JP5756841B2 - Method for producing cured film and method for producing electronic component - Google Patents

Description

  The present invention relates to a method for producing a cured product film in which a cured product film is formed using a curable composition having photocurability and thermosetting properties. Moreover, this invention relates to the manufacturing method and electronic component of an electronic component which applied the manufacturing method of the said hardened | cured material film.

  In an electronic device, various other electronic components are mounted on an electronic component such as a substrate, and the electronic components are electrically connected by wiring. In addition, a resist pattern or a partition wall is formed between the wirings that electrically connect the electronic components in order to ensure insulation or to function as a protective film.

  A resist pattern on a printed wiring board is generally formed by photolithography including an exposure process and a development process using a resist material called a photoresist.

  When producing a printed wiring board having a resist pattern and a copper circuit, for example, a resist layer is formed on the entire surface of the printed wiring board having a copper circuit, and the resist layer is partially exposed through a mask and developed. To partially remove the resist layer. A resist pattern is formed by development, and a printed wiring board having the resist pattern and a copper circuit is obtained.

  An example of a method for manufacturing such a printed wiring board is disclosed in Patent Document 1 below. In Patent Document 1, an exposure process and a development process in photolithography are performed.

  Another example of a method for manufacturing a printed wiring board is disclosed in Patent Document 2 below. In Patent Document 2, a resist material, which is a photocurable thermosetting composition for inkjet, is ejected from an inkjet device onto a substrate to cure the resist material.

JP-A-5-211941 WO2004 / 099272A1

  In the conventional method for manufacturing a printed wiring board as described in Patent Document 1, in order to form a resist layer, many processes such as an exposure process and a development process in photolithography are required. For this reason, the manufacturing efficiency of a printed wiring board is bad.

  Furthermore, in the conventional method for manufacturing a printed wiring board, since a development process using a chemical solution such as an acid or an alkali is performed, the environmental load is large. Furthermore, extra resist material must be used to form the resist layer portion that is removed by development. Further, the resist layer portion removed by development becomes waste. Furthermore, the copper layer removed by etching also becomes waste. For this reason, since there is much quantity of waste, there exists a problem that environmental impact is large and also the material cost of a printed wiring board also becomes high.

  In addition, in a method using a conventional ink jet apparatus as described in Patent Document 2, a resist pattern may not be formed with high accuracy. In particular, when forming a fine resist pattern, the formation accuracy tends to be further deteriorated. In addition, when the resist pattern is multilayered, the formation accuracy is likely to be further deteriorated.

  For example, there is a problem that the resist pattern cannot be formed in a predetermined shape or the resist pattern is easily peeled off from the substrate. If the resist pattern is peeled off from the substrate, the insulation may not be sufficiently secured.

  The objective of this invention is providing the manufacturing method of the hardened | cured material film which can improve the formation precision of the hardened | cured material film with thick thickness, and can improve the adhesiveness of a hardened | cured material film. It is another object of the present invention to provide an electronic component manufacturing method and an electronic component to which the cured film manufacturing method is applied.

  According to a wide aspect of the present invention, an application step of applying a liquid curable composition having photocurability and thermosetting using an inkjet device, and a first light irradiation after the application step The first irradiating step of irradiating the curable composition with light from the part to advance the curing of the curable composition to form a precured film, and after the first irradiating step On the preliminary-cured material film, the coating step and the first light irradiation step are performed, and another preliminary-cured material film is formed on the preliminary-cured material film, thereby forming a multilayer preliminary-cured material film. A multilayering step to be formed; and a heating step of heating the multilayer preliminary-cured material film after the multilayering step to cure the multilayer preliminary-cured material film to form a cured material film, An ink jet device includes an ink tank in which the curable composition is stored; A discharge portion that is connected to the ink tank and from which the curable composition is discharged; one end is connected to the discharge portion; the other end is connected to the ink tank portion; In the coating step, the curable composition is not discharged from the discharge section after being moved from the ink tank to the discharge section in the ink jet apparatus. Further, there is provided a method for producing a cured film, wherein the curable composition is applied while circulating the curable composition by flowing the curable composition through the circulation flow path portion and moving it to the ink tank.

  In a specific aspect of the method for manufacturing a cured product film according to the present invention, the method for manufacturing the cured product film is different from the first light irradiation unit after the multilayering step and before the heating step. The second light irradiation unit further includes a second light irradiation step of irradiating the multilayer preliminary-cured material film with light to further advance the curing of the multilayer preliminary-cured material film.

  On the specific situation with the manufacturing method of the hardened | cured material film | membrane which concerns on this invention, the said circulation flow path part contains the buffer tank by which the said curable composition is temporarily stored in the said circulation flow path part.

  On the specific situation with the manufacturing method of the hardened | cured material film | membrane which concerns on this invention, the temperature of the said curable composition currently circulated is 40 degreeC or more and 100 degrees C or less.

  In a specific aspect of the method for producing a cured product film according to the present invention, the inkjet device is an inkjet device using a piezo-type inkjet head, and the curable composition is applied by an action of a piezo element in the coating step. Apply.

  On the specific situation with the manufacturing method of the hardened | cured material film | membrane which concerns on this invention, the viscosity at the time of discharge of the said curable composition is 3 mPa * s or more and 1500 mPa * s or less.

  In a specific aspect of the method for producing a cured film according to the present invention, the curable composition comprises a photocurable compound, light and a thermosetting compound, a thermosetting compound, a photopolymerization initiator, And a thermosetting agent.

  On the specific situation with the manufacturing method of the hardened | cured material film | membrane which concerns on this invention, the said photocurable compound has a (meth) acryloyl group, and the said light and a thermosetting compound are a (meth) acryloyl group and cyclic ether. And the thermosetting compound has a cyclic ether group.

  In a specific aspect of the method for producing a cured film according to the present invention, the curable composition has, as the photocurable compound, a monofunctional compound having one (meth) acryloyl group, and a (meth) acryloyl group. And a polyfunctional compound having 2 or more.

  In a certain aspect of the method for producing a cured film according to the present invention, the total content of the photocurable compound and the light and thermosetting compound is 40% by weight in 100% by weight of the curable composition. As mentioned above, it is 90 weight% or less.

  According to a wide aspect of the present invention, the method includes a step of forming a cured product film on the electronic component body by the above-described method for producing a cured product film, the electronic component body, and the cured product film on the electronic component body. An electronic component manufacturing method for obtaining an electronic component comprising:

  According to a wide aspect of the present invention, there is provided an electronic component comprising an electronic component body and a cured film obtained by the above-described method for producing a cured film on the electronic component body.

  The method for producing a cured film according to the present invention includes the first light irradiation described above after the coating step of applying a liquid curable composition having photocurability and thermosetting using an inkjet apparatus. Next, the coating step and the first light irradiation step are performed on the preliminary-cured material film after the first light irradiation step described above, and another material is applied on the preliminary-cured material film. Since the heating process described above is performed after the multilayering process for forming the multilayer preliminary-cured film by forming the preliminary-cured material film, the inkjet device further includes the ink tank, the ejection unit, and the like. In the coating step, the curing that has not been ejected from the ejection unit after the curable composition is moved from the ink tank to the ejection unit in the inkjet device in the application step. The composition is By flowing through the flow path and moving to the ink tank, the curable composition is applied while being circulated, so that the formation accuracy of a thick cured film can be increased and the cured film can be closely adhered. Can increase the sex.

Drawing 1 (a)-(e) is a sectional view for explaining each process of a manufacturing method of a hardened material film concerning one embodiment of the present invention. FIG. 2 is a front cross-sectional view schematically showing an electronic component including a cured product film obtained by the method for producing a cured product film according to an embodiment of the present invention. FIG. 3 is a schematic configuration diagram showing an example of an ink jet apparatus used in the method for producing a cured film according to an embodiment of the present invention. FIG. 4 is a schematic configuration diagram showing another example of an ink jet apparatus used in the method for manufacturing a cured film according to an embodiment of the present invention.

  Hereinafter, the present invention will be described in detail.

  The manufacturing method of the hardened | cured material film | membrane which concerns on this invention is equipped with the application | coating process which apply | coats the liquid curable composition which has photocurability and thermosetting using an inkjet apparatus. Moreover, the manufacturing method of the hardened | cured material film | membrane which concerns on this invention irradiates light to the said curable composition from the 1st light irradiation part after the said application | coating process, advances hardening of the said curable composition, A first light irradiation step for forming a precured material film is provided. Furthermore, the manufacturing method of the hardened | cured material film | membrane which concerns on this invention performs the said application | coating process and the said 1st light irradiation process on the said precured material film after the said 1st light irradiation process, and performs the said precuring. A multi-layering step of forming a multi-layer precured material film by forming another precured material film on the material film is provided. Furthermore, in the method for producing a cured film according to the present invention, after the multilayering step, the multilayer precured film is heated to cure the multilayer precured film to form a cured film. A heating process is further provided.

  In the method for producing a cured film according to the present invention, the inkjet device is connected to the ink tank in which the curable composition is stored, the ink tank, and the curable composition is discharged. The discharge section has one end connected to the discharge section, the other end connected to the ink tank section, and a circulation flow path section through which the curable composition flows.

  In the method for producing a cured film according to the present invention, in the coating step, the curable composition was not ejected from the ejection unit after being moved from the ink tank to the ejection unit in the inkjet apparatus. The curable composition is applied while circulating the curable composition by flowing through the circulation channel and moving to the ink tank.

  In the present invention, the specific application step, the specific first light irradiation step, the specific multi-layering step, and the specific heating step are performed. In the apparatus, after the curable composition is moved from the ink tank to the discharge portion, the curable composition that has not been discharged from the discharge portion is allowed to flow through the circulation flow path portion to the ink tank. By moving, the curable composition is applied while being circulated, so that the formation accuracy of the cured film having a large thickness can be increased and the adhesion of the cured film can be increased. In order to obtain the effects of the present invention, it is significant to apply the curable composition while circulating it.

  Moreover, in this invention, even if it is a hardened | cured material film | membrane multilayered, it can form finely and with high precision. In the present invention, a fine cured product film can be formed with high accuracy.

  Furthermore, in the present invention, it is possible to form a cured product film having a good predetermined shape without performing many steps such as an exposure step and a development step in photolithography. For this reason, the amount of waste can be reduced, the environmental load can be reduced, and the material cost for forming the electronic component can also be reduced.

  Hereinafter, the present invention will be clarified by describing specific embodiments and examples of the present invention with reference to the drawings.

  FIG. 2: is sectional drawing which shows an electronic component provided with the hardened | cured material film obtained by the manufacturing method of the hardened | cured material film which concerns on one Embodiment of this invention.

  An electronic component 1 shown in FIG. 2 includes an electronic component main body 2 (first electronic component main body) and a multilayer cured film 3 disposed on the surface of the electronic component main body 2. The multilayer cured product film 3 has a plurality of cured product films 3A, 3B, 3C. In the multilayer cured product film 3, a plurality of cured product films 3A, 3B, 3C are laminated. The multilayer cured product film 3 is a cured product film after heating. The second electronic component main body may be disposed on the surface of the multilayer cured product 3 opposite to the first electronic component main body 2 side.

  Specific examples of the electronic component body include semiconductor chips, semiconductor wafers after dicing (divided semiconductor wafers), capacitors, diodes, printed boards, flexible printed boards, glass epoxy boards, and glass boards. The electronic component body may have a cured product film on the surface. In the electronic component main body having a cured product film, a cured product film may be formed on the cured product film.

  The manufacturing method of the hardened | cured material film | membrane which concerns on one embodiment of the following this invention is demonstrated.

  First, as shown to Fig.1 (a), the curable composition 12 which has photocurability and thermosetting, and is liquid is apply | coated on the electronic component main body 2 using the inkjet apparatus 11 (application | coating). Process). Here, the curable composition 12 is applied to the entire surface of the electronic component body 2. After application, the droplets of the curable composition 12 are mixed with each other, and the state shown in FIG.

  As shown in FIG. 3, the ink jet device 11 includes an ink tank 21, a discharge unit 22, and a circulation flow path unit 23 inside.

  The circulation channel unit 23 includes a buffer tank 23A and a pump 23B in the circulation channel unit 23. However, like the ink jet device 11X shown in FIG. 4, the circulation flow path portion 23X may not have a buffer tank and a pump in the circulation flow path portion 23X. The circulation channel section preferably has the buffer tank in the circulation channel section, and preferably has the pump. Moreover, the said circulation flow path part may have a flowmeter, a thermometer, a filter, etc. other than a buffer tank and a pump in the said circulation flow path part.

  The ink tank 21 stores the curable composition. The said curable composition is discharged from the discharge part 22 (inkjet head). The discharge unit 22 includes a discharge nozzle. A discharge unit 22 is connected to the ink tank 21. The ink tank 21 and the ejection part 22 are connected via a flow path. One end of the circulation flow path portion 23 is connected to the ejection portion 22, and the other end is connected to the ink tank 21. The curable composition flows through the circulation channel portion 23.

  When the buffer tank 23A or the pump 23B is provided, the buffer tank 23A and the pump 23B are preferably disposed between the ejection unit 22 and the ink tank 21, respectively. The buffer tank 23A is disposed closer to the discharge unit 22 than the pump 23B. The pump 23B is disposed closer to the ink tank 21 than the buffer tank 23A. The curable composition is temporarily stored in the buffer tank 23A.

  Examples of the ejection unit include a thermal type, bubble jet type, electromagnetic valve type, or piezoelectric type inkjet head. Further, examples of the circulation flow path section in the discharge section include an end shooter type branching from a common circulation flow path (manifold) to the coating nozzle and a side shooter type in which ink circulates through the coating nozzle. From the viewpoint of further improving the discharge accuracy of the curable composition and further improving the formation accuracy of the fine cured product film, the inkjet device is an inkjet device using a piezoelectric inkjet head, and in the coating step, a piezoelectric element is used. It is preferable to apply the curable composition by the action of the above.

  Regarding the method for circulating the curable composition, it is possible to circulate by utilizing the weight of the ink or by applying pressure, depressurization or the like using a pump or the like. A plurality of these may be used in combination. Examples of the pump include a cylinder-type non-pulsation pump, a propeller pump, a gear pump, and a diaphragm pump. From the viewpoint of increasing the circulation efficiency and further improving the formation accuracy of the fine cured product film, the circulation channel part preferably includes a pump for transferring the curable composition into the circulation channel part.

  In the coating nozzle of the discharge unit, it is preferable that the pressure is kept at an appropriate pressure and that the pressure fluctuation (pulsation) is small within the range. When a pump or the like is used, it is preferable to provide an attenuator between the pump and the discharge unit in order to suppress pump pulsation. Examples of such an attenuator include a buffer tank in which the curable composition is temporarily stored and a membrane damper.

  From the viewpoint of further increasing the formation accuracy of the cured product film having a large thickness, the circulation channel part preferably includes a buffer tank in which the curable composition is temporarily stored in the circulation channel part.

  In the application step, after the curable composition is moved from the ink tank 21 to the discharge unit 22 in the ink jet apparatus 11, the curable composition that has not been discharged from the discharge unit 22 is removed from the circulation flow path unit. 23 is moved to the ink tank 21. Thereby, in the application step, the curable composition is applied while being circulated.

  Next, as shown in FIGS. 1B and 1C, after the coating step, the curable composition 12 after application is irradiated with light from the first light irradiation unit 13, and the curable composition is then irradiated. 12 is allowed to proceed (first light irradiation step). Thereby, the precured material film 12 </ b> A irradiated with light by the first light irradiation unit 13 is formed. When light is irradiated from the second light irradiation unit 14 to be described later, the wavelength or irradiation intensity of light irradiated from the first light irradiation unit 13 and the light irradiated from the second light irradiation unit 14 to be described later The wavelength and irradiation intensity may be the same or different. From the viewpoint of further improving the curability of the cured film, the irradiation intensity of the light irradiated from the second light irradiation unit 14 is stronger than the irradiation intensity of the light irradiated from the first light irradiation unit 13. preferable. When using a photocurable compound and light and a thermosetting compound, in order to control photocurability, it is preferable to perform the said 1st light irradiation process and the 2nd light irradiation process mentioned later. .

  In addition, in order to “light the curable composition 12 after application from the first light irradiating unit 13 and advance the curing of the curable composition 12”, the reaction is allowed to proceed to increase the viscosity. It is also included.

  The device that performs light irradiation is not particularly limited, and examples thereof include a light emitting diode (UV-LED) that generates ultraviolet rays, a metal halide lamp, a high pressure mercury lamp, and an ultrahigh pressure mercury lamp. From the viewpoint of further improving the accuracy of forming the cured film, it is particularly preferable to use a UV-LED for the first light irradiation section.

  Next, as shown in FIGS. 1C and 1D, on the preliminary-cured material film 12A after the first light irradiation step, the coating step and the first light irradiation step are performed. And forming the other preliminary-cured material films 12B and 12C on the preliminary-cured material film 12A, thereby forming a multilayer preliminary-cured material film 12X (multilayering step). The multilayer precured material film 12X includes precured material films 12A, 12B, and 12C. The coating step and the first light irradiation step are performed a plurality of times to increase the number of stacked layers.

  Next, as shown in FIGS. 1D and 1E, after the multi-layering step, a multi-layer precured material film is formed from the second light irradiation unit 14 different from the first light irradiation unit 13. 12X (preliminarily cured material films 12A, 12B, 12C) is irradiated with light to further advance the curing of the multilayered preliminary cured material film 12X (second light irradiation step). Thereby, the preliminary-cured material film 12Y irradiated with light by the second light irradiation unit 14 is formed.

  The second light irradiation step is preferably performed before the heating step described later. From the viewpoint of further increasing the formation accuracy of the thick cured film, it is preferable that the second light irradiation step is performed. However, the second light irradiation step is not necessarily performed, and a heating step described later may be performed after the multilayering step without performing the second light irradiation step.

  Next, after the multilayering step and the second light irradiation step, the preliminary-cured material film 12Y is heated to cure the preliminary-cured material film 12Y irradiated with light by the second light irradiation unit 14. Then, the cured product film 3 is formed (heating step). If the second light irradiation step is not performed after the multilayering step, the multilayer preliminary-cured material film 12X is heated after the multilayering step to cure the multilayer preliminary-cured material film 12X. Thus, a cured product film can be formed (heating step). In this way, the electronic component 1 shown in FIG. 2 can be obtained.

  In the manufacturing method of said hardened | cured material film, the said curable composition currently circulated from a viewpoint which raises the discharge property and transportability of a curable composition, and raises the formation precision of a hardened | cured material film with thick thickness further. The temperature is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, preferably 120 ° C. or lower, more preferably 100 ° C. or lower.

  From the viewpoint of increasing the dischargeability of the curable composition and further increasing the accuracy of forming a thick cured film, the viscosity at the time of discharging the curable composition is preferably 3 mPa · s or more, more preferably 5 mPa. S or more, preferably 1500 mPa · s or less, more preferably 1200 mPa · s or less.

  The viscosity is measured at an ejection temperature using an E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.) in accordance with JIS K2283.

  The said curable composition has photocurability and thermosetting. The said curable composition contains a photocurable component and a thermosetting component. The curable composition includes a photocurable compound (a curable compound that can be cured by light irradiation), a thermosetting compound (a curable compound that can be cured by heating), a photopolymerization initiator, and a thermosetting agent. Are preferably included. The curable composition comprises a photocurable compound, a light and thermosetting compound (a curable compound that can be cured by both light irradiation and heating), a thermosetting compound, a photopolymerization initiator, and heat. It preferably contains a curing agent. It is preferable that the said curable composition contains a hardening accelerator.

  Hereinafter, the detail of each component contained in the said curable composition is demonstrated.

(Curable compound)
(Photocurable compound)
Examples of the photocurable compound include a curable compound having a (meth) acryloyl group, a curable compound having a vinyl group, and a curable compound having a maleimide group. From the viewpoint of further improving the formation accuracy of the cured film having a large thickness, the photocurable compound preferably has a (meth) acryloyl group (one or more). As for the said photocurable compound, only 1 type may be used and 2 or more types may be used together.

  In the present specification, the curable compound having the (meth) acryloyl group means a compound having at least one of a methacryloyl group and an acryloyl group.

  As the photocurable compound, a polyfunctional compound (A1) having two or more photoreactive groups may be used, or a monofunctional compound (A2) having one photoreactive group may be used.

  From the viewpoint of further increasing the formation accuracy of a cured product film having a large thickness, the curable composition has, as the photocurable compound, a monofunctional compound (A2) having one (meth) acryloyl group, And a polyfunctional compound (A1) having two or more acryloyl groups.

  Examples of the polyfunctional compound (A1) include (meth) acrylic acid adducts of polyhydric alcohols, (meth) acrylic acid adducts of alkylene oxide modified products of polyhydric alcohols, urethane (meth) acrylates, and polyesters (meta ) Acrylates and the like. Examples of the polyhydric alcohol include diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, trimethylol propane, cyclohexane dimethanol, tricyclodecane dimethanol, an alkylene oxide adduct of bisphenol A, and Examples include pentaerythritol.

    Specific examples of the polyfunctional compound (A1) include tricyclodecane dimethanol di (meth) acrylate, isobornyl dimethanol di (meth) acrylate, dicyclopentenyl dimethanol di (meth) acrylate, and the like. Especially, it is preferable that the said polyfunctional compound (A1) is tricyclodecane dimethanol di (meth) acrylate from a viewpoint of improving the heat-and-moisture resistance of hardened | cured material further. The term “(meth) acrylate” refers to acrylate and methacrylate.

  The term “(meth) acrylate” refers to acrylate or methacrylate. The term “(meth) acryl” refers to acryl or methacryl.

  The polyfunctional compound (A1) is preferably a polyfunctional compound (A1) having a polycyclic skeleton and having two or more (meth) acryloyl groups. The use of the polyfunctional compound (A1) can increase the heat and moisture resistance of the cured product of the curable composition. Therefore, the reliability of the electronic component can be increased.

  The polyfunctional compound (A1) is not particularly limited as long as it has a polycyclic skeleton and two or more (meth) acryloyl groups. As the polyfunctional compound (A1), a conventionally known polyfunctional compound having a polycyclic skeleton and having two or more (meth) acryloyl groups can be used. Since the polyfunctional compound (A1) has two or more (meth) acryloyl groups, the polymerization proceeds and is cured by light irradiation. As for the said polyfunctional compound (A1), only 1 type may be used and 2 or more types may be used together.

  Specific examples of the polyfunctional compound (A1) include tricyclodecane dimethanol di (meth) acrylate, isobornyl dimethanol di (meth) acrylate, dicyclopentenyl dimethanol di (meth) acrylate, and the like. Especially, it is preferable that the said polyfunctional compound (A1) is tricyclodecane dimethanol di (meth) acrylate from a viewpoint of improving the heat-and-moisture resistance of hardened | cured material further.

  The “polycyclic skeleton” in the polyfunctional compound (A1) and the monofunctional compound (A2) described later indicates a structure having a plurality of cyclic skeletons continuously. Examples of the polycyclic skeleton in the polyfunctional compound (A1) and the monofunctional compound (A2) include a polycyclic alicyclic skeleton and a polycyclic aromatic skeleton.

  Examples of the polycyclic alicyclic skeleton include a bicycloalkane skeleton, a tricycloalkane skeleton, a tetracycloalkane skeleton, and an isobornyl skeleton.

  Examples of the polycyclic aromatic skeleton include naphthalene ring skeleton, anthracene ring skeleton, phenanthrene ring skeleton, tetracene ring skeleton, chrysene ring skeleton, triphenylene ring skeleton, tetraphen ring skeleton, pyrene ring skeleton, pentacene ring skeleton, picene ring skeleton and Examples include perylene ring skeletons.

  Specific examples of the monofunctional compound (A2) include isobornyl (meth) acrylate, dihydroxycyclopentadienyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopenta Examples include nyl (meth) acrylate and naphthyl (meth) acrylate. Among these, from the viewpoint of further improving the heat and heat resistance of the cured product, the monofunctional compound (A2) is composed of isobornyl (meth) acrylate, dihydroxycyclopentadienyl (meth) acrylate, dicyclopentenyl (meth) acrylate, di It is preferably at least one selected from the group consisting of cyclopentenyloxyethyl (meth) acrylate and dicyclopentanyl (meth) acrylate.

  Examples of the compound having a vinyl group include vinyl ethers, ethylene derivatives, styrene, chloromethyl styrene, α-methyl styrene, maleic anhydride, dicyclopentadiene, N-vinyl pyrrolidone, and N-vinyl formamide.

  The compound having a maleimide group is not particularly limited. For example, N-methylmaleimide, N-ethylmaleimide, N-hexylmaleimide, N-propylmaleimide, N-butylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, Np-carboxyphenylmaleimide, Np-hydroxyphenylmaleimide, Np-chlorophenylmaleimide, Np-tolylmaleimide, Np-xylylmaleimide, N- o-chlorophenylmaleimide, N-o-tolylmaleimide, N-benzylmaleimide, N-2,5-diethylphenylmaleimide, N-2,5-dimethylphenylmaleimide, Nm-tolylmaleimide, N-α-naphthylmaleimide , N-o Xylylmaleimide, Nm-xylylmaleimide, bismaleimide methane, 1,2-bismaleimide ethane, 1,6-bismaleimide hexane, bismaleimide dodecane, N, N′-m-phenylenedimaleimide, N, N '-P-phenylenedimaleimide, 4,4'-bismaleimide diphenyl ether, 4,4'-bismaleimide diphenylmethane, 4,4'-bismaleimide-di (3-methylphenyl) methane, 4,4'-bismaleimide -Di (3-ethylphenyl) methane, 4,4'-bismaleimide-di (3-methyl-5-ethyl-phenyl) methane, N, N '-(2,2-bis- (4-phenoxyphenyl) Propane) dimaleimide, N, N'-2,4-tolylene dialeimide, N, N'-2,6-tolylene dialeimide, and N, N'-m-xylylene dimaleimide and the like can be mentioned.

  From the viewpoint of further increasing the insulation reliability and adhesion reliability, the photocurable compound preferably has a dicyclopentadiene skeleton.

  From the viewpoint of further increasing the accuracy of forming a cured film having a large thickness, the content of the photocurable compound is preferably 40% by weight or more, more preferably 50% by weight in 100% by weight of the curable composition. As mentioned above, Preferably it is 90 weight% or less, More preferably, it is 85 weight% or less.

(Light and thermosetting compounds)
Examples of the light and thermosetting compounds include compounds having various photocurable functional groups and various thermosetting functional groups. From the viewpoint of further increasing the formation accuracy of a cured film having a large thickness, the light and thermosetting compound preferably has a (meth) acryloyl group and a cyclic ether group, and a (meth) acryloyl group and an epoxy group. It is preferable to have. As for the said light and a thermosetting compound, only 1 type may be used and 2 or more types may be used together.

  Although it does not specifically limit as said light and a thermosetting compound, The compound which has a (meth) acryloyl group and an epoxy group, the partial (meth) acrylate of an epoxy compound, a urethane modified (meth) acryl epoxy compound, etc. are mentioned. .

  Examples of the compound having the (meth) acryloyl group and the epoxy group include glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether.

  The partial (meth) acrylated product of the epoxy compound can be obtained by reacting an epoxy compound and (meth) acrylic acid in the presence of a catalyst according to a conventional method. Examples of the epoxy compound that can be used for the partial (meth) acrylate of the epoxy compound include novolac-type epoxy compounds and bisphenol-type epoxy compounds. Examples of the novolak type epoxy compound include a phenol novolak type epoxy compound, a cresol novolak type epoxy compound, a biphenyl novolak type epoxy compound, a trisphenol novolak type epoxy compound, a dicyclopentadiene novolak type epoxy compound, and the like. Examples of the bisphenol type epoxy compound include a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a 2,2′-diallyl bisphenol A type epoxy compound, a hydrogenated bisphenol type epoxy compound, and a polyoxypropylene bisphenol A type epoxy compound. Can be mentioned. By appropriately changing the blending amount of the epoxy compound and (meth) acrylic acid, an epoxy compound having a desired acrylate ratio can be obtained. The blending amount of the carboxylic acid with respect to 1 equivalent of epoxy group is preferably 0.1 equivalent or more, more preferably 0.2 equivalent or more, preferably 0.7 equivalent or less, more preferably 0.5 equivalent or less.

  The urethane-modified (meth) acryl epoxy compound is obtained, for example, by the following method. A polyol and a bifunctional or higher functional isocyanate are reacted, and the remaining isocyanate group is reacted with a (meth) acryl monomer having an acid group and glycidol. Alternatively, a (meth) acryl monomer having a hydroxyl group in a bifunctional or higher isocyanate and glycidol may be reacted without using a polyol. Alternatively, the urethane-modified (meth) acryl epoxy compound can be obtained by reacting glycidol with a (meth) acrylate monomer having an isocyanate group. Specifically, for example, first, 1 mol of trimethylolpropane and 3 mol of isophorone diisocyanate are reacted under a tin-based catalyst. The urethane-modified (meth) acrylic epoxy compound is obtained by reacting the isocyanate group remaining in the obtained compound with hydroxyethyl acrylate which is an acrylic monomer having a hydroxyl group and glycidol which is an epoxy having a hydroxyl group.

  The polyol is not particularly limited, and examples thereof include ethylene glycol, glycerin, sorbitol, trimethylolpropane, and (poly) propylene glycol.

  The isocyanate is not particularly limited as long as it is bifunctional or higher. Examples of the isocyanate include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4′-diisocyanate (MDI), and hydrogenated MDI. , Polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethyl Examples include xylene diisocyanate and 1,6,10-undecane triisocyanate.

  From the viewpoint of further increasing the formation accuracy of the cured product film having a large thickness, the content of the light and thermosetting compound in the curable composition of 100% by weight is preferably 0.5% by weight or more, more preferably. Is 1% by weight or more, preferably 60% by weight or less, more preferably 50% by weight or less.

  From the viewpoint of further increasing the formation accuracy of the cured film having a large thickness, the total content of the photocurable compound and the light and thermosetting compound in 100% by weight of the curable composition is preferably It is 40% by weight or more, more preferably 50% by weight or more, preferably 90% by weight or less, more preferably 85% by weight or less.

(Thermosetting compound)
Examples of the thermosetting compound include a thermosetting compound having a cyclic ether group, a thermosetting compound having a thiirane group, and the like. From the viewpoint of further increasing the formation accuracy of the cured film having a large thickness, the thermosetting compound is preferably a thermosetting compound having a cyclic ether group, and a thermosetting compound having an epoxy group (epoxy compound). ) Is more preferable. As for the said thermosetting compound, only 1 type may be used and 2 or more types may be used together.

  The epoxy compound is not particularly limited, and examples thereof include novolak type epoxy compounds and bisphenol type epoxy compounds. Examples of the novolak type epoxy compound include a phenol novolak type epoxy compound, a cresol novolak type epoxy compound, a biphenyl novolak type epoxy compound, a trisphenol novolak type epoxy compound, a dicyclopentadiene novolak type epoxy compound, and the like. Examples of the bisphenol type epoxy compound include a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a 2,2′-diallyl bisphenol A type epoxy compound, a hydrogenated bisphenol type epoxy compound, and a polyoxypropylene bisphenol A type epoxy compound. Can be mentioned. In addition, examples of the epoxy compound include a cycloaliphatic epoxy compound and glycidylamine.

  From the viewpoint of further improving the accuracy of forming a cured film having a large thickness, the content of the thermosetting compound is preferably 3% by weight or more, more preferably 5% by weight in 100% by weight of the curable composition. As mentioned above, Preferably it is 60 weight% or less, More preferably, it is 50 weight% or less.

(Photopolymerization initiator)
Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. As for the said photoinitiator, only 1 type may be used and 2 or more types may be used together.

  The photo radical polymerization initiator is not particularly limited. The photo radical polymerization initiator is a compound for generating radicals upon light irradiation and initiating a radical polymerization reaction. Specific examples of the photo radical polymerization initiator include, for example, benzoin, benzoin alkyl ethers, acetophenones, aminoacetophenones, anthraquinones, thioxanthones, ketals, 2,4,5-triarylimidazole dimers, Examples include riboflavin tetrabutyrate, thiol compounds, 2,4,6-tris-s-triazine, organic halogen compounds, benzophenones, xanthones, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. As for the said radical photopolymerization initiator, only 1 type may be used and 2 or more types may be used together.

  A photopolymerization initiation assistant may be used together with the photo radical polymerization initiator. Examples of the photopolymerization initiation assistant include N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine. Photopolymerization initiation assistants other than these may be used. As for the said photoinitiation adjuvant, only 1 type may be used and 2 or more types may be used together.

  In addition, a titanocene compound such as CGI-784 (manufactured by Ciba Specialty Chemicals) having absorption in the visible light region may be used to promote the photoreaction.

  It does not specifically limit as said photocationic polymerization initiator, For example, a sulfonium salt, an iodonium salt, a metallocene compound, a benzoin tosylate etc. are mentioned. As for the said photocationic polymerization initiator, only 1 type may be used and 2 or more types may be used together.

  In 100% by weight of the curable composition, the content of the photopolymerization initiator is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, preferably 10% by weight or less, more preferably 5% by weight. % Or less.

(Thermosetting agent)
Examples of the thermosetting agent include organic acids, amine compounds, amide compounds, hydrazide compounds, imidazole compounds, imidazoline compounds, phenol compounds, urea compounds, polysulfide compounds, and acid anhydrides. A modified polyamine compound such as an amine-epoxy adduct may be used as the thermosetting agent. Thermosetting agents other than these may be used. As for the said thermosetting agent, only 1 type may be used and 2 or more types may be used together.

  The amine compound means a compound having one or more primary to tertiary amino groups. Examples of the amine compound include (1) aliphatic polyamines, (2) alicyclic polyamines, (3) aromatic polyamines, (4) hydrazides, and (5) guanidine derivatives. In addition, epoxy compound addition polyamine (reaction product of epoxy compound and polyamine), Michael addition polyamine (reaction product of α, β unsaturated ketone and polyamine), Mannich addition polyamine (condensate of polyamine, formalin and phenol), thiourea addition Adducts such as polyamine (reaction product of thiourea and polyamine) and ketone-capped polyamine (reaction product of ketone compound and polyamine [ketimine]) may also be used.

  Examples of the (1) aliphatic polyamine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and diethylaminopropylamine.

  Examples of the (2) alicyclic polyamine include mensendiamine, isophoronediamine, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5, 5) Undecane adduct, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane and the like.

  Examples of the aromatic polyamine (3) include m-phenylenediamine, p-phenylenediamine, o-xylenediamine, m-xylenediamine, p-xylenediamine, 4,4-diaminodiphenylmethane, 4,4-diaminodiphenylpropane, 4,4-diaminodiphenylsulfone, 4,4-diaminodicyclohexane, bis (4-aminophenyl) phenylmethane, 1,5-diaminonaphthalene, 1,1-bis (4-aminophenyl) cyclohexane, 2,2- Bis [(4-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] sulfone, 1,3-bis (4-aminophenoxy) benzene, 4,4-methylene-bis (2-chloro) Aniline), and 4,4-diaminodiphenylsulfone It is.

  Examples of (4) hydrazide include carbodihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, and isophthalic acid dihydrazide.

  Examples of the guanidine derivative (5) include dicyandiamide, 1-o-tolyldiguanide, α-2,5-dimethylguanide, α, ω-diphenyldiguanide, α, α-bisguanylguanidinodiphenyl ether, p-chlorophenyldiguanide, Examples include α, α-hexamethylenebis [ω- (p-chlorophenol)] diguanide, phenyldiguanide oxalate, acetylguanidine, and diethylcyanoacetylguanidine.

  Examples of the phenol compound include polyhydric phenol compounds. Examples of the polyhydric phenol compound include phenol, cresol, ethylphenol, butylphenol, octylphenol, bisphenol A, tetrabromobisphenol A, bisphenol F, bisphenol S, 4,4′-biphenylphenol, naphthalene skeleton-containing phenol novolac resin, Examples thereof include a xylylene skeleton-containing phenol novolak resin, a dicyclopentadiene skeleton-containing phenol novolak resin, and a fluorene skeleton-containing phenol novolak resin.

  Examples of the acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, dodecyl succinic anhydride, chlorendic acid, pyromellitic anhydride, Examples include benzophenone tetracarboxylic acid anhydride, methylcyclohexene tetracarboxylic acid anhydride, trimellitic anhydride, and polyazeline acid anhydride.

  In 100% by weight of the curable composition, the content of the thermosetting agent is preferably 1% by weight or more, more preferably 5% by weight or more, preferably 60% by weight or less, more preferably 50% by weight or less.

(Curing accelerator)
Examples of the curing accelerator include tertiary amines, imidazoles, quaternary ammonium salts, quaternary phosphonium salts, organometallic salts, phosphorus compounds, urea compounds, and the like.

  In 100% by weight of the curable composition, the content of the curing accelerator is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 10% by weight or less, more preferably 5% by weight. It is as follows.

(Other ingredients)
The curable composition may contain other components. Although it does not specifically limit as another component, Adhesion adjuvants, such as a coupling agent, a pigment, dye, a leveling agent, an antifoamer, a polymerization inhibitor, etc. are mentioned.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited only to the following examples.

(Synthesis Example 1)
In a three-necked separable flask equipped with a stirrer, a thermometer, and a dropping funnel, 50 g of methyl cellosolve, 15 g of dicyandiamide, and 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl 1 g of -s-triazine was added and heated to 100 ° C. to dissolve dicyandiamide. After dissolution, 130 g of butyl glycidyl ether was added dropwise from the dropping funnel over 20 minutes and reacted for 1 hour. Thereafter, the temperature was lowered to 60 ° C., and the solvent was removed under reduced pressure to obtain a pale yellow reaction viscous product (thermosetting agent A).

(Preparation of curable composition A)
30 parts by weight of trimethylolpropane triacrylate (TMPTA, manufactured by Daicel Ornex) as a photocurable compound, 30 parts by weight of tricyclodecane dimethanol diacrylate (IRR-214K, manufactured by Daicel Ornex) as a photocurable compound, 10 parts by weight of an acrylic acid adduct of bisphenol A type epoxy compound (UVACURE 1561, manufactured by Daicel Ornex) as a light and thermosetting compound, and 30 parts by weight of bisphenol A type epoxy compound (EXA850CRP, manufactured by DIC) as a thermosetting compound , 7.5 parts by weight of thermosetting agent A (synthesized in Synthesis Example 1) as a thermosetting agent, 1 part by weight of DBU-octylate (UCAT SA102, manufactured by San Apro) as a curing accelerator, and 2 parts as a photopolymerization initiator -Benzyl-2-dimethylamino-4 A curable composition A was obtained by uniformly mixing 5 parts by weight of morpholinobyllophenone (IRUGACURE369, manufactured by BASF).

  Using a viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.) at a circulation temperature (temperature at the time of discharge) during film formation and fine pattern formation described below, the viscosity of the curable composition A obtained was 10 rpm. It was measured.

(Preparation of curable compositions B to H)
The components shown in Table 1 below were prepared in the same manner as in the preparation of the curable composition A except that the components shown in Table 2 below were added. The viscosity of the obtained curable compositions B to H was also measured in the same manner as the viscosity of the curable composition A.

Example 1
(1) Film formation An FR-4 substrate (“R-1705” manufactured by Panasonic Electric Works Co., Ltd. (plate thickness 0.8 mm)) and a catalyst (“Catalyst 44” manufactured by Rohm and Haas) and a copper plating solution (Rohm and Haas) “Cuposit 253” manufactured by the company was disposed, and a copper plating layer as a copper wiring was partially formed to obtain a substrate (copper-clad laminate).

  In accordance with the electronic component manufacturing method according to the embodiment of the present invention described above, the cured product is subjected to the steps shown in FIGS. 1A to 1E (however, the conditions are set as shown in Table 3 below). A film was formed. While the curable composition A is circulated, the coating step for coating and the first light irradiation step are repeated 10 times, and then the heating step is performed to form a cured product film, which is an electronic component. A printed wiring board was obtained. In the coating step, coating was performed while circulating the curable composition. The coating pattern was a flat film of 5 cm × 5 cm, and 20 films were formed.

(2) Fine pattern formation A FR-4 substrate (“R-1705” manufactured by Panasonic Electric Works Co., Ltd. (plate thickness: 0.8 mm)) and a catalyst (“Catalyst 44” manufactured by Rohm and Haas)) and a copper plating solution (Rohm and A “Cuposit 253” manufactured by Haas Co., Ltd.) was placed, and a copper plating layer as a copper wiring was partially formed to obtain a substrate (copper-clad laminate).

  In accordance with the electronic component manufacturing method according to the embodiment of the present invention described above, the cured product is subjected to the steps shown in FIGS. 1A to 1E (however, the conditions are set as shown in Table 3 below). A film was formed. While the curable composition A is circulated, the coating step for coating and the first light irradiation step are repeated 10 times, and then the heating step is performed to form a cured product film, which is an electronic component. A printed wiring board was obtained. In the coating step, coating was performed while circulating the curable composition. The coating pattern was coated so that the line width was 150 μm and the distance between the lines was 300 μm.

(Examples 2 to 11 and Comparative Examples 1 to 4)
Film formation and fine pattern formation were performed in the same manner as in Example 1 except that the type of the curable composition and the production conditions were changed as shown in Table 3 below.

(Evaluation)
(1) Evaluation of the substrate on which the film was formed (confirmation of missing coating)
The film was confirmed with a stereomicroscope ("SMZ-10" manufactured by Nikon Corporation), and liquid leakage was confirmed.

[Criteria for film formation]
○: The pattern with omission is 0/20
Δ: Missing pattern is 1/20 or more, 4/20 or less. X: Missing pattern is 5/20 or more.

(2) Evaluation of substrate on which fine pattern was formed Using an optical microscope (digital microscope VH-Z100, manufactured by Keyence Corporation), the line and the interval between the lines were measured at 30 points (excluding the part where there was a drop during application). .

[Judgment criteria for fine pattern formation]
○○: Line width is 150 ± 30μm
○: Not equivalent to ○○, line width is 150 ± 50μm
Δ: Not equivalent to ○○ and ○, line width is 150 ± 80 μm
×: Does not correspond to ○○, ○ and △, and the line width is 150 ± 120 μm
XX: There is no gap between lines

(3) Evaluation of adhesion of cured film on substrate on which film is formed (long-term reliability: evaluation of thermal cycle)
The substrate on which the film was formed was held at −50 ° C. for 5 minutes using a liquid tank thermal shock tester (“TSB-51” manufactured by ESPEC), then heated to 125 ° C. and 5 ° C. at 125 ° C. A cold cycle test was conducted in which the temperature was lowered to -50 ° C after being held for 1 minute, and the cycle was one cycle. The substrate was taken out after 500 cycles.

  The substrate was observed with a stereomicroscope ("SMZ-10" manufactured by Nikon Corporation), and peeling was confirmed.

[Adhesion criteria]
○: not peeled △: slightly peeled (no problem in use)
×: Exfoliated greatly (there is a problem in use)

  The results are shown in Table 3 below.

DESCRIPTION OF SYMBOLS 1 ... Electronic component 2 ... Electronic component main body 3 ... Multilayer hardened | cured material film (after a heating)
3A, 3B, 3C ... cured product film (after heating)
DESCRIPTION OF SYMBOLS 11, 11X ... Inkjet apparatus 12 ... Curable composition 12A, 12B, 12C ... Precured material film irradiated with light by 1st light irradiation part 12X ... Multilayer precured material film 12Y ... 2nd light irradiation part Multi-layer pre-cured product film irradiated with light 13... First light irradiation unit 14... Second light irradiation unit 21... Ink tank 22 ... Ejection unit 23, 23X ... Circulation flow path unit 23A ... Buffer tank 23B ... pump

Claims (7)

An application step of applying a liquid curable composition having photocurability and thermosetting using an inkjet device;
A first light irradiation step of forming a preliminary-cured product film by irradiating the curable composition with light from a first light irradiation unit after the coating step to advance the curing of the curable composition; ,
Performing the coating step and the first light irradiation step on the preliminary-cured material film after the first light irradiation step to form another preliminary-cured material film on the preliminary-cured material film. A multilayering process for forming a multilayer precured film,
A heating step of heating the multilayer preliminary-cured material film after the multilayering step, curing the multilayer preliminary-cured material film, and forming a cured material film;
The ink jet device includes an ink tank in which the curable composition is stored, a discharge unit that is connected to the ink tank and discharges the curable composition, and one end connected to the discharge unit. The other end is connected to the ink tank portion, and has a circulation flow path portion through which the curable composition flows.
In the application step, after the curable composition is moved from the ink tank to the discharge unit in the ink jet apparatus, the curable composition that has not been discharged from the discharge unit is placed in the circulation channel unit. The cured product film is applied by circulating and moving the curable composition by circulating it to the ink tank.   After the multilayering step and before the heating step, the multilayer preliminary-cured material film is irradiated with light from a second light-irradiation unit different from the first light-irradiation unit, and the multilayer preliminary curing is performed. The manufacturing method of the hardened | cured material film | membrane of Claim 1 further equipped with the 2nd light irradiation process which further advances hardening of a physical film.   The manufacturing method of the hardened | cured material film | membrane of Claim 1 or 2 with which the said circulation flow path part contains the buffer tank by which the said curable composition is temporarily stored in the said circulation flow path part.   The manufacturing method of the hardened | cured material film | membrane of any one of Claims 1-3 whose temperature of the said curable composition currently circulated is 40 degreeC or more and 100 degrees C or less. The inkjet device is an inkjet device using a piezoelectric inkjet head;
The manufacturing method of the hardened | cured material film of any one of Claims 1-4 which apply | coats the said curable composition by the effect | action of a piezo element in the said application | coating process.   The manufacturing method of the hardened | cured material film of any one of Claims 1-5 whose viscosity at the time of discharge of the said curable composition is 3 mPa * s or more and 1500 mPa * s or less. A step of forming a cured product film on the electronic component main body by the method for producing a cured product film according to any one of claims 1 to 6 ,
The manufacturing method of an electronic component which obtains an electronic component provided with an electronic component main body and the said hardened | cured material film on the said electronic component main body.

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