TW201010538A - Entry sheet for drilling - Google Patents

Abstract

An entry sheet for drilling a copper-clad laminate, obtained by laminating a water-soluble resin composition (B) containing 100 parts by weight of a water-soluble resin mixture (A) comprising 80 to 98 parts by weight of a polyethylene glycol having a number average molecular weight of 15, 000 to 35, 000and 2 to 20 parts by weight of a polyethylene oxide having a number average molecular weight of 50, 000 to 200, 000 and 0.1 to 5 parts by weight of at least one water-soluble substance selected from the group consisting of polyhydric alcohols, amino acid derivative alcohols, organic acids and organic acid salts, on at least one side of a metal foil having a thickness of 0.05 to 0.5mm and integrating the water-soluble resin composition (B) and the metal foil, which entry sheet is excellent in hole registration accuracy, is almost free from the winding of a resin around a drill and is therefore capable of decreasing the breakage rate of a drill.

Description

201010538 VI. Description of the Invention: [Technical Field to Which the Invention Is Applicable] This is a cover plate for drilling for drilling a copper clad laminate or a multi-layer board. [Prior Art] A method of using a copper-clad laminate or a multi-layer board for drilling in a printed wiring board material is generally performed by forming a simple pig or a surface of one of the aluminum foils before drilling. A sheet obtained by a resin composition layer (this sheet is generally referred to as "a cover for drilling" in the following description) is provided on a copper clad laminate, a multilayer board, or two or more copper clad layers. A method of serving as an auxiliary sheet on the top surface of a stack of plates or multilayer boards. Regarding printed wiring sheet materials, in recent years, in order to improve the reliability and the demand for high density progress, high-quality drill holes such as improved hole alignment accuracy or reduced hole wall roughness are required. In order to achieve the above demand, a hole making method using a material such as a sheet made of a water-soluble resin such as polyethylene glycol (for example, JP-A-4-92494) has been proposed and actually adopted. A hole for lubricating a hole obtained by forming a resin layer on a metal foil (for example, JP_A_5_丨694〇〇) and a hole for forming a hole by forming a thermosetting resin film on an aluminum foil and further forming a water-soluble resin layer Cover plate (for example, Jp-A-2〇〇3-136485). In recent years, the density of the printed wiring board has been increased to a higher density, and the reliability of the copper-clad laminate or the multilayered layer = the processed hole is required. In order to achieve this demand, it is necessary to further improve the accuracy of the hole. In addition, it is also necessary to reduce the bit breakage rate by reducing the entanglement of the resin around the head of the drill 098119360 201010538, and thus improve the productivity. Therefore, there is a need for a cover for drilling which is formed of a water-soluble resin layer and which has the effect of improving the accuracy of the alignment of the holes and the effect of reducing the circumference of the resin around the drill. SUMMARY OF THE INVENTION One object of the present invention is to provide a drilling cover plate whose hole alignment accuracy is superior to that of a conventional drilling cover plate, and almost no resin is wound around the drill bit, and is improved by drilling. The dischargeability of the generated chips reduces the fracture rate of the drill bit. The present inventors conducted various studies to achieve the above object, and as a result, found a hole obtained by forming a water-soluble resin composition containing a specific polyethylene glycol, a specific polyethylene oxide, and a specific water-soluble substance on one surface of a metal foil. The above purpose can be achieved by using a cover plate. The present invention provides a cover plate for drilling a copper clad laminate by laminating a water-soluble resin composition (B) on at least one side of a metal foil, and the water-soluble resin composition is B) obtained by integrating with a metal foil, wherein the water-soluble resin composition (B) contains a water-soluble resin mixture (A) and at least one water-soluble substance, and the water-soluble resin mixture (A) contains 8 to 98 parts. a polyethylene glycol having an average molecular weight of 15,000 to 35,000 and 2 to 20 parts by weight of polyoxyethylene-ethylene having a number average molecular weight of 50 to 2, and the water solubility The substance is selected from the group consisting of polyhydric alcohols, amino acid-derived alcohols, organic acids and organic acid salts, and is contained in an amount of from 〇j to 5 parts by weight based on 1 (9) parts by weight of the water-soluble resin mixture (A). 098119360 201010538 The polydispersity (Mw/Mn) of the polyethylene oxide contained in the water-soluble resin mixture (A) of the present invention is preferably 2.5 or less. The water-soluble resin mixture (A) of the present invention preferably further comprises a water-soluble lubricant resin in an amount of from 1 to 80 parts by weight based on 1% by weight of the total of polyethylene glycol and polyethylene oxide, and the water-soluble lubricant resin The lubricant resin preferably has a number average molecular weight of 15 or less and a melt viscosity of 10 Pa.s or less at i〇〇°c. Further, in the drilling cover plate provided by the present invention, the thickness of the metal town is preferably 0.05 to 0.5 mm, and the layer thickness of the water-soluble resin composition (B) formed on at least one side of the metal foil is preferably The system is from 2 to 〇3 mm. (Effect of the Invention) The use of the drilling cover plate provided by the present invention can reduce the entanglement of the resin around the drill bit' and can also improve the dischargeability of the chips generated by the drilling, so that the hole alignment during drilling can be improved. Accuracy and reduced bit breakage. Therefore, drilling with excellent quality and productivity can be achieved. [Embodiment] The present invention relates to a at least _ water-soluble substance of the metal foil, which is a viscous resin composition (b). A drilling cover plate comprising a metal foil and a layer formed on the side of the layer containing the water-soluble resin mixture (A) and the molecular weight of the general Q refers to a method for calculating the average knife value of the various molecular weights of the polymer Typically, the number average molecular weight Μη (which is (4) is calculated as the average molecular weight per molecule) or the weight average molecular weight MW (which is calculated by weighting by weight 4). Using the value measured by GPC as 098119360 201010538 is the molecular weight in the present invention. Regarding the method for measuring the number average molecular weight in the present invention, the measurement is carried out under the conditions of water GPC analysis. In the measurement, the columns of sh〇dexSB_G, ShodexSB-803HQ, and Sh〇dexSB_8〇6MHQ (supplied by Sh〇wa Denk〇 κ κ) were connected in series. The measurement system was measured by using a differential refractometer (RID-6A, supplied by Shimadzu Corporation) via a 5 mM NaOH aqueous solution of NaC1 as a carrier for the analysis sample at a flow rate of 20 μl, a flow rate of 0.25 ml/min, and an oven temperature of 35 φ C. The number average molecular weight and weight average molecular weight of the polymer compound were calculated by using a polyethylene glycol kit (supplied by p〇LYMEr LABORATORIES Ltd.) as a standard substance. The polydispersity Mw/Mn is obtained by dividing the weight average molecular weight Mw of the polymer compound having a molecular weight distribution by the number average molecular weight ηη of the polymer compound having a molecular weight distribution. As the value of polydispersity increases, the molecular weight distribution broadens. As the value of the multi-dispersibility decreases, the molecular weight distribution becomes narrow. Φ using a polyethylene glycol having a number average molecular weight of from 15,000 to 35,000, preferably from 18,000 to 25,000, and a mixture of polyethylene oxide having a number average molecular weight of from 50,000 to 200,000, preferably from 60,000 to 150,000, as a drill hole provided by the present invention A water-soluble resin mixture (Α) with a cover plate. With respect to the amount of the mixture added, the amount of the polyethylene glycol is from 80 to 98 parts by weight and the amount of the polyethylene oxide is from 2 to 20 parts by weight. When the number average molecular weight of the polyethylene glycol is out of the above range, the water-soluble resin composition layer (Β) disadvantageously becomes brittle, so that the hole alignment accuracy is reduced and the amount of resin wrapped around the drill bit is 098119360 7 201010538 Increased anxiety. When the number average molecular weight of the polyethylene oxide is out of the above range, there is a disadvantage that the amount of the resin wound around the iron head is increased to break or the hole alignment accuracy is lowered. When the amount of polyethylene glycol is less than 80 parts by weight, the resin may be disadvantageously wound around the drill bit, which may cause side effects such as reduced hole alignment accuracy and bit breakage. When it is larger than the scratch weight I, the water-soluble resin composition layer (8) becomes brittle, so that the sheet cannot be formed and there is a fear that the hole alignment accuracy is lowered. ..., in this fortune, the polyoxyethylene sigmoid multi-touch is preferably or more preferably 2.0 to τ. #料化乙叙多分朗&=Increased in the amount of drilling, which causes side effects such as system reduction and bit breakage. Indeed = in this correction (four) hanging no special _, free multi-alcohol, amino acid derived U ~ water-soluble substances can be. A group consisting of at least two kinds of water-soluble substances, and three kinds of water-soluble substances, and three kinds of materials are used as needed. Preferred examples of the water-soluble substance 'multi- _ include erjia Shi- _ Yin main T violent propane neodymidine, neopentyl, triterpene, sorbitol, xylitol Preferred examples include _acid and glycosylamine; organic acid ==, malonic acid, succinic acid, cis-butanic acid, propionic acid, and hard riding; and preferred examples of organic _ include the above organic Acid metal salt. In terms of 10 (), the amount of the water-soluble substance is 〇!: The gluten resin mixture (8) The amount of the mass is from 0.1 to 5 parts by weight, preferably from 0.3 to 4 parts, 098,119,360, 201010,538 by weight. When the amount of the water-soluble substance is out of the above range, there is a disadvantage that the amount of the resin wound around the drill bit during drilling is increased, the hole alignment accuracy is lowered, or the bit breakage occurs. In the present invention, by further adding a water-soluble lubricant resin to the water-soluble resin mixture (A) which is a mixture of -ethylene glycol and ethylene oxide, the hole alignment accuracy during drilling can be improved, and the improvement can be improved. The smear of the chips produced by the drilling and the reduction of the bit breakage rate. • A water-soluble lubricant resin having a number average molecular weight of 15,000 or less is preferably used as the water-soluble lubricant resin used in the drilling cover plate provided by the present invention. Further, the water-soluble lubricant resin preferably has a structure in which a substituent is provided at one terminal of the polyoxyalkylene group. Preferably, a group selected from the group consisting of an ether group, an amine group, a guanamine group, and an ester group or at least two groups is used as a substituent. The _ group is preferably a hard fat test, an oil base, an isostearyl group, a phenyl ether or the like. The amine group is preferably a first alkylamine, a second alkylamine or a # analog thereof. The guanamine group is preferably a alkylguanamine or an analog thereof. The ester group is preferably a fatty acid ester, a fatty acid diester or the like. Further, the water-soluble lubricant resin preferably has a melt viscosity at 100 Torr of 10 Pa.s or less. When the melt viscosity of the water-soluble lubricant resin exceeds 10 pa.s, the amount of the resin wound around the drill bit increases, so that there is a concern that the hole alignment accuracy is deteriorated and the bit breakage occurs. The amount of the water-soluble lubricant resin is from 1 to 80 parts by weight based on 100 parts by weight of the total of polyethylene glycol and polyethylene oxide. 098119360 9 201010538 It is preferred to add a compound such as a sorbitan fatty acid ester or an oleate as a lubricant. The test apparatus for measuring the melt viscosity of the water-soluble lubricant resin includes a unit of a cylinder, which has a heater for mounting a replaceable capillary inside the same bottom. The air is used to fill the molten sample filled in the cylinder = plus test pressure. The diameter of the capillary is Q5 mm and its length is (7) 〇 mm Μ under the measurement conditions, the test temperature is t and the test pressure is 980000 pa 〇

The metal species of the metal ruthenium used in the drilling cover plate provided by the present invention is preferably in the name. The thickness of the gold (four) is generally G.G5 to 〇·5 mm, preferably 〇·05 to 〇.3 mm. When the thickness of the aluminum foil is less than 0.05 mm, the burrs of the laminate are easily generated when the hole is drilled. When it exceeds Q 5 mm, it is difficult to discharge the chips generated during the drilling of the material of (4), and aluminum having at least purity is preferable. Specific examples thereof include 5〇52, 3〇〇4, 3〇〇3, in3〇, ❹ 、, 删, Gu, 秘, and 简, which are each defined in the muscle leg. The use of high purity (4) as a metal crucible can reduce the impact of the drill cone and improve the bite of the iron cone (4). The silky hybrid tree test on 纟(4) (8) The lubrication effect of the drill cone, the hole of the machined hole is good. In the case of adhesion to the water-soluble resin composition (B), it is preferred that the pot has a thickness of 0 on the side of the thickness to the reading of mm. Examples of the adhesive used for the adhesive film include an amine group (IV) adhesive, a vinyl acetate adhesive, a vinyl chloride adhesive, a poly-coating agent, and a total of 098119360 10 201010538 polymer adhesives and rings of these compounds. Oxygen adhesive and cyanate adhesive. The method of forming the water-soluble resin composition (B) layer on at least one side of the metal foil, for example, directly using the hot-melt material or solution of the water-soluble resin composition (B) by a coating process or the like a method of applying to a side of a metal foil to a lesser side, followed by drying; and a method of bonding a sheet of the previously prepared water-soluble resin composition (B) to a metal foil. In such a case, when the adhesive film is previously formed on the metal foil, the layer of the metal foil and the water-soluble resin composition (B) can be easily laminated and integrated. The layer thickness of the water-soluble resin composition (B) in the drilling cover plate provided by the present invention depends on the diameter of the drill cone used for drilling or the structure of the copper-clad laminate or multilayer plate to be drilled. The layer thickness of the isoindene water-soluble resin composition (B) is generally in the range of 0.02 to 0.3 mm, preferably in the range of 〇〇2 to 〇.2 mm. When the layer thickness of the water-soluble resin composition is less than 〇 2 mm, sufficient lubricating effect cannot be obtained, so that the load applied to the drill bit is increased and the bit breakage occurs. When it exceeds 〇3 mm, in some cases, the amount of winding of the cover resin around the drill cone increases. The method for measuring the layer thickness of the water-soluble resin composition (B), using horizontal

A cross-section polishing machine (CORSS_SECTION POLISHER SM-09010; supplied by JEOL DATUM LTD.) cuts the cover from the side of the resin composition layer of the cover, and then observes it in a direction perpendicular to the cross section by SEM (VE-7800; supplied by KEYENCE). Cross section. The measurement was performed at 9 (8) magnification in the field of view. Five points of thickness were measured for each field of view. The average value is regarded as the layer thickness 098119360 11 201010538 degrees. When drilling a printed wiring board material such as a copper clad laminate or a multi-layer board, the drilling cover plate provided by the present invention is provided on a copper clad laminate, a multi-layer board or a plurality of copper-clad laminate or multi-layer board The stack is on at least one of the page surfaces such that the metal foil side of the cover is in contact with the printed wiring board material. Drilling is performed from the side of the water-soluble resin composition (B) of the cover plate for drilling. [Examples] The present invention will be specifically described with reference to the following examples and comparative examples. In the examples and comparative examples in this specification, "polyethylene glycol" and "polyethylene oxide" may be referred to as "PEG" and "PEO", respectively. (Example 1) 98 parts by weight of a number average molecular weight of 2 Å, ruthenium polyethylene glycol (PEG 20000, supplied by Sanyo Chemical Industries, Ltd.), and 2 parts by weight of a polydispersity Mw/Mn and A polyemulsified acetamidine (ALKOX L-6, supplied by Meisei Chemical Works, Ltd.) having a number average molecular weight Μ of 60,000 was dissolved in water so that the solid of 100 parts by weight or more of the water-soluble resin mixture became 30 parts by weight. Further, 1.0 part by weight (based on 1% by weight of the solid of the water-soluble resin mixture) of sodium decanoate was added and completely dissolved to obtain an aqueous solution of the water-soluble resin composition. The aqueous solution of the water-soluble resin composition was applied to a storage box (1N30 'Mitssubishi Aluminum Co., Ltd.) having a thickness of 亳1 利用 by a strip coater so that the layer of the water-soluble resin composition after drying had 〇· 〇 3 mm thickness. The coated aqueous solution was applied at 12 Torr using a dryer 098119360 12 201010538. (: Dry for 3 minutes, and get the cover for drilling. Place the drill cover plate on four copper-clad laminates with a thickness of 2 mm each (CCL-HL832, 12 micrometers on both sides of the copper box, _ Chemical Company, lnc. supplied) the top of the stack so that the water-soluble resin composition layer of the cover plate is side-up. The backing plate (electric wood) is placed on the lower side of the stack of copper-clad laminates. Drilling is performed under the condition of a diameter of 15 mm, a rotation frequency of 200,00 rpm and a feed rate of 20 μm/rev. Each drill has a strike number of 3,000 and is drilled with 20 drill cones. Drilling. The δ flattening of the hole alignment accuracy and the amount of the tree enthalpy around the drill cone is shown. The results are shown in Table 1. In addition, the drill fracture evaluation is performed as follows: The drilling cover is set at four thicknesses. 01 mm copper clad laminate (CCL-HL832HS, copper foil on both sides 4 micron, Mitsubishi Gas

The top of the stack of the Chemical Company, Inc. was supplied so that the water-soluble resin composition layer of the cover plate was turned sideways. A backing plate (electric wood) is placed on the underside of the stack of copper clad laminates. Drilling is performed under the conditions of a diameter of 8 mm, a rotation frequency of 300,000 ipm, and a feed rate of 8 μm/rev. The number of shots of the female drill cone is 3, 〇〇〇, and drilling is performed using 2 boring drill cones. Table 1 also shows the results of bit fracture development. Good values are obtained for hole alignment accuracy, resin winding, and bit breakage. (Example 2) 98 parts by weight of a number average molecular weight of 35, ruthenium polyethylene glycol (available from Clariant (Japan) K.K.) and 2 parts by weight of polydispersity 098119360 13 201010538

Mw/Mn and a polyoxyethylene (available from ALKOX L-6 ' Meisei Chemical Works, Ltd.) having a number average molecular weight of Mn of 60,000 were dissolved in water so that the solid of 100 parts by weight or more of the water-soluble resin mixture became 30 parts by weight. Further, L0 part by weight (based on the solid of the water-soluble resin mixture) of sodium formate was added and completely dissolved to obtain an aqueous solution of the water-soluble resin composition. An aqueous solution of the water-soluble resin composition was applied to an aluminum foil having a thickness of 0.1 mm by a bar coater (1Ν3〇, Mitsubishi Aluminum c〇.

Ltd, supplied), so that the layer of the water-soluble resin composition after drying has a thickness of 〇(7) mm. The coated aqueous solution was passed through a drying machine at 12 Torr. Dry it for 3 minutes, and use a cover plate for drilling. Drilling was performed in the same manner as in Example 。. Evaluate the accuracy of the hole alignment, the amount of resin wrapped around the drill cone, and the fracture of the drill bit. The table shows the results. Good values were obtained for hole alignment accuracy, resin winding, and bit breakage. (Example 3) 90 parts by weight of a number average molecular weight of 2 〇, 〇〇〇 polyethylene glycol (PEG 20000, Sanyo Chemical 娜 叫 ω supply) and parts by weight with a dispersion of 1.5 ^ 8 〇 The number of polyethylene oxides (ALK〇x L_8, (3) coffee (four) w_, supplied) having a number average molecular weight Μη was dissolved in water, so that the solid of the water-soluble resin mixture above the weight was 30 parts by weight. Further, 1 part by weight (based on the water-soluble resin composition) of the nail was added, and it was completely dissolved, and water-soluble and water-soluble liquid was obtained. The (10) coater applies an aqueous solution of water-soluble resin composition 098119360 201010538 to a material of thickness α1 mm (in3〇, Mitsubishi (10). supply), so that the layer of the water-soluble (tetra) lipid composition has O.G3. The thickness of millimeters. The dried machine was coated with water and dried at 120 C for 3 minutes to obtain a cover for drilling. The hole drilling is performed in the same manner as in the embodiment to evaluate the accuracy of the hole alignment, the amount of resin around the drill cone, and the fracture of the bit. The table shows the result. Good values are obtained for hole back accuracy, resin winding, and bit breakage. ❹ (Example 4) 90 parts by weight of a number average molecular weight of 2 〇, face of polyethylene glycol Sanyo Chemical Industries, Ud supply) and 1 part by weight of 1.5 polydispersity _ and 11 〇〇〇〇 The number average molecular weight Μη of polyethylene oxide (仏(10), 伽^,

The product supplied by Ltd. is dissolved in water so that i (9) parts by weight or more of the solid of the water-soluble resin mixture becomes 30 parts by weight. Further, 1 part by weight (in the form of a water-soluble sapphire compound) M_ was added and (4) was completely rotated to obtain an aqueous solution of a water-soluble resin composition. The water-repellent liquid of the water-soluble resin composition is applied to a thickness of 〇J亳 by a bar coater (available from the wrist, SUbishi Aluminum CG., Ltd.), so that the water-soluble resin composition after drying is The layer has a thickness of G.G3 mm. The coated aqueous solution was dried at 12 ° C for 3 minutes to obtain a cover for drilling. In the same manner as in the embodiment i, the borehole was added: L. Evaluate the accuracy of the hole alignment, the amount of resin wrapped around the drill cone, and the fracture of the drill bit. The table shows the results. Off 098119360 201010538 Good values for hole alignment accuracy, tree splicing and bit breakage. (Example 5) 95 parts by weight of a polyethylene glycol having a number average molecular weight of 2 Å (available from PEG 2 〇 'Sany〇 Chemical Industries, Ltd.) and 5 parts by weight of a polydispersity Mw/ of 1.5 Polyethylene oxide (ALKOXL_ll, supplied by Meisei Chemical Works, Ltd.) having a number average molecular weight Mn of Mn and 11 Å was dissolved in water so that the solid of the water-soluble resin mixture of 1 part by weight or more or more became 30 parts by weight. Further, 1 part by weight (based on the solid of the water-soluble resin mixture) of pentaerythritol was added and completely dissolved to obtain an aqueous solution of the water-soluble resin composition. Applying an aqueous solution of the water-soluble resin composition to a millimeter-thick aluminum foil (1N3(), using a strip coater,

The Mitsubishi Aluminum Co, Ltd. supply) is such that the layer of the water-soluble resin composition after drying has a thickness of 0.03 mm. The coated aqueous solution was dried at 120 ° C for 3 minutes using a drying machine to obtain a cover for drilling. Drilling was carried out in the same manner as in Example 1. Evaluate the accuracy of the hole alignment, the amount of resin wrapped around the drill cone, and the fracture of the drill bit. Table i shows the results. Good values were obtained regarding hole alignment accuracy, resin winding, and bit breakage. (Example 6) 90 parts by weight of a polyethylene glycol having a number average molecular weight of 20,000 (available from PEG 20000 'Sanyo Chemical Industries, Ltd.) and an average of 1.5 parts by weight of a polydispersity Mw/Mn of 1.5 and an average of 150,000 Molecular 098119360 16 201010538 A quantity of polyethylene oxide (ALK〇X L-15 's supplied by Meisei Chemical Works, Ltd.) was dissolved in water so that i (10) parts by weight or more of the solid of the water-soluble resin mixture became 3 parts by weight. Further, an amount of i g of the weight (in terms of the water-soluble tree hull of the body) was added to the new fine alcohol, and the aqueous solution was obtained. The water-soluble resin and the water/glutle solution of the product are applied to an aluminum foil (1 Ν 3 〇, Mitsubishi Aluminum Co" Ud) having a thickness of 5,000 mm by a strip coater, so that the water-soluble enamel resin composition after drying is used. The layer has a thickness of 〇.〇3 mm. The coated water is dried at 12 (TC) for 3 minutes using a drying machine to obtain a secret cover plate. Drilling is performed in the same manner as in Example 1. Alignment accuracy, amount of resin wrapped around the drill cone, and evaluation of bit fracture. Table shows the results. Good values were obtained for hole alignment accuracy, resin winding, and bit break. (Example 7) Number of 95 parts by weight An average molecular weight of 2 Å, ruthenium polyethylene glycol (available from PEG 20000 'Sanyo Chemical Industries, Ltd.), 5 parts by weight of polydisperse having a polydispersity Mw/Mn of 1.5 and a number average molecular weight Μη of 80,000 (ALKOX L-8, supplied by Meisei Chemical Works, Ltd.) and 2 parts by weight (based on loo by weight of a mixture of polyethylene glycol and polyethylene oxide-containing water-soluble resin) of polyoxyethylene ethyl stearyl ether (s_22〇: supplied by NOF Corporation) was dissolved in water so that the solid hydrazine of the water-soluble resin mixture became 30 parts by weight. Further, 1.0 part by weight of sodium formate based on the solid of the water-soluble 098119360 17 201010538 resin mixture was added and allowed to be It is completely dissolved to obtain an aqueous solution of a water-soluble resin composition. The aqueous solution of the water-repellent resin composition is applied to (4) (1N3G, supplied by Mitsubishi Aluminum Co., Ltd.) having a thickness of G·1 mm so that after drying The layer of the water-soluble resin composition has a thickness of (10) 3 mil. The drying machine dries the coated aqueous solution at 120 C for 3 minutes to obtain a cover plate for drilling. Drilling is performed in the same manner as in Example 1. The evaluation of the accuracy of the hole alignment, the amount of resin wound around the drill cone, and the fracture of the drill bit were performed. The results are shown in the table. Good values were obtained regarding the hole alignment accuracy, resin winding, and bit breakage. (Example 8) 95 The weight average number of molecular weights is 2 〇, 〇〇〇 polyethylene glycol (PEG20000 'Sanyo Chemical Industries, Ltd. supplied), 5 parts by weight a disperse Mw/Mn of 80 and a number of polyoxyethylene (ALKOX L-8, supplied by Meisei Chemical Works, Ltd.) having a number average molecular weight of 80η, and 10 parts by weight (containing 100 parts by weight of polyethylene glycol and The polyoxyethylene ethyl stearyl complex (S-220: supplied by NOF Corporation) of the water-soluble resin mixture of polyethylene oxide was dissolved in water so that the solid amount of the water-soluble resin mixture became 30 parts by weight. Further, 1.0 part by weight of sodium decanoate (based on the solid of the water-soluble resin mixture) was added and completely dissolved to obtain an aqueous solution of the water-soluble resin composition. An aqueous solution of a water-soluble resin composition was applied to an aluminum foil (1N30, supplied by Mitsubishi Aluminum Co., Ltd.) having a thickness of 0.1 mm by a bar coater so that water-soluble 098119360 18 201010538 after drying * the layer of the resin composition has 0 · Thickness of 03 mm. The coated aqueous solution was dried at 12 Torr for 3 minutes using a drying machine to obtain a cover for drilling. Drilling was performed in the same manner as in Example 1. Evaluate the accuracy of the hole alignment, the amount of resin wrapped around the drill cone, and the fracture of the drill bit. Table 1 shows no results. Good values were obtained regarding hole alignment accuracy, resin winding, and bit breakage. (Example 9) • 95 parts by weight of polyethylene glycol (average PEG 20000, supplied by Sanyo Chemical Industries, Ltd.) having an average molecular weight of 20,000, 5 parts by weight of polydispersity Mw/Mn of 1.5 and 80, 〇〇 Polyethylene oxide (Alk〇X L-8, supplied by Meisei Chemical W〇rks, Ltd.) having an average molecular weight of Μη and 80 parts by weight (100 parts by weight of a water-soluble resin containing polyethylene glycol and polyethylene oxide) The polyoxyethylene ethyl stearyl ether (S-220: supplied by NOF Corporation) of the mixture was dissolved in water so that the solid amount of the water-soluble tree-lipid mixture became 30 parts by weight. Further, 1 part by weight (based on the solid of the water-soluble resin mixture) of sodium formate was added and completely dissolved to obtain an aqueous solution of the water-soluble resin composition. An aqueous solution of the water-soluble resin composition was applied to a thickness of glutinous rice (iN3〇, supplied by -Mitsubishi Aluminum Co. Ltd.) using a bar coater so that the layer of the water-soluble resin composition after drying had 0.03 mm. The thickness of the coated aqueous solution was dried by using a drying machine at 12 (TC for 3 minutes to obtain a drill cover. The drilling process was performed in the same manner as in Example 1. The alignment was performed with respect to the hole alignment 098119360 19 201010538, The amount of resin wrapped around the drill cone and the evaluation of the bit fracture. Table 1 shows the results. Good values were obtained for hole alignment accuracy, resin winding and bit breakage. (Comparative Example 1) 98 parts by weight of the average molecular weight of 10,000 Polyethylene glycol (PEG 10000, supplied by Sanyo Chemical Industries, Ltd.) and 2 parts by weight of polyoxyethylene having a polydispersity Mw/Mn of 1.5 and a number average molecular weight of 60,000 (ALKOX L-6, Meisei Chemical Works, Ltd. supplies) dissolved in water such that 100 parts by weight or more of the solid of the water-soluble resin mixture becomes 30 parts by weight. In addition, 1 part by weight is added (by water) The solid solution of the soluble resin mixture is sodium citrate and completely dissolved to obtain an aqueous solution of the water-soluble resin composition. The aqueous solution of the water-soluble resin composition is applied to the thickness by a bar coater (U 亳 之 ( ( 1 (four), hall (four) also

Aluminum Co., Ltd. is supplied so that the layer of the water-soluble resin composition after drying has a thickness of G.G3 mm. The coated aqueous solution was dried at 12 G C for 3 minutes using a drying machine to obtain a hole for the iron hole to be drilled in the same manner as in the example. The accuracy of the hole alignment was wrapped around the drill cone. Evaluation of the amount of resin and the fracture of the drill bit. Table! The results are shown. The sufficient sheet strength is not obtained, the hole alignment accuracy is deteriorated, and the number of broken drill bits is increased. (Comparative Example 2) The number of 98 wound weights is 40,000. KAoki 098119360 201010538

Oil IndUstrial Co., Ltd. supplies) and 2 parts of weight! a polydispersity Mw/Mn of 5 and a number average molecular weight of polyethylene oxide (available from ALKOX L-6 ' Meisei Chemical Works, Ltd.) dissolved in water' such that 100 parts by weight or more of the water-soluble resin mixture The solid becomes *30 injury weight. Further, i.0 parts by weight of formic acid steel (based on the solid of the water-soluble resin mixture) was added and completely dissolved to obtain an aqueous solution of a water-soluble resin composition. An aqueous solution of a water-soluble resin composition is applied to a millimeter-thick foil (1N30, Mitsubishi Aluminum C., using a bar coater).

Ltd. supplies) so that the layer of the water-soluble resin composition after drying has a thickness of 〇〇3 mm. The coated aqueous solution was passed through a drying machine at 12 Torr. Dry it for 3 minutes, and use a cover plate for drilling. Drilling was performed in the same manner as in Example 。. Evaluate the accuracy of the hole alignment, the resin 1 wrapped around the drill cone, and the fracture of the drill bit. The table shows the results. When sufficient sheet strength was not obtained, it was observed that the hole alignment accuracy was deteriorated and the number of broken drill bits was increased. (Comparative Example 3) 90 parts by weight of a number average molecular weight of 2 〇, 〇〇〇 polyethylene glycol (PEG 2 〇〇〇〇, supplied by Sanyo Chemical Industries, Ltd.) and a portion of the weight of the dispersion of 1.5 The Mw/Mn and the 48,000 number average molecular weight Μη of polyethylene oxide (supplied by Meisei Chemical Works, Ltd.) were dissolved in water so that 100 parts of the solid of the above water-soluble resin mixture was reset to 3 parts by weight. Further, an aqueous solution of a water-soluble resin composition of 098119360 21 201010538 was obtained by adding 1% by weight of sodium formate (based on the solid of the water-soluble resin mixture) and completely dissolving it. An aqueous solution of a water-soluble resin composition was applied to a foil having a finish of 0.1 mm using a bar coater (1N30, Mitsubishi Aluminum Co,

Ltd. supplies, so that the layer of the water-soluble resin composition after drying has a thickness of 0.03 mm. The coated aqueous solution was dried at 12 (rc) for 3 minutes using a drying machine to obtain a drilling cover plate. Drilling was performed in the same manner as in Example 。. The accuracy of the hole alignment was wrapped around the drill cone. The amount of resin and the evaluation of the fracture of the drill bit. The results are shown. The amount of resin winding is increased, so that the deterioration of the alignment accuracy of the hole is observed and the number of broken iron heads is increased. (Comparative Example 4) The number average molecular weight of 90 parts by weight is 2 Polyethylene glycol (PEG20000 'Sany〇Chemical Ιη__, ω supply) and 忉 part of the weight of 1.5 polydisperse Mw / Mn and 3 〇〇〇〇〇 number average molecular weight of the application of polyethylene oxide (R_1〇〇〇, ❽师(五)版^, supplied) dissolved in water so that 100 parts by weight or more of the solid of the water-soluble resin mixture becomes 30 parts by weight. In addition, 1 part by weight (by water-soluble resin mixture) The solids of the solids) are completely dissolved, and the water-soluble resin composition is obtained. The scraper coater applies an aqueous solution of the water-repellent resin composition to a thickness of Μm (4) ( ‘Mitsubishi

Ahnninumc^, Ud•supply)] such that the layer of the water-soluble resin composition after drying has a thickness of 〇·〇3 mm. The coated aqueous solution was dried at 12 Gt for 3 minutes using a drying machine to obtain a drill cover. It is processed in the same manner as in the embodiment i. Perform an assessment of the accuracy of the hole alignment, winding 098119360 22 201010538 The amount of resin around the drill cone and the fracture of the drill bit. Table 1 shows the results. The amount of resin winding is increased, so that the accuracy of the alignment accuracy of the holes is observed and the number of broken drill bits is increased. (Comparative Example 5) 75 parts by weight of a polyethylene glycol having a number average molecular weight of 20,000 (available from PEG 20000 'Sanyo Chemical Industries, Ltd.) and 25 parts by weight of a polydispersity Mw/Mn of 1.5 and 11 Å, 〇〇 The number average molecular weight Mn of polyethylene oxide (ALKOX L-ll, supplied by Meisei Chemical Works, Ltd.) was dissolved in water so that the solid of the above water-soluble resin mixture of loo parts by weight was 30 parts by weight. Further, 1 part by weight (based on the solid of the water-soluble resin mixture) of sodium formate was added and completely dissolved to obtain an aqueous solution of the water-soluble resin composition. The aqueous solution of the water-soluble resin composition is applied to a thickness of 0 gt; 1 亳 of aluminum bismuth (1N3 〇, using a strip coater), and the layer of the water-soluble resin composition of the squid .G3 mm thickness. The coated aqueous solution was dried by a drying machine at 120 Torr for 3 minutes to obtain a drilling cover plate. Drilling was performed in the same manner as in Example i, and X was precisely aligned. Degree, the amount of resin wrapped around the drill cone, and the evaluation of (4). The results are shown in the table. The amount of the entanglement of the tree is increased, so that the accuracy of the alignment accuracy of the holes is observed and the number of broken drill bits is increased. (Comparative Example 6) Polyethylene glycol (PEG20000, Sanyo will have a number average molecular weight of 20,000 098119360 23 201010538

Chemical Industries, Ltd. supplies) dissolved in water, so that IQ. The solid weight of the polyethylene glycol was 30 parts by weight. Further, 1 part by weight (based on the solids of the water-soluble resin) of sodium ruthenate was added and completely dissolved to obtain an aqueous solution of the water-soluble resin composition. The aqueous solution of the water-soluble resin composition was applied to a thickness of 〇.丨mm of aluminum pig (1N3〇, supplied by Mitsubishi Aluminum Co., Ltd.) by a strip coater so that the layer of the water-soluble resin composition after drying had 0.03 The thickness of millimeters. The coated aqueous solution was dried at 120 ° C for 3 minutes using a drying machine to obtain a cover plate for drilling. Drilling was performed in the same manner as in Example i. Evaluate the accuracy of the hole alignment, the amount of resin wrapped around the drill cone, and the fracture of the drill bit. The table shows the results. Sufficient sheet strength was not obtained, so that the accuracy of the hole alignment accuracy was observed and the number of broken drill bits was increased. (Comparative Example 7) 95 parts by weight of a number average molecular weight of 2 Å, ruthenium polyethylene glycol (PEG 20000, supplied by Sanyo Chemical Industries, Ltd.) and 5 parts by weight of a polydispersity Mw/Mn of 1.5 and 11〇, a polyoxyethylene (ALKOXL-1 Bu Meisei Chemical Works, Ltd.) having a number average molecular weight of Mn is dissolved in water so that the solid content of the water-soluble resin mixture is 30 parts by weight or more. weight. The aqueous solution of the water-soluble resin composition thus obtained was applied to an aluminum foil (1N30, supplied by Mitsubishi Aluminum Co., Ltd.) having a thickness of 0.1 mm by a bar coater so that the layer of the water-soluble resin composition after drying had a ruthenium. 〇 3 mm thickness. The coated aqueous solution was dried at 12 (TC for 3 minutes using a dryer 098119360 24 201010538 to obtain a cover for the iron hole. The drilling process was performed in the same manner as in Example 1. The accuracy of the hole alignment and the winding were performed. Evaluation of the amount of resin around the drill cone and the fracture of the drill bit. Table 1 shows the results. The amount of resin winding is increased, so that the accuracy of the hole alignment is observed and the number of broken drill bits is increased. (Comparative Example 8) 95 parts by weight The number average molecular weight of 2 〇, 聚 polyethylene glycol • (PEG20000 'Sany〇 Chemical Industries, Ltd. supplied) and 5 parts by weight with a polydispersity of 1.5 Mw / Mn and 11 〇〇〇〇 Polyethylene oxide with an average molecular weight of Μη (ALK0XL_U, MeiseiQiemicai w〇rks,

The product supplied by Ltd. was dissolved in water so that the solid of the water-soluble resin mixture of 1 part by weight became 30 parts by weight. Further, 75 parts by weight of a new fine alcohol (based on the above water-soluble resin mixture) was added and completely dissolved to obtain a water-soluble (tetra) water. _ Applying the water-soluble resin _ composition of the aqueous solution to the thick 纟 01 4 m 雀吕箱 (10) 〇, Mitsubishi AlUmimim C. "Supplied by Ltd.", so that the layer of the water-soluble resin composition after drying has a thickness of 〇·03 mm. The coated water + liquid S12GC is dried by a drying machine for 3 minutes to obtain a cover for iron holes. Drilling and cultivating in the same manner as in the case of the actual example 1. The evaluation of the amount of resin and the fracture of the bit around the drill cone with respect to the hole alignment was performed. Table 1 shows, ''mouth, due to excessive addition of water-soluble substance Since the maximum value of the hole alignment accuracy becomes large, the hole alignment accuracy is deteriorated. In addition, the number of fracture drills = 098119360 25 201010538 is increased. (Comparative Example 9) 90 parts by weight of the average molecular weight of 20,000 polyethylene Alcohol (PEG 20000, supplied by Sanyo Chemical Industries, Ltd.) and 10 parts by weight of polyoxyethylene bake with a polydispersity Mw/Mn of 4.5 and a number average molecular weight of 150,000 (ALTOP R-400, Meisei Chemical Works,

Ltd. supplies) dissolved in water, so that more than 1 part by weight of water-soluble resin mixed

The solid of the compound became 30 parts by weight. Further, 1 part by weight (based on the solid of the water-soluble resin mixture) of pentaerythritol was added and completely dissolved to obtain an aqueous solution of the water core I·shengshuyue composition. Applying an aqueous solution of a water-soluble resin composition to a thickness by a bar coater (U € m (4)

Mitsubishi Aluminum c〇, to supply), so that the water-soluble tree sap after drying, the layer of the product has a thickness of 〇 3 亳. The coated aqueous solution was applied to a crucible using a drying machine.匚 妒 A ^ Bu 蚝 蚝 3 minutes, and the hole is used for the cover. Take

The boring process was carried out in the same manner as in Example 1. An evaluation was made regarding the alignment of the holes in the greenness, the amount of resin wound around the circumference of the drill cone, and the breakage of the drill bit. Table 1 shows no,,, and results. The amount of resin winding is deteriorated and the number of broken drill bits = '. 072119360 26 201010538 with hole alignment accuracy [Table 1] Example 1 Real k Example 2 Example 3 Example 4 Example 5 Hole alignment accuracy average value +3σ Average 13.1 μηη 13.4 μιη Ι3.5 μιη 13.4μιη 14.2μηι Average of the maximum value 16μπι Ι6μιη 17μιη 17μιη 17μιη Resin winding amount 20 heads average (mm3) 0 0 0 0 0 Number of broken drill bits Number of broken drill bits in 20 drill bits 0 0 0 0 0 [Table 1] (Continued) Example 6 Example 'An Example 8 Example 9 Average value of hole alignment accuracy +3 (average average of 14.1 μm 13.2 μm 13.5 μιη 13.4 μιη max. average 17 μιη Ι4 μπι 16 μιη 16 μιη Resin winding amount of 20 heads average (mm3) 0 0 0 0 Number of broken drill bits Number of broken drill bits in 20 drill bits 0 0 0 0 [Table 1] (continued) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Hole alignment accuracy average The average value of +3σ is 17.3μηη 16.7μιη 16.8μιη Ιό.όμιη 15.8μιη The average of the maximum 25 um 20μιη 23μιη 22μηι 19μιη 20 resin winding amount Average of drill bits (mm3) 0 0.02 0 0.06 0.04 Number of broken drill bits Number of broken drill bits in 20 drill bits 5 2 4 4 1 098119360 27 201010538 [Table 1] (continued) Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Hole Alignment Accuracy Average +3 (Τ14.7μιηηηηηηηη1 919.9μιη 16.3μπι Maximum Average 18μπι 19μιη 29μιη 19μιη Resin Winding Amount of 20 Drills Average (mm3) 0 0.02 0 0.04 Number of Broken Bits 20 Bits Number of medium-breaking drill bits 5 2 4 1 <Evaluation method> 1) Resin winding amount: Each of 20 drill cones after 3,000-hole drilling was observed at a magnification of 25 times using a microscope to be based on the diameter of the drill cone and The axial length of the drill bit of the resin is measured by the maximum diameter of the resin wound around the drill cone. The volume of the resin wound around the drill cone is obtained. The average value of the wound resin volume of 20 drill bits is calculated. 2) Hole alignment accuracy: utilization A hole analyzer (available from Hitachi Via Mechanics, Ltd.) measures the position of the hole formed by 3,000 shots for each drill cone and the copper-clad laminate at the bottom of the stacked copper-clad laminate. The displacement of the target coordinates on the back side. Calculate the mean and standard deviation (σ). Therefore, "average + 3σ" and "maximum value" are calculated. Table 1 shows the average values of "average + 3σ" and "maximum value" in 20 drilling processes. 3) Number of broken drill bits: Holes were made using 20 drill bits. Calculate the number of broken drill bits in 20 drill bits. 098119360 28

Claims (1)

201010538 VII. Patent Application Range··1. A cover plate for drilling a copper-clad laminate, which is laminated on at least the side of the metal case by water-soluble resin composition (8), and dissolves the water The resin composition (8) is obtained by integration with the metal falling, wherein the water-soluble tree f & group money (8) contains 1 GG parts by weight of the water-soluble resin mixture (A) and at least 0.1 to 5 parts by weight - a free polyhydric alcohol, an amino acid-derived alcohol, an organic acid, and a water-soluble substance having a group of the salt (4), and the water-soluble resin mixture (8) of the lake weight t contains 80 to 98 parts by weight of 15,_ to 35,000 parts of the average molecular weight of polyethylene glycol and 2 to parts by weight of polyethylene oxide having a number average molecular weight of 50,000 to 2 G_G. 2. The cover sheet of the patent application, wherein the core resin mixture (A) further comprises a water-soluble lubricant resin, and is! The water-soluble lubricant resin is used in an amount of from 1 to 80 parts by weight based on the total of the polyethylene glycol and the polyethylene oxide of (8) parts by weight. 3. The cover sheet of claim 1 or 2, wherein the polyoxyethylene has a polydispersity of 2.5 or less (Mw/Mn). 4. The cover sheet of claim 2, wherein the water-soluble lubricant resin has a number average molecular weight of 15 〇〇 or less and a melt viscosity of 100 c c δ or less at 100 ° C. 5. The cover sheet of claim 1 wherein the thickness of the metal pig is 〇_〇5 to 0.5 mm and the water-soluble resin composition (B) formed on at least one side of the metal foil The layer thickness is from 〇〇2 to 〇3 mm. 098119360 29 201010538 IV. Designation of representative drawings: (1) The representative representative of the case is: None (2) The symbol of the symbol of the representative figure is simple: No. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: no 098119360 3