TW201801909A - Auxiliary plate for drilling and drilling method using the same - Google Patents

Abstract

The present invention provides an auxiliary plate for drilling, comprising: a metal foil; and a polyurethane resin (A) and a water-soluble resin which are formed on at least one side of the metal foil without interposing an adhesive layer. The content of the resin composition layer of the resin (B); the content of the polyurethane resin (A) in the resin composition-containing layer, relative to the polyurethane resin (A) and the water-soluble resin (B The total 100 parts by mass is 28 parts by mass or more and 60 parts by mass or less. The polyurethane resin (A) is a copolymer having a constituent unit derived from an alicyclic diisocyanate and a constituent unit derived from an aliphatic polyol.

Description

Auxiliary plate for drilling and drilling processing method using the auxiliary plate

The present invention relates to an auxiliary plate for drilling and a drilling processing method using the auxiliary plate.

As for the drilling processing method of a laminated board or a multilayer board used as a printed circuit board material, generally, the following method is adopted: One or more laminated boards or multilayer boards are stacked, and the topmost board is arranged as an abutting board. Metal foils such as aluminum foil or metal foils that form a layer containing a resin composition on the surface of the metal foil (hereinafter, the "sheet" in this specification is also referred to as "auxiliary plate for drilling", or "auxiliary for drilling" Plate ") and drilled.

In recent years, along with the requirements for the reliability improvement of printed circuit boards and the progress of high density, the drilling of laminated or multilayer boards used in printed circuit boards has also required improved hole position accuracy and reduced hole wall roughness. And other high-quality processing.

In order to respond to the above-mentioned requirements such as improvement in hole position accuracy and reduction in hole wall roughness, for example, Patent Document 1 proposes a hole-cutting method using a plate made of a water-soluble resin such as polyethylene glycol. Further, Patent Document 2 proposes a lubricant sheet for openings in which a water-soluble resin layer is formed on a metal foil. Further, Patent Document 3 proposes an auxiliary plate for openings obtained by forming a water-soluble resin layer on an aluminum foil on which a thermosetting resin film has been formed. In addition, Patent Document 4 proposes a lubricant sheet for openings obtained by blending a lubricating resin composition with a non-halogen coloring agent.

As one form of the auxiliary plate for drilling, a form composed of a metal foil and a resin composition-containing layer (hereinafter, referred to as a "resin composition layer") formed on at least one side of the metal foil has been proposed. However, the adhesion strength between the metal foil and the resin composition layer is weak. Therefore, in the auxiliary plate for drilling in which the metal foil and the resin composition layer are in direct contact, the resin composition layer is peeled from the metal foil during the drilling process, and the drill bit follows the peeled resin composition layer, which often causes Deterioration of the accuracy of hole position and deterioration of the break frequency of the drill. In addition, the auxiliary board for drilling is usually arranged on both sides of a plurality of laminated boards or multilayer boards, and then the holes are processed in a state in which these are formed into a bundle by a fixing tape. However, since the fixing tape is peeled from the bundle together with the resin composition layer, as a result, the position of the auxiliary plate may be deviated. Therefore, in order to improve the adhesion strength between the metal foil and the resin composition layer during actual use, the urethane-based compound, vinyl acetate-based compound, and vinyl chloride-based compound are formed between the metal foil and the resin composition layer. In the form of an adhesive layer (adhesive film) composed of a polyester-based compound, these polymers, an epoxy-based compound, a cyanate-based compound, etc., an auxiliary plate is used (for example, refer to Patent Document 5). [Prior Art Literature] [Patent Literature]

Patent Document 1: Japanese Patent Application Laid-Open No. 4-92494 Patent Document 2: Japanese Patent Application Laid-Open No. 5-169400 Patent Literature 3: Japanese Patent Application Laid-Open No. 2003-136485 Patent Literature 4: Japanese Patent Application Laid-Open No. 2004-230470 5: Japanese Patent Application Laid-Open No. 2011-183548

[Problems to be Solved by the Invention] However, if an adhesive layer is provided between a metal foil and a resin composition layer as described in Patent Document 5, the adhesive layer hinders the lubricating effect of the resin composition. As a result, the hole position accuracy and the hole wall roughness which are important characteristics required for the auxiliary plate for drilling may be deteriorated. Therefore, it is desired to develop an auxiliary plate for drilling, in which the adhesion strength between the metal foil and the resin composition layer is strong, and the hole position accuracy and the inner wall roughness are excellent, although no adhesion layer is provided between the metal foil and the resin composition layer. .

In view of such a situation, an object of the present invention is to provide an auxiliary plate for drilling, which is composed of a metal foil and a layer containing a resin composition formed on at least one side of the metal foil without interposing an adhesive layer. Moreover, the adhesion strength of the metal foil and the layer containing the resin composition is strong, and further, the hole position accuracy during drilling processing is excellent; and a drilling processing method using the auxiliary plate is provided. [Means for solving problems]

The present inventors have conducted various studies in order to solve the above-mentioned problems. As a result, it was found that an auxiliary plate for drilling includes a metal foil and a layer containing a resin composition formed on at least one side of the metal foil without interposing an adhesive layer, and the layer containing the resin composition includes The specific resin has a specific content in a specific range; the metal foil has a strong adhesive strength with the layer containing the resin composition, and further has excellent hole position accuracy during drilling, and completed the present invention.

That is, the present invention is as follows. [1] An auxiliary plate for drilling, comprising: a metal foil; and a polyurethane resin (A) and a water-soluble resin which are formed on at least one side of the metal foil without interposing an adhesive layer. The resin composition layer of the resin (B); the content of the polyurethane resin (A) in the resin composition-containing layer relative to the polyurethane resin (A) and the water-soluble content The total 100 parts by mass of the resin (B) is 28 parts by mass or more and 60 parts by mass or less. The polyurethane resin (A) has a constituent unit derived from an alicyclic diisocyanate and a constituent unit derived from an aliphatic polyol. Of copolymers. [2] The auxiliary plate for drilling according to [1], wherein the content of the water-soluble resin (B) in the resin composition-containing layer is higher than that of the polyurethane resin (A) and the water-soluble resin. The total 100 parts by mass of the resin (B) is 40 parts by mass or more and 72 parts by mass or less. [3] The auxiliary plate for drilling according to [1] or [2], wherein the polyurethane resin (A) is composed of the constituent unit derived from the alicyclic diisocyanate and the aliphatic polyol derived from Copolymer made up of constituent units. [4] The auxiliary plate for drilling according to any one of [1] to [3], wherein the alicyclic diisocyanate includes isophorone diisocyanate. [5] The auxiliary plate for drilling according to [4], wherein the ratio of the constituent unit derived from isophorone diisocyanate to the constituent unit derived from aliphatic polyol possessed by the copolymer is in moles The molar number of the structural unit derived from isophorone diisocyanate: The molar number of the structural unit derived from an aliphatic polyol is in a range of 3:97 to 9:91. [6] The auxiliary plate for drilling according to any one of [1] to [5], wherein the number average molecular weight of the polyurethane resin (A) is 5,000 or more and 50,000 or less. [7] The auxiliary plate for drilling according to any one of [1] to [6], wherein the water-soluble resin (B) is selected from the group consisting of polyethylene oxide, polypropylene oxide, and polyvinyl group. Pyrrolidone, cellulose derivative, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, monoether compound of polyoxyethylene, polyoxyethylene monostearate, polyoxyethylene sorbitan monostearic acid One or two or more of the group consisting of esters, polyglycerol monostearate, polyethylene oxide-polypropylene oxide copolymers, and their derivatives. [8] The auxiliary board for drilling according to [7], wherein the water-soluble resin (B) contains a high-molecular-weight water-soluble resin (b1) having a weight average molecular weight of 50,000 or more and 1,500,000 or less, and a polymer water-soluble resin (b1) of 1,000 or more and 30,000 or less Low-molecular-weight water-soluble resin (b2) having a weight-average molecular weight, and the high-molecular water-soluble resin (b1) contains a material selected from the group consisting of polyethylene oxide, polypropylene oxide, polyvinylpyrrolidone, and cellulose derivatives. At least one member of the group, the low-molecular-weight water-soluble resin (b2) contains a monoether compound selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxyethylene, and polyoxyethylene monomer At least one selected from the group consisting of stearates, polyoxyethylene sorbitan monostearate, and polyethylene oxide-polypropylene oxide copolymers, and their derivatives. [9] The auxiliary plate for drilling according to any one of [1] to [8], wherein the thickness of the layer containing the resin composition is 0.02 mm or more and 0.3 mm or less. [10] The auxiliary plate for drilling according to any one of [1] to [9], wherein the thickness of the metal foil is 0.05 mm or more and 0.5 mm or less. [11] A method for drilling processing by arranging an auxiliary plate for drilling according to any one of [1] to [10] on the top surface of a laminated board or a multilayer board, and The laminated board or multilayer board is drilled on the top surface of the auxiliary board, and holes are formed in the laminated board or multilayer board. [Effect of the invention]

According to the present invention, an auxiliary plate for drilling can be provided, which is composed of a metal foil and a layer containing a resin composition formed on at least one side of the metal foil without interposing an adhesive layer, and the metal foil and the The layer containing the resin composition has strong adhesive strength, and further, the hole position accuracy during drilling is excellent; and a drilling method using the auxiliary plate can be provided.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail, but the present invention is not limited to the following embodiment, and various modifications can be made without departing from the gist thereof.

[I: Auxiliary plate for drilling] The auxiliary plate for drilling according to this embodiment is provided with a metal foil, and is formed on at least one side of the metal foil without interposing an adhesive layer, and contains polyurethane. A layer of a resin composition of an ethyl resin (A) and a water-soluble resin (B) (hereinafter, referred to as a "resin composition layer"), an auxiliary plate for drilling, and polyurethane in the resin composition layer. The content of the ester resin (A) is 28 mass parts or more and 60 mass parts or less based on 100 mass parts of the total of the polyurethane resin (A) and the water-soluble resin (B). The polyurethane resin ( A) is a copolymer having a constituent unit derived from an alicyclic diisocyanate and a constituent unit derived from an aliphatic polyol.

The auxiliary plate for drilling according to this embodiment is composed of a metal foil and a resin composition layer formed on at least one side of the metal foil without interposing an adhesive layer. That is, there is no adhesive layer (resin film) for adhering the metal foil and the resin composition between the metal foil and the resin composition layer, and the metal foil and the resin composition layer are in direct contact with each other. When the resin composition layer includes a polyurethane resin (A) and a water-soluble resin (B), the content of the polyurethane resin (A) in the resin composition layer is within the above range, and the polyamine The urethane resin (A) is a copolymer having a constitutional unit derived from an alicyclic diisocyanate and a constitutional unit derived from an aliphatic polyhydric alcohol. Even if the adhesive layer is not interposed between the metal foil and the resin composition layer, the metal The adhesive strength of the foil and the resin composition layer is also strong, and the hole position accuracy during drilling is excellent.

The auxiliary plate for drilling in this embodiment is economical in both the raw material and the manufacturing steps of the auxiliary plate. That is, the drilling auxiliary plate of this embodiment does not need to interpose the adhesive layer, so it can reduce the cost of raw materials, and it does not require a step of forming an adhesive layer. Compared with conventional drilling auxiliary plates, it is economical. Also excellent. The resin composition layer may be in the form of being formed on one side of a metal foil or in the form of being formed on both sides. When the resin composition layers are formed on both sides, the composition of the resin composition in these layers may be the same or different.

[II: Polyurethane Resin (A)] The polyurethane resin (A) contained in the resin composition layer in the auxiliary plate for drilling according to this embodiment has an alicyclic diamine A copolymer of a constituent unit of an isocyanate and a constituent unit derived from an aliphatic polyol. This copolymer is not particularly limited as long as it has a constituent unit derived from an alicyclic diisocyanate and a constituent unit derived from an aliphatic polyol.

The constituent unit derived from an alicyclic diisocyanate refers to a constituent unit (skeleton) derived from an alicyclic diisocyanate in a polymer that is used as a raw material for a polymerization reaction when a polymer is formed. The constituent unit derived from an aliphatic polyol refers to a constituent unit (skeleton) derived from an aliphatic polyol used as a raw material for a polymerization reaction when a polymer is formed in a polymer. That is, in the above-mentioned copolymer, at least the alicyclic diisocyanate which provides the structural unit derived from the alicyclic diisocyanate and the aliphatic polyol which provides the structural unit derived from the aliphatic polyol are copolymerized when the polymer is formed. Receiver of the response.

Since the polyurethane resin (A) is a copolymer having a constituent unit derived from an alicyclic diisocyanate and a constituent unit derived from an aliphatic polyol, the auxiliary plate for drilling according to this embodiment includes a metal foil and a resin. The composition layer tends to have strong adhesive strength and excellent hole position accuracy during drilling. The reason for this is not particularly limited, but it is thought that the adhesion strength of the metal foil and the resin composition layer is mainly due to the copolymer having constituent units derived from alicyclic diisocyanate, and mainly due to the copolymer having aliphatic multicomponent origin. As the constituent unit of alcohol, the resin composition layer has excellent lubricity, so the hole position accuracy during drilling is excellent.

The alicyclic diisocyanate which provides the structural unit derived from an alicyclic diisocyanate is not particularly limited as long as it is an alicyclic organic compound having two isocyanate groups in the molecule, and may be a monomer or a polymer . Examples of such a compound include isophorone diisocyanate, 1,3-diisocyanoxycyclohexane, 1,4-diisocyanoxycyclohexane, and 4,4-dicyclohexylmethanediamine. Isocyanate, cyclohexyl diisocyanate, methyl cyclohexyl diisocyanate, bis (2-isocyanoxyethyl) -4-cyclohexene-1,2-dicarboxylic acid ester, 2,5-norbornane Diisocyanates and 2,6-norbornane diisocyanates. Among these, from the viewpoint that the purpose of the implementation form can be more effectively and surely considered, isophorone diisocyanate, 1,3-diisocyanoxycyclohexane, and 1,4-diisocyanate are preferable. Oxycyclohexane is more preferred, and isophorone diisocyanate is particularly preferred. These alicyclic diisocyanates may be used individually by 1 type, and may use 2 or more types together.

The aliphatic polyol which provides the structural unit derived from an aliphatic polyol is not particularly limited as long as it is an aliphatic organic compound having two or more hydroxyl groups in the molecule, and may be a monomer or a polymer. Examples of such compounds include ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propylene glycol, triethylene glycol, 2-methyl-1,3-propanediol, and 2,2-diethylene glycol. Methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 2-methyl-1,4-butanediol, 2-methyl 3-methyl-1,4-butanediol, 3-methyl-1,5-pentanediol, 1,5-pentanediol, 1,6-hexanediol, and 6-hydroxyadipic acid -1-hexanolide (the reaction product of caprolactone and 1,6-hexanediol). Among these, from the viewpoint that the purpose of the implementation form can be more effectively and reliably considered, ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, and 6- Hydroxy adipate-1-hexanoate is preferred, and 1,6-hexanediol and 6-hydroxyadipate-1-hexanoate are particularly preferred. These aliphatic polyhydric alcohols may be used individually by 1 type, and may use 2 or more types together.

The ratio of the alicyclic diisocyanate-derived constitutional unit to the aliphatic polyol-containing constitutional unit in the copolymer having the alicyclic diisocyanate-derived constitutional unit and the aliphatic polyol-derived constitutional unit is not particularly limited. Molar number of the constituent unit of the alicyclic diisocyanate: The molar number of the constituent unit derived from the aliphatic polyol is preferably in a range of 3:97 to 9:91. When the ratio of the molar number of the constituent units derived from the alicyclic diisocyanate to the total molar number 100 of these constituent units is 3 or more, the adhesion strength between the resin composition layer and the metal foil is more sufficient. Since the resin composition layer becomes more difficult to peel, the hole position accuracy tends to be more excellent. On the other hand, if the ratio of the number of moles of the constituent units derived from the aliphatic polyol to the total number of moles of these constituent units 100 is 91 or more, the lubricity during drilling is better, so processing The dischargeability of the generated cutting chips is further improved, whereby the hole position accuracy is more excellent, and / or the drill working life tends to be longer.

The copolymer having a constitutional unit derived from an alicyclic diisocyanate and a constitutional unit derived from an aliphatic polyhydric alcohol may include a constitutional unit derived from an alicyclic diisocyanate and a fat derived from the fatty acid as long as the purpose of this embodiment is not impaired. A constituent unit other than the constituent unit of the group polyol (hereinafter, also referred to as "other constituent unit" in the present specification). That is, a copolymer having a constitutional unit derived from an alicyclic diisocyanate and a constitutional unit derived from an aliphatic polyhydric alcohol may be an alicyclic diisocyanate that provides a constitutional unit derived from an alicyclic diisocyanate when forming a polymer. 2. A copolymer obtained by copolymerizing an aliphatic polyol that provides a constituent unit derived from an aliphatic polyol, and a compound that provides other constituent units as needed. The other constituent units are not particularly limited as long as they do not impair the purpose of this embodiment, and examples thereof include oxalic acid, succinic acid, adipic acid, pimelic acid, sebacic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, 1,2-cyclohexane Alkanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxy) methane, and Structural units of polycarboxylic acids such as 1,2,7,8-octatetetracarboxylic acid; derived from ethylene, propylene, 1-butene, 2-butene, 1,3-butadiene, 1-pentene, 3- Structural units of olefins such as pentene, 1,3-pentadiene, and 1,5-pentadiene; and structural units derived from unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and fumaric acid.

Among copolymers having a constituent unit derived from an alicyclic diisocyanate, a constituent unit derived from an aliphatic polyol, and other constituent units, a constituent unit derived from an alicyclic diisocyanate, a constituent unit derived from an aliphatic polyol, and others The combination of constituent units is not particularly limited. The content of the other constituent units in the copolymer having a constituent unit derived from an alicyclic diisocyanate, a constituent unit derived from an aliphatic polyol, and other constituent units may be a range that does not impair the purpose of this embodiment, It is not particularly limited. However, considering the viewpoint of achieving the purpose of the implementation form more effectively and reliably, the number of moles of the constituent units derived from the alicyclic diisocyanate, the number of moles of the constituent units derived from the aliphatic polyol, and When the total number of moles of other constituent units is 100 moles, it is preferably 1 to 5 moles.

As for the polyurethane resin (A), a copolymer having a constitutional unit derived from an alicyclic diisocyanate, a constitutional unit derived from an aliphatic polyol, and other constitutional units as necessary may be used alone, Two or more types can also be used.

In this embodiment, the polyurethane resin (A) is a copolymer composed of a constituent unit derived from an alicyclic diisocyanate and a constituent unit derived from an aliphatic polyol, that is, a alicyclic diisocyanate-fat Group polyol copolymers. If the polyurethane resin (A) is a copolymer composed of a structural unit derived from an alicyclic diisocyanate and a structural unit derived from an aliphatic polyol, the auxiliary plate for drilling according to this embodiment includes a metal foil and a resin. The composition layer tends to have higher adhesive strength and more excellent hole position accuracy during drilling.

The copolymer which consists of a structural unit derived from an alicyclic diisocyanate and a structural unit derived from an aliphatic polyol is not specifically limited, For example, the alicyclic diisocyanate which provided the said structural unit derived from an alicyclic diisocyanate is mentioned. A copolymer obtained by copolymerizing with an aliphatic polyol provided as a constituent unit derived from an aliphatic polyol described above. In the copolymer composed of a constituent unit derived from an alicyclic diisocyanate and a constituent unit derived from an aliphatic polyol, a combination of a constituent unit derived from an alicyclic diisocyanate and a constituent unit derived from an aliphatic polyol is not particularly limited. Moreover, as for the polyurethane resin (A), the copolymer which consists of the structural unit derived from an alicyclic diisocyanate, and the structural unit derived from an aliphatic polyhydric alcohol can be used individually by 1 type, and 2 types can also be used. Used above.

The ratio of the alicyclic diisocyanate-derived unit to the aliphatic polyol-containing constituent unit in the copolymer composed of the alicyclic diisocyanate-based constituent unit and the aliphatic polyol-derived constituent unit is not particularly limited, Molar number from the constituent units of the alicyclic diisocyanate: The molar number from the constituent units of the aliphatic polyol is preferably in the range of 3:97 to 9:91. When the ratio of the molar number of the constituent units derived from the alicyclic diisocyanate to the total molar number 100 of these constituent units is 3 or more, the adhesion strength between the resin composition layer and the metal foil is more sufficient. Since the resin composition layer becomes more difficult to peel, the hole position accuracy tends to be more excellent. On the other hand, if the ratio of the number of moles of the constituent units derived from the aliphatic polyol to the total number of moles of these constituent units 100 is 91 or more, the lubricity during drilling is better, so processing The dischargeability of the generated cutting chips is further improved, whereby the hole position accuracy is more excellent, and / or the drill working life tends to be longer.

Considering the viewpoint that the purpose of the embodiment is more effectively and reliably achieved, the alicyclic diisocyanate synthesized in the polyurethane resin (A) should preferably include isophorone diisocyanate. It is preferably isophorone. Ketone diisocyanates are more preferred. More specifically, as for the polyurethane resin (A), as for the copolymer containing the structural unit derived from an alicyclic diisocyanate and the structural unit derived from an aliphatic polyhydric alcohol, it is preferable to include a copolymer derived from isophor Copolymers of the structural unit of ketene diisocyanate and the structural unit derived from an aliphatic polyol are preferred. In addition, as for the polyurethane resin (A), the above-mentioned copolymer composed of a constituent unit derived from an alicyclic diisocyanate and a constituent unit derived from an aliphatic polyol is preferably isophorone. A copolymer composed of a constituent unit of a diisocyanate and a constituent unit derived from an aliphatic polyol is more preferable, that is, a copolymer containing an isophorone diisocyanate-aliphatic polyol is more preferable.

The isophorone diisocyanate-aliphatic polyol copolymer is not particularly limited. For example, the isophorone diisocyanate may be obtained by copolymerizing an isophorone diisocyanate with an aliphatic polyol provided as a constituent unit derived from an aliphatic polyol. Copolymer. Among them, isophorone diisocyanate-1,6-hexanediol copolymer, isophorone diisocyanate-6-hydroxyadipate-1-hexanoate copolymer, and isophorone diisocyanate-1 The copolymer of 6-hexanediol-6-hydroxyadipate-1-hexanoate is preferred. As for the polyurethane resin (A), these copolymers may be used singly or in combination of two or more kinds. If the polyurethane resin (A) is such a copolymer, the auxiliary plate for drilling according to this embodiment has more excellent adhesion strength between the metal foil and the resin composition layer and better hole position accuracy during drilling processing. tendency.

Copolymers containing constituent units derived from isophorone diisocyanate and constituent units derived from aliphatic polyols, or copolymers consisting of constituent units derived from isophorone diisocyanate and constituent units derived from aliphatic polyols The ratio of the structural unit derived from isophorone diisocyanate to the structural unit derived from an aliphatic polyol is not particularly limited. However, the ratio is preferably in the range of 3:97 to 9:91 in terms of the molar number of the structural unit derived from isophorone diisocyanate: the molar number of the structural unit derived from an aliphatic polyol. Better. If the ratio of the number of moles of the constituent units derived from isophorone diisocyanate to the total number of moles of these constituent units is 100 or more, the adhesion strength between the resin composition layer and the metal foil is more sufficient, and the drilling process is performed. As the resin composition layer becomes more difficult to peel off, the accuracy of the hole position tends to be more excellent. On the other hand, if the ratio of the number of moles of the constituent units derived from the aliphatic polyol to the total number of moles of these constituent units 100 is 91 or more, the lubricity during drilling is better, so processing The dischargeability of the generated cutting chips is further improved, whereby the hole position accuracy is more excellent, and / or the drill working life tends to be longer.

The content of the polyurethane resin (A) contained in the resin composition layer in the auxiliary plate for drilling according to this embodiment is greater than that of the polyurethane resin (A) and the water-soluble resin (B) described later. The total 100 parts by mass is 28 parts by mass or more and 60 parts by mass or less, preferably 30 parts by mass or more and 60 parts by mass or less, and more preferably 35 parts by mass or more and 50 parts by mass or less. When the content of the polyurethane resin (A) is 28 parts by mass or more, the adhesion strength between the metal foil and the resin composition layer becomes more sufficient. As a result, the hole position accuracy is poor during drilling and peeling of the resin composition layer due to drill breakage is less likely to occur. Therefore, the hole position accuracy is more excellent and the drill processing life tends to be longer. On the other hand, when the content of the polyurethane resin (A) is 60 parts by mass or less, the content of the water-soluble resin (B) in the resin composition layer can be adjusted so that the drilling process can have sufficient lubrication. The accuracy of the hole position during drilling is further improved. In particular, when the content of the polyurethane resin (A) is 28 mass parts or more and 60 mass parts or less based on 100 mass parts of the total of the polyurethane resin (A) and the water-soluble resin (B) described later, Both the adhesive strength of the metal foil and the resin composition layer and the accuracy of the hole position during the drilling process tend to be more excellent.

The number average molecular weight of the polyurethane resin (A) is not particularly limited, but it is preferably from 5,000 to 50,000, and more preferably from 20,000 to 50,000. When the number average molecular weight is 5000 or more, the occurrence of blocking can be further suppressed, and the workability tends to be more favorable. On the other hand, if the number average molecular weight is 50,000 or less, the chip dischargeability becomes better during drilling processing, thereby improving the hole position accuracy and / or preventing the drill from being broken. The number average molecular weight of the polyurethane resin (A) can be measured using a GPC column according to a conventional method, and polystyrene is used as a standard substance. More specifically, it can be measured according to the method described in the examples.

The manufacturing method and manufacturing conditions of a polyurethane resin (A) are not specifically limited, A well-known method and conditions can be employ | adopted. When the polyurethane resin (A) is an alicyclic diisocyanate-aliphatic polyol copolymer such as isophorone diisocyanate-aliphatic polyol copolymer, the isophorone diisocyanate, Cycloaliphatic diisocyanates such as 1,3-diisocyanoxycyclohexane and 1,4-diisocyanoxycyclohexane, and ethylene glycol, diethylene glycol, 1,4-butanediol, Aliphatic polyhydric alcohols such as 1,6-hexanediol and 6-hydroxyadipate-1-hexane esters are produced by copolymerization reaction by a known method. The raw materials that can be used in the production of the polyurethane resin (A) are the above-mentioned alicyclic diisocyanates that provide the constituent units derived from the alicyclic diisocyanate, and the aliphatic polybasics that provide the constituent units derived from the aliphatic polyol. Alcohols, and compounds that provide other constituent units, as long as they do not impair the purpose of this embodiment.

Polyurethane resin (A) may contain ingredients, such as raw materials, a catalyst, and a solvent used for manufacture of a copolymer. In addition, it may contain components such as stabilizers and dispersants for products such as water and amines.

In the case of the polyurethane resin (A), when the resin composition layer in the auxiliary plate for drilling according to this embodiment is formed, it is preferably used in the form of an aqueous dispersion. That is, the state of the polyurethane resin (A) when the resin composition layer is formed is not particularly limited, and the state of the aqueous dispersion is preferred. The manufacturing method of the aqueous dispersion of a polyurethane resin (A) is not specifically limited, A well-known method can be employ | adopted. Examples of the method for producing the aqueous dispersion include a method of stirring the other components such as the above-mentioned polyurethane resin (A), an aqueous solvent, and optionally an alkali, an emulsifier, and the like using a solid-liquid stirring device.

As the aqueous dispersion of the polyurethane resin (A), a commercially available product can be used. A commercially available product of an aqueous dispersion of a polyurethane resin (A) can be exemplified by the product name "HYDRAN WLS210" (isophorone diisocyanate-1,6-hexanediol- Copolymer of 6-hydroxyadipate-1-hexamethylene ester, number-average molecular weight: 35000, mole number of constituent units derived from isophorone diisocyanate: ratio of mole number of constituent units derived from aliphatic polyol = 6:94).

[III: Water-Soluble Resin (B)] The water-soluble resin (B) contained in the resin composition layer in the auxiliary board for drilling according to this embodiment is not particularly limited as long as it is a water-soluble resin. A polymer water-soluble resin (b1) and a low-molecular water-soluble resin (b2) are preferably used. The "water-soluble resin" refers to a resin that is soluble in more than 1 g with respect to 100 g of water at 25 ° C and 1 atmosphere.

The polymer water-soluble resin (b1) is not particularly limited. For example, it is preferably one selected from the group consisting of polyethylene oxide, polypropylene oxide, polyvinylpyrrolidone, and cellulose derivatives. Or two or more kinds are preferable. These compounds may be used individually by 1 type, and may use 2 or more types together. Since these compounds have particularly good sheet formation properties, the use of these compounds tends to make the composition and thickness of the resin composition layer in the auxiliary plate for drilling according to this embodiment more uniform. The weight-average molecular weight of the polymer water-soluble resin (b1) is not particularly limited, but it is 50,000 or more and 1,500,000 or less, and it is preferable to consider the viewpoint of further improving the film forming property of the resin composition layer when manufacturing the auxiliary plate for drilling. Considering the same viewpoint, the weight average molecular weight is more preferably from 100,000 to 1,000,000, and more preferably from 200,000 to 800,000. The weight average molecular weight can be measured by a general method such as a liquid chromatography method including a GPC column. More specifically, the polystyrene standard material used in the production of the calibration curve can be changed from those having various number average molecular weights to those having various weight average molecular weights, in addition to the number average in the examples described later. The method for measuring the molecular weight is performed in the same manner, and the weight-average molecular weight is measured (the same applies hereinafter).

The low-molecular-weight water-soluble resin (b2) is not particularly limited. For example, it is preferably selected from glycol compounds such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; polyoxyethylene oleyl ether, polyoxyl Monoether compounds of polyoxyethylene such as ethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, and polyoxyethylene octylphenyl ether; polyoxyethylene monostearic acid Esters, polyoxyethylene sorbitan monostearate, polyglycerol monostearate compounds, and polyethylene oxide-polypropylene oxide copolymers and their derivatives Or two or more kinds are preferable. These compounds and copolymers may be used individually by 1 type, and may be used in combination of 2 or more type. By using these compounds, the auxiliary plate for drilling according to the present embodiment tends to sufficiently exhibit the lubricity effect during drilling. The weight-average molecular weight of the low-molecular-weight water-soluble resin (b2) is not particularly limited. When the weight-average molecular weight is 1,000 or more and 30,000 or less, it is preferable to consider that the lubricity during drilling is further improved. In consideration of the same viewpoint, the weight average molecular weight is preferably 1,000 to 20,000, more preferably 1,500 to 10,000. The weight average molecular weight can be measured by a general method such as a liquid chromatography method including a GPC column.

Among the above, the water-soluble resin (B) is preferably selected from the group consisting of polyethylene oxide, polypropylene oxide, polyvinylpyrrolidone, cellulose derivatives, polyethylene glycol, polypropylene glycol, and polytetramethylene. Methylene glycol, polyoxyethylene monoether compound, polyoxyethylene monostearate, polyoxyethylene sorbitan monostearate, polyglycerol monostearate, and polyethylene oxide- One or two or more of the polypropylene oxide copolymers and their derivatives are preferred. By using such a water-soluble resin (B), the film forming property and the hole position accuracy of the resin composition layer tend to be more improved.

In addition, when the water-soluble resin (B) includes a polymer water-soluble resin (b1) having a weight average molecular weight of 50,000 to 150, 000 and less, and a low-molecular water-soluble resin (b2) having a weight average molecular weight of 1,000 to 30,000, The polymer water-soluble resin (b1) includes at least one selected from the group consisting of polyethylene oxide, polypropylene oxide, polyvinylpyrrolidone, and cellulose derivatives, and the low-molecular water-soluble resin ( b2) contains a monoether compound selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxyethylene, polyoxyethylene monostearate, polyoxyethylene sorbitan monostearic acid At least one of the group consisting of an ester, a polyethylene oxide-polypropylene oxide copolymer, and their derivatives is preferred. By using such a water-soluble resin (B), the film forming property and the hole position accuracy of the resin composition layer tend to be more improved.

The content of the water-soluble resin (B) in the resin composition layer is not particularly limited, and it is preferably 40 parts by mass or more based on 100 parts by mass of the total of the polyurethane resin (A) and the water-soluble resin (B). 72 The content is preferably not more than 40 parts by mass, more preferably not less than 40 parts by mass and not more than 65 parts by mass. When the content of the water-soluble resin (B) is 40 parts by mass or more, a more uniform resin composition layer can be formed, and more sufficient lubricity can be imparted to the resin composition layer during drilling processing. As a result, the hole position accuracy at the time of drilling tends to be more excellent. On the other hand, when the content of the water-soluble resin (B) is 72 parts by mass or less, the content of the polyurethane resin (A) in the resin composition layer can be adjusted so that The amount of the adhesive strength is more favorable, so the hole position accuracy at the time of drilling tends to be more excellent.

The content of the polymer water-soluble resin (b1) in the resin composition layer is not particularly limited as long as it is within the content range of the water-soluble resin (B) in the resin composition layer. However, the content is preferably 5 mass parts or more and 30 mass parts or less, and more preferably 5 mass parts or more and 10 mass parts or less, based on 100 mass parts of the total of the polyurethane resin (A) and the water-soluble resin (B). 5 parts by mass and 7 parts by mass are particularly preferred. When the content of the high-molecular-weight water-soluble resin (b1) is within the above-mentioned range, the film-forming property and pore position accuracy of the resin composition layer tend to be further improved.

The content of the low-molecular-weight water-soluble resin (b2) in the resin composition layer is not particularly limited as long as it is within the content range of the water-soluble resin (B) in the resin composition layer. However, it is preferable that the content is 40 mass parts or more and 65 mass parts or less, and more preferably 45 mass parts or more and 65 mass parts or less, based on 100 mass parts of the total of the polyurethane resin (A) and the water-soluble resin (B). Preferably, 45 mass parts or more and 60 mass parts or less are particularly preferred. When the content of the low-molecular-weight water-soluble resin (b2) is in the aforementioned range, both of the adhesive strength of the metal foil and the resin composition layer and the accuracy of the hole position during the hole-opening process tend to be more excellent.

[IV: Other Components] The resin composition layer in the auxiliary plate for drilling according to the present embodiment may contain additives as long as the object of the present embodiment is not impaired. The type of the additive is not particularly limited, and examples thereof include a surface conditioner, a leveling agent, an antistatic agent, an emulsifier, an antifoaming agent, a wax additive, a coupling agent, a rheology control agent, a preservative, a mold inhibitor, Antioxidants, light stabilizers, nucleating agents such as sodium formate, solid lubricants such as graphite, organic fillers, inorganic fillers, thermal stabilizers, and coloring agents. These may be used individually by 1 type, and may use 2 or more types together.

The thickness of the resin composition layer in this embodiment can be appropriately selected according to the diameter of the drill used in the drilling process, the structure of the object to be processed (for example, a printed circuit board material such as a laminated board or a multilayer board), and the like. Therefore, it is not particularly limited. However, the thickness is preferably in a range of 0.02 mm to 0.3 mm, more preferably in a range of 0.02 mm to 0.2 mm, and more preferably in a range of 0.02 mm to 0.1 mm. When the thickness of the resin composition layer is 0.02 mm or more, a more sufficient lubricating effect can be obtained, and the load on the drill can be reduced, so there is a tendency that the breakage of the drill can be further suppressed. In addition, when the thickness of the resin composition layer is 0.3 mm or less, the resin composition tends to be further prevented from being wound around the drill.

[V: Metal foil] The metal foil included in the auxiliary plate for drilling according to this embodiment is not particularly limited, and is preferably a metal material having high adhesion to the resin composition layer and capable of withstanding the impact caused by the drill. Better. The metal type of the metal foil is considered from the viewpoints of availability, cost, and processability, and examples thereof include aluminum. The material of the aluminum foil is preferably aluminum with a purity of 95% or more. Examples of such aluminum foil include 5052, 3004, 3003, 1N30, 1N99, 1050, 1070, 1085, and 8021 specified in JIS-H4160. The use of aluminum foil with an aluminum purity of 95% or more by the metal foil can alleviate the impact caused by the drill, further improve the penetration with the front end of the drill, and interact with the lubrication effect of the drill caused by the resin composition. The hole position accuracy of the processed hole is further improved.

The thickness of the metal foil is not particularly limited, but it is preferably from 0.05 mm to 0.5 mm, and more preferably from 0.05 mm to 0.3 mm. When the thickness of the metal foil is 0.05 mm or more, it is possible to more effectively suppress the occurrence of burrs in a hole-opening object (for example, a printed circuit board material such as a laminated board or a multilayer board) during drilling. In addition, when the thickness of the metal foil is 0.5 mm or less, the discharge of chips generated during the drilling process becomes easier.

The thickness of each layer constituting the auxiliary plate for drilling according to this embodiment is measured as follows. First, use a profile polisher (manufactured by Japan Electronic Data Corporation, trade name "CROSS-SECTION POLISHER SM-09010"), or an ultra-micro cutter (manufactured by Leica, article number "EM UC7") to assist the board Cut in the direction of the layers. Then, using a SEM (Scanning Electron Microscope, for example, Keyence Corporation's product number "VE-7800"), the cross section is viewed from a direction perpendicular to the cut section, and the layers constituting it are measured. For example, the thickness of a metal foil and a resin composition layer is measured. The thickness at five places was measured for one field of view, and the average thickness was used as the thickness of each layer.

In the auxiliary plate for drilling according to this embodiment, the adhesion between the resin composition layer and the metal foil measured according to the method described in the examples described below is preferably 200 gf or more. The hole position accuracy measured by the method described in the examples described below is preferably 18.0 μm or less.

[VI: Manufacturing method of auxiliary plate for drilling] The manufacturing method of the auxiliary plate for drilling in this embodiment is not particularly limited, and a general manufacturing method can be used. For example, an auxiliary plate for drilling can be manufactured as follows. The auxiliary plate for drilling according to this embodiment is manufactured by forming a resin composition layer on at least one side of a metal foil. The method for forming the resin composition layer is not particularly limited, and a known method can be adopted. Examples of such a method include a resin composition obtained by dissolving or dispersing an aqueous dispersion of a polyurethane resin (A), a water-soluble resin (B), and an additive added as necessary in a solvent. The solution is applied to a metal foil by a method such as a coating method, and is further dried and / or cooled and solidified.

When a solution of a resin composition is applied to a metal foil by a coating method or the like and further dried to form a resin composition layer, the solvent used for the solution of the resin composition is preferably water and a boiling point lower than water. A mixed solution composed of a solvent is preferred. By using a mixed solution composed of water and a solvent having a lower boiling point than water, it is possible to more effectively reduce the residual bubbles in the resin composition layer. The type of the solvent having a lower boiling point than water is not particularly limited, and examples thereof include alcohol compounds such as ethanol, methanol, and isopropanol, and low boiling point solvents such as methyl ethyl ketone and acetone may also be used. As for other solvents, water and / or an alcohol compound may be used as a solvent obtained by mixing a part of tetrahydrofuran and / or acetonitrile with high compatibility with the resin composition.

[VII: Drilling processing method] The drilling processing method of this embodiment has a hole forming step, and uses the above-mentioned auxiliary board for drilling to form holes in a laminated board or a multilayer board. More specifically, in the hole forming step, the auxiliary board for drilling is arranged on the topmost surface of the laminated board or the multilayer board, and the laminated board or the multilayer board is formed from the top surface of the auxiliary board for drilling. Drill holes while forming holes in laminated or multilayer boards. In addition, if the drilling is performed by using a drill having a diameter (drill diameter) of 0.30 mmφ or less, the purpose of this embodiment can be more effectively and reliably achieved. In particular, for the use of drills with a diameter of 0.05mmφ to 0.30mmφ, and the use of small diameter drills with a hole diameter accuracy of 0.05mmφ to 0.20mmφ, which is important, it is more desirable to consider the aspects that can greatly improve the accuracy of hole position and drill life. . In addition, the drill diameter of 0.05mmφ is the lower limit of the drill diameter that can be obtained. If a smaller diameter drill can be obtained, there is no such limitation. In addition, in drilling processing using a drill having a diameter exceeding 0.30 mmφ, the auxiliary plate for drilling according to this embodiment can also be used without any problem. In addition, as for the laminated board, a copper-clad laminated board is generally used, and the laminated board of this embodiment may be a laminated board without an outer layer provided with copper foil. That is, in this embodiment, unless otherwise specified, a laminated board refers to a copper-clad laminated board and / or a laminated board without an outer layer of copper foil.

The auxiliary board for drilling according to this embodiment can be suitably used when, for example, drilling is performed on a printed circuit board material, and more specifically, on a laminated board or a multilayer board. Specifically, an auxiliary board for drilling can be arranged on at least the topmost surface where one or more laminated boards or multilayer boards (for example, printed circuit board materials) are superimposed so that the metal foil side contacts the printed circuit board materials. Drilling is performed from the top surface of the auxiliary plate (the resin composition layer side).

As mentioned above, although this embodiment was described, this invention is not limited to the said embodiment. Various changes can be added to the present invention without departing from the gist thereof. [Example]

Hereinafter, examples of the present invention and comparative examples that fall outside the scope of the present invention will be described in comparison. In addition, the following "polyethylene glycol" is sometimes abbreviated as "PEG", and "polyethylene oxide" is sometimes abbreviated as "PEO".

Hereinafter, a method for measuring the adhesive force and a method for measuring the hole position accuracy in the examples and comparative examples will be described. <Method for Measuring Adhesive Strength> The adhesive strength is measured as follows. First, three samples were prepared by cutting the auxiliary plate for drilling produced in the examples and comparative examples into a width of 3 mm and a length of 100 mm. Then, a double-sided tape is attached to the entire surface of the resin composition layer of the sample, and the sample is attached to a fixed stage by the double-sided tape. Then, peel off 10 mm from one end of the sample to which the double-sided tape was attached between the resin composition layer and the metal foil, and attach a jig for mounting a spring scale to the metal foil portion of the peeled sample. Install a spring scale (manufactured by SANKO with a maximum measurable value of 1000 gf) on the jig, stretch at a speed of 1 cm / sec in a direction 180 ° with respect to the attachment surface, and read the index value of the spring scale. The measurement was performed on three samples, and the average value of the three additions was taken as the value of the adhesive force. When there is no peeling between the metal foil and the resin composition layer, it is marked as "> 1000".

<Measurement of Hole Position Accuracy> The hole position accuracy was measured as follows. The top surface of a copper-clad laminated board obtained by stacking five copper-clad laminated boards (trade name: HL832, copper foil thickness: 12 μm, double-sided board, manufactured by Mitsubishi Gas Chemical Co., Ltd.) having a thickness of 0.2 mm is arranged. The auxiliary plate for drilling produced in Examples and Comparative Examples was such that the resin composition layer side became the top surface. Further, an abutment plate (paper phenol laminated board, trade name "PS1160-G") manufactured by Lichang Co., Ltd. was disposed on the back (bottom) of the lowermost plate of the copper-clad laminated board obtained by stacking. ). A 0.2mmφ drill (trade name: C-CFU020S, manufactured by Tungaloy Co., Ltd.) was used, and a total of 6000 holes were made under the conditions of a rotation speed: 200,000 rpm, a delivery speed: 2.6 m / min, and the number of openings: 3,000 holes per drill Drilling process.

(此處，n表示所使用之鑽頭的根數。)A hole analyzer (model: HA-1AM, manufactured by Hitachi-Via-Mechanics Co., Ltd.) was used to measure the holes of the 3000th hole (the first drill bit) and the 6000th hole (the second drill bit). The deviation between the position of the hole on the back (bottom) of the lowermost plate of the copper-clad laminate and the specified coordinates. With respect to the component of one drill bit, an average 値 and a standard deviation (σ) are calculated for the deviation, and “average 値 + 3σ” is calculated. After that, as the accuracy of the hole position of the entire drilling process, an average 对 for each “average 値 + 3σ” was calculated for the two drill bits used. The formula used for the calculation of the hole position accuracy is as follows (1). [Number 1]

(Here, n is the number of drills used.)

<Raw Materials> Table 1 shows the main specifications of the polyurethane resin (A), water-soluble resin (B), additives, solvents, and metal foils used in the manufacture of auxiliary boards for drilling in Examples and Comparative Examples. And manufacturers.

【Table 1】

Table 2 shows the details of the polyurethane resin (A) used in the examples and comparative examples. The ratio of the molar number of the constitutional unit derived from the diisocyanate to the molar number of the constitutional unit derived from the polyol (Mole ratio) in Table 2 is a ¹ H-NMR method and a DQF- Calculated by the COSY method. The number average molecular weight is measured by a method described later. In terms of resin solid content concentration, the polyurethane resin (A) used in the form of an aqueous dispersion is the amount (mass%) of the resin solid content in the aqueous dispersion.

【Table 2】

The resin-based alicyclic diisocyanate-aliphatic polyol copolymer with a trade name of "HYDRAN WLS210" is an isophorone diisocyanate-aliphatic polyol copolymer. The constituent units derived from diisocyanate in the copolymer are derived from isophorone diisocyanate, and the constituent units derived from aliphatic polyols are derived from 1,6-hexanediol and 6-hydroxyadipate-1-hexane. Ester (reaction product of caprolactone and 1,6-hexanediol). Regarding the isophorone diisocyanate-aliphatic polyol copolymer, the diisocyanate-derived unit has a structure (alicyclic ring) of an aliphatic cyclic hydrocarbon instead of an aromatic ring.

The ratio of the molar number of the constituent units derived from the diisocyanate to the molar number of the constituent units derived from the aliphatic polyol (the ratio of the constituent units derived from the diisocyanate to the constituent units derived from the aliphatic polyol) is a ratio derived from the diisocyanate. Molar number of constituent unit: Molar number of constituent unit derived from aliphatic polyol = 6: 94. In this case, the Mohr number derived from the constituent unit of the aliphatic polyol is the Mohr number derived from the 1,6-hexanediol constituent unit and the 6-hydroxyadipate-1- Total number of moles of hexamethylene ester constituent units.

The resin-based aromatic diisocyanate-aliphatic polyol copolymer under the trade name "SUPER FLEX 820" is a 2,4-toluene diisocyanate-aliphatic polyol copolymer. The constituent unit derived from diisocyanate in the copolymer is derived from 2,4-toluene diisocyanate, and the constituent unit derived from aliphatic polyol is derived from 3-methyl-1,5-pentanediol, 1,4-cyclo Hexane dimethanol and triethylene glycol. Regarding the 2,4-toluene diisocyanate-aliphatic polyol copolymer, the diisocyanate-derived unit has an aromatic ring (structure of an aromatic cyclic hydrocarbon).

The ratio of the molar number of the constituent unit from the diisocyanate to the molar number of the constituent unit from the aliphatic polyol is the molar number of the constituent unit from the diisocyanate: the molar number of the constituent unit from the aliphatic polyol = 28:72. In this case, the molar number derived from the constituent unit of the aliphatic polyol is a molar number derived from the constituent unit of 3-methyl-1,5-pentanediol and derived from the 1,4-ring. The total number of moles of the constituent units of hexanedimethanol and the number of moles of the constituent units derived from triethylene glycol.

The resin-based aliphatic diisocyanate-aromatic polyol copolymer with a trade name of "HYDRAN APX101H" is a hexamethylene diisocyanate-aromatic polyol copolymer. The constituent units derived from diisocyanate in the copolymer are derived from hexamethylene diisocyanate, and the constituent units derived from aromatic polyol are derived from diethylene glycol-terephthalic acid copolymer. Regarding the hexamethylene diisocyanate-aromatic polyol copolymer, the constituent unit derived from the diisocyanate does not have an alicyclic ring, and the constituent unit derived from the aromatic polyol has an aromatic ring. The ratio of the molar number of the constituent unit from the diisocyanate to the molar number of the constituent unit from the aromatic polyol is the molar number of the constituent unit from the diisocyanate: the molar number of the constituent unit from the aromatic polyol = 7:93.

<Method for measuring number average molecular weight of polyurethane resin (A)> The number average molecular weight of polyurethane resin (A) is a liquid chromatography method using a GPC column (Shimadzu Corporation ( Co., Ltd.), measured using polystyrene as a reference material, and calculated as a relative average molecular weight. The equipment and analysis conditions are shown below. [Used equipment] Shimadzu High Performance Liquid Chromatograph ProminenceLIQUID System controller: CBM-20A Infusion unit: LC-20AD Online degasser: DGU-20A3 Automatic sampler: SIL-20AHT column oven: CTO-20A Differential refraction Rate detector: RID-10A LC workstation: LCSolution [Analytical conditions] Column: Phenogel 5μ 10E5A 7.8 × 300 × 1, Phenogel 5μ 10E4A 7.8 × 300 × 1, Phenogel 5μ 10E3A 7.8 × 300 × 1, manufactured by Phenomenex Guard column: 7.8 × 50 × 1 Phenogel guard column, eluent made by Phenomenex: tetrahydrofuran for high performance liquid chromatography manufactured by Kanto Chemical Co., Ltd. Flow rate: 1.00mL / min Column temperature: 45 ° C Polystyrene for wire production ＞ Shodex standard SL105, SM105 manufactured by Showa Denko Polystyrene with number average molecular weights of 580, 1390, 2750, 6790, 13200, 18500, 50600, 123000, 259000, 639000, 1320000, and 2480000

Hereinafter, the manufacturing method of the auxiliary board for drilling in an Example and a comparative example is demonstrated. <Example 1> An aqueous dispersion of isophorone diisocyanate-aliphatic polyol copolymer (trade name: HYDRAN WLS210, number average molecular weight: 35,000, derived from isofluoride) as a polyurethane resin (A) Molar number of the constituent unit of phorone diisocyanate: Molar number of the constituent unit derived from an aliphatic polyol = 6: 94, resin solid content concentration: 35% by mass, manufactured by DIC Co., Ltd.) 105 parts by mass ( Polyethylene oxide (trade name: ALKOX E-45, weight-average molecular weight: 560000, manufactured by Mingcheng Chemical Industry Co., Ltd.) as a polymer water-soluble resin (b1) based on the solid content of the resin) 7.0 parts by mass and 63.0 parts by mass of polyethylene glycol (trade name: PEG4000S, weight average molecular weight: 3300, manufactured by Sanyo Chemical Industry Co., Ltd.) as a low-molecular-weight water-soluble resin (b2) were dissolved in a water / methanol mixed solvent (Mass ratio 50/50), a solution having a solid content concentration of the resin composition of 30% by mass was prepared.

With respect to 100 parts by mass of the solid content of the resin composition in the solution, 1.2 parts by mass of a surface conditioner (BYK349, BYK-Japan) was added, and 100 parts by mass of the solid content of the resin composition in the solution was added. 0.25 parts by mass of sodium formate (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added and dispersed uniformly to obtain a resin composition solution for forming a resin composition layer.

The obtained solution of the resin composition was applied to an aluminum foil (using aluminum foil: JIS-A1100H1.80, thickness: 0.1 mm, manufactured by Mitsubishi Aluminum Co., Ltd.) as a metal foil with a coating bar, and the resin was dried and cured. The thickness of the composition layer was 0.05 mm. Then, it dried at 120 degreeC for 3 minutes using the dryer, and it was made to cool and solidify, and the auxiliary board for drilling was produced.

The adhesive force between the metal foil and the resin composition layer of the drilling auxiliary plate three times was measured by the method described above, and the added average value was calculated. In addition, drilling was performed by the method described above, and the hole position accuracy was measured. These results are shown in Table 3.

<Examples 2 to 5> According to the method described in Example 1, a resin composition solution was prepared according to the types of raw materials and blending amounts shown in Table 3, and the thickness of the resin composition layer after drying and curing was prepared as follows: 0.05mm auxiliary board for drilling. With respect to the obtained auxiliary plate for drilling, the adhesion between the metal foil and the resin composition layer and the hole position accuracy during the drilling process were measured. These results are shown in Table 3.

<Comparative Examples 1 to 6> According to the method described in Example 1, a resin composition solution was prepared according to the types of raw materials and blending amounts shown in Table 3, and the thickness of the resin composition layer after drying and curing was prepared as follows: 0.05mm auxiliary board for drilling. With respect to the obtained auxiliary plate for drilling, the adhesion between the metal foil and the resin composition layer and the hole position accuracy during the drilling process were measured. These results are shown in Table 3.

<Judgment criteria> The criteria for judging the adhesion shown in Table 3 are as follows. A load is applied to the auxiliary plate during the drilling process and during the processing. Therefore, if the adhesion between the metal foil and the resin composition layer is weak, the resin composition layer may peel off. As a result of diligent research, the inventors of the present case have determined that the resin composition layer does not peel off during the drilling process when the adhesive force is 200 gf or more. Therefore, the determination criterion of the adhesive force is judged as "A" if it is 200 gf or more, and judged as "B" if it is less than 200 gf.

The criteria for judging the accuracy of the hole position shown in Table 3 are as follows. When the hole position accuracy calculated from the calculation formula of the above formula (1) is 18 μm or less, it is marked as “A” with excellent characteristics, and when it is greater than 18 μm, it is marked as “B”.

The criteria for the comprehensive judgment shown in Table 3 are as follows. If both the determination result of the adhesive force and the determination result of the hole position accuracy are "A", the adhesion between the metal foil and the resin composition layer is strong and the hole position accuracy is excellent. Therefore, the comprehensive determination mark is "A" and the hole position When at least one of the determination result of accuracy and the determination result of adhesion is "B", the comprehensive determination flag is "B".

＜黏著力判定基準＞ 200gf以上：A 未達200gf：B ＜孔位置精度判定基準＞ 18μm以下：A 超過18μm：B ＜綜合判定的基準＞ 黏著力判定結果及孔位置精度判定結果之兩者為A：A 黏著力判定結果及孔位置精度判定結果中之至少一者為B：B【table 3】

<Adhesion determination criterion> 200 gf or more: A less than 200 gf: B <Hole position accuracy judgment criterion> 18 μm or less: A exceeding 18 μm: B <Comprehensive judgment criterion> Both the adhesion judgment result and the hole position accuracy judgment result are A: A At least one of the determination result of the adhesion force and the determination result of the hole position accuracy is B: B

From the results of Examples 1 to 5 shown in Table 3, it can be seen that the polyurethane resin (A) in the resin composition layer of the auxiliary plate for drilling is a unit having a unit derived from an alicyclic diisocyanate and a unit derived from The copolymer of the constituent units of the aliphatic polyol, the content of the polyurethane resin (A) is 30 masses based on 100 mass parts of the total of the polyurethane resin (A) and the water-soluble resin (B). When the content is more than 60 parts by mass, the adhesion between the metal foil and the resin composition layer of the auxiliary plate for drilling is strong, and the hole position accuracy using the auxiliary plate for hole processing is also good.

On the other hand, from the results of Comparative Examples 1 and 2, it can be seen that even if the polyurethane resin (A) in the resin composition layer has a constitutional unit derived from an alicyclic diisocyanate and a constitution derived from an aliphatic polyol If the content of the unit copolymer is less than 30 parts by mass relative to 100 parts by mass of the total of the polyurethane resin (A) and the water-soluble resin (B), The adhesion between the metal foil and the resin composition layer of the auxiliary plate for drilling is still weak. In addition, the hole forming process of the auxiliary plate causes the resin composition layer to peel off, and the hole position accuracy is deteriorated.

Further, in Comparative Examples 3 to 5, the constitutional unit derived from a diisocyanate in the polyurethane resin (A) was a constitutional unit derived from an aromatic diisocyanate, and not a constitutional unit derived from an alicyclic diisocyanate. In these Comparative Examples 3 to 5, even if the content of the polyurethane resin (A) in the resin composition layer is 100% with respect to the total of the polyurethane resin (A) and the water-soluble resin (B) The mass part is 30 mass parts or more and 60 mass parts or less. Although the adhesion force between the metal foil and the resin composition layer of the auxiliary plate for drilling is strong, the accuracy of the hole position of the hole processing using the auxiliary plate is poor. The reason is that the resin composition layer in the auxiliary board lacks lubricity due to the high cohesion and the rigidity of the aromatic ring due to the urethane bond derived from the aromatic diisocyanate.

In Comparative Example 6, the diisocyanate unit in the polyurethane resin (A) was a structural unit derived from an aliphatic diisocyanate having no alicyclic ring, and the polyol unit was a structural unit derived from an aromatic polyol. In Comparative Example 6, even if the content of the polyurethane resin (A) in the resin composition layer is 100 parts by mass based on the total of the polyurethane resin (A) and the water-soluble resin (B), 30 mass parts or more and 60 mass parts or less, the resin composition layer of the auxiliary plate still lacks lubricity, and the hole position accuracy of drilling processing using the auxiliary plate is poor. The reason for this is the high cohesion caused by the urethane bond of the aromatic polyol and the high rigidity of the aromatic ring.

From the above conclusions, it can be seen that the content of the polyurethane resin (A) in the resin composition layer constituting the auxiliary plate for drilling is higher than that of the polyurethane resin (A) and the water-soluble resin (B). If the total 100 parts by mass is 28 parts by mass or more and 60 parts by mass or less, the polyurethane resin (A) is a copolymer having a constituent unit derived from an alicyclic diisocyanate and a constituent unit derived from an aliphatic polyol. The adhesion between the metal foil and the resin composition layer in the auxiliary plate for holes is strong, and the accuracy of the hole position in the hole-making process using the auxiliary plate is also good.

According to this embodiment, an auxiliary plate for drilling can be provided. Compared with the conventional auxiliary plate for drilling, the hole position accuracy is excellent, and the occurrence of drill breakage due to peeling between the metal foil and the resin composition layer is affected. Suppression and no need for an adhesive layer that was necessary in the past, so it is also economical.

This application is based on a Japanese patent application filed on March 11, 2016 (Japanese Patent Application No. 2016-047989), the contents of which are incorporated herein by reference. [Industrial availability]

The present invention can provide an auxiliary plate for drilling composed of a metal foil and a layer containing a resin composition formed on at least one side of the metal foil without interposing an adhesive layer, the metal foil and the resin composition The layer has strong adhesive strength and excellent hole position accuracy during drilling. Therefore, the present invention has industrial applicability in such a field.

no

Claims (11)

An auxiliary plate for drilling, comprising: a metal foil; and a polyurethane resin (A) and a water-soluble resin (B) formed on at least one side of the metal foil without interposing an adhesive layer. ) Of the resin composition layer; the content of the polyurethane resin (A) in the resin composition-containing layer relative to the polyurethane resin (A) and the water-soluble resin (B A total of 100 parts by mass is 28 parts by mass or more and 60 parts by mass or less. The polyurethane resin (A) is a copolymer having a constituent unit derived from an alicyclic diisocyanate and a constituent unit derived from an aliphatic polyol. . For example, the auxiliary board for drilling according to item 1 of the scope of patent application, wherein the content of the water-soluble resin (B) in the resin-containing layer is relative to that of the polyurethane resin (A) and the water-soluble resin. The total 100 parts by mass of the resin (B) is 40 parts by mass or more and 72 parts by mass or less. For example, the auxiliary plate for drilling according to item 1 or 2 of the patent application scope, wherein the polyurethane resin (A) is composed of the alicyclic diisocyanate-derived unit and the aliphatic polyol Copolymer of units. For example, the auxiliary plate for drilling according to item 1 or 2 of the patent application scope, wherein the alicyclic diisocyanate includes isophorone diisocyanate. For example, the auxiliary plate for drilling in item 4 of the scope of patent application, in which the ratio of the constituent unit derived from isophorone diisocyanate to the constituent unit derived from aliphatic polyol owned by the copolymer is measured in moles The molar number of the constituent unit from the isophorone diisocyanate: The molar number of the constituent unit from the aliphatic polyol is in a range of 3:97 to 9:91. For example, the auxiliary plate for drilling according to item 1 or 2 of the patent application scope, wherein the number average molecular weight of the polyurethane resin (A) is 5,000 or more and 50,000 or less. For example, the auxiliary plate for drilling according to item 1 or 2 of the patent application scope, wherein the water-soluble resin (B) is selected from the group consisting of polyethylene oxide, polypropylene oxide, polyvinylpyrrolidone, and cellulose derivatives. , Polyethylene glycol, polypropylene glycol, polytetramethylene glycol, monoether compounds of polyoxyethylene, polyoxyethylene monostearate, polyoxyethylene sorbitan monostearate, polyglycerol monostearate One or more types of fatty acid esters, polyethylene oxide-polypropylene oxide copolymers, and their derivatives. For example, the auxiliary plate for drilling according to item 7 of the scope of patent application, wherein the water-soluble resin (B) contains a high-molecular-weight water-soluble resin (b1) having a weight-average molecular weight of 50,000 to 1,500,000, and 1,000 to 30,000. Low-molecular-weight water-soluble resin (b2) having a weight-average molecular weight, and the high-molecular water-soluble resin (b1) contains a material selected from the group consisting of polyethylene oxide, polypropylene oxide, polyvinylpyrrolidone, and cellulose derivatives. At least one member of the group, the low-molecular-weight water-soluble resin (b2) contains a monoether compound selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxyethylene, and polyoxyethylene monomer At least one selected from the group consisting of stearates, polyoxyethylene sorbitan monostearate, and polyethylene oxide-polypropylene oxide copolymers, and their derivatives. For example, the auxiliary plate for drilling according to item 1 or 2 of the scope of patent application, wherein the thickness of the layer containing the resin composition is 0.02 mm or more and 0.3 mm or less. For example, the auxiliary plate for drilling according to item 1 or 2 of the patent application scope, wherein the thickness of the metal foil is 0.05 mm or more and 0.5 mm or less. A method for drilling processing by arranging an auxiliary plate for drilling as in any one of claims 1 to 10 on the top surface of a laminated board or a multilayer board, and from the auxiliary plate for drilling The top surface is subjected to drilling of the laminated board or multilayer board, and holes are formed in the laminated board or multilayer board.