TW201431919A - Laser sensitive additive and method for manufacturing the same, thermoset resin/woven fiber composite, method for manufacturing pre-soaking sheet thereof and method for manufacturing rigid circuit board thereof, laser sensitive ink, flexible resin film - Google Patents

Abstract

The invention provides a surface modified laser sensitive additive including metallic oxides powder or metallic salts powder and a surface treating agent adhering or bonding to the metallic oxides powder or metallic salts powder. By implementing the special process of modification of surface chemical property of the laser sensitive additive, that is, making the surface treating agent adhere or bond to the surface of the metallic oxides powder or metallic salts powder, it can greatly raise the dispersion ability of the laser sensitive additive in the resin substrate, and therefore increase the number of ''seeds'' of the laser-burnt surface to promote the fast formation of chemical coating conductive wires efficiently.

Description

Laser sensitive additive and preparation method thereof, thermosetting resin/fiber fabric composite, prepreg sheet manufacturing method thereof and manufacturing method thereof, laser sensitive ink, flexible resin film and A method of manufacturing a flexible circuit board.

The invention relates to a laser sensitive additive and a preparation method thereof, a thermosetting resin/fiber fabric composite, a prepreg sheet manufacturing method thereof and a method for manufacturing the same, a laser sensitive ink and a flexibility A resin film and a method of manufacturing the same.

As the development of the electrical and electronic industry tends to be multi-functional, the components of electronic products are also moving toward light, thin, short, and small, especially the wide application of high-density integrated circuit technology, resulting in high performance of electronic products. High reliability and high security requirements. As a result, the core material of electronic products—printed circuit boards (including rigid printed circuit boards, flexible printed circuit boards, or a combination of both) – faces higher technical requirements and a more severe use environment. However, the conventional printed circuit board preparation process has the following technical defects:

(1) The electronic loop pattern preparation process of the printed circuit board is relatively complicated, and requires a process of laminating, sensitizing, etching, drilling, centering, pressing, electroplating, etc., and the preparation process is complicated. Taking the circuit design and modification of the rigid printed circuit board as an example, it involves the design and modification of the film and the pressing mold, thereby wasting labor and material resources, reducing the production efficiency, and increasing the production cost.

(2) At present, the design of circuits for printed circuit boards tends to be high-density and highly integrated. Therefore, for high-precision circuits, the original film development technology of the film is difficult to apply, and it is more efficient and more analytical. High wire loop preparation process.

(3) In the conventional printed circuit board, the through holes and blind holes for the series connection between the layers are difficult to prepare, and the electroplating process is immature, which often leads to loop disconnection and poor products.

In view of the above-mentioned shortcomings in the preparation process of the conventional printed circuit board, the industry has developed a technique for forming a precise and tight wire loop pattern on the surface of a thermoplastic plastic by using a 3D laser engraving forming (hereinafter referred to as LDS) method, thereby forming no Electronic, electrical and mechatronic products for printed circuit boards.

However, existing LDS materials and processing techniques still need to be improved. For example, these materials have poor dimensional stability, easy warpage (especially after laser engraving and chemical plating processes), insufficient heat resistance, and light weight. Low level, not suitable for certain high strength and structural requirements, etc.

For example, US 2009/0292048 discloses an application for the addition of a laser-sensitive additive to such LDS materials, characterized in that the laser-sensitive additive can be rapidly dispersed after being dispersed in a resin substrate and subjected to irradiation with a specific laser light. The reduced metal atoms are released, and the reduced metal atoms are exposed to the surface of the resin substrate ablated by the laser. These reduced metal atoms are referred to as "seeds" and can be used to induce and catalyze the adsorption and deposition of metal atoms reduced in the electroless plating bath and contribute to the formation of electroless plating wires.

However, in the case where the laser-sensitive additive is added too little, the number of "seeds" is small, the electroless plating time is relatively long, and even the electroless plating activity may not be exhibited; on the other hand, the laser-sensitive additive is added. Excessive occasions can lead to serious degradation of material properties and even affect processing performance.

Therefore, how to add a smaller amount of laser-sensitive additives to LDS materials, while producing more "seeds", is one of the possible improvements in the processability and application range of such LDS materials.

In order to achieve the above object, the present invention provides a surface-modified laser-sensitive additive comprising a metal oxide powder or a metal salt powder and adsorbed or bonded to the metal oxide powder or metal salt. a surface treatment agent for powder, wherein the metal oxide powder system is selected from the group consisting of copper oxide, cuprous oxide, copper molybdenum oxide, and a mixture thereof, the metal salt powder system being selected from the group consisting of copper phosphate, copper sulfate, and hydroxyphosphoric acid. One of copper, copper pyrophosphate, cuprous thiocyanate, cuprous sulfide, copper chromite, and a mixture thereof, the surface treatment agent is selected from the group consisting of a decane coupling agent, a titanate coupling agent, and a hard fat. One of an acid, a stearate, a stearate, and a mixture thereof.

In order to achieve the above object, the present invention further provides a method for preparing a surface-modified laser-sensitive additive, which comprises the following steps:

(A) preparing an aqueous solution containing a first surfactant selected from the group consisting of an anionic surfactant, a nonionic surfactant, and a mixture thereof, and the hydrophilicity of the first surfactant The hydrophobic equilibrium value (HLB value) is between 8-18;

(B) preparing a water-emulsified dispersion of a metal oxide powder or a metal salt powder containing the surface-modified laser-sensitive additive, which is added to the surfactant-containing aqueous solution of the step (A) a metal oxide powder or a metal salt powder and stirred;

(C) preparing a non-polar solution containing a second surfactant, adding a second surfactant in a non-polar solvent and stirring to a clear state, the non-polar solution being selected from one of benzene, toluene and xylene, The second surfactant is selected from one of an anionic surfactant, a nonionic surfactant, and a mixture thereof, and the second surfactant has a hydrophilic hydrophobic balance value of 3-6;

(D) preparing a non-polar solvent dispersion of the surface treatment agent containing the surface-modified laser-sensitive additive by adding the surface treatment agent to the non-polar solution containing the second surfactant of the step (C) And stirring; and

(E) a surface-modified laser-sensitive additive obtained by the step of preparing a water-emulsified dispersion of the metal oxide-containing powder or metal salt powder of the step (B) and the surface treatment agent of the step (D) The non-polar solvent dispersion is mixed into a reaction system and heated and stirred, then the formed steam is condensed to form a condensate, the water in the condensate is separated, and the non-polar solvent in the condensate is refluxed to the reaction system. When the temperature of the reaction system is higher than the boiling point of the non-polar solvent, the heating is stopped and the residual material is taken out, and the residual material is dried and then pulverized to obtain the surface-modified laser-sensitive additive.
In order to achieve the above object, the present invention further provides an additive type laser-engravable thermosetting resin/fiber fabric composite comprising the following components:

25-75 wt% thermosetting resin;

25-75 wt% continuous fiber fabric;

0.1-10 wt% of the surface modified laser sensitive additive.

In order to achieve the above object, the present invention further provides a method for producing a pre-impregnated sheet of an additive type laser-engravable thermosetting resin/fiber fabric composite, which comprises the following steps:

(A) preparing a sizing solution by adding a thermosetting resin monomer, a curing agent and a solvent in a reactor, stirring the reaction in a heating environment for a period of time to obtain a thermosetting resin prepolymer, and then adding the same in the reactor. Surface-modified laser-sensitive additive and continuous stirring, then cooling and adding a curing accelerator, uniformly mixing to obtain the sizing solution;

(B) immersing a fiber fabric in a first dipping tank containing a surface treating agent solution, followed by dipping into a second dipping tank containing the sizing liquid, and then heating and drying the fiber fabric to be semi-cured In the state, the prepreg is obtained by cutting.

In order to achieve the above object, the present invention further provides an additive type laser-engravable thermosetting resin/fiber fabric-based rigid circuit board manufacturing method, which comprises the following steps:

(A) curing and cutting the prepreg obtained by the method for producing a pre-impregnated sheet of the additive-type laser-engravable thermosetting resin/fiber fabric composite to obtain a rigid circuit substrate;

(B) performing surface laser engraving on the rigid circuit substrate, and forming a circuit pattern on the surface of the rigid circuit substrate;

(C) placing the rigid circuit substrate of step (B) in an electroless copper plating solution to deposit a wire loop;

(D) stacking the rigid circuit substrate of the step (C) between two sheets of the prepreg, and then thermosetting the rigid circuit substrate and the two prepreg sheets;

(E) Steps (B) to (D) are repeated to produce the additive type laser-engravable thermosetting resin/fiber fabric-based rigid circuit board having a multilayered rigid circuit substrate.

In order to achieve the above object, the present invention further provides a laser sensitive ink comprising the following components:

30-70 wt% of film-forming resin;
0.1-10 wt% of a laser-sensitive additive as described above;
1-3 wt% of a UV photoinitiator; and 15-25 wt% of a reactive diluent.

In order to achieve the above object, the present invention further provides a method for producing a precoated sheet of a surface-coated laser-engravable thermosetting resin/fiber fabric composite, which comprises the following steps:

(A) preparing a sizing solution by adding a thermosetting resin monomer, a curing agent and a solvent in a reactor, stirring the reaction in a heating environment for a period of time to obtain a thermosetting resin prepolymer, and then cooling the temperature and adding a curing accelerator. After uniformly mixing, the sizing solution is obtained;

(B) immersing a fiber fabric in a first dipping tank containing a surface treating agent solution, followed by dipping into a second dipping tank containing the sizing liquid, and then heating and drying the fiber fabric to be semi-cured In the state, the prepreg is obtained by cutting.

In order to achieve the above object, the present invention further provides a method for manufacturing a surface-coated laser-engravable thermosetting resin/fiber fabric-based rigid circuit board, which comprises the following steps:

(A) curing and cutting a prepreg obtained by the method of producing a surface-coated laser-formable thermosetting resin/fiber fabric composite prepreg sheet to obtain a rigid circuit substrate ;

(B) coating a surface of the rigid circuit substrate with a layer of laser-sensitive ink and irradiating the UV light, thereby forming a laser-sensitive paint film on the surface of the rigid circuit substrate;

(C) performing surface laser engraving on the rigid circuit substrate of the step (B), and forming a circuit pattern on the surface of the rigid circuit substrate;

(D) placing the rigid circuit substrate of step (C) into an electroless copper plating solution to deposit a wire loop;

(E) stacking the rigid circuit substrate of the step (D) between two sheets of the prepreg, and then thermosetting the rigid circuit substrate and the two prepreg sheets;

(F) Steps (B) to (E) are repeated to produce the surface-coated laser-engravable thermosetting resin/fiber fabric-based rigid circuit board having a plurality of rigid circuit substrates.

In order to achieve the above object, the present invention further provides an additive type laser-engravable flexible resin film comprising the following components:
30-70 wt% of a film resin polymer;
0.1-10 wt% of a laser-sensitive additive as described above;
0.1-15 wt% of flame retardant; and 5-25 wt% of filler.

In order to achieve the above object, the present invention further provides a method of manufacturing a flexible circuit board using the additive type laser-engravable flexible resin film, which comprises the following steps:

(A) preparing the additive type laser-engravable flexible resin film;

(B) performing surface laser engraving on the flexible resin film, and forming a circuit pattern on the surface of the flexible resin film;

(C) placing the flexible resin film of the step (B) in an electroless copper plating solution to deposit a wire loop;

(D) laminating the flexible resin film of the step (C) on the other flexible resin film, and then the flexible resin film which has formed the wire loop and the added type laser-engravable which has not yet formed a wire loop Formed flexible resin film by thermocompression curing;

(E) Steps (B) to (D) are repeated to obtain the flexible circuit board having a multilayered flexible resin film.
In order to achieve the above object, the present invention further provides a method of manufacturing a flexible circuit board comprising the following steps:

(A) preparing a surface-coated laser-engravable flexible resin film;

(B) coating a surface of the flexible resin film with a laser sensitive ink as described above and irradiating the UV light to form a laser sensitive paint film on the surface of the flexible resin film;

(C) subjecting the flexible resin film of the step (B) to surface laser engraving, and forming a circuit pattern on the surface of the flexible resin film;

(D) placing the flexible resin film of the step (C) in an electroless copper plating solution to deposit a wire loop;

(E) laminating the flexible resin film of the step (D) on the other flexible resin film, and then the flexible resin film which has formed the wire loop and the added type laser-engravable which has not yet formed a wire loop Formed flexible resin film by thermocompression curing;

(F) Steps (B) to (E) are repeated to obtain the flexible circuit board having a multilayered flexible resin film.
The embodiments of the present invention and the effects thereof will be described in detail below, but the following examples are not intended to limit the scope of the present invention.

10. . . Fiber fabric

20. . . First dipping tank

30. . . Second dipping tank

40. . . Prepreg sheet

The first figure is a flow chart of a method for manufacturing a thermosetting resin/fiber fabric-based rigid circuit board of the present invention.
The second figure is a flow chart of a method of manufacturing a flexible circuit board of the present invention.
The third figure is a schematic view of a double-dip tank continuous gluing device applied in the present invention.
The fourth figure is a schematic view of a rigid circuit substrate of the present invention.
The fifth drawing is a schematic view showing the state of use of the laser engraving and molding machine used in the present invention.
Figure 6 is a schematic view of a rigid circuit substrate having a circuit pattern formed by the present invention.
The seventh figure is a schematic view of a rigid circuit substrate deposited with a wire loop of the present invention.
The eighth drawing is a schematic view showing the state of use of the hot press forming apparatus used in the present invention.
The ninth drawing is a schematic view of an additive type laser-formable thermosetting resin/fiber fabric-based rigid circuit board of the present invention.
The tenth drawing is a schematic view showing development of a rigid circuit substrate of the present invention.
Figure 11 is a schematic view of a rigid circuit substrate having a laser-sensitive paint film of the present invention.
Figure 12 is a schematic view of a rigid circuit substrate having a circuit pattern formed by the present invention.
Figure 13 is a schematic view of a rigid circuit substrate having a wire loop deposited in accordance with the present invention.
Figure 14 is a schematic view showing a surface-coated laser-engravable thermosetting resin/fiber fabric-based rigid circuit board of the present invention.

Firstly, the present invention provides a surface-modified laser-sensitive additive comprising a metal oxide powder or a metal salt powder and a powder adsorbed or bonded to the metal oxide powder or metal salt powder. a surface treatment agent, wherein the metal oxide powder system is selected from the group consisting of copper oxide, cuprous oxide, copper molybdenum oxide, and a mixture thereof, the metal salt powder system is selected from the group consisting of copper phosphate, copper sulfate, copper hydroxyphosphate, and coke. One of copper phosphate, cuprous thiocyanate, cuprous sulfide, copper chromite, and a mixture thereof, and the surface treatment agent is selected from the group consisting of a decane coupling agent, a titanate coupling agent, and a stearic acid. One of stearates, stearates, and mixtures thereof.

When the surface treatment agent includes a decane coupling agent, the decane coupling agent may be selected from the group consisting of γ-aminopropyl triethoxy decane, γ-mercaptopropyltriethoxy decane, and 2-styryl. Trimethoxy decane, N-β-(aminoethyl)-γ-aminopropyltriethoxy decane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-ring One of oxypropoxypropyltrimethoxydecane, phenyltrimethoxydecane, methyldimethoxydecane, and mixtures thereof.

When the surface treatment agent includes a titanate coupling agent, the titanate coupling agent may be selected from the group consisting of isopropyl triisostearate titanate and isopropyl tris(dioctyl pyrophosphate). Titanate, isopropyl tris(dimethylpropenyl)isostearyl decyl titanate, isopropyl tris(N,N-diaminoethyl) titanate, isopropyl tris(12 Alkylbenzenesulfonyl) titanate, isopropylisostearylnonyldipropenyl titanate, isopropyl tris(dioctyl phosphate) titanate, tetraoctyl bis(phosphoric acid) Dialkyl) ester, titanate, tetrakis(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphate titanate, bis(pyrophosphate) Octyl) glycolate titanate, bis(dioctyl pyrophosphate) ethylene titanate, and mixtures thereof.

In addition, the weight of the surface treatment agent is preferably 0.5-3% of the total weight of the metal oxide powder or the metal salt powder. If the amount is too large, the physical properties of the material are lowered, and if the amount is too small, the modification effect is not obvious enough.

Since the present invention uses a surface-modified laser-sensitive additive, that is, the surface thereof is chemically modified, when it is melt-blended with a resin substrate or heated in a solution, the powder particles/resin substrate The interface tension tends to decrease, thereby improving physical compatibility; in addition, where a coupling agent is used, certain chemical functional groups in the surface-modified laser-sensitive additive may be combined with a resin-based The long chain end groups of the material produce a chemical reaction that increases the chemical compatibility of the interface. Therefore, the modified laser-sensitive additive and the material to which the additive is applied can be significantly improved in terms of molding processing or physical and mechanical properties.

The inventors of the present invention have found that by performing surface chemical modification of the special process of the laser sensitive additive, that is, the surface of the metal oxide powder or the metal salt powder is adsorbed or bonded to the surface treatment agent, The ability of the laser-sensitive additive to disperse in the resin substrate is increased to increase the number of "seeds" on the laser ablated surface, and the rapid formation of the electroless plating wire is effectively promoted. From another point of view, since the laser-sensitive additive of the present invention can be subjected to surface modification treatment to achieve an excellent dispersion effect, even if only a small amount of the laser-sensitive additive of the present invention is added, compared with the addition In the case of a large number of conventional laser-sensitive additives, the same "seed" quantity and electroless plating efficiency can still be obtained by the present invention. At the same time, the reduction in the content of the laser-sensitive additive and the increase in the degree of dispersion contribute to the improved performance of the molded product and the reduction in cost.
In order to prepare the above surface-modified laser-sensitive additive, a preparation method comprising the following steps can be utilized:
(A) preparing an aqueous solution containing a first surfactant selected from the group consisting of an anionic surfactant, a nonionic surfactant, and a mixture thereof, and the hydrophilicity of the first surfactant The hydrophobic balance value (HLB value) is between 8 and 18, which is an O/W type surfactant, wherein the first surfactant is preferably added in an amount of 0.1-0.5 g/100 ml of water and not more than the surface active agent. Critical micelle concentration of the agent; when the first surfactant comprises an anionic surfactant, it may be selected from sodium dodecylbenzenesulfonate (SDBS), sodium dodecyl sulfate (SDS) and One of the mixtures; when the first surfactant comprises a nonionic surfactant, it may be selected from the group consisting of octylphenol polyoxyethylene ether (OP-10), polyoxyethylene lauric acid ether, polyoxyethylene One of cetyl ether, polyoxyethylene stearate, and a mixture thereof; the inventors of the present invention have further found that if the first surface ionic active agent comprises both an anionic surfactant and a nonionic surfactant Mixture can effectively increase metal oxidation The degree of dispersion of the powder or metal salt powder in water, wherein the ratio of the anionic surfactant to the nonionic surfactant is preferably 1-5:1, more preferably 2-3:1, the ratio Too large or too small may affect the dispersion of the aforementioned powder in water;
(B) preparing an aqueous emulsified dispersion containing the above metal oxide powder or metal salt powder, which is added to the surfactant-containing aqueous solution of the step (A), and the metal oxide powder or metal salt powder is added The pH value is adjusted between 3.5 and 4.0, followed by stirring to emulsify the dispersion to obtain the dispersion; wherein the metal oxide powder or the metal salt powder may have an average diameter (D ₅₀ ) of 0.5 -5 μm, preferably 0.6-2.5 μm, and more preferably 0.9-1.2 μm. Because the particle diameter is too large, the physical properties of the material are degraded, and the electroless plating efficiency is also lowered, resulting in a rough surface of the electroless plating and affecting the finished product. quality;
(C) preparing a non-polar solution containing a second surfactant, adding a second surfactant to the non-polar solvent, followed by stirring at a constant speed to a clear state by an electromagnetic stirring device, and heating slightly during the stirring process, the non-polar The polar solution is selected from one of benzene, toluene and xylene, and the second surfactant is selected from one of an anionic surfactant, a nonionic surfactant and a mixture thereof, and the second surfactant The hydrophilic hydrophobic balance value is between 3 and 6 and is a W/O type surfactant, wherein the second surfactant is selected from the group consisting of glyceryl monostearate, glyceryl tristearate, propylene glycol fatty acid ester and One of the mixture, and the second surfactant is preferably added in an amount of 0.1-1 g/100 ml of a non-polar aqueous solution;
(D) preparing a non-polar solvent dispersion containing the above surface treatment agent by adding the surface treatment agent to the non-polar solution containing the second surfactant of the step (C) and vigorously stirring; and (E) The surface-modified laser-sensitive additive is a water-emulsified dispersion of the metal oxide powder or metal salt powder of the step (B) and a non-polar solvent containing the surface treatment agent of the step (D). The dispersion is mixed into a reaction system and heated and stirred in a three-necked flask, and then the formed vapor is condensed to form a condensate, and the water in the condensate is separated, and the non-polar solvent in the condensate is refluxed. To the reaction system, when the temperature of the reaction system is higher than the boiling point of the non-polar solvent, the heating is stopped and the residual material is taken out, and the remaining material is filtered, washed with absolute ethanol and dried, and then pulverized to obtain the surface modification. Laser sensitive additive.

The above surface-modified laser-sensitive additive can be applied to an additive type laser-engravable thermosetting resin fiber fabric composite comprising the following components:
25-75 wt% of a thermosetting resin which may be selected from the group consisting of epoxy resin, phenol resin, urea resin, melamine-formaldehyde resin, unsaturated polyester resin, BT resin (bismaleimide triazine resin) and a mixture thereof
25-75 wt% continuous fiber fabric;
0.1-10 wt% of the aforementioned surface-modified laser-sensitive additive; and 0-15 wt% of an auxiliary agent selected from reactive diluents, leveling agents, antifoaming agents, flame retardants, and toughening One of a dose, an antioxidant, a light stabilizer, a filler adjuvant, and a mixture thereof.

In order to make the composite can withstand the high temperature environment of electroless plating, the glass transition temperature should have a glass transition temperature as high as possible, and it is recommended to be greater than 90 ° C to avoid the problem of warpage after the material forming process, and the influence Product quality, accuracy and yield.

The invention further provides a method for manufacturing an additive type laser-engravable thermosetting resin/fiber fabric-based rigid circuit board, which can be applied as shown in the first drawing, which comprises preparing a prepreg sheet in advance. Made using a manufacturing method that includes the following steps:
(A) preparing a sizing solution by adding a thermosetting resin monomer, a curing agent and a solvent in a reactor, stirring the reaction in a heating environment for a period of time to obtain a thermosetting resin prepolymer, and then adding the aforementioned surface to the reactor. The modified laser-sensitive additive is continuously stirred, and a small amount of solvent may be added to adjust the resin content, and then the temperature is lowered and a curing accelerator is added, and the mixture is uniformly mixed to obtain the sizing solution; and (B) as shown in the third figure, A continuous fiber fabric 10 is immersed in a first dipping tank 20 containing a dilute surface treatment agent, and then immersed in a second dipping tank 30 containing the sizing liquid, and then the fiber fabric 10 is heated and dried to be In a semi-cured state, the prepreg sheet 40 is obtained by cutting; wherein the continuous fiber fabric 10 may be a glass fiber cloth, a carbon fiber cloth, a basalt fiber cloth, an aramid fiber cloth, a Teflon fiber cloth, Super high molecular weight polyethylene fiber cloth, superimposed mixing or mixing of various fiber cloths; the surface treatment agent contained in the first dipping tank 20 is selected from the group consisting of a decane coupling agent, a titanate coupling agent, and a polyol. One of a fatty acid ester, a compatibilizer, a film former, a lubricant, a wetting agent, a leveling agent, and a mixture thereof; and when the surface treating agent includes a decane coupling agent, the decane coupling agent It may be selected from the group consisting of γ-aminopropyltriethoxydecane, γ-mercaptopropyltriethoxydecane, 2-styrylethyltrimethoxydecane, and N-β-(aminoethyl)-γ-amino group. Propyltriethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, phenyltrimethoxydecane, A One of dimethoxy decane and a mixture thereof; when the surface treatment agent includes a titanate coupling agent, the titanate coupling agent may be selected from isopropyl triisostearate titanium Acid ester, isopropyl tris(dioctyl pyrophosphate) titanate, isopropyl tris(dimethylpropenyl)isostearyl decyl titanate, isopropyl tris(N,N-diamino Ethyl) titanate, isopropyl tris(dodecylbenzenesulfonyl) titanate, isopropylisostearyl decyldipropionate titanate, isopropyl tris(dioctyl phosphate) ) titanate, tetraoctyl double ( Acid di(dodecyl) ester titanate, tetrakis(2,2-diallyloxymethyl-1-butyl)bis(di(tridecyl))phosphate titanate, double (dioctyl pyrophosphate) one of glycolate titanate, bis(dioctyl pyrophosphate)ethyl titanate, and a mixture thereof; when the surface treatment agent includes a polyol, the polyol It may be polyethylene glycol; when the surface treatment agent includes a fatty acid ester, the fatty acid ester may be selected from the group consisting of glyceryl stearate, glyceryl oleate, glyceryl ethylene bisstearate, and ethylene double hard. One of the fatty amines and mixtures thereof; where the surface treatment agent comprises a compatibilizer, the compatibilizer may be selected from small molecule compatibilizers containing reactive groups (eg, AC modification sold by Honeywell Corporation) Wax), macromolecular compatibilizer containing reactive groups (such as AX8900 sold by Atochem), copolymerized with maleic anhydride (MAH), glycidyl methacrylate (GMA) or graft modified One of the compatibilizers and mixtures thereof; whereby the mechanical and electrical properties of the prepreg 40 can be improved.

After the prepreg sheet is prepared, the subsequent processing of the additive type laser engraved thermosetting resin/fiber fabric-based rigid circuit board can be continued, which includes the following steps:
(A) as shown in the fourth figure, the prepreg sheet is cured and cut at a predetermined temperature, pressure and pressurization time to obtain a rigid circuit substrate;
(B) as shown in the fifth figure, the surface of the rigid circuit substrate is directly laser-engraved by a laser engraving and molding machine, and a circuit pattern as shown in FIG. 6 is formed on the surface of the rigid circuit substrate;
(C) as shown in the seventh figure, the rigid circuit substrate of step (B) is placed in an electroless copper plating solution to deposit a wire loop;
(D) stacking the rigid circuit substrate of the step (C) between two sheets of the prepreg using a hot press molding apparatus as shown in FIG. 8, and then pre-impregnating the rigid circuit substrate and the two The sheet is hot pressed and cured, and subjected to subsequent processing such as positioning, trimming, drilling, etc.; and (E) repeating steps (B) to (D) to obtain a multilayer rigid circuit substrate as shown in FIG. An additive type laser-formable thermosetting resin/fiber fabric-based rigid circuit board.

The additive type laser-formed thermosetting resin/fiber fabric-based rigid circuit board is called "additive type" because the composition of the prepreg sheet has been added with the aforementioned surface-modified laser sensitivity. Sexual additives, so it is no longer necessary to apply a laser-sensitive ink to the surface of the circuit substrate before performing the laser engraving operation.

The manufacturing method of the rigid circuit board can also be appropriately adjusted. For example, the rigid circuit substrate having the wire loop obtained by the above step (C) can be directly subjected to appearance treatment, thereby achieving high dimensional stability, light weight, and low thickness. Laser engraving and forming products; or, by hot pressing equipment and ultra-thin wall hot pressing mold (product wall thickness less than or equal to 0.2 mm), the prepreg sheet is directly hot pressed into a target product shape and has a card Internal components such as grooves, hooks, screw posts, reinforcing ribs, etc., including but not limited to in-mold injection molding technology, followed by laser engraving of the substrate with the target product shape and direct ablation on the surface The circuit pattern is drawn, and then the metal wire loop is deposited in the electroless plating solution, and finally, the ultra-thin wall laser engraving and forming product is obtained after the appearance treatment, and the product has the characteristics of small thickness and high volume utilization, so it is suitable for high Density, high integration of electronics and home appliances.

On the other hand, for a surface-coated, laser-engravable thermosetting resin/fiber-based rigid circuit board in which the composition of the prepreg sheet does not include the surface-modified laser-sensitive additive, it is required to be carried out. A laser-sensitive ink is applied to the circuit substrate before the laser engraving operation, and the laser-sensitive ink includes the following components:
30-70 wt% of a film-forming resin selected from the group consisting of unsaturated polyester resins, epoxy acrylate resins, urethane acrylate resins, polyester acrylate resins, and polyether acrylate resins One of a polyacrylate resin and a mixture thereof;
0.1-10 wt% of the aforementioned surface-modified laser-sensitive additive;
1-3 wt% of UV photoinitiator;
15-25% by weight of a reactive diluent; and 1-10% by weight of an auxiliary agent selected from the group consisting of a filler, a leveling agent, an antifoaming agent, and a mixture thereof.

In addition, the surface-coated pre-impregnated sheet used in the laser-formed thermosetting resin/fiber fabric-based rigid circuit board uses a manufacturing method including the following steps:
(A) preparing a sizing solution by adding a thermosetting resin monomer, a curing agent and a solvent in a reactor, stirring the reaction in a heating environment for a period of time to obtain a thermosetting resin prepolymer, and then cooling the temperature and adding a curing accelerator. After uniformly mixing, the sizing solution is obtained; in particular, the sizing solution is not added with the above-mentioned surface-modified laser-sensitive additive, which is an additive-type laser-engravable thermosetting resin/ One of the differences in the method of manufacturing a fiber-based rigid circuit board;
(B) As shown in the third figure, a continuous fiber fabric 10 is immersed in a first dipping tank 20 containing a dilute solution of a surface treating agent, and then immersed in a second dipping tank 30 containing the sizing liquid, Then, the fiber fabric 10 is heated and dried to be semi-cured, and the prepreg 40 is obtained by cutting; wherein the continuous fiber fabric 10 and the surface treatment agent are selected and the aforementioned additive type laser engraving The prepreg sheet of the formed thermosetting resin/fiber fabric composite is the same as the user, and will not be further described herein.

After the preparation of the aforementioned prepreg sheet is completed, the following steps may be followed to produce the surface-coated laser-engravable thermosetting resin/fiber fabric-based rigid circuit board, as shown in the lower half of the first figure:
(A) curing and cutting the prepreg sheet to obtain a rigid circuit substrate;
(B) As shown in the tenth figure, a layer of laser-sensitive ink is coated on the surface of the rigid circuit substrate by mechanical spraying or screen printing, and the photoresist is applied by a developing technique to irradiate the light and finally irradiate the light. Removing the resist to form a laser-sensitive paint film as shown in FIG. 11 on the surface of the rigid circuit substrate;
(C) performing surface laser engraving on the rigid circuit substrate of the step (B) by using a laser engraving machine as shown in FIG. 5, and forming a circuit pattern as shown in FIG. 12 on the surface of the rigid circuit substrate;
(D) as shown in Fig. 13, the rigid circuit substrate of the step (C) is placed in an electroless copper plating solution to deposit a wire loop;
(E) stacking the rigid circuit substrate of the step (D) between two sheets of the prepreg using a hot press molding apparatus as shown in FIG. 8, and then the rigid circuit substrate and the two prepregs The material is hot-pressed and cured, and subjected to subsequent processing such as positioning, trimming, drilling, etc.; and (F) repeating steps (B) to (E) to obtain a multilayer rigid circuit substrate as shown in FIG. A surface-coated, laser-engravable thermosetting resin/fiber fabric-based rigid circuit board.

The manufacturing method of the rigid circuit board can also be appropriately adjusted. For example, the rigid circuit substrate having the wire loop obtained in the above step (D) can be directly processed to obtain high dimensional stability, light weight, and low thickness. Laser engraving and forming products; or, by hot pressing equipment and ultra-thin wall hot pressing mold (product wall thickness less than or equal to 0.2 mm), the prepreg sheet is directly hot pressed into a target product shape and has a card Internal components such as grooves, hooks, screw posts, reinforcing ribs, etc., including but not limited to in-mold injection molding technology, followed by coating the surface of the substrate with the target product with laser-sensitive ink and irradiating UV The light is cured, and then laser engraving is performed to directly ablate the circuit pattern on the surface thereof, and then the metal wire loop is deposited in the electroless plating solution, and finally, the appearance processing is performed to obtain an ultra-thin wall laser engraving and forming product. The product has the characteristics of small thickness and high volume utilization, so it is suitable for high-density, high-integration electronics and home appliances.

On the other hand, the surface-modified laser-sensitive additive of the present invention can also be applied to the field of flexible resin films. For example, an additive type laser-engravable flexible resin film can include the following components:
30-70 wt% of a film resin polymer selected from the group consisting of ethylene vinyl acetate copolymer (EVA), polyethylene terephthalate (PET), polycarbonate (PC), and polyphthalamide One of an amine (PI) and a mixture thereof;
0.1-10 wt% of the aforementioned surface-modified laser-sensitive additive;
0.1-15 wt% of flame retardant;
5-25 wt% of a filler; and 1-10 wt% of an adjuvant selected from one of a toughening agent, a lubricant, a dispersing agent, an antioxidant, a light stabilizer, and a mixture thereof.

With the above-mentioned additive type laser-engravable flexible resin film, a flexible circuit board can be further manufactured, and the manufacturing method thereof (as shown in the second figure) includes the following steps:
(A) preparing the additive type laser-engravable flexible resin film;
(B) performing surface laser engraving on the flexible resin film, and forming a circuit pattern on the surface of the flexible resin film;
(C) placing the flexible resin film of the step (B) in an electroless copper plating solution to deposit a wire loop;
(D) laminating the flexible resin film of the step (C) on the other flexible resin film, and then the flexible resin film which has formed the wire loop and the added type laser-engravable which has not yet formed a wire loop The formed flexible resin film is autoclaved; and (E) the steps (B) to (D) are repeated to obtain the flexible circuit board having a multilayer flexible resin film.
Wherein, in the case where the film resin polymer of the step (A) is selected from the group consisting of ethylene vinyl acetate copolymer, polyethylene terephthalate, polycarbonate, and a mixture thereof, the step (A) includes using high-speed mixing. The film resin polymer, the surface-modified laser-sensitive additive, the flame retardant and the filler are uniformly mixed to form a pre-mix, and then the pre-mix is melt-mixed and then flowed by a twin-screw extruder. The die-casting die is extruded and stretched to prepare the additive type laser-engravable flexible resin film.

On the other hand, in the case where the film resin polymer of the step (A) is a polyimine (PI), since it cannot be melt-extruded into a film, the step (A) may be changed to a polyamine. The acid (ie, the precursor of polyimine) is dissolved in a good solvent (such as DMAc, DMF, etc.), and the surface-modified laser-sensitive additive, flame retardant and filler are added to form a mixture. The liquid is uniformly applied to the mirror steel plate, and after the good solvent is volatilized, the temperature is raised until the mixed liquid is imidized to obtain the additive type laser-engravable flexible resin film.

The additive type laser-engravable flexible resin film produced is called "additive type" because the composition of the prepreg sheet has been added with the aforementioned surface-modified laser-sensitive additive, so It is not necessary to apply a laser-sensitive ink to the surface of the circuit substrate before performing the laser engraving operation.

The method for manufacturing the flexible circuit board may be appropriately adjusted. For example, before the step (B), the flexible resin film is preliminarily molded into a card groove, a hook, a screw column, a reinforcing rib, etc. by means of in-mold injection molding. After the internal components, and then the steps (B) and (C), the ultra-thin wall laser engraving and molding products can be obtained by the appearance treatment, and the product has the characteristics of small thickness and high volume utilization, so it is suitable for high density and high. Integrated electronics and home appliances.

On the other hand, in the case of a surface-added laser-engravable flexible resin film in which the composition of the prepreg sheet does not include the surface-modified laser-sensitive additive, it is necessary to perform a laser engraving operation. A laser-sensitive ink is applied to the flexible resin film, which has been described above and will not be described here.

The surface-coated laser-engravable flexible resin film can also be used to manufacture a flexible circuit board, and the manufacturing method thereof comprises the following steps:
(A) preparing a surface-coated laser-engravable flexible resin film;
(B) coating a layer of the aforementioned laser-sensitive ink on the surface of the flexible resin film and irradiating the UV light, thereby forming a laser-sensitive paint film on the surface of the flexible resin film;
(C) subjecting the flexible resin film of the step (B) to surface laser engraving, and forming a circuit pattern on the surface of the flexible resin film;
(D) placing the flexible resin film of the step (C) in an electroless copper plating solution to deposit a wire loop;
(E) laminating the flexible resin film of the step (D) on the other flexible resin film, and then the flexible resin film which has formed the wire loop and the added type laser-engravable which has not yet formed a wire loop The formed flexible resin film is autoclaved and subjected to subsequent processing such as positioning, trimming, drilling, etc.; and (F) repeating steps (B) to (E) to obtain the above-mentioned scratch having a multilayer flexible resin film Sex board.

Wherein, in the case where the film resin polymer of the step (A) is selected from the group consisting of ethylene vinyl acetate copolymer, polyethylene terephthalate, polycarbonate, and a mixture thereof, the step (A) includes the film resin. The polymer, the flame retardant and the filler are uniformly mixed to form a premix, and the premix is melt-mixed, extruded and drawn to prepare the surface-coated laser-engravable flexible resin film.

On the other hand, in the case where the film resin polymer of the step (A) is a polyimine (PI), the step (A) comprises dissolving the polyaminic acid (i.e., the polyimine precursor) in its good form. a solvent and a flame retardant and a filler are added to form a mixed solution, and the mixture is uniformly applied to a mirror steel plate, and after the good solvent is volatilized, the temperature is raised until the mixture is imidized. A surface-applied flexible resin film that can be laser-engraved.

The method for manufacturing the flexible wiring board described above may be appropriately adjusted. For example, before the step (C), the flexible resin film is preliminarily molded into a card groove, a hook, a screw column, a reinforcing rib, etc. by means of in-mold injection molding or the like. After the internal components, and then the steps (C) and (D), the appearance treatment can be used to obtain an ultra-thin wall laser engraving molding product, which has the characteristics of small thickness and high volume utilization, and is therefore suitable for high density and high density. Integrated electronics and home appliances.

The present invention is further illustrated by the following examples:

Preparation of sample 1 (surface organically modified copper chromite powder)
Add 400 ml of deionized water, 0.4 g of sodium dodecylbenzene sulfonate (SDBS), and 0.2 g of octylphenol polyoxyethylene ether (OP-10) in a 1 liter beaker, using an electromagnetic stirring device to 350 Stir well at rpm until clear the clear solution. In another 1 liter round bottom flask, 200 g of copper chromite powder (D ₅₀ particle size: 1.2 μm) was added, and an aqueous solution of the above surfactant was added thereto, and the mixture was stirred at 500 rpm by a mechanical stirring device to adjust the environment. The pH was between 3.5 and 4.0, and then stirred at 2000 rpm to carry out an emulsification reaction, and after 30 minutes, an aqueous emulsified dispersion of copper chromite was obtained.
400 ml of toluene, 2 g of γ-aminopropyltriethoxydecane (added to a mechanical stirring apparatus, and stirred and stirred at 1000 rpm for 30 minutes to obtain a decane coupling agent/toluene dispersion was used.
The above decane coupling agent/toluene dispersion was added to a condensing reflux reactor, and an aqueous emulsified dispersion of copper chromite was gradually added, heated and vigorously stirred. The mixed steam is condensed and the water is discharged from the reaction unit, and the toluene is refluxed again into the reaction vessel. When the reaction temperature of the mixture system reaches the boiling point of toluene (95 ° C under normal temperature and normal pressure), the surface treatment operation of the copper chromite powder is completed, and after removing, the excess toluene is filtered off, and the mixture is washed with hot anhydrous ethanol. -3 times, dry pulverization to obtain a surface organically modified copper chromite powder.

Preparation of Sample 2 (dilute solution of surface treatment agent for treating continuous fiber fabric)
100 parts by weight of deionized water, 6.5 parts by weight of an epoxy resin film former, 1.6 parts by weight of a decane coupling agent, 0.7 parts by weight of dioxane, added to the reaction vessel and stirred at a constant speed, followed by addition of 0.2 part by weight of a lubricant and wetting The agent is adjusted to a pH of 3.5 to 4.5 with acetic acid to prepare a dilute solution of the surface treatment agent for treating the continuous fiber fabric.

Preparation of sample 3 (laser sensitive ink)
30 parts by weight of urethane acrylate resin, 25 parts by weight of epoxy acrylate resin, 2 parts by weight of phosphoric acid phosphate, and 5 parts by weight of surface-organized modified copper chromite powder (ie, sample 1) were added to the reaction vessel. Stir well and mix well. The laser-sensitive ink was prepared by adding 22 parts by weight of mica powder, 15 parts by weight of a reactive diluent, and finally adding 1 part by weight of a UV photoinitiator.

Preparation of Sample 4 (Additional Laser Engravable Epoxy/Glass Fiber Composite Prepreg)
15 parts by weight of ethylene glycol methyl ether and 10 parts by weight of dimethylformamide were mixed to prepare a mixed solvent, and then 125 parts by weight of a brominated epoxy resin (content: 80% by weight) was added, and then 5 parts by weight were added. The surface chlorinated copper chromite powder (ie, sample 1) was continuously stirred and uniformly mixed. 0.05 part by weight of 2-methylimidazole was previously mixed with 5 parts by weight of dimethylformamide, and then gradually added to the above epoxy resin mixed solution to prepare an epoxy resin sizing solution, which was stored in storage and used.
The continuous fiber fabric is dipped by the "double dipping tank continuous gluing" apparatus and method: that is, the surface of the continuous dipping fabric 20 is placed in the first dipping tank 20 of the continuous gluing device shown in FIG. The treatment agent dilute solution (ie, sample 2), the second dipping tank 30 holds the above epoxy resin sizing solution, and the continuous fiber woven fabric 10 used is a model 2116 type alkali-free glass fiber cloth. The semi-cured prepreg 40 is stored at room temperature so that the volatile content is less than 5% by weight, and then dried at 65 ° C to a volatile content of less than 1% by weight, pasted into a release paper, and cut into a specified shape.

Preparation of Sample 5 (surface coated type laser engraved epoxy resin/glass fiber composite material prepreg)
15 parts by weight of ethylene glycol methyl ether and 10 parts by weight of dimethylformamide were mixed to prepare a mixed solvent, and then 125 parts by weight of a brominated epoxy resin (content: 80% by weight) was added, and the mixture was continuously stirred and uniformly mixed. 0.05 part by weight of 2-methylimidazole was previously mixed with 5 parts by weight of dimethylformamide, and then gradually added to the above epoxy resin mixed solution to prepare an epoxy resin sizing solution, which was stored in storage and used.

The continuous fiber fabric is dipped by the "double dipping tank continuous gluing" apparatus and method: that is, the surface of the continuous dipping fabric 20 is placed in the first dipping tank 20 of the continuous gluing device shown in FIG. The treatment agent dilute solution (ie, sample 2), the second dipping tank 30 contains the above epoxy resin sizing solution, and the continuous fiber woven fabric 10 used is a type 2116 type alkali-free glass fiber cloth. The semi-cured prepreg 40 is stored at room temperature so that the volatile content is less than 5% by weight, and then dried at 65 ° C to a volatile content of less than 1% by weight, pasted into a release paper, and cut into a specified shape.

Preparation of sample 6 (addition type laser engraved flexible polyimide film material)
Weigh 21.8g of pyromellitic dianhydride (PMDA) and 23.6g of 4,4-diaminodiphenyl ether (ODA), maintain the ambient temperature between 20-40 ° C, and uniformly and slowly add PMDA powder to ODA solution. When the remaining amount of PMDA powder is about 5% wt, while adding, the viscosity of the reaction system is adjusted by dimethylacetamide (DMAC), the total amount of DMAC added is 260 g, and finally 2.4 g of surface organic is added. The modified copper chromite powder is stirred uniformly to obtain a polyaminic acid solution mixture.
The solution is casted on the surface of a high-mirror stainless steel plate, and the liquid film is placed in a 50 ° C and 300 ° C environment for drying for 3-5 hours, and then heated at 500 ° C for 5 minutes to obtain the solution. Addition type laser engraved and formed flexible polyimide film.

Preparation of Sample 7 (Surface-coated type laser-engravable flexible polyimide film material)
Weigh 21.8g of pyromellitic dianhydride (PMDA) and 23.6g of 4,4-diaminodiphenyl ether (ODA), maintain the ambient temperature between 20-40 ° C, and uniformly and slowly add PMDA powder to ODA solution. In the case where the remaining amount of the PMDA powder is about 5% by weight, the viscosity of the reaction system is adjusted by dimethylacetamide (DMAC) while the total amount of DMAC is 260 g to prepare a poly-proline solution. .

The solution is casted on the surface of a high-mirror stainless steel plate, and the liquid film is placed in a 50 ° C and 300 ° C environment for drying for 3-5 hours, and then heated at 500 ° C for 5 minutes to obtain the solution. A surface-coated, laser-engravable flexible polyimide film material.

no.

Claims (10)

A surface-modified laser-sensitive additive comprising:
a metal oxide powder or a metal salt powder, wherein the metal oxide powder system is selected from the group consisting of copper oxide, cuprous oxide, copper molybdenum oxide and a mixture thereof, the metal salt powder system being selected from the group consisting of copper phosphate , one of copper sulfate, copper hydroxyphosphate, copper pyrophosphate, cuprous thiocyanate, cuprous sulfide, copper chromite and mixtures thereof;
a surface treatment agent adsorbed or bonded to the metal oxide powder or metal salt powder, wherein the surface treatment agent is selected from the group consisting of a decane coupling agent, a titanate coupling agent, a stearic acid, and a hard One of a fatty acid type, a stearic acid ester, and a mixture thereof. A method for preparing a surface-modified laser-sensitive additive comprises the following steps:
(A) preparing an aqueous solution containing a first surfactant selected from the group consisting of an anionic surfactant, a nonionic surfactant, and a mixture thereof, and the hydrophilicity of the first surfactant The hydrophobic equilibrium value (HLB value) is between 8-18;
(B) A water-emulsified dispersion of a metal oxide powder or a metal salt powder containing the surface-modified laser-sensitized additive according to claim 1, which is an aqueous solution containing a surfactant in the step (A) Adding the metal oxide powder or the metal salt powder to the mixture and stirring;
(C) preparing a non-polar solution containing a second surfactant, adding a second surfactant in a non-polar solvent and stirring to a clear state, the non-polar solution being selected from one of benzene, toluene and xylene, The second surfactant is selected from one of an anionic surfactant, a nonionic surfactant, and a mixture thereof, and the second surfactant has a hydrophilic hydrophobic balance value of 3-6;
(D) preparing a non-polar solvent dispersion containing the surface treatment agent of the surface-modified laser-sensitized additive of claim 1, wherein the surface treatment agent is added to the second surfactant-containing non-step surfactant a polar solution prepared by stirring; and (E) a surface-modified laser-sensitive additive obtained by emulsification dispersion of the metal oxide powder or metal salt powder of the step (B) The non-polar solvent dispersion containing the surface treatment agent of the step (D) is mixed with a reaction system and heated and stirred, and then the formed steam is condensed to form a condensate, the water in the condensate is separated, and the condensate is removed. The non-polar solvent is refluxed to the reaction system, and when the temperature of the reaction system is higher than the boiling point of the non-polar solvent, the heating is stopped and the residual material is taken out, and after the obtained residual material is dried, the pulverization is performed to obtain the surface-modified laser-sensitive Sex additives. An additive type laser engraved thermosetting resin/fiber fabric composite comprising the following components:
25-75 wt% thermosetting resin;
25-75 wt% continuous fiber fabric;
0.1-10 wt% of a surface-modified laser-sensitive additive as claimed in claim 1. A method for manufacturing a pre-impregnated sheet of an additive type laser-engravable thermosetting resin/fiber fabric composite, comprising the following steps:
(A) preparing a sizing solution by adding a thermosetting resin monomer, a curing agent and a solvent in a reactor, stirring the reaction in a heating environment for a period of time to obtain a thermosetting resin prepolymer, and then adding in the reactor as requested The surface-modified laser-sensitive additive of item 1 is continuously stirred, and then cooled and added with a curing accelerator, uniformly mixed to obtain the sizing solution; and (B) immersing a fiber fabric in a surface treatment agent solution The first dipping tank is then immersed in the second dipping tank containing the gluing liquid, and then the fiber fabric is heated and dried to be semi-cured, and the prepreg is obtained by cutting. . An additive type laser-engravable thermosetting resin/fiber fabric-based rigid circuit board manufacturing method comprising the following steps:
(A) The prepreg obtained by the method for producing a pre-impregnated sheet of a thermoformable resin/fiber fabric composite of the addition type laser-engravable molding according to claim 4 is cured and cut to obtain a rigidity. Circuit substrate
(B) performing surface laser engraving on the rigid circuit substrate, and forming a circuit pattern on the surface of the rigid circuit substrate;
(C) placing the rigid circuit substrate of step (B) in an electroless copper plating solution to deposit a wire loop;
(D) stacking the rigid circuit substrate of the step (C) between two sheets of the prepreg, and then thermosetting the rigid circuit substrate and the two prepreg sheets; and (E) repeating the steps (B) to (D) to produce the additive type laser-engravable thermosetting resin/fiber fabric-based rigid circuit board having a plurality of rigid circuit substrates. A laser sensitive ink that includes the following ingredients:
30-70 wt% of film-forming resin;
0.1-10 wt% of a laser-sensitive additive for surface modification as described in claim 1;
1-3 wt% of UV photoinitiator;
15-25% by weight of reactive diluent. A method for manufacturing a precoated sheet of a surface-coated laser-engravable thermosetting resin/fiber fabric composite, comprising the following steps:
(A) preparing a sizing solution by adding a thermosetting resin monomer, a curing agent and a solvent in a reactor, stirring the reaction in a heating environment for a period of time to obtain a thermosetting resin prepolymer, and then cooling the temperature and adding a curing accelerator. After uniformly mixing, the sizing solution is obtained;
(B) immersing a fiber fabric in a first dipping tank containing a surface treating agent solution, followed by dipping into a second dipping tank containing the sizing liquid, and then heating and drying the fiber fabric to be semi-cured In the state, the prepreg is obtained by cutting. A method for manufacturing a surface-coated laser-engravable thermosetting resin/fiber fabric-based rigid circuit board, comprising the following steps:
(A) The prepreg obtained by the method for producing a precoated sheet of a surface-coated laser-engravable thermosetting resin/fiber fabric composite according to claim 7 is cured and cut to obtain a prepreg sheet. a rigid circuit substrate;
(B) coating a surface of the rigid circuit substrate with a layer of laser-sensitive ink and irradiating the UV light, thereby forming a laser-sensitive paint film on the surface of the rigid circuit substrate;
(C) performing surface laser engraving on the rigid circuit substrate of the step (B), and forming a circuit pattern on the surface of the rigid circuit substrate;
(D) placing the rigid circuit substrate of step (C) into an electroless copper plating solution to deposit a wire loop;
(E) stacking the rigid circuit substrate of the step (D) between two sheets of the prepreg, and then thermosetting the rigid circuit substrate and the two prepreg sheets; and (F) repeating the steps (B) to (E) for producing a surface-coated laser-engravable thermosetting resin/fiber fabric-based rigid circuit board having a plurality of rigid circuit substrates. An additive type laser-engravable flexible resin film comprising the following components:
30-70 wt% of a film resin polymer;
0.1-10 wt% of a laser-sensitive additive for surface modification as described in claim 1;
0.1-15 wt% of flame retardant;
5-25 wt% filler. A method for manufacturing a flexible circuit board using the addition type laser-engravable flexible resin film according to claim 9, comprising the following steps:
(A) preparing the additive type laser-engravable flexible resin film;
(B) performing surface laser engraving on the flexible resin film, and forming a circuit pattern on the surface of the flexible resin film;
(C) placing the flexible resin film of the step (B) in an electroless copper plating solution to deposit a wire loop;
(D) laminating the flexible resin film of the step (C) on the other flexible resin film, and then the flexible resin film which has formed the wire loop and the added type laser-engravable which has not yet formed a wire loop The formed flexible resin film is autoclaved; and (E) the steps (B) to (D) are repeated to obtain the flexible circuit board having a multilayer flexible resin film.