CN107848135A - Cover plate for drilling hole and use its drilling method - Google Patents

Abstract

A kind of cover plate for drilling hole, it possesses：Metal foil；With, not sandwiched adhesive linkage and be formed at the layer containing resin combination at least on one side of the metal foil, the resin combination includes polyurethane resin (A) and water-soluble resin (B), the content of polyurethane resin (A) in layer containing resin combination is that polyurethane resin (A) is the copolymer with the construction unit from ester ring type diisocyanate and the construction unit from aliphatic polyol more than 28 mass parts and below 60 mass parts relative to the mass parts of total 100 of polyurethane resin (A) and water-soluble resin (B).

Description

Cover plate for drilling hole and use its drilling method

Technical field

The present invention relates to cover plate for drilling hole and use its drilling method.

Background technology

It is general using such as lower section as plywood, the multiple-plate drilling method used in printed circuit board material Method：Overlapping 1 or the plywood or multi-layer sheet of multiple, the metal foil as aluminium foil is configured with its topmost in a contact fashion Monomer or metal foil surface shape have the sheet material of the layer comprising resin combination as plate (it is following, should " sheet material " in this specification Also referred to as " cover plate for drilling hole " or referred to as " cover plate "), carry out perforate processing.

In recent years, along with the requirement of reliability raising to printed circuit board (PCB) and the progress of densification, for printing The Drilling operation of the plywood or multi-layer sheet used in circuit board, also require to improve hole site precision and reduce Hole Wall Roughness etc. The processing of high-quality.

Require to tackle above-mentioned raising hole site precision and reduce Hole Wall Roughness etc., such as proposed in patent document 1 , use the perforate processing method of the sheet material formed by water-soluble resins such as polyethylene glycol.In addition, proposed in patent document 2, gold Belong to the with lubricator sheet material of the perforate formed with water-soluble resin layer on paper tinsel.And then proposed in patent document 3, formed with heat Perforate cover plate obtained from forming water-soluble resin layer on the aluminium foil of thermosetting resin film.And then proposed in patent document 4 , compounded with the perforate with lubricator sheet material of halogen-free colouring agent in lubricating resin composition.

A mode as cover plate for drilling hole, it is proposed that following manner：By metal foil and it is formed at the metal foil extremely The formation of the layer (hereinafter referred to as " resin composition layer ") comprising resin combination of few one side.However, metal foil and resin combination Nitride layer they between adhesive strength it is weak.Therefore, the cover plate for drilling hole directly contacted with resin composition layer for metal foil, During Drilling operation, resin composition layer is peeled off from metal foil, is drilled through the resin composition layer of the stripping so as to cause hole site The situation for losing frequency deterioration that precision deteriorates and bored is more.In addition, cover plate for drilling hole is by being generally disposed in multiple stackings After plate or multiple-plate two sides, implement perforate processing with fixed adhesive tape so that they to be formed to the state of 1 beam.It is however, solid Surely adhesive tape can be peeled off together with resin composition layer from the beam, therefore, as a result, also mistake occurs for the position of cover plate sometimes Position.Therefore, in practicality, in order to improve the adhesive strength of metal foil and resin composition layer, with metal foil and resin combination Formed with including carbamate based compound, vinyl acetate based compound, vinyl chloride compound, Polyester between layer The form of the adhesive linkage (bonding overlay film) of compound and their polymer, epoxy based compound and cyanate based compound etc. and Use cover plate (referring for example to patent document 5).

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 4-92494 publications

Patent document 2：Japanese Unexamined Patent Publication 5-169400 publications

Patent document 3：Japanese Unexamined Patent Publication 2003-136485 publications

Patent document 4：Japanese Unexamined Patent Publication 2004-230470 publications

Patent document 5：Japanese Unexamined Patent Publication 2011-183548 publications

The content of the invention

Problems to be solved by the invention

If however, setting adhesive linkage between metal foil and resin composition layer as described in patent document 5, glue Connect the lubricant effect that layer hinders resin combination.As a result, important characteristic required by cover plate for drilling hole, i.e., hole site essence Degree and Hole Wall Roughness deteriorate sometimes.Although it is not provided with gluing between metal foil and resin composition layer therefore, it is desirable to develop Connect the adhesive strength of layer, metal foil and resin composition layer also strong and hole site precision and excellent boring of inner wall roughness Cover plate.

In view of such present situation, problem of the invention is, there is provided：It is formed at by metal foil and non-sandwiched adhesive linkage The layer containing resin combination at least on one side of the metal foil formed and metal foil and the layer containing resin combination it is viscous The excellent cover plate for drilling hole of hole site precision when connecing intensity strong and then Drilling operation；With use its drilling method.

The solution used to solve the problem

The present inventor etc. have carried out various researchs to solve above-mentioned problem.Its result is found：Possesses metal foil and not Sandwiched adhesive linkage and be formed at the cover plate for drilling hole of the layer containing resin combination at least on one side of the metal foil and contain The cover plate for drilling hole that the layer of resin combination includes specific resin, the content of the specific resin is specific scope, metal The adhesive strength of paper tinsel and the layer containing resin combination is strong, and then, hole site precision during Drilling operation is excellent, so far completes The present invention.

That is, the present invention as described below.

(1) a kind of cover plate for drilling hole, it possesses：Metal foil；With, not sandwiched adhesive linkage and be formed at the metal foil at least The layer containing resin combination on one side, the resin combination includes polyurethane resin (A) and water-soluble resin (B), preceding The content of the foregoing polyurethane resin (A) in the layer containing resin combination is stated relative to foregoing polyurethane resin (A) and foregoing The mass parts of total 100 of water-soluble resin (B) are that foregoing polyurethane resin (A) is more than 28 mass parts and below 60 mass parts Copolymer with the construction unit from ester ring type diisocyanate and the construction unit from aliphatic polyol.

(2) cover plate for drilling hole according to (1), wherein, the foregoing water solubility in the foregoing layer containing resin combination The content of resin (B) is 40 matter relative to the mass parts of total 100 of foregoing polyurethane resin (A) and foregoing water-soluble resin (B) Measure more than part and below 72 mass parts.

(3) cover plate for drilling hole according to (1) or (2), wherein, foregoing polyurethane resin (A) is to be derived from fat by foregoing The copolymer that the construction unit of ring type diisocyanate and the foregoing construction unit from aliphatic polyol are formed.

(4) cover plate for drilling hole according to any one of (1)~(3), wherein, foregoing ester ring type diisocyanate includes IPDI.

(5) according to the cover plate for drilling hole described in (4), wherein, possessed by aforementioned copolymer, foregoing it is derived from isophorone two The ratio of the construction unit of isocyanates and the foregoing construction unit from aliphatic polyol is derived from isophorone two with foregoing The molal quantity of the construction unit of isocyanates：The molal quantity of construction unit from aliphatic polyol is calculated as 3：97~9：91 Scope.

(6) cover plate for drilling hole according to any one of (1)~(5), wherein, the number of foregoing polyurethane resin (A) is equal Molecular weight is more than 5000 and less than 50000.

(7) according to the cover plate for drilling hole any one of (1)~(6), wherein, foregoing water-soluble resin (B) be selected from By PEO, PPOX, polyvinylpyrrolidone, cellulose derivative, polyethylene glycol, polypropylene glycol, polybutadiene It is alcohol, polyoxyethylated monoether compounds, polyoxyl 40 stearate, polyoxyethylene sorbitan monostearate, poly- Glyceryl monostearate and PEO-polypropylene oxide copolymers and they derivative composition group in a kind or Two or more.

(8) according to the cover plate for drilling hole described in (7), wherein, foregoing water-soluble resin (B) include with more than 50000 and The macromolecular water-soluble resin (b1) of less than 1500000 weight average molecular weight and with more than 1000 and less than 30000 weight it is equal The low molecule water-soluble resin (b2) of molecular weight, foregoing macromolecular water-soluble resin (b1), which includes, to be selected from by PEO, gathers Expoxy propane, polyvinylpyrrolidone and cellulose derivative group into group at least one kind of, foregoing low molecule water-soluble resin (b2) include and be selected from by polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxyethylated monoether compounds, polyoxyethylene list tristearin Acid esters, polyoxyethylene sorbitan monostearate and PEO-polypropylene oxide copolymers and they spread out It is at least one kind of in the group of biotic component.

(9) cover plate for drilling hole according to any one of (1)~(8), wherein, the foregoing layer containing resin combination Thickness is more than 0.02mm and below 0.3mm.

(10) cover plate for drilling hole according to any one of (1)~(9), wherein, the thickness of aforementioned metal paper tinsel is More than 0.05mm and below 0.5mm.

(11) a kind of drilling method, the cover plate for drilling hole any one of (1)~(10) is configured at stacking by it Plate or multiple-plate the top, foregoing plywood or multiple-plate drilling are carried out above foregoing cover plate for drilling hole, so that Hole is formed in foregoing plywood or multi-layer sheet.

The effect of invention

According to the present invention it is possible to provide：At least one side of the metal foil is formed at by metal foil and non-sandwiched adhesive linkage On layer containing resin combination formed and the adhesive strength of metal foil and the layer containing resin combination is strong and then drills The excellent cover plate for drilling hole of hole site precision during processing；With use its boring method.

Embodiment

Hereinafter, the scheme (hereinafter referred to as " present embodiment ") for implementing present embodiment is described in detail, but The present invention is not limited to following present embodiments, and various modifications can be carried out in the range of its purport is not departed from.

[I：Cover plate for drilling hole]

The cover plate for drilling hole of present embodiment is that possess：Metal foil；With, not sandwiched adhesive linkage and be formed at the metal foil The cover plate for drilling hole of the layer (hereinafter referred to as " resin composition layer ") containing resin combination at least on one side, the resin Composition includes polyurethane resin (A) and water-soluble resin (B), the content phase of the polyurethane resin (A) in resin composition layer For the mass parts of total 100 of polyurethane resin (A) and water-soluble resin (B) be 28 mass parts more than and 60 mass parts below, Polyurethane resin (A) is with the construction unit from ester ring type diisocyanate and the construction unit from aliphatic polyol Copolymer.

The cover plate for drilling hole of present embodiment is formed at least single of the metal foil by metal foil and non-sandwiched adhesive linkage Resin composition layer on face is formed.That is, for metal foil is directly contacted with resin composition layer and in metal foil and resin combination Do not have the form of the adhesive linkage (resin coating) for bonded metal paper tinsel and resin combination between nitride layer.Resin composition layer Comprising polyurethane resin (A) and water-soluble resin (B), the content of the polyurethane resin (A) in resin composition layer is above-mentioned model Enclose, and polyurethane resin (A) is with the construction unit from ester ring type diisocyanate and the knot from aliphatic polyol The copolymer of structure unit, so as to even in not sandwiched adhesive linkage between metal foil and resin composition layer, metal foil and resin group The adhesive strength of compound layer is also strong, and hole site precision during Drilling operation is also excellent.

The cover plate for drilling hole of present embodiment is economical in manufacturing process's these two aspects of its raw material and cover plate.I.e., originally The cover plate for drilling hole of embodiment can not sandwiched adhesive linkage, therefore, cost of raw and processed materials can be reduced, in addition, not necessarily forming viscous The process for connecing layer is in terms of economy and excellent compared with conventional cover plate for drilling hole.Resin composition layer can be shape Into the form of the one side in metal foil, or be formed at the form on two sides.When forming resin composition layer on two sides, these The composition of resin combination in layer can with it is mutually the same can also be different.

[II：Polyurethane resin (A)]

In resin composition layer in the cover plate for drilling hole of present embodiment contained polyurethane resin (A) be with from The copolymer of the construction unit of ester ring type diisocyanate and construction unit from aliphatic polyol.As long as the copolymer is Copolymerization with the construction unit from ester ring type diisocyanate and the construction unit from aliphatic polyol as composition Thing is just not particularly limited.

Construction unit from ester ring type diisocyanate refers to, when forming polymer, from the original as polymerisation Construction unit (skeleton) in the polymer for the ester ring type diisocyanate that material uses.Construction unit from aliphatic polyol Refer to, when forming polymer, the structure list in the polymer of the aliphatic polyol used from the raw material as polymerisation First (skeleton).That is, the structure from ester ring type diisocyanate is provided when above-mentioned copolymer is by least making to be formed polymer The aliphatic polyol of the construction unit of ester ring type diisocyanate and offer from aliphatic polyol of unit is copolymerized Obtained from reaction.

Polyurethane resin (A) is with the construction unit from ester ring type diisocyanate and from aliphatic polyol The copolymer of construction unit, there are metal foil and the adhesive strength of resin composition layer so as to the cover plate for drilling hole of present embodiment The excellent tendency of hole site precision by force and during Drilling operation.Its reason is not particularly limited in this, but thinks：Have with copolymer There are metal foil and the change of the adhesive strength of resin composition layer for main cause of the construction unit from ester ring type diisocyanate By force, and using copolymer with from aliphatic polyol construction unit as main cause and resin composition layer with excellent Lubricity, therefore, hole site precision during Drilling operation are excellent.

As long as the ester ring type diisocyanate for providing the construction unit from ester ring type diisocyanate has 2 for intramolecular The organic compound of the ester ring type of individual NCO is just not particularly limited, and can be that monomer can also be polymer.As Such compound, such as IPDI, the isocyanatocyclohexanes of 1,3- bis-, the isocyanide of Isosorbide-5-Nitrae-two can be enumerated Acid group trimethylcyclohexane, 4,4- dicyclohexyl methyl hydride diisocyanates, cyclohexylene diisocyanate, the isocyanide of methylcyclohexylidene two Acid esters, double (2- isocyanatoethyls) -4- cyclohexene -1,2- dicarboxylic esters, 2,5- norbornene alkyl diisocyanates and 2,6- Norbornene alkyl diisocyanate.Wherein, from more effective and from the viewpoint of positively reaching the purpose of present embodiment, more preferably IPDI, the isocyanatocyclohexanes of 1,3- bis- and the isocyanatocyclohexane of Isosorbide-5-Nitrae-two, it is particularly preferably different Isophorone diisocyanate.These ester ring type diisocyanate can be used singly or in combination of two or more and Use.

As long as the aliphatic polyol for providing the construction unit from aliphatic polyol is to have more than 2 in intramolecular The aliphatic organic compound of hydroxyl is just not particularly limited, and can be that monomer can also be polymer.It is used as suchization Compound, such as ethylene glycol, diethylene glycol, 1,3-PD, 1,2-PD, triethylene glycol, 2- methyl isophthalic acids, 3- third can be enumerated Glycol, 2,2- dimethyl -1,3- propane diols, 2-butyl-2-ethyl-1,3-propanediol, 1,4- butanediols, 2- methyl isophthalic acids, 4- fourths Glycol, 2- methyl -3- methyl isophthalic acids, 4- butanediols, 3- methyl isophthalic acids, 5- pentanediols, 1,5- pentanediols, 3- methyl isophthalic acids, 5- pentanediols, 1,6-HD and 6- hydroxyl adipic acid -1- hexanoyls base esters (reaction product of caprolactone and 1,6-HD).Wherein, from more From the viewpoint of reaching effectively and positively the purpose of present embodiment, preferably ethylene glycol, diethylene glycol, BDO, 1, 6- hexylene glycols and 6- hydroxyl adipic acid -1- hexanoyl base esters, particularly preferred 1,6- hexylene glycols and 6- hydroxyl adipic acid -1- caproyls Ester.These aliphatic polyols can be used singly or in combination of two or more and use.

Copolymerization with the construction unit from ester ring type diisocyanate and the construction unit from aliphatic polyol The no spy of ratio of construction unit in thing, from ester ring type diisocyanate and the construction unit from aliphatic polyol Do not limit, with the molal quantity of the construction unit from ester ring type diisocyanate：Construction unit from aliphatic polyol Molal quantity meter is preferably 3：97~9：91 scope.The molal quantity of construction unit from ester ring type diisocyanate is relative to this The ratio between molal quantity 100 of total of a little construction units is if more than 3, then the adhesive strength of resin composition layer and metal foil is more Fully, resin composition layer is less easily peelable during Drilling operation, therefore, it is more excellent to have the tendency of hole site precision.On the other hand, If the molal quantity of the construction unit from aliphatic polyol is relative to the ratio between molal quantity 100 of the total of these construction units For more than 91, then lubricity during Drilling operation becomes better, therefore, because processing and the discharge of caused cutting swarf is entered One step improve, thus, have the tendency of hole site precision it is more excellent and/or bore processing the life-span become longer.

Copolymerization with the construction unit from ester ring type diisocyanate and the construction unit from aliphatic polyol Thing can include construction unit and source from ester ring type diisocyanate in the range of the purpose of present embodiment is not damaged Construction unit (following, in this specification also referred to as " other structures unit ") from beyond the construction unit of aliphatic polyol. That is, have the copolymer of the construction unit from ester ring type diisocyanate and construction unit from aliphatic polyol can be with Ester ring type diisocyanate and the offer source of construction unit from ester ring type diisocyanate are provided during to make to be formed polymer Aliphatic polyol from the construction unit of aliphatic polyol, enter with the compound of offer other structures unit as needed Copolymer obtained from row copolyreaction.As long as construction unit of the other structures unit for the purpose not damaging present embodiment It is not particularly limited, such as can enumerates：From oxalic acid, butanedioic acid, adipic acid, pimelic acid, decanedioic acid, 1,2,4- butane tricarboxylics Acid, 1,2,5- hexanes tricarboxylic acids, 1,3- dicarboxyl -2- methyl -2- methylene carboxyls propane, 1,2- cyclohexane dicarboxylic acids, 1,3- Cyclohexane dicarboxylic acid, 1,4- cyclohexane dicarboxylic acids, 1,2,4- cyclohexanetricarboxylic acids, four (methylene carboxyl) methane and 1,2,7,8- The construction unit of the polycarboxylic acids such as octane tetrabasic carboxylic acid；From ethene, propylene, 1- butylene, 2- butylene, 1,3- butadiene, 1- amylenes, 3- The construction unit of the alkene such as amylene, 1,3- pentadienes and 1,5- pentadienes；And, from acrylic acid, methacrylic acid, maleic acid With the construction unit of the unsaturated carboxylic acid such as fumaric acid.

With the construction unit from ester ring type diisocyanate, from the construction unit of aliphatic polyol and other knots In the copolymer of structure unit, construction unit from ester ring type diisocyanate and the construction unit from aliphatic polyol with The combination of other structures unit is not particularly limited.With the construction unit from ester ring type diisocyanate, from aliphatic As long as the content of the construction unit of polyalcohol and the other structures unit in the copolymer of other structures unit is not damage this reality Apply and be just not particularly limited in the range of the purpose of mode.Wherein, from more effective and positively reach the purpose of present embodiment From the viewpoint of, by the molal quantity of the construction unit from ester ring type diisocyanate in copolymer and it is derived from aliphatic polybasic When the total amount of the molal quantity of the construction unit of alcohol and the molal quantity of other structures unit is set to 100 moles, preferably 1~5 mole.

As polyurethane resin (A), there is the construction unit from ester ring type diisocyanate, from aliphatic polyol Construction unit and the copolymer of other structures unit as needed can be used alone, can also be applied in combination 2 kinds with Above use.

In present embodiment, polyurethane resin (A) is by the construction unit from ester ring type diisocyanate and from fat Copolymer, i.e. ester ring type diisocyanate-aliphatic polybasic alcohol copolymer that the construction unit of fat race polyalcohol is formed.Polyurethane Resin (A) is to be total to by what the construction unit from ester ring type diisocyanate and the construction unit from aliphatic polyol were formed During polymers, the cover plate for drilling hole of present embodiment has metal foil and the adhesive strength of resin composition layer is stronger and Drilling operation When the more excellent tendency of hole site precision.

It is total to by what the construction unit from ester ring type diisocyanate and the construction unit from aliphatic polyol were formed Polymers is not particularly limited, such as can enumerate：Above-mentioned offer is set to be derived from the alicyclic ring of the construction unit of ester ring type diisocyanate Formula diisocyanate, with above-mentioned offer be derived from aliphatic polyol construction unit aliphatic polyol carry out copolyreaction and Obtained copolymer.Formed by the construction unit from ester ring type diisocyanate and the construction unit from aliphatic polyol Copolymer in, the combination of construction unit from ester ring type diisocyanate and the construction unit from aliphatic polyol does not have It is particularly limited to.In addition, as polyurethane resin (A), by the construction unit from ester ring type diisocyanate and from fat The copolymer that the construction unit of race's polyalcohol is formed can be used singly or in combination of two or more and use.

It is total to by what the construction unit from ester ring type diisocyanate and the construction unit from aliphatic polyol were formed The ratio of construction unit in polymers, from ester ring type diisocyanate and the construction unit from aliphatic polyol does not have It is particularly limited to, with the molal quantity of the construction unit from ester ring type diisocyanate：Construction unit from aliphatic polyol Molal quantity meter be preferably 3：97~9：91 scope.The molal quantity of construction unit from ester ring type diisocyanate relative to The ratio between molal quantity 100 of the total of these construction units is if more than 3, then the adhesive strength of resin composition layer and metal foil More fully, during Drilling operation, resin composition layer is less easily peelable, therefore, it is more excellent to have the tendency of hole site precision.The opposing party Face, the molal quantity of the construction unit from aliphatic polyol is relative to the ratio between molal quantity 100 of the total of these construction units If more than 91, then lubricity during Drilling operation becomes better, thus due to processing caused cutting swarf discharge Property further improve, thus, have the tendency of hole site precision it is more excellent and/or bore processing the life-span become longer.

From more effective and from the viewpoint of positively reaching the purpose of present embodiment, in the synthesis of polyurethane resin (A) The ester ring type diisocyanate used preferably comprises IPDI, more preferably IPDI. More particularly, for polyurethane resin (A), as the above-mentioned construction unit included from ester ring type diisocyanate and it is derived from The copolymer of the construction unit of aliphatic polyol, preferably include construction unit and source from IPDI From the copolymer of the construction unit of aliphatic polyol.In addition, for polyurethane resin (A), as above-mentioned by from ester ring type The copolymer that the construction unit of diisocyanate and construction unit from aliphatic polyol are formed, more preferably by from different Buddhist Copolymer that the construction unit of your ketone diisocyanate and the construction unit from aliphatic polyol are formed, i.e., include different Buddhist That ketone diisocyanate-aliphatic polybasic alcohol copolymer.

As IPDI-aliphatic polybasic alcohol copolymer, it is not particularly limited, such as can enumerates： The aliphatic polyol of the construction unit of IPDI and above-mentioned offer from aliphatic polyol is provided Copolymer obtained from poly- reaction.Wherein, preferably IPDI -1,6- hexylene glycol copolymer, isophorone two Isocyanates -6- hydroxyl adipic acid -1- caproyls ester copolymers and IPDI -1,6-HD -6- hydroxyls Adipic acid -1- caproyl ester copolymers.As polyurethane resin (A), these copolymers can be used alone, can also group Close using two or more and use.When polyurethane resin (A) is these copolymers, the cover plate for drilling hole of present embodiment has metal The more excellent tendency of hole site precision when the adhesive strength and Drilling operation of paper tinsel and resin composition layer.

Being total to comprising the construction unit from IPDI and the construction unit from aliphatic polyol Polymers or formed by the construction unit from IPDI and the construction unit from aliphatic polyol Copolymer in, the ratio of construction unit from IPDI and the construction unit from aliphatic polyol Example is not particularly limited.Wherein, its ratio is with the molal quantity of the construction unit from IPDI：From fat The ratio between molal quantity of construction unit of race's polyalcohol meter is preferably 3：97~9：91 scope.From IPDI Construction unit molal quantity relative to the ratio between molal quantity 100 of the total of these construction units if more than 3, then resin group The adhesive strength of compound layer and metal foil is more abundant, and during Drilling operation, resin composition layer is less easily peelable, therefore, there is hole position Put the more excellent tendency of precision.On the other hand, the molal quantity of the construction unit from aliphatic polyol is relative to these structures The ratio between molal quantity 100 of the total of unit becomes better if more than 91, then lubricity during Drilling operation, therefore, by Further improved in the discharge of the caused cutting swarf of processing, thus, have hole site precision more excellent and/or bore the processing life-span Become longer tendency.

The content of contained polyurethane resin (A) is relative in resin composition layer in the cover plate for drilling hole of present embodiment In the mass parts of total 100 of polyurethane resin (A) and water-soluble resin described later (B) be 28 mass parts more than and 60 mass parts with Under, be preferably more than 30 mass parts and below 60 mass parts, more preferably more than 35 mass parts and below 50 mass parts.Polyurethane When the content of resin (A) is more than 28 mass parts, the adhesive strength of metal foil and resin composition layer becomes more abundant.It is tied Fruit, during Drilling operation, hole site precision it is bad, be less susceptible to draw as the stripping for the resin composition layer for boring the reason for losing Rise, therefore, have the tendency of hole site precision it is more excellent, bore processing the life-span become longer.On the other hand, polyurethane resin (A) Content if 60 mass parts below, then the content of the water-soluble resin (B) in resin composition layer can be adjusted to as To the amount of Drilling operation more fully lubricity, therefore, hole site precision during Drilling operation becomes more excellent.Particularly, gather The content of urethane resin (A) is 28 relative to the mass parts of total 100 of polyurethane resin (A) and water-soluble resin described later (B) When more than mass parts and below 60 mass parts, there is hole when metal foil and the adhesive strength and Drilling operation of resin composition layer The more excellent tendency of both positional precisions.

The number-average molecular weight of polyurethane resin (A) is not particularly limited, and preferably more than 5000 and less than 50000, more excellent Elect more than 20000 and less than 50000 as.When number-average molecular weight is more than 5000, it can further suppress the generation of adhesion, there is behaviour Become better tendency as property.On the other hand, when number-average molecular weight is less than 50000, the discharge of cutting swarf during Drilling operation Property become better, thus, hole site precision further improves and/or further can prevent brill from losing.Polyurethane resin (A) Number-average molecular weight can determine according to conventional methods, using GPC posts, using polystyrene as standard substance, more specifically, It can be determined by the method described in embodiment.

The manufacture method and manufacturing condition of polyurethane resin (A) are not particularly limited, and can use known method and bar Part.Polyurethane resin (A) is IPDI-isocyanic acid of ester ring type two as aliphatic polybasic alcohol copolymer In the case of ester-aliphatic polybasic alcohol copolymer, above-mentioned IPDI, the isocyano cyclizations of 1,3- bis- can be made The ester ring type diisocyanate such as hexane and the isocyanatocyclohexanes of 1,4- bis-, with ethylene glycol, diethylene glycol, 1,4- butanediols, The aliphatic polyol such as 1,6-HD and 6- hydroxyl adipic acid -1- hexanoyl base esters carries out copolyreaction in a known manner and made Make.As the raw material that can be used in polyurethane resin (A) manufacture, for structure of the above-mentioned offer from ester ring type diisocyanate The ester ring type diisocyanate of unit, offer are derived from the aliphatic polyol of the construction unit of aliphatic polyol and not had The compound of the offer other structures unit selected in the range of the purpose of present embodiment is provided.

Raw material, the composition such as catalysts and solvents used in the manufacture that polyurethane resin (A) can include copolymer.Separately Outside, the stabilizer of product and the compositions of dispersant such as water, amine can also be included.

Polyurethane resin (A) formed present embodiment cover plate for drilling hole in resin composition layer when preferably with moisture The mode of granular media uses.That is, the mode of the polyurethane resin (A) when forming resin composition layer is not particularly limited, and is preferably The mode of aqueous dispersion.The manufacture method of the aqueous dispersion of polyurethane resin (A) is not particularly limited, and can use known side Method.As the manufacture method of aqueous dispersion, for example, can enumerate using solid-liquid agitating device etc. by above-mentioned polyurethane resin (A), The method that the other compositions such as aqueous solvent and alkali as needed, emulsifying agent are stirred.

As polyurethane resin (A) aqueous dispersion, commercially available product can be used.Moisture as polyurethane resin (A) dissipates The commercially available product of body, can enumerate Dainippon Ink Chemicals product name " HYDRANWLS210 " (IPDI -1, 6- hexylene glycol -6- hydroxyl adipic acid -1- caproyls ester copolymer, number-average molecular weight：35000th, from isophorone diisocyanate The molal quantity of the construction unit of ester：The ratio between molal quantity of construction unit from aliphatic polyol=6：94).

[III：Water-soluble resin (B)]

Contained water-soluble resin (B) in resin composition layer in the cover plate for drilling hole of present embodiment is as long as be water-soluble Property resin be just not particularly limited, preferably by macromolecular water-soluble resin (b1) and low molecule water-soluble resin (b2) combination make With.It should be noted that " water miscible resin " refers to, under 25 DEG C, 1 atmospheric pressure, dissolve more than 1g's for water 100g Resin.

As macromolecular water-soluble resin (b1), it is not particularly limited, such as is preferably selected from by PEO, polycyclic Ethylene Oxide, polyvinylpyrrolidone and cellulose derivative group into group in it is one kind or two or more.These compounds can be single 1 kind is solely used, two or more use can also be combined.These compounds have especially good sheet material formative, therefore, pass through Using these compounds, by the forming of the resin composition layer that can make in the cover plate for drilling hole of present embodiment, thickness evenly Tendency.The weight average molecular weight of macromolecular water-soluble resin (b1) is not particularly limited, and boring lid is manufactured from further improve From the viewpoint of the Film making properties of resin composition layer during plate, preferably more than 50000 and less than 1500000.For same Viewpoint, its weight average molecular weight is more preferably more than 100000 and less than 1000000, more preferably more than 200000 and Less than 800000.Weight average molecular weight, which can utilize, possesses the in general such as liquid chromatography of GPC posts method measure.In more detail and Speech, for the polystyrene as the standard substance used when standard curve is made, from the material with various number-average molecular weights The material with various weight average molecular weight is changed into, in addition, the measure side with the number-average molecular weight in embodiment described later Method is likewise it is possible to determine weight average molecular weight (below equally.).

As low molecule water-soluble resin (b2), it is not particularly limited, such as is preferably selected from by polyethylene glycol, poly- the third two The diol compound such as alcohol and polytetramethylene glycol；Polyoxyl 10 oleyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxy second The polyoxyethylated monoether compounds such as alkene bay ether, ethylene nonyl phenylate and polyoxethylene octylphenyl phenylate；Polyoxyethylene list Stearate, polyoxyethylene sorbitan monostearate, polyglycerol monostearate compound and PEO- It is one kind or two or more in the group of polypropylene oxide copolymers and their derivative composition.These compounds, copolymer can To be used alone a kind, two or more use can also be combined.By using these compounds, the cover plate for drilling hole of present embodiment The effect of lubricity can be more fully played when having the tendency of Drilling operation.The weight average molecular weight of low molecule water-soluble resin (b2) Be not particularly limited, from Drilling operation when further improve lubricity from the viewpoint of, preferably more than 1000 and 30000 with Under.For same viewpoint, the weight average molecular weight is more preferably more than 1000 and less than 20000, more preferably 1500 with It is upper and less than 10000.Weight average molecular weight, which can utilize, possesses the in general such as liquid chromatography of GPC posts method measure.

In above-mentioned, as water-soluble resin (B), preferably using selected from by PEO, PPOX, polyethylene pyrrole Pyrrolidone, cellulose derivative, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxyethylated monoether compounds, polyoxyethylene Monostearate, polyoxyethylene sorbitan monostearate, polyglycerol monostearate and PEO-polycyclic It is one kind or two or more in the group of Ethylene Oxide copolymer and their derivative composition.By using such water-soluble resin (B), there are the Film making properties of resin composition layer and hole site precision further improves.

Divide equally again with more than 50000 and less than 1500000 in addition it is particularly preferred that water-soluble resin (B) includes The macromolecular water-soluble resin (b1) of son amount and the low molecule with more than 1000 and less than 30000 weight average molecular weight are water-soluble Property resin (b2) in the case of, macromolecular water-soluble resin (b1), which includes, to be selected from by PEO, PPOX, polyethylene Pyrrolidones and cellulose derivative group into group in it is at least one kind of, low molecule water-soluble resin (b2) include be selected from by poly- second Glycol, polypropylene glycol, polytetramethylene glycol, polyoxyethylated monoether compounds, polyoxyl 40 stearate, polyoxyethylene sorbitan mountain In the group of pears sugar alcohol monostearate and PEO-polypropylene oxide copolymers and their derivative composition extremely It is few a kind.By using such water-soluble resin (B), the Film making properties and hole site precision for having resin composition layer further carry High tendency.

The content of water-soluble resin (B) in resin composition layer is not particularly limited, relative to polyurethane resin (A) and The mass parts of total 100 of water-soluble resin (B) are preferably more than 40 mass parts and below 72 mass parts, more preferably 40 mass parts with Below upper and 70 mass parts, more than further preferred 50 mass parts and below 65 mass parts.Water-soluble resin (B) if content More than 40 mass parts, then resin composition layer evenly can be formed, Drilling operation can assign more to resin composition layer Sufficient lubricity.As a result, hole site precision when having the tendency of Drilling operation is more excellent.On the other hand, water-soluble resin (B) content if 72 mass parts below, then the content in polyurethane resin (A) resin composition layer can be adjusted to Metal foil and the adhesive strength of resin composition layer become better amount, and therefore, hole site precision when having a Drilling operation is more Excellent tendency.

Macromolecular water-soluble resin (b1) in resin composition layer if content in above-mentioned resin composition layer Just it is not particularly limited in the range of the content of water-soluble resin (B).Wherein, its content is relative to polyurethane resin (A) and water The mass parts of total 100 of soluble resin (B) be preferably more than 5 mass parts and below 30 mass parts, more preferably more than 5 mass parts and Below 10 mass parts, more than further preferred 5 mass parts and below 7 mass parts.Pass through containing for macromolecular water-soluble resin (b1) Measure and further improved in above range, to have the tendency of the Film making properties of resin composition layer and hole site precision.

Low molecule water-soluble resin (b2) in resin composition layer if content in above-mentioned resin composition layer Just it is not particularly limited in the range of the content of water-soluble resin (B).Wherein, its content is relative to polyurethane resin (A) and water The mass parts of total 100 of soluble resin (B) are preferably more than 40 mass parts and below 65 mass parts, more preferably more than 45 mass parts And 65 below mass parts, more than further preferred 45 mass parts and below 60 mass parts.Low molecule water-soluble resin (b2's) contains Measure for aforementioned range when, have metal foil and resin composition layer adhesive strength and perforate process when hole site precision this two The more excellent tendency of person.

[IV：Other compositions]

The scope of resin composition layer in the cover plate for drilling hole of present embodiment in the purpose for not damaging present embodiment It is interior to contain additive.The species of additive is not particularly limited, such as can enumerate surface conditioner, levelling agent, anti-quiet Electric agent, emulsifying agent, defoamer, wax additive, coupling agent, rheology control agent, preservative, mould inhibitor, antioxidant, light are stable The kollags such as the nucleators such as agent, sodium formate, graphite, organic filler, inorganic filler, heat stabilizer and colouring agent.They can To be used alone a kind or combine two or more use.

The bit diameter that is used when the thickness of resin composition layer in present embodiment is according to Drilling operation, processing are opened Composition of hole object (such as the printed circuit board material such as plywood or multi-layer sheet) etc. and suitably select, therefore, without special Limit.Wherein, its thickness be preferably more than 0.02mm and below 0.3mm scope, more preferably more than 0.02mm and 0.2mm with Under scope, more preferably more than 0.02mm and below 0.1mm scope.It is by the thickness of resin composition layer More than 0.02mm, more fully lubricant effect can be obtained, the load to drill bit can be mitigated, therefore, having further to press down The tendency that drill bit processed is lost.In addition, the thickness for passing through resin composition layer is below 0.3mm, resin can further be suppressed by having The tendency of winding of the composition to drill bit.

[V：Metal foil]

Contained metal foil is not particularly limited in the cover plate for drilling hole of present embodiment, preferably with above-mentioned resin combination The adaptation of nitride layer is high, is resistant to the metal material of the impact based on drill bit.As the metal species of metal foil, from obtaining From the viewpoint of property, cost and processability, such as aluminium can be enumerated.As the aluminium of the material of aluminium foil, preferably purity more than 95%, As such aluminium foil, for example, can enumerate 5052 specified in JIS-H4160,3004,3003,1N30,1N99,1050, 1070th, 1085 and 8021.By metal foil use aluminium purity more than 95% aluminium foil, the mitigation of the impact based on drill bit and with The occlusion in chisel edge portion further improves, can be further together with the lubricant effect of the drill bit based on resin combination Improve the hole site precision in processing hole.

The thickness of metal foil is not particularly limited, preferably more than 0.05mm and below 0.5mm, more preferably 0.05mm with Upper and below 0.3mm.The thickness of metal foil then can more effectively suppress perforate during Drilling operation if more than 0.05mm The generation of flash in object (such as the printed circuit board material such as plywood or multi-layer sheet).In addition, the thickness of metal foil is such as Fruit is below 0.5mm, then the discharge of the flour occurred during Drilling operation becomes easier to.

The thickness for forming each layer of the cover plate for drilling hole of present embodiment determines as follows.First, using Cross section polishing machine (day This electronic data Co. Ltd. system, trade name " CROSS-SECTION POLISHER SM-09010 ") or ultra-thin cutting machine (Leica Co. Ltd. systems, goods number " EM UC7 "), stacked direction of the cover plate along each layer is cut off.Afterwards, (swept using SEM Retouch type electron microscope (Scanning Electron Microscope), the goods number of such as KEYENCE Co., Ltd. " VE-7800 "), it is vertical direction from the section occurred with cut-out, its section is observed, determines each layer, the example of composition Such as metal foil and the thickness of resin composition layer.For 1 visual field, the thickness at 5 positions is determined, value is averaged and is used as each layer Thickness.

For the cover plate for drilling hole of present embodiment, determined, resin according to the method described in embodiment described later Bonding force between composition layer and metal foil is more preferably more than 200gf.In addition, the side described according to embodiment described later Method and the hole site precision that determines is preferably less than 18.0 μm.

[VI：The manufacture method of cover plate for drilling hole]

The manufacture method of the cover plate for drilling hole of present embodiment is not particularly limited, and can utilize in general manufacture method. Such as can be such as following manufacture cover plate for drilling hole.The cover plate for drilling hole of present embodiment forms tree in metal foil at least on one side Oil/fat composition layer and manufacture.The method for forming resin composition layer is not particularly limited, and can use known method.It is used as this The method of sample, such as following method can be enumerated：The methods of using rubbing method, it will be dissolved in solvent or be dispersed with polyurethane resin (A) solution of the resin combination of aqueous dispersion, water-soluble resin (B) and the additive being added as needed on is coated on metal On paper tinsel, and it is further set to dry and/or cool and solidify.

By rubbing method etc., on metal foil the solution of coating resin combination and it is further dried and forms resin During composition layer, the solvent used in the solution of resin combination is preferably less than the mixing that the solvent of water is formed by water and boiling point Solution., less than the mixed solution that the solvent of water is formed, resin combination can be more effectively reduced by using by water and boiling point Residual bubble in layer.Boiling point is not particularly limited less than the species of the solvent of water, such as can enumerate ethanol, methanol and isopropyl Alcoholic compound as alcohol, the low boiling point solvents such as MEK and acetone can also be used.As other solvents, water can be used And/or mix some tetrahydrofuran high with the compatibility of resin combination in alcoholic compound and/or acetonitrile form it is molten Agent.

[VII：Drilling method]

The drilling method of present embodiment possesses such as lower opening formation process：Using above-mentioned cover plate for drilling hole, it is being laminated Hole is formed on plate or multi-layer sheet.More specifically, in the formation process of hole, cover plate for drilling hole is configured at plywood or multi-layer sheet Topmost, the drilling of plywood or multi-layer sheet is carried out above the cover plate for drilling hole, so as to the shape in plywood or multi-layer sheet Pore-forming.In addition, when the Drilling operation is the Drilling operation using diameter (bit diameter) below 0.30mm φ drill bit, Ke Yigeng Play effectively and positively the purpose of present embodiment.Particularly, for using more than diameter 0.05mm φ and below 0.30mm φ, And then hole site precision is when turning into important more than diameter 0.05mm φ and the processing of the drill bit of below 0.20mm φ path, from It is to be more suitable for that hole site precision, which can be greatly improved, and bore the aspect in life-span.It should be noted that 0.05mm φ bit diameter For the lower limit for the bit diameter that can be obtained, if it is possible to obtain and go back the drill bit of path than it, be then not limited to above-mentioned.In addition, The cover plate for drilling hole of present embodiment is used also to have no problem more than in the Drilling operation of 0.30mm φ drill bit using diameter.Need It is noted that as plywood, copper-clad laminated board can be typically used, the plywood of present embodiment can be for layer outside not Possesses the plywood of copper foil.That is, in present embodiment, unless otherwise specified, plywood refers to, copper-clad laminated board and/or Outer layer does not have the plywood of copper foil.

The cover plate for drilling hole of present embodiment for example can to printed circuit board material, more specifically plywood or multilayer Plate carries out being adapted to use during Drilling operation.Specifically, can be formed by the plywood or multi-layer sheet for overlapping with 1 or multiple Plate (such as printed circuit board material) at least topmost, in a manner of being in contact by metal foil side with printed circuit board material, Cover plate for drilling hole is configured, Drilling operation is carried out from the upper surface of the cover plate (resin composition layer side).

More than, present embodiment is illustrated, but the present invention is not limited to above-mentioned present embodiment.The present invention is not Various changes can be subject in the range of its purport by departing from.

Embodiment

Hereinafter, embodiments of the invention compared with comparative example not within the scope of the invention and are illustrated.Need Illustrate, " polyethylene glycol " is abbreviated sometimes in following and makees " PEG ", " PEO " is abbreviated and makees " PEO ".

Hereinafter, the assay method to the bonding force in embodiment and comparative example, the assay method of hole site precision are said It is bright.

The assay method ＞ of ＜ bonding forces

Bonding force determines as follows.First, prepare 3 and the cover plate for drilling hole made in embodiment and comparative example is cut into 3mm Wide, 100mm length sample.Then, the whole surface for resin composition layer two-sided tape being adhered in sample, utilizes this pair Face adhesive tape, sample is adhered to fixed platform.Afterwards, by between resin composition layer and metal foil from being stained with two-sided tape 10mm is peeled off in one end of sample, and the fixture for installing spring scale is installed in the metal foil portion for the sample peeled off.In fixture Upper installation spring scale (SANKO company systems, the maximum that can be measured are 1000gf), with the speed of 1cm/ seconds along relative to adhesion Face is that 180 ° of direction is stretched, and reads the numerical value shown in spring scale.3 samples are measured, by the arithmetic average of 3 times It is worth the numerical value as bonding force.Situation about being not peeled off between metal foil and resin composition layer be denoted as ">1000”.

The measure ＞ of ＜ hole sites precision

Hole site precision determines as follows.There is 5 thickness 0.2mm copper-clad laminated board (trade name in accumulation：HL832, copper foil Thickness：12 μm, two panels, Mitsubishi Gas Chemical Co., Ltd's system) copper-clad laminated board above, with its resin composition layer side The cover plate for drilling hole made in embodiment and comparative example is configured as mode above.And then in the copper-clad laminated board accumulated Most lower plate back side (below) configuration thickness 1.5mm backing plate (paper phenolic aldehyde plywood, trade name：PS1160-G, the prosperous strain formula of profit Commercial firm's system).Then, using 0.2mm φ drill bit (trade names：C-CFU020S, Tungaloy Corporation systems), in rotating speed： 200000rpm, transporting velocity：2.6m/ minutes, perforate number：Under conditions of every 1 3000 hole of drill bit, carry out counting 6000 holes Drilling operation.

For the hole of the 3000th hole (the 1st, drill bit) and the 6000th hole (the 2nd, drill bit), hole analyzer (model is used： HA-1AM, Hitachi Via Mechanics, Ltd. systems) in the back side (below) of the most lower plate of copper-clad laminated board accumulated of measure Hole site and specified coordinate deviation.For every 1 amount of drill bit, for its deviation, average value and standard deviation (σ) are calculated, Calculate " the σ " of average value+3.Afterwards, the hole site precision overall as Drilling operation, for 2 drill bits used, calculate relative In each " average value of the σ " of average value+3 value.Hole site precision calculates the middle formula used such as following formula (1).

(herein, n represents the radical of the brill used.)

＜ raw material ＞

Polyurethane resin (A), the water solubility used in the manufacture of the cover plate for drilling hole of embodiment and comparative example is shown in table 1 Resin (B), additive, main specifications and the manufacturer of solvent and metal foil.

[table 1]

The details of polyurethane resin (A) used in embodiment and comparative example is shown in table 2.Two are derived from table 2 The molal quantity of the construction unit of isocyanates and the ratio between the molal quantity of construction unit (mol ratio) from polyalcohol by the use of as One of nuclear magnetic resonance optical spectroscopy¹H-NMR methods and DQF-COSY methods calculate.Number-average molecular weight is determined using method described later.Tree Fat solid component concentration be for used in the form of aqueous dispersion polyurethane resin (A), the resin solid in aqueous dispersion The amount (quality %) of composition.

[table 2]

" HYDRAN WLS210 " resin is ester ring type diisocyanate-aliphatic polybasic alcohol copolymer to trade name, is different Isophorone diisocyanate-aliphatic polybasic alcohol copolymer.The construction unit from diisocyanate in copolymer is derived from different Isophorone diisocyanate, the construction unit from aliphatic polyol be derived from 1,6- hexylene glycols and 6- hydroxyl adipic acids -1- oneself Acyl ester (reaction product of caprolactone and 1,6-HD).IPDI-aliphatic polybasic alcohol copolymer exists There is the structure (alicyclic ring) for the aliphatic cyclic hydrocarbon for not being aromatic rings in construction unit from diisocyanate.

The molal quantity of the molal quantity of construction unit from diisocyanate and the construction unit from aliphatic polyol The ratio between (be derived from diisocyanate construction unit with from aliphatic polyol construction unit ratio) be from two isocyanides The molal quantity of the construction unit of acid esters：Molal quantity=6 of construction unit from aliphatic polyol：94.Now be derived from fat The molal quantity of the construction unit of fat race polyalcohol is molal quantity, the He Yuan of the construction unit from 1,6-HD in copolymer From the total of the molal quantity of the construction unit of 6- hydroxyl adipic acid -1- hexanoyl base esters.

Trade name " Superflex 820 " resin is aromatic diisocyanate-aliphatic polybasic alcohol copolymer, is 2, 4- toluene di-isocyanate(TDI)s-aliphatic polybasic alcohol copolymer.The construction unit from diisocyanate in copolymer is derived from 2, 4- toluene di-isocyanate(TDI)s, the construction unit from aliphatic polyol are derived from 3- methyl isophthalic acids, and 5- pentanediols, Isosorbide-5-Nitrae-hexamethylene are double Methanol and triethylene glycol.2,4 toluene diisocyanate-aliphatic polybasic alcohol copolymer is in the structure list from diisocyanate There is aromatic rings (structure of aromatic cyclic hydrocarbon) in member.

The molal quantity of the molal quantity of construction unit from diisocyanate and the construction unit from aliphatic polyol The ratio between be the construction unit from diisocyanate molal quantity：The molal quantity of construction unit from aliphatic polyol= 28：72.The molal quantity of the construction unit from aliphatic polyol now is to be derived from 3- methyl isophthalic acids, 5- penta 2 in copolymer The molal quantity of the construction unit of alcohol, the molal quantity of construction unit from 1,4- cyclohexane dimethanols and from triethylene glycol The total of the molal quantity of construction unit.

" HYDRAN APX101H " resin is aliphatic diisocyanate-aromatic polyvalent alcohol copolymer to trade name, is Hexamethylene diisocyanate-aromatic polyvalent alcohol copolymer.The construction unit from diisocyanate in copolymer is derived from Hexamethylene diisocyanate, the construction unit from aromatic polyol are derived from diethylene glycol-terephthaldehyde's acid copolymer.Six Methylene diisocyanate-aromatic polyvalent alcohol copolymer does not have alicyclic ring, and source in the construction unit from diisocyanate There is aromatic rings from the construction unit of aromatic polyol.

The molal quantity of the molal quantity of construction unit from diisocyanate and the construction unit from aromatic polyol The ratio between be the construction unit from diisocyanate molal quantity：Molal quantity=7 of construction unit from aromatic polyol： 93。

The assay method ＞ of the number-average molecular weight of ＜ polyurethane resins (A)

The number-average molecular weight of polyurethane resin (A) uses the liquid chromatography (Shimadzu Scisakusho Ltd for possessing GPC posts System), determine by standard substance of polystyrene, calculated with Relative average molecular weight.Hereinafter, equipment and analysis bar are shown with Part.

(using equipment)

Shimadzu high performance liquid chromatograph ProminenceLIQUID

System controller：CBM-20A

Liquid send unit：LC-20AD

On-line degassing：DGU-20A3

Automatic sampler：SIL-20AHT

Column oven：CTO-20A

Differential refractive index detector：RID-10A

LC work stations：LCSolution

(analysis condition)

Post：5 μ 10E5A of Phenogel 7.8 × 300 × 1,5 μ 10E4A of Phenogel 7.8 × 300 × 1, 5 μ 10E3A of Phenogel 7.8 × 300 × 1, Phenomenex systems

Pre-column：Phenogel guard column 7.8 × 50 × 1, Phenomenex systems

Eluent：High performance liquid chromatograph tetrahydrofuran Kanto Kagaku K. K. system

Flow：1.00mL/ minute

Column temperature：45℃

＜ standard curve makings polystyrene ＞

Showa electrician Shodex standard SL105, SM105

Number-average molecular weight 580,1390,2750,6790,13200,18500,50600,123000,259000,639000, 1320000th, 2480000 polystyrene

Hereinafter, the manufacture method of the cover plate for drilling hole in embodiment and comparative example is illustrated.

The ＞ of ＜ embodiments 1

Will be as the aqueous dispersion of IPDI-aliphatic polybasic alcohol copolymer of polyurethane resin (A) (trade name：HYDRAN WLS210, number-average molecular weight：35000th, mole of the construction unit from IPDI Number：Molal quantity=6 of construction unit from aliphatic polyol：94th, resin solid content concentration：35 mass %, DIC strain formulas Commercial firm's system) 105 mass parts (30 mass parts are calculated as using resin solid content conversion), it is used as the poly- of macromolecular water-soluble resin (b1) Oxirane (trade name：Alcox E-45, weight average molecular weight：560000th, it is bright into chemical industry Co. Ltd. system) 7.0 mass Part and the polyethylene glycol (trade name as low molecule water-soluble resin (b2)：PEG4000S, weight average molecular weight：3300th, Sanyo Chemical conversion industry Co. Ltd. system) 63.0 mass parts are dissolved in water/methanol mixed solvent (mass ratio 50/50), and preparation is used as resin The solid component concentration of composition is 30 mass % solution.

Relative to the mass parts of resin combination solid constituent 100 in the solution, the surface conditioner of 1.2 mass parts of addition (BYK349, BYK Japan Co. Ltd. systems), and then relative to the mass parts of resin combination solid constituent 100 in solution, add Add the sodium formate (Mitsubishi Gas Chemical Co., Ltd's system) of 0.25 mass parts, make its dispersed, obtain being used to form resin group The solution of the resin combination of compound layer.

Using bar coater, by the solution of gained resin combination with the thickness of the resin composition layer after dry solidification into It is coated on the aluminium foil used as metal foil for 0.05mm mode and (uses aluminium foil：JIS-A1100H1.80, thickness：0.1mm、 Mitsubishi Aluminum Co., Ltd.'s system).Then, using drying machine, dried 3 minutes with 120 DEG C, cool down, solidify afterwards, make boring lid Plate.

The bonding force 3 times between the metal foil of drilling cover plate and resin composition layer is determined using the above method, obtains it Arithmetic mean of instantaneous value.In addition, carrying out Drilling operation using the above method, hole site precision is determined.These results are shown in table 3.

The ＞ of ＜ embodiments 2~5

According to the method described in embodiment 1, resin combination is prepared with the species and compounding amount of the raw material shown in table 3 Solution, the thickness for making the resin composition layer after dry solidification is 0.05mm cover plate for drilling hole.It is boring for gained Hole site precision when the bonding force and Drilling operation of cover plate, measure metal foil and resin composition layer.These are shown in table 3 As a result.

The ＞ of ＜ comparative examples 1~6

According to the method described in embodiment 1, resin combination is prepared with the species and compounding amount of the raw material shown in table 3 Solution, the thickness for making the resin composition layer after dry solidification is 0.05mm cover plate for drilling hole.It is boring for gained Hole site precision when the bonding force and Drilling operation of cover plate, measure metal foil and resin composition layer.These are shown in table 3 As a result.

＜ judgment standards ＞

The determinating reference of bonding force shown in table 3 is as described below.During Drilling operation, processing when load put on cover plate, Therefore, if metal foil and the bonding force of resin composition layer are weak, resin composition layer can be peeled off.The present inventor etc. is carried out Further investigation, result judgement, bonding force is if more than 200gf, then resin composition layer will not be peeled off during Drilling operation.Cause This, the determinating reference of bonding force is as follows：Then it is determined as " A " if more than 200gf, is determined as " B " if 200gf is less than.

The judgment standard of hole site precision shown in table 3 is as described below.The hole site calculated with the calculating formula of above-mentioned formula (1) " A " is denoted as when precision is less than 18 μm, during excellent, is denoted as " B " during more than 18 μm.

The benchmark of synthetic determination shown in table 3 is as described below.The result of determination of bonding force and the judgement knot of hole site precision Both fruits are if " A ", then the metal foil and bonding force of resin composition layer is strong and hole site precision is excellent, therefore, as Synthetic determination is denoted as " A ", when at least one of the result of determination of hole site precision and the result of determination of bonding force are " B ", is made It is denoted as " B " for synthetic determination.

[table 3]

It can be seen from the result of the embodiment 1~5 shown in table 3, the polyurethane in the resin composition layer of cover plate for drilling hole Resin (A) is the copolymerization with the construction unit from ester ring type diisocyanate and the construction unit from aliphatic polyol Thing, the content of polyurethane resin (A) are 30 matter relative to the mass parts of total 100 of polyurethane resin (A) and water-soluble resin (B) When more than amount part and below 60 mass parts, the metal foil of cover plate for drilling hole and the bonding force of resin composition layer are strong, use the lid Hole site precision in the perforate processing of plate is also good.

On the other hand, it can be seen from the result of comparative example 1 and 2, polyurethane resin (A) in resin composition layer be with The copolymer of construction unit from ester ring type diisocyanate and the construction unit from aliphatic polyol, polyurethane resin (A) when content is less than 30 mass parts relative to the mass parts of total 100 of polyurethane resin (A) and water-soluble resin (B), drilling It is also weak with the metal foil of cover plate and the bonding force of resin composition layer.In addition, using in the perforate processing of the cover plate, resin occurs The stripping of composition layer, hole site deterioration in accuracy.

And then in comparative example 3~5, the construction unit from diisocyanate in polyurethane resin (A) is from fragrance The construction unit of (cyclo) aliphatic diisocyanates, it is not derived from the construction unit of ester ring type diisocyanate.In these comparative examples 3~5, i.e., Make the content of the polyurethane resin (A) in resin composition layer relative to the total of polyurethane resin (A) and water-soluble resin (B) It is more than 30 mass parts and below 60 mass parts, although the metal foil and resin composition layer of cover plate for drilling hole to count 100 mass parts Bonding force it is strong, but use the cover plate Drilling operation hole site precision it is also poor.This is because, it is based on being derived from aromatic series two The high outspoken nature of the high aggregation force and aromatic rings of the amino-formate bond of isocyanates, so as to cause the resin combination in cover plate Nitride layer lacks lubricity.

In addition, in comparative example 6, the diisocyanate unit in polyurethane resin (A) is derived from the fat without alicyclic ring The construction unit of the diisocyanate of race, polyol unit are derived from the construction unit of aromatic polyol.In the comparative example 6, Even if make the content of the polyurethane resin (A) in resin composition layer relative to polyurethane resin (A) and water-soluble resin (B) 100 mass parts are amounted to as more than 30 mass parts and below 60 mass parts, the resin composition layer of cover plate also lacks lubricity, are used The hole site low precision of the Drilling operation of the cover plate.The reason is that based on the amino-formate bond from aromatic polyol High aggregation force and aromatic rings high outspoken nature.

As known from the above, form the content of the polyurethane resin (A) in the resin composition layer of cover plate for drilling hole relative to The mass parts of total 100 of polyurethane resin (A) and water-soluble resin (B) are poly- ammonia more than 28 mass parts and below 60 mass parts Ester resin (A) is being total to the construction unit from ester ring type diisocyanate and the construction unit from aliphatic polyol During polymers, the bonding force of metal foil and resin composition layer in cover plate for drilling hole is strong and uses in the perforate of cover plate processing Hole site precision it is also good.

According to present embodiment, can provide：Compared with conventional cover plate for drilling hole, hole site precision is excellent, metal foil Brill caused by stripping between resin composition layer, which is lost, to be suppressed, without turning into necessary adhesive linkage in the past, Therefore economy also excellent cover plate for drilling hole.

The application is based on Japanese patent application (Japanese Patent Application 2016-047989) filed in 11 days March in 2016, by it Hold and introduced so far as reference.

Industrial applicability

The present invention can provide：At least on one side of the metal foil is formed at by metal foil and non-sandwiched adhesive linkage The cover plate for drilling hole that layer containing resin combination is formed, and the adhesive strength of metal foil and the layer containing resin combination it is strong, And then excellent cover plate for drilling hole of hole site precision during Drilling operation etc..Therefore, the present invention has industry in such field On utilizability.

Claims (11)

1. a kind of cover plate for drilling hole, it possesses：Metal foil；With, not sandwiched adhesive linkage and be formed at least one side of the metal foil On the layer containing resin combination, the resin combination includes polyurethane resin (A) and water-soluble resin (B), described to contain There is the content of the polyurethane resin (A) in the layer of resin combination relative to the polyurethane resin (A) and described water-soluble Property resin (B) the mass parts of total 100 for more than 28 mass parts and below 60 mass parts, the polyurethane resin (A) be with The copolymer of construction unit from ester ring type diisocyanate and the construction unit from aliphatic polyol.

2. cover plate for drilling hole according to claim 1, wherein, the water solubility in the layer containing resin combination The content of resin (B) is 40 matter relative to the mass parts of total 100 of the polyurethane resin (A) and the water-soluble resin (B) Measure more than part and below 72 mass parts.

3. cover plate for drilling hole according to claim 1 or 2, wherein, the polyurethane resin (A) is to be derived from alicyclic ring by described The copolymer that the construction unit of formula diisocyanate and the construction unit from aliphatic polyol are formed.

4. according to cover plate for drilling hole according to any one of claims 1 to 3, wherein, the ester ring type diisocyanate includes IPDI.

5. cover plate for drilling hole according to claim 4, wherein, possessed by the copolymer, described it is derived from isophorone The ratio of the construction unit of diisocyanate and the construction unit from aliphatic polyol is derived from isophorone with described The molal quantity of the construction unit of diisocyanate：The molal quantity of construction unit from aliphatic polyol is calculated as 3：97~9：91 Scope.

6. according to cover plate for drilling hole according to any one of claims 1 to 5, wherein, the number of the polyurethane resin (A) is divided equally Son amount is more than 5000 and less than 50000.

7. according to cover plate for drilling hole according to any one of claims 1 to 6, wherein, the water-soluble resin (B) be selected from by PEO, PPOX, polyvinylpyrrolidone, cellulose derivative, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, Polyoxyethylated monoether compounds, polyoxyl 40 stearate, polyoxyethylene sorbitan monostearate, polyglycereol 1 kind or 2 kinds in the group of monostearate and PEO-polypropylene oxide copolymers and their derivative composition More than.

8. cover plate for drilling hole according to claim 7, wherein, the water-soluble resin (B) include with more than 50000 and The macromolecular water-soluble resin (b1) of less than 1500000 weight average molecular weight and with more than 1000 and less than 30000 weight it is equal The low molecule water-soluble resin (b2) of molecular weight, the macromolecular water-soluble resin (b1), which includes, to be selected from by PEO, gathers Expoxy propane, polyvinylpyrrolidone and cellulose derivative group into group at least one kind of, the low molecule water-soluble resin (b2) include and be selected from by polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxyethylated monoether compounds, polyoxyethylene list tristearin Acid esters, polyoxyethylene sorbitan monostearate and PEO-polypropylene oxide copolymers and they spread out It is at least one kind of in the group of biotic component.

9. according to cover plate for drilling hole according to any one of claims 1 to 8, wherein, the layer containing resin combination Thickness is more than 0.02mm and below 0.3mm.

10. according to cover plate for drilling hole according to any one of claims 1 to 9, wherein, the thickness of the metal foil is 0.05mm Above and below 0.5mm.

11. a kind of drilling method, cover plate for drilling hole according to any one of claims 1 to 10 is configured at plywood by it Or multiple-plate the top, the drilling of the plywood or multi-layer sheet is carried out above the cover plate for drilling hole, so as in institute State and hole is formed in plywood or multi-layer sheet.