TW201208793A - Drill hole entry sheet - Google Patents

Abstract

Provided is a drill hole entry sheet that: is formed on at least one side of a metal support foil from a crystalline, water-soluble resin compound as a layer 0.02-0.3 mm thick; has excellent hole position accuracy; is formed from a resin that does not cling to the drill bit; and protects the drill bit from damage. The crystal particles of the water-soluble resin compound have an average diameter of 5-70 μm and a standard deviation of 25 μm or less. The drill entry surface of the layer formed from the water-soluble resin compound has a surface roughness (Sm) of 8 μm or less. After a hot melt of the water soluble resin compound is directly applied to the metallic support foil or after a solution that contains the water soluble resin compound is applied to the metallic support foil and dried, the aforementioned layer is formed by being cooled from 120-160 DEG C to 25-40 DEG C within 60 seconds at a cooling speed of 1.5 DEG C/s or greater.

Description

201208793 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a drilling cover plate for use in drilling and affixing a steel laminated board and a multilayer board. [Prior Art] As a method of drilling a laminate of a laminated board and a multi-layer board used as a material of a printed wiring board, it is generally used to arrange a copper-clad laminate or a multi-layer board, or to overlap a plurality of sheets, and to cut the metal material. A sheet in which a resin composition layer is formed on a metal support surface (hereinafter, in the present specification, the sheet is generally referred to as a "wei cover" as a plate that is placed against the uppermost portion, and is subjected to the hole processing. In recent years, the requirements for copper-clad laminates and multi-layer boards belonging to printed wiring board materials are high-density 'productivity improvement and cost reduction, and high-quality holes for increasing hole position accuracy are required. In order to cope with this requirement, for example, Patent Document 1 proposes an opening and squeezing method using a sheet made of a water-soluble resin such as polyethylene glycol. x, which is proposed in the special 2, in the metal foil A slip sheet for opening a water-soluble resin layer is formed thereon. Even in Patent Document 3, a cover for opening a water-soluble resin layer is formed on a film having a thermosetting resin film. Compared with the development of high-density technology for semiconductors, the development of high-density technology for printed wiring boards is slow, and there is a gap. Therefore, the requirements for high density of printed wiring board materials are further increased. This is 100121203 3 201208793. It is necessary to further improve the accuracy of the hole position, and it is expected to develop the drilling cover with better hole position accuracy. In addition, it is considered to be caused by globalization. The fierce competition and the demand of emerging countries have more intense requirements for productivity improvement and cost reduction. Therefore, in order to further improve the hole position accuracy, the number of overlapping openings can be increased, and the hope is increased. Japanese Patent Laid-Open Publication No. Hei No. Hei-4-92494 (Patent Document 2) Japanese Patent Laid-Open Publication No. Hei No. Hei-5-9694 No. [Patent Document 3] Japan Patent Publication No. 2〇〇3_136485 [Draft of the Invention] (Problems to be Solved by the Invention) Copper-clad laminates and layers belonging to printed wiring board materials As described above, in order to increase the density, productivity, and cost, the details are as follows: The hole processing property is required to improve the hole position accuracy. The first problem is the high density of the riding wire plate. The system can directly indicate the change of the minimum hole diameter. For mass production, it has evolved to a diameter of 33mm, 〇.25mm 〇.2 ugly, and can be drilled to a degree of 〇15mm, 〇.i05mm. The minimum hole diameter is 〇.08, o.075mm, 0 06mm 0.05mm is very small (four), the use of laser opening. The reason is because (1) hard metal (four) made of small diameter drilled and folded, so In the prior art, the drilling of the shovel towel was made by the 容 四 四 四 四 四 四 四 四 四 四 四 四 四 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 What could not be solved. The second problem is that the bit that adheres to the resin, which is attached to the center of gravity when it is rotated by its axis, causes the core to vibrate, which detracts from the positional accuracy of the hole. The drill with a very small diameter is a small amount of resin _ that is easy to bow the core vibration. Further, in the case where the resin drop position is the same as the drill position, the drill bit may hit the dropped resin, and the damage to the core property may cause the hole position accuracy to deteriorate or the drill bit to be broken. Therefore, for the outline of the extremely small path, Caijin-step reduces the need for the resin attached to the drill bit. For the drill with a very small diameter, the spiral groove of the cutting object is too fine, so the resin tends to adhere to the drill bit. Above, this is a problem that was not solved by prior art. Further, the above-mentioned core-finding property refers to the forward direction of the cutting direction at the time of cutting. The third problem is that the drill bit slides while contacting the resin composition layer of the cover, and the front end blade is cut into the resin composition layer. Here, the slip is detrimental to the centering property, and since it is used to achieve a high density of the pinch bit, it is important to reduce the amount of slip to improve the hole position accuracy. However, the drill having a very small diameter is also slid by the slight difference in the surface state of the resin composition layer, and when the amount of sliding is too large, the drill may be broken. Regarding the reduction of the amount of sliding and the accuracy of the position of the lifting hole, it has not been solved by the prior art. The fourth problem is irrelevant to the diameter of the drill bit, and there is a market demand for productivity improvement and cost reduction. The background is to consider the intense competition caused by globalization, 100121203 5 201208793 plus the need for emerging countries, and the need to reduce the size of inventory. In addition, the increase in the number of holes by the high density, the long processing time of the opening, and the competition with the laser opening technology are the driving forces for promoting productivity improvement and cost reduction. For example, because of globalization, problems that can be cheaply produced in countries with different cost structures can cause serious competition, and it is a very cheap cost to consider the needs of emerging countries where income levels are very low. That is to say, the market demand for productivity improvement and cost reduction is not strong compared with the previous ones. It is necessary to further improve the hole position accuracy and increase the number of overlaps of the laminated sheets and the multilayer boards of the secondary openings. , : To obtain productivity improvement, _ hole material preparation investment amount, cost reduction. ^ The more stringent cost and the number of overlapping pieces are not solved by the technology. In addition, the addition of the number of overlapping sheets means that the positions of the uppermost and lowermost holes of the multi-layered plate are accurately and well maintained, and the copper laminate and the multilayer board are attached in the range allowed by the length of the drilling insert. In order to solve the above problems, the object of the present invention is to provide a drilling cover plate which is superior to the prior art, which is capable of preventing the drill bit from being folded, and the hole position is excellent in accuracy, and the resin is difficult to adhere to the drill hole. The cover of the present invention (the means for solving the problem) The inventors of the present invention have made it important to solve the above problems (4) to continue the inspection of the material into the surface: it is the knot of the water-soluble silk-age-time average _=; 6 201208793 ^, the surface roughness of the drill entry surface of the tree raft (the average interval of the unevenness). Then, by specifying the cooling conditions at the time of manufacture, the crystallinity of the water-soluble resin composition can be controlled. As a result, it was found that dense crystals having a small crystal grain size and a small standard deviation were mostly formed, and the surface roughness was coarse.

Sm is also small. As a result, the drill bit can be improved and the drill can be made with a high positional accuracy, a resin which can be attached to the drill bit, and a drill having a very small diameter which can reduce the breakage of the drill bit. The present invention has been completed based on the above knowledge, and the gist thereof is as follows. (1) A cover plate for drilling is formed on at least one side of a metal branch, and a layer having a thickness of 0.02 0.3 mm composed of a crystalline water-soluble resin composition is formed, which is characterized by the above-mentioned water solubility. The average grain size of the crystal grain of the resin composition is in the range of 5 to 7 and the standard deviation is as follows: the layer having the water-soluble resin composition of ± is formed on the surface of the drill entering surface, and the roughness Sm is 8 μm or less. The layer composed of the water-soluble resin composition is applied to the metal branching box, and after directly applying the hot melt of the water-soluble tree sorghum composition, or containing the water-soluble resin composition After the solution is applied and dried, it is cooled to 25 at a temperature of from 12 Torr to 16 Torr in a cooling rate of / sec or more. It is formed by the temperature of 〇~4〇1. (7) The cover sheet for drilling according to the above aspect, wherein the water-soluble resin composition has a crystal grain size average particle diameter of 5 to 4 Å/im, and a standard deviation of 17 μm or less. The layer composed of the above water-soluble resin composition has a surface roughness Sm of 7 Juni or less on the surface of the head of the drill 100121203 201208793. (3) The water-repellent resin composition according to (1), wherein the water-soluble resin composition contains a water-soluble resin (A), and further contains a hydrophobic substance (B1), and a melting point higher than the water-soluble one The substance (B2) of the resin and at least one selected from the substance (B3) which improves the compatibility with the water-soluble resin (A). (4) The drilling cover according to (1), wherein the solution containing the water-soluble resin composition further contains water and a solvent having a boiling point lower than that of water. (5) The cover plate for drilling according to (1), wherein the thickness of the metal-removing foil is in the range of 0.05 to 0.5 mm. (6) The drilling cover plate according to (1), which is used for processing a copper laminated board. (Effect of the Invention) The hole for the drilling of the present invention is such that the crystal grains of the water-soluble resin composition layer are small, and the dense crystals having a small standard deviation are mostly formed, and the surface roughness Sm is also small, so that the drill bit can be improved. The core is excellent in positional accuracy, and the resin adhered to the drill can be reduced. As a result, the breakage of the drill during the drilling process can be greatly reduced. Thereby, it is possible to perform the drilling process with excellent productivity with high quality. [Embodiment] The cover plate for drilling according to the present invention is formed on at least one surface of a metal support plate to form a layer composed of a water-soluble resin composition having crystallinity (hereinafter referred to as 100121203 201208793 "Water-soluble tree slit" The cover for the "layer"). Next, regarding the drilling material of the present invention, the particle having the specific content (4) in the composition of the water-resin resin ==:: drilling the average particle diameter of the crystal grain having the special _ (tetra) la product for drilling processing In terms of the accuracy of the position of the lifting hole, it is necessary to use a range of 5 to qing (7), preferably a range of 5 to 5 〇, more preferably a range, and even more preferably a range of 5 to 30 qing. The range of 5~2〇清, and the best is the range of 5ΙΟμιη. When the average particle diameter of the crystal grains is less than $, it can be found that the surface of the above water-soluble resin composition becomes too uniform, and the blade of the front end of the drill bit slides, which will grasp the surface of the cover plate. The decrease in properties is detrimental to the core property, and as a result, the crystal grains become small, and the effect of improving the hole position accuracy cannot be obtained. On the other hand, in the case of more than 7 〇/mi, it can be found from the experiment that the entry of the drill bit toward the surface of the cover plate affects the unevenness of the crystal grain and detracts from the core-seeking property. As a result, the hole position accuracy is obtained. Debating doubts. Here, FIG. 2A is a view schematically showing a state in which the drilling cover plate of the prior art is used for the drilling process, and FIG. 3 is a view schematically showing the use of the drilling cover plate of the present invention for the hole drilling process. The map of the state. In the case of using the water-soluble resin composition layer 2 of the present invention, as shown in Fig. 3, it is possible to form crystal grains constituting the water-soluble resin composition layer 2 in accordance with the size of the drill tip end 1 by S. 100121203 9 201208793. Since the average particle diameter of 2a to 2g is optimized, the grasping property of the drill tip 1 and the water-soluble resin composition layer 2 is good, and the hole position accuracy can be improved. On the other hand, in the case of using the resin composition layer 20 of the prior art, as shown in Fig. 2, the crystal grains 2a to 2 constituting the resin composition layer 20 are compared with the size of the front end of the drill. Since 〇c becomes large, there is a concern that the tip end 1 of the drill causes sliding on the surface of each of the crystal grains 2〇a to 2〇c, and the phase is inferior to the core, and the hole position accuracy is deteriorated. Here, the particle diameter of the crystal grain of the so-called water-soluble resin composition of the present invention (hereinafter, referred to as "crystal grain size") means that it is present in the water-soluble resin when viewed from the upper side of the cover plate. Among the crystal grains on the surface of the composition layer, it is the largest diameter. Further, 'the method of measuring the average value of the crystal grain size of the above-mentioned water-soluble resin composition' is a resin composition for a drilling cover plate using a V-LASER microscope (model number νκ·9700, KEYENCE CORPORATION) with a field of view of 200 times. The surface of the layer was observed, and the maximum diameter of each of the arbitrarily selected crystal grains was measured by the same microscope, and the average value (number average) was taken as the average particle diameter of the water-soluble resin composition. Further, in the present invention, the crystal grain size is less than 1 μm and is removed and calculated. Further, in order to improve the hole position accuracy during the drilling process, in addition to optimizing the particle size of the crystal particles of the water-soluble resin composition, there is also a standard of the average particle size of the crystal grains of 100121203 10 201208793 The deviation of 25/lm or less is less than 20/mi, more preferably 17 μm or less, still more preferably 15 #m or less, particularly preferably l〇^m or less, and most preferably 5 μm or less. The reason for limiting the above-mentioned deviation is because the critical point is found in the experiment, and even if the average particle diameter of the crystal grain is small and the standard deviation exceeds 25 μm, the large-diameter particles are dispersed, The bump is too large, and there is a doubt that the accuracy of the hole position is deteriorated. The method for calculating the standard deviation of the average particle diameter of the crystal grains of the above water-soluble resin composition is a resin composition layer for a drilling cover plate using a V_LASER microscope (model νκ_97〇〇, KEYENCE CORPORATION) with a field of view of 200 times. The surface was observed, and the average diameter of each of the 5 结晶 crystal grains of any selection was measured by the same microscope, and the average value was calculated. The standard deviation of each of the largest diameters of the measured 5 crystal grains can be further calculated. Further, the surface roughness of the entry point of the layer-based drill comprising the water-soluble resin composition (in more detail, the average interval of the irregularities defined by JIS-B0601-1994) Sm must be 8 μm or less, preferably It is 7 μm or less, more preferably 6 μm or less, still more preferably 5 μηι or less, and most preferably 4 gm or less. Because the critical point was found in the experiment, in the case of more than 8 qing, the entry of the drill bit toward the surface of the cover plate will affect the surface irregularities and detract from the core property, so that there is a concern that the accuracy of the hole position is deteriorated. The acquisition of the surface roughness Sm of the above water-soluble resin composition layer 100121203 , , 201208793

The V-LASER microscope (model VK-9700, KEYENCE CORPORATION) was used to observe the surface of the resin composition layer with a field of view of 200 times, to remove noise, and to perform tilt correction (face tilt correction and automatic correction of height range). The surface roughness of the 500 Mm evaluation length in any direction in the observed image was measured (JIS-B0601: Line roughness of 1994). The same measurement can be performed in the same observation image, and measured 5 times, and the average value thereof is set to the above Sm. The water-soluble resin composition layer used in the drilling cover sheet of the present invention is obtained by directly coating a hot melt of a water-soluble resin composition on the metal supporting foil, or cooling the layer The solution containing the water-soluble resin composition described above is applied by a coating method or the like, and dried and cooled. The water-soluble resin composition used in the drilling cover sheet of the present invention contains a composition of a water-soluble resin (A) and has crystallinity. Specifically, a mixture of a water-soluble resin (A) and another substance or the like can be exemplified. Other substances herein include various inorganic compounds, organic compounds, mixtures, complexes, complexes, low molecular weights, monomers, polymerizers, ruthenium molecules, polymers, natural resins, fibers, minerals. Hydrophobic substance f, hydrophilic substance, and the like. The type of the water-soluble resin (4) is not particularly limited as long as it is a water-soluble resin having crystallinity, and is preferably a water-soluble resin having high crystallinity, for example, polyepoxide, sodium polyacrylate, or polyacrylamide. One of the groups consisting of 竣methylcellulose, polytetramethylene glycol, and polycondensation diol (4) is preferably selected from the group consisting of 100121203 12 201208793 or more. As an example of the above polyepoxide, polyethylene oxide, polypropylene oxide or the like is preferred. Further, it is more preferable that poly-oxygen ethane which does not cause steric hindrance in the molecular structure. The polyester of the polyalkylene glycol refers to a condensate obtained by reacting a polyalkylene glycol with a monobasic acid. As the polyalkylene glycol, preferred are polyethylene glycol, polypropylene glycol, polytetramethylene glycol or glycols exemplified in the form of such copolymers. Further, as the dibasic acid, those selected from the group consisting of phthalic acid, isophthalic acid, p-dibenzoic acid, sebacic acid, and pyrogallic acid, such as a partial ester or an acid anhydride, are preferred. Further, it is more preferable to use polyethylene glycol which does not cause steric hindrance in the molecular structure as a condensate of the main chain. Further, the water-soluble resin composition of the present invention is such that the water-soluble resin (a) and the hydrophobic substance (B1) have a higher melting point than the water-soluble resin (A) (B2) and the water-soluble resin can be improved ( A) A composition comprising at least one of a substance (B3) compatible with a solvent is preferred. The hydrophobic substance (B1) is formulated into the above water-soluble resin composition, and the force B (B1) is dispersed in the water-soluble resin composition, and the water-soluble resin composition is cooled to be cured. In the p-sac, the hydrophobic substance (B1) acts as a nucleus formed by crystals due to hydrophobicity, and the crystal particles of the water-soluble resin composition are small and precipitated a lot. By formulating the substance (B2) having a higher melting point than the water-soluble resin (A) to the water-soluble resin composition, the water-soluble resin composition can be cooled to a curing speed of 100121203 _ 201208793 when the lamp is cured. Make a difference. That is, the substance having a high melting point (4) acts as a core for crystal formation by solidifying the material t at an earlier time point. The crystal grains of the water-soluble resin composition may be made small and precipitated in a large amount. In the substance (B2) having a higher melting point than the water-soluble resin (A), the effect of lowering the surface roughness Sm of the water-soluble resin composition layer is higher than that of the above-mentioned water-soluble resin composition layer. substance. By blending the substance (B3) which is compatible with the above-mentioned water-soluble resin (A) and the solvent into the upper water-soluble resin group yarn, the water-soluble one of the molecular structures of (8)) Since the resin (A) is uniformly dispersed in the solvent, when the water-cooling resin composition is cured by drying and cooling, the crucible particles are small and are mostly produced. Further, in the substance (B3) which improves the compatibility of the water-soluble resin (A) and the solvent, not only the crystal grains are reduced, but also the surface roughness of the water-soluble resin composition layer is lowered by 3 claws. A substance with a high effect. Further, the hydrophobic substance (B1), the substance (B2) having a higher melting point than the water-soluble resin (A), and the substance (B3) capable of improving the compatibility of the water-soluble resin (A) with the solvent may be composed of a single substance. The composition may also be composed of a mixture of two or more substances. Further, the hydrophobic substance (B1), the substance (B2) having a higher melting point than the water-soluble resin (A), and the substance (B3) which can improve the compatibility of the water-soluble resin (A) and the solvent can be used in combination. Further, the hydrophobic substance (B1), the substance (B2) having a higher melting point than the water-soluble resin (A), and the substance (b3) capable of improving the compatibility of the water-soluble resin (A) with the solvent are relative to 100121203, 201208793 It is difficult to read the water in the second day (A_ parts by weight, in total, it is necessary to mix 5 parts by weight, preferably 0. Γ parts by weight ~ 3 weight = preferably 0.2 parts by weight to 3 parts by weight) In the case of less than 2 parts by weight, it is difficult to develop a dense crystalline raw material. On the other hand, if it exceeds 5 parts by weight, it is economically not B? B: It is reasonable to select a substance which exhibits an effect in a small amount (B1, a second place) with respect to the above-mentioned hydrophobic substance (four), as long as it is hydrophobic, then: properties, determination. For example, hydrophobic polymerization may be employed. Examples of the compound, the long-chain alcohol, the sulfonium, the cerium, and the inorganic scaly. Specific examples thereof include a carboxylic acid such as a carboxylic acid, a system, an acrylic acid, or the like, and (i) an imine. , Polyimine, Polyvinyl Chloride-Ethyl Acetate Ethylamine, Powder_^, Polyacetic Acid Ethyl, Poly, Polymethyl Resin, B Ethylene cellulose derivative, polyethyl condensate scale, phenoxy alcohol copolymer resin, polytetrafluoroethylene powder and contact; can be cited as thermosetting polymerized cup, phenol resin, urea -... , eucalyptus acrylic resin, double item propylene polyethylene glycol dimethyl phenol resin, cyanate axis, :: 醯: amine resin, dicis butyl hydrazine with imine three listed as long-chain Bensamine Powders and fine particles of resin; etc.; can be a - known of lauryl alcohol, whale algaol, stearin, argon, galenol, etc.; 歹帏 ... * thiol alcohol, oil-based zinc molybdate, Graphite, the second diabase as an inorganic compound, a disulfide key, a __-, a gasified carbon, a nitrided material; the system can be used in the 2012-20793 to use the above-mentioned species or a suitable mixture of the above-mentioned hydrophobic effects of the invention Sexual substance °x' ° high zinc, graphite, _ is preferred. Dicentric stearyl alcohol 'acid acid, .^ 』 "The mouth has the advantage of high dispersibility relative to the water-soluble (four) composition solution The result is that the above melting point is higher than that of the water-soluble resin (A), and the melting point is still above the above tree. (A), then 〃 Shoot 5 h Temple is limited to. For example, you can use amino acids, organic acids, organic acids _ tons of pain ... to organic salts, organic phosphorus salts, polysaccharides, rosins and Inorganic compounds, etc., and Iϋ# 八体和吕, may be listed as amino acids, such as Chuan Amino acid, etc.; can be listed as strict + + as an organic acid malic acid, propylene dihydrazine, No. Alkenedioic acid, cis-butane diacid, cyanuric acid, etc. : Column: There are aromatic acid salts, malonic acid, amber, anti-butadiene dioxime, maleic acid, a metal salt of an organic acid such as formic acid, acetic acid, propionic acid, stearic acid or trimeric acid; and examples thereof include melamine cyanurate as an organic salt; and Kexian as an organic Wei salt sodium phosphate Salt, etc., may be mentioned as cellulose, chitin, starch, glycogen, yoghurt, and fruit as polysaccharides; slick oil, slick oil, etc. There are gasification sodium, sodium sulphate, sulfur _ and the like as inorganic compounds. Further, as a substance (Β2) having a higher melting point than the water-soluble resin (Β2), which is an effect of the present invention, sodium branamide, succinic acid, sodium citrate, calcium formate, sodium stearate, and stearic acid are used. Calcium acid, cellulose, etc. are preferred. The above-mentioned substance (Β3) which can improve the compatibility of the water-soluble resin (Α) with the solvent, for example, may be a polyol having a molecular structure such as a polyol having a hydroxyl group, 100121203 16 201208793, a sugar alcohol, an amino acid derivative. Alcohol, etc. The polyhydric alcohol is a polymer obtained by removing polyethylene glycol or the like which is contained in the water-soluble refractory (4), and (4) is a poly-Si-series other than poly-methane, and may be exemplified by trimethyl ketone, pentaerythritol, neodecanediol, and the like. Examples of the mercaptoacetone and the like include sorbitol, wood, alcohol, and cyclohexanol as sugar alcohols; and anilide, oxyaniline, and ketone which are alcohols of amino acid derivatives; Amine acid, amino deoxy sugar, and the like. Further, as the substance (B3) which enhances the solubility of the water-soluble tree and which improves the effect of the present invention, pentaerythritol, sorbitol, xylitol, cyclohexanol or the like is preferable. The thickness of the water-soluble tree test layer is different depending on the composition of the blue-layered slab layer to be reinforced by the lion age used in the drilling process, and is 〇〇2 to 〇3 mm. The range is preferably in the range of 〇.〇2 to 0.2 mm. When the thickness of the water-soluble resin composition layer is less than 〇.〇2_, a sufficient lubricating effect cannot be obtained, and the burden on the drill bit becomes large, and there is a fear that the drilling loss occurs. On the other hand, when the thickness of the water-soluble resin is more than Q 3 mm, the resin adheres to the drill. Further, in the case where a solution containing the above water-soluble resin composition is directly applied to a metal support tank by a coating method or the like, the solution used has a read boiling point lower than water (preferably A solution of a solvent having a low temperature of 15 (above) is preferable. A crane having a solvent lower than that of water is not particularly limited, and examples thereof include ethanol, methanol, and isopropyl alcohol such as alcohols.

S 100121203 17 201208793 A low boiling point solvent such as methyl ethyl ketone or acetone is used. When the solvent having a boiling point lower than water is contained, the particle diameter of the crystal grain is reduced and the surface roughness Sm is lowered, and the hole position accuracy is improved. Depending on the solvent, each has its own advantages. Ethanol contributes to the reduction of the particle size of the crucible, while methyl ethyl ketone contributes to the reduction of the surface roughness Sm. The efficiency of the ethanol hole position is improved. As the low boiling point solvent, ethanol and acetone are preferred. Generally, the amount of the low-boiling solvent is increased in that the particle size of the crystal grain is reduced, the surface roughness Sm is lowered, and the standard deviation of the crystal grain is reduced. However, while the amount of low-boiling solvent is continuously increased, the effect of improving the hole position accuracy is gradually saturated. Further, the low-boiling solvent is less than 15 at a difference from the boiling point of water. 〇 When it is difficult, it will be difficult to show the effect. The mixing ratio of the above water and the solvent having a boiling point lower than water is necessary in the range of 90/10 to 50/50, preferably in the range of 8 〇 / 2 〇 to 5 〇 / 5 Torr, and the best is Range of 70/30 to 50/50. When the mixing ratio of the solvent having a boiling point lower than water is less than 10, it may be difficult to exhibit a dense crystal formation effect. When the blending ratio of the solvent having a boiling point lower than water exceeds 5 ,, the economic aspect is unreasonable, and there is a concern that there is a hindrance in the stability of Ji industrial production. In the case where the hot melt of the above water-soluble resin composition is directly applied to a method of metal support bonding and cooling, the method for producing the cover is not particularly limited. The method of kneading the above water-soluble resin composition can be carried out by a kneading method of generally 100121203 201208793. For example, a twin-shaft roll, a mixer, a double-winch kneader, a plunger press, or the like is preferably used. Further, when the water-soluble resin composition is kneaded, it is preferred to carry out the kneading in a nitrogen atmosphere in order to suppress decomposition of the water-soluble resin composition. Further, in order to uniformly disperse the above water-soluble resin composition, it is preferred to knead the water-soluble resin composition at a temperature of from 120 C to 160 Torr. When the kneading temperature is less than 120 ,, the water-soluble resin composition becomes uneven, and there is a possibility that the appearance and the hole position accuracy are adversely affected, and it is more than 16 〇. When it is ruined, it causes decomposition of the water-soluble resin composition, and there is a possibility that the characteristics such as the hole position accuracy are adversely affected. Further, the method of directly applying the water-soluble resin composition to the metal-supported foil is not particularly limited. A coating device of ruthenium may be used, and for example, a knife coater, an extrusion coater, a die coater, a curtain coater or the like is preferably used. In the case where the thickness of the water-soluble resin composition layer is uneven (four), since there is a possibility that the hole position accuracy or the like is adversely affected, the above coating machine is used to thermally melt the water-soluble resin composition. Uniform coating is preferred. It is to be understood that the coating method of the above-mentioned cover sheet is not particularly limited by the above-mentioned coating method or the like, in which the above-mentioned water-soluble resin composition containing liquid is directly applied to the metal support (4), and the method of cooling is performed. A general coating device can be used. For example, 'as a coating means for making the thickness of the water-soluble resin composition layer into a uniform sentence, a gravure coater, a roll coater, a knife coater, and an extrusion coating using a general coating means are used. Machine, mold coating machine, 100121203 201208793 curtain coating is better. In the case where the thickness of the water-soluble resin group is not uniform, there is a possibility that the characteristics such as the hole position accuracy are adversely affected. Therefore, it is preferred to use the above method to make the solution of the water-soluble resin composition uniform. Coating. Further, after the solution of the water-hybrid assay is directly applied to the metal support, the condition for drying the solution of the water-soluble resin composition is based on the thickness and the amount of water of the water-soluble resin composition layer. It is better to optimize it. Specifically, it is necessary to make it at a temperature of 120 ° C ~ 16 (TC hold 10 seconds ~ 600 privately known to dry ' preferably is made in 12 generations ~ lake.. Hold 10 seconds ~ 500 seconds For drying, it is more preferable to keep it in the 12th generation to (10). c for 15 seconds to _ seconds for drying, and it is particularly preferable to keep it at 120O15GC for 20 seconds to 2 seconds for drying. When the temperature is not full or when the holding time at the drying temperature is less than 10 seconds, there is a possibility that the solvent remains in the water-soluble resin through the layer of the resin, or 使 because the water and the gluten resin composition are subjected to The amount of heat necessary for melting is insufficient, and there is a possibility that the layer of the water-soluble resin composition becomes uneven. On the other hand, when the dry temperature exceeds 2 (8) C, or when the holding time exceeds _ private clock, there will be The decomposition of the water-soluble resin composition described above causes a problem in appearance. In addition, when the solution of the water-soluble resin composition is applied to a metal support box and dried, the water obtained after drying is dissolved. Residue in the resin composition layer 100121203 20 2012087 93 The concentration of the solvent to be retained is preferably less than 5%. Among them, in order to form dense crystals in the resin composition layer, ultrasonic vibration or vacuum drying may be used in combination at the time of drying. The cooling condition of the resin composition is because the cooling arrest of the prior art is less than 12. 〇 / sec. Therefore, the particle size of the crystal granule is large, and there is a concern that the standard deviation and the surface roughness Sm become large. There is a problem of the accuracy of the hole position, the adhesion of the resin, etc. Therefore, as the cooling condition of the present invention, it is preferable to use a cooling rate of 15 ΐ / sec or more, within 6 〇 seconds 'from the cooling start temperature i20 〇 In the case where the cooling end temperature exceeds 4 CTC, the diameter of the crystal grains belonging to the present invention cannot be reduced and uniformized. In the case where the cold portion time exceeds 60 seconds, the diameter of the crystal grains belonging to the present invention cannot be reduced and the uniformity is achieved. On the other hand, in the case where the cooling end temperature is excessively low or low. It may cause reversal on the above-mentioned cover plate and become the cause of condensation in the subsequent steps, so it is not good. When the above cooling rate is less than 2 seconds, there will be more than 6 seconds after the cooling time increases. Therefore, it is not preferable. In terms of obtaining a higher effect of reducing the diameter and homogenization of the crystal grains, the above cooling condition is preferably a cooling rate of 2 Torr/sec or more, within 2 seconds, from the temperature.峨 cold to the temperature of 25 ΐ: ~ 4 〇ΐ, more preferably 2.5t / sec or more cooling fan, in (four), clock, from the field 100121203 201208793 degrees 12 (TC ~ 1603⁄4 cooling to temperature More preferably, it is a cooling rate of more than two seconds, within 3G secret, from temperature 12 (TC ~ ι60 冷却 cooling to temperature 25 Ϊ ~ thief, especially good cooling rate of 4.rc / second or more, Within 20 seconds, the temperature is 12 〇. 〇~16〇 It cools to a temperature of 25. (:~4 (TC' is best at a cooling rate of 6. 〇/sec or more, within = seconds, from a temperature of 12CTC to 160 °C to a temperature of 25 °C ~ 4 〇. (:. About The metal supporting foil used for the drilling cover plate of the present invention is not particularly limited as long as it has high adhesion to the water-soluble resin composition and can withstand the impact of the impact caused by the drill. For the metal type of the metal supporting foil, for example, aluminum may be used, and the thickness of the metal supporting foil is usually 0.05 to 0.5 mm', preferably 〇〇5 to 〇3. When the thickness of the aluminum foil is less than 〇〇5, the drill bit is When processing, it is easy to produce the burrs of the laminate, and when it exceeds 0.5 mm, it will be difficult to discharge the cutting dust during the processing of the drill. The material of the above-mentioned Ming foil is made of aluminum with a purity of 95% or more. Preferably, it is exemplified as 5052, 3004, 3003, 1N30, 1N99, 1050, 1070, 1085, 11A, 8021, etc. as defined by JIS-H4100, H4160, and H4170. By using high-purity aluminum foil as a Metal support foil for improved impact relief or drilling with drill bits The occlusion property of the tip end portion of the head is accompanied by the lubricating effect by the water-soluble resin composition, and the hole position accuracy of the processing hole can be improved. Further, from the viewpoint of the adhesion property with the water-soluble resin composition, it is preferable. For the pre-use of a resin film having a thickness of 0.001 to 〇.〇2 mm formed on the surface, & 100121203 22 201208793 foil' thickness of the resin film is preferably 〇·〇〇1~〇.15mm, preferably 0.001~0.1mm It is particularly preferable that the resin used in the resin film is not particularly limited as long as it can be used as a water-soluble resin composition, and a thermoplastic resin or a thermosetting resin can be used. For example, examples of the thermoplastic resin include urethane-based, vinyl acetate-based, vinyl chloride-based, and polyester-based copolymers. Examples of the thermosetting resin include a thermosetting resin. In the present invention, the metal supporting foil may be coated on a commercially available metal foil by a known method in advance. The drilling cover plate is used for drilling a printed wiring material (for example, a copper laminated board or a multilayer board). Specifically, the copper laminated board or the multilayer board is overlapped by one or a plurality of sheets. The uppermost portion is disposed so that the metal supporting foil side contacts the printed wiring material, and can be drilled from the surface of the water-soluble resin composition layer of the drilling cover sheet. (Example) • The present invention is described with reference to the embodiments and the comparative examples. The following embodiments are merely illustrative of one embodiment of the present invention, and are not limited thereto. In the present embodiment, Polyethylene glycol is abbreviated as "PEG", and "polyethylene oxide" is abbreviated as "PEO". Table 1 shows the specifications of the resin, solvent, additive, and metal supporting foil used in the manufacture of the drilling cover sheets of the examples and the comparative examples, and the cooling conditions, and also shows the diameter of the drill bit used in the drilling. condition. 100121203 23 201208793 [Table l] Distinguish between (a) or strip with polyethylene oxide trade name Altop MG150 Weishang Mingcheng Chemical Industry Co., Ltd. Remarks Mn=l 50,000 (b) __^Ethylene oxide Alkox Lll Mingcheng Chemical Industry Co., Ltd. Mn=l 10,000 Resin (c) Polyethylene glycol PEG 20000 Sanyo Chemical Co., Ltd. Mn=20,000 (d) Polyethylene glycol------- PEG 4000 San purification into a company Mn= 4,000 (e) Polyethylene glycol terephthalate dimethyl condensate Biogen PP-15 First Industrial Pharmaceutical Co., Ltd. Mn=100,000 (1) Water ion exchange water bp=100°C (g) MeOH and 汜 pure medicine Industrial Co., Ltd. bp=64.7〇C, purity 99.9% (h) MEK 才口无纯药工业股份有限公司 bp=79.5°C, purity 99.9% Solvent (0 IPA and No Pure Festival Industrial Co., Ltd. S1 bp= 83〇C, purity 99.9% 0 EtOH 柞 No pure pharmaceutical industry shares have 1 ^ public ^ 1 bp = 78.4 〇 C, purity 99.9% (k) Acetone 柞 no pure pharmaceutical industry shares limited § 1 bp = 56.1 〇 C, Purity 99.9% (Β1) Hydrophobic substance (1) Propionic acid-based thermoplastic polymerization BYK-011 BYK Co., Ltd. (4) Tantalum Thermoplastic Compound BYK-349 «ΥΚ股份有_ Limited company - Additive (Β2) High melting point substance (6) Sodium citrate Diman Gas Chemical Co., Ltd. 〇) Nabukou Nippon Pure Chemical Industry Co., Ltd. — (Β3) Substance to improve compatibility (P) Pentaerythritol and Kokon Pure Chemical Industries Co., Ltd. — Metal Branch (t) Shou 70μ Γ二烫铝股份有限公司JIS specification * Ming will total number 1100 foil (9) Aluminum 100μ II Aluminum Co., Ltd. JIS specification, aluminum alloy number 11 (8) (q) Quenching H 'clock (120 ° 〇 dry 3 minutes ~> 25. 卩 § 卩Milk cooling rate (r) quenching 2.2 C / sec (160 ° C drying for 3 minutes - 30eC cooling fin dry, (8). Slow cooling ll (J / sec - (lg 〇 _ dry 3 minutes - 25 ° C Cooling 90 fine (v) 0.08mm φ KMVJ948 0.08x12 gangan tool stock; finite male drill diameter (w) 0.105mm 0 KMCL518A 0.105x1.8 Xianggan Tools Co., Ltd. (8) 〇.15mm0 NEU L004 0.15x2.5 Limited PCT q <Example 1> In such a manner that the resin solid content becomes 30%, The number average molecular weight is 24 100121203 201208793 15〇, and the polyethylene oxide (AltopMcM5〇, manufactured by Mingcheng Chemical Industry Co., Ltd.) is 8g parts by weight and the number average molecular weight is 2G, and the polyethylene glycol (PEG20000, Sanyo) Chemical Industry Co., Ltd.) 2 〇 ^ parts are dissolved in water. Next, sodium formate (Mitsubishi Gas Chemical Co., Ltd.) having a solid content of 0.5% by weight with respect to the water-soluble resin mixture was added, and completely dissolved. The dry water-soluble resin composition layer is formed into a crucible (4) (4). The water-soluble resin composition is formed by forming a resin film having a thickness of 0.01 mm on one side (using aluminum pigs: Gift, (thickness 0.07 匪) on the Mitsubishi Shout Co., Ltd.), dried at 12CTC for 3 minutes using a dryer, and then cooled at a cooling rate of 3·1ΐ/# and the clock to make a cover for drilling. (Refer to Table 2). The obtained drilled cover plate was formed by laminating six copper-clad laminates (CCL-HL832HS, both sides of the steel ring 5/πη, manufactured by Mitsubishi Gas Chemical Co., Ltd.) having a thickness of Q lmm, and then a water-soluble resin composition. The layer is configured in the above way. 'The lower side of the laminated copper-clad laminate is equipped with abutment plate (drying plate), and the drill bit: 0.105mm is used to grasp MC L518A, 〇1〇5χ18, manufactured by United Tools Co., Ltd.) The number of rotations: 330, _rpm, conveying speed: 8 calls/jump conditions, and drilling 2 roots for each drill bit at 3,000 hits (refer to Table 2). Then, Table 3 shows the average particle diameter (μιη) of the crystal grain of the water-soluble resin composition, the standard deviation of the day-to-day particle diameter (4), and the surface roughness of the cover plate ((4). 100121203 201208793 Examples 2 to 20 'Comparative Examples 1 to 36> With respect to the examples 2 to 20 and the comparative examples 1 to 36, the water-soluble resin compositions shown in Tables 1 and 2 were prepared on the basis of Example 1, and It is applied to an aluminum foil, dried, and cooled to prepare a drilling cover plate, and is drilled. For example, in Example 2, the number average molecular weight is 150,000 in such a manner that the resin solid content is 3% by mass. 20 parts by weight of polyethylene oxide (Alt〇p MG_15〇, manufactured by Mingcheng Chemical Industry Co., Ltd.) and 20 parts by weight of polyethylene glycol (PEG 20000, manufactured by Sanyo Chemical Industry Co., Ltd.) having a number average molecular weight of 20,000 are dissolved in In a water/MeOH (methanol) mixed solution, the ratio of water to MeOH is set to 90 parts by weight per 1 part by weight. Thus, there are also examples in which a low boiling point solvent having a boiling point lower than that of water is used. Example 26 uses the commercially available Sang-A Flontec Co "LXl2〇" manufactured by Ltd., Comparative Example 27 is a commercially available product "AL-100040" manufactured by Y〇ng u chuan Industrial Co., Ltd., and Comparative Example 29 is manufactured by a commercially available Uniplus Electronics Co., Ltd. LAE-1007. Then, Table 3 shows the results of the average particle diameter 〇im) of the crystal particles of the water-soluble resin composition, the standard deviation (μπι) of the crystal grain size, and the surface roughness sm (gm) of the cover sheet. Further, Fig. 1 is an enlarged view showing the surface state of the water-soluble resin composition layer of the specific samples (Examples 2, 3, 1 and 12, and Comparative Examples 2, 10, 20, 26 and 28). 100121203 26 20 s___I_I______I_20! 11 Money head diameter, ____ 0.15 mm0 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇0.105 πκηφ 〇〇〇〇〇〇〇〇〇$ 0.08 τταηφ 〇Metal branch foil S Aluminium 1 ΙΟΟμτη 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇β Aluminium 70μτη 〇〇〇〇〇〇〇〇〇〇® Slow cold l.rc mt S quenching 2.TC 1 / machine 〇〇〇〇 s cold 3.I °C i mi 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 〇〇〇〇〇〇〇〇Additives/*·< S <single ppqg ο ο g ρ ο ρ ρ ρ ρ ρ Q ο ρ ο ο ρ ρ ρ g Q oo Q gppoo © $ Amount ♦1 opq ο W-) ρ ίη ρ ρ ρ ρ ρ ό ρ ρ ο ρ ο ο ο ο ο ο Q oopoooo W) $ A _ 1_ g ΓΛ ΓΛ ΓΛ 5 ρ γ Λ ΓΛ S ρ ρ ο rn ρ ρ 5 ρ ρ ρ g 5 ppppppo / -S β 1 ppo ρ ρ ρ ρ ο g ρ ρ ο ο ρ ο ο ο ρ ρ ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο Oppq Q r*) g 1 s BM boiling point 56.rc ooo ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο 筘ooooo R ooo © sss ο 冢RS g SSSS g S 冢SSS 8 gs, sgssgsss resin s Biogoi PP-15 ooo ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ooooooooos PEG 20000 1_ 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异ο ο ο ο S ο ο S soogooooo Altop MG-150 ggg ο gg ο g ο gggg ο § g ο g ο g S ο ο ossossss 8 I 1 embodiment 2 | 1 1 embodiment 4 1 IT) 1 <〇 I 1 embodiment 7 1 οο 1 1 embodiment 9 1 丨 embodiment Η) 1 1 CN I cn I 21 II 1 embodiment 16 1 1 embodiment 17 1 00 1 + «? σ \ I 1 embodiment 20 1 1 Ttfe example ι 1 1 tbfe example 2 1 1 tbfe example 3 ! 1 her case 4 ί 1 tbfe example 5 ! 1 tbft example 6 1 1 flavor example 7 1 1 tbfe example 8 I tbfe example 9 0 1 1 tbfe example 11 ! 1 Tbfe example 12 i 1 fcbfe example 13 i 1 can column 14 jn 1 i

Li εοζ-Ιοοι 20 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 1 1 1 1 1 1 〇〇〇〇〇〇〇1 1 〇1 〇〇〇〇〇〇〇pp ρ ρ Ρ ρ ρ ρ ρ ρ 1 1 ρ 1 ο ρ ρ Q pp ο ops ο ο V) w- > ρ ρ ρ 1 1 ο 1 ο ο ο ρ ο ρ ο o § p ρ Ρ 2 ρ ρ ρ 1 1 ρ 1 ρ ρ ρ ο ο ρ ρ ρ pp ο ο ρ ρ ρ ρ ρ 1 1 ρ 1 ρ ρ ρ ο ρ ρ ρ p cn o ρ ο ο ρ ρ ρ ρ 1 1 ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο 宕 1 1 ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ooo ο ο ο ο ο ο ο 1 1 ο 1 ο ο ο ο ο ο ο sss SSSS g 1 1 S 1 8 8 S 8 8 8 gooo ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο 1 1 ο 1 ο ο 沄宕 ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο π 1 1 18 Example 18 1 1 味 Example 19 1 1 Comparative Example 20 1 丨tbfe Example 21 1 1 Comparative Example 22 1 1 fcbfe Example 23 1 1 Comparative Example 24 1 "Comparative Example 25 1 1 Comparative Example 26 1 "tb| Example 27] 1 Comparative Example 28 1 "Comparative Example 29 1 1 Comparative Example 30 1 1 tbi Intersection 31 1 "tbl Intersection 32] Comparative Example 33 1 Comparative Example 34 1 tb♦ Intersection 35 1 "Comparative Example 36 1 snnool 201208793 <Evaluation method> The following evaluations were performed for each sample of the drilling cover sheets produced in the examples and the comparative examples. (Drilling processing) Each sample obtained was evaluated, and drilling was performed under the following conditions. The drilling process with a drill diameter of 0.15 is based on a four-layer copper-clad laminate (CCL-HL832, two-sided copper foil 12 μm, manufactured by Mitsubishi Gas Chemical Co., Ltd.) having a thickness of 0.2 mm, and the water-soluble resin composition of each sample is used. The layer is configured in the above manner, and the abutting plate (for the dry plate) is disposed on the lower side of the overlapped copper laminated plate, and the drill bit: O.15mm0 (NEU L004, 0.15x2.5, ear outer tool Co., Ltd. The system has a rotation number of 200,000 rpm and a conveying speed of 20 pm/rev. For each drill bit, 20 holes are drilled with 3, 〇〇〇hits. The drilling process with a drill diameter of 0.105 mm0 is performed by laminating six copper-clad laminates of 0.1 mm thickness (CCL-HL832HS, 5μηι on both sides of the copper foil, manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the layer of the water-soluble resin composition is The above method is configured to arrange the abutting plate (drying plate) on the lower side of the overlapped copper laminated board to drill: 〇1〇5mm0 (KMCL518A, 0.105x1.8, manufactured by United Tools Co., Ltd.) Rotation number: 330,000 rpm, conveying speed: 8 μm η / · conditions, drilling 20 holes for each drill bit at 3,000 hits. 100121203 29 201208793 Drilling process with a drill diameter of 0.08 mm</> is carried out after overlapping four sheets of O.lmm copper-clad laminate (CCL-HL832HS 'copper foil on both sides 5μιη, manufactured by Mitsubishi Gas Chemical Co., Ltd.) The layer of the water-soluble resin composition is disposed on the lower side of the laminated copper-clad laminate, and the abutting plate (drying plate) is arranged to drill: 〇.〇8mm0 (KMV J948, 0.08x1.2 , Co., Ltd.), rotation number: 330,000 rpm, conveying speed: 6 μπι / Γβν, and drilling 20 holes for each drill with 3, 〇〇〇hits. (Evaluation 1) Hole Position Accuracy The 3,000hits hole position and designation on the back side of the lowermost layer of the overlapping copper-clad laminates were measured using a hole position coordinate measuring device (model HA-1AM, manufactured by Via Mechanics Co., Ltd.). The deviation of the coordinates, the average value and standard deviation (σ) of each bit of the drill are calculated, and the average value +3σ is calculated. Then, the average value of the average value +3σ, which is 2 times of the drilling process is calculated. Table 3 shows the evaluation results of the hole position accuracy. In addition, in FIG. 4, FIG. 5 and FIG. A graph showing the standard deviation of the average particle diameter of the crystal grain and the surface roughness Sm and the relationship with the hole position accuracy. (Evaluation 2) The adhesion amount of the resin is a microscope with a magnification of 25 times (model VHK-100, KEYENCE Co., Ltd.) The amount of adhesion to the resin of the drill diameter was observed for the drill bit after the drilling of 3,00 〇hits. The observed results were evaluated according to the following criteria. The results are shown in Table 3. 100121203 201208793 〇: The maximum diameter of the adhesive resin is less than 15 times the diameter of the drill △: The maximum diameter of the adhesive resin is more than 15 times the diameter of the drill. The resin adhered to the drill is drilled. Dropped to the surface of the cover (Evaluation 3) The number of breaks of the drill bit is drilled using 20 drill bits, and the number of breaks of the drill is counted. The results of the number of drill breaks are shown in Table 3. According to the above evaluations 1 to 3, ○: The average particle diameter of the crystal grains is 40/mi or less / the standard deviation of the average particle diameter of the crystal grains is less than or equal to the surface roughness Sm47Mm, and the hole position accuracy is 23_ or less. Drill bit damage, no resin adhesion 〇: the average particle size of the crystal grain is less than the m / the standard deviation of the average grain size of the crystal grain is less than 25 / rni / the surface roughness is below 纟 (10), the hole position accuracy is 25 In the following, there is no bit breakage and no resin adhesion. △ • The average deviation of the average grain size of the crystal grain #/the average grain size of the crystal grain / Table = the sugar content S4 satisfies the requirements of the patent application, and the hole position accuracy is 25 μm or less. No drill deer has a drill bit to know, no resin sticking X. The average particle diameter of the crystal grain / spider hopper, D standard particle size deviation / surface roughness Sm does not meet the application true ^ _ j軏The state of the required parts, the hole position fineness exceeds 25/rni, there is no drill bit, and there is no resin adhesion. The average particle size of the crystal grain / the coarse surface of the knot surface Sm does not satisfy the application, the heart " ten ice position' quasi- Difference / tree breakage or 4 heteroatoms attached state of the elements of interest off, there is a drill 100121203 s 201208793 [Table 3]

No. Evaluation of results "Average particle size of the determined crystal grains (μτη) Standard deviation of the average particle size of the crystal grains (m) Surface roughness ratio ^!m 〇um) (1) (2) (3) Hole position accuracy average +3 (average value of 7 fwm) Bit damage resin adhesion actual -1 28.5 9.85 3.2 21.2 〇〇◎ Implementation order | 2 18.2 3.92 3.6 19.5 〇〇◎ Implementation order '3 20.1 5.00 3.9 20.6 〇〇◎ Implementation order 4 37.9 7.66 4.0 22.5 〇〇◎ Implementation Order 18.5 18.7 5.93 4.1 18.8 〇〇◎ rm ! 6 18.5 4.55 4.3 21.4 〇〇◎ #施合丨' 7 39.6 8.64 4.6 22.1 〇〇◎ Implementation Order 8 8 14.4 4.06 5.1 24.5 〇 〇〇Implementation order丨 9 58.3 23.05 5.1 24.9 〇〇〇10 34.4 8.19 5.2 20.3 〇〇◎ Implementation of the crowd 11 21.3 6.00 5.9 21.1 〇〇 ◎ Implementation of the package 12 39.4 7.86 5.9 21.4 〇〇 ◎ Implementation of the public 13 17.3 4.14 6.2 18.9 〇〇 ◎ Injury 14 66.9 15.67 6.6 20.9 〇〇〇Implementation 15 58.4 17.04 6.7 20.4 〇〇〇Implementation 19.16 19.6 7.52 6.8 20.3 〇〇◎ Implementation 17 55.1 19.28 6.8 21.3 〇〇〇Implementation彳18 40.1 12.25 6.9 23.7 〇〇〇Implementation 侥 19 61.1 12.08 7.3 20.6 〇〇〇Implementation 20 20.5 4.55 4.3 14.2 〇〇 ◎ Comparison 1 69.2 28.05 4.1 24.6 〇〇△ Comparison 彳歹2 70.9 29.52 4.3 26.5 〇〇X 3 61.7 26.11 5.4 27.9 〇〇Comparative 4 67.2 28.00 5.9 24.6 〇〇Δ Comparison Order 5 62.1 26.83 6.2 23.8 〇〇Δ Ratio Board 6 88.2 32.40 6.2 23.3 〇〇Δ Ratio ίYou 7 79.1 30.57 6.3 22.2 〇〇Δ Ratio歹8 69.7 27.13 6.8 20.9 〇〇Δ For example 9 75.6 30.64 7.8 25.6 〇〇X Compare you 10 90.2 34.68 8.1 25.1 〇〇X Compare you 11 52.2 23.04 8.2 25.2 〇〇tbte 12 80.9 21.57 8.7 26.5 〇〇 Compare you 13 53.0 15.18 8.8 26.8 〇〇Compare you 14 52.5 13.54 9.3 26.5 〇〇X Compare you 15 32.1 12.90 9.5 21.4 〇〇Δ 16 54.8 19.36 9.6 24.5 〇〇Δ Compare you 17 65.4 18.91 9.6 22.1 〇〇Δ Compare 彳歹! 18 37.9 12.59 9.8 27.1 〇〇X than fe' 19 61.4 21.24 10.5 26.8 〇〇X ratio ' 20 203.1 29.53 13.7 27.7 〇〇X 丨 丨 21 37. 7 10.97 8.8 15.8 〇 Δ XX Compare you 22 37.7 10.97 8.8 25.5 〇 Δ XX Compare you 23 170.3 53.28 9.7 27.9 〇 Δ XX is finer! 24 61.4 21.24 10.5 17.7 〇Δ XX Compare you 25 199.6 51.09 11.4 25.2 〇△ ior Compare you 26 87.9 30.88 11.5 21.2 〇Δ than you 27 69.9 19.33 11.9 26.8 〇△ Compare you 28 135.7 54.44 12.3 28.6 〇Δ ratio·! 29 243.2 86.60 17.6 25.7 〇Δ ior Compare you. 30 274.0 101.94 18.2 31.9 〇Δ Compare you 31 285.0 101.87 19.1 29.2 〇Δ Compare you 32 330.3 117.41 21.2 29.9 〇Δ than the initial '33 155.8 34.00 36.2 27.6 〇△ 丨 丨. 34 409.4 134.41 10.3 29.6 〇X 7<x Comparison#. 35 185.0 47.83 12.6 29.8 〇ior Age 丨36 83.1 29.53 13.7 One X Ί<χ· 100121203 32 201208793 It can be seen from Table 3 about the comparison of commercially available prior art products In Example 26, in comparison with the vehicle, Example 27 and Comparative Example 29, the average particle diameter of the crystal grains, the standard deviation of the average particle diameter of the crystal grains, and the surface roughness were all not small. Further, from the results of Tables 3, 1], 4, and 115, and Fig. 6, it is understood that the average particle size and crystal of the crystal grain of the water-soluble resin composition of the sample of n~2〇 are compared with those of Comparative Examples 1 to 36'. The standard deviation of the average particle diameter of the particles and the surface confidentiality Sm of the above water-soluble resin composition layer and the relationship with the hole position accuracy show a clear material. The water-soluble resin composition of the sample of the age-old cockroach was excellent in the results of _1 to 36, and Yushu transferred (4) head loss. The diameter of the crystal grain of the above-mentioned water-soluble resin composition of the head C and the standard deviation thereof are superior to those of the slave, and the accuracy of the placement is excellent, and in the case where the surface of the cover sheet is small, the Sm is small. The tendency of the resin to adhere. In addition, in Table 2 and Table 3, only Example 2G and Comparative Example 21 in which the drill diameter of 0.08 mm was drilled into the lamp was not shown in Table 2, and as a result of Table 4, it was found that when the drill #(10) 8 mm was processed, By making the quenching effect when the layer composed of the water-soluble tree test substance is produced, the average grain of the crystal grain is only the same; the quasi-deviation, the surface roughness Sm, the hole position accuracy, and the resin adhesion are excellent. the result of.

S 100121203 33 201208793 尨 尨 comprehensive judgment ◎ characteristic evaluation result g 1 j resin adhesion 〇 < V_^ 1 ! bit damage 〇〇 § Γ Γ Γ ^ V 1 δΗ t> ^ <N CO id physical property evaluation result g surface rough ^^.Sm (/mi) cn 00 od 3 iti P $ inch * Cs o V-✓ 平均 average grain size of 丨 crystal grains (4) IT) od bit diameter 2 0.08 mm0 〇〇 metal support foil β is 70μηι 〇〇 cooling General s slow cold i.rc/ mi 〇 〇 3.1 ° C / machine 〇 1 additive β s Ou 纠 VS3 ^ inch inch d S EtOH boiling point 78.4 °C oo MeOH boiling point 64.7 °C oos tree month system © PEG 20000 Altop MG150 8 8 Example 20 Comparative Example 21 snzlool 201208793 In addition, Table 5 shows that Examples 5 and 6 and Comparative Example 22 which are drilled with a drill diameter of 0.105 mm are shown in Tables 2 and 3, respectively. As a result of the results of Table 5, when the drill diameter is 0.105 mm, the average particle diameter of the crystal grains and the standard deviation and surface roughness thereof are obtained by the rapid cooling effect when the layer composed of the water-soluble resin composition is produced. Sm, hole position is accurate Both the degree of adhesion and resin adhesion showed excellent results. 100121203 35 201208793 IS ◎ ◎ \ 1 Special round results S 〇〇0 S Short I 〇〇〇§ Λ poor I street f 6H D iV ξ inch Μ W-) (born by result $ surface 梱 chain degree Sm (μπι 1_ ψ < ΓΛ 〇〇00* g $ ^ 1|1 wS inch · 平均 crystal grain average 43⁄4 is (4) g «Ο οο 卜 · bit diameter 1 0.105 ΐϊκηφ 〇〇〇 metal branch: support foil 1_ © aluminum 70μιη 〇〇〇Cooling sensitivity 1 Slow cooling i.rc / Machine 1_ 〇佥P f 4) ^ ^ 〇〇 Additive B ir\ ®potential O 〇1 ΒΟΗ Boiling point 78.4 V o ο 〇3 MeOH Boiling point 64.7 °C o 2 〇 S resin PEG 20000 x 3 Ahq) MG150 1 Example 5 Example ό tb$ 交例 22 9 £ snolool 201208793 (industrial availability) According to the present invention, it is possible to provide a drill hole compared to the prior art A cover plate for drilling holes having excellent hole position accuracy, less resin adhering to the drill bit, and reduced drill bit damage. Then, in the field of extremely small diameters in the field of laser opening up to now, drilling can be performed with excellent positional accuracy, which can reduce the resin adhering to the drill bit and reduce the breakage of the drill bit, resulting in cost reduction and productivity. It has contributed to the improvement, so it has great value in the industry. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a photograph showing an enlarged view of the surface state of a water-soluble resin composition layer of each of Examples and Comparative Examples. Fig. 2 is a schematic cross-sectional view showing a state in which the drilling cover plate of the prior art is used for the drilling process. Fig. 3 is a schematic cross-sectional view showing a state in which the drilling cover plate of the present invention is used for the drilling process. Fig. 4 is a graph showing the relationship between the average particle diameter of crystal grains of the water-soluble resin composition layer and the hole position accuracy for each of Examples and Comparative Examples. Fig. 5 is a graph showing the relationship between the standard deviation of the crystal grain size of the water-soluble resin composition layer and the hole position accuracy for each of Examples and Comparative Examples. Fig. 6 is a graph showing the relationship between the surface roughness Sin of the water-soluble resin composition layer and the hole position accuracy for each of Examples and Comparative Examples'. [Description of main components] 100121203 37 201208793 1 Front end of drill bit 2 ' 20 Resin composition layer 2a~2g Crystal grain 3 Metal support foil 20a~20c Crystal grain 100121203 38

Claims (1)

201208793 VII. Patent application scope 1. The seeding cover plate is formed on at least one side of the metal support box, and a layer having a thickness of 0.02 to 0.3 mm formed of a crystalline water-soluble resin composition is formed. The water-soluble resin composition has a crystal grain average particle size of 5 to 5, and a standard deviation of 25 μm or less, and the layer composed of the water-soluble resin composition is on the surface of the drill entering the surface. The roughness Sm is 8 μm or less, and the layer composed of the water-soluble resin composition is on the metal supporting foil, and after directly applying the hot melt of the water-soluble resin composition, or containing the water-soluble resin After the solution of the composition is applied and dried, it is cooled from 25 C to 160 C to 25 at a cooling rate of 1 to 5 ° C /sec or more in 6 seconds. 2. The method for forming a hole for drilling according to the first aspect of the invention, wherein the water-soluble resin composition has a crystal grain size average particle diameter of 5 to 4 〇 ^m. In the range, the standard deviation is 17 μm or less, and the surface roughness Sm of the layer formed of the water-soluble resin composition on the drill entry surface is 7 μm or less. 3. The drilling cover plate according to claim 1 The water-soluble resin composition contains a water-soluble resin (Α), and further contains a substance (Β2) having a water-soluble resin (Α1) and a melting point higher than the water-soluble resin (Β2), and The water-soluble resin (Α) compatible substance (Β3) is selected to be 100121203 39 201208793. The drilling cover plate according to the first aspect of the patent application contains the above water-soluble resin composition. The solution further comprises water and a solvent having a boiling point lower than that of water. 5. The casing for drilling according to the first aspect of the invention, wherein the thickness of the metal supporting foil is in the range of 0.05 to 0.5 mm. Apply for patent item 1 Cover hole, which based on the use of copper-clad laminates processing. 10012120340