KR20110021629A - Entry sheet for drilling hole in printed circuit boards, lubricant resin composition and method for preparing the same - Google Patents

Abstract

PURPOSE: An entry sheet for boring a printed circuit board, capable of improving the uniformity and accuracy of holes, and water-soluble lubricant resin composition used for the same, and a manufacturing method thereof are provided to prevent the cracks on the surface of an entry sheet in spite of a lower temperature. CONSTITUTION: An entry sheet for boring a printed circuit board comprises a metallic foil layer(a) and a water-soluble lubricant resin layer(b). The water-soluble lubricant resin layer is formed on a printed circuit board. The water-soluble lubricant resin layer contains water-soluble polyester resin 100wt.%, vinyl chloride-vinyl acetate copolymer 0.5~3wt.%, and hydrogenated hydrocarbon resin 0.5~3 wt.%.

Description

Entry sheet for perforation of printed circuit board, water-soluble lubricating resin composition and manufacturing method therefor {Entry Sheet for Drilling hole in Printed Circuit Boards, Lubricant Resin Composition and Method for Preparing the Same}

The present invention relates to an entry sheet for perforating a printed circuit board, and more particularly, to a printed circuit having excellent uniformity and accuracy of perforated holes, excellent bonding force to a metal thin film, and no cracking or peeling on the surface even at low temperatures. An entry sheet for perforating a substrate and a method for producing a water-soluble lubricant resin composition formed on the entry sheet.

Recently, high-quality drilling techniques such as hole position accuracy have been demanded in order to improve reliability or increase density in printed circuit boards. To this end, entry sheets are used for perforation of printed circuit boards. Entry sheet is widely used because it can disperse heat generated during hole processing, it can lubricate as the coating layer of entry sheet melts during drilling, and can be washed with water during hole processing when water-soluble resin is used. .

In this regard, Japanese Patent Laid-Open No. 2003-175412 discloses a method of forming a thin film sheet by mixing a water-soluble resin and a water-insoluble lubricant and attaching it to a thin plate such as aluminum. As water-soluble resins, water-soluble resins such as polyethylene glycol, polyethylene oxide, polypropylene glycol, polyvinyl alcohol, polyacrylamide, polyether ester and the like are disclosed.

In addition, Japanese Patent Application Laid-Open No. 2003-136485 forms a coating film of a thermosetting resin having an average thickness of 1-10 microns on one surface of an aluminum sheet having a thickness of 20-200 microns, and attaching a water-soluble resin sheet having a thickness of 20-500 microns thereon. A method is disclosed.

However, these methods are susceptible to heat deterioration, the thickness of the resin layer is thick, bubbles are generated due to the low boiling point during the coating process of the water-soluble resin composition, and the accuracy of the hole position is reduced by the bubbles remaining in the resin layer. There is a problem falling.

Meanwhile, Korean Patent Publication No. 10-2007-15783 dissolves a resin composition containing a water-soluble resin in a mixed solvent containing water and isopropyl alcohol and having a water: isopropyl alcohol mixing ratio of 60:40 to 95: 5% by weight. A method of producing a resin layer on the substrate is disclosed by applying the solution to a sheet-like substrate and drying the applied solution after obtaining the solution. However, this method has a problem that the manufacturing process is complicated and it is difficult to control the solubility in organic solvents and water using a plurality of resins.

In addition, Korean Patent No. 10-672775 discloses a coating material for lubricity sheets, wherein a water-soluble copolyester resin having a number average molecular weight of 10,000 to 80,000 and a polyether ester having a molecular weight of 3,000-40,000 having an ether group and an ester group having an acid at the terminal group at the same time A method of using a water-soluble lubricant and a polymer containing a molecular weight of 600-1000 ether groups has been proposed. However, when the lubricant material is directly coated on the metal substrate without the primer layer, there is a problem that the adhesive strength is lowered and peeling occurs in the winter and fine cracks in the coating layer.

Therefore, it is necessary to develop a new entry sheet having excellent adhesion but no surface stickiness.

The first technical problem to be solved by the present invention is the excellent uniformity and accuracy of the holes to be drilled, there is no surface stickiness good work characteristics, excellent adhesion to the metal thin film is a phenomenon that cracks or peeling on the surface even at low temperatures It is to provide an entry sheet for perforation of a printed circuit board without this.

The second technical problem to be solved by the present invention is to provide a water-soluble lubricant resin composition for forming the entry sheet for perforating the printed circuit board.

The third technical problem to be solved by the present invention relates to a method for producing the water-soluble lubricant resin composition.

The present invention, in order to solve the first technical problem, a metal thin film substrate; And a water-soluble lubricant resin layer formed on the substrate, wherein the water-soluble lubricant resin layer is 100 parts by weight of a water-soluble polyester resin, 0.5 to 3 parts by weight of a vinyl chloride-vinylacetate copolymer, and a hydrogenated hydrocarbon resin 0.5 Provided is an entry sheet for perforation of a printed circuit board, comprising: 3 parts by weight.

According to one embodiment of the invention, the metal thin film substrate is preferably an aluminum thin film of 0.05 ~ 0.2 mm thick.

According to another embodiment of the present invention, the water-soluble polyester resin is a) polyol: b) 1.5 parts by weight of a water-soluble component: c) carboxylic acid or carboxylic acid ester in a molar ratio of 1: 0.1: 0.8 to 2: 0.2: 1.0 It may be prepared by the reaction, and preferably prepared by reacting at a molar ratio of 1.5: 0.15: 0.85.

According to another embodiment of the present invention, the polyol is 1,4-butanediol, diethylene glycol, propylene glycol, neopentyl glycol, diethylene glycol, polyethylene glycol, 1,3-propanediol, 1,2-butanediol, 1 It can be selected from the group consisting of, 3-butanediol, 1,4-butanediol, 1,6-hexanediol.

According to another embodiment of the present invention, the water-soluble component may be a sulfonic acid alkali metal salt, dimethyl-5-sulfoisophthalate sodium salt, dimethyl-4-sulfoisophthalate sodium salt, dimethyl-5- sulfotere It is preferable to select at least one type from the group consisting of phthalate sodium salt and diethyl-5-sulfoterephthalate sodium salt.

According to another embodiment of the present invention, the carboxylic acid or carboxylic acid ester is adipic acid, succinic acid, dibasic ester, dimethyl terephthalate, dimethyl isophthalate, glutaric acid, sebacic acid, succinic anhydride, dimethyl succinate, dimethyl glycol It may be selected from the group consisting of rutarate, dimethyl adipate, terephthalic acid, phthalic acid, isophthalic acid, the molecular weight of the water-soluble polyester resin is preferably 10,000 ~ 100,000.

According to another embodiment of the present invention, the vinyl chloride-vinylacetate copolymer is a carboxyl-modified vinyl chloride / vinylacetate copolymer, an epoxy-modified vinyl chloride / vinylacetate copolymer, a hydroxy-modified vinyl chloride / vinylacetate One or more of the copolymers may be selected, the content of vinyl chloride is 70 to 90% by weight, and the content of vinyl acetate is preferably 10 to 30% by weight.

According to another embodiment of the present invention, the hydrogenated hydrocarbon resin preferably has a molecular weight of 500 ~ 900.

According to another embodiment of the present invention, the thickness of the water-soluble lubricant resin layer is preferably 5-200 μm.

In order to solve the second technical problem, the present invention provides a water-soluble lubricating resin composition for forming an entry sheet for perforation of printed circuit board, 100 parts by weight of water-soluble polyester resin, 0.5 to 3 parts by weight of vinyl chloride-vinylacetate copolymer and It provides a water-soluble lubricant resin composition comprising 0.5 to 3 parts by weight of the hydrogenated hydrocarbon resin.

According to one embodiment of the present invention, the water-soluble polyester resin is a) polyol: b) 1.5 parts by weight of a water-soluble component: c) carboxylic acid or carboxylic acid ester in a molar ratio of 1: 0.1: 0.8 to 2: 0.2: 1.0 It may be prepared by the reaction, more preferably prepared by reacting at a molar ratio of 1.5: 0.15: 0.85.

The present invention, in order to solve the third technical problem, polyol: water-soluble component: carboxylic acid or carboxylic acid ester by reacting in a molar ratio of 1: 0.1: 0.8 ~ 2: 0.2: 1.0 and then polycondensation to prepare a water-soluble polyester resin Making;

Based on 100 parts by weight of the water-soluble polyester resin, 0.5 to 3 parts by weight of a copolymer of vinyl chloride and vinyl acetate and 0.5 to 3 parts by weight of a hydrogenated hydrocarbon resin by mixing and curing; an entry sheet comprising a It provides a method for producing a water-soluble lubricant resin composition.

In addition, according to one embodiment of the present invention, the water-soluble polyester resin is a step of transesterifying the carboxylic acid or carboxylic acid ester and the water-soluble component; Esterifying the carboxylic acid and polyol solvated in the step to obtain an intermediate product; And condensation polymerization of the intermediate product, wherein the ester reaction is performed at a temperature of 160 to 220 ° C., and the polycondensation reaction is performed under reduced pressure at a temperature of 230 to 260 ° C. It is preferable.

In addition, according to another embodiment of the present invention, the ester reaction may be carried out using one or more catalysts selected from tetrabutyl titanate, zinc acetate, calcium acetate, magnesium acetate, trimethyl phosphate, triphenyl phosphate, and cobalt acetate. have.

The entry sheet for perforation of the printed circuit board according to the present invention is excellent in the uniformity and accuracy of the perforated hole, excellent bonding force to the metal thin film, there is no phenomenon that cracks or peeling on the surface even at low temperatures. In addition, a separate lubrication component or additional primer layer is not required, so the manufacturing process is simple and very economical.

Figure 1a is a photograph showing a crack-free surface of the entry sheet according to the present invention, Figure 1b is a photograph showing the surface of the entry sheet of the comparative example in which a crack is formed on the surface.
2A, 2B and 2C are AOI (Automated Optical Inspection) results of measuring the drilled hole precision of the entry sheet according to Example 2- (1) of the present invention.
3 and 4 show AOI results when an aluminum sheet (0.15T) without lubricant is used.
5 and 6 show AOI results when LE-800 manufactured by Mitsubishi Gas Chemical Co., Ltd., Japan.
7 and 8 show AOI results when the lubricant resin coated entry sheet prepared in Example 2- (2) of the present invention was used.
FIG. 9 is an AOI result using a domestic creative company product currently being applied to a company, and FIG. 10 is an AOI result after drilling using the product of Example 2- (3) of the present invention.
11 and 12 show AOI results of evaluating products according to Example 2- (4) of the present invention.

The present invention will be described in more detail with reference to the following examples.

Entry sheet for punching a printed circuit board according to the present invention is a metal thin film substrate; And a water-soluble lubricant resin layer formed on the substrate, wherein the water-soluble lubricant resin layer is 100 parts by weight of a water-soluble polyester resin, 0.5 to 3 parts by weight of a vinyl chloride-vinylacetate copolymer, and 0.5 to 3 parts by weight of a hydrogenated hydrocarbon resin. It is characterized by including.

It is preferable that the metal thin film base material used for this invention is an aluminum thin film of 0.05-0.2 mm thickness.

In addition, the water-soluble polyester resin forming the water-soluble lubricating resin layer according to the present invention is prepared by reacting a) a polyol: b) a water-soluble component: c) a carboxylic acid or a carboxylic acid ester in a molar ratio of 1: 0.1: 0.8 to 2: 0.2: 1.0. It is more preferable to manufacture by reacting in the molar ratio of 1.5: 0.15: 0.85.

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-butanediol, 1,4-butanediol , 1,6-hexanediol may be selected from the group consisting of 1,4-butanediol, diethylene glycol and the like.

In addition, the water-soluble component used in the water-soluble polyester resin of the present invention is a component having a functional group used to make the lubricant resin water-soluble, a material having a -COOH group, -NH ₂ group, and / or -SO ₃ H group Or salts thereof. Representative solubilizing ingredients include sulfonic acid alkali metal salts, specifically, dimethyl-4-sulfoisophthalate sodium salt, dimethyl-5-sulfoisophthalate sodium salt, dimethyl-5-sulfoterephthalate sodium salt, di One or more types of ethyl-5-sulfoterephthalate sodium salt can be selected and used.

In addition, the carboxylic acid or carboxylic acid ester used in the water-soluble polyester resin of the present invention is adipic acid, succinic acid, dibasic ester, dimethyl terephthalate, dimethyl isophthalate, glutaric acid, sebacic acid, succinic anhydride, dimethyl succinate, dimethyl It may be selected from the group consisting of glutarate, dimethyl adipate, terephthalic acid, phthalic acid, isophthalic acid. At this time, the molecular weight of the water-soluble polyester resin is preferably about 10,000 ~ 100,000, more preferably about 20,000 ~ 60,000, most preferably about 30,000-50,000. When the molecular weight exceeds 100,000, the synthesis becomes difficult, and when the molecular weight of the polymer is low, there is a problem that processing characteristics during drilling or coating are lowered.

On the other hand, in order to prepare the water-soluble polyester resin according to the present invention, it is reacted with an alkali metal salt of sulfonic acid to impart water solubility to the carboxylic acid or the carboxylic acid ester. At this time, the sulfonic acid alkali metal salt and the carboxylic acid are preferably reacted at a molar ratio of 0.1: 0.8 to 0.2: 1.0, and most preferably at a molar ratio of 0.15: 0.85. Too low or too high metal salt content may degrade water solubility and coating properties.

The solvated carboxylic acid thus prepared is subjected to an ester reaction or transesterification reaction with a polyol under a catalyst and an additive, and condensation polymerization under vacuum conditions by addition of a polycondensation reaction additive to the intermediate product. The polyol and the carboxylic acid solvated are preferably reacted in a molar ratio of 1: 0.8 to 2: 1, most preferably in a molar ratio of 1.5: 0.85.

At this time, a suitable esterification temperature is 160-220 degreeC. If it is 160 degrees C or less, reaction rate will become slow and if it is 220 degrees C or more, thermal decomposition of a polymerization reaction may occur.

In addition, if the content of the polyol used is too low, it is difficult to obtain a high molecular weight polymer, if the content is too high side reaction may occur, the amount of by-products are increased, the reaction rate is also slowed.

After the ester reaction or transesterification reaction is completed, the polycondensation catalyst and various additives are added to the polycondensation reaction under reduced pressure at the reaction temperature of 230 ~ 260 ℃. If the reaction temperature is 230 ° C. or lower, the polycondensation reaction is slowed down, and if it is 260 ° C. or higher, thermal decomposition of the polymer occurs, making it difficult to obtain a high molecular weight polymer. In addition, during the polycondensation reaction, a high vacuum condition is established under reduced pressure, but if the pressure is 2torr or more, it is difficult to remove side reaction substances, oligomers, excess glycol, etc. generated during the reaction, and it is difficult to obtain a high molecular weight polymer. Therefore, it is desirable to maintain a vacuum degree of 0.5 torr or less.

At the beginning or end of the ester reaction, transesterification, or polycondensation reaction, various additives may be added to promote the polymerization reaction, and the catalyst may be tetrabutyltin titanate, zinc acetate, calcium acetate, magnesium acetate, trimethyl. Mixtures of one or more selected from phosphate, triphenylphosphate, cobalt acetate can be used. The amount of use is appropriately 0.03 to 0.5 mol% based on the total resin, but less than 0.03 mol% slows down the reaction rate and makes it difficult to obtain a high molecular weight resin. In addition, if the amount is 0.5 mol% or more, the reaction rate is high, but the color of the polymerization product is dark brown due to yellowing, and pyrolysis occurs.

In addition, in this invention, the said water-soluble polyester resin can be mixed and used with a small amount of other water-soluble resin. Other water-soluble resins include, for example, polyethylene glycol, polyethylene oxide, polypropylene glycol, polypropylene oxide, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, gum arabic, sodium polyacrylate (soda), carboxymethyl cellulose And the like, and may be used by mixing one or more of these.

The vinyl chloride-vinylacetate copolymer usable in the present invention is a copolymer containing vinyl chloride and vinyl acetate as a main component, preferably a copolymer having a vinyl chloride and vinyl acetate content of 90% or more, more preferably a copolymer of 95% or more. The most preferred is a copolymer of 98% or more.

The vinyl chloride-vinylacetate copolymer used in the present invention is one of carboxyl-modified vinyl chloride / vinylacetate copolymers, epoxy-modified vinyl chloride / vinylacetate copolymers, and hydroxy-modified vinyl chloride / vinylacetate copolymers. Can be selected. For example, the VMCH series sold by Dow Chemical may be used as the carboxyl modified vinyl chloride / vinylacetate copolymer.

In addition, the vinyl chloride-vinylacetate copolymer used in the present invention preferably has a vinyl chloride content of 70 to 90% by weight, and a vinyl acetate content of 10 to 30% by weight.

In addition, the hydrogenated hydrocarbon resin (hydrogenated hydrocarbon resin) used in the present invention has a molecular weight of 500 to 900, for example, the Arkon series commercially available from Arakawa, Japan. Of these, it is preferable to use Arkon-p125.

In the present invention, the hydrogenated hydrocarbon resin and the vinyl chloride-vinylacetate 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 when the amount of the hydrogenated hydrocarbon resin and the vinyl chloride-vinylacetate copolymer is small, the adhesive strength may be lowered and low temperature peeling or surface cracking may occur, and when the amount of the resin is high, the surface may be sticky and workability The reason for this is that the surface of the coating surface becomes coarse and difficult to use.

Meanwhile, according to one embodiment of the present invention, the thickness of the water-soluble lubricant resin layer in the entry sheet is appropriately 5-200 μm, and preferably in the range of 30-120 μm. If the thickness of the resin layer after drying is less than 5 μm, the roughness of the wall surface of the machined hole may increase due to insufficient lubricity, and if it exceeds 200 μm, the drill bit in small-diameter hole formation Is easily wrapped with the resin layer, which may deteriorate the accuracy of the hole position.

The thickness of the resin layer after drying may be adjusted, for example, according to the concentration of the lubricant resin composition, and may be adjusted in any known manner.

In addition, in this invention, if the method of apply | coating the water-soluble lubricating resin solution containing water-soluble polyester resin to a metal thin film base material will not be restrict | limited especially if it is known by the method used industrially. For example, the lubricant resin composition may be coated on a substrate using a die coater such as a knife coater, comma coating, slot die coating, and the solvent may be natural or hot air dried. At this time, the appropriate viscosity of the resin solution for application may be appropriately adjusted according to the coating conditions, if the viscosity of the resin solution is too high or low, a pattern is formed on the coating surface or the thickness of the resin layer is too thick, continuous Ridges may appear on the surface or bubble defects may appear.

In addition, the drying method of the substrate on which the coating layer of the water-soluble lubricating resin composition is formed is not particularly limited as long as it is known as an industrially used method. In many cases, hot air drying is adopted, and heating by infrared rays, microwave or high frequency may also be used together. have. Conditions for drying may be appropriately selected depending on the size and performance of the drying machine, the expected resin layer thickness and the coating speed.

Meanwhile, in the present invention, the water-soluble lubricant resin composition may include various conventional additives such as a leveling agent, an antifoaming agent, a flow improving agent, a humectant, and a surfactant depending on the coating conditions and the surface of the coated body.

The method of punching a printed circuit board using the entry sheet according to the present invention is to arrange the entry sheet on top of a printed wiring board surface such as a copper clad laminate or a multilayer board so that the substrate surface of the entry sheet is in contact with the printed wiring board, and the entry sheet. The hole is drilled into the printed wiring board from the surface side of the lubricating resin layer.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, this is only an example of the present invention, and the scope of the present invention should not be construed as being limited thereto.

Example 1 Preparation of Water-Soluble Lubricant Compositions for Entry Sheets

Example 1- (1)

A 500 ml two-necked flask was replaced with nitrogen, and 135.18 g (1.5 mol) of 1,4-butanediol was used as glycol, and 44.43 g (0.15 mol) of dimethyl 5-sulfoisophthalate sodium salt was added as an soluble component. It was. Then, 0.2 g of tetrabutyl titanate is added as a catalyst, and the ester exchange reaction proceeds while keeping the internal temperature at 200 ° C. or lower while gradually increasing the temperature in a nitrogen atmosphere. When the by-product methanol completely flows out, 0.85 mole of adipic acid, a dicarboxylic acid, is added, 0.2 g of tetrabutyl titanate as a catalyst, and 0.1 g of triphenyl phosphate as a stabilizer are added. To drain the by-product water. When the esterification reaction is completed, 0.1 g of tetrabutyl titanate, 0.1 g of zinc acetate, and 0.1 g of trimethyl phosphate as stabilizer are added to the reactor, and while the temperature is raised to 240 ° C., vacuum is gradually added to the reactor and 1 Torr is applied. Make it below. The condensation polymerization reaction was performed for 100 minutes in the reaction state.

The vinyl chloride-vinylacetate copolymer as 100 parts by weight of the water-soluble polyester resin thus prepared is 85 parts by weight of vinyl chloride, 14 parts by weight of vinyl acetate, and 1 part by weight of maleic acid, commercially available from Dow Chemical Company. Carboxyl-Modified Vinyl Copolymer) and a molecular weight of 750 Arkon p-125 (hydrogenated hydrocarbon resin commercially available from ARAKAWA Chemical) were mixed at 0.1 parts by weight, respectively, and the coating was cured, and then adhesion and surface stickiness were measured.

Example 1- (2)

The water-soluble polyester resin is the same as in Example 1- (1), and the content of VMCH and P-125 are mixed and coated at 0.2 parts by weight, respectively, and the state is observed.

Example 1- (3)

The water-soluble polyester resin is the same as in Example 1- (1), and the content of VMCH and P-125 are mixed and coated at 0.3 parts by weight, respectively, and the state is observed.

Example 1- (4)

The water-soluble polyester resin is the same as in Example 1- (1), and the content of VMCH and P-125 are mixed and coated at 0.5 parts by weight, respectively, and the state is observed.

Example 1- (5)

The water-soluble polyester resin is the same as in Example 1- (1), the content of VMCH, P-125 is mixed and coated in 1 parts by weight, respectively, and the state was observed.

Example 1- (6)

The water-soluble polyester resin is the same as in Example 1- (1), and the content of VMCH and P-125 are mixed and coated at 2 parts by weight, respectively, and the state is observed.

Example 1- (7)

The water-soluble polyester resin is the same as in Example 1- (1), and the content of VMCH and P-125 are mixed and coated at 3 parts by weight, respectively, and the state is observed.

Example 1- (8)

The water-soluble polyester resin is the same as in Example 1- (1), and the content of VMCH and P-125 are mixed and coated at 5 parts by weight, respectively, and the state is observed.

Example 1- (9)

The water-soluble polyester resin was the same as in Example 1- (1), and coated with 1 part by weight of VMCH and 3 parts by weight of P-125, and the state was observed.

Example 1- (10)

The water-soluble polyester resin was the same as in Example 1- (1) and coated with 3 parts by weight of VMCH and 1 part by weight of P-125, and the state was observed.

Example 1- (11)

The water-soluble polyester resin is 135.18 g (1.5 mol) of 1,4-butanediol as glycol, 59.25 g (0.2 mol) of dimethyl 5-sulfoisophthalate sodium salt as a water solubility component, and 94.47 g (0.8) of succinic acid as dicarboxylic acid. Mole). The polymerization method is the same as that in Example 1- (1).

The content of VMCH and P-125 in 100 parts by weight of the water-soluble polyester resin thus prepared were mixed by 0.1 parts by weight, respectively, to observe the state.

Example 1- (12)

The water-soluble polyester resin is the same as in Example 1- (11), and the content of VMCH and P-125 are mixed and coated at 0.2 parts by weight, respectively, and the state is observed.

Example 1- (13)

The water-soluble polyester resin was the same as in Example 1- (11), and the content of VMCH and P-125 were mixed and coated with 0.3 parts by weight, respectively, and the state thereof was observed.

Example 1- (14)

The water-soluble polyester resin is the same as in Example 1- (11), and the content of VMCH and P-125 are mixed and coated at 0.5 parts by weight, respectively, and the state was observed.

Example 1- (15)

The water-soluble polyester resin is the same as in Example 1- (11), and the content of VMCH and P-125 are mixed and coated in 1 parts by weight, respectively, and the state of the water was observed.

Example 1- (16)

The water-soluble polyester resin was the same as in Example 1- (11), and the content of VMCH and P-125 were mixed and coated at 2 parts by weight, respectively, and the state thereof was observed.

Example 1- (17)

The water-soluble polyester resin was the same as in Example 1- (11), and the content of VMCH and P-125 were mixed and coated at 3 parts by weight, respectively, and the state was observed.

Example 1- (18)

The water-soluble polyester resin is the same as in Example 1- (11), the content of VMCH, P-125 is mixed and coated at 5 parts by weight, respectively, and the state was observed.

Example 1- (19)

The water-soluble polyester resin was the same as in Example 1- (11) and coated with 1 part by weight of VMCH and 3 parts by weight of P-125, and the state of the coating was observed.

Example 1- (20)

The water-soluble polyester resin was the same as in Example 1- (11), and coated with 3 parts by weight of VMCH and 1 part by weight of P-125, and the state was observed.

Example 1- (21)

The water-soluble polyester resin is 135.18 g (1.5 mol) of 1,4-butanediol as glycol, 44.43 g (0.15 mol) of dimethyl 5-sulfoisophthalate sodium salt as a solubilizing component, and 50.19 g (0.425) of succinic acid as dicarboxylic acid Mole) and adipic acid were added in an amount of 62.11 g (0.425 mole). The polymerization method is the same as that in Example 1- (21).

The content of VMCH and P-125 in 100 parts by weight of the water-soluble polyester resin thus prepared were mixed by 0.1 parts by weight, respectively, to observe the state.

Example 1- (22)

The water-soluble polyester resin was the same as in Example 1- (21), and the content of VMCH and P-125 were mixed and coated at 0.2 parts by weight, respectively, and the state thereof was observed.

Example 1- (23)

The water-soluble polyester resin was the same as in Example 1- (21), and the content of VMCH and P-125 were mixed and coated at 0.3 parts by weight, respectively, and the state was observed.

Example 1- (24)

The water-soluble polyester resin is the same as in Example 1- (21), and the content of VMCH and P-125 are mixed and coated at 0.5 parts by weight, respectively, and the state was observed.

Example 1- (25)

The water-soluble polyester resin is the same as in Example 1- (21), and the content of VMCH and P-125 are mixed and coated at 1 parts by weight, respectively, and the state of the water is observed.

Example 1- (26)

The water-soluble polyester resin was the same as in Example 1- (21), and the content of VMCH and P-125 were mixed and coated at 2 parts by weight, respectively, and the state thereof was observed.

Example 1- (27)

The water-soluble polyester resin was the same as in Example 1- (21), and the content of VMCH and P-125 were mixed and coated at 3 parts by weight, respectively, and the state thereof was observed.

Example 1- (28)

The water-soluble polyester resin is the same as in Example 1- (21), and the content of VMCH and P-125 are mixed and coated at 5 parts by weight, respectively, and the state was observed.

Example 1- (29)

The water-soluble polyester resin was the same as in Example 1- (21) and coated with 1 part by weight of VMCH and 3 parts by weight of P-125, and the state of the coating was observed.

Example 1- (30)

The water-soluble polyester resin was the same as in Example 1- (21), and coated with 3 parts by weight of VMCH and 1 part by weight of P-125, and the state was observed.

Example 1- (31)

The water-soluble polyester resin is 135.18 g (1.5 moles) of 1,4-butanediol as glycol, 44.43 g (0.15 moles) of dimethyl 5-sulfoisophthalate sodium salt as the solubilizing component, and 49.69 g of adipic acid as the dicarboxylic acid. (0.34 mol) and succinic acid were added in an amount of 60.23 g (0.51 mol). The polymerization method is the same as that in Example 1- (1).

The content of VMCH and P-125 in 100 parts by weight of the water-soluble polyester resin thus prepared were mixed by 0.1 parts by weight, respectively, to observe the state.

Example 1- (32)

The water-soluble polyester resin is the same as in Example 1- (31), and the content of VMCH and P-125 are mixed and coated at 0.2 parts by weight, respectively, and the state was observed.

Example 1- (33)

The water-soluble polyester resin is the same as in Example 1- (31), and the content of VMCH and P-125 are mixed by 0.3 parts by weight, respectively, and the state of the coating is observed.

Example 1- (34)

The water-soluble polyester resin is the same as in Example 1- (31), the content of VMCH, P-125 is mixed and coated in 0.5 parts by weight, respectively, and the state was observed.

Example 1- (35)

The water-soluble polyester resin is the same as in Example 1- (31), the content of VMCH, P-125 is mixed and coated in 1 parts by weight, respectively, and the state was observed.

Example 1- (36)

The water-soluble polyester resin is the same as in Example 1- (31), and the content of VMCH and P-125 are mixed and coated at 2 parts by weight, respectively, and the state was observed.

Example 1- (37)

The water-soluble polyester resin is the same as in Example 1- (31) and the content of VMCH, P-125 is mixed by 3 parts by weight, respectively, and coated, and the state was observed.

Example 1- (38)

The water-soluble polyester resin is the same as in Example 1- (31), the content of VMCH, P-125 is mixed by coating 5 parts by weight, respectively, and observed the state.

Example 1- (39)

The water-soluble polyester resin was the same as in Example 1- (31), and coated with 1 part by weight of VMCH and 3 parts by weight of P-125, and the state was observed.

Example 1- (40)

The water-soluble polyester resin was the same as in Example 1- (31), and coated with 3 parts by weight of VMCH and 1 part by weight of P-125, and the state was observed.

Example 1- (41)

The water-soluble polyester resin is 135.18 g (1.5 moles) of 1,4-butanediol as glycol, 44.43 g (0.15 moles) of dimethyl 5-sulfoisophthalate sodium salt as the solubilizing component, and 36.54 g of adipic acid as the dicarboxylic acid. (0.25 mol) and succinic acid were added in an amount of 70.85 g (0.6 mol). The polymerization method is the same as that in Example 1- (1).

The content of VMCH and P-125 in 100 parts by weight of the water-soluble polyester resin thus prepared were mixed by 0.1 parts by weight, respectively, to observe the state.

Example 1- (42)

The water-soluble polyester resin was the same as in Example 1- (41), and the content of VMCH and P-125 were mixed and coated at 0.2 parts by weight, respectively, and the state thereof was observed.

Example 1- (43)

The water-soluble polyester resin was the same as in Example 1- (41), and the content of VMCH and P-125 were mixed and coated at 0.3 parts by weight, respectively, and the state thereof was observed.

Example 1- (44)

The water-soluble polyester resin is the same as in Example 1- (41), and the content of VMCH and P-125 are mixed and coated at 0.5 parts by weight, respectively, and the state was observed.

Example 1- (45)

The water-soluble polyester resin was the same as in Example 1- (41), and the content of VMCH and P-125 was mixed and coated in 1 parts by weight, respectively, and the state thereof was observed.

Example 1- (46)

The water-soluble polyester resin is the same as in Example 1- (41), and the content of VMCH and P-125 are mixed and coated at 2 parts by weight, respectively, and the state is observed.

Example 1- (47)

The water-soluble polyester resin is the same as in Example 1- (41), and the content of VMCH and P-125 are mixed and coated at 3 parts by weight, respectively, and the state is observed.

Example 1- (48)

The water-soluble polyester resin was the same as in Example 1- (41), and the content of VMCH and P-125 was mixed and coated at 5 parts by weight, respectively, and the state thereof was observed.

Example 1- (49)

The water-soluble polyester resin was the same as in Example 1- (41), and coated with 1 part by weight of VMCH and 3 parts by weight of P-125, and the state was observed.

Example 1- (50)

The water-soluble polyester resin was the same as in Example 1- (41), and coated with 3 parts by weight of VMCH and 1 part by weight of P-125, and the state was observed.

Example 1- (51)

The water-soluble polyester resin is 114.9 g (1.275 mole) of 1,4-butanediol as glycol, 23.88 g (0.225 mole) of diethylene glycol, 44.43 g (0.15 mole) of dimethyl 5 sulfoisophthalate sodium salt as a water solubility component, As dicarboxylic acid, 36.54 g (0.25 mol) of adipic acid and 70.85 g (0.6 mol) of succinic acid were added. The polymerization method is the same as that in Example 1- (1).

The content of VMCH and P-125 in 100 parts by weight of the water-soluble polyester resin thus prepared were mixed by 0.1 parts by weight, respectively, to observe the state.

Example 1- (52)

The water-soluble polyester resin is the same as in Example 1- (51), and the content of VMCH and P-125 are mixed and coated at 0.2 parts by weight, respectively, and the state was observed.

Example 1- (53)

The water-soluble polyester resin is the same as in Example 1- (51), the content of VMCH, P-125 is mixed by 0.3 parts by weight, respectively, and coated, and the state was observed.

Example 1- (54)

The water-soluble polyester resin is the same as in Example 1- (51), and the content of VMCH and P-125 are mixed and coated at 0.5 parts by weight, respectively, and the state was observed.

Example 1- (55)

The water-soluble polyester resin is the same as in Example 1- (51), the content of VMCH, P-125 is mixed and coated in 1 parts by weight, respectively, and the state was observed.

Example 1- (56)

The water-soluble polyester resin is the same as in Example 1- (51), the content of VMCH, P-125 is mixed and coated in 2 parts by weight, respectively, and the state was observed.

Example 1- (57)

The water-soluble polyester resin is the same as in Example 1- (51), the content of VMCH, P-125 is mixed by 3 parts by weight, respectively, and coated, and the state was observed.

Example 1- (58)

The water-soluble polyester resin is the same as in Example 1- (51), and the content of VMCH and P-125 are mixed and coated at 5 parts by weight, respectively, and the state was observed.

Example 1- (59)

The water-soluble polyester resin was the same as in Example 1- (51) and coated with 1 part by weight of VMCH and 3 parts by weight of P-125, and the state was observed.

Example 1- (60)

The water-soluble polyester resin was the same as in Example 1- (51), and coated with 3 parts by weight of VMCH and 1 part by weight of P-125, and the state was observed.

Example 1- (61)

The water-soluble polyester resin is 135.18 g (1.5 mol) of 1,4-butanediol as glycol, and 44.43 g (0.15 mol) of dimethyl 5-sulfoisophthalate sodium salt as the solubilizing component. 0.3 mol), 54.32 g (0.46 mol) of succinic acid and 14.31 g (0.09 mol) of dibasic ester were added thereto. The polymerization method is the same as that in Example 1- (1).

The content of VMCH and P-125 in 100 parts by weight of the water-soluble polyester resin thus prepared were mixed by 0.1 parts by weight, respectively, to observe the state.

Example 1- (62)

The water-soluble polyester resin is the same as in Example 1- (61), and the content of VMCH and P-125 are mixed and coated at 0.2 parts by weight, respectively, and the state is observed.

Example 1- (63)

The water-soluble polyester resin is the same as in Example 1- (61), the content of VMCH, P-125 is mixed by mixing 0.3 parts by weight, respectively, and observed the state.

Example 1- (64)

The water-soluble polyester resin is the same as in Example 1- (61), and the content of VMCH and P-125 are mixed and coated at 0.5 parts by weight, respectively, and the state was observed.

Example 1- (65)

The water-soluble polyester resin is the same as in Example 1- (61), the content of VMCH, P-125 is mixed and coated in 1 parts by weight, respectively, and the state was observed.

Example 1- (66)

The water-soluble polyester resin is the same as in Example 1- (61), and the content of VMCH and P-125 are mixed and coated at 2 parts by weight, respectively, and the state was observed.

Example 1- (67)

The water-soluble polyester resin is the same as in Example 1- (61), and the content of VMCH and P-125 are mixed and coated at 3 parts by weight, respectively, and the state is observed.

Example 1- (68)

The water-soluble polyester resin is the same as in Example 1- (61), the content of VMCH, P-125 is mixed and coated at 5 parts by weight, respectively, and the state was observed.

Example 1- (69)

The water-soluble polyester resin was the same as in Example 1- (61) and coated with 1 part by weight of VMCH and 3 parts by weight of P-125, and the state was observed.

Example 1- (70)

The water-soluble polyester resin was the same as in Example 1- (61) and coated with 3 parts by weight of VMCH and 1 part by weight of P-125, and the state was observed.

Example 1- (71)

The water-soluble polyester resin is 77.68 g (0.4 mol) of dimethyl terephthalate as dicarboxylic acid, 44.43 g (0.15 mol) of dimethyl 5-sulfoisophthalate sodium salt as a water solubility component, and 135.18 g (1,4-butanediol as glycol) 1.5 mole) was added for transesterification, and 65.76 g (0.45 mole) of adipic acid, which is a dicarboxylic acid, was added thereto. The additive content and polymerization method are the same as those of Example 1- (1).

The content of VMCH and P-125 in 100 parts by weight of the water-soluble polyester resin thus prepared were mixed by 0.1 parts by weight, respectively, to observe the state.

Example 1- (72)

The water-soluble polyester resin was the same as in Example 1- (71), and the content of VMCH and P-125 were mixed and coated at 0.2 parts by weight, respectively, and the state thereof was observed.

Example 1- (73)

The water-soluble polyester resin was the same as in Example 1- (71), and the content of VMCH and P-125 were mixed and coated with 0.3 parts by weight, respectively, and the state thereof was observed.

Example 1- (74)

The water-soluble polyester resin was the same as in Example 1- (71), and the content of VMCH and P-125 were mixed and coated at 0.5 parts by weight, respectively, and the state thereof was observed.

Example 1- (75)

The water-soluble polyester resin was the same as in Example 1- (71), and the content of VMCH and P-125 were mixed and coated at 1 parts by weight, respectively, and the state thereof was observed.

Example 1- (76)

The water-soluble polyester resin was the same as in Example 1- (71), and the content of VMCH and P-125 were mixed and coated at 2 parts by weight, respectively, and the state thereof was observed.

Example 1- (77)

The water-soluble polyester resin is the same as in Example 1- (71), and the content of VMCH and P-125 were mixed and coated at 3 parts by weight, respectively, and the state thereof was observed.

Example 1- (78)

The water-soluble polyester resin was the same as in Example 1- (71), and the content of VMCH and P-125 were mixed and coated at 5 parts by weight, respectively, and the state thereof was observed.

Example 1- (79)

The water-soluble polyester resin was the same as in Example 1- (71), and coated with 1 part by weight of VMCH and 3 parts by weight of P-125, and the state was observed.

Example 1- (80)

The water-soluble polyester resin was the same as in Example 1- (71), and coated with 3 parts by weight of VMCH and 1 part by weight of P-125, and the state was observed.

Example 1- (81)

The water-soluble polyester resin is 87.39 g (0.45 mole) of dimethyl terephthalate as dicarboxylic acid, 44.43 g (0.15 mole) of dimethyl 5-sulfoisophthalate sodium salt as a water solubility component, and 135.18 g of 1,4-butanediol as glycol 1.5 mole) was added for transesterification, and 58.46 g (0.4 mole) of adipic acid, which is a dicarboxylic acid, was added to proceed with the ester reaction. The additive content and polymerization method are the same as those of Example 1- (1).

The content of VMCH and P-125 in 100 parts by weight of the water-soluble polyester resin thus prepared were mixed by 0.1 parts by weight, respectively, to observe the state.

Example 1- (82)

The water-soluble polyester resin was the same as in Example 1- (81), and the content of VMCH and P-125 were mixed and coated at 0.2 parts by weight, respectively, and the state thereof was observed.

Example 1- (83)

The water-soluble polyester resin is the same as in Example 1- (81), and the content of VMCH and P-125 are mixed by 0.3 parts by weight, respectively, and the state of the coating is observed.

Example 1- (84)

The water-soluble polyester resin was the same as in Example 1- (81), and the content of VMCH and P-125 were mixed and coated at 0.5 parts by weight, respectively, and the state thereof was observed.

Example 1- (85)

The water-soluble polyester resin is the same as in Example 1- (81), and the content of VMCH and P-125 are mixed and coated in 1 parts by weight, respectively, and the state thereof was observed.

Example 1- (86)

The water-soluble polyester resin is the same as in Example 1- (81), and the content of VMCH and P-125 are mixed and coated at 2 parts by weight, respectively, and the state thereof was observed.

Example 1- (87)

The water-soluble polyester resin is the same as in Example 1- (81), and the content of VMCH and P-125 are mixed and coated at 3 parts by weight, respectively, and the state is observed.

Example 1- (88)

The water-soluble polyester resin is the same as in Example 1- (81), and the content of VMCH and P-125 are mixed and coated at 5 parts by weight, respectively, and the state was observed.

Example 1- (89)

The water-soluble polyester resin was the same as in Example 1- (81), and coated with 1 part by weight of VMCH and 3 parts by weight of P-125, and the state was observed.

Example 1- (90)

The water-soluble polyester resin was the same as in Example 1- (81), and coated with 3 parts by weight of VMCH and 1 part by weight of P-125, and the state was observed.

Example 1- (91)

The water-soluble polyester resin is 90.3 g (0.465 mol) of dimethyl terephthalate as dicarboxylic acid, 44.43 g (0.15 mol) of dimethyl 5-sulfoisophthalate sodium salt as a water solubility component, and 135.18 g (1,4-butanediol as glycol) 1.5 mole) was added for transesterification, and 5.26 g (0.385 mole) of adipic acid, which is a dicarboxylic acid, was added thereto to proceed with esterification. The additive content and polymerization method are the same as those of Example 1- (1).

The content of VMCH and P-125 in 100 parts by weight of the water-soluble polyester resin thus prepared were mixed by 0.1 parts by weight, respectively, to observe the state.

Example 1- (92)

The water-soluble polyester resin is the same as in Example 1- (91), and the content of VMCH and P-125 are mixed and coated at 0.2 parts by weight, respectively, and the state was observed.

Example 1- (93)

The water-soluble polyester resin is the same as in Example 1- (91), and the content of VMCH and P-125 are mixed by 0.3 parts by weight, respectively, and the state of the coating is observed.

Example 1- (94)

The water-soluble polyester resin is the same as in Example 1- (91), the content of VMCH, P-125 is mixed and coated in 0.5 parts by weight, respectively, and the state was observed.

Example 1- (95)

The water-soluble polyester resin is the same as in Example 1- (91), and the content of VMCH and P-125 are mixed and coated in 1 parts by weight, respectively, and the state was observed.

Example 1- (96)

The water-soluble polyester resin is the same as in Example 1- (91), and the content of VMCH and P-125 are mixed and coated at 2 parts by weight, respectively, and the state was observed.

Example 1- (97)

The water-soluble polyester resin is the same as in Example 1- (91), and the content of VMCH and P-125 are mixed and coated at 3 parts by weight, respectively, and the state was observed.

Example 1- (98)

The water-soluble polyester resin is the same as in Example 1- (91), the content of VMCH, P-125 is mixed by coating 5 parts by weight, respectively, and observed the state.

Example 1- (99)

The water-soluble polyester resin was the same as in Example 1- (91), and coated with 1 part by weight of VMCH and 3 parts by weight of P-125, and the state was observed.

Example 1- (100)

The water-soluble polyester resin was the same as in Example 1- (91), and coated with 3 parts by weight of VMCH and 1 part by weight of P-125, and the state was observed.

Example 1- (101)

The water-soluble polyester resin is 9.71 g (0.05 mol) of dimethyl terephthalate as dicarboxylic acid, 9.71 g (0.05 mol) of dimethyl isophthalate, 44.43 g (0.15 mol) of dimethyl 5 sulfoisophthalate sodium salt as a water solubility component, glycol As a reaction, 135.18 g (1.5 mole) of 1,4-butanediol was added thereto for transesterification, and then 109.62 g (0.75 mole) of adipic acid, which is a dicarboxylic acid, was added thereto. The additive content and polymerization method are the same as those of Example 1- (1).

The content of VMCH and P-125 in 100 parts by weight of the water-soluble polyester resin thus prepared were mixed by 0.1 parts by weight, respectively, to observe the state.

Example 1- (102)

The water-soluble polyester resin is the same as in Example 1- (101), and the content of VMCH and P-125 are mixed and coated at 0.2 parts by weight, respectively, and the state was observed.

Example 1- (103)

The water-soluble polyester resin is the same as in Example 1- (101), and the content of VMCH, P-125 is mixed by 0.3 parts by weight, respectively, and the state of the coating is observed.

Example 1- (104)

The water-soluble polyester resin is the same as in Example 1- (101), and the content of VMCH and P-125 are mixed and coated at 0.5 parts by weight, respectively, and the state was observed.

Example 1- (105)

The water-soluble polyester resin is the same as in Example 1- (101), the content of VMCH, P-125 is mixed and coated in 1 parts by weight, respectively, and the state was observed.

Example 1- (106)

The water-soluble polyester resin is the same as in Example 1- (101), the content of VMCH, P-125 is mixed and coated in 2 parts by weight, respectively, and the state was observed.

Example 1- (107)

The water-soluble polyester resin is the same as in Example 1- (101), the content of VMCH, P-125 is mixed and coated in 3 parts by weight, respectively, and observed the state.

Example 1- (108)

The water-soluble polyester resin is the same as in Example 1- (101), the content of VMCH, P-125 is mixed and coated at 5 parts by weight, respectively, and the state was observed.

Example 1- (109)

The water-soluble polyester resin was the same as in Example 1- (101), and coated with 1 part by weight of VMCH and 3 parts by weight of P-125, and the state was observed.

Example 1- (110)

The water-soluble polyester resin was the same as in Example 1- (101), and coated with 3 parts by weight of VMCH and 1 part by weight of P-125, and the state was observed.

Example 1- (111)

The water-soluble polyester resin is 19.42 g (0.1 mole) of dimethyl terephthalate as dicarboxylic acid, 77.68 g (0.4 mole) of dimethyl isophthalate, 135.18 g (1.5 mole) of 1,4-butanediol as glycol, and 5 dimethyl as a solubilizing component. Poisophthalate sodium salt was added in the amount of 44.43 g (0.15 mole) to undergo transesterification, and then the reaction was carried out by adding 51.15 g (0.35 mole) of adipic acid, which is dicarboxylic acid. The additive content and polymerization method are the same as those of Example 1- (1).

The content of VMCH and P-125 in 100 parts by weight of the water-soluble polyester resin thus prepared were mixed by 0.1 parts by weight, respectively, to observe the state.

Example 1- (112)

The water-soluble polyester resin is the same as in Example 1- (111), and the content of VMCH and P-125 are mixed and coated at 0.2 parts by weight, respectively, and the state is observed.

Example 1-113

The water-soluble polyester resin is the same as in Example 1- (111), and the content of VMCH and P-125 are mixed and coated with 0.3 parts by weight, respectively, and the state is observed.

Example 1- (114)

The water-soluble polyester resin is the same as in Example 1- (111), and the content of VMCH and P-125 are mixed and coated at 0.5 parts by weight, respectively, and the state is observed.

Example 1-115

The water-soluble polyester resin is the same as in Example 1- (111), and the content of VMCH and P-125 are mixed and coated at 1 parts by weight, respectively, and the state of the water was observed.

Example 1- (116)

The water-soluble polyester resin is the same as in Example 1- (111), and the content of VMCH and P-125 are mixed and coated at 2 parts by weight, respectively, and the state is observed.

Example 1- (117)

The water-soluble polyester resin is the same as in Example 1- (111), and the content of VMCH and P-125 were mixed and coated at 3 parts by weight, respectively, and the state thereof was observed.

Example 1- (118)

The water-soluble polyester resin is the same as in Example 1- (111), and the content of VMCH and P-125 are mixed and coated at 5 parts by weight, respectively, and the state is observed.

Example 1- (119)

The water-soluble polyester resin was the same as in Example 1- (111) and coated with 1 part by weight of VMCH and 3 parts by weight of P-125, and the state of the coating was observed.

Example 1- (120)

The water-soluble polyester resin was the same as in Example 1- (111), and coated with 3 parts by weight of VMCH and 1 part by weight of P-125, and the state was observed.

Example 1- (121)

The water-soluble polyester resin is 13.59 g (0.07 mole) of dimethyl terephthalate as dicarboxylic acid, 64.08 g (0.33 mole) of dimethyl isophthalate, 135.18 g (1.5 mole) of 1,4-butanediol as glycol, and 5 dimethyl as a solubilizing component. Poisophthalate sodium salt was added in the amount of 44.43 g (0.15 mole) to undergo transesterification, and then 65.76 g (0.45 mole) of adipic acid, a dicarboxylic acid, was added to carry out the ester reaction. The additive content and polymerization method are the same as those of Example 1- (1).

The content of VMCH and P-125 in 100 parts by weight of the water-soluble polyester resin thus prepared were mixed by 0.1 parts by weight, respectively, to observe the state.

Example 1- (122)

The water-soluble polyester resin is the same as in Example 1-121, and the content of VMCH and P-125 are mixed and coated at 0.2 parts by weight, respectively, and the state is observed.

Example 1- (123)

The water-soluble polyester resin is the same as in Example 1-121, and the content of VMCH and P-125 are mixed by 0.3 parts by weight, respectively, and the state of the coating is observed.

Example 1- (124)

The water-soluble polyester resin is the same as in Example 1-121, and the content of VMCH and P-125 were mixed and coated at 0.5 parts by weight, respectively, and the state thereof was observed.

Example 1- (125)

The water-soluble polyester resin is the same as in Example 1-121, and the content of VMCH and P-125 are mixed and coated in 1 parts by weight, respectively, and the state is observed.

Example 1- (126)

The water-soluble polyester resin is the same as in Example 1-121, and the content of VMCH and P-125 were mixed and coated at 2 parts by weight, respectively, and the state thereof was observed.

Example 1- (127)

The water-soluble polyester resin is the same as in Example 1-121, and the content of VMCH and P-125 are mixed and coated at 3 parts by weight, respectively, and the state is observed.

Example 1- (128)

The water-soluble polyester resin is the same as in Example 121, the content of VMCH, P-125 is mixed by coating 5 parts by weight, respectively, and the state was observed.

Example 1- (129)

The water-soluble polyester resin was the same as in Example 1-121, and coated with 1 part by weight of VMCH and 3 parts by weight of P-125, and the state was observed.

Example 1- (130)

The water-soluble polyester resin was the same as in Example 1-121, and coated with 3 parts by weight of VMCH and 1 part by weight of P-125, and the state was observed.

Comparative example

Comparative Example 1

The water-soluble polyester prepared in Example 1- (1) was coated using a resin alone without additive mixing.

Comparative Example 2

The water-soluble polyester prepared in Example 1- (11) was coated using a resin alone without additive mixing.

Comparative Example 3

The water-soluble polyester prepared in Example 1- (21) was coated using a resin alone without additive mixing.

Comparative Example 4

The water-soluble polyester prepared in Example 1- (31) was coated using a resin alone without additive mixing.

Comparative Example 5

The water-soluble polyester prepared in Example 1- (41) was coated using a resin alone without additive mixing.

Comparative Example 6

The water-soluble polyester prepared in Example 1- (51) was coated using a resin alone without additive mixing.

Comparative Example 7

The water-soluble polyester prepared in Example 1- (61) was coated using a resin alone without additive mixing.

Comparative Example 8

The water-soluble polyester prepared in Example 1- (71) was coated using a resin alone without additive mixing.

Comparative Example 9

The water-soluble polyester prepared in Example 1- (81) was coated using a resin alone without additive mixing.

Comparative Example 10

The water-soluble polyester prepared in Example 1- (91) was coated using a resin alone without additive mixing.

Comparative Example 11

The water-soluble polyester prepared in Example 1-101 was coated using a resin alone without additive mixing.

Comparative Example 12

The water-soluble polyester prepared in Example 1- (111) was coated using a resin alone without additive mixing.

Comparative Example 13

The water-soluble polyester prepared in Example 1-121 was coated using a resin alone without additive mixing.

Test Example 1: Cohesion, surface stickiness, surface crack measurement

The adhesion, surface stickiness, and surface cracks of the lubricant resin composition for entry sheets prepared in the above examples were measured.

The adhesive strength was stored for 30 days at minus 20 ℃ coating specimen, and folded the specimen to observe whether the coating surface falling from the metal thin plate, it was displayed as follows.

◎: Very good adhesion, ○: Good, △: Normal, X: Poor

The surface stickiness was observed after 24 hours after the coating surface was cured, and whether the surface was sticky after applying 10 kg of coating specimens and a pressure of 1 kg.

◎: Very good without surface stickiness, ○: Good, △: Normal, X: Poor

The surface cracks were stored for 15 days at -20 ° C. for the coated specimens, and then visually confirmed whether cracks were generated on the surface.

◎: very good without surface crack, ○: good, △: normal, X: poor

As a result of the observation, it was found that as the amount of VMCH and P-125 used increased, the adhesive force increased than when not used. However, if a large amount is used, stickiness remains on the surface of the coating after drying, which causes the metal thin films to stick together in roll production, causing a lot of product defects. In addition, the entry sheet is attached to the bushing marks and the bit fixing device during drilling so that the operation is not performed. On the other hand, in the comparative example with too little or no amount, the surface stickiness after drying is much improved, but when it is stored for a long time at low temperature, the adhesion to the metal thin film is reduced, resulting in a drop in the surface crack or metal thin film. do.

Therefore, it can be seen from the above test results that the hydrogenated hydrocarbon resin and the vinyl chloride-vinylacetate copolymer in the present invention preferably use 0.5 to 3 parts by weight based on 100 parts by weight of the water-soluble polyester resin.

Example 2 Preparation and Perforation Test Results of Entry Sheet

The water-soluble lubricating resin composition prepared according to Example 1 was coated on an aluminum substrate using a coma coater of a hot air drying type to prepare an entry sheet.

A water-soluble lubricating resin composition was applied to an aluminum substrate having a thickness of 50 to 200 microns using a comma coater of a roll to roll method so as to have a dry thickness of 5 to 200 microns. The solvent component of the applied water-soluble lubricating resin was removed and dried at 50 to 160 degrees in a hot air drying furnace so that the resin layer could be fixed on the aluminum substrate. The hot air drying furnace consists of 4 ~ 6 sections, and the temperature conditions for each section were set sequentially from low temperature to high temperature for bubble removal and surface smoothness of the resin layer.

The drill lubrication sheet to be used can control the thickness of the aluminum and the thickness of the lubricant resin layer according to the intended use, such as the thickness of the PCB to be processed, the number of PCB laminateds, the structure of the inner layer and the diameter of the drill.

The dried resin-coated aluminum is manufactured in sheet form using a roll slitting machine for cutting in the width direction, a sheet leveler for maintaining the smoothness of the entry sheet, and a cutter for cutting in the longitudinal direction according to user specifications.

Example 2- (1)

Example 1- (96), 1- (99) and 1- (100) of the lubricant resin composition 40 microns were applied to 120 microns of an aluminum substrate to prepare a drill lubricant sheet. The manufactured entry sheet was processed under the following drilling conditions, and the quality was evaluated by repeating three times based on the bottom plate of the processed PCB.

PCB Material / Structure: H / F (Halogen Free) FR-4 Type PCB Board, 4 Layer Structure, Thickness is 0.51T

Stacking: Three PCB substrates were laminated, and a backup board was stacked on the bottom, and an entry sheet of the invention was stacked on the top.

CNC drilling condition: Japan's Hitachi rotation speed 200,000 RPM, drill diameter 0.2 mm product, 100,000 hole processing standard

For the quality evaluation of the entry sheet, (1) the position precision of the drilled hole was examined by the Cpk value, the degree of drill hole (deviation out of the error during drilling) was examined, and (2) the damage rate of the drill bit during drilling was hit. The number of breakages was compared with the number, and (3) the discharge state of the chips cut during drilling and the abnormality on the surface of the entry sheet were visually observed.

2 is an AOI (Automated Optical Inspection) result of measuring the drilled hole precision of the entry sheet according to Example 2- (1) of the present invention. As a result of the evaluation, it was found that the entry sheet of the present invention can be applied to mass production.

Table 1 below shows the perforation test results of the entry sheets made of the lubrication resin layers of Examples 1- (96), (99) and (100).

object Test Items 1 time Episode 2 3rd time Remarks Example
1- (96) CPK 1.777 1.732 1.614 Standard:> 1.33 Drill break none none none Chip Double Output /
Appearance condition Good Good Good Example
1- (99) CPK 1.675 1.712 1.547 Standard:> 1.33 Drill break none none none Chip Double Output /
Appearance condition Good Good Good Example
1- (100) CPK 1.814 1.65 1.64 Standard:> 1.33 Drill break none none none Chip Double Output /
Appearance condition Good Good Good

Example 2- (2)

In order to evaluate the effectiveness of the entry sheet according to the present invention, the general aluminum sheet, manufactured by Mitsubishi Gas Chemical Co., Ltd., and the entry sheet according to the present invention were drilled under the following conditions to compare and evaluate the quality. The entry sheet according to the present invention was prepared according to the method of Example 2 by applying 40 microns of the lubricating resin composition according to Example 1- (96) to 120 microns of an aluminum substrate.

PCB Material / Structure: H / F (Halogen Free) FR-4 Type PCB Board, Thickness 0.6T

Stacking: Four PCB substrates were laminated, and a backup board was stacked on the bottom, and an entry sheet of the invention was stacked on the top.

CNC drilling condition: 160,000 RPM rotation speed of Hitachi, Japan, 0.2 mm drill diameter, 20,000 Hit

Evaluation items were carried out in the same manner as in Example 1.

3 and 4 show AOI results when an aluminum sheet (0.15T) without lubricant is used.

5 and 6 show AOI results when LE-800 manufactured by Mitsubishi Gas Chemical Co., Ltd., Japan.

7 and 8 show AOI results when the lubricant resin coated entry sheet prepared in Example 2- (2) was used.

Table 2 below shows the perforation test results of the aluminum sheet, manufactured by MGC Japan, and the entry sheet made of the lubricant resin composition according to the present invention.

Aluminum sheet Japan MGC Example 2- (2) 3 4 5 6 7 8 Cpk (UL = 75) 2.181 1.532 2.475 2.710 2.419 2.918 Drill break none 1 breakage none none none none Chip Double Output /
Appearance condition Burr occurrence Burr occurrence Good Good Good Good

From the results of the evaluation, it can be seen that the use of the entry sheet according to the present invention greatly improves the positional accuracy of the hole during the drill, and the breakage rate of the bit is also low. In addition, it can be seen that it has improved characteristics in the positional accuracy field compared to the Japanese products which are widely used at present.

Example 2- (3)

The lubricant resin composition 50 microns according to the lubricant resin composition (Examples 1- (96)) according to the present invention was applied to 70 microns of an aluminum substrate to prepare a drill lubricant sheet. The manufactured entry sheet was processed under the following drilling conditions to evaluate the quality.

PCB Material / Structure: H / F (Halogen Free) FR-4 Type PCB Board, 4 Layer Structure, Thickness 0.48T

Stacking: Two PCB substrates were laminated, and a backup board was stacked on the bottom, and an entry sheet of the invention was stacked on the top.

CNC drilling conditions: Rotation speed 180,000 RPM, drill diameter 0.15 mm, based on 70,000 holes

FIG. 9 is an AOI result using a domestic creative company product currently being applied to a company, and FIG. 10 is an AOI result after drilling using the product of the present Example 2- (3).

Domestic competitor
9 Example 2- (3)
10 Cpk (UL = 75) 3.287 3.835 Drill break none none Chip Double Output /
Appearance condition Good Good

As a result, it can be seen that the quality of the lubricity resin coated entry sheet of Example 3 is superior to that of competitors currently in use, and is applicable to actual production.

Example 2- (4)

Lubricating resin composition according to the present invention (Example 1- (96)) 60 micron was applied to an aluminum substrate 120 micron to prepare a drill lubricant sheet. The manufactured entry sheet was processed under the following drilling conditions to evaluate the quality. In order to verify the deviation of each drilling machine, the same product was evaluated on six axes of the drilling machine to verify the machining mechanical errors. 11 and 12 are AOI results of evaluating the product of Example 2- (4) of the present invention using a domestic water-soluble resin product currently being applied to a company.

As a result of the evaluation, it was found that the entry sheet of Example 2- (4) was superior in quality to the existing product, regardless of the deviation of each drilling machine axis, and showed excellent evaluation result even when applied to actual mass production level. there was.

Claims (20)

Metal thin film base material; And
An entry sheet comprising a water-soluble lubricant resin layer formed on the substrate,
The water-soluble lubricating resin layer is 100 parts by weight of water-soluble polyester resin, 0.5 to 3 parts by weight of vinyl chloride-vinylacetate copolymer and 0.5 to 3 parts by weight of hydrogenated hydrocarbon resin, the entry sheet for punching a printed circuit board. The method of claim 1,
The metal thin film substrate is an entry sheet for punching a printed circuit board, characterized in that the aluminum thin film of 0.05 ~ 0.2 mm thickness. The method of claim 1,
The water-soluble polyester resin is a printed circuit comprising a) a polyol: b) 1.5 parts by weight of a water-soluble component: c) a carboxylic acid or a carboxylic acid ester in a molar ratio of 1: 0.1: 0.8 to 2: 0.2: 1.0 Entry sheet for substrate drilling. The method of claim 3,
The water-soluble polyester resin is a) a polyol: b) water-soluble component: c) entry sheet for punching a printed circuit board, characterized in that produced by reacting the carboxylic acid or carboxylic acid ester in a molar ratio of 1.5: 0.15: 0.85. The method of claim 3,
The polyol is 1,4-butanediol, diethylene glycol, propylene glycol, neopentyl glycol, diethylene glycol, polyethylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4- Entry sheet for punching a printed circuit board, characterized in that at least one selected from the group consisting of butanediol and 1,6-hexanediol. The method of claim 3,
And the water-soluble component is a sulfonic acid alkali metal salt. The method of claim 4, wherein
The sulfonic acid alkali metal salt is a group consisting of dimethyl-5-sulfoisophthalate sodium salt, dimethyl-4-sulfoisophthalate sodium salt, dimethyl-5-sulfoterephthalate sodium salt, and diethyl-5-sulfoterephthalate sodium salt. Entry sheet for punching a printed circuit board, characterized in that at least one selected from. The method of claim 3,
The carboxylic acid or carboxylic acid ester is adipic acid, succinic acid, dibasic ester, dimethyl terephthalate, dimethyl isophthalate, glutaric acid, sebacic acid, succinic anhydride, dimethyl succinate, dimethyl glutarate, dimethyl adipate, terephthalic acid, Entry sheet for punching a printed circuit board, characterized in that at least one selected from the group consisting of phthalic acid and isophthalic acid. The method of claim 1,
The entry sheet for punching a printed circuit board, characterized in that the molecular weight of the water-soluble polyester resin is 10,000 ~ 100,000. The method of claim 1,
The vinyl chloride-vinylacetate copolymer may be selected from at least one selected from carboxyl-modified vinyl chloride / vinylacetate copolymers, epoxy-modified vinyl chloride / vinylacetate copolymers, and hydroxy-modified vinyl chloride / vinylacetate copolymers. An entry sheet for punching a printed circuit board. The method of claim 1,
The vinyl chloride-vinylacetate copolymer is an entry sheet for punching a printed circuit board, characterized in that the content of vinyl chloride is 70 to 90% by weight, the content of vinyl acetate is 10 to 30% by weight. The method of claim 1,
The hydrogenated hydrocarbon resin is an entry sheet for punching a printed circuit board, characterized in that the molecular weight is 500 ~ 900. The method of claim 1,
The entry sheet for punching a printed circuit board, characterized in that the thickness of the water-soluble lubricant resin layer is 5-200 ㎛. A water-soluble lubricating resin composition for forming an entry sheet for perforation of a printed circuit board, comprising: 100 parts by weight of a water-soluble polyester resin, 0.5 to 3 parts by weight of a vinyl chloride-vinylacetate copolymer, and 0.5 to 3 parts by weight of a hydrogenated hydrocarbon resin. Water-soluble lubricant resin composition characterized in. The method of claim 14,
The water-soluble polyester resin is a water-soluble lubrication, characterized in that prepared by reacting a) polyol: b) 1.5 parts by weight of a water-soluble component: c) carboxylic acid or carboxylic acid ester in a molar ratio of 1: 0.1: 0.8 to 2: 0.2: 1.0 Resin composition.
In the method for producing a lubricant resin composition for forming a printed circuit board entry sheet,
a) a polyol: b) 1.5 parts by weight of a water-soluble component: c) esterifying a carboxylic acid or a carboxylic acid ester in a molar ratio of 1: 0.1: 0.8 to 2: 0.2: 1.0, followed by condensation polymerization to prepare a water-soluble polyester resin;
100 parts by weight of the water-soluble polyester resin, 0.5 to 3 parts by weight of the copolymer of vinyl chloride and vinyl acetate and 0.5 to 3 parts by weight of the hydrogenated hydrocarbon resin by mixing and curing; water-soluble for the entry sheet comprising a Method for preparing a lubricant resin composition. The method of claim 16,
The water-soluble polyester resin
Transesterifying the carboxylic acid or carboxylic acid ester with the water-soluble component,
Esterifying the carboxylic acid and polyol solvated in the step to obtain an intermediate product; And
Condensation polymerization of the intermediate product; Method for producing a water-soluble lubricating resin composition for an entry sheet, characterized in that it is prepared according to the process comprising a. The method of claim 16,
The ester reaction is a method for producing a water-soluble lubricant resin composition for an entry sheet, characterized in that carried out at a temperature of 160 ~ 220 ℃. The method of claim 16,
The polycondensation reaction is a method for producing a water-soluble lubricant resin composition for entry sheet, characterized in that carried out under reduced pressure at a temperature of 230 ~ 260 ℃. The method of claim 16,
The ester reaction may be performed using at least one catalyst selected from tetrabutyl titanate, zinc acetate, calcium acetate, magnesium acetate, trimethyl phosphate, triphenyl phosphate, and cobalt acetate. How to make.

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