WO2012035771A1 - Entry sheet for drilling - Google Patents
Entry sheet for drilling Download PDFInfo
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- WO2012035771A1 WO2012035771A1 PCT/JP2011/005190 JP2011005190W WO2012035771A1 WO 2012035771 A1 WO2012035771 A1 WO 2012035771A1 JP 2011005190 W JP2011005190 W JP 2011005190W WO 2012035771 A1 WO2012035771 A1 WO 2012035771A1
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- WIPO (PCT)
- Prior art keywords
- water
- soluble resin
- resin composition
- drilling
- entry sheet
- Prior art date
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Classifications
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0011—Working of insulating substrates or insulating layers
- H05K3/0044—Mechanical working of the substrate, e.g. drilling or punching
- H05K3/0047—Drilling of holes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B26—HAND CUTTING TOOLS; CUTTING; SEVERING
- B26F—PERFORATING; PUNCHING; CUTTING-OUT; STAMPING-OUT; SEVERING BY MEANS OTHER THAN CUTTING
- B26F1/00—Perforating; Punching; Cutting-out; Stamping-out; Apparatus therefor
- B26F1/16—Perforating by tool or tools of the drill type
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B26—HAND CUTTING TOOLS; CUTTING; SEVERING
- B26D—CUTTING; DETAILS COMMON TO MACHINES FOR PERFORATING, PUNCHING, CUTTING-OUT, STAMPING-OUT OR SEVERING
- B26D7/00—Details of apparatus for cutting, cutting-out, stamping-out, punching, perforating, or severing by means other than cutting
- B26D7/08—Means for treating work or cutting member to facilitate cutting
- B26D7/088—Means for treating work or cutting member to facilitate cutting by cleaning or lubricating
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/02—Details related to mechanical or acoustic processing, e.g. drilling, punching, cutting, using ultrasound
- H05K2203/0214—Back-up or entry material, e.g. for mechanical drilling
Definitions
- the present invention relates to an entry sheet for drilling used for drilling a copper-clad laminate or multilayer board.
- a drilling method for copper-clad laminates and multilayer boards used for printed circuit boards one or more copper-clad laminates or multilayer boards are stacked, and an aluminum foil or aluminum is used as a backing plate on the top.
- a method in which a sheet having a resin composition layer formed on the foil surface (hereinafter referred to as “sheet for drilling” in the present specification is referred to as “entry sheet for drilling”) and drilling is generally employed. Yes.
- Recent trends include the following characteristics.
- the globalization of printed circuit board producers is shifting from Japan to Taiwan, South Korea, China, and other Asian countries, driven by cost reduction and industrial integration with semiconductors.
- drill drilling entry sheets must be transferred from short-term transportation such as domestic transportation or air transportation to long-term room-temperature transportation such as shipping normal temperature container transportation. Moreover, since it may be stored in a temperature environment higher than that in Japan, it is required to exhibit excellent hole position accuracy even after such a temperature history of transportation and storage. In other words, there is a strong demand for the development of a drilling entry sheet that exhibits excellent hole position accuracy even after a temperature history higher than that of the prior art.
- an object of the present invention is to provide an entry sheet for drilling that exhibits excellent hole position accuracy even when transported at room temperature for a long time and / or stored in a temperature environment higher than Japan. .
- the present inventors have added a specific colorant to the water-soluble resin composition layer formed on the surface of the drill hole entry sheet.
- the present inventors have found that the above problem can be solved by increasing the crystallinity and exhibiting excellent hole position accuracy even after the accelerated thermal degradation test. That is, the present invention is as follows.
- a drilling entry sheet for a laminate or multilayer board comprising a metal support foil and a water-soluble resin composition layer formed on at least one side of the metal support foil,
- the water-soluble resin composition comprises a water-soluble resin, a water-soluble lubricant, and 2,7-naphthalenedisulfonic acid, 3-hydroxy-4-[(4-sulfo-1-naphthalene) azo]-, trisodium salt (red 2)
- the layer of the water-soluble resin composition was dried after applying a hot melt of the water-soluble resin composition on the metal support foil or by applying a solution containing the water-soluble resin composition. Thereafter, it is formed by cooling from a cooling start temperature of 120 ° C. to 160 ° C.
- the water-soluble resin composition has a crystallinity of 1.2 or more, Wherein the standard deviation ⁇ of the surface hardness of the layer of the water-soluble resin composition is 2 or less, drilling drilling for entry sheet, wherein the surface hardness of 8.5 N / mm 2 or more 20 N / mm 2 or less.
- the water-soluble resin is at least one selected from the group consisting of polyethylene oxide and polyalkylene glycol polyester, and the water-soluble lubricant is polyethylene glycol [1] Entry sheet for drilling as described in.
- the addition amount of the red No. 2 is 0.01 part by weight or more and 10 parts by weight or less with respect to a total of 100 parts by weight of the water-soluble resin and the water-soluble lubricant. ] Is an entry sheet for drilling.
- the addition amount of the sodium formate is 0.01 parts by weight or more and 1.5 parts by weight or less with respect to 100 parts by weight in total of the water-soluble resin and the water-soluble lubricant. Entry sheet for drilling according to 4].
- the thickness of the metal supporting foil is 0.05 mm or more and 0.5 mm or less, and the thickness of the water-soluble resin composition layer is 0.01 mm or more and 0.3 mm or less. Entry sheet for drilling.
- the entry sheet for drilling according to the present invention has an excellent rate of change in hole position accuracy within + 10% after a thermal degradation acceleration test condition, for example, a thermal degradation acceleration test at 50 ° C. for 1 hour. Even if it is transported and / or stored under a temperature environment higher than that of Japan, it contributes to preventing or improving the thermal deterioration of the hole position accuracy. This has enabled high-density drilling to meet globalization and demand fluctuations.
- the present invention is an entry sheet for drilling for a laminate or multilayer board comprising a metal support foil and a layer of a water-soluble resin composition formed on at least one side of the metal support foil, Water-soluble resin, water-soluble lubricant and 2,7-naphthalenedisulfonic acid, 3-hydroxy-4-[(4-sulfo-1-naphthalene) azo]-, trisodium salt (Red No. 2)
- the water-soluble resin composition layer is applied to the metal support foil after the hot melt of the water-soluble resin composition is applied or a solution containing the water-soluble resin composition is applied. After being dried, it is formed by cooling from a cooling start temperature of 120 ° C. to 160 ° C. to a cooling end temperature of 25 ° C.
- the water-soluble resin composition has a crystallinity of 1.2 or more, The standard deviation of the surface hardness of the layer of fat composition ⁇ 2 or less, the surface hardness of an entry sheet for drilling boring, characterized in that it is 8.5 N / mm 2 or more 20 N / mm 2 or less.
- the water-soluble resin in the present invention has a relatively high molecular weight.
- film formability is required, and the water-soluble resin is blended to impart film formability to the water-soluble resin composition, and its molecular structure is not limited.
- Mw weight average molecular weight
- the water-soluble resin is at least one selected from the group consisting of polyethylene oxide, polypropylene oxide, polyacrylic acid soda, polyacrylamide, polyvinylpyrrolidone, carboxymethylcellulose, polytetramethylene glycol, and polyalkylene glycol polyester. It is preferable.
- the polyester of polyalkylene glycol is a condensate obtained by reacting polyalkylene glycol and dibasic acid.
- the polyalkylene glycol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and glycols exemplified by these copolymers.
- the dibasic acid include phthalic acid, isophthalic acid, terephthalic acid, sebacic acid and the like.
- a polycarboxylic acid such as pyromellitic acid may be partially esterified to have two carboxyl groups. These may be acid anhydrides. These can be used alone or in combination of two or more, but polyethylene oxide (PEO) is more preferred.
- the water-soluble lubricant in the present invention has a relatively low molecular weight.
- the water-soluble lubricant is blended to impart lubricity to the water-soluble resin composition, and its molecular structure is not limited, but the weight average molecular weight (Mw) is in the range of 500 to 25,000. preferable.
- water-soluble lubricants include polyethylene glycol, polypropylene glycol; polyoxyethylene oleyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxy Polyoxyethylene monoethers exemplified by ethylene octylphenyl ether; polyoxyethylene monostearate, polyoxyethylene sorbitan monostearate; poly exemplified by hexaglycerin monostearate, decahexaglycerin monostearate, etc. Examples include glycerin monostearates; polyoxyethylene propylene copolymers and the like, and one or more kinds may be appropriately blended and used. Although, it is more preferably a polyethylene glycol (PEG).
- PEG polyethylene glycol
- the blending amount of the water-soluble resin and the water-soluble lubricant in the present invention is preferably in the range of 3 to 80 parts by weight of the water-soluble resin and 20 to 97 parts by weight of the water-soluble lubricant.
- the total of the water-soluble resin mixture of the water-soluble resin and the water-soluble lubricant is 100 parts by weight. If the water-soluble resin is less than 3 parts by weight, the sheet formability is poor. On the other hand, if the water-soluble resin exceeds 80 parts by weight, resin wrapping around the drill bit increases, which is not preferable.
- the crystallinity of the water-soluble resin composition is 1.2 or more.
- 2,7-Naphthalenedisulfonic acid, 3-hydroxy-4-[(4-sulfo-1-naphthalene) azo]-, trisodium salt (red No. 2) is water soluble in the drill hole entry sheet of the present invention.
- red No. 2 is water soluble in the drill hole entry sheet of the present invention.
- it has the effect of increasing the crystallinity of the resin composition and improving the hole position accuracy, but especially after the thermal deterioration accelerated test conditions, for example, the thermal deterioration accelerated test at 50 ° C. for 1 hour, The present inventors have found that a characteristic action and effect of improving the resistance is exhibited.
- Red No. 2 2,7-Naphthalenedisulfonic acid, 3-hydroxy-4-[(4-sulfo-1-naphthalene) azo]-, trisodium salt
- the thermal degradation accelerated test condition refers to a condition of keeping at a temperature higher than normal temperature for a predetermined time.
- the temperature is appropriately set to a temperature higher than the solidification temperature of the water-soluble resin composition and lower than the melting point.
- the addition amount of Red No. 2 is preferably 0.01 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight in total of the water-soluble resin and the water-soluble lubricant.
- the amount of Red No. 2 is less than 0.01 parts by weight, it is difficult to obtain the effect.
- the addition amount of Red No. 2 exceeds 10 parts by weight, it becomes difficult to uniformly disperse Red No. 2 in the water-soluble resin composition, and Red No. 2 from the surface of the water-soluble resin composition layer. May precipitate.
- red No. 2 is deposited, the drill bit hits the drill bit, the hole position accuracy deteriorates and the drill bit breaks, and red No. 2 may remain in the hole wall after drilling. Therefore, the amount of Red No.
- Red No. 2 added is preferably 0.01 parts by weight or more and 10 parts by weight or less, and is desirably optimized as appropriate.
- the addition amount of Red No. 2 is more preferably 0.05 parts by weight or more and 8 parts by weight or less, and still more preferably 0.1 parts by weight or more and 6 parts by weight or less.
- the water-soluble resin composition used for the entry sheet for drilling according to the present invention preferably further contains sodium formate.
- the sodium formate when added to the water-soluble resin composition, acts to increase the crystallinity of the water-soluble resin composition, and is a nucleating agent that contributes to improving the accuracy of pore position.
- the amount of sodium formate added is preferably 0.01 parts by weight or more and 1.5 parts by weight or less with respect to 100 parts by weight in total of the water-soluble resin and the water-soluble lubricant. When the amount of sodium formate added is less than 0.01 parts by weight, the effect of increasing the crystallinity is hardly exhibited.
- the amount of sodium formate added is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, still more preferably 0.1 parts by weight or more, and particularly preferably 0.0. 25 parts by weight or more and 1.0 parts by weight or less.
- the amount of sodium formate added exceeds 1.5 parts by weight, sodium formate may be deposited on the surface of the water-soluble resin composition layer, which may cause problems.
- red No. 2 and sodium formate in the present invention have different intended actions. For this reason, it is preferable to use Red No. 2 and sodium formate in combination rather than Red No. 2 alone.
- Red No. 2 and sodium formate in combination rather than Red No. 2 alone.
- a comparative example to be described later in the case of a resin composition to which Red No. 2 and sodium formate are not added, compared to the hole position accuracy before a thermal degradation acceleration test at 50 ° C. for 1 hour, There is an example in which the hole position accuracy deteriorates after the accelerated thermal degradation test.
- the inventors have a three-dimensional crystal structure, spherulites are crushed in the plane direction (XY direction), and spherulites are layered in the depth method (Z direction). Since it is a structure that forms a layer, and all of the polymer does not spheroidize and there is an amorphous part, the water-soluble red No. 2 is dispersed in the details of the three-dimensional structure, It is believed that it contributes to the formation of spherulites in the crystal part and has the effect of further increasing the formation of dense spherulites and their crystallinity.
- Red No. 2 is preferable from the viewpoint of the environment because it is a colorant containing no halogen. Also, Red No. 2 is preferable because it is water-soluble, and even if it remains on the hole wall after drilling, it can be washed with water.
- Red No. 2 may be dissolved in water or a solvent in advance and then added to the water-soluble resin composition, or may be added directly to the water-soluble resin composition.
- the method of dissolving Red No. 2 in water or a solvent in advance and then adding it to the water-soluble resin composition is easy to uniformly disperse.
- Examples of methods for measuring the crystallinity include X-ray diffraction, DSC (Differential Scanning Calorimetry), and the present invention defines the crystallinity as a relative value using DSC.
- the standard resin composition (A) is red No. 2 with respect to 100 parts by weight of polyethylene oxide having a weight average molecular weight (Mw) of 110,000 (Alcox L11 manufactured by Meisei Kogyo Kagaku Co., Ltd.). Is added 5 parts by weight.
- Mw weight average molecular weight
- the degree of crystallinity of the standard resin composition (A) is calculated by using DSC to calculate the amount of solidification when the temperature is lowered for the second time. The degree is defined as 1.0.
- the crystallinity of each sample is calculated by the following procedure.
- the DSC analysis is performed, and the amount of heat of solidification at the second temperature drop is calculated.
- the crystallinity of the sample is calculated from the following equation.
- Sample crystallinity solidification heat of sample ⁇ solidification heat of standard resin composition (A)
- the solidification temperature of the water-soluble resin composition is determined by DSC measurement as described above.
- the measurement conditions are the same as those for the crystallinity measurement, and the peak top temperature of the exothermic peak at the time of solidification at the second temperature drop is used as the solidification temperature.
- the inventors of the present invention have a state of the water-soluble resin composition layer that affects the performance of the entry sheet when the water-soluble resin composition layer formed on the surface of the metal supporting foil is cooled from the molten state and solidifies. I think it will be decided. Therefore, it is necessary to pay attention to the solidification temperature and the heat of solidification while lowering the temperature as described above, not the melting temperature and the heat of fusion while raising the temperature. Specifically, the higher the solidification temperature of the water-soluble resin composition, the higher the crystallinity and the more stable against heat. As a result, the crystal state of the water-soluble resin composition of the entry sheet for drilling is not easily affected by the heat history of the transportation and / or storage environment, and the hole position accuracy is improved.
- the addition of Red No. 2 or Red No. 2 and sodium formate to the water-soluble resin composition increases the solidification temperature as compared to the case where these are not added, so that the crystallinity is improved.
- the hole position accuracy can be made an excellent value.
- the solidification temperature of the water-soluble resin composition is preferably 30 ° C or higher, more preferably 35 ° C or higher, still more preferably 40 ° C or higher, still more preferably 42 ° C or higher, still more preferably 44 ° C or higher, particularly preferably. It is 46 ° C. or higher.
- the solidification temperature of the water-soluble resin composition is preferably 70 ° C. or less, more preferably 65 ° C. or less, and still more preferably 60 ° C. or less.
- the present inventors have found that a high numerical value of crystallinity contributes to improvement in hole position accuracy.
- the addition of Red No. 2 or Red No. 2 and sodium formate to the water-soluble resin composition increases the crystallinity compared to the case where these are not added, and as a result, The accuracy can be improved.
- Red No. 2 has a different function from sodium formate as described above.
- the crystallinity of the water-soluble resin composition is 1.2 or more, preferably 1.25 or more, and more preferably 1.3 or more.
- the surface hardness value of the water-soluble resin composition layer affects the hole position accuracy during drilling.
- variation in the surface hardness of the water-soluble resin composition layer is important, and it is necessary to control the surface hardness uniformly.
- the addition of Red No. 2 or Red No. 2 and sodium formate to the water-soluble resin composition improves the crystallinity and causes variations in surface hardness compared to the case where these are not added. Can be small.
- the variation in surface hardness can be reduced after a thermal degradation accelerated test, for example, a thermal degradation accelerated test at 50 ° C. for 1 hour. As a result, the hole position accuracy can be made excellent.
- a dynamic ultra-micro hardness meter manufactured by Shimadzu Corporation, DUH-211 was used, indenter: Triangular 115, sample force: 10 mN, loading speed: 0. 7316 mN / sec, load holding time: 10 sec, Poisson's ratio: 0.07 Surface hardness (Martens hardness) of the water-soluble resin composition layer at any 10 points from the vertical upper part of the drilling entry sheet ). The average value and standard deviation ⁇ of the surface hardness obtained at that time are calculated.
- the standard deviation ⁇ of the surface hardness of the water-soluble resin composition layer needs to be 2 or less.
- the standard deviation ⁇ of the surface hardness of the layer of the water-soluble resin composition is 2 or less, preferably 1.0 or less, and most preferably 0.5 or less.
- the surface hardness value of the layer of the water-soluble resin composition is at 8.5 N / mm 2 or more, preferably 9N / mm 2 or more, more preferably 9.5 N / mm 2 or more, even more preferably 10 N / mm 2 or more.
- the surface hardness value of the layer of the water-soluble resin composition is 20 N / mm 2 or less.
- the thermal stability of the entry sheet for drilling according to the present invention can be confirmed by the hole position accuracy change rate (%) before and after the thermal deterioration acceleration test and the standard deviation (N / mm 2 ) of the surface hardness.
- the thermal degradation accelerated test condition refers to a condition of keeping at a temperature higher than normal temperature for a predetermined time. Specifically, using an explosion-proof dryer (SPHH-202 manufactured by ESPEC), an entry sheet for drilling that is cut to a size of 50 ⁇ 100 mm under an open atmosphere (in an air atmosphere) is used as a water-soluble resin. The composition layer is placed on the top (with the metal supporting foil as the lower layer) and placed flat, for example, left at 50 ° C.
- the thermal degradation acceleration test temperature is appropriately set to a temperature higher than the solidification temperature of the water-soluble resin composition and lower than the melting point. If the temperature is higher than the melting point, the water-soluble resin composition is melted, and the performance provided before melting cannot be understood, so that it is not possible to evaluate the characteristics as an entry sheet for drilling. On the other hand, at a temperature lower than the solidification temperature, it is not an accelerated test for examining thermal stability.
- the hole position accuracy of the drilling entry sheet differs depending on the processing base material, drilling processing conditions, drill bit diameter, and the like. Therefore, in order to make a relative comparison rather than comparing simple hole location accuracy values, the thermal location acceleration test conditions, for example, the hole location accuracy before and after the thermal degradation acceleration test for 1 hour at 50 ° C. A method of comparing the rate of change (%) can be taken.
- the change rate of the hole position accuracy can be calculated from the following equation.
- Rate of change in hole position accuracy (Hole position accuracy after thermal degradation acceleration test-Hole location accuracy before thermal degradation acceleration test) ⁇ Pole position accuracy before thermal degradation acceleration test ⁇ 100
- the change rate (%) of the hole position accuracy before and after the thermal degradation accelerated test condition at 50 ° C. for 1 hour, for example, is within + 10%.
- the change rate of the hole position accuracy before and after the thermal deterioration acceleration test is preferably within + 10%, more preferably within + 5%, further preferably 0%, and even more preferably within ⁇ 5%.
- a method for preparing a water-soluble resin composition single or plural water-soluble resin components are dissolved in a solvent, and then red No. 2 or red No. 2 and sodium formate are added to the solution to obtain a water-soluble resin.
- the method of making the composition solution and the single or plural water-soluble resin components are dissolved in heat, and then red No. 2 or red No. 2 and sodium formate are added to the hot-dissolution of the water-soluble resin composition Examples of such methods are as follows.
- the water-soluble resin composition is appropriately heat-dissolved or applied to at least one surface of the metal support foil as a liquid dissolved or dispersed in a solvent.
- a manufacturing method of a water-soluble resin composition layer if it is a well-known method used industrially, it will not specifically limit.
- the water-soluble resin composition is appropriately heated and melted and mixed using a roll or kneader or other kneading means, and the water-soluble resin composition is formed on the release film by a roll method or a curtain coat method.
- a roll method or a curtain coat method examples thereof include a method of forming a physical layer, and a method of forming a water-soluble resin composition into a water-soluble resin composition sheet having a desired thickness in advance using a roll, a T-die extruder, or the like.
- the conditions for drying the water-soluble resin composition solution after coating the water-soluble resin composition solution directly on the metal support foil are optimized depending on the thickness of the water-soluble resin composition layer. It is desirable. Specifically, the temperature is preferably 120 to 160 ° C. for 10 seconds to 600 seconds for drying, more preferably the temperature of 120 to 160 ° C. for 10 seconds to 500 seconds for drying, It is more preferable that the temperature is 120 ° C. to 160 ° C. for 15 seconds to 400 seconds to dry, and it is particularly preferable that the temperature is 120 ° C. to 150 ° C. for 20 seconds to 300 seconds for drying.
- the solvent may remain inside the water-soluble resin composition layer, or the water-soluble resin composition may be Since the amount of heat necessary for melting is insufficient, there is a possibility that a non-uniform water-soluble resin composition layer is formed.
- the drying temperature is higher than 200 ° C., or when the holding time exceeds 600 seconds, the water-soluble resin composition may be decomposed to cause a problem in appearance.
- the cooling condition of the water-soluble resin composition of the entry sheet for drilling is generally a cooling rate of less than 1.2 ° C./second.
- the cooling condition of the water-soluble resin composition in the present invention may be a cooling rate of less than 1.2 ° C./second, but it takes 60 seconds from a cooling start temperature of 120 ° C. to 160 ° C. to a cooling end temperature of 25 ° C. to 40 ° C. And cooling at a cooling rate of 1.5 ° C./second or more.
- the cooling end temperature needs to be set to a temperature lower than the solidification temperature of the water-soluble resin composition. However, when the cooling end temperature is lower than 15 ° C., the entry sheet is warped and may cause condensation in a subsequent process, which is not preferable.
- the cooling condition is more preferably that the temperature is reduced from 120 ° C. to 160 ° C. to the temperature 25 ° C. to 40 ° C. within 50 seconds at a cooling rate of 2 ° C./second or more. It is more preferable to cool to a temperature of 25 ° C. to 40 ° C. within 40 seconds at a cooling rate of 2.5 ° C./second or more. From a temperature of 120 ° C. to 160 ° C. to a temperature of 25 ° C.
- the cooling rate is more preferably 3 ° C./second or more, and the cooling rate is 4.5 ° C./second or more within 20 seconds from the temperature 120 ° C. to 160 ° C. to the temperature 25 ° C. to 40 ° C. It is more preferable to cool at a temperature of 120 ° C. to 160 ° C., and it is most preferable to cool at a cooling rate of 6 ° C./second or more within 15 seconds from a temperature of 120 ° C. to 160 ° C.
- the metal species of the metal support foil used in the entry sheet for drilling according to the present invention is preferably aluminum, and the thickness of the metal support foil is usually 0.05 to 0.5 mm, preferably 0.05 to 0.3 mm. is there. If the thickness of the metal support foil is less than 0.05 mm, burrs of the laminated plate are likely to occur during drilling, whereas if it exceeds 0.5 mm, it is difficult to discharge chips generated during drilling. .
- the material of the aluminum foil is preferably aluminum having a purity of 95% or more, and specifically, 5052, 3004, 3003, 1N30, 1N99, 1050, 1070, 1085, 8021, etc. defined in JIS-H4160 are exemplified. Is done.
- the metal support foil By using high-purity aluminum foil as the metal support foil, the impact and biting properties of the drill bit are reduced, and the hole position accuracy of the machined hole is combined with the lubrication effect of the drill bit by the water-soluble resin composition. Will improve.
- the resin used for the resin film is not particularly limited, and may be either a thermoplastic resin or a thermosetting resin.
- the thermoplastic resin include urethane polymers, vinyl acetate polymers, vinyl chloride polymers, polyester polymers, and copolymers thereof.
- the thermosetting resin include resins such as epoxy resins and cyanate resins.
- the metal supporting foil used in the present invention a commercially available metal foil previously coated with a resin film by a known method may be used.
- Red No. 2 The action of Red No. 2 is to add to the water-soluble resin composition as described above to improve the crystallinity. As a result, the variation in surface hardness can be reduced, and the hole position accuracy can be made an excellent value. Therefore, even if it is added to the resin film, the expected effect is not exhibited.
- the drill drilling entry sheet of the present invention is assumed to be used for drill drilling with a drill bit diameter of 0.05 mm ⁇ or more and 0.3 mm ⁇ or less in the drilling processing of a laminate or multilayer board.
- it is suitable for applications having a small diameter of 0.05 mm ⁇ to 0.15 mm ⁇ in which accuracy of the hole position is important, and particularly to applications having an extremely small diameter of 0.05 mm ⁇ to 0.105 mm ⁇ .
- the thickness of the water-soluble resin composition layer in the drill hole entry sheet of the present invention varies depending on the diameter of the drill bit used when drilling, the configuration of the copper-clad laminate or multilayer board to be processed, etc.
- the range is 0.01 to 0.3 mm, preferably 0.02 to 0.2 mm, and more preferably 0.02 to 0.12 mm.
- the thickness of the water-soluble resin composition layer is less than 0.01 mm, a sufficient lubricating effect cannot be obtained, the hole wall roughness is deteriorated, the load on the drill bit is increased, and the drill bit is broken.
- the thickness of the water-soluble resin composition layer exceeds 0.3 mm, resin wrapping around the drill bit may increase.
- each layer constituting the drill hole entry sheet is measured as follows. Entry for drilling from the water-soluble resin composition layer surface of the drilling entry sheet with a cross section polisher (CROSS-SECTIONION / POLISHER SM-09010 made by JEOL Datum Co., Ltd.) or ultramicrotome (EM UC7 made by Leica) After the sheet was cut in a direction perpendicular to the water-soluble resin composition layer, the cross section was observed from the direction perpendicular to the cross section with SEM (scanning electron microscope, Scanning Electron Microscope, VE-7800 manufactured by KEYENCE Corp.), and 900 The thickness of the aluminum layer and the water-soluble resin composition layer is measured with a double field of view. The thickness of five places is measured for one visual field, and the average is defined as the thickness of each layer.
- the entry sheet for drilling when drilling a printed circuit board material, for example, a copper-clad laminate or a multilayer board, one piece of the copper-clad laminate or multilayer board or At least the top surface of the stack of multiple sheets is placed so that the metal support foil side of the entry sheet is in contact with the printed circuit board material, and drilling is performed from the surface of the water-soluble resin composition layer of the entry sheet for drilling. Is to do.
- polyethylene glycol may be abbreviated as “PEG”, “polyethylene oxide” as “PEO”, and “polyether ester” as “PEE”.
- Table 1 shows the specifications of raw materials such as resins and colorants used for manufacturing the drilling entry sheets of Examples and Comparative Examples.
- Example 1 80 parts by weight of polyethylene oxide having a weight average molecular weight of 110,000 (manufactured by Meisei Chemical Industry Co., Ltd., Alcox L11) and 20 parts by weight of 20,000 polyethylene glycol (manufactured by Sanyo Chemical Industries, Ltd., PEG 20000) The mixture was completely dissolved in a mixed solution of water and MeOH so that the content was 30%. The ratio of water and MeOH at this time is 70 parts by weight to 30 parts by weight.
- Red No. 2 (Amaranth, manufactured by Kanto Chemical Co., Inc.) was added to 100 parts by weight of the solid content of the water-soluble resin mixture, and completely dissolved.
- the water-soluble resin composition layer is coated to a thickness of 0.05 mm, dried at 120 ° C. for 5 minutes in a drier, and further cooled at a cooling rate of 3.1 ° C./second to drill holes.
- An entry sheet was prepared.
- the cooling start temperature was 120 ° C.
- the cooling end temperature was 27 ° C.
- cooling was performed from the cooling start temperature to the cooling end temperature in 30 seconds at a cooling rate of 3.1 ° C./second.
- the obtained drill hole entry sheet was made by stacking 5 sheets of copper-clad laminate (CCL-HL832, copper foil both sides 12 ⁇ m, manufactured by Mitsubishi Gas Chemical Co., Ltd.) with a thickness of 0.2 mm, and a water-soluble resin composition. Arranged with the material layer facing upward, a backing plate (baked plate) is placed on the lower side of the stacked copper-clad laminate, and a drill bit: 0.2 mm ⁇ (manufactured by Tungaloy Co., Ltd., CFU020S), rotation speed: 200, Four drill holes were drilled at 3,000 hits per drill bit under the conditions of 000 rpm and feed rate: 2.6 m / min.
- CCL-HL832 copper foil both sides 12 ⁇ m, manufactured by Mitsubishi Gas Chemical Co., Ltd.
- the unused entry sheet for drilling which was cut into a size of 50 ⁇ 100 mm under an open atmosphere (under an air atmosphere), was dissolved in water.
- the resin layer was placed flat with the conductive resin composition layer as the upper layer (with the metal support foil as the lower layer), allowed to stand at 50 ° C. for 1 hour, and then left in a room temperature (25 ° C.) atmosphere.
- 5 sheets of copper-clad laminate (CCL-HL832, copper foil both sides 12 ⁇ m, manufactured by Mitsubishi Gas Chemical Co., Ltd.) having a thickness of 0.2 mm were stacked on this entry sheet for drilling, and a water-soluble resin composition.
- a backing plate (baked plate) is placed on the lower side of the stacked copper-clad laminate, and a drill bit: 0.2 mm ⁇ (manufactured by Tungaloy Co., Ltd., CFU020S), rotation speed: 200, Four drill holes were drilled at 3,000 hits per drill bit under the conditions of 000 rpm and feed rate: 2.6 m / min.
- Table 3 shows the hole position accuracy Ave. + 3 ⁇ ( ⁇ m), hole position accuracy variation ⁇ Ave. + 3 ⁇ ( ⁇ m), hole position accuracy change rate Ave. + 3 ⁇ (%), solidification temperature (° C.), heat of solidification (J / mg), crystallinity, surface hardness Ave. (N / mm 2 ), standard deviation ⁇ (N / mm 2 ) of surface hardness, and the result of comprehensive judgment are shown.
- Example 2 to 5 and Comparative Examples 1 to 24 the water-soluble resin compositions shown in Tables 1 and 2 were prepared according to Example 1, and applied to an aluminum foil, dried, cooled, and drilled. An entry sheet for punching was prepared. Among these, for Example 5, an entry sheet for drilling was prepared at a cooling rate after coating and drying of 2.0 ° C./second. The cooling start temperature was 120 ° C., the cooling end temperature was 27 ° C., and cooling was performed from the cooling start temperature to the cooling end temperature in 46 seconds at a cooling rate of 2.0 ° C./sec.
- drilling entry sheets were prepared at a cooling rate of 1.0 ° C./second after coating and drying.
- the cooling start temperature was 120 ° C.
- the cooling end temperature was 27 ° C.
- cooling was performed from the cooling start temperature to the cooling end temperature in 93 seconds at a cooling rate of 1.0 ° C./sec.
- drilling processing was performed according to Example 1 using this entry sheet for drilling.
- using an explosion-proof dryer (SPHH-202 manufactured by ESPEC) left at 50 ° C. for 1 hour, and then left in a room temperature (25 ° C.) atmosphere.
- An entry sheet for drilling after the acceleration test was prepared and drilled.
- ⁇ Standard sample> Polyethylene oxide having a weight average molecular weight of 110,000 (Alcox L11, manufactured by Meisei Chemical Industry Co., Ltd.) was completely dissolved in a mixed solution of water and MeOH so that the resin solid content was 30%. The ratio of water and MeOH at this time is 70 parts by weight to 30 parts by weight.
- a solution of a water-soluble resin composition obtained by adding 5 parts by weight of Red No. 2 to 100 parts by weight of polyethylene oxide was used to form an aluminum foil (JIS standard 1100, thickness 0. 1 mm, manufactured by Mitsubishi Aluminum Co., Ltd.) using a bar coater so that the water-soluble resin composition layer after drying has a thickness of 0.05 mm, and dried in a dryer at 120 ° C. for 5 minutes. 3.
- An entry sheet for drilling was produced by cooling at a cooling rate of 3.1 ° C./second. This cooling condition is the same as in the first embodiment. This was used as a standard sample for measuring crystallinity.
- DSC differential scanning calorimeter, DSC 6220 manufactured by SII Nano technology Inc.
- the cooling rate is ⁇ 3 ° C./min. This cycle is carried out twice, and the amount of heat of solidification at the second temperature drop is calculated.
- the measurement condition of the solidification temperature of the water-soluble resin composition is the same as the crystallinity of 1), and the peak top temperature of the exothermic peak at the time of the second temperature decrease is the solidification temperature.
- the surface hardness of the water-soluble resin composition layer is measured using a dynamic ultra-hardness meter (DUH-211, manufactured by Shimadzu Corporation) from the vertical upper part of the drill hole entry sheet.
- Indenter Triangular 115, Sample force: 10 mN, Loading speed: 0.7316 mN / sec, Load holding time: 10 sec, Poisson's ratio: 0.07
- the surface hardness (Martens hardness) of the water-soluble resin composition layer at the point is measured.
- the average value and standard deviation ⁇ of the surface hardness obtained at that time are calculated.
- Drill drilling was performed for each sample under the following conditions. 5 holes of copper-clad laminate (CCL-HL832, copper foil both sides 12 ⁇ m, manufactured by Mitsubishi Gas Chemical Co., Ltd.) with a thickness of 0.2mm are stacked on top of each other. A sheet is placed, a backing plate (baked plate) is placed below the stacked copper-clad laminate, and a drill bit: 0.2 mm ⁇ (manufactured by CFU020S Tungaloy Co., Ltd.) is used, and the rotational speed is 200,000 rpm. The drilling was performed at 3,000 hits per drill bit under a processing condition of feed rate: 2.6 m / min.
- the hole position accuracy of the drill hole entry sheet is determined by measuring the deviation between the hole position of the 3,000 holes on the back surface of the bottom plate of the stacked copper clad laminate and the designated coordinates. (Measured by Hitachi Via Mechanics, HA-1AM) The average value and standard deviation ( ⁇ ) are calculated for each drill bit, and the average value + 3 ⁇ and the maximum value are calculated. Thereafter, the average value of the “average value + 3 ⁇ ” value of the drill bit was calculated and expressed as the hole position accuracy of the entire drilling process.
- the formula is as follows.
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Abstract
Description
第一に、プリント基板の高密度は、とどまることがなく、銅張積層板や多層板の加工孔の導通信頼性が求められている。すなわち、優れた孔位置精度が必要になる。
第二に、プリント基板の生産国は、コスト低減と半導体との産業集積を動機として、日本から、台湾・韓国・中国・その他のアジア諸国に移行するグローバル化が進行しつつある。
第三に、台湾・韓国には、ドリル孔明け用エントリーシートメーカーが勃興しており、これらローカルメーカーと競争する市場環境が生まれつつある。
第四に、半導体関連産業であるためその需要変動が大きく、需要急減期にはドリル孔明け用エントリーシートの在庫がサプライチェーンに発生し、需要回復期まで保管されたのち使用されることがある。また、プリント基板の高密度化により、保管後においても優れた孔位置精度が求められている。 Recent trends include the following characteristics.
First, the high density of a printed circuit board does not stay, and there is a need for the conduction reliability of processed holes in copper-clad laminates and multilayer boards. That is, excellent hole position accuracy is required.
Secondly, the globalization of printed circuit board producers is shifting from Japan to Taiwan, South Korea, China, and other Asian countries, driven by cost reduction and industrial integration with semiconductors.
Third, in Taiwan and Korea, entry sheet manufacturers for drilling are emerging, and a market environment that is competing with these local manufacturers is emerging.
Fourth, because it is a semiconductor-related industry, its demand fluctuation is large, and inventory of drilling entry sheets is generated in the supply chain during the rapid decline of demand and may be used after being stored until the demand recovery period . Further, due to the higher density of printed circuit boards, excellent hole position accuracy is required even after storage.
前記水溶性樹脂組成物が、水溶性樹脂、水溶性潤滑剤および2,7-ナフタレンジスルホン酸,3-ヒドロキシ-4-[(4-スルホ-1-ナフタレン)アゾ]-,トリナトリウム塩(赤色2号)を含み、
前記水溶性樹脂組成物の層は、前記金属支持箔上に前記水溶性樹脂組成物の熱溶融物を塗工した後または前記水溶性樹脂組成物を含有する溶液を塗工して乾燥させた後、冷却開始温度120℃~160℃から冷却終了温度25℃~40℃へと、60秒以内に、1.5℃/秒以上の冷却速度で冷却して形成されるものであり、
前記水溶性樹脂組成物の結晶化度が1.2以上であり、
前記水溶性樹脂組成物の層の表面硬度の標準偏差σが2以下で、表面硬度が8.5N/mm2以上20N/mm2以下である
ことを特徴とするドリル孔明け用エントリーシート。 [1] A drilling entry sheet for a laminate or multilayer board comprising a metal support foil and a water-soluble resin composition layer formed on at least one side of the metal support foil,
The water-soluble resin composition comprises a water-soluble resin, a water-soluble lubricant, and 2,7-naphthalenedisulfonic acid, 3-hydroxy-4-[(4-sulfo-1-naphthalene) azo]-, trisodium salt (red 2)
The layer of the water-soluble resin composition was dried after applying a hot melt of the water-soluble resin composition on the metal support foil or by applying a solution containing the water-soluble resin composition. Thereafter, it is formed by cooling from a cooling start temperature of 120 ° C. to 160 ° C. to a cooling end temperature of 25 ° C. to 40 ° C. within 60 seconds at a cooling rate of 1.5 ° C./second or more.
The water-soluble resin composition has a crystallinity of 1.2 or more,
Wherein the standard deviation σ of the surface hardness of the layer of the water-soluble resin composition is 2 or less, drilling drilling for entry sheet, wherein the surface hardness of 8.5 N / mm 2 or more 20 N / mm 2 or less.
試料の結晶化度=試料の固化熱量÷標準樹脂組成物(A)の固化熱量 Third, in the present invention, the crystallinity of each sample is calculated by the following procedure. For example, in the case of the example and the comparative example, the DSC analysis is performed, and the amount of heat of solidification at the second temperature drop is calculated. Then, the crystallinity of the sample is calculated from the following equation.
Sample crystallinity = solidification heat of sample ÷ solidification heat of standard resin composition (A)
(熱劣化加速試験後の孔位置精度-熱劣化加速試験前の孔位置精度)
÷熱劣化加速試験前の孔位置精度×100 Rate of change in hole position accuracy (%) =
(Hole position accuracy after thermal degradation acceleration test-Hole location accuracy before thermal degradation acceleration test)
÷ Pole position accuracy before thermal degradation acceleration test × 100
Table 1 shows the specifications of raw materials such as resins and colorants used for manufacturing the drilling entry sheets of Examples and Comparative Examples.
重量平均分子量 110,000のポリエチレンオキサイド(明成化学工業株式会社製、アルコックスL11)80重量部と重量平均分子量 20,000ポリエチレングリコール(三洋化成工業株式会社製、PEG20000)20重量部を、樹脂固形分が30%になるように、水とMeOHの混合溶液に完全に溶解させた。この時の水とMeOHとの比率を70重量部対30重量部としている。 <Example 1>
80 parts by weight of polyethylene oxide having a weight average molecular weight of 110,000 (manufactured by Meisei Chemical Industry Co., Ltd., Alcox L11) and 20 parts by weight of 20,000 polyethylene glycol (manufactured by Sanyo Chemical Industries, Ltd., PEG 20000) The mixture was completely dissolved in a mixed solution of water and MeOH so that the content was 30%. The ratio of water and MeOH at this time is 70 parts by weight to 30 parts by weight.
実施例2~5及び比較例1~24については、実施例1に準じて、表1及び表2に示す水溶性樹脂組成物を調製し、アルミニウム箔に塗工、乾燥、冷却して、ドリル孔明け用エントリーシートを作製した。
このうち、実施例5については、塗工、乾燥後の冷却速度を2.0℃/秒にて、ドリル孔明け用エントリーシートを作製した。その冷却開始温度は120℃であり、冷却終了温度は27℃であり、2.0℃/秒の冷却速度で46秒で冷却開始温度から冷却終了温度まで冷却した。
また、比較例2,3,5,6,8,10,11,13については、塗工、乾燥後の冷却速度を1.0℃/秒にて、ドリル孔明け用エントリーシートを作製した。その冷却開始温度は120℃であり、冷却終了温度は27℃であり、1.0℃/秒の冷却速度で93秒で冷却開始温度から冷却終了温度まで冷却した。
次に、このドリル孔明け用エントリーシートを用いて、実施例1に準じて、ドリル孔明け加工を行った。
また、実施例1に準じて、防爆型乾燥機(ESPEC社製 SPHH-202)を用いて、50℃、1時間放置し、その後、室温(25℃)雰囲気下に放置する方法で、熱劣化加速試験後のドリル孔明け用エントリーシートを作製し、ドリル孔明け加工を行った。 <Examples 2 to 5 and Comparative Examples 1 to 24>
For Examples 2 to 5 and Comparative Examples 1 to 24, the water-soluble resin compositions shown in Tables 1 and 2 were prepared according to Example 1, and applied to an aluminum foil, dried, cooled, and drilled. An entry sheet for punching was prepared.
Among these, for Example 5, an entry sheet for drilling was prepared at a cooling rate after coating and drying of 2.0 ° C./second. The cooling start temperature was 120 ° C., the cooling end temperature was 27 ° C., and cooling was performed from the cooling start temperature to the cooling end temperature in 46 seconds at a cooling rate of 2.0 ° C./sec.
For Comparative Examples 2, 3, 5, 6, 8, 10, 11, and 13, drilling entry sheets were prepared at a cooling rate of 1.0 ° C./second after coating and drying. The cooling start temperature was 120 ° C., the cooling end temperature was 27 ° C., and cooling was performed from the cooling start temperature to the cooling end temperature in 93 seconds at a cooling rate of 1.0 ° C./sec.
Next, drilling processing was performed according to Example 1 using this entry sheet for drilling.
Further, according to Example 1, using an explosion-proof dryer (SPHH-202 manufactured by ESPEC), left at 50 ° C. for 1 hour, and then left in a room temperature (25 ° C.) atmosphere. An entry sheet for drilling after the acceleration test was prepared and drilled.
重量平均分子量 110,000のポリエチレンオキサイド(アルコックスL11、明成化学工業株式会社製)を樹脂固形分が30%になるように、水とMeOHの混合溶液に完全に溶解させた。この時の水とMeOHとの比率を70重量部対30重量部としている。ポリエチレンオキサイド100重量部に対して赤色2号を5重量部添加した水溶性樹脂組成物の溶液を、片面に厚み0.01mmのエポキシ樹脂皮膜を形成したアルミニウム箔(JIS規格1100、厚さ0.1mm、三菱アルミニウム株式会社製)にバーコーターを用いて乾燥後の水溶性樹脂組成物層の厚みが0.05mmになるように塗工し、乾燥機にて120℃、5分間乾燥させ、さらに3.1℃/秒の冷却速度で冷却することで、ドリル孔明け用エントリーシートを作製した。なお、この冷却条件は、実施例1と同一である。これを結晶化度測定用標準試料とした。 <Standard sample>
Polyethylene oxide having a weight average molecular weight of 110,000 (Alcox L11, manufactured by Meisei Chemical Industry Co., Ltd.) was completely dissolved in a mixed solution of water and MeOH so that the resin solid content was 30%. The ratio of water and MeOH at this time is 70 parts by weight to 30 parts by weight. A solution of a water-soluble resin composition obtained by adding 5 parts by weight of Red No. 2 to 100 parts by weight of polyethylene oxide was used to form an aluminum foil (JIS standard 1100,
樹脂組成A PEO:PEG=80重量部:20重量部
樹脂組成B PEO:PEG=20重量部:80重量部
樹脂組成C PEE:PEG=20重量部:80重量部
樹脂組成D PEO100重量部 <Resin composition>
Resin composition A PEO: PEG = 80 parts by weight: 20 parts by weight Resin composition B PEO: PEG = 20 parts by weight: 80 parts by weight Resin composition C PEE: PEG = 20 parts by weight: 80 parts by weight Resin composition D PEO 100 parts by weight
a 赤色2号
b 黄色5号
c 青色1号
- 非添加 <Colorant>
a Red No. 2 b Yellow No. 5 c Blue No. 1-No addition
1)結晶化度
本発明では、水溶性樹脂組成物の結晶化度測定方法として、得られた水溶性樹脂組成物に対してDSC(示差走査熱量計、SII Nano technology Inc.製 DSC6220)を用いる。
条件として、30℃から100℃に昇温後、100℃で3分間保持、次いで、100℃から30℃に冷却後、30℃で3分間保持し、このとき昇温速度は+3℃/分、冷却速度は-3℃/分である。このサイクルを2回実施し、2回目の降温時の固化熱量を算出する。その際、10mgの水溶性樹脂組成物試料を用いて測定を行い、得られたデータから試料1mgあたりの固化熱量を算出し、それを水溶性樹脂組成物試料の固化熱量とする。
一方、重量平均分子量(Mw)が110,000のポリエチレンオキサイド(明成工業化学株式会社製 アルコックスL11)100重量部に対して赤色2号を5重量部添加したものを、標準樹脂組成物(A)とする。前記標準樹脂組成物(A)の結晶化度は、同じくDSCを用いて、2回目の降温時の固化熱量を算出し、この固化熱量を結晶化度1.0と定義する。
次に、前記水溶性樹脂組成物試料の固化熱量を、標準樹脂組成物(A)の固化熱量で割り、水溶性樹脂組成物試料の結晶化度を算出する。
試料の結晶化度=試料の固化熱量÷標準樹脂組成物(A)の固化熱量 <Evaluation method>
1) Crystallinity In the present invention, as a method for measuring the crystallinity of a water-soluble resin composition, DSC (differential scanning calorimeter, DSC 6220 manufactured by SII Nano technology Inc.) is used for the obtained water-soluble resin composition. .
As a condition, the temperature was raised from 30 ° C. to 100 ° C., held at 100 ° C. for 3 minutes, then cooled from 100 ° C. to 30 ° C. and then held at 30 ° C. for 3 minutes. The cooling rate is −3 ° C./min. This cycle is carried out twice, and the amount of heat of solidification at the second temperature drop is calculated. At that time, measurement is performed using 10 mg of the water-soluble resin composition sample, and the amount of solidification per 1 mg of the sample is calculated from the obtained data, which is used as the amount of heat of solidification of the water-soluble resin composition sample.
On the other hand, a standard resin composition (A) in which 5 parts by weight of Red No. 2 was added to 100 parts by weight of polyethylene oxide having a weight average molecular weight (Mw) of 110,000 (Malsei Industrial Chemical Co., Ltd., Alcox L11). ). As for the crystallinity of the standard resin composition (A), DSC is used to calculate the amount of heat of solidification when the temperature is lowered for the second time, and this amount of heat of solidification is defined as crystallinity of 1.0.
Next, the heat of solidification of the water-soluble resin composition sample is divided by the heat of solidification of the standard resin composition (A) to calculate the crystallinity of the water-soluble resin composition sample.
Sample crystallinity = solidification heat of sample ÷ solidification heat of standard resin composition (A)
本発明では、水溶性樹脂組成物の固化温度の測定条件は、1)の結晶化度と同じ条件で、2回目の降温時の固化時の発熱ピークのピークトップ温度を固化温度として用いる。 2) Solidification temperature In the present invention, the measurement condition of the solidification temperature of the water-soluble resin composition is the same as the crystallinity of 1), and the peak top temperature of the exothermic peak at the time of the second temperature decrease is the solidification temperature. Used as
本発明では、水溶性樹脂組成物の層の表面硬度は、ドリル孔明け用エントリーシートの垂直上部より、ダイナミック超微小硬度計(株式会社島津製作所製、DUH-211)を用いて、圧子:Triangular115、試料力:10mN、負荷速度:0.7316mN/sec、負荷保持時間:10sec、ポアソン比:0.07の条件下で、ドリル孔明け用エントリーシートの垂直上部より、任意10点の水溶性樹脂組成物層の表面硬度(マルテンス硬さ)を測定する。その際の得られた表面硬度の平均値と標準偏差σを算出する。 3) Surface Hardness In the present invention, the surface hardness of the water-soluble resin composition layer is measured using a dynamic ultra-hardness meter (DUH-211, manufactured by Shimadzu Corporation) from the vertical upper part of the drill hole entry sheet. Indenter: Triangular 115, Sample force: 10 mN, Loading speed: 0.7316 mN / sec, Load holding time: 10 sec, Poisson's ratio: 0.07 The surface hardness (Martens hardness) of the water-soluble resin composition layer at the point is measured. The average value and standard deviation σ of the surface hardness obtained at that time are calculated.
本発明では、各サンプルについて、以下の条件でドリル孔明け加工を行った。
厚さ0.2mmの銅張積層板(CCL-HL832、銅箔両面12μm、三菱ガス化学株式会社製)を5枚重ねた上に、水溶性樹脂組成物層を上にしてドリル孔明け用エントリーシートを配置し、重ねた銅張積層板の下側には当て板(ベーク板)を配置して、ドリルビット:0.2mmφ(CFU020S タンガロイ株式会社製)を用いて、回転数:200,000rpm、送り速度:2.6m/minの加工条件で、ドリルビット1本につき3,000hitsでドリル孔明け加工を行った。 4) Drill drilling In the present invention, drilling was performed for each sample under the following conditions.
5 holes of copper-clad laminate (CCL-HL832, copper foil both sides 12μm, manufactured by Mitsubishi Gas Chemical Co., Ltd.) with a thickness of 0.2mm are stacked on top of each other. A sheet is placed, a backing plate (baked plate) is placed below the stacked copper-clad laminate, and a drill bit: 0.2 mmφ (manufactured by CFU020S Tungaloy Co., Ltd.) is used, and the rotational speed is 200,000 rpm. The drilling was performed at 3,000 hits per drill bit under a processing condition of feed rate: 2.6 m / min.
本発明では、ドリル孔明け用エントリーシートの孔位置精度は、重ねた銅張積層板の最下板の裏面における3,000穴の孔位置と指定座標とのズレをホールアナライザー(日立ビアメカニクス製、HA-1AM)にて測定し、ドリルビット1本分ごとに平均値と標準偏差(σ)を計算して、平均値+3σと最大値を算出する。その後、ドリル孔明け加工全体の孔位置精度として、ドリルビットの「平均値+3σ」値の平均値を算出して表記した。式は、次のとおりである。
Claims (8)
- 金属支持箔と、該金属支持箔の少なくとも片面に形成された水溶性樹脂組成物の層とを具える積層板または多層板用のドリル孔明け用エントリーシートであって、
前記水溶性樹脂組成物が、水溶性樹脂、水溶性潤滑剤および2,7-ナフタレンジスルホン酸,3-ヒドロキシ-4-[(4-スルホ-1-ナフタレン)アゾ]-,トリナトリウム塩(赤色2号)を含み、
前記水溶性樹脂組成物の層は、前記金属支持箔上に前記水溶性樹脂組成物の熱溶融物を塗工した後または前記水溶性樹脂組成物を含有する溶液を塗工して乾燥させた後、冷却開始温度120℃~160℃から冷却終了温度25℃~40℃へと、60秒以内に、1.5℃/秒以上の冷却速度で冷却して形成されるものであり、
前記水溶性樹脂組成物の結晶化度が1.2以上であり、
前記水溶性樹脂組成物の層の表面硬度の標準偏差σが2以下で、表面硬度が8.5N/mm2以上20N/mm2以下である
ことを特徴とするドリル孔明け用エントリーシート。 An entry sheet for drilling for a laminate or multilayer board comprising a metal support foil and a layer of a water-soluble resin composition formed on at least one side of the metal support foil,
The water-soluble resin composition comprises a water-soluble resin, a water-soluble lubricant, and 2,7-naphthalenedisulfonic acid, 3-hydroxy-4-[(4-sulfo-1-naphthalene) azo]-, trisodium salt (red 2)
The layer of the water-soluble resin composition was dried after applying a hot melt of the water-soluble resin composition on the metal support foil or by applying a solution containing the water-soluble resin composition. Thereafter, it is formed by cooling from a cooling start temperature of 120 ° C. to 160 ° C. to a cooling end temperature of 25 ° C. to 40 ° C. within 60 seconds at a cooling rate of 1.5 ° C./second or more.
The water-soluble resin composition has a crystallinity of 1.2 or more,
Wherein the standard deviation σ of the surface hardness of the layer of the water-soluble resin composition is 2 or less, drilling drilling for entry sheet, wherein the surface hardness of 8.5 N / mm 2 or more 20 N / mm 2 or less. - 前記水溶性樹脂が、ポリエチレンオキサイド、及びポリアルキレングリコールのポリエステルからなる群から選択される1種類以上であり、
前記水溶性潤滑剤がポリエチレングリコールである
ことを特徴とする請求項1に記載のドリル孔明け用エントリーシート。 The water-soluble resin is at least one selected from the group consisting of polyethylene oxide and polyalkylene glycol polyesters,
The entry sheet for drilling according to claim 1, wherein the water-soluble lubricant is polyethylene glycol. - 前記赤色2号の添加量が、前記水溶性樹脂と前記水溶性潤滑剤の合計100重量部に対して0.01重量部以上10重量部以下であることを特徴とする請求項1に記載のドリル孔明け用エントリーシート。 The addition amount of the red No. 2 is 0.01 parts by weight or more and 10 parts by weight or less based on 100 parts by weight of the total of the water-soluble resin and the water-soluble lubricant. Entry sheet for drilling.
- 前記水溶性樹脂組成物が、更にギ酸ナトリウムを含むことを特徴とする請求項1に記載のドリル孔明け用エントリーシート。 2. The entry sheet for drilling according to claim 1, wherein the water-soluble resin composition further contains sodium formate.
- 前記ギ酸ナトリウムの添加量が、前記水溶性樹脂と前記水溶性潤滑剤の合計100重量部に対して0.01重量部以上1.5重量部以下であることを特徴とする請求項4に記載のドリル孔明け用エントリーシート。 The addition amount of the said sodium formate is 0.01 to 1.5 weight part with respect to a total of 100 weight part of the said water-soluble resin and the said water-soluble lubricant. Entry sheet for drilling.
- 前記水溶性樹脂組成物は、固化温度が30℃以上70℃以下であることを特徴とする請求項1に記載のドリル孔明け用エントリーシート。 2. The entry sheet for drilling according to claim 1, wherein the water-soluble resin composition has a solidification temperature of 30 ° C. or higher and 70 ° C. or lower.
- 積層板または多層板のドリル孔明け加工において、ドリルビット径が0.05mmφ以上0.3mmφ以下のドリル孔明け加工に使用される請求項1に記載のドリル孔明け用エントリーシート。 2. The drill drilling entry sheet according to claim 1, which is used for drilling a drill bit having a drill bit diameter of 0.05 mmφ or more and 0.3 mmφ or less in the drilling processing of a laminated board or a multilayer board.
- 前記金属支持箔の厚みが0.05mm以上0.5mm以下であり、
前記水溶性樹脂組成物の層の厚みが0.01mm以上0.3mm以下である、
請求項1に記載のドリル孔明け用エントリーシート。 The thickness of the metal support foil is 0.05 mm or more and 0.5 mm or less,
The water-soluble resin composition layer has a thickness of 0.01 mm or more and 0.3 mm or less.
The entry sheet for drilling according to claim 1.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011548714A JP5845901B2 (en) | 2010-09-17 | 2011-09-14 | Entry sheet for drilling |
CN201180044690.5A CN103108730B (en) | 2010-09-17 | 2011-09-14 | Entry sheet for drilling |
RU2013106756/02A RU2526106C1 (en) | 2010-09-17 | 2011-09-14 | Stencil for hole drilling |
BR112013006112A BR112013006112A2 (en) | 2010-09-17 | 2011-09-14 | punch input sheet |
KR1020137006972A KR101705064B1 (en) | 2010-09-17 | 2011-09-14 | Entry sheet for drilling |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010209476 | 2010-09-17 | ||
JP2010-209476 | 2010-09-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012035771A1 true WO2012035771A1 (en) | 2012-03-22 |
Family
ID=45831257
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/005190 WO2012035771A1 (en) | 2010-09-17 | 2011-09-14 | Entry sheet for drilling |
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Country | Link |
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JP (1) | JP5845901B2 (en) |
KR (1) | KR101705064B1 (en) |
CN (1) | CN103108730B (en) |
BR (1) | BR112013006112A2 (en) |
MY (1) | MY165940A (en) |
RU (1) | RU2526106C1 (en) |
TW (1) | TWI470017B (en) |
WO (1) | WO2012035771A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013132837A1 (en) * | 2012-03-09 | 2013-09-12 | 三菱瓦斯化学株式会社 | Entry sheet for drilling use |
JP2014188653A (en) * | 2013-03-28 | 2014-10-06 | Mitsubishi Gas Chemical Co Inc | Entry sheet for drilling holes |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN108025450B (en) * | 2015-09-02 | 2018-12-07 | 三菱瓦斯化学株式会社 | Cover plate for drilling hole and the drilling method for using it |
CN105538387A (en) * | 2016-01-21 | 2016-05-04 | 烟台柳鑫新材料科技有限公司 | Cover plate for PCB drilling |
CN108811325B (en) * | 2017-05-02 | 2020-12-29 | 北大方正集团有限公司 | Pressing method and manufacturing method of printed circuit board |
CN108366491B (en) * | 2018-03-22 | 2022-09-23 | 深圳市中科恒润科技发展有限公司 | PCB circuit board drilling protection apron |
CN114713484A (en) * | 2022-04-28 | 2022-07-08 | 苏州罗恒电子材料有限公司 | PEO (polyethylene oxide) melting direct coating method and water-soluble film-coated aluminum foil for drilling circuit board |
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- 2011-09-14 RU RU2013106756/02A patent/RU2526106C1/en not_active IP Right Cessation
- 2011-09-14 MY MYPI2013000692A patent/MY165940A/en unknown
- 2011-09-14 JP JP2011548714A patent/JP5845901B2/en not_active Expired - Fee Related
- 2011-09-14 KR KR1020137006972A patent/KR101705064B1/en active IP Right Grant
- 2011-09-14 WO PCT/JP2011/005190 patent/WO2012035771A1/en active Application Filing
- 2011-09-14 BR BR112013006112A patent/BR112013006112A2/en not_active Application Discontinuation
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Also Published As
Publication number | Publication date |
---|---|
CN103108730A (en) | 2013-05-15 |
MY165940A (en) | 2018-05-18 |
KR101705064B1 (en) | 2017-02-09 |
JPWO2012035771A1 (en) | 2014-01-20 |
CN103108730B (en) | 2015-03-04 |
KR20140012612A (en) | 2014-02-03 |
TW201247761A (en) | 2012-12-01 |
JP5845901B2 (en) | 2016-01-20 |
BR112013006112A2 (en) | 2017-09-19 |
TWI470017B (en) | 2015-01-21 |
RU2526106C1 (en) | 2014-08-20 |
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