TW201713174A - Circuit board to open hole by photosensing having a cover layer unit formed of a compound containing the epoxy group, and a photosensitive composition of photosensitive polyimide which can react with the epoxy group to obtain heat resistance and flexibility after a microlithography process - Google Patents

Abstract

A circuit board to open hole by photosensing is disclosed, which comprises a lamination unit, conductor unit, and a cover layer unit. The lamination unit comprises: an insulation layer; the first circuitized conductor layer and the second circuitized conductor layer formed on the two opposite sides of the insulation layer respectively; and at least a through-hole surface defining the through-hole extending from the upper surface of the first circuitized conductor layer to the lower surface of the second circuitized conductor layer through the insulation layer. The conductor unit is formed on the at least one through-hole surface. The cover layer unit is formed of a compound containing the epoxy group, a photosensitive composition of photosensitive polyimide which can react with the epoxy group in the compound containing the epoxy group, and comprises the first cover layer formed in the first circuitized conductor layer and extending into and filling the through-hole. By the photosensitive composition in the cover layer unit, the circuit board to open hole by photosensing is made into a circuit board having photo-sensing openings and having heat endurance and flexibility after a microlithography process.

Description

Photosensitive apertured circuit board

The present invention relates to a circuit board, and more particularly to a circuit board that can be photosensitively opened.

Referring to FIG. 1, Taiwan Patent Publication No. 201316858 discloses a printed circuit board comprising a laminated body 1 defining a plurality of spaced-apart electrical vias 11 and a photosensitive solder resist 2 filled in the electrical vias 11. And two solder resist layers 3 formed on opposite sides of the laminated body 1. The laminated body 1 includes an insulating substrate 12 and two line conductor layers 13 formed on opposite sides of the insulating substrate 12. However, the main material of the photosensitive solder resist 2 and the solder resist layer 3 described in the patent is generally a photocurable epoxy resin, so that the heat resistance and flexibility of the printed circuit board are not good, and the Industry demand. Therefore, improving the printed circuit board to have better heat resistance and flexibility is a subject that can be further broken by those skilled in the art.

Accordingly, it is an object of the present invention to provide a circuit board that is photosensitive apertured. The sensible apertured circuit board can be formed into a circuit board having a photosensitive opening with heat resistance and flexibility after the lithography process.

Thus, the photosensitive apertured circuit board of the present invention comprises a laminate unit, a conductor unit, and a cover layer unit. The layering unit includes an insulating layer, a first lined conductive layer and a second lined conductive layer respectively formed on opposite sides of the insulating layer, and at least a uniform hole surface. The at least uniform aperture defines a via extending from an upper surface of the first lined conductive layer and via the insulating layer to a lower surface of the second lined conductor layer. The conductor unit is formed on the at least uniform aperture surface and is configured to electrically connect the first lined conductive layer to the second lined conductive layer. The cover unit includes a first cover layer formed on the first lined conductive layer of the build-up unit and extending into the through-hole. The cover layer unit is formed of a photosensitive composition, and the photosensitive composition comprises an epoxy group-containing compound and a photosensitive polyimine which can react with an epoxy group in the epoxy group-containing compound. .

< Laminated unit >

The insulating layer is, for example but not limited to, an epoxy resin layer, a polyimide resin layer, a polyester resin layer, a fluorine-containing resin layer, or a liquid crystal polymer layer. Preferably, the insulating layer is a flexible insulating layer. Preferably, the insulating layer is a polyimide film. The thickness of the insulating layer is not particularly limited, and may be changed according to the application requirements of the photosensitive open-hole circuit board, so that the circuit board with the photosensitive opening or the circuit board with the photosensitive opening may be subjected to the lithography process. The subsequently formed circuit board having the photosensitive opening has better flexibility. Preferably, the insulating layer has a thickness ranging from 5 μm to 50 μm.

The material of the first lined conductive layer and the second lined conductive layer is, for example but not limited to, a conductive metal, a conductive polymer, or a composite material containing a conductive metal and a polymer. The conductive metal is, for example but not limited to, copper, aluminum, gold, silver, or a composite metal or the like. Preferably, the conductive metal is copper. The thickness of the first lined conductive layer and the second lined conductive layer is not particularly limited, and may be changed according to the application requirements of the photosensitive open circuit board, so that the circuit board capable of photosensitive opening may be The circuit board with the photosensitive opening is thinned by the lithographic process and has a thinned circuit board, and preferably, the thickness of the first lined conductive layer and the second lined conductive layer It is from 3 μm to 50 μm.

The aperture of the through hole is not particularly limited, and may be changed according to the application requirements of the photosensitive open circuit board, in order to increase the line and the second line of the first lined conductive layer of the photosensitive open circuit board. The density of the electrical connection of the conductive layer is preferably greater than 0 mm to 0.25 mm. It should be noted that the number of the through holes is not limited to one, and may be changed according to the application requirements of the photosensitive open circuit board. In other variations of the present invention, two, three, or four may be used. and many more. The number of at least the uniform apertures varies according to the number of the apertures. Therefore, the number of the at least consistent apertures is not limited to one. In other variations of the present invention, two, three, and four may also be used. And so on.

< Conductor unit >

The material of the conductor unit is, for example but not limited to, a conductive metal or a conductive polymer. The conductive metal is, for example but not limited to, copper or the like. The manner in which the conductor unit is formed on the at least one continuous hole surface can be in a conventional manner, such as, but not limited to, electroless plating.

< Overlay unit >

The thickness of the first cover layer is not particularly limited, and may be changed according to the application requirements of the photosensitive open-hole circuit board, so that the first cover layer has a better volume resistance, so that the photosensitive opening can be made. The circuit board having the photosensitive opening formed by the lithography process has a high value of the punching voltage, and then has better insulation. Preferably, the thickness of the first covering layer ranges from 5 μm to 50 μm.

The cover layer unit further includes a second cover layer formed on the second lined conductive layer of the buildup unit and extending into the through hole. The thickness of the second cover layer is not particularly limited, and may be changed according to the application requirements of the photosensitive open-hole circuit board, so that the second cover layer has a better volume resistance, so that the photosensitive opening can be made The circuit board having the photosensitive opening formed by the lithography process has a high punching voltage value, and then has better insulation. Preferably, the second cover layer has a thickness ranging from 5 μm to 50 μm.

The cover layer unit not only protects the first lined conductive layer and the second lined conductive layer of the layered unit from oxidation, but also forms a cover layer unit having a photosensitive opening by a lithography process, so that the first lined conductive layer Or the second circuitized conductive layer is exposed outside the photosensitive openings for a process of assembly, soldering or build-up. The aperture of the photosensitive opening is smaller than the aperture of the opening formed by mechanical drilling or laser drilling, and can meet the current demand for miniaturized opening. In addition, the cover layer unit can also serve as a plug member of the through hole of the buildup unit to prevent air from being present in the through hole, thereby generating a thermal expansion and contraction effect, so that the dimensional stability of the photosensitive openable circuit board is achieved. Deterioration, even deformation.

The cover layer unit is formed on the buildup unit by forming a photosensitive composition on the first lined conductive layer and the second lined conductive layer of the buildup unit by a coating process, and the photosensitive composition It will flow into the through hole and fill the through hole. Next, a baking treatment is performed to remove the solvent in the photosensitive composition. The coating process is, for example but not limited to, spin coating, roller coating, screen coating, curtain coating, dip coating, or spray coating. Spray coating, etc. The temperature and time of the baking treatment are not particularly limited, and may vary depending on the kind of the solvent in the photosensitive composition to facilitate removal of the solvent or to shape the coating layer unit. In order to reduce the reaction of the epoxy group-containing compound and the photosensitive polyimide reaction in the cover layer unit, preferably, the baking treatment is carried out at a temperature ranging from 70 ° C to 120 ° C.

[ Photosensitive composition ]

The photosensitive composition contains a compound containing an epoxy group and a photosensitive polyimine which can react with an epoxy group in the epoxy group-containing compound.

<< Epoxy-containing compound >>

In order to reduce the amount of the solvent to increase the solid content of the photosensitive composition and to reduce the volume shrinkage of the coating layer unit, it is preferred that the epoxy group-containing compound be a liquid epoxy group-containing compound. The epoxy group-containing compound may be used singly or in combination of two or more, and the epoxy group-containing compound such as, but not limited to, neopentyl glycol diglycidyl ether, 1,4-butanediol II 1,4-butanediol diglycidyl ether, diglycidyl 1,2-cyclohexanedicarboxylate, bisphenol A diglycidyl ether, 1 , 2-propanediol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol propoxylate triglycidyl ether, Resorcinol diglycidyl ether, or dimer acid diglycidyl ester represented by formula (1), Equation (1), etc. In order to make the circuit board having the photosensitive opening have better heat resistance and acid resistance, preferably, the content of the epoxy group-containing compound is in the range of 100 parts by weight of the photosensitive polyimide. It is 10 parts by weight to 70 parts by weight.

<< Photosensitive polyimine >>

The photosensitive polyimide can be subjected to a photocrosslinking reaction and can be reacted with a baking treatment after the epoxy group-containing compound is developed in a lithography process. The photosensitive polyimine has, in addition to a photosensitive group (for example, a double bond), at least one reactive functional group reacts with an epoxy group in the epoxy group-containing compound, and the at least one reactive functional group is, for example, However, it is not limited to a carboxylic acid group (-COOH) or an amine group (-NH ₂ ). The photosensitive polyimine is, for example, a soluble polyimine having a photosensitive group and a carboxylic acid group. In order to enable the photosensitive polyimine to have better developability when developed in a lithography process, preferably, the photosensitive polyimide is a photosensitive polyimide having the structure of the formula (I); R ¹ , R ² and R ³ are each a tetravalent group; X ¹ is a divalent group; X ² is a divalent group having a carboxylic acid group; and X ³ is having (2-hydroxy-3) a divalent group of a propyl acrylate group or a divalent group having a (2-hydroxy-3-methylpropionate) propyl group; the total number of m+n+o is 100 m is a positive integer of 30 to 70, the n is a positive integer of 10 to 45, and the o is a positive integer of 10 to 35; wherein, a plurality of R ¹ are the same or different, and the plurality of X ¹ are the same Or different, plural R ² are the same or different, a plurality of X ² are the same or different, a plurality of R ³ are the same or different, and a plurality of X ³ are the same or different.

The tetravalent group is for example but not limited to , , , , ,or Wait.

The divalent group is for example but not limited to , p is 1 to 20, ,or Wait.

The divalent group having a carboxylic acid group (-COOH) is, for example but not limited to or Wait.

The divalent group having a (2-hydroxy-3-propionate) propyl group is, for example but not limited to , , ,or .

The divalent group having a (2-hydroxy-3-methylpropionate) propyl group is, for example but not limited to, , , ,or Wait.

The method for producing a photosensitive polyimine having the structure of the formula (I) comprises the steps of reacting a tetracarboxylic dianhydride compound and a diamine component to form a polyamic acid mixture, wherein the The amine component comprises a diamine compound having a carboxylic acid group, and other diamine compounds; a catalyst is added to the polyamido acid mixture for chemical cyclization to form a polyimine, wherein the catalyst and chemical cyclization The temperature of the reaction may be the one currently used to prepare the thermal polyimine by chemical cyclization; then, glycidyl (meth)acrylate is added, and the glycidyl (meth)acrylate is added. The epoxy group in the ester reacts with the carboxylic acid group in the polyimine at 60 ° C to 130 ° C to form a photosensitive polyimine having the structure of the formula (I). The glycidyl (meth)acrylate refers to glycidyl acrylate or glycidyl methacrylate. The tetracarboxylic dianhydride-based compound is not particularly limited, and a tetracarboxylic dianhydride-based compound used in the field can be used. The tetracarboxylic dianhydride compound is, for example but not limited to, bicyclo[2,2,2]oct-7-alkenyl-2,3,5,6-tetracarboxylic dianhydride (bicyclo[2,2,2]oct -7-ene-2,3,5,6-tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2 -5-(2,5-dioxotetrahydro-3-furanyl-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride], cyclobutanetetracarboxylic dianhydride (cyclobutane-1, 2, 3 , 4-tetracarboxylic dianhydride, or 4,4'-(hexafluoroisopropylidene) diphthalic anhydride. The diamine compound having a carboxylic acid group such as, but not limited to, 3,5-diaminobenzoic acid, or 2,2-bis[4-(4-aminophenoxy)benzene Base] propane {2,2-bis[4-(4-aminophenoxyl)phenyl]propane}. The other diamine compound is not particularly limited, and a diamine compound used in the field can be employed. The other diamine compound such as, but not limited to, 1,3-bis(4'-aminophenoxy)benzene [4,4'-(1,3-phenylenedioxy)dianiline], or bisaminopropyltetramethyl Bisaminopropyltetramethyldisiloxane and the like.

The photosensitive apertured circuit board of the present invention is subjected to a lithography process to form a cover layer unit having a photosensitive opening, and in order to accelerate the photocrosslinking reaction of the photosensitive polyimide, preferably, The photosensitive composition also contains a photoinitiator.

<< Photoinitiator >>

The photoinitiator may be used alone or in combination of two or more, and the photoinitiator is, for example but not limited to, phenylbis(2,4,6-trimethylbenzylidene)phosphine oxide [phenyl bis (2,4) ,6-trimethylbenzoyl)-phosphine oxide], 2-benzyl-2-(dimethylamino)-1-(4-morpholinyl)-1-butanone [2-benzyl-2-dimethylamino-1 -1(4-morpholinophenyl)-butanone], (2,4,6-trimethyl benzoyl)diphenyl phosphine oxide [(2,4,6-trimethyl benzoyl)diphenyl phosphine oxide], double (. Eta.5-2,4-cyclopentadien-1-enyl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyltitanium [bis(.eta.5-2) , 4-cyclopentadien-1-y1)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl titanium], 4,4'-bis(dimethylamino)diphenyl ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino)benzophenone, or N-phenyldiethanol N-phenyldiethanolamine, etc. Preferably, the photoinitiator is contained in an amount ranging from 0.1 part by weight to 30 parts by weight based on 100 parts by weight of the photosensitive polyimide.

In order to make the photosensitive composition have better fluidity, it is preferred that the photosensitive composition further contains a solvent. Preferably, the total amount of the photosensitive composition is 100% by weight, and the solid content of the photosensitive composition ranges from 40% by weight to 90% by weight.

<< Solvent >>

The solvent is, for example but not limited to, an aprotic solvent or the like. In order to enhance the photocrosslinking reaction of the photosensitive polyimine, the solvent is preferably the aprotic solvent. The aprotic solvent may be used singly or in combination of two or more. The aprotic solvent is, for example but not limited to, N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamidine. N, N-dimethylacetamide (DMAc), γ-butyrolactone (GBL), xylene, or toluene.

The photosensitive apertured circuit board of the present invention undergoes a lithography process including exposure, development and baking, and causes photo-crosslinking reaction of the photosensitive polyimide in the photosensitive composition of the cover layer unit during exposure. During development, the illuminating cover layer unit is retained, and the unilluminated cover layer unit is removed to form a photosensitive opening, and upon baking, the photo-crosslinked photosensitive polyimide is promoted in the photosensitive composition. The reactive functional group such as a carboxylic acid group reacts with the epoxy group in the epoxy group-containing compound, and at the same time, the moisture or the solvent is removed, and a circuit board having photosensitive opening is obtained. Light rays used for the exposure are, for example but not limited to, X-ray rays, electron beam rays, ultraviolet rays, or visible rays. The developer used in the development is, for example but not limited to, an inorganic base, an organic amine, or a quaternary ammonium salt or the like. The inorganic base is, for example but not limited to, sodium carbonate, potassium hydroxide or sodium hydroxide. The organic amine is, for example but not limited to, a primary amine organic compound, a secondary amine organic compound, or a tertiary amine organic compound or the like. The primary amine organic compound is, for example but not limited to, ethylamine or the like. The secondary amine organic compound is, for example, but not limited to, diethylamine or the like. The tertiary amine organic compound is, for example, but not limited to, triethylamine or the like. The quaternary ammonium salt is, for example but not limited to, tetramethylammonium hydroxide (TMAH) or the like. In order to promote the reaction of the photosensitive polyimine with the epoxy group-containing compound, preferably, the baking is carried out at a temperature ranging from 150 ° C to 250 ° C. The absorption peak of the infrared absorption spectrum analysis of the cover layer unit having the photosensitive opening in the photosensitive opening having a photosensitive opening has a sulfonium group of 1769 to 1778 cm ^-1 (C=O in plane), 1702醯 of the oxime imine group of 1708.6 cm ^-1 (C=O out of plane), CNC of the quinone imine group of 1383 to 1394.4 cm ^-1 , 1254 to 1259 cm ^-1 and 791 to 795.1 cm ^-1 C-Si of the quinone imine group, -OH of 3416 to 3472.3 cm ^-1 .

The effect of the invention is that the cover layer unit has the function of protecting the first circuitized conductive layer and the second circuitized conductive layer, and can also serve as a plug hole for the through hole of the laminated unit. The photosensitive apertured circuit board of the invention is subjected to a lithography process, so that the cover layer unit forms a cover layer unit having a photosensitive opening, and the photosensitive composition in the cover layer unit is formed to have heat resistance and flexibility. A circuit board with a photosensitive opening.

The invention is further described in the following examples, but it should be understood that these examples are for illustrative purposes only and are not to be construed as limiting.

Synthesis example 1

16.95 g (0.111 mol) of 3,5-diaminobenzoic acid, 13.07 g (0.032 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 75.60 Glucose (0.080 mol) of bisaminopropyltetramethyldioxane and 126.72 g of N-methyl-2-pyrrolidone were combined to form a homogeneous mixture. 46.61 g (0.188 mol) of bicyclo[2,2,2]oct-7-alkenyl-2,3,5,6-tetracarboxylic acid dianhydride was added to the homogeneous mixture and stirred for 2 hours. Next, 14.85 g (0.033 mol) of 4,4'-(hexafluoroextension) bis-phthalic anhydride was added and stirred at room temperature for 4 hours. Then, after adding 65 g of xylene, the temperature was raised to the temperature at which the polymerization was carried out, and stirred for 3 to 6 hours. Next, after cooling to 80 ° C, 7.92 g (0.056 mol) of glycidyl methacrylate was added, and stirred at 80 ° C to 120 ° C for 12 hours. Then, the temperature was lowered to 25 ° C to obtain a component containing 30.72 g of a photosensitive polyimine. The total amount of the photosensitive polyimide-containing component was 100% by weight, and the solid content of the photosensitive polyimide-containing component was 58% by weight [(16.95+13.07+75.60+46.61+14.85+7.92) ×100/(16.95+13.07+75.60+46.61+14.85+7.92+126.72)], and the content of the photosensitive polyimine is 58% by weight [(16.95+13.07+75.60+46.61+14.85+7.92)×100/ (16.95+13.07+75.60+46.61+14.85+7.92+126.72)].

Synthesis Example 2

16.45 g (0.108 mol) of 3,5-diaminobenzoic acid, 6.77 g (0.032 mol) of 1,3-bis(4'-aminophenoxy)benzene, 80.70 g (0.085 mol) Diaminopropyltetramethyldioxane, and 168.14 grams of N-methyl-2-pyrrolidone are combined to form a homogeneous mixture. 46.93 g (0.178 mol) of 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride was added to the homogeneous phase. The mixture was stirred for 2 hours. Next, 16.46 g (0.037 mol) of 4,4'-(hexafluoroextension) bis-phthalic anhydride was added and stirred at room temperature for 4 hours. Then, after adding 65 g of xylene, the temperature was raised to the temperature at which the polymerization was carried out, and stirred for 3 to 6 hours. Next, after cooling to 80 ° C, 7.68 g (0.054 mol) of glycidyl methacrylate was added, and stirred at 80 ° C to 120 ° C for 12 hours. Then, the temperature was lowered to 25 ° C to obtain a photosensitive polyimide-containing component having a weight of 343.13 g. The total amount of the photosensitive polyimide-containing component is 100% by weight, and the photosensitive polyimide-containing component has a solid content of 50.998% by weight [(16.45+6.77+80.70+46.93+16.46+7.68) ) × 100 / (16.45 + 6.77 + 80.70 + 46.93 + 16.46 + 7.68 + 168.14)], and the content of the photosensitive polyimine is 50.998 wt% [(16.45 + 6.77 + 80.70 + 46.93 + 16.46 + 7.68) × 100/(16.45+6.77+80.70+46.93+16.46+7.68+168.14)].

Synthesis Example 3

18.62 g (0.122 mol) of 3,5-diaminobenzoic acid, 17.94 g (0.044 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 74.73 Glucose (0.079 mol) of bisaminopropyltetramethyldioxane and 231.98 g of N-methyl-2-pyrrolidone were combined to form a homogeneous mixture. 41.82 g (0.213 mol) of cyclobutane tetracarboxylic dianhydride was added to the homogeneous mixture and stirred for 2 hours. Next, 13.20 g (0.030 mol) of 4,4'-(hexafluoroextension) bis-phthalic anhydride was added and stirred at room temperature for 4 hours. Then, after adding 65 g of xylene, the temperature was raised to the temperature at which the polymerization was carried out, and stirred for 3 to 6 hours. Next, after cooling to 80 ° C, 8.70 g (0.061 mol) of glycidyl methacrylate was added, and stirred at 80 ° C to 120 ° C for 12 hours. Then, the temperature was lowered to 25 ° C to form a 406.99 g-weight photosensitive polyimide-containing component. The total amount of the photosensitive polyimide-containing component is 100% by weight, and the solid content of the photosensitive polyimide-containing component is 43.00% by weight [(18.62+17.94+74.73+41.82+13.20+8.70) ×100/(18.62+17.94+74.73+41.82+13.20+8.70+231.98)], and the content of the photosensitive polyimine is 43.00% by weight [(18.62+17.94+74.73+41.82+13.20+8.70)× 100/(18.62+17.94+74.73+41.82+13.20+8.70+231.98)].

Preparation Example 1 Photosensitive Composition

41.48 g of bisphenol A diglycidyl ether, 3.37 g of phenyl bis(2,4,6-trimethylbenzylidene) phosphine oxide (label: BASF; model Irgacure® 819), and 301.72 g The photosensitive polyimide-containing component of Synthesis Example 1 was mixed. The total amount of the photosensitive composition was 100% by weight, and the solid content of the photosensitive composition was 63.44% by weight [(41.48+3.37+175)×100/(41.48+3.37+301.72)], and the photosensitive polymerization was carried out. The content of quinone imine was 50.49 wt% [175 x 100 / (41.48 + 3.37 + 301.72)].

Preparation Examples 2 to 6

Preparation Examples 2 to 6 The photosensitive compositions were prepared in the same manner as in Preparation Example 1, except that the types and amounts of the epoxy resins were changed as shown in Table 1.

Preparation Example 7 Photosensitive Composition

52.15 g of bisphenol A diglycidyl ether, 3.37 g of phenylbis(2,4,6-trimethylbenzylidene)phosphine oxide, and 343.13 g of the photosensitive polyimide containing the synthesis example 2 The components of the amine are mixed. The total amount of the photosensitive composition is 100% by weight, and the solid content of the photosensitive composition is 57.82% by weight [(52.15+3.37+174.99)×100/(52.15+3.37+343.13)], and the photosensitive polymerization The content of quinone imine was 43.90 wt% [174.99 x 100 / (52.15 + 3.37 + 343.13)].

Preparation Examples 8 to 9

Preparation Examples 8 to 9 The photosensitive compositions were prepared in the same manner as in Preparation Example 7, except that the kinds and amounts of the epoxy resins were changed as shown in Table 1.

Preparation Example 10 Photosensitive Composition

67.90 g of the dimer acid diglycidyl ester represented by the above formula (1), 3.37 g of phenylbis(2,4,6-trimethylbenzylidene)phosphine oxide, and 406.99 g of a synthesis The component containing the photosensitive polyimine of Example 3 was mixed. The total amount of the photosensitive composition was 100% by weight, and the solid content of the photosensitive composition was 51.50% by weight [(67.90+3.37+175.01)×100/(67.90+3.37+406.99)], and the photosensitive polymerization was carried out. The content of quinone imine was 36.59 wt% [175.01 x 100 / (67.90 + 3.37 + 406.99)].

Preparation Example 11

Preparation Example 11 The photosensitive composition was prepared in the same manner as in Preparation Example 10 except that the kind and amount of the epoxy resin were changed as shown in Table 1.

Preparation Example 12 Photosensitive Composition

3.37 g of phenylbis(2,4,6-trimethylbenzylidene)phosphine oxide was mixed with 301.72 g of the photosensitive polyimide-containing component of Synthesis Example 1. The total amount of the photosensitive composition is 100% by weight, and the solid content of the photosensitive composition is 5.846% by weight [(3.37+175)×100/(3.37+301.72)], and the photosensitive polyimide The content was 57.36 wt% [175 x 100 / (3.37 + 301.72)].

Preparation Examples 13 to 14

Preparation Examples 13 to 14 The photosensitive compositions were prepared in the same manner as in Preparation Example 12 except that the kinds and amounts of the components containing the photosensitive polyimide were changed as shown in Table 1.

Embodiment 1 Photosensitive apertured circuit board

Referring to Figure 2, a first embodiment of a photosensitive apertured circuit board of the present invention includes a laminate unit 4, a copper conductor unit 5, and a cover layer unit 6. The layering unit 4 includes a polyimide layer 41, a first lined copper conductive layer 42 and a second lined copper conductive layer 43 respectively formed on opposite sides of the polyimide layer 41. And a through hole face 44. The through hole surface 44 defines a through hole 441 extending from an upper surface of the first lined copper conductive layer 42 to a lower surface of the second lined copper conductor layer 43. The cover layer unit 6 is formed on the first lined copper conductive layer 42 and the second lined copper conductor layer 43 respectively, and extends into the first cover layer 61 and the second cover layer 62 which fill the through hole. .

The preparation method of the first embodiment comprises the steps of providing a laminate comprising a laminate unit 4 and a copper conductor unit 5. The laminate unit 4 includes a polyimide layer 41 having a thickness of 12 μm, a first lined copper conductive layer 42 having a thickness of 12 μm formed on opposite sides of the polyimide layer 41, and a thickness. It is a 12 μm second lined copper conductive layer 43 and a through hole face 44. The through hole surface 44 defines a through hole 441 extending from the upper surface of the first lined copper conductive layer 42 to the lower surface of the second lined copper conductor layer 43 and having a hole diameter of about 0.1 mm. The copper conductor unit 5 is formed on the through hole surface by electroless plating and is used to electrically connect the first lined copper conductive layer 42 and the second lined copper conductive layer 43. The photosensitive composition of Preparation Example 1 was coated on the first lined copper conductive layer 42 and the second lined copper conductive layer 43 in a coating manner, and filled through the through hole 441, and then placed at 80 ° C. In a hot air oven, baking for 10 minutes, a first cover layer 61 having a film thickness of about 20 μm and a second cover layer 62 having a film thickness of about 20 μm were obtained. The first cover layer 61 and the second cover layer 62 form the cover layer unit 6.

Examples 2 to 11 and Comparative Examples 1 to 3

Examples 2 to 11 and Comparative Examples 1 to 3 were prepared in the same manner as in Example 1 except that the type of the photosensitive composition was changed as shown in Table 1.

Comparative example 4

Comparative Example 4 was prepared in the same manner as in Example 1 except that the photosensitive composition was a photosensitive epoxy resin (label: TAYIO INK; model: PSR-4000). EG23; solid content: 79% by weight).

Application example 1

The photosensitive open-hole circuit board of Example 1 was irradiated with a mercury arc lamp having a wavelength of from 250 nm to 400 nm, and subjected to exposure treatment. The exposure energy of this exposure treatment was 800 mJ, and the exposure time was 18 seconds. Then, a 1.5 wt% aqueous sodium carbonate solution was used as a developer, and developed at 30 ° C for 60 seconds. Next, it was washed with deionized water for 30 seconds and dried with an air gun. Finally, baking was performed in a hot air circulating oven at 200 ° C for 60 minutes to obtain a circuit board having photosensitive openings, wherein the cover layer unit formed a cover layer unit having a photosensitive opening of 20 μm. The position of the infrared absorption peak of the cover layer unit having the photosensitive opening in the circuit board having the photosensitive opening of the application example 1 is shown in Fig. 3.

Application Examples 2 to 11 and Comparative Application Examples 1 to 4

Application Examples 2 to 11 and Comparative Application Examples 1 to 4 are the same steps as in Application Example 1 to prepare a circuit board having photosensitive opening, except that the type of the circuit board capable of photosensitive opening is changed, as shown in Table 1. Shown. The infrared absorption peak positions of the cover layer unit having the photosensitive opening in the circuit boards having the photosensitive openings of the application examples 2 to 11 and the comparative application examples 1 to 4 are respectively referred to Figs. 4 to 17.

<<Evaluation project>>

Flexibility test: The circuit boards having the photosensitive openings of Application Examples 1 to 11 and Comparative Application Examples 1 to 4 were bent, and the bend was pressed for 60 seconds using a 500 gram weight, and then the The weight is returned to the original shape, and then the cover unit having the photosensitive opening is observed for cracking or falling off. If not, the bending is again performed and pressed with the weight for 60 seconds, removed, returned to the original state and observed until observation. The above steps can be stopped until the cover unit having the photosensitive opening is cracked or peeled off, and the number of times of bending is recorded.

Acid resistance test: The circuit boards with photosensitive openings of Application Examples 1 to 11 and Comparative Application Examples 1 to 4 were each immersed in a 10 wt% hydrochloric acid solution at 25 ° C for 30 minutes, and then rinsed with water and dried to form 15 A test item, and the 100% test of the waiting test product by the IPC-TM-650 2.4.28.1 standard method. The test method of the hundred-square test is to draw a test area on the surface of the waiting test piece with a hundred-grain knife. The test area has 10 x 10 (100) small grids of dimensions 1 mm x 1 mm, each of which is deep and has a bottom layer of the cover unit with photosensitive apertures. Brush the debris from the test area with a brush. A small mesh in the test area was adhered with a 3M No. 600 tape and a pressure of 2 kg was applied to firmly adhere the tape to the test area. Next, the tape was quickly peeled off in the vertical direction (90°). The evaluation criteria are as follows: ISO grade 0: The cut edge is completely smooth and there is no peeling in the test area. ISO Class 1: There is a small piece of peeling at the intersection of the cuts, and the damage area in the test area is 5%. ISO grade 2: Peeling at the edge or intersection of the cut, and the area of damage in the test area is greater than 5% to 15%. ISO grade 3: Partial peeling at the cutting edge or intersection, or partial small mesh peeling off, and the damaged area in the test area is greater than 15% to 35%. ISO Grade 4: Large areas of the cut edge are peeled off or some small meshes are partially or completely peeled off, and the damaged area in the test area is greater than 35% to 65%. ISO Grade 5: Peeling at the edge of the cut and at the intersection, and the area of damage in the test area is greater than 65%.

Heat resistance test: The circuit boards having the photosensitive openings of Application Examples 1 to 11 and Comparative Application Examples 1 to 4 were placed in a furnace containing 300 ° C and containing tin, and after immersing for 10 seconds, they were taken out, and the appearance was judged by a microscope at a magnification of 20 times. Explosion, if not, soak for another 10 seconds and take out and observe until the appearance of the explosion is observed to stop the above steps, and record the number of soaks.

Filling hole measurement: The circuit board having the photosensitive opening of Application Example 7, Comparative Application Example 1 and Comparative Application Example 4 was fixed between two sheets of acrylic sheets, and then the photosensitive openings were made by the cutting force of the sandpaper. The board was ground to the center of the through hole, and the degree of porosity of the cover unit at the position of the through hole was observed using a polarizing microscope (label: OLYMPUS; model: BX51). The degree of porosity of the cover layer unit of the circuit board having the photosensitive opening of the application example 7 and the comparative application example 1 and the comparative application example 4 at the through hole position is referred to FIGS. 18 to 20, respectively.

Table 1 E-1: bisphenol A diglycidyl ether; E-2: dimer acid diglycidyl ester represented by formula (1); E-3: m-catechol diglycidyl ether; P-1: Phenyl bis(2,4,6-trimethylbenzylidene) phosphine oxide.

Referring to FIGS. 18 to 20, the cover unit of the circuit board having the photosensitive opening of the application examples 1 and 4 at the through hole position has a hole, such as a round frame, so that the circuit board having the photosensitive opening is subjected to heat resistance test. At the time, the problem of the blasting plate is caused by the existing pores, and the circuit board having the photosensitive opening formed by the circuit board capable of photosensitive opening of the present invention has no pores at the position of the through hole, and thus does not There is a problem with the explosion.

In summary, the cover layer unit of the photosensitive open-hole circuit board of the present invention has the functions of protecting the first lined conductive layer and the second lined conductive layer, and can also serve as a plug for the through hole of the laminated unit. Hole piece. The photosensitive apertured circuit board of the invention is subjected to a lithography process, so that the cover layer unit forms a cover layer unit having a photosensitive opening, and the photosensitive composition in the cover layer unit is formed to have heat resistance and flexibility. A circuit board having a photosensitive opening can indeed achieve the object of the present invention.

However, the above is only the embodiment of the present invention, and the scope of the invention is not limited thereto, and all the equivalent equivalent changes and modifications according to the scope of the patent application and the patent specification of the present invention are still The scope of the invention is covered.

4‧‧‧Layer unit
41‧‧‧Insulation
42‧‧‧First lined conductive layer
43‧‧‧Second lined conductive layer
44‧‧‧through hole surface
441‧‧‧through holes
5‧‧‧Conductor unit
6‧‧‧Overlay unit
61‧‧‧First cover
62‧‧‧second cover

Other features and effects of the present invention will be apparent from the following description of the drawings, wherein: FIG. 1 is a schematic cross-sectional view of a conventional printed circuit board; FIG. 2 is a circuit board of a photosensitive opening of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 3 to FIG. 13 are infrared absorption spectrum diagrams for explaining infrared absorption peak positions of a cover unit having photosensitive openings in a circuit board having photosensitive openings of Application Examples 1 to 11, respectively. And FIGS. 14 to 17 are infrared absorption spectrum patterns for explaining the infrared absorption peak positions of the cover layer unit having the photosensitive opening in the circuit board having the photosensitive opening of Comparative Examples 1 to 4, respectively; and FIG. FIG. 20 is a photographic view for explaining the degree of porosity of the cover layer unit in the position of the through hole in the circuit board having the photosensitive opening of Application Example 7, Comparative Application Example 1, and Comparative Application Example 4.

4‧‧‧Layer unit

41‧‧‧Insulation

42‧‧‧First lined conductive layer

43‧‧‧Second lined conductive layer

44‧‧‧through hole surface

441‧‧‧through holes

5‧‧‧Conductor unit

6‧‧‧Overlay unit

61‧‧‧First cover

62‧‧‧second cover

Claims (10)

A circuit board capable of photosensitive opening, comprising: a laminated unit comprising an insulating layer, a first lined conductive layer and a second lined conductive layer respectively formed on opposite sides of the insulating layer, and a defining a via surface extending from an upper surface of the first lined conductive layer and passing through the insulating layer to a through hole of a lower surface of the second lined conductor layer; a conductor unit formed on the at least consistent hole surface And for electrically connecting the first lined conductive layer and the second lined conductive layer; and a cover layer unit including a first lined conductive layer formed on the build unit and extending into the fill a first cover layer of the hole, wherein the cover layer unit is formed of a photosensitive composition, and the photosensitive composition comprises an epoxy group-containing compound and an epoxy group capable of reacting with the epoxy group-containing compound The photosensitive polyimide of the reaction. The photosensitive open-hole circuit board according to claim 1, wherein the epoxy group-containing compound is contained in an amount ranging from 10 parts by weight to 70% by weight based on 100 parts by weight of the photosensitive polyimide. Share. The photosensitive open-hole circuit board of claim 1, wherein the photosensitive polyimide is a photosensitive polyimide having the structure of the formula (1); R ¹ , R ² and R ³ are each a tetravalent group; X ¹ is a divalent group; X ² is a divalent group having a carboxylic acid group; and X ³ is having (2-hydroxy-3) a divalent group of a propyl acrylate group or a divalent group having a (2-hydroxy-3-methylpropionate) propyl group; the total number of m+n+o is 100 m is a positive integer of 30 to 70, the n is a positive integer of 10 to 45, and the o is a positive integer of 10 to 35; wherein, a plurality of R ¹ are the same or different, and the plurality of X ¹ are the same Or different, plural R ² are the same or different, a plurality of X ² are the same or different, a plurality of R ³ are the same or different, and a plurality of X ³ are the same or different. The photosensitive open-hole circuit board of claim 3, wherein the divalent group having a carboxylic acid group is or . The photosensitive apertured circuit board of claim 3, wherein the divalent group is , p is 1 to 20, ,or . The photosensitive open-hole circuit board according to claim 1, wherein the epoxy group-containing compound is selected from neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, and 1 , 2-cyclohexanedicarboxylic acid diglycidyl ester, bisphenol A diglycidyl ether, 1,2-propanediol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol tripropoxy triglycidyl ether , a resorcinol diglycidyl ether, a dimer acid diglycidyl ester represented by the formula (1), or a combination thereof Formula 1). The photosensitive apertured circuit board of claim 1, wherein the cover layer unit further comprises a second lined layer formed on the second lined conductive layer of the layering unit and extending into the through hole. . The photosensitive apertured circuit board of claim 1, wherein the through hole has a diameter ranging from greater than 0 mm to 0.25 mm. The photosensitive apertured circuit board of claim 1, wherein the insulating layer is a flexible insulating layer. The circuit board of the photosensitive opening according to claim 1, wherein the material of the conductor unit is selected from a conductive metal, a conductive polymer, or a combination thereof.