TW201124279A - Entry sheet for drilling hole in printed circuit boards, lubricant resin composition and method for preparing the same - Google Patents

Abstract

The present invention relates to an entry sheet for printed circuit board hole boring, comprising: a metal thin film substrate; and a water-soluble lubricating resin layer formed on the substrate, wherein the water-soluble lubricating resin layer comprises 100 parts by weight of a water-soluble polyester resin, from 0.5 to 3 parts by weight of a vinyl chloride - vinyl acetate copolymer and from 0.5 to 3 parts by weight of a hydrogenated hydrocarbon resin. In entry sheets produced in this way, the uniformity and accuracy of the bored holes is outstanding, the force of binding onto the metal thin film is exceptional, and there is no peeling or crack generation on the surface even at low temperature.

Description

201124279 w VI. Description of the invention: Technical field of the invention of the invention 3 The present invention relates to a cover sheet for perforation of a printed circuit board, and more particularly to the uniformity and correctness of a perforated hole, and A method for producing a water-soluble lubricating resin composition formed on the cover sheet, which is excellent in the bonding strength of the metal thin film and which is not cracked or peeled off on the surface at a low temperature. [4^:Good winter] Recently, in response to the improvement of the reliability of printed circuit boards or the high density. The requirement for reinforcement, it is required to ensure the correctness of the hole position. For this purpose, a cover sheet is used for the perforation of the printed circuit board. The cover sheet has a heat which can be generated during the piercing process, and when the film is perforated, the coating layer of the cover sheet is melted to have a lubricating effect, and further, in the case of using a water-soluble resin, in the punching process It can be widely used when it can be washed. In the related patent document i, a method of mixing a water-soluble resin with a water-insoluble lubricant, forming a film sheet, and adhering it to a thin plate as described above is disclosed. As the water-soluble resin, water-soluble resins such as polyethylene glycol, polyepoxyethane, polypropylene glycol, polyethylene, polyacrylamide, poly(tetra), and the like are disclosed. Further, in Patent Document 2, it is disclosed that a coating film of a thermosetting resin having an average thickness of (four) micrometers is formed on the surface of a thin plate having a thickness of 2 Å to 2 μm, and is adhered to the thickness thereof. Micron water soluble resin 201124279 sheet method. However, 'these methods are susceptible to deterioration due to heat, or the thickness of the resin layer is too thick, bubbles are generated during the coating process of the water-soluble resin composition due to low boiling point, and bubbles are left in the resin layer. The problem of the correctness of the hole position is reduced. On the other hand, in the patent document 3, it is disclosed that the resin composition containing a water-soluble hydrazine is dissolved in water containing water and isopropyl alcohol, and having a mixing ratio of 60.40 to 95.5% by weight. A method for producing a resin layer on the substrate by applying a solution of isopropyl alcohol to a sheet-form substrate after drying the solution, and drying the solution. However, this method has a complicated manufacturing process, and it is difficult to adjust the problem of solubility to an organic solvent and water due to the use of most resins. Further, Patent Document 4 discloses a proposal to use a water-soluble copolyester resin containing a coating material for a lubricious sheet and having a number average molecular weight of from 1 Å to 10,000 Å to 80,000 and having an acid at the terminal group at the same time. The polyether ester having a molecular weight of 3,000 to 40,000 and the first water-soluble lubricant having an ester group and an ether group-containing polymer having a molecular weight of 600 to 1,000. However, when the lubricating substance is directly applied to the metal substrate without the underlayer, there is a problem that peeling occurs in the winter when the adhesion force is lowered and the coating layer is slightly cracked. Therefore, there is a need to develop a novel cover sheet which is excellent in adhesion and has no surface stickiness. [PRIOR ART DOCUMENT] [Patent Document 1]: JP-A-2003-175412 [Patent Document 2]: JP-A-2003-136485 [Patent Document 3]: Republic of Korea Patent Publication No. 10- [Patent Document 4]: Korean Patent No. 10-672775 [Description of the Invention] [Problem to be Solved by the Invention] The problem of the first technique to be solved by the present invention is to provide uniformity and correctness of a perforated hole. A cover sheet for punching a printed circuit board which is excellent in surface properties, has excellent workability, and has excellent adhesion to a metal film, and which does not crack or peel off the surface even at a low temperature. According to a second aspect of the present invention, a water-soluble lubricating resin composition for forming a cover sheet for perforating a printed circuit board can be provided. The problem of the third technique to be solved by the present invention is to provide a method for producing the above-described water-soluble lubricating resin composition. [Means for Solving the Problem] In order to solve the above-described problems of the first technique, the present invention provides a cover sheet for perforating a printed circuit board, comprising a metal thin film substrate and a water-soluble lubricating resin layer formed on the substrate. The water-soluble lubricating resin layer comprises 100 parts by weight of a water-soluble polyester resin, 0.5 to 3 parts by weight of a gas ethylene-ethylene acetate copolymer, and 0.5 to 3 parts by weight of hydrogenated Hydrocarbon resin. According to an embodiment of the present invention, the metal film substrate is preferably an Ilu film having a thickness of 0.05 to 0.2 mm. 201124279 According to another embodiment of the present invention, the water-soluble polyester resin can be 1: 〇_1: 0.8 molar ratio to 2: 0.2: 1. 莫 molar ratio 'to make a) polyol: b) 1.5 The water-soluble component in parts by weight: c) is produced by reacting a carboxylic acid or a carboxylic acid ester, and is preferably a molar ratio reaction of 1·5 : 0.15 : 0.85. According to another embodiment of the present invention, the polyol may be 1,4-butanediol, monoethylene glycol, propylene glycol, neopentyl glycol, diethylene glycol, polyethylene glycol, 13 propylene glycol, 1, 2 One or more selected from the group consisting of butylene glycol, 1,3-butylene glycol, iota, butanediol, and 1,6-hexanediol. According to another embodiment of the present invention, the water-soluble component may be a continuous alkali metal salt and may be composed of sodium dimethyl-5-sulfonate isophthalate, dimercapto 4 sulfonate sodium isononate. One or more selected from the group consisting of a salt, a dimercapto-5-sulfonic acid sodium citrate salt, a hydrazine salt, a sodium citrate salt, and a sodium citrate salt are selected according to the present invention. An example of a 'carboxylic acid or a carboxylic acid ester from hexanoic acid, succinic acid, diacid ester, dinonyl phthalate, dimethyl sulphate, glutamic acid, bismuth Acid, succinic anhydride, dimethyl succinate, sebacic acid _ ester, dinonyl adipate, one or more selected from the group consisting of citric acid, citric acid, and isophthalic acid. The polyester resin is preferably in the range of 10,000 to 100,000. According to another embodiment of the present invention, the gas-ethylene-ethylene acetate duck copolymer is modified by a modified base of ethylene-ethylene/ethylene acetate, and an epoxy modified ethylene/ethylene acetate. One or more kinds of copolymers and hydroxy-modified vinyl chloride/ethylene acetate copolymers are selected, and the content of ethylene and ethylene is 7〇~9〇% by weight, and the content of ethylene acetate is 1〇~3〇. % is better. According to another embodiment of the present invention, the molecular weight of the hydrogenated hydrocarbon resin is preferably from 500 to 900. According to another embodiment of the present invention, the thickness of the water-soluble lubricating resin layer is preferably from 5 to 200 μη. In order to solve the problems of the second technique, the present invention provides a water-soluble lubricating resin composition characterized by comprising 100 parts by weight of a water-soluble polyester resin, and 0.5 to 3 parts by weight of a gas ethylene-ethylene acetate copolymer. And 0.5 to 3 parts by weight of the hydrogenated hydrocarbon resin as a water-soluble lubricating resin composition for forming a cover sheet for perforation of a printed circuit board. According to an embodiment of the present invention, the water-soluble polyester resin may have a molar ratio of * 1 : 0.1 : 0.8 to a molar ratio of 2 : 0.2 : 1.0, such that a) a plurality of alcohols: b) 1.5 parts by weight The water-soluble component: c) is produced by reacting a carboxylic acid or a carboxylic acid ester, and is preferably a molar ratio reaction of 1.5:0.15:0.85. In order to solve the problems of the third technique, the present invention provides a method for producing a water-soluble lubricating resin composition for a cover sheet, which comprises the following steps: a step of producing a water-soluble polyester resin, which is 1:0.1: 0.8 molar ratio to 2: 0.2: 1.0 molar ratio, the polyol: water-soluble component: carboxylic acid or carboxylate esterification reaction, and then condensation polymerization to produce; and 100 parts by weight Based on the above water-soluble polyester resin, 0.5 to 3 parts by weight of a copolymer of ethylene and ethylene acetate and 0.5 to 3 parts by weight of a hydrogenated hydrocarbon resin are mixed and hardened. Furthermore, in accordance with an embodiment of the present invention, the water-soluble polystyrene resin can be produced by a procedure comprising the steps of: transesterifying a carboxylic acid or a carboxylic acid ester with water 201124279; In the foregoing step, the step of esterifying the water-soluble carboxylic acid with a polyol to obtain an intermediate product; and the step of subjecting the intermediate product to a condensation polymerization, at which time, the esterification reaction is at 160~ It is preferably carried out at a temperature of 220 ° C, and the condensation polymerization reaction is carried out under reduced pressure at a temperature of from 230 to 260 ° C. Further, according to another embodiment of the present invention, the esterification reaction is carried out using one selected from the group consisting of tetrabutyl phthalate, zinc acetate, calcium acetate, magnesium acetate, trimethyl phosphate, triphenyl phosphate, and cobalt acetate. The above catalyst is carried out. [Effect of the Invention] The cover sheet-based perforated hole for punching a printed circuit board of the present invention is excellent in uniformity and correctness, and is excellent in adhesion to a metal thin film, and does not cause surface cracking or peeling at a low temperature. Furthermore, since no additional lubricating components or additional underlayers are required, the manufacturing steps are simple and economical. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1a is a photograph showing a crack-free surface of a cover sheet of the present invention; and Fig. 1b is a photograph showing a surface of a cover sheet of a comparative example in which a crack is formed on the surface. Fig. 2A is a result of AOI (Automated Optical Inspection) for performing the hole punching precision measurement of the cover sheet of Example 2-(1) of the present invention. Fig. 2B is an A0I result of the measurement of the hole precision of the perforation processing of the cover sheet of Example 2-(1) of the present invention. 2C is a perforation of the cover sheet of Example 2-(1) of the present invention. 201124279 AOI result of the measurement of the precision of the hole. Figure 3 shows the AOI results when aluminum flakes (0.15T) not covered with lubricant were used. Figure 4 shows the AOI results when using aluminum flakes (0.15T) that are not covered with lubricant. Figure 5 shows the AOI results when using the LE-800 of Japan MGC (Mitsubishi Gas Chemical). Fig. 6 is an AOI result when the LE-800 of Japan MGC (Mitsubishi Gas Chemical) Co., Ltd. is used. Fig. 7 is an AOI result when a cover sheet coated with a lubricating resin produced in Example 2-(2) of the present invention was used. Fig. 8 is an AOI result when a cover sheet coated with a lubricating resin produced in Example 2-(2) of the present invention was used. Figure 9 shows the AOI results of the company's products created in Korea, which is currently used in the industry. Figure 10 is an AOI result after drilling of the article of Example 2-(3) of the present invention. Figure 11 is an AOI result of evaluation of the article of Example 2-(4) of the present invention. Figure 12 is an AOI result of evaluation of the article of Example 2-(4) of the present invention. t. Embodiments 3 Hereinafter, the present invention will be described in more detail with reference to the embodiments. The cover sheet for perforating a printed circuit board of the present invention comprises a metal 201124279 film substrate and a water-soluble lubricating resin layer formed on the substrate, and in this case, the water-soluble lubricating resin layer contains 100 parts by weight of water-soluble solvent. The polyester resin, 0.5 to 3 parts by weight of the ethylene-ethylene acetate copolymer, and 0.5 to 3 parts by weight of the hydrogenated smoky resin. The metal thin film substrate used in the present invention is preferably an aluminum thin film having a thickness of 0.05 to 0.2 mm. Further, the water-soluble polyester resin forming the water-soluble lubricating resin layer of the present invention may have a molar ratio of 1:0.1:0.8 to a molar ratio of 2:0.2:1.0, so that a) the polyol: b) water dissolves Ingredients: c) a carboxylic acid or a carboxylic acid ester is produced by reaction, and a molar ratio reaction of 1.5:0.15:0.85 is preferred. The polyol used in the water-soluble polyester resin of the present invention is diethylene glycol 'propylene glycol, neopentyl glycol, polyethylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3- One or more selected from the group consisting of butanediol, 1,4-butanediol, and 1,6-hexanediol are preferred, and 1,4-butanediol, diethylene glycol, and the like are preferred. Further, the water-soluble component used in the water-soluble polyester resin of the present invention has a component for imparting a water-soluble action group to the lubricating resin, that is, has -COOH group, -NH2 group, and/or -S〇 a 3H-based substance, or a salt thereof. The water-soluble component as a representative ' can be exemplified by an alkali metal sulfonate, specifically, a sodium dimethyl-4-sulfonate isophthalate salt, a dimethyl-5-acid acid-iso-sodium acid One or more selected from the group consisting of sodium salt, dimercapto-5-thanoic acid group, and sodium salt of diethyl-5-supply acid phthalate are used. Further, the carboxylic acid or carboxylic acid ester used in the water-soluble polyester resin of the present invention may be adipic acid, succinic acid, diacid acid ester, dimethyl phthalate, dimethyl isononanoate, Glutaric acid, azelaic acid, succinic anhydride, dimethyl succinate 10 201124279

One or more selected from the group consisting of zeshin, azelaic acid dimethyl sulphate, adipic acid bismuth, and citric acid, ugly acid, and leuchoic acid. At this time, the molecular weight of the water-soluble condensing resin is preferably from about 10,000 to 100,000, more preferably from about 2 Torr to about 30,000 to 50,000. When the molecular weight exceeds 1 Torr, the synthesis becomes difficult, and when the molecule 2 of the above polymer exceeds =, there is a problem that the processing property is deteriorated when perforated or coated. On the other hand, in order to produce the water-soluble condensed resin of the present invention, the carboxylic acid or carboxylic acid is used to impart water solubility, and is reacted with an alkali metal sulfonate: at this time, the alkali metal sulfonate and the carboxylic acid are 〇i : 08 uo Wang Hao · 2 : The molar ratio of 1.0 is better than that of ' 而 · 15 : 〇 · 85 molar ratio is best. When the content of the metal salt is too high, the water and coating properties will deteriorate. 1 The water-soluble edge acid produced in the above is subjected to a S-reaction or a S-exchange reaction with a polyol under the catalyst and the additive, thereby adding a condensation polymerization additive to the intermediate product obtained therefrom. And in the vacuum strip = condensation polymerization. The polyol and the water-soluble (4) are preferably reacted at a molar ratio of i U to 2:1, and the reaction is preferably carried out at a molar ratio of 丨5: 〇85. At this time, an appropriate esterification reaction temperature is 16 〇 to 22 〇 < t. If it is below ι6〇τ, the reaction rate will be slow, and if it is above 22 (rc, thermal decomposition of the polymerization reaction may occur. Furthermore, when the content of the polyol used is too low, it is difficult to obtain a high molecular weight. The polymer, and when the content is too high, the system will show a side reaction, the amount of by-products will increase, and the reaction rate will also become slow. 201124279 April _ 14s after the completion of the reaction or transesterification reaction Adding a condensation polymerization catalyst and various additives, and formulating a condensation polymerization reaction under a reduced pressure from a reaction temperature of 230 to 26 CTC. If the reaction temperature is below 230 ° C, the condensation polymerization reaction will be slow, and the temperature is 260 ° C. In the above, it is difficult to obtain a polymer having a high molecular weight by thermally decomposing the I polymer, and further, in the condensation polymerization reaction, high vacuum conditions are caused by the pressure reduction in the enthalpy, and if the pressure is 2 tGIT or more, it is difficult to remove the reaction. It is difficult to obtain a polymer having a high molecular weight by a side reaction substance or oligomer, a punctured ethylene glycol or the like which is formed in the film. Therefore, it is preferable to maintain a vacuum of 0.5 ton· or less. The initial or final stage of the lysing reaction or the transesterification reaction or the condensation polymerization may be added with various additives for promoting the polymerization. '匕齐丨' can be used from tetrabutyl phthalate, zinc acetate, acetic acid, 1 bow, acetic acid. One or more kinds of corpses are selected from the group consisting of dimethyl phthalate, triphenyl phosphate and cobalt acetate. The 曰^ 彳 history is set to be 相对.〇3~〇·5 摩尔% relative to the whole resin. 2. If the right is Daxie·〇3mol%, the reaction speed will be slower, and it will be difficult to obtain the resin of the door knife. In addition, if the addition amount is above 〇5mol%, the reaction speed is fast, but because of The yellowing phenomenon will cause the hue of the polymerized product to appear as strong tea, η, and bar, and also exhibit thermal decomposition. In another aspect, in the present invention, the aforementioned water-soluble polyester resin can be mixed with a small amount of other water-soluble resin. Other water-soluble resins may, for example, be polyethanol, polyethylene oxide, polypropylene glycol, polypropylene oxide, polyvinyl alcohol, polypropylene decylamine, polyvinylpyrrolidone, arabic gum, polyacrylic acid. Sodium carbonate (soda), carboxymethyl fiber And the like, and may be used in combination of one or more of them. 12 201124279 The vinyl chloride-ethylene acetate copolymer which can be used in the present invention is a copolymer containing ethylene ethylene and ethylene acetate as a main component. Preferably, the copolymer of ethylene and ethylene acetate is 90% or more, more preferably 95% or more, and more preferably 98% or more. The ethylene ethylene-ethylene B which can be used in the present invention. The acid ester copolymer is a gas ethylene/ethylene acetate copolymer modified from a carboxyl group, an epoxy-modified ethylene/ethylene acetate copolymer, and a hydroxyl-modified ethylene/ethylene acetate. One or more kinds of the ester copolymers are selected. For example, as the gas-modified ethylene/ethylene acetate copolymer modified by the carboxyl group, the VMCH series commercially available from The Dow Chemical Company can be used. Further, the gas-ethylene-vinyl acetate copolymer used in the present invention preferably has a gas content of 70 to 90% by weight and an ethylene acetate content of 10 to 30% by weight. Further, the hydrogenated hydrocarbon resin used in the present invention has a molecular weight of 500 to 900. For example, the Arkon series sold by Arakawa Co., Ltd. is. Among them, Arkon-P125 is preferred. In the present invention, the hydrogenated hydrocarbon resin and the ethylene-ethylene acetate copolymer are preferably used in an amount of 0.5 to 3 parts by weight based on 100 parts by weight of the water-soluble polyester resin. The reason is that if the amount of the hydrogenated hydrocarbon resin and the ethylene-ethylene acetate copolymer is too small, a decrease in the adhesion force and a low-temperature peeling or surface cracking may occur, and if the amount of the resin is too large, the surface is sticky. The workability is lowered, and the state of the coated surface becomes thick and becomes difficult to use. 13 201124279 On the other hand, according to one embodiment of the present invention, the thickness of the soluble lubricating resin layer is 5~200 qing as the water in the slice, and the range is 30 to 120 rpm. After drying, if the resin layer of the house X does not reach 5 qing, it is: "The surface of the hole wall of the hole can be increased" - if it exceeds 200 _, it is formed by a small diameter hole. The drill bit and the resin layer are easily wrap, which may deteriorate the correctness. % perforation position

= After drying, the thickness of the resin layer can be adjusted, for example, by the spread of the lubricating resin composition, and the thickness can be adjusted in a known manner. Further, in the present invention, a method of applying a solution containing a water-soluble poly (P:::) fat to a metal thin film substrate is known, and it is not particularly limited. For example, the old coat, such as knife coating machine a - Ο, sound difference coating (c ° mma = = sewing "cloth mold (four) coating machine (four) lubricating resin composition coated on the right substrate, and the solvent can be borrowed It is dried by natural or hot air. At this time, the appropriate division for the material tree lining liquid is suitable for the coating condition, and the two degrees of the resin solution are too high or too low. ^, or the thickness of the resin layer is excessively thickened, or the continuous bulging on the surface, or the bubble is bad. In addition, the dry operation method of forming the cut-sliding tree is the industry. The method used is a method known to the manufacturer == ^, but most of the cases are selected by hot air drying, and the conditions of drying by the infrared ratio of (four) ° are due to drying "'Ί,所#秘的树脂The thickness of the layer and the coating speed can be appropriately selected from 201124279. On the other hand, in the present invention, the water-soluble lubricating resin composition may contain, for example, a leveling agent depending on the coating conditions and the surface of the non-coated body. , defoamer, fluidity improver, wetting agent, surfactant, etc. The method for perforating a printed circuit board by using the cover sheet of the present invention is to provide a cover sheet on the surface of the surface of the printed wiring board such as a copper foil laminate or a multilayer board, so that the surface of the substrate covering the sheet and the printed wiring The sheets are in contact with each other and are formed by opening the surface of the lubricating resin layer covering the sheet on the printed wiring board. * Hereinafter, the present invention will be described in more detail by way of examples. However, the embodiment is only used. The present invention is not intended to limit the scope of the present invention. Example 1: Production of a water-soluble lubricating resin composition for covering a sheet Example 1-(1) A 500 ml two-necked flask was replaced with nitrogen. At 135. 18g (l. 5 mol) 1,4-butanediol (as ethylene glycol), to 44. 43g (0. The content of 15 moles of bisinyl-5-supply acid iso- ruthenium salt (as a water-soluble component) was added. Then, join 0. As a catalyst, 2 g of tetrabutyl methacrylate was gradually heated in an air atmosphere, and the transesterification reaction was carried out while maintaining the internal temperature at 200 °C or lower. After the by-product sterol is completely discharged, it is put into 0. 85 moles of adipic acid (two tarts), 0. 2g of sour acid tetrabutyl g (catalyst), and added O. In the same manner, while the internal temperature is maintained at 200 ° C or lower, the glycerol trimethoate is used as a stabilizer, and the by-product water is allowed to flow out. After the end of the vinegarization reaction 15 201124279, add again to the reaction group. Lg of tetrabutyl phthalate and o. Lg of acetic acid zinc as a catalyst, o. As a stabilizer, lg of trimethyl phosphate was heated to 240 ° C while a vacuum was gradually applied to the reaction group to prepare ITorr or less. In the above reaction state, a condensation polymerization reaction was carried out for 100 minutes. In 100 parts by weight of the water-soluble polyester resin produced in this manner, the contents of VMCH and P-125 are respectively 0. After 1 part by weight of the mixture was mixed and cured by coating, the adhesion of the adhesive force to the surface was measured (in terms of a gas ethylene content of 85 parts by weight, a ethylene acetate S content of 14 parts by weight, and a maleic acid content). 1 part by weight of VMCH (carboxy-modified vinyl copolymer sold by The Dow Chemical Company) as a gas-ethylene-vinyl acetate copolymer, and P-125 (available by ARAKAWA Chemical Co., Ltd.) The molecular weight of the hydrogenated hydrocarbon resin is 750 Arkon). Example 1-(2) The water-soluble polyester resin is the same as the above-mentioned Example 1-(1), and the content of VMCH and P-125 is 0. 2 parts by weight were mixed, and then coated, and the state thereof was observed. Example 1-(3) The water-soluble polyester resin is the same as the above-mentioned Example 1-(1), and the contents of VMCH and P-125 are respectively 0. 3 parts by weight was mixed, and then coated, and the state thereof was observed. Example 1-(4) The water-soluble polyester resin is the same as the above-mentioned Example 1-(1), and the contents of VMCH and P-125 are respectively 0. 5 parts by weight were mixed, and then, 16 201124279, and the state was observed. Example 1 - (5) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(1), and the content of VMCH and P-125 was 1 part by weight, respectively, and then coated, and the state thereof was observed. Example 1 - (6) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(1), and the content of VMCH and P-125 was 2 parts by weight, respectively, and then coated, and the state thereof was observed. Example 1 - (7) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(1), and the content of VMCH and P-125 was 3 parts by weight, respectively, and then coated, and the state thereof was observed. Example 1 - (8) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(1), and the content of VMCH and P-125 was 5 parts by weight, respectively, and then coated, and the state thereof was observed. Example 1-(9) The water-soluble polyester resin was mixed with 1 part by weight of VMCH and 3 parts by weight of P-125 in the same manner as in the above Example 1-(1), and then coated, and observed. status. Example 1-(10) The water-soluble polyester resin was mixed with 3 parts by weight of VMCH and 1 part by weight of P-125 in the same manner as in the above Example 1-(1), and then coated in 17 201124279, And observe its status. Example 1-(11) The water-soluble polyester resin is 135. 18g (1. 5 moles of 1,4-butanediol (as ethylene glycol), to 59. 25g (0. 2 Mo) dimercapto-5-sulfonate isoindole sodium salt (as a water-soluble component), 94. 47g (0. 8 mol) of succinic acid (as a dicarboxylic acid) was added. The polymerization method was the same as that of the above Example 1-(1). In 100 parts by weight of the water-soluble polyester resin thus produced, the contents of VMCH and P-125 are respectively 0. After mixing 1 part by weight, the state was observed. Example 1-(12) The water-soluble polyester resin is the same as the above-mentioned Example 1-(11), and the contents of VMCH and P-125 are respectively 0. 2 parts by weight were mixed, and then coated, and the state thereof was observed. Example 1-(13) The water-soluble polyester resin is the same as the above-mentioned Example 1-(11), and the contents of VMCH and P-125 are respectively 0. 3 parts by weight was mixed, and then coated, and the state thereof was observed. Example 1-(14) The water-soluble polyester resin is the same as the above-mentioned Example 1-(11), and the contents of VMCH and P-125 are respectively 0. 5 parts by weight was mixed, and then coated, and the state thereof was observed. Example 1 - (15) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(11), and the content of 18 201124279 % VMCH and P-125 was 1 part by weight, respectively, and then coated, and observed. status. Example 1 - (16) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(11), and the content of VMCH and P-125 was 2 parts by weight, respectively, and then coated, and the state thereof was observed. Example 1 - (17) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(11), and the content of VMCH and P-125 was 3 parts by weight, respectively, and then coated, and the state thereof was observed. : Example 1-(18) - The water-soluble polyester resin was mixed with the contents of VMCH and P-125 in an amount of 5 parts by weight, respectively, and then coated, and the state thereof was observed, in the same manner as in the above Example 1-(11). . Example 1 - (19) The water-soluble polyester resin was mixed with 1 part by weight of VMCH and 3 parts by weight of P-125 in the same manner as in the above Example 1-(11), and then coated, and observed. status. Example 1 - (20) The water-soluble polyester resin was mixed with 3 parts by weight of VMCH and 1 part by weight of P-125 in the same manner as in the above Example 1-(11), and then coated, and observed. status. Example 1-(21) The water-soluble polyester resin is 135. 18g (1. 5 moles of 1,4-butanediol 19 201124279 (as ethylene glycol), to 44. 43g (0. 15 moles of dimercapto-5-sulfonate isoindole sodium salt (as a water-soluble component), to 50. 19g (0. 425 moles of succinic acid, 62. 11g (0. 425 moles of adipic acid (as a dicarboxylic acid) is added. The polymerization method was the same as that of the above Example 1-(21). In 100 parts by weight of the water-soluble polyester resin thus produced, the contents of VMCH and P-125 are respectively 0. After mixing 1 part by weight, the state was observed. Example 1-(22) The water-soluble polyester resin is the same as the above-mentioned Example 1-(21), and the contents of VMCH and P-125 are respectively 0. 2 parts by weight were mixed, and then coated, and the state thereof was observed. Example 1-(23) The water-soluble polyester resin is the same as the above-mentioned Example 1-(21), and the contents of VMCH and P-125 are respectively 0. 3 parts by weight was mixed, and then coated, and the state thereof was observed. Example 1-(24) The water-soluble polyester resin is the same as the above-mentioned Example 1-(21), and the contents of VMCH and P-125 are respectively 0. 5 parts by weight was mixed, and then coated, and the state thereof was observed. Example 1 - (25) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(21), and the content of VMCH and P-125 was 1 part by weight, respectively, and then coated, and the state thereof was observed. Example 1-(26) 20 201124279 The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(21), and the content of VMCH and P-125 was 2 parts by weight, respectively, and then coated, and the state thereof was observed. . Example 1 - (27) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(21), and the contents of VMCH and P-125 were respectively 3 parts by weight, and then coated, and the state thereof was observed. Example 1-(28) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(21), and the content of VMCH and P-125 was 5 parts by weight, respectively, and then coated, and the state thereof was observed. Example 1-(29) The water-soluble polyester resin was mixed with 1 part by weight of VMCH and 3 parts by weight of P-125 in the same manner as in the above Example 1-(21), and then coated, and observed. status. Example 1-(30) The water-soluble polyester resin was mixed with 3 parts by weight of VMCH and 1 part by weight of P-125 in the same manner as in the above Example 1-(21), and then coated, and observed. status. Example 1-(31) The water-soluble polyester resin is 135. 18g (1. 5 moles of 1,4-butanediol (as ethylene glycol), to 44. 43g (0. 15 moles of dimercapto-5-sulfonate isoindole sodium salt (as a water-soluble component), 49. 69g (0. 34 moles of adipic acid, 60. 23g (0. 51 moles of succinic acid (as dicarboxylic acid) was added. Poly 21 201124279 The method is the same as the method of the above embodiment ι-(ι). In 100 parts by weight of the water-soluble polyester resin thus produced, the contents of VMCH and P-125 are respectively 0. After mixing 1 part by weight, the state was observed. Example 1-(32) The water-soluble polyester resin is the same as the above-mentioned Example 1-(31), and the content of VMCH and P-125 is 0. 2 parts by weight were mixed, and then coated, and the state thereof was observed. Example 1-(33) The water-soluble polyester resin is the same as the above-mentioned Example 1-(31), and the contents of VMCH and P-125 are respectively 0. 3 parts by weight was mixed, and then coated, and the state thereof was observed. Example 1-(34) The water-soluble poly@ resin is the same as the above-mentioned Example 1-(31), and the contents of VMCH and P-125 are respectively 0. 5 parts by weight was mixed, and then coated, and the state thereof was observed. Example 1 - (35) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(31), and the content of VMCH and P-125 was 1 part by weight, respectively, and then coated, and the state thereof was observed. Example 1 - (36) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(31), and the content of VMCH and P-125 was 2 parts by weight, respectively, and then coated, and the state thereof was observed. 22 201124279 - Example 1-(37) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(31), and the content of VMCH and P-125 was 3 parts by weight, respectively, and then coated, and observed. status. Example 1-(38) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(31), and the content of VMCH and P-125 was 5 parts by weight, respectively, and then coated, and the state thereof was observed. Example 1-(39) The water-soluble polyester resin was mixed with 1 part by weight of VMCH and 3 parts by weight of P-125 in the same manner as in the above Example 1-(31), and then coated and observed. Its status. Example 1-(40) The water-soluble polyester resin was mixed with 3 parts by weight of VMCH and 1 part by weight of P-125 in the same manner as in the above Example 1-(31), and then coated, and observed. status. Example 1-(41) The water-soluble polyester resin is 135. 18g (1. 5 moles of 1,4-butanediol (as ethylene glycol), to 44. 43g (0. 15 mol) of dimethyl-5-sulfonate isoindole sodium salt (as a water-soluble component), to 36. 54g (0. 25 moles of adipic acid, 70. 85g (0. 6 moles of succinic acid (as dicarboxylic acid) is added. The polymerization method was the same as that of the above Example 1-(1). In 100 parts by weight of the water-soluble polyester resin thus produced, the contents of VMCH and P-125 are respectively 0. After mixing 1 part by weight, observe the state of 23 201124279. Example 1-(42) The water-soluble polyester resin is the same as the above-mentioned Example 1-(41), and the contents of VMCH and P-125 are respectively 0. 2 parts by weight were mixed, and then coated, and the state thereof was observed. Example 1-(43) The water-soluble polyester resin is the same as the above-mentioned Example 1-(41), and the content of VMCH and P-125 is 0. 3 parts by weight was mixed, and then coated, and the state thereof was observed. Example 1-(44) The water-soluble polyester resin is the same as the above-mentioned Example 1-(41), and the content of VMCH and P-125 is 0. 5 parts by weight was mixed, and then coated, and the state thereof was observed. Example 1 - (45) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(41), and the content of VMCH and P-125 was 1 part by weight, respectively, and then coated, and the state thereof was observed. Example 1-(46) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(41), and the content of VMCH and P-125 was 2 parts by weight, respectively, and then coated, and the state thereof was observed. Example 1-(47) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(41), and the content of VMCH and P-125 was 3 parts by weight, respectively, and then coated at 24 201124279, and the state thereof was observed. . Example 1 - (48) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(41), and the content of VMCH and P-125 was 5 parts by weight, respectively, and then coated, and the state thereof was observed. Example 1-(49) The water-soluble polyester resin was mixed with 1 part by weight of VMCH and 3 parts by weight of P-125 in the same manner as in the above Example 1-(41), and then coated, and observed. status. Example 1 - (50) The water-soluble polyester resin was mixed with 3 parts by weight of VMCH and 1 part by weight of P-125 in the same manner as in the above Example 1-(41), and then coated, and observed. status. Example 1-(51) The water-soluble polyester resin is 114. 9g (1. 275 moles of 1,4-butanediol, 23. 88g (0. 225 moles of diethylene glycol (as ethylene glycol), to 44. 43g (0. 15 moles of dimercapto-5-sulfonate isodecanoate (as a water-soluble component) to 36. 54g (0. 25 moles of adipic acid, 70. 85g (0. 6 moles of succinic acid (as dicarboxylic acid) is added. The polymerization method was the same as that of the above-mentioned Example 1 - (1). In 100 parts by weight of the water-soluble polyester resin thus produced, the contents of VMCH and P-125 are respectively 0. After mixing 1 part by weight, the state was observed. Example 1-(52) 25 201124279 The water-soluble polyester resin is the same as the above-mentioned Example 1-(51), and the contents of VMCH and P-125 are respectively 0. 2 parts by weight were mixed, and then coated, and the state thereof was observed. Example 1-(53) The water-soluble polyester resin is the same as the above-mentioned Example 1-(51), and the contents of VMCH and P-125 are respectively 0. 3 parts by weight was mixed, and then coated, and the state thereof was observed. Example 1-(54) The water-soluble polyester resin is the same as the above-mentioned Example 1-(51), and the contents of VMCH and P-125 are respectively 0. 5 parts by weight was mixed, and then coated, and the state thereof was observed. Example 1-(55) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(51), and the content of VMCH and P-125 was 1 part by weight, respectively, and then coated, and the state thereof was observed. Example 1 - (56) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(51), and the content of VMCH and P-125 was 2 parts by weight, respectively, and then coated, and the state thereof was observed. Example 1-(57) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(51), and the content of VMCH and P-125 was 3 parts by weight, respectively, and then coated, and the state thereof was observed. Example 1-(58) 26 201124279 The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(51), and the content of VMCH and P-125 was 5 parts by weight, respectively, and then coated, and the state thereof was observed. . Example 1-(59) The water-soluble polyester resin was mixed with 1 part by weight of VMCH and 3 parts by weight of P-125 in the same manner as in the above Example 1-(51), and then coated, and observed. status. Example 1-(60) The water-soluble polyester resin was mixed with 3 parts by weight of VMCH and 1 part by weight of P-125 in the same manner as in the above Example 1-(51), and then coated, and observed. status. Example 1-(61) Water-soluble polyester resin is 135. 18g (l. 5 moles of 1,4-butanediol (as ethylene glycol), to 44. 43g (0. 15 moles of dimercapto-5-sulfonate isoindole sodium salt (as a water-soluble component), to 3. 84g (0. 3 moles of adipic acid, 54. 32g (0. 46 moles of succinic acid, 14. 31g (0. The content of 09 moles of diacid acid ester (as a dicarboxylic acid) was added. The polymerization method was the same as that of the above Example 1-(1). In 100 parts by weight of the water-soluble polyester resin thus produced, the contents of VMCH and P-125 are respectively 0. After mixing 1 part by weight, the state was observed. Example 1-(62) The water-soluble polyester resin is the same as the above-mentioned Example 1-(61), and the contents of VMCH and P-125 are respectively 0. 2 parts by weight were mixed, and then proceeded to 27 201124279 for coating, and the state was observed. Example 1-(63) The water-soluble polyester resin is the same as the above-mentioned Example 1-(61), and the content of VMCH and P-125 is 0. 3 parts by weight was mixed, and then coated, and the state thereof was observed. Example 1-(64) The water-soluble polyester resin is the same as the above-mentioned Example 1-(61), and the contents of VMCH and P-125 are respectively 0. 5 parts by weight was mixed, and then coated, and the state thereof was observed. Example 1 - (65) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(61), and the content of VMCH and P-125 was 1 part by weight, respectively, and then coated, and the state thereof was observed. Example 1-(66) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(61), and the content of VMCH and P-125 was 2 parts by weight, respectively, and then coated, and the state thereof was observed. Example 1-(67) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(61), and the content of VMCH and P-125 was 3 parts by weight, respectively, and then coated, and the state thereof was observed. Example 1-(68) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(61), and the content of VMCH and P-125 was 5 parts by weight, respectively, and then coated at 28 201124279, and the state thereof was observed. . Example 1-(69) The water-soluble polyester resin was mixed with 1 part by weight of VMCH and 3 parts by weight of P-125 in the same manner as in the above Example 1-(61), and then coated, and observed. status. Example 1-(70) The water-soluble polyester resin was mixed with 3 parts by weight of VMCH and 1 part by weight of P-125 in the same manner as in the above Example 1-(61), and then coated, and observed. status. Example 1-(71) Water-soluble polyester resin was put into 77. 68g (0. 4 mol) of dimethyl phthalate (as dicarboxylic acid), 44. 43g (0. 15 moles of dimethyl-5-sulfonate isoindole sodium salt (as a water-soluble component), 135. 18g (1. 5 mol) of 1,4-butanediol (as ethylene glycol) and transesterification reaction, and then put 65. 76g (0. The esterification reaction is carried out with adipic acid (dicarboxylic acid) of 45 moles. The additive content and polymerization method were the same as those of the above Example 1-(1). In 100 parts by weight of the water-soluble polyester resin thus produced, the contents of VMCH and P-125 are respectively 0. After mixing 1 part by weight, the state was observed. Example 1-(72) The water-soluble polyester resin is the same as the above-mentioned Example 1-(71), and the contents of VMCH and P-125 are respectively 0. 2 parts by weight were mixed, and then coated, and the state thereof was observed. Example 1-(73) 29 201124279 The water-soluble polyglycol resin is the same as the above-mentioned Example 1-(71), and the content of VMCH and P-125 is 0. 3 parts by weight was mixed, and then coated, and the state thereof was observed. Example 1-(74) The water-soluble polyester resin is the same as the above-mentioned Example 1-(71), and the contents of VMCH and P-125 are respectively 0. 5 parts by weight was mixed, and then coated, and the state thereof was observed. Example 1 - (75) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(71), and the content of VMCH and P-125 was 1 part by weight, respectively, and then coated, and the state thereof was observed. Example 1-(76) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(71), and the content of VMCH and P-125 was 2 parts by weight, respectively, and then coated, and the state thereof was observed. Example 1-(77) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(71), and the content of VMCH and P-125 was further divided into 3 parts by weight, and then coated, and observed. status. Example 1 - (78) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(71), and the content of VMCH and P-125 was 5 parts by weight, respectively, and then coated, and the state thereof was observed. Example 1-(79) 30 201124279 The water-soluble polyester resin was mixed with 1 part by weight of VMCH and 3 parts by weight of p_125 in the same manner as in the above Example 1 (71), and then coated, and the state thereof was observed. . Example 1 - (80) The water-soluble polyester resin was mixed with 3 parts by weight of VMCH and 1 part by weight of P_125 in the same manner as in the above Example i-(7l), and then coated, and the state thereof was observed. Example 1-(81) Water-soluble polyester resin was put into 87. 39g (0. 45 moles of bismuth citrate (as diacidified acid)' 44. 43g (0. 15 moles of dimethyl_5_sodium sulphate isophthalate (as a water-soluble component), 135 18g (1 5 moles) of 14 butanediol (as ethylene glycol) for S After the exchange reaction, 're-investment 58. 46g (0. 4 (mole) of adipic acid (two tests) and (four) reaction. The additive content and polymerization method are the same as those described above for the implementation of m•(1). In 100 parts by weight of the water-soluble polymer resin produced in this manner, the contents of VMCH and P-(2) were mixed (10) parts by weight, respectively, and the state was observed. Example 1-(82) The water-soluble polyester resin was mixed with the contents of VMCH and P-125 in a part by weight, respectively, in the same manner as in the previous month, and then coated, and the state thereof was observed. . Example 1-(83) The same as Example 1-(81), the mixture was mixed in parts, and the content of the water-soluble polyester resin and the above-mentioned real VMCH and P-125 were respectively 〇3 weight 31 201124279, And observe its status. Example 1-(84) The water-soluble polyester resin is the same as the above-mentioned Example 1-(81), and the contents of VMCH and P-125 are respectively 0. 5 parts by weight was mixed, and then coated, and the state thereof was observed. Example 1-(85) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(81), and the content of VMCH and P-125 was further divided into 1 part by weight, and then coated, and observed. status. Example 1-(86) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(81), and the content of VMCH and P-125 was 2 parts by weight, respectively, and then coated, and the state thereof was observed. Example 1-(87) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(81), and the content of VMCH and P-125 was 3 parts by weight, respectively, and then coated, and the state thereof was observed. Example 1-(88) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(81), and the content of VMCH and P-125 was 5 parts by weight, respectively, and then coated, and the state thereof was observed. Example 1-(89) The water-soluble polyester resin was mixed with 1 part by weight of VMCH and 3 parts by weight of P-125 in the same manner as in the above Example 1-(81), and then advanced into 32 201124279. And observe its status. Example 1-(90) The water-soluble polyester resin was mixed with 3 parts by weight of VMCH and 1 part by weight of P-125 in the same manner as in the above Example 1-(81), and then coated, and observed. status. Example 1-(91) Water-soluble polyester resin was put into 90. 3g (0. 465 moles of di-decyl phthalate (as a dicarboxylic acid), 44. 43g (0. 15 moles of dimethyl-5-sulfonate isophthalic acid sodium salt (as a water-soluble component), 135. 18g (l. 5 mol) of 1,4-butanediol (as ethylene glycol) and transesterification reaction, and then put into 5. 26g (0. The esterification reaction is carried out by adipic acid (dicarboxylic acid) of 385 : Mohr). The additive content and the polymerization method were the same as those of the foregoing Example 1 - (1). In 100 parts by weight of the water-soluble polyester resin thus produced, the contents of VMCH and P-125 are respectively 0. After mixing 1 part by weight, the state was observed. Example 1-(92) The water-soluble polyester resin is the same as the above-mentioned Example 1-(91), and the content of VMCH and P-125 is 0. 2 parts by weight were mixed, and then coated, and the state thereof was observed. Example 1-(93) The water-soluble polyester resin is the same as the above-mentioned Example 1-(91), and the contents of VMCH and P-125 are respectively 0. 3 parts by weight was mixed, and then coated, and the state thereof was observed. Example 1-(94) 33 201124279 The water-soluble polyester resin is the same as the above-mentioned Example 1-(91), and the contents of VMCH and P-125 are respectively 0. 5 parts by weight was mixed, and then coated, and the state thereof was observed. Example 1 - (95) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(91), and the content of VMCH and P-125 was 1 part by weight, respectively, and then coated, and the state thereof was observed. Example 1 - (96) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(91), and the content of VMCH and P-125 was 2 parts by weight, respectively, and then coated, and the state thereof was observed. Example 1 - (97) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(91), and the content of VMCH and P-125 was 3 parts by weight, respectively, and then coated, and the state thereof was observed. Example 1 - (98) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(91), and the content of VMCH and P-125 was 5 parts by weight, respectively, and then coated, and the state thereof was observed. Example 1-(99) The water-soluble polyester resin was mixed with 1 part by weight of VMCH and 3 parts by weight of P-125 in the same manner as in the above Example 1-(91), and then coated, and observed. status. Example 1-(100) 34 201124279 The water-soluble polyester resin was mixed with 3 parts by weight of VMCH and 1 part by weight of P-125 in the same manner as in the above Example 1-(91), and then coated. Observe its status. Example 1-(101) Water-soluble polyester resin was put into 9. 71g (0. 05 Moer) of di-decanoic acid ester, 9. 71g (0. 05 Moer) isocyanuric acid diester (as a dicarboxylic acid), 44. 43g (0. 15 moles of dimercapto-5-sulfonate isodecanoate (as a water-soluble component), 135. 18g (1. After 5 transesterification of 1,4-butanediol (as ethylene glycol), it was again put into 109. 62g (0. The esterification reaction is carried out with 75 moles of adipic acid (dicarboxylic acid). The additive content and polymerization method were the same as those of the above-mentioned Example 1-(1). In 100 parts by weight of the water-soluble polyester resin thus produced, the contents of VMCH and P-125 are respectively 0. After mixing 1 part by weight, the state was observed. Example 1-(102) The water-soluble polyester resin is the same as the above-mentioned Example 1-(101), and the content of VMCH and P-125 is 0. 2 parts by weight were mixed, and then coated, and the state thereof was observed. Example 1-(103) The water-soluble polyester resin is the same as the above-mentioned Example 1-(101), and the contents of VMCH and P-125 are respectively 0. 3 parts by weight was mixed, and then coated, and the state thereof was observed. Example 1-(104) The water-soluble polyester resin is the same as the above-mentioned Example 1-(101), and the content of VM 2011 and P-125 is 0. 5 parts by weight was mixed, and then coated, and the state thereof was observed. Example 1 - (105) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(101), and the content of VMCH and P-125 was 1 part by weight, respectively, and then coated, and the state thereof was observed. Example 1 - (106) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(101), and the content of VMCH and P-125 was 2 parts by weight, respectively, and then coated, and the state thereof was observed. Example 1 - (107) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(101), and the content of VMCH and P-125 was 3 parts by weight, respectively, and then coated, and the state thereof was observed. Example 1 - (108) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(101), and the content of VMCH and P-125 was 5 parts by weight, respectively, and then coated, and the state thereof was observed. Example 1-(109) The water-soluble polyester resin was mixed with 1 part by weight of VMCH and 3 parts by weight of P-125 in the same manner as in the above Example 1-(101), and then coated, and observed. status. Example 1-(110) The water-soluble polyester resin was mixed with the content of 3 parts of 36 201124279 'VMCH, 1 part by weight of P-125, and then coated, as in the above Example 1-(101). And observe its status. Example 1-(111) Water-soluble polyester resin is 19. 42g (0. 1 mole) of di-decanoic acid ester, 77. 68g (0. 4 mol) of dimethyl isononanoate (as dicarboxylic acid) to 135. 18g (1. 5 moles of 1,4-butanediol (as ethylene glycol) to 44. 43g (0. 15 mol) of the decyl-5-sulfonic acid isononium salt (as a water-soluble component) is added, and after transesterification, it is again charged. 15g (0. 35 moles of adipic acid (dicarboxylic acid) for esterification. The additive content and polymerization method are the same as those of the above-mentioned Example 1-(1). : In 100 parts by weight of the water-soluble polyester resin thus produced, the contents of --VMCH and P-125 are respectively 0. After mixing 1 part by weight, the state was observed. Example 1-(112) The water-soluble polyester resin is the same as the above-mentioned Example 1-(111), and the contents of VMCH and P-125 are respectively 0. 2 parts by weight were mixed, and then coated, and the state thereof was observed. Example 1-(113) The water-soluble polyester resin is the same as the above-mentioned Example 1-(111), and the contents of VMCH and P-125 are respectively 0. 3 parts by weight was mixed, and then coated, and the state thereof was observed. Example 1-(114) The water-soluble polyester resin is the same as the above-mentioned Example 1-(111), and the contents of VMCH and P-125 are respectively 0. 5 parts by weight were mixed, and then applied to 37 201124279, and the state was observed. Example 1 - (115) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(111), and the content of VMCH and P-125 was 1 part by weight, respectively, and then coated, and the state thereof was observed. Example 1 - (116) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(111), and the content of VMCH and P-125 was 2 parts by weight, respectively, and then coated, and the state thereof was observed. Example 1-(117) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(111), and the content of VMCH and P-125 was 3 parts by weight, respectively, and then coated, and the state thereof was observed. Example 1 - (118) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(111), and the content of VMCH and P-125 was 5 parts by weight, respectively, and then coated, and the state thereof was observed. Example 1-(119) The water-soluble polyester resin was mixed with 1 part by weight of VMCH and 3 parts by weight of P-125 in the same manner as in the above Example 1-(111), and then coated, and observed. status. Example 1-(120) The water-soluble polyester resin was mixed with 3 parts by weight of VMCH and 1 part by weight of P-125 in the same manner as in the above Example 1-(111), and then coated at 38 201124279, and Observe its status. Example 1-(121) The water-soluble polyester resin is 13. 59g (0. 07 Moer) of di-decanoic acid ester, 64. 08g (0. 33 moles of isophthalic acid diterpene vinegar (as dicarboxylic acid) to 135. 18g (1. 5 moles of 1,4-butanediol (as ethylene glycol) to 44. 43g (0. 15 mol) of the decyl-5-sulfonic acid isononium salt (as a water-soluble component) is added, and after transesterification, it is re-introduced. 76g (0. 45 moles of adipic acid (dicarboxylic acid) for esterification. The additive content and polymerization method are the same as those of the above-mentioned Example 1-(1). In 100 parts by weight of the water-soluble polyester resin thus produced, the contents of VMCH and P-125 are respectively 0. After mixing 1 part by weight, the state was observed. Example 1-(122) The water-soluble polyester resin is the same as the above-mentioned Example 1-(121), and the content of VMCH and P-125 is 0. 2 parts by weight were mixed, and then coated, and the state thereof was observed. Example 1-(123) The water-soluble polyester resin is the same as the above-mentioned Example 1-(121), and the contents of VMCH and P-125 are respectively 0. 3 parts by weight was mixed, and then coated, and the state thereof was observed. Example 1-(124) The water-soluble polyester resin is the same as the above-mentioned Example 1-(121), and the contents of VMCH and P-125 are respectively 0. 5 parts by weight was mixed, and then coated, and the state thereof was observed. 39 201124279 Example 1-(125) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(121), and the content of VMCH and P-125 was 1 part by weight, respectively, and then coated, and the state thereof was observed. . Example 1-(126) The water-soluble poly-resin resin was the same as in the above-mentioned Example 1-(121). The content of VMCH and P-125 was 2 parts by weight, respectively, and then coated, and the state thereof was observed. Example 1 - (127) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(121), and the content of VMCH and P-125 was 3 parts by weight, respectively, and then coated, and the state thereof was observed. Example 1 - (128) The water-soluble polyester resin was mixed in the same manner as in the above Example 1-(121), and the content of VMCH and P-125 was 5 parts by weight, respectively, and then coated, and the state thereof was observed. Example 1-(129) The water-soluble polyester resin was mixed with 1 part by weight of VMCH and 3 parts by weight of P-125 in the same manner as in the above Example 1-(121), and then coated, and observed. status. Example 1-(130) The water-soluble polyester resin was mixed with 3 parts by weight of VMCH and 1 part by weight of P-125 in the same manner as in the above Example 1-(121), and then coated, and observed. status. 40 201124279 Comparative Example Comparative Example 1 The coating was carried out by using the water-soluble polyester resin of the above-mentioned examples alone without mixing the additives. Comparative Example 2 The coating was carried out by using the water-soluble polyester resin of the foregoing examples alone without mixing the additives. Comparative Example 3 The coating was carried out by using the water-soluble polyester resin of the foregoing examples alone without mixing the additives. Comparative Example 4 The coating was carried out by using the water-soluble polyester resin of the foregoing examples alone without mixing the additives. Comparative Example 5 The coating was carried out by using the water-soluble polyester resin of the foregoing examples alone without mixing the additives. Comparative Example 6 The coating was carried out by using the water-soluble polyester resin of the foregoing examples alone without mixing the additives. Comparative Example 7 The water-soluble polyester resin of the foregoing examples was used alone without mixing the additives, and Comparative Example 8 was used alone without using the additive, and the 1-(21) produced by the above Example 1-(1) was used alone. - (31) A water-soluble (tetra) resin produced by 1-(71) manufactured by 1-(61) manufactured by 1-(51), manufactured by 1-(41), manufactured by 1-(41), 41 201124279, which is coated. Comparative Example 9 The water-soluble poly-m, which was produced by the above-mentioned Example H81, was used alone, without coating, and was coated. Comparative Example 1 - (91) Manufactured without mixing the additive 卞. The coating was carried out by using the water-soluble (four) tree of the above Example 1 alone. Comparative Example 11 A water-soluble polyester resin produced without mixing an additive, Comparative Example 12 A water-soluble polyester resin produced without mixing an additive, and Comparative Example 13' was applied by using the above-mentioned examples alone. Coating was carried out using the foregoing examples alone. The water-soluble poly-lipid produced by the above-mentioned Example Η121) was coated under the non-kun & additive. Test Example 1: Adhesive force, surface measurement, front surface property, and surface cracking. The adhesive force of the product, and the lubricating resin group for the cover sheet of k. The force was used to crack the ir surface. The test piece was broken, and the two pieces of the coating were observed to be minus 2 (the rc was stored for 30 days, and it will be expressed. 'The ruler has a metal plate peeling off, and is as follows: ◎: The force is very good ± ® ^ H , , , 〇. Good; △: Ordinary; X: Bad (4) After coating surface, and the presence or absence of surface adhesion 42 201124279 By applying 10 pieces of coated test piece and applying pressure with a weight of lkg, after 24 hours Observe and express as follows. ◎: The surface is not very viscous; 〇: good; △: normal; X: bad surface cracking The coated test piece is stored at minus 20 ° C for 15 days, and the presence or absence of surface cracking is visually confirmed. As indicated below. ◎: no crack on the surface was very good; 〇: good; △: normal; X: poor [Table 1] After surface drying, surface viscous surface cracking Example 1 ◎ Example 2 ◎ Example 3 Δ ◎ Example 4 〇 ◎ Example 5 ◎ 〇 △ Example 6 ◎ 〇 Δ Example 7 ◎ Δ 〇 Example 8 ◎ ◎ Example 9 ◎ Δ 〇 Example 10 ◎ Δ 〇 Example 41 ◎ Example 42 ◎ Example 43 ◎ Example 44 ◎ Example 45 Δ 〇 Example 46 Δ 〇 Δ Example 47 ◎ Δ 〇 Example 48 ◎ 〇 43 201124279 Example 49 〇〇〇 Example 50 〇〇〇 Example 81 Δ ◎ Δ Example 82 Δ Δ Δ Example 83 〇 ◎ Δ Example 84 〇 ◎ Example 85 ◎ 〇〇 Example 86 ◎ 〇〇 Example 87 ◎ Δ ◎ Example 88 ◎ ◎ Example 89 ◎ 〇〇 Example 90 ◎ 〇〇 Example 91 A ◎ Example 92 Δ ◎ Example 93 Δ ◎ Example 94 Δ ◎ Δ Example 95 〇〇 Δ Example 96 〇〇〇 Example 97 ◎ Δ 〇 Example 98 ◎ Δ ◎ Example 99 〇〇〇Example 100 〇〇〇Example 121 Δ ◎ Δ Example 122 Δ ◎ Δ Example 123 Δ ◎ Δ Example 124 〇〇 Δ Example 125 〇〇〇 Example 126 ◎ Δ 〇 Example 127 ◎ ◎ Example 128 ◎ ◎ Example 129 〇〇〇 44 201124279 Example 130 〇〇〇 Comparative Example 1 ◎ Comparative Example 2 ◎ Comparative Example 3 〇 Comparative Example 4 〇 Comparative Example 5 ◎ Comparative Example 6 Δ Δ Δ Comparative Example 7 Δ Comparative Example 8 Δ Comparative Example 9 Δ 〇 Δ Comparative Example 10 〇〇〇 Comparative Example 11 〇 Δ 〇 Comparative Example 12 Δ 〇 Δ Comparative Example 13 〇 Δ 〇 With reference to the foregoing observation, it can be understood that VMCH and P-125 are obtained. When the amount of use is increased, the adhesion force is increased compared to when it is not used. However, if an excessive amount is used, the surface of the coated surface becomes sticky after drying, and the metal film may become adhered to each other during the production of the roll, which may cause the product to be poor. Further, when the drilling is performed, a bushing mark adheres to the drill fixing device to cover the sheet, and the work becomes impossible. On the other hand, in the comparative example using a small amount or not used, the viscosity of the surface after drying was greatly improved, but when it was stored at a low temperature for a long period of time, the adhesion to the metal film was poor, and surface cracking appeared. Or the phenomenon of peeling off from the metal film, which becomes the main cause of defects in drilling. Therefore, from the above test results, it can be confirmed that in the present invention, the hydrogenated hydrocarbon resin and the ethylene-ethylene acetate copolymer are used in an amount of 0. by weight based on 100 parts by weight of the water-soluble polyester resin. It is preferably 5 to 3 parts by weight. 45 201124279 Example 2 · Covering test results of the manufacturing of the escaping hole {The water-soluble lubricating resin composition manufactured by the above Example ” was applied to the wire using a hot air drying type difference coater" Cover sheet manufacturing. Use a light-to-dry roll (R〇11 To-type difference coating machine to apply a water-soluble lubricating tree (4) to a dry thickness of 5 to fine micron to a material with a thickness of 50 to micron. (4) The coated water-soluble ruthenium (4) component is removed, and the gelatin layer is smeared on the substrate, and dried in a hot air dryness. The hot air drying furnace is divided into 4~ 6 In order to remove the bubbles of the resin layer and obtain the smoothness of the surface, the temperature conditions of each section are set in the order of low temperature to high temperature. The lubricating sheet used for perforation is the thickness of the PCB and the PCB layer to be processed. The number of products, the material of (4) and the diameter of the perforated hole for reinforcement can be adjusted for the degree of rotation and lubrication of the grease layer. The dried resin-coated aluminum is used for the width direction according to the user's specifications. The cutting and rolling machine (Roll Slitting), in order to maintain the smoothness of the cover sheet, and the cutting machine for cutting in the long direction, etc., is formed into a sheet shape. Example 2-(1) The micronized lubricating resin composition of the above-mentioned embodiments (H99) and 丨7 (8) is coated on a 120-micron aluminum substrate, and a lubricant sheet for producing a perforation is manufactured as follows. The processing under the drilling conditions is based on the lowest plate of the processed PCB, and the evaluation is repeated.

PCB material/structure·· h/F (no-prime) fr-4 type PCB substrate, 4-layer structure, thickness 0.51T Stacking: 3 layers of PCB substrate are laminated, the lower part is the support board, and the upper part is The cover sheets of the invention are laminated. CNC drilling conditions: Japan Hitachi's rotating speed of 20 million RpM equipment; perforation diameter is 〇.2mm products; 100,000 hole processing reference cover sheet quality evaluation system (1) Cpk値 to review the positional accuracy of the drilled holes, And review the degree of leap of the perforated hole (the level outside the error when drilling); (2) compare the damage rate of the perforated drill bit with the number of hits (Hit) in the drilling, and grasp the number of damage; (3) The naked eye was observed with the cut state of the cut chip and the presence or absence of abnormality on the surface of the cover sheet. Fig. 2 is a result of AOI (Automated Optical Inspection) for performing the measurement of the hole punching accuracy of the cover sheet of Example 2-(1) of the present invention. As a result of the evaluation, it is understood that the cover sheet of the present invention can be reviewed for mass production. Table 1 below shows the test results of the perforation of the cover sheets produced by the lubricating resin layers of the above-mentioned Examples 1-(96), 1-(99), and 1-(100). [Table 2] Example 1-(96) Example 1-(99) Test item 1 time 2 times 3 times Remarks CPK 1.777 1.732 1.614 Benchmark: > 1.33 Perforation damage No benefit slice discharge force / Appearance state Good good Good CPK 1.675 1.712 1.547 Benchmark: >1.33 Perforation damage is not beneficial • »»> Benefit 47 201124279 Slice discharge force / good appearance Good good Example 1 - (100) CPK 1.814 1.65 1.64 Benchmark: > 1.33 Perforation damage without or without slice The discharge force/appearance state is good and good. Example 2-2 (2) In order to evaluate the effectiveness of the cover sheet of the present invention, a general aluminum sheet, a product of Mitsubishi Gas Chemical Co., Ltd. of Japan, and a cover sheet of the present invention are as follows. Drill holes under normal conditions and compare the quality of the evaluation. The cover sheet of the present invention was coated on a 120 μm aluminum substrate with 40 μm of the lubricating resin composition of the above Example 1-(96), and was produced by the method of the above Example 2.

PCB material/structure: H/F (halogen-free) FR-4 type PCB substrate, thickness 0.6T Stacking: stacking 4 PCB substrates, the lower part is the support plate, and the upper part is the laminated cover of the invention. . CNC drilling conditions: Hitachi's rotation speed of 160,000 RPM equipment; perforation diameter of 0.2 mm product; 20,000 hit processing standard evaluation item was carried out in the same manner as in Example 1. Figures 3 and 4 show AOI results when aluminum flakes (0.15T) not covered with lubricant are used. Fig. 5 and Fig. 6 show the AOI results when the LE-800 of Japan MGC (Mitsubishi Gas Chemical) Co., Ltd. was used. Fig. 7 and Fig. 8 are AOI results when a cover sheet coated with a lubricating resin produced in Example 2-(2) of the present invention was used. 48 201124279 Table 2 below shows the test results of the punching of the cover sheet manufactured by the products of the Japanese MGC company and the lubricating resin composition of the present invention. 【table 3】

Cpk(UL=75 μιιι) Figure 3 2.181 Perforation damage Appearance status

Burr occurred in Japan MGC Example: ^L__ Figure 5 Figure 6 Figure 7 Figure 8 - ^532 2.475 2.710 2.419 2.918 Biirr Nothing Good and Good Good, good, good, good, good, good, good The positional accuracy of the hole when the cover sheet of the present invention is 'drilled_' is greatly improved, and the crack of the drill bit is also low. Furthermore, compared with the currently widely used system, it is possible to have a characteristic that the positional accuracy is partially improved. Example 2 (3) A lubricant composition of the lubricating resin composition of the present invention (Example 1-(96)) of 5 μm was applied to a 7Q micron-reduced material to produce a lubricated (four) sheet for perforation. . The manufactured cover sheet was processed and evaluated in the following drilling conditions.

PCB material/structure: H/F (no element) FR 4 type pCB substrate, 4-layer structure, thickness 0.48T Stacking: 2 layers of PCB substrate are laminated, the lower part is the support board, and the upper part is the cover of invention The sheets are laminated. CNC drilling conditions: Rotating speed of 180,000 RpM equipment; perforation diameter of 0·15mm product; 70,000 hole processing standard. Fig. 9 is the AOI result of the use of the Korean creation company's product 49 201124279. Fig. 10 is a graph showing the results of A01 after drilling using the product of Example 2-(3) of the present invention. [Table 4] Korean competitor company Figure 9 Example 2-(3) Figure 10 Cpk (UL=75 um) 3.287 3.835 Perforation damage without slice discharge force / Good appearance. As the above results, it can be understood that In comparison with the competitors currently in use, the quality of the cover sheet coated with the lubricative resin of Example 3 is excellent, and it is shown to be applicable to actual production. Example 2 (4) A 60 μm lubricating resin composition of the present invention (Example ι_(96)) was applied onto a 120 μm aluminum substrate to prepare a smoothing agent sheet for perforation. The manufactured cover sheet was processed in the following drilling conditions and evaluated for °. In order to verify the deviation of each axis of the drilling machine, the same product is evaluated on the six axes of the drilling machine to verify the error with respect to the machining machine. Fig. 11 and Fig. 12 show the results of the 'οι evaluation using the products of the competitors of the Korean company which are currently used in the industry, and the products of the embodiment 2_(4) of the present invention. 【table 5】

50 201124279 8 1 1.846 2.458 1.310 - 2.153 2.533 1.463 - 2 1.743 1.724 1.496 - 2.133 2.126 1.580 - 3 - - - - - - - - 4 2.662 2.620 1.869 1 2.711 2.614 1.949 1 5 2.244 1.981 1.758 1 2.334 2.035 1.837 1 6 1.716 1.913 1.514 - 2.447 2.450 1.746 1 Total 10.211 10.696 7.947 2 11.778 11.758 8.575 3 Average 2.042 2.139 1.589 0.4 2.356 2.352 1.715 0.6 [Table 6] Example No. Axis No compensation compensation CPK XY 80 μηι (point) CPK X Υ 80 jL /mt (point) 8 1 1.715 1.514 1.548 1 2.160 1.832 1.706 1 2 2.417 2.301 1.849 1 2.574 2.424 1.926 1 3 2.749 2.512 2.047 - 3.037 2.606 2.286 1 4 2.433 2.554 1.733 - 2.667 2.665 1.902 - 5 2.822 2,285 2.305 - 2.941 2.415 2.324 - 6 1.854 2.384 1.288 1 2.160 2.478 1.437 1 Total 13.990 13.550 10.770 3 15.539 14.420 11.581 4 Average 2.332 2.258 1.795 0.5 2.590 2.403 1.930 0.7 As can be seen from the above evaluation results, independent of the deviation of the axes of the drilling machine, Example 2 (4) The cover sheet has excellent contrast quality with the existing products in use. Even if it is suitable for actual mass production, it shows excellent evaluation results. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1a is a photograph showing a crack-free surface of a cover sheet of the present invention; and Fig. 1b is a photograph showing a surface of a cover sheet of a comparative example in which a crack is formed on the surface. Fig. 2A is an AOI for performing the hole punching of the cover sheet of the embodiment 2-(1) of the present invention (automatic optical scanning: Automated 51 201124279)

Optical Inspection) results. Fig. 2B is an A0I result of the measurement of the hole precision of the perforation processing of the cover sheet of Example 2-(1) of the present invention. Fig. 2C is an A0I result of the measurement of the hole precision of the perforation of the cover sheet of Example 2-(1) of the present invention. Figure 3 shows the A0I results when an aluminum foil (〇. 15T) not covered with a lubricant is used. Figure 4 shows the A0I results when using an aluminum foil (〇. 15T) that is not covered with a lubricant. Figure 5 shows the A0I results when using the LE-800 of Japan MGC (Mitsubishi Gas Chemical). Fig. 6 shows the A0I results when using LE_800 of Japan mgc (Mitsubishi Gas Chemical). Fig. 7 is an A0I result when the cover sheet coated with the lubricating resin produced in Example 2-(2) of the present invention was used. Fig. 8 is a graph showing the results of A〇I when a cover sheet coated with a lubricating resin produced in Example 2-(2) of the present invention was used. Figure 9 shows the A0I results of the company's products created in Korea, which is currently used in the industry. The 10th circle is the A0I result after drilling the product of the embodiment 2-(3) of the present invention. Figure 11 is an AII result of evaluation of the article of Example 2-(4) of the present invention. Figure 12 is an evaluation of the product of Example 2-(4) of the present invention. 52 201124279 • AOI results. [Main component symbol description] (none) 53

Claims (1)

201124279 VII. Patent application scope: 1. A cover sheet for perforating a printed circuit board, comprising a metal film substrate and a water-soluble lubricating resin layer formed on the substrate, wherein the water-soluble lubricating resin layer It comprises 100 parts by weight of a water-soluble polyester resin, 0.5 to 3 parts by weight of a gas ethylene-ethylene acetate copolymer, and 0.5 to 3 parts by weight of a hydrogenated hydrocarbon resin. 2. The cover sheet for perforating a printed circuit board according to the first aspect of the invention, wherein the metal film substrate is an aluminum film having a thickness of 0.05 to 0.2 mm. 3. The cover sheet for perforating a printed circuit board according to claim 1, wherein the water-soluble polyester resin has a molar ratio of 1:0.1:0.8 to a molar ratio of 2:0.2:1.0, so that a Polyol: b) 1.5 parts by weight of a water-soluble component: c) a carboxylic acid or a carboxylic acid ester is produced by reaction. 4. The cover sheet for perforation of a printed circuit board according to claim 3, wherein the water-soluble polyester resin has a molar ratio of 1.5:0.15:0.85, a) a polyol: b) a water-soluble component: c) Manufactured by reaction of a carboxylic acid or a carboxylic acid ester. 5. The cover sheet for perforating a printed circuit board according to claim 3, wherein the polyol is 1,4-butanediol, diethylene glycol, propylene glycol, neopentyl glycol, diethylene glycol, Select 1 from the group consisting of polyethylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,6-hexanediol More than one. 6. The cover sheet for perforating a printed circuit board according to item 3 of claim 3, wherein the water-soluble component is a sulfonic acid metal salt. 7. The cover sheet for perforating a printed circuit board according to claim 4, wherein the foregoing acid-recovering metal salt is composed of dimethyl-5-supply acid sodium sulphate, dimercapto-4-sulfonate One or more selected from the group consisting of sodium acid isophthalide, sodium dimethyl-5-sulfonate sodium citrate, and diethyl 5-sulfonate sodium citrate. 8. The cover sheet for perforating a printed circuit board according to claim 3, wherein the carboxylic acid or carboxylic acid ester is derived from adipic acid, succinic acid, diacid acid ester, dinonyl phthalate, and the like. Dimethyl phthalate, glutaric acid, azelaic acid, succinic anhydride, dimethyl succinate, dimethyl glutarate, adipic acid: dimethyl ester, citric acid, citric acid, isophthalic acid Among the groups formed, 1 '; 9. The cover sheet for perforating a printed circuit board according to claim 1, wherein the water-soluble polyester resin has a molecular weight of 10,000 to 100,000. 10. The cover sheet for perforation of a printed circuit board according to claim 1, wherein the gas ethylene-ethylene acetate copolymer is a carboxyl group-modified vinyl chloride/ethylene acetate copolymer, epoxy One or more selected from the group consisting of a modified ethylene/ethylene acetate copolymer and a hydroxy-modified ethylene/ethylene acetate copolymer. 11. The cover sheet for perforating a printed circuit board according to claim 1, wherein the gas-ethylene content of the gas-ethylene-vinyl acetate copolymer is 70 to 90% by weight, and the ethylene acetate content is 10%. 30% by weight. 12. The cover sheet of the printed circuit board for perforating according to claim 1 of claim 1 is a film of 55, 2011,279, wherein the hydrogenated hydrocarbon resin has a molecular weight of 500 to 900. 13. The cover sheet for perforating a printed circuit board according to claim 1, wherein the water-soluble lubricating resin layer has a thickness of 5 to 200 μm. A water-soluble lubricating resin composition characterized by comprising 100 parts by weight of a water-soluble polyester resin, 0.5 to 3 parts by weight of a gas ethylene-ethylene acetate copolymer, and 0.5 to 3 parts by weight of hydrogenated A hydrocarbon resin is a water-soluble lubricating resin composition which forms a cover sheet for perforation of a printed circuit board. 15. The water-soluble lubricating resin composition according to claim 14, wherein the water-soluble polyester resin has a molar ratio of 1:0.1:0.8 to a molar ratio of 2:0.2:1.0, so that a) is plural Alcohol: b) 1.5 parts by weight of a water-soluble component: c) a carboxylic acid or a carboxylic acid ester is produced by reaction. A method for producing a water-soluble lubricating resin composition for covering a sheet, characterized in that in the method for producing a lubricating resin composition for forming a cover sheet for perforating a printed circuit board, the method comprises the steps of: producing a water-soluble polyester resin The step is to use a molar ratio of 1:0.1:0.8 to a molar ratio of 2:0.2:1.0 to a) a polyol: b) 1.5 parts by weight of a water-soluble component: c) a carboxylic acid or a carboxylic acid ester After the esterification reaction, the product is further subjected to condensation polymerization; and 100 parts by weight of the water-soluble polyester resin, 0.5 to 3 parts by weight of a copolymer of ethylene and ethylene acetate, and 0.5 to 3 parts by weight. The step of mixing and hardening the hydrogenated hydrocarbon resin. 17. The method of producing a water-soluble lubricating resin composition for covering a sheet according to claim 16, wherein the water-soluble polyester resin is manufactured by the method of the following steps in 56 201124279: causing acid or a step of transesterification of a retinic acid ester with a water-soluble component; in the foregoing step, a step of esterifying a water-soluble carboxylic acid with a polyhydric alcohol to obtain an intermediate product; and condensing the intermediate product The step of polymerization. 18. A method of producing a water-soluble lubricating resin composition for covering a sheet according to claim 16, wherein the esterification reaction is carried out at a temperature of from 160 to 220 ° C. 19. The method of producing a water-soluble lubricating resin composition for covering a sheet according to claim 16, wherein the condensation polymerization is carried out under reduced pressure at a temperature of from 230 to 260 °C. 20. The method of claim 16, wherein the esterification reaction is selected from the group consisting of tetrabutyl titanate, zinc acetate, calcium acetate, magnesium acetate, and phosphoric acid. It is carried out by using one or more kinds of catalysts of methyl ester, triphenyl phosphate, and cobalt acetate. 57