JP4479878B2 - Colored metal drill drill lubricant sheet - Google Patents

Description

【００１９】
＜孔位置精度測定方法＞
3枚重ね積層板の最下板の裏側について、ビット5本＊3000穴／本=15000穴の孔の指令座標とのズレを測定し、その平均値＋３σと最大値を示した。
【００２０】
【発明の効果】
本発明の着色した滑剤シートを用いることにより、表裏の間違いもなく配置でき、水溶性樹脂を使用したものは孔壁に樹脂が付着した場合にもその後の工程で水洗除去でき、工業的に実用性の高いものが得られた。[0001]
[Industrial application fields]
The present invention relates to a lubricant sheet that is used when a printed wiring board is manufactured and used to make a hole with a metal drill by placing it on the surface of a copper-clad laminate. Used as a through hole for a small printed wiring board, used as a semiconductor plastic package having a small diameter through hole, a mother board or the like.
[0002]
[Prior art]
In high-density printed wiring boards used for semiconductor plastic packages and the like, through holes have become increasingly smaller in diameter in recent years, and those with a minimum diameter of 0.15 mm or less have become common. As an entry sheet for making such a small diameter hole, problems such as the fact that the aluminum foil alone cannot reduce the wear of the drill, the hole position accuracy does not improve, and the hole wall roughness is large have occurred. Correspondingly, in recent years, a lubricant resin is attached to one side of a metal foil such as aluminum, which has been used to extend the life of drills, improve the accuracy of hole location, and improve the roughness of hole walls. ing. For this purpose, it is known that a resin composition layer is attached to a thickness of 0.1 to 3.0 mm on one side of a metal foil (see, for example, Patent Document 1). Therefore, when the resin layer is thin, when using a lubricant sheet, the problem of using it upside down by placing it with the surface to which the lubricant resin was originally attached has frequently occurred. Had occurred.
[0003]
[Patent Document 1]
Japanese Patent Laid-Open No. 5-169400 [0004]
[Problems to be solved by the invention]
In order to solve the above problems, the present invention adds a colorant, more preferably a non-halogen water-soluble colorant, to the primer layer or the primer layer and the resin composition layer to clarify the front and back of the lubricant sheet. It is.
[0005]
[Means for Solving the Problems]
In order to solve the above-described problems, the present invention provides a primer sheet or primer layer and a lubricant resin in a laminated sheet or a plastic sheet for punching a plastic sheet in which a primer layer and a resin composition layer are attached to one side of a metal foil. The composition layer is preferably blended with a non-halogen colorant to make the front and back clear and eliminate misplacement during drilling. Rather than coloring the resin composition layer alone, coloring the primer layer or the primer layer and the resin composition layer is less likely to cause spots and can be colored neatly. Further, by incorporating a non-halogen colorant, it is possible to obtain a lubricant sheet for drilling in consideration of the environment. In addition, some of the lubricant resin layers use a resin that does not dissolve in water, but it is water-soluble so that it can be easily dissolved and removed when aluminum is recycled and the lubricant resin adheres to the copper-clad laminate through-hole. In this case, a water-soluble colorant is preferably used.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a perforating lubricant sheet with a clear distinction between front and back, in which a lubricant resin layer is formed after adhering a primer resin layer preferably containing a non-halogen colorant on at least one surface of a metal foil. As the resin for the lubricant sheet of the present invention, generally known resins are used. This is a well-known one using a general thermosetting resin and / or thermoplastic resin, and further a water-soluble resin, and a colorant is selected in the primer resin used to improve the adhesion to the metal foil. And add. A lubricant sheet using a water-soluble resin is preferably used so that it does not remain as a foreign substance in the drilled through hole. Even if this water-soluble resin remains in the pores, it can be dissolved and removed by washing with water.
[0007]
The resin used for the lubricant sheet used in the present invention is not particularly limited, and examples thereof include thermosetting resins disclosed in JP-A No. 13-347493, JP-A No. 13-146600, JP-A No. 13-347602, and the like. Thermoplastic resin, used in JP-A-5-16940, Japanese Patent No. 2855819, Japanese Patent No. 2855820, Japanese Patent No. 2858281, Japanese Patent No. 2855823, Japanese Patent No. 2855824, Japanese Patent No. 2828129, Japanese Patent No. 3169026, etc. The water-soluble resin etc. which can be used can be used. Further, known thermosetting resin compositions, thermoplastic resin compositions, photocuring properties, other resin compositions can be used, and mixtures thereof can also be used. Various additives can be added to the resin composition, and specifically, various organic and inorganic fillers are appropriately added according to the purpose.
[0008]
When the adhesion between the metal foil and the resin composition is poor, first, a primer layer generally made of a resin is preferably deposited on the metal foil to a thickness of 0.5 to 15 μm in order to improve the adhesion. In this invention, the coloring agent for confirming the front and back is mix | blended with this primer layer at least. Of course, it can also be added to the lubricant resin layer formed thereon, but it is sufficient that the front and back sides can be confirmed, and it is preferably added only to the primer layer.
[0009]
As the colorant of the present invention, generally known organic, inorganic pigments or dyes can be used. Specifically, as an organic pigment, azo pigments such as lake red, hansa yellow, β-naphthol, naphthol AS, benzimidazolone, disazo yellow, pyrazolone, phthalocyanine, quinacridone, dioxazine, perylene, thioindigo, ansanthrone, Polycyclic pigments such as isoindoline, isoindolinone, indanthrene, quinophthalone, metal complex, pyrrolopyrrole, phthalocyanine green, copper phthalocyanine blue, nickel phthalocyanine blue, aluminum phthalocyanine blue, alkali blue, sky blue, bitumen, Examples include ultramarine blue, indigo, monoazo yellow, benzimidazolone yellow, and anthraquinone yellow, and one or a combination of two or more is used as the target color tone.
[0010]
As the organic dye, food coloring is preferably used. Most of these are water-soluble and have extremely low toxicity, which is preferable from this point. Specifically, 1H-pyrazole-3-carboxylic acid, 4,5-dihydro-5-oxy-1- (4-sulfonyl) -4-[(4-sulfonyl) azo]-, trisodium salt (yellow 4 No.), yellow dyes such as 2-naphthalenesulfonic acid, 6-hydroxy-5-[(4-sulfonyl) azo]-, disodium salt (yellow No. 5); 2,7-naphthalenedisulfonic acid, 3-hydroxy -4-[(4-sulfo-1-naphthalene) azo]-, trisodium salt (red No. 2), spiro- [isobenzofuran-1 (3H), 9 '-[9H] xanthone] -3-one- 3 ', 6'-dihydroxy-2', 4 ', 5', 7'-tetraiodo-, disodium salt (red 3), 6-hydroxy-5-[(2-methoxy-5-methyl-4- Sulfophenyl) azo] -2-naphthalenesulfonic acid disodium salt (red 40), 1,3-naphthalenedisulfonic acid, 7-hydroxy-8-[(4-sulfo-1-naphthalene) azo]-, trisodium Salt (Red No. 102), Su Pyro [isobenzofuran-1 (3H), 9- [9H] xanthene] -3-one, 2 ', 4', 5 ', 7'-tetrabromo-4,5,6,7- tetracholoro-3', 6 '-Dihydroxy-, disodium salt (red No. 104), spiro [isobenzofuran-1 (3H), 9'-[9H] xanthene] -3-one, 4,5,6,7-tetrachloro-3 ' Red pigments such as, 6'-dihydroxy-2 ', 4', 5 ', 7'-tetraiodo-, dipotassium salt (red No. 105); benzenemethananium, N-ethyl-N- [4-[[ 4- [ethyl [(3-sulfenyl) methyl] amino] phenyl] (2-sulfophenyl) methylene] -2,5-cyclohexadiene-1-ylidine] -3-sulfo-, hydroxide, inner salt, Disodium salt (Blue No. 1), 1H-indole-5-sulfonic acid, 2- (1,3-dihydroxy-3-oxo-5-sulfo-2H-indole-2-ylidine) -2,3-dihydro- And blue dyes such as 3-oxo- and disodium salts. These colorants may be either halogen-containing materials or non-halogen-containing materials. Among these, pigments that do not contain halogen are preferable from the environmental viewpoint. Further, when a water-soluble material remains in the pores, it can be removed by washing with water, which is preferable. The addition amount is not particularly limited, but preferably 0.1 to 5% by weight in the resin is added. Examples of the inorganic pigment include known color pigments such as titanium oxide. Of course, mixtures with organic and inorganic pigments can also be used. Also, known dyes can be used.
[0011]
The resin layer may be formed on one side or both sides of the metal foil. When forming resin layers on both sides of the metal foil, for example, a hard resin that prevents burrs is placed on the drilling object side, and a soft resin containing a lubricant is placed on the drill side, so that the roles of both sides of the resin are shared. Is also possible. In the case of such a lubricant sheet, the distinction between the front and the back is important. In this case, the front and back sides can be distinguished by a method of coloring only one side or a method of coloring both sides with different colors. Of course, (1) a method using a thermosetting resin and / or thermoplastic resin that is not water-soluble as a primer resin, and a colorant that is not water-soluble or water-soluble, and (2) a primer resin A water-soluble resin is used, and a water-soluble colorant is preferably added thereto, but a colorant that is not water-soluble can also be used, and is used after being uniformly dispersed. (3) As a primer resin, a mixture of these resins is used and the coloring agent is not water-soluble or water-soluble, (4) The primer resin itself is colored, etc. Any combination is possible and not limiting. However, a combination of a water-soluble resin and a water-soluble colorant is preferable from the viewpoint of recovery and recycling of the metal foil after use, and it becomes easy to recycle the metal foil after dissolution and removal with water after use. In the present invention, the term “non-halogen” means that the halogen content of each of chlorine and bromine is 0.09% (900 ppm) or less according to the ICP measurement method described in the JPCA standard (JPCA-ES-01-1999).
[0012]
Known methods can be used for mixing these pigments and dyes with the primer resin. The method for preparing the composition comprising the pigment, dye and resin is not particularly limited. For example, a method of kneading at a high temperature without solvent with a kneader or the like and extruding it into a sheet form, or using a resin composition dissolved in a solvent or water Add colorant powder to this, dissolve and disperse by stirring and mixing uniformly, apply to the surface of the metal foil as a paint, dry to form a film, spray directly on the surface of the metal foil, apply to film Generally known methods such as a method of drying to form a sheet, a method of impregnating an organic or inorganic base material, and drying to form a base material-containing sheet can be used. Preferably, it is applied directly to the metal foil. Fine pigments are used, which are dispersed or dissolved in the primer resin composition. The dye is dissolved or dispersed in a solvent and / or water and added to the primer resin composition, or the dye is directly added and dispersed or dissolved in the primer resin composition. The thickness of the primer resin layer is not particularly limited, but is preferably 0.5 to 15 μm. or. Not only the primer resin layer but also a lubricant resin layer adhered thereon may be added with a colorant.
[0013]
The metal foil to which the primer resin composition is applied is not particularly limited, and for example, those used in the above-mentioned patent can be used. Preferably, the thickness is 50 to 500 μm, more preferably 80 to 200 μm. Alternatively, an aluminum foil of this combination (Japanese Patent Laid-Open No. 11-48196 etc.) is used. Specifically, hard aluminum, soft aluminum, pure aluminum, soft iron, nickel, copper, etc., and alloys thereof can be used. Aluminum is preferably used from the viewpoints of price and workability. Furthermore, it is also possible to use an aluminum surface provided with irregularities of 0.5 to 4 μm by a known method such as physical or chemical treatment.
[0014]
The lubricant sheet of the present invention is disposed on at least the uppermost surface of a laminated plate or plastic plate, and is used when drilling with a metal drill from the uppermost surface side. The laminated plate or plastic plate used for drilling is a laminated plate without a copper foil, a copper-clad laminated plate with a copper foil on one or both sides, a multilayer plate obtained using this, a copper-clad flexible sheet , Rigid flexible boards, polycarbonate boards, acrylic boards and the like.
[0015]
【Example】
The present invention will be specifically described below with reference to examples and comparative examples. Unless otherwise specified, “parts” represents parts by weight.
(Example 1)
As a lubricant resin, 35 parts of polyethylene oxide having a molecular weight of 500,000 and 65 parts of polyglycerin monostearate having a molecular weight of 900 are kneaded for 1 hour under a nitrogen gas seal using a 130 ° C. kneader, and the viscosity is 160,000 poise. A mixture was obtained. Using this, a sheet A having a thickness of 0.05 mm was obtained through a heating roll at 130 ° C. On the other hand, 10 parts of a saturated polyester resin with a terminal hydroxyl group having a molecular weight of 20,000 to 25,000 and 800 poise (at 200 ° C.) and 3 parts of hexamethylene diisocyanate on one side of a hard aluminum foil having a thickness of 100 μm and toluene / methyl ethyl ketone = 3/1. After dissolving in a mixed solvent to a concentration of 10 wt%, 3 parts of a blue pigment containing no halogen (phthalocyanine blue) was added to this, and the mixture was uniformly dissolved and mixed. A 5 μm primer film was formed. The sheet A was overlaid on the film of the film-forming aluminum foil obtained above, and was integrated by pressure bonding with a hot roll to obtain a lubricant sheet B colored on one side in blue. The distinction between front and back is obvious. Place this lubricant sheet B on the upper side of three 0.4mm thick BT resin copper clad laminates with the lubricant resin layer facing up, and place a 1.5mm thick paper phenol laminate on the lower side, Holes were evaluated by drilling with a drill bit of 0.15 mmφ, a rotation speed of 160,000 rpm, and a feed rate of 15 μm / rev. The evaluation results are shown in Table 1.
[0016]
(Example 2)
100 μm thick double-sided unevenness (unevenness average 1.6 μm) so that the water-soluble polyurethane resin composition in which 2 parts of red non-halogen colorant (edible red No. 2) is added to 100 parts as the primer resin is 10 μm thick , Max. 2.7μm) Applied to one side of hard aluminum foil, and over this, laminated resin sheet A obtained in Example 1, laminated and bonded, integrated to produce metal drill through hole drilling lubricant sheet D did. The resulting lubricant sheet D was evaluated for punching in the same manner as in Example 1. The evaluation results are shown in Table 1.
[0017]
(Comparative Examples 1 and 2)
In Examples 1 and 2, holes were made in an arrangement in which the resin layer of the lubricant sheet faced down without using a colorant. The evaluation results are shown in Table 1.
(Comparative Example 3)
In Example 1, drilling was performed under the same conditions using only aluminum foil. The evaluation results are shown in Table 1.
[0018]

[0019]
<Hole position accuracy measurement method>
On the back side of the lowermost plate of the three-ply laminate, the deviation from the command coordinates of the holes of 5 bits * 3000 holes / piece = 15000 holes was measured, and the average value + 3σ and the maximum value were shown.
[0020]
【The invention's effect】
By using the colored lubricant sheet of the present invention, it can be placed without mistakes on the front and back sides, and those using water-soluble resin can be washed away with water in the subsequent process even when the resin adheres to the hole wall, industrially practical The thing with high property was obtained.

Claims (4)

In the metal foil, a colorant is blended in the primer layer or primer layer and the resin composition layer of the lubricant sheet for punching the laminated plate or plastic plate to which the primer layer and the resin composition layer are attached. A colored lubricant sheet for drilling metal drills, wherein the resin composition layer is disposed facing upward . 2. The colored metal drill drilling lubricant sheet according to claim 1, wherein the colorant is water-soluble. The colored lubricant sheet for drilling metal drills according to claim 1 or 2, wherein the colorant is a non-halogen colorant. The colored lubricant sheet for drilling metal drills according to claim 1, 2 or 3, wherein the resin of the lubricant sheet is a water-soluble resin.