TWI490272B - Water soluble composition, entry board for drilling and production method of water soluble composition - Google Patents

Description

Water-soluble composition, drilling cover plate and water-soluble composition manufacturing method

The present invention relates to a water-soluble composition, a method for producing a water-soluble composition, and a cover for drilling a water-soluble composition.

Drilling methods for copper-clad laminates or multi-layer boards used in printed circuit board materials today, usually before drilling, a cover is used as an auxiliary board placed on top of a copper-clad laminate or multi-layer board. On the surface.

In recent years, with the demand for improved reliability of printed circuit board materials or the progress of high density, in order to cope with the demand for reliability growth and the development of high densification, printed circuit boards also require high-quality drill holes, for example: Improve hole accuracy, hole quality and effectively reduce needle breakage.

At present, the auxiliary board on the market has a three-layer structure, which comprises a layer of aluminum foil, a layer of water-insoluble resin as a primer and more than one layer of water-soluble resin as a top coating, wherein the primer is effective to strengthen the water-soluble resin and aluminum foil. Board's adhesion Force, but this may remain inside the hole of the copper-clad laminate or multi-layer board after drilling, and the water washing in the back-end process of the printed circuit board cannot be removed to cause poor copper plating quality or even short circuit.

The invention provides a water-soluble composition and a preparation method thereof, so that the water-soluble composition has better adhesion with respect to the metal substrate, and the cover plate applied thereto has better lubrication degree and heat dissipation effect when drilling. .

The water-soluble composition of the present invention is suitable for use in a cover plate for drilling. The water soluble composition includes an aqueous polyurethane resin and a polyethylene oxide copolymer. The polyethylene oxide copolymer has an alkyl group on its side chain, and the polyethylene oxide copolymer has a viscosity of from 1000 cps to 10,000 cps.

The drilling cover plate of the present invention comprises a substrate and a water-soluble composition, wherein the water-soluble composition is disposed on the surface of the substrate.

The method for preparing the water-soluble composition of the present invention comprises: providing an aqueous polyurethane resin; mixing polyethylene glycol, polypropylene glycol, polyethylene oxide copolymer and polyvinylpyrrolidone to form a premixed solution; mixing aqueous polyurethane resin, interfacial activity The agent, the polyether-oxirane copolymer, the branched alkane copolymer and the premixed solution form a water-soluble composition.

In an embodiment of the invention, the above polyethylene oxide copolymer has an average molecular weight of between 150,000 and 400,000.

In an embodiment of the invention, the alkyl group on the side chain of the polyethylene oxide copolymer comprises methyl (CH ₃ ), propylene methyl ether (CH ₂ OCH ₂ CH=CH ₂ ) or a mixed composition thereof. .

In an embodiment of the invention, the aqueous polyurethane resin has an average molecular weight of between 10,000 and 400,000, and the Shore Hardness of the water-soluble composition ranges from 20 to 40, and The main chain of the aqueous polyurethane resin contains an ethylene oxide hydrophilic group and an emulsified hydrophilic group containing sodium sulfonate ethylene glycol in a side chain.

In an embodiment of the invention, the aqueous polyurethane resin comprises an overall solid content of the water-soluble composition of between 10% by weight and 45% by weight.

In an embodiment of the invention, the water soluble composition further comprises polyethylene glycol, polypropylene glycol, a polyether-xanylene oxide copolymer, a branched alkane copolymer, and polyvinylpyrrolidone (PVP).

In an embodiment of the invention, the ratio of the polyethylene oxide copolymer content to the polyvinylpyrrolidone content is between 1:4 and 4:1.

In an embodiment of the invention, the polyethylene glycol has an average molecular weight of between 2,000 and 10,000, and the polyvinylpyrrolidone has an average molecular weight of between 10,000 and 200,000.

In an embodiment of the invention, the ratio of the polyethylene oxide copolymer solid content to the aqueous polyurethane resin content is between 1:1 and 1:4.

In an embodiment of the invention, the polyvinylpyrrolidone has a solid content of from 15% by weight to 40% by weight based on the total solid content of the water-soluble composition.

In an embodiment of the invention, the above polyethylene glycol solid content and water The ratio of the content of the urethane resin is between 1:1 and 1:4.

In an embodiment of the invention, the material of the substrate comprises aluminum.

Based on the above, in the above embodiment of the present invention, by adding a polyethylene oxide copolymer having a side chain containing an alkyl group to the water-soluble composition, and the viscosity of the polyethylene oxide copolymer is from 1000 cps to 10000 cps, When the water-soluble composition is disposed on the substrate and used as a cover for drilling, the lubricating effect during drilling can be improved by the characteristics of the polyethylene-epoxy copolymer, that is, when the water-soluble composition can buffer the penetration of the drill needle Impacts the force and reduces the heat generated by the high-speed friction of the borehole, thereby effectively improving the drilling accuracy, extending the life of the drill and reducing the processing cost.

The above described features and advantages of the invention will be apparent from the following description.

100‧‧‧Drilling cover

110‧‧‧Substrate

120‧‧‧Water-soluble composition

200‧‧‧Printed circuit board

300‧‧‧lower pad

S310~S330‧‧‧Steps

1 is a schematic view of a cover plate for drilling according to an embodiment of the present invention.

Figure 2 is a schematic view of the application of the drilling cover of Figure 1.

Fig. 3 is a schematic view showing the blending of a water-soluble composition according to an embodiment of the present invention.

1 is a schematic view of a cover plate for drilling according to an embodiment of the present invention. 2 is a schematic view of the application of the drilling cover plate of FIG. 1 for illustrating the drilling of the printed circuit board 200 by using the drilling cover plate 100 of the present embodiment. Please also refer to Figure 1 with 2, in the present embodiment, the drilling cover 100 includes a substrate 110 and a water-soluble composition 120 disposed on one surface of the substrate 110. The substrate 110 is, for example, a conductive substrate whose material contains aluminum, and in the present embodiment, the substrate 110 is an aluminum foil plate having a thickness of 30 um to 250 um. Then, the water-soluble composition 120 is disposed on one surface of the aluminum foil plate by coating (or related process), and after completion, the drilling cover plate 100 is covered on the printed circuit board 200 for drilling. Process.

Further, the water-soluble composition 120 of the present embodiment comprises an aqueous polyurethane resin and a polyethylene oxide copolymer, wherein the formula of the aqueous polyurethane resin is as follows:

The average molecular particle size is less than 0.2 um, generally between 0.0001 um and 0.2 um, and the average molecular weight is between 10,000 and 400,000. The liquid-type aqueous polyurethane resin (without moisture) has 0.1% to 15% by weight of an ethylene oxide hydrophilic group in the main chain and 0.1% to 15% of sodium sulfonate B in the side chain. The diamine emulsifies the hydrophilic group, and the overall hydrophilic group ratio is between 5% and 30%. Further, the effective solid content of the aqueous polyurethane resin relative to the water-soluble composition 120 is between 10% by weight and 455% by weight, and the preferred Shore Hardness of the Shore D range is from 20 to 40. between. It should also be mentioned that, in the test, it is found that when the Shore D of the Shore Hardness is greater than 40, the needle breakage is likely to occur during drilling, and below 20, the surface is easily adhered.

The aqueous polyurethane resin used in this embodiment belongs to one of green chemistry Materials are excellent materials that use water to replace the general solvent-based polyurethane reaction conditions. In the process of using water as a carrier, water replaces most or all of the volatile organic compounds (VOC) and Hazardous Air Pollutant (HAP) used in traditional solvent-based polyurethane coatings. However, the performance of the lubricating layer is not reduced. In addition, when the heat dissipating plate of the embodiment is used, the material remaining on the drill pin after the drilling is removed by water shock cleaning without remaining on the drill pin, which saves cost and reduces pollution in cleaning. Effect.

It is also worth noting that the general formula and structure of the polyethylene-epoxy copolymer of the present embodiment are as follows:

It has an effective solids content of between 5 wt% and 15 wt% relative to the water soluble composition 120, wherein the polyethylene oxide copolymer has an average molecular weight between 150,000 and 400,000 and which is included on the side chain of the epoxy structure alkyl. Here, the alkyl group located on the side chain of the polyethylene oxide copolymer comprises methyl (CH ₃ ), propylene methyl ether (CH ₂ OCH ₂ CH=CH ₂ ) or a mixed composition thereof, and polyethylene oxide The viscosity of the copolymer is from 1000 cps to 10,000 cps, and the viscosity of the synthesized water-soluble composition 120 is between about 500 cps and 3000 cps. Accordingly, the polyepoxyethylene copolymer of the water-soluble composition 120 is effectively improved in the lubricity applied to the drilling cover 100, wherein the water-soluble composition is further buffered by the drill through the printed circuit. The impact force generated by the plate 200 can effectively reduce the heat energy generated by the high-speed friction of the drill hole, thereby improving the drilling accuracy, extending the life of the drill needle, and reducing the processing cost.

On the other hand, the water-soluble composition 120 of the present embodiment further includes polyethylene glycol, polypropylene glycol, a polyether-oxyalkylene copolymer, a branched alkane copolymer, and polyvinylpyrrolidone (PVP), wherein the poly The ratio of ethylene oxide copolymer content to polyvinylpyrrolidone content is between 1:4 and 4:1, the average molecular weight of polyethylene glycol is between 2,000 and 10,000, and the average molecular weight of polyvinylpyrrolidone is between 10,000 and 10,000. Between 200000, the ratio of the solid content of the polyethylene oxide copolymer to the content of the aqueous polyurethane resin is between 1:1 and 1:4, and the solid content of the polyvinylpyrrolidone accounts for 15% by weight of the total solid content of the water-soluble composition. Between 40wt%.

It is also to be noted that in the present embodiment, the lubricity and hydrophilicity of the water-soluble composition 120 are adjusted by controlling the ratio of the content of the polyethylene oxide copolymer to the polyvinylpyrrolidone content. It has been experimentally found that if the content ratio of the polyethylene oxide copolymer is too high, the lubricating layer formed by the water-soluble composition 120 coated on the substrate is liable to cause cracks or crystal grains of the turtle, resulting in poor appearance of the film surface. And too low leads to lubrication Poor, insufficient heat dissipation, easy to cause the drill bit to break. Similarly, if the content ratio of polyvinylpyrrolidone is too high, the hydrophilicity is high and the adhesion is likely to occur, and if it is too low, the water solubility is poor.

Fig. 3 is a schematic view showing the blending of a water-soluble composition according to an embodiment of the present invention. Referring to FIG. 3, in step S310, an aqueous polyurethane resin is provided. Further, the aqueous polyurethane resin may be subjected to an emulsification treatment to homogenize the micelles at a normal temperature, and a surfactant is added and heated.

Further, in step S320, polyethylene glycol, polypropylene glycol, a polyethylene oxide copolymer, and polyvinylpyrrolidone are mixed to form a premixed solution. Further, after the emulsified polyethylene glycol is mixed with the polypropylene glycol, the polyethylene oxide copolymer and the polyvinylpyrrolidone are added to form a colloidal premixed solution, wherein the polyethylene glycol and the polyvinylpyrrolidone are compatible. Poorly, it is necessary to grind polyvinylpyrrolidone and add epoxy resin.

Finally, in step S330, the water-soluble polyurethane resin and the surfactant, the premixed solution, and the polyether-oxyalkylene copolymer and the branched alkane copolymer are mixed at normal temperature to complete the water solubility of the present embodiment. Composition 120.

Based on the above, the drilling cover 100 of the present invention is subjected to the drilling test in the following experimental example after completion of the above, and the drilling schematic shown in FIG. 2 is referred to. Here, the drilling cover plate 100 of the present invention is used as an experimental group, and the prior art drilling cover plate is used as a control group. Here, the process capability index (Cpk) is used as the basis for judging the accuracy and accuracy of the drilling location, and the results of Table 1 and Table 2 are obtained.

[Experimental parameters]

Drilling machine: HITACHI-0105 U2

Speed: 300 krpm

Feeding speed: 2.4 m/min

Return speed: 1000 in/min

Hole limit: 13500 hits

Number of laminations: BT_HS x 0.11mm x 6

Lower pad (labeled as 300 in Figure 2): 1.5 mm thick urea plate (can also be pulp or phenolic)

It can be clearly seen from the process capability analysis charts of Tables 1 and 2 that the drilling cover plate 100 of the present case has better accuracy and precision in drilling and the roughness generated on the printed circuit board 200 than the existing drilling holes. It is better to use a cover plate.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.

100‧‧‧Drilling cover

110‧‧‧Substrate

120‧‧‧Water-soluble composition

Claims (13)

A water-soluble composition suitable for use in a drilling cover plate comprising: an aqueous polyurethane resin, a polyethylene oxide copolymer and a polyvinylpyrrolidone, wherein the polyethylene oxide copolymer comprises an alkane on a side chain thereof The poly(ethylene oxide) copolymer has a viscosity of from 1000 cps to 10,000 cps, and the ratio of the polyethylene oxide copolymer content to the polyvinylpyrrolidone content is between 1:4 and 4:1. The water-soluble composition of claim 1, wherein the alkyl group on the side chain of the polyethylene oxide copolymer comprises methyl (CH ₃ ), propylene methyl ether (CH ₂ OCH ₂ CH=CH ₂ ) or a mixture thereof. The water-soluble composition of claim 1, wherein the polyethylene oxide copolymer has an average molecular weight of between 150,000 and 400,000. The water-soluble composition according to claim 1, wherein the aqueous polyurethane resin has an average molecular weight of from 10,000 to 400,000, and the Shore Hardness of the water-soluble composition has a Shore D range of from 20 to Between 40, the main chain of the aqueous polyurethane resin contains an ethylene oxide hydrophilic group and an emulsified hydrophilic group containing sodium sulfonate ethylenediamine in the side chain. The water-soluble composition according to claim 1, wherein the aqueous polyurethane resin accounts for between 10% by weight and 45% by weight of the total solid content of the water-soluble composition. The water-soluble composition according to claim 1, further comprising polyethylene glycol, polypropylene glycol, a polyether-xanylene oxide copolymer, and a branched alkane copolymer. The water-soluble composition according to claim 6, wherein the polyethylene glycol has an average molecular weight of from 2,000 to 10,000, and the polyvinylpyrrolidone has an average molecular weight of from 10,000 to 200,000. The water-soluble composition according to claim 6, wherein the ratio of the solid content of the polyethylene oxide copolymer to the content of the aqueous polyurethane resin is between 1:1 and 1:4. The water-soluble composition according to claim 6, wherein the polyvinylpyrrolidone has a solid content of from 15% by weight to 40% by weight based on the total solid content of the water-soluble composition. The water-soluble composition according to claim 6, wherein the ratio of the polyethylene glycol solid content to the aqueous polyurethane resin content is between 1:1 and 1:4. A cover plate for drilling, comprising: a substrate; and the water-soluble composition according to any one of claims 1 to 10, which is disposed on a surface of the substrate. The cover for drilling according to claim 11, wherein the material of the substrate comprises aluminum. A method for preparing a water-soluble composition, comprising: providing an aqueous polyurethane resin; mixing polyethylene glycol, polypropylene glycol, polyethylene oxide copolymer and polyvinylpyrrolidone to form a premixed solution, wherein the polyethylene is mixed before mixing Pyrrolidone Nanocrystallization grinding, wherein the polyethylene oxide copolymer has an alkyl group on its side chain, and the viscosity of the polyethylene oxide copolymer is from 1000 cps to 10000 cps, and the content of the polyethylene oxide copolymer and the polyvinylpyrrolidone content a ratio of between 1:4 and 4:1; and a mixed aqueous polyurethane resin, a surfactant, a polyether-oxyalkylene copolymer, a branched alkane copolymer and the premixed solution to form the water-soluble composition Things.