resin composition layer becoming brittle, and a decrease in melt viscosity of the water-soluble resin composition There is concern about the deterioration.
• the number average molecular weight of the water-soluble resin (A) exceeds 400,000, the amount of the resin wound around the drill increases, and there is a concern that the hole position accuracy may be lowered.
• the number average molecular weight of polyethylene glycol (B) is less than 15,000, the water-soluble resin composition layer becomes brittle.
• the blending amount of the water-soluble resin (A) is less than 30 parts by weight, the pore wall roughness is deteriorated due to a decrease in the melt viscosity of the water-soluble resin composition. There is a concern that the amount of resin wrapping around will increase and the hole position accuracy will deteriorate. Further, when the blending amount of polyethylene glycol (B) is less than 10 parts by weight, the sheet surface becomes soft and the pore position accuracy deteriorates. On the other hand, when it exceeds 60 parts by weight, the melt viscosity of the water-soluble resin composition is reduced. The deterioration of the pore wall roughness occurs due to the decrease.
• the blending amount of the water-soluble lubricant resin (C) is less than 5 parts by weight, the chip dischargeability is deteriorated, the hole wall roughness is deteriorated and the drill breakage occurs. There is a concern that the sheet surface becomes soft and the hole position accuracy deteriorates.
• the water-soluble resin (A) preferably used in the present invention includes polyethylene oxide, polypropylene oxide, sodium polyacrylate, polyacrylamide, polyvinyl pyrrolidone, carboxymethyl cellulose, polytetramethylene glycol, and polyalkylene glycol polyester. 1 type or 2 types or more selected from are preferable.
• the polyester of polyalkylene glycol is a condensate obtained by reacting polyalkylene glycol and dibasic acid.
• polyalkylene glycol examples include glycols exemplified by polyethylene glycol, polypropylene glycol, polytetramethylene glycol and copolymers thereof, and dibasic acids include phthalic acid, isophthalic acid, terephthalic acid, It is preferable to select from sebacic acid, partial esters of polyvalent carboxylic acids such as pyromellitic acid, their acid anhydrides, and the like.
• the water-soluble lubricant resin (C) used in the present invention preferably has a structure represented by the following structural formula (1).
• m represents an integer of 10 to 450, preferably 10 to 200
• n represents an integer of 1 to 5, preferably 1 to 3.
• R2 is hydrogen or an alkyl group having 1 to 3 carbon atoms
• R1 is an alkoxy group, an alkenyloxy group, an aryloxy group, an amino group, an amide group represented by the following formula (2), and the following formula (3) It is group selected from the ester group represented by these.
• R 3 represents hydrogen, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms.
• R1 is more specifically a stearyloxy group corresponding to an ether bond such as an alkyl ether such as stearyl ether or isostearyl ether, an alkenyl ether such as oleyl ether or allyl ether, an aryl ether or a substituted aryl ether, or isostearyl.
• Alkoxy groups such as oxy groups, alkenyloxy groups such as oleyloxy groups and allyloxy groups, aryloxy groups such as phenoxy groups and substituted phenoxy groups; amino groups such as alkylamino; amide groups such as alkylamides; and oleic acid esters It is preferably selected from the group consisting of ester groups such as stearates.
• the water-soluble lubricant resin (C) can be used alone or in combination of two or more.
• the molecular weight of a polymer refers to the average value of polymers having various molecular weights.
• Methods for calculating the average molecular weight include number average molecular weight Mn calculated as an average molecular weight per molecule, weight average molecular weight Mw calculated by weighting the weight, and the like.
• the molecular weight in the present invention is a numerical value measured by GPC.
• the number average molecular weight in the present invention is a value obtained by measuring columns of Shodex SB-G, Shodex SB-803HQ and Shodex SB-806MHQ (manufactured by Showa Denko KK) in series under water-based GPC analysis conditions.
• a differential refractometer (RID-6A, manufactured by Shimadzu Corporation) is used under the conditions that the carrier of the analysis sample is a 50 mM aqueous NaCl solution, the injection volume is 20 ⁇ l, the flow rate is 0.7 ⁇ ml / min, and the oven temperature is 35 ° C.
• a number average molecular weight and a weight average molecular weight of the polymer compound are calculated using a polyethylene glycol kit (manufactured by POLYMERMELABORATORIES LTD.) As a standard substance. Furthermore, each peak component is fractionated based on the obtained GPC data, and component identification is performed using FT-IR (FT / IR-6100 manufactured by JASCO Corporation).
• the water-soluble resin composition used in the entry sheet for drilling according to the present invention has a melt viscosity at 100 ° C. of preferably 50 Pa ⁇ s or more, more preferably 50 to 600 Pa ⁇ s. If the melt viscosity of the water-soluble resin composition is 50 Pa ⁇ s or more, the pore wall roughness is excellent, and if it is 600 Pa ⁇ s or less, resin wrapping around the drill is reduced.
• the method for measuring the melt viscosity of a water-soluble resin composition is a melt viscosity measuring device (CFT-500D: manufactured by SHIMADZU Co., Ltd.) comprising a cylinder with a heater provided with a replaceable capillary at the bottom of the inner hole.
• CFT-500D manufactured by SHIMADZU Co., Ltd.
• a test pressure is applied by air pressure to the molten sample filled in the cylinder.
• a capillary having a diameter of 0.5 mm and a length of 10.0 mm was used.
• the measurement conditions at this time were as follows: melt viscosity was measured under the conditions of a test temperature of 100 ° C. and a test pressure of 980,000 Pa.
• the water-soluble substance (Y) used in the present invention is not particularly limited as long as it is a water-soluble substance selected from the group consisting of polyhydric alcohols, amino acid derivative alcohols, organic acids and organic acid salts. It is also possible to use 1 type or 2 types or more mixed appropriately.
• Preferred examples of the water-soluble substance (Y) include trimethylolpropane, pentaerythritol, neopentylglycol, trimethylolethane, sorbitol, xylitol, inositol and the like as polyhydric alcohols, and amino acid derivative alcohols as tyrosine, Glycosylamine, etc.
• organic acids such as malic acid, malonic acid, succinic acid, fumaric acid, maleic acid, formic acid, acetic acid, propionic acid, stearic acid, etc.
• organic acid salts are the metals of the organic acids listed above. Examples include salts.
• examples of the metal salts include sodium salts.
• the amount of the water-soluble substance (Y) is 0.1 to 5 parts by weight, preferably 0.3 to 4 parts by weight, per 100 parts by weight of the water-soluble resin mixture (X). When the blending amount of the water-soluble substance (Y) is out of the above range, it is not preferable because the hole position accuracy decreases, the resin winding around the drill increases, and the drill breaks during drill drilling.
• a water-soluble resin mixture (X) comprising a water-soluble resin (A), polyethylene glycol (B) and a water-soluble lubricant resin (C) is dissolved in a solvent, and then the solution Or a water-soluble resin mixture (X) comprising a water-soluble resin (A), polyethylene glycol (B) and a water-soluble lubricant resin (C). And the like, and then a water-soluble substance (Y) is further added to make a water-soluble resin composition as a hot melt.
• the metal species of the metal foil used for the drilling entry sheet of the present invention is preferably aluminum, and the thickness of the metal foil is usually 0.05 to 0.5 mm, preferably 0.05 to 0.3 mm. If the thickness of the metal foil is less than 0.05 mm, burrs of the laminated plate are likely to occur during drilling. On the other hand, if the thickness exceeds 0.5 mm, it is difficult to discharge chips generated during drilling.
• the material of the aluminum foil is preferably aluminum with a purity of 95% or more. Specifically, examples include 5052, 3004, 3003, 1N30, 1N99, 1050, 1070, 1085, 8021, etc. defined in JIS-H4160. Is done.
• the metal foil By using high-purity aluminum foil as the metal foil, the impact of the drill bit is reduced and the biting property is improved. Combined with the lubrication effect of the drill bit by the water-soluble resin composition, the hole position accuracy of the processed hole is improved. improves.
• the resin used for the resin film is not particularly limited, and may be either a thermoplastic resin or a thermosetting resin.
• the thermoplastic resin include urethane, vinyl acetate, vinyl chloride, polyester, and copolymers thereof.
• the thermosetting resin include epoxy resins and cyanate resins.
• the metal foil of the present invention a commercially available metal foil previously coated with a resin by a known method may be used.
• a sheet of a water-soluble resin composition is prepared in advance, and a hot-melt laminating method in which the sheet is bonded to the metal foil, or a water-soluble resin composition
• a hot-melt laminating method in which the sheet is bonded to the metal foil, or a water-soluble resin composition
• examples thereof include a coating method in which a hot melt or solution is directly applied to a metal foil and dried.
• the entry sheet produced by the coating method can reduce the thickness of the water-soluble resin composition layer as compared with the sheet produced by the conventional hot-melt laminating method, but the water-soluble resin composition of the present invention can be reduced.
• the hole position accuracy at the time of drilling is not lowered, and the hole wall roughness is further reduced, and the excellent characteristics of having less resin wrapping around the drill are retained.
• the metal foil and the water-soluble resin composition layer it is convenient for the metal foil and the water-soluble resin composition layer to be laminated and integrated that the resin film is previously formed on the metal foil in both the hot-melt laminating method and the coating method.
• the thickness of the water-soluble resin composition layer in the drill punching entry sheet of the present invention varies depending on the drill diameter used when drilling, the configuration of the copper-clad laminate or multilayer board to be processed, etc.
• the range is 0.01 to 0.3 mm, preferably 0.02 to 0.2 mm, and more preferably 0.03 to 0.12 mm. If the thickness of the water-soluble resin composition layer is less than 0.01 mm, a sufficient lubricating effect cannot be obtained, the hole wall roughness is deteriorated, the load on the drill is increased, and drill breakage occurs. On the other hand, when the thickness of the water-soluble resin composition layer exceeds 0.3 mm, the winding of the resin around the drill may increase.
• each layer constituting the drill hole entry sheet is measured as follows. After cutting the entry sheet from the water-soluble resin composition layer surface of the entry sheet with a cross section polisher (CROSS-SECTION POLISHER SM-09010: manufactured by JEOL Datum Co., Ltd.) or ultramicrotome (Leica), SEM (VE -7800 (manufactured by KEYENCE), observe the cross section from the direction perpendicular to the cross section, and measure the thickness of the aluminum layer and the water-soluble resin composition layer with a field of view of 900 times. The thickness of five places is measured for one visual field, and the average is taken as the thickness.
• a cross section polisher CROSS-SECTION POLISHER SM-09010: manufactured by JEOL Datum Co., Ltd.
• ultramicrotome Leica
• SEM VE -7800 (manufactured by KEYENCE)
• observe the cross section from the direction perpendicular to the cross section and measure the thickness of the aluminum layer and the water-
• the entry sheet for drilling according to the present invention is not limited to drilling of copper-clad laminates and multilayer boards, but can be applied to processing of resin formed products, metal casings, solar cells and the like.
• Example 1 60 parts by weight of polyethylene oxide (Alcox L-11, manufactured by Meisei Chemical Co., Ltd.) with a number average molecular weight of 110,000 and 20 parts by weight of polyethylene glycol (PEG 20000, manufactured by Sanyo Chemical Industries, Ltd.) with a number average molecular weight of 20,000 and polyoxyethylene stearyl 20 parts by weight of amine (S-220: manufactured by Aoki Oil & Fat Co., Ltd.) was dissolved in water so that 100 parts by weight of the water-soluble resin mixture had a solid content of 30% by weight.
• polyethylene oxide Alcox L-11, manufactured by Meisei Chemical Co., Ltd.
• PEG 20000 polyethylene glycol
• S-220 manufactured by Aoki Oil & Fat Co., Ltd.
• the aqueous solution of this water-soluble resin composition was dried using a bar coater on an aluminum foil (used aluminum foil: 1N30, (thickness: 0.1 mm) manufactured by Mitsubishi Aluminum Co., Ltd.) with a 0.01 mm thick epoxy resin film formed on one side.
• the subsequent water-soluble resin composition layer was applied so that the thickness was 0.05 mm, and dried at 120 ° C. for 3 minutes with a dryer to obtain an entry sheet for drilling.
• This drilling entry sheet was stacked with three sheets of 0.8 mm thick copper clad laminate (CCL-HL832HS LT, copper foil both sides 12 ⁇ m, manufactured by Mitsubishi Gas Chemical Co., Ltd.) Layers are placed on top, and a backing plate (bake plate) is placed under the stacked copper clad laminate.
• Drill bit 0.25 mm ⁇
• rotation speed 120,000 rpm
• feed rate 2.4 m / min
• 20 drill holes were drilled at 3,000 hits per drill bit, and the hole wall roughness, hole position accuracy, and amount of resin wrapped around the drill bit were evaluated.
• Table 2 were obtained. .
• Example 2 Number average molecular weight 110,000 polyethylene oxide (Alcox L-11, Meisei Chemical Co., Ltd.) 30 parts by weight and number average molecular weight 20,000 polyethylene glycol (PEG 20000, Sanyo Chemical Industries Co., Ltd.) 60 parts by weight and number average molecular weight 1,000 10 parts by weight of polyoxyethylene stearyl ether (Nonion S-220: manufactured by NOF Corporation) was dissolved in water so that 100 parts by weight of the water-soluble resin mixture had a solid content of 30% by weight.
• Nonion S-220 manufactured by NOF Corporation
• Example 3 Polyethylene glycol dimethyl terephthalate polycondensate having a number average molecular weight of 100,000 (Paogen PP-15, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and polyethylene glycol having a number average molecular weight of 20,000 (PEG 20000, manufactured by Sanyo Chemical Industries, Ltd.) 55 wt. And 5 parts by weight of polyoxyethylene stearyl ether (SR-7200: Aoki Yushi Kogyo Co., Ltd.) having a number average molecular weight of 7,000 were dissolved in water so that 100 parts by weight of the water-soluble resin mixture had a solid content of 30% by weight. .
• polyoxyethylene stearyl ether SR-7200: Aoki Yushi Kogyo Co., Ltd.
• polyethylene glycol / dimethyl terephthalate polycondensate having a number average molecular weight of 101,000, 38.5 parts by weight, polyethylene glycol having a number average molecular weight of 21,200, 55.9 parts by weight, number average molecular weight of 6,800 5.6 parts by weight of polyoxyethylene stearyl ether and 1.0 part by weight of sodium formate.
• an entry sheet for drilling was prepared, and drilling workability was evaluated. The evaluation results are shown in Table 2. Good numerical values were obtained for the hole wall roughness, hole position accuracy, and resin winding.
• Example 4 Number average molecular weight 110,000 polyethylene oxide (Alcox L-11, Meisei Chemical Co., Ltd.) 85 parts by weight and number average molecular weight 20,000 polyethylene glycol (PEG 20000, Sanyo Chemical Industries, Ltd.) 10 parts by weight and number average molecular weight 1,000 5 parts by weight of polyoxyethylene stearyl ether (Nonion S-220: manufactured by NOF Corporation) was dissolved in water so that 100 parts by weight of the water-soluble resin mixture had a solid content of 30% by weight. Furthermore, 1.0 part by weight of sodium formate (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added to 100 parts by weight of the solid content of the water-soluble resin mixture and completely dissolved to obtain a water-soluble resin composition.
• sodium formate manufactured by Mitsubishi Gas Chemical Co., Ltd.
• the melt viscosity of this water-soluble resin composition was measured in the same manner as in Example 1, and the results are shown in Table 2.
• polyethylene oxide with a number average molecular weight of 100,000 82.4 parts by weight polyethylene glycol with a number average molecular weight of 18,300 11.3 parts by weight, polyoxyethylene stearyl ether with a number average molecular weight of 1,560 6.4 parts by weight and 1.0 part by weight of sodium formate.
• an entry sheet for drilling was prepared, and drilling workability was evaluated. The evaluation results are shown in Table 2. Good numerical values were obtained for the hole wall roughness, hole position accuracy, and resin winding.
• Example 5 60 parts by weight of polyethylene oxide having a number average molecular weight of 80,000 (Alcox L-8, manufactured by Meisei Chemical Co., Ltd.), 10 parts by weight of polyethylene glycol having a number average molecular weight of 20,000 (PEG 20000, manufactured by Sanyo Chemical Industries, Ltd.) and polyoxyethylene stearyl 30 parts by weight of amine (S-220: manufactured by Aoki Oil & Fat Co., Ltd.) was dissolved in water so that 100 parts by weight of the water-soluble resin mixture had a solid content of 30% by weight.
• Example 6 Polyethylene glycol dimethyl terephthalate polycondensate having a number average molecular weight of 100,000 (Paogen PP-15, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and polyethylene glycol having a number average molecular weight of 20,000 (PEG 20000, manufactured by Sanyo Chemical Industries, Ltd.) 55 wt. And 5 parts by weight of polyoxyethylene monostearate (Nonion S-40: NOF Corporation) with a number average molecular weight of 3,500 are dissolved in water so that 100 parts by weight of the water-soluble resin mixture has a solid content of 30% by weight. It was.
• Example 7 Polyethylene glycol dimethyl terephthalate polycondensate having a number average molecular weight of 100,000 (Paogen PP-15, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and polyethylene glycol having a number average molecular weight of 20,000 (PEG 20000, manufactured by Sanyo Chemical Industries, Ltd.) 55 wt. And 5 parts by weight of polyoxyethylene monostearate (Nonion S-40: NOF Corporation) with a number average molecular weight of 3,500 are dissolved in water so that 100 parts by weight of the water-soluble resin mixture has a solid content of 30% by weight. It was.
• Comparative Example 1 10 parts by weight of polyethylene oxide (Alcox L-11, Meisei Chemical Co., Ltd.) having a number average molecular weight of 110,000, 60 parts by weight of polyethylene glycol (PEG 20000, Sanyo Chemical Industries, Ltd.) having a number average molecular weight of 20,000, and polyoxyethylene stearyl 30 parts by weight of amine (S-220: manufactured by Aoki Oil & Fat Co., Ltd.) was dissolved in water so that 100 parts by weight of the water-soluble resin mixture had a solid content of 30% by weight.
• polyethylene oxide Alcox L-11, Meisei Chemical Co., Ltd.
• PEG 20000 polyethylene glycol
• S-220 manufactured by Aoki Oil & Fat Co., Ltd.
• Example 2 1.0 part by weight of sodium formate (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added to 100 parts by weight of the solid content of the water-soluble resin mixture and completely dissolved to obtain a water-soluble resin composition.
• the melt viscosity of this water-soluble resin composition was measured in the same manner as in Example 1, and the results are shown in Table 2. Further, in the same manner as in Example 1, an entry sheet for drilling was prepared, and drilling workability was evaluated. The evaluation results are shown in Table 2. The result that the hole wall roughness deteriorated was obtained.
• Comparative Example 2 90 parts by weight of polyethylene oxide (Alcox L-11, manufactured by Meisei Chemical Co., Ltd.) having a number average molecular weight of 110,000 and 8 parts by weight of polyethylene glycol (PEG 20000, manufactured by Sanyo Chemical Industries, Ltd.) having a number average molecular weight and polyoxyethylene stearyl 2 parts by weight of amine (S-220: manufactured by Aoki Oil & Fat Co., Ltd.) was dissolved in water so that the solid content of the water-soluble resin mixture was 30% by weight.
• polyethylene oxide Alcox L-11, manufactured by Meisei Chemical Co., Ltd.
• PEG 20000 polyethylene glycol
• S-220 manufactured by Aoki Oil & Fat Co., Ltd.
• Comparative Example 3 40 parts by weight of polyethylene oxide (Alcox L-6, manufactured by Meisei Chemical Co., Ltd.) having a number average molecular weight of 60,000 and 55 parts by weight of polyethylene glycol (PEG 20000, manufactured by Sanyo Chemical Industries, Ltd.) having a number average molecular weight of 20,000 and polyoxyethylene stearyl 5 parts by weight of amine (S-220: manufactured by Aoki Oil & Fat Co., Ltd.) was dissolved in water so that the solid content of the water-soluble resin mixture was 30% by weight.
• polyethylene oxide Alcox L-6, manufactured by Meisei Chemical Co., Ltd.
• PEG 20000 polyethylene glycol
• S-220 manufactured by Aoki Oil & Fat Co., Ltd.
• the melt viscosity of this water-soluble resin composition was measured in the same manner as in Example 1, and the results are shown in Table 2.
• the water-soluble resin composition was analyzed by GPC and IR spectrum measurement, 40.7 parts by weight of a polyethylene glycol dimethyl terephthalate polycondensate having a number average molecular weight of 95,400, 59.3 parts by weight of polyoxyethylene monostearate having a number average molecular weight of 3,600, and Sodium formate was 1.0 part by weight.
• an entry sheet for drilling was prepared, and drilling workability was evaluated. The evaluation results are shown in Table 2. The result that hole wall roughness and hole position accuracy deteriorated was obtained.
• the melt viscosity of this water-soluble resin composition was measured in the same manner as in Example 1, and the results are shown in Table 2.
• the water-soluble resin composition was analyzed by GPC and IR spectrum measurement, 50.4 parts by weight of a polyethylene glycol dimethyl terephthalate polycondensate having a number average molecular weight of 90,800, 49.6 parts by weight of polyoxyethylene monostearate having a number average molecular weight of 3,700, and Sodium formate was 1.0 part by weight.
• an entry sheet for drilling was prepared, and drilling workability was evaluated. The evaluation results are shown in Table 2. The result that the hole wall roughness deteriorated was obtained.
• CFT-500D manufactured by SHIMADZU
• Resin wrapping amount Each of the 20 drill bits after 3,000 hit processing was observed with a microscope with a magnification of 25 times, and the maximum diameter of the resin wrap and the length in the drill axis direction relative to the drill bit diameter were measured, and the volume of the wound resin was obtained. The average value of 20 was calculated.
• Shodex SB-G Number average molecular weight and component identification: Shodex SB-G, Shodex SB-803HQ and Shodex SB-806MHQ (manufactured by Showa Denko KK) were used under the water-based GPC analysis conditions in which columns were arranged in series.
• the analysis sample carrier is 50 mM-NaCl aqueous solution, measured with a differential refractometer (RID-6A, manufactured by Shimadzu Corporation) under the conditions of injection volume 20 ⁇ l, flow rate 0.7 ml / min, oven temperature 35 ° C.

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• Engineering & Computer Science (AREA)
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• Life Sciences & Earth Sciences (AREA)
• Forests & Forestry (AREA)
• Manufacturing & Machinery (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Perforating, Stamping-Out Or Severing By Means Other Than Cutting (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Lubricants (AREA)
• Laminated Bodies (AREA)
• Drilling And Boring (AREA)

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• 2010
  • 2010-05-28 JP JP2010541366A patent/JP4798308B2/ja active Active
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  • 2010-05-28 RU RU2011148789/02A patent/RU2534178C2/ru active
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