JP2013166811A - Ink set, semiconductor-mounting board, and electronic equipment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink set capable of forming a printed portion excellent in visibility in a component member (for example, semiconductor device etc.) of a semiconductor-mounting board; to provide the semiconductor-mounting board provided with a member having a printed portion excellent in visibility; and electronic equipment provided with the semiconductor-mounting board.SOLUTION: An ink set includes a plurality of inks to be imparted to a component member of a semiconductor-mounting board, the plurality of inks comprising: a first ink containing a colorant; and a second ink containing powder formed of an electromagnetic wave-suppressing material. Preferably the first and second inks are jetted by an inkjet method. Preferably the powder formed of the electromagnetic wave-suppressing material is in a scale-like form.

Description

  The present invention relates to an ink set, a semiconductor mounting substrate, and an electronic device.

For example, a large number of semiconductor devices (IC chips and the like) are used in various electronic devices.
There are various types of such semiconductor devices, and some have different production times. In some cases, from the viewpoint of production management, it is desired to display information such as a model and a manufacturing time (manufacturing number, lot number, etc.) on the semiconductor device. In addition, for example, in a manufacturer that contracts with a plurality of companies to manufacture a product with the brand name of the other party, so-called OEM (original brand product manufacturing), each semiconductor device has “ "Brand name" needs to be displayed.
Conventionally, the above information and the like have been printed using a laser marking device (see, for example, Patent Document 1).
However, printing using a laser marking device has poor visibility, and it may be difficult to accurately read the above information and the like.

JP 2003-88967 A

  An object of the present invention is to provide an ink set capable of forming a printed portion with excellent visibility on a component (for example, a semiconductor device) of a semiconductor mounting substrate, and to have a printed portion with excellent visibility. To provide a semiconductor mounting board provided with a member, and to provide an electronic device including the semiconductor mounting board.

Such an object is achieved by the present invention described below.
The ink set of the present invention is an ink set comprising a plurality of types of ink applied to the constituent members of the semiconductor mounting substrate,
A first ink containing a colorant;
And a second ink containing powder composed of an electromagnetic wave suppressing material.

  Thereby, the ink set which can form the printing part excellent in visibility in the structural member of a semiconductor mounting board can be provided. In addition, in conventional semiconductor mounting boards, electromagnetic waves generated by the flow of current may have an adverse effect on electronic equipment, etc., but by using the ink set of the present invention, the occurrence of adverse effects due to electromagnetic waves can be reliably prevented. can do.

In the ink set of the present invention, it is preferable that the first ink and the second ink are ejected by an ink jet method.
Thereby, a printing part can be formed more efficiently. In addition, it does not require a version and is excellent in on-demand.
In the ink set of the present invention, it is preferable that the powder composed of the electromagnetic wave suppressing material has a scaly shape.
Thereby, the electromagnetic wave shielding effect by the printing part formed using an ink set can be made especially excellent. Further, since the amount of ink necessary to obtain a sufficient electromagnetic wave shielding effect can be reduced, it is advantageous from the viewpoint of cost and the efficiency (productivity) of forming the printing portion. Moreover, the adhesiveness of the printing part with respect to the structural member (base material) of the semiconductor mounting substrate can be made particularly excellent.

In the ink set of the present invention, the second ink includes a powder composed of a material including a Ni—Fe alloy and / or a Fe—Al—Si alloy as the powder composed of the electromagnetic wave suppressing material. It is preferable to contain a powder composed of a material.
Thereby, the electromagnetic wave shielding effect by the printing part formed using an ink set can be made especially excellent. In addition, the storage stability and ejection stability of the second ink can be made particularly excellent. Moreover, the visibility of the printing part formed using an ink set can be made especially excellent.

In the ink set of the present invention, it is preferable that the first ink and the second ink include a polymerizable compound that is polymerized by irradiation with ultraviolet rays.
Thereby, the efficiency (productivity) of formation of a printing part can be made especially excellent. Moreover, the adhesiveness of the printing part with respect to the structural member (base material) of the semiconductor mounting substrate can be made particularly excellent. Moreover, the selection range of the material on the surface of the constituent member of the semiconductor mounting substrate on which the printing part is to be formed can be made wider.

In the ink set of the present invention, it is preferable that the first ink and the second ink do not contain a volatile solvent.
As a result, it is possible to more reliably prevent an adverse effect (for example, a short circuit) from occurring on the constituent members of the semiconductor mounting substrate on which the printed portion is formed. Moreover, generation | occurrence | production of the problem of a volatile organic compound (VOC) can be prevented effectively.

In the ink set of the present invention, it is preferable that the first ink and the second ink contain phenoxyethyl acrylate as the polymerizable compound.
As a result, the first ink and the second ink have excellent storage stability and discharge stability, and the first ink and the second ink after discharge by the inkjet method have particularly excellent reactivity. And the formation efficiency (productivity) of the printed portion can be made particularly excellent. Moreover, the adhesiveness of the printing part with respect to the structural member (base material) of the semiconductor mounting substrate can be made particularly excellent.

  In the ink set of the present invention, the first ink and the second ink include N-vinyl caprolactam, N-vinyl pyrrolidone, acrylic acid 2- (2-) in addition to the phenoxyethyl acrylate as the polymerizable compound. Vinyloxyethoxy) ethyl, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 2-hydroxy-3-phenoxypropyl acrylate, and at least one selected from the group consisting of 4-hydroxybutyl acrylate are preferable. .

  Accordingly, the storage stability and ejection stability of the first ink and the second ink are excellent, and the reactivity of the first ink and the second ink after ejection by the ink jet method is further enhanced. In addition, the efficiency (productivity) of forming the printing portion can be further improved. Moreover, the adhesiveness of the printing part with respect to the structural member (base material) of the semiconductor mounting substrate can be further improved.

  In the ink set of the present invention, the first ink and the second ink are dimethylol tricyclodecane diacrylate, dimethylol dicyclopentane diacrylate, dicyclopentenyl acrylate, dicyclopenta as the polymerizable compound. Nyl acrylate, isobornyl acrylate, acryloylmorpholine, tetrahydrofurfuryl acrylate, ethyl carbitol acrylate, and at least one selected from the group consisting of methoxytriethylene glycol acrylate are preferable.

  As a result, the storage stability and ejection stability of the first ink and the second ink are improved, and the reactivity of the first ink and the second ink after ejection by the inkjet method is further improved. It is possible to further improve the efficiency (productivity) of forming the printing portion. Moreover, the adhesiveness of the printing part with respect to the structural member (base material) of the semiconductor mounting substrate can be further improved.

In the ink set of the present invention, it is preferable that a plurality of types of inks are provided as the first ink.
Thereby, the visibility of the printing part formed using an ink set can be made especially excellent. Moreover, the high-class feeling of the component of the semiconductor mounting substrate having the printing portion can be made particularly excellent, and differentiation from other companies' products by branding becomes easier.

In the ink set of the present invention, it is preferable that the first ink includes a violet ink, a magenta ink, and a yellow ink.
As a result, the color gamut that can be expressed by using the ink set can be made wider, and the high-class feeling of the component parts of the semiconductor mounting substrate having the printing part can be made particularly excellent. Differentiation from the product becomes easier.

In the ink set of the present invention, it is preferable that a white or black ink is provided as the first ink.
Thereby, the visibility of the printing part formed using an ink set can be made especially excellent. Moreover, the selection range of the material on the surface of the constituent member of the semiconductor mounting substrate on which the printing part is to be formed can be made wider.

In the ink set of the present invention, it is preferable that the average particle size of the powder composed of the electromagnetic wave suppressing material is 500 nm or more and 3.0 μm or less.
Thereby, the electromagnetic wave shielding effect by the printing part formed using an ink set can be made especially excellent. In addition, the storage stability and ejection stability of the second ink can be made particularly excellent.

The semiconductor mounting board of the present invention is characterized by comprising a member having a printing portion formed using the ink set of the present invention.
Thereby, the semiconductor mounting board provided with the member which has the printing part excellent in visibility can be provided. In addition, it is possible to reliably prevent adverse effects on electronic devices and the like due to electromagnetic waves generated by the constituent member (base material) of the semiconductor mounting substrate.
An electronic apparatus according to the present invention includes the semiconductor mounting substrate according to the present invention.
Thereby, the electronic device provided with the structural member of the semiconductor mounting board | substrate which has a printing part excellent in visibility can be provided. In addition, it is possible to provide an electronic device in which adverse effects due to electromagnetic waves generated by the constituent member (base material) of the semiconductor mounting substrate are reliably prevented.

Hereinafter, preferred embodiments of the present invention will be described in detail.
<Ink set>
First, the ink set of the present invention will be described.
By the way, a large number of semiconductor devices (IC chips and the like) are used in various electronic devices.

  There are various types of such semiconductor devices, and some have different production times. In some cases, from the viewpoint of production management, it is desired to display information such as a model and a manufacturing time (manufacturing number, lot number, etc.) on the semiconductor device. In addition, for example, in a manufacturer that contracts with a plurality of companies to manufacture a product with the brand name of the other party, so-called OEM (original brand product manufacturing), each semiconductor device has “ "Brand name" needs to be displayed.

Conventionally, the above information and the like have been printed using a laser marking device.
However, printing using a laser marking device has poor visibility, and it may be difficult to accurately read the above information and the like.
Therefore, the inventor has intensively studied for the purpose of solving the above problems, and as a result, has reached the present invention. That is, the ink set of the present invention includes a plurality of types of inks applied to the constituent members of the semiconductor mounting substrate, and includes a first ink containing a colorant and a powder composed of an electromagnetic wave suppressing material. Second ink. Thereby, the ink set which can form the printing part excellent in visibility in the structural member of a semiconductor mounting board can be provided. In addition, in conventional semiconductor mounting boards, electromagnetic waves generated by the flow of current may have an adverse effect on electronic equipment, etc., but by using the ink set of the present invention, the occurrence of adverse effects due to electromagnetic waves can be reliably prevented. can do.

  In addition, circuit design of electronic equipment is performed in consideration of noise due to electromagnetic waves, but unexpected electromagnetic noise may occur when a circuit is actually assembled. In such a case, adjustment is performed by attaching the electromagnetic wave suppression sheet to the target portion of the constituent member of the semiconductor mounting substrate. However, such an electromagnetic wave suppression sheet needs to be cut into a suitable size at a preferable size and then attached one by one, resulting in a low manufacturing yield of electronic devices and a significant reduction in productivity. There was a problem. Moreover, in the above sheet materials, an adhesive layer is required for adhering to the constituent members of the semiconductor mounting substrate, which is disadvantageous in reducing the size and thickness of the final product.

  On the other hand, by using the ink set of the present invention, it is possible to efficiently form a printed part (electromagnetic wave shielding film) having an electromagnetic wave shielding effect, contributing to the downsizing and thinning of electronic devices as final products. can do. Further, in the conventional method using the sheet material, the portion that is not attached to the semiconductor component is discarded. However, in the present invention, there is no such waste, which is advantageous from the viewpoint of resource saving and the like. Moreover, the electromagnetic shielding film of the fine pattern which was difficult by the method using the conventional sheet | seat material can also be formed suitably.

The first ink and the second ink may be applied to the component before assembly of the semiconductor mounting substrate, or may be applied to the component after assembly of the semiconductor mounting substrate. May be.
The first ink and the second ink may be applied on the constituent member of the semiconductor mounting substrate using any printing method, but both are ejected by an ink jet method. preferable. Thereby, a printing part can be formed more efficiently. In addition, it does not require a version and is excellent in on-demand. In the following description, the case where both the first ink and the second ink are ejected by the inkjet method will be mainly described.

<First ink>
(Coloring agent)
As described above, the first ink contains a colorant.
As the colorant, for example, various pigments and various dyes can be used. Especially, it is preferable to contain a pigment as a coloring agent. Thereby, the durability of the printing part formed using the ink set can be made particularly excellent, and excellent visibility can be secured stably over a longer period of time.

  The ink set of the present invention may be provided with at least one kind of each of the first ink and the second ink, but is preferably provided with a plurality of kinds of inks as the first ink. Thereby, the visibility of the printing part formed using an ink set can be made especially excellent. Moreover, the high-class feeling of the component of the semiconductor mounting substrate having the printing portion can be made particularly excellent, and differentiation from other companies' products by branding becomes easier. In addition, examples of the plurality of types of first inks include inks of different colors (those having different colorant compositions), but are not limited thereto, and the ink set of the present invention includes, for example, other than the colorant A plurality of types of first inks having different component compositions (for example, a composition of a polymerizable compound described in detail later) may be provided.

When the ink set of the present invention includes a plurality of types of first inks, the first ink includes indigo purple (cyan) ink, reddish purple (magenta) ink, and yellow (yellow) ink. It is preferable. As a result, the color gamut that can be expressed by using the ink set can be made wider, and the high-class feeling of the component parts of the semiconductor mounting substrate having the printing part can be made particularly excellent. Differentiation from the product becomes easier.
In addition, the ink set of the present invention preferably includes a white or black ink as the first ink. Thereby, the visibility of the printing part formed using an ink set can be made especially excellent. Moreover, the selection range of the material on the surface of the constituent member of the semiconductor mounting substrate on which the printing part is to be formed can be made wider.

(Polymerizable compound)
The first ink only needs to contain the colorant as described above, but preferably further contains a polymerizable compound that is polymerized by irradiation with ultraviolet rays. Thereby, the efficiency (productivity) of formation of a printing part can be made especially excellent. Moreover, the adhesiveness of the printing part with respect to the structural member (base material) of the semiconductor mounting substrate can be made particularly excellent. Moreover, the selection range of the material on the surface of the constituent member of the semiconductor mounting substrate on which the printing part is to be formed can be made wider.

In the following description, the case where the first ink contains a polymerizable compound that is polymerized by irradiation with ultraviolet rays will be mainly described.
The polymerizable compound is preferably a liquid. Accordingly, it is not necessary to separately include a liquid component that is removed (evaporated) in the formation process of the printing portion in the first ink, and it is necessary to provide a step of removing the liquid component in the formation of the printing portion. Therefore, the formation efficiency of the printed part can be made particularly excellent. Moreover, since it is not necessary to use a component that is generally used as an organic solvent, it is possible to prevent the occurrence of a problem of a volatile organic compound (VOC).

  The polymerizable compound may be any component that can be polymerized by irradiation with ultraviolet rays. For example, various monomers and various oligomers (including dimers and trimers) can be used. The first ink is a polymerizable compound. It is preferable that at least a monomer component is included. Since the monomer is generally a component having a low viscosity as compared with the oligomer component or the like, it is advantageous for making the discharge stability of the first ink particularly excellent.

  Examples of the monomer as the polymerizable compound include isobornyl acrylate, 4-hydroxybutyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, phenoxyethyl acrylate, isooctyl acrylate, stearyl acrylate, cyclohexyl acrylate, 2-ethoxyethyl acrylate, Benzyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, t-butyl acrylate, tetrahydrofurfuryl acrylate , Ethyl carbitol acrylate, 2,2,2-trifluoroethyl acrylate, 2, , 2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl acrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol acrylate, PO-modified nonylphenol acrylate, EO-modified nonylphenol acrylate, EO-modified 2-ethylhexyl acrylate, EO modified nonylphenol acrylate, phenyl glycidyl ether acrylate, phenoxydiethylene glycol acrylate, EO modified phenol acrylate, phenoxyethyl acrylate, EO modified phenol acrylate, EO modified cresol acrylate, methoxy polyethylene glycol acrylate, dipropylene glycol acrylate, dicyclopentenyl acrylate, dicyclo Tertenyloxyethyl acrylate, 2-n-butyl-2-ethyl-1,3-propanediol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, 1.9-nonanediol diacrylate, 1,4- Butanediol diacrylate, bisphenol A EO modified diacrylate, 1.6-hexanediol diacrylate, polyethylene glycol 200 diacrylate, polyethylene glycol 300 diacrylate, neopentyl glycol hydroxypiparate diacrylate, 2-ethyl-2-butyl- Propanediol diacrylate, polyethylene glycol 400 diacrylate, polyethylene glycol 600 diacrylate, polypropylene glycol diacrylate 1.9-nonanediol diacrylate, 1.6-hexanediol diacrylate, bisphenol A EO modified diacrylate, bisphenol A EO modified diacrylate, bisphenol A EO modified diacrylate, PO modified bisphenol A diacrylate, EO modified water Bisphenol A diacrylate, dipropylene glycol diacrylate, polypropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, trimethylolpropane EO-modified triacrylate, glycerin PO-added triacrylate, trisacryloyloxyethyl phosphate, penta Erythritol tetraacrylate, PO-modified trimethylolpropane triacrylate, P Modified trimethylolpropane triacrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, 2- (2-vinyloxyethoxy) ethyl acrylate, 1-adamantylmethyl acrylate 1-adamantyl acrylate, 2-acryloyloxyethyl phthalate, isobornyl acrylate, 3-acryloyloxypropyl acrylate, acryloyl morpholine, lipoxy SP series, dicyclopentanyl acrylate, 2-hydroxy 3-phenoxypropyl acrylate, w -Carboxyacryloyloxyethyl phthalate, dimethylol dicyclopentane diacrylate, diacrylated iso Arureto / triacrylated mixture, neopentyl glycol diacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol penta / hexaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane PO-modified triacrylate, diethylene glycol diethyl ether, and the like. Among them, 4-hydroxybutyl acrylate, phenoxyethyl acrylate, phenoxyethyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, dipropylene glycol diacrylate, trimethylolpropane tri Preferred are acrylate, trimethylolpropane EO-modified triacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, and 2- (2-vinyloxyethoxy) ethyl acrylate.

  In particular, the first ink preferably contains phenoxyethyl acrylate as the polymerizable compound. As a result, the storage stability and ejection stability of the first ink are excellent, while the reactivity of the first ink after ejection by the ink jet method is particularly excellent, and the efficiency (production of production of the printed part) Property) can be made particularly excellent. Moreover, the adhesiveness of the printing part with respect to the structural member (base material) of the semiconductor mounting substrate can be made particularly excellent.

  In addition to phenoxyethyl acrylate, the first ink contains N-vinylcaprolactam, N-vinylpyrrolidone, 2- (2-vinyloxyethoxy) ethyl acrylate, dipropylene glycol diacrylate, tripropylene as a polymerizable compound. It is preferable that it contains at least one selected from the group consisting of glycol diacrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 4-hydroxybutyl acrylate. As a result, the storage stability and ejection stability of the first ink are improved, and the reactivity of the first ink after ejection by the ink jet method is further improved, and the efficiency of forming the printed portion (production) Property) can be further improved. Moreover, the adhesiveness of the printing part with respect to the structural member (base material) of the semiconductor mounting substrate can be further improved.

  In addition, the first ink contains dimethylol tricyclodecane diacrylate, dimethylol dicyclopentane diacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, isobornyl acrylate, acryloyl morpholine, tetrahydrofluoro as a polymerizable compound. It is preferable that it contains at least one selected from the group consisting of furyl acrylate, ethyl carbitol acrylate, and methoxytriethylene glycol acrylate. As a result, the storage stability and ejection stability of the first ink are further improved, and the reactivity of the first ink after ejection by the ink jet method is further enhanced, and the efficiency of forming the printing portion ( (Productivity) can be further improved. Moreover, the adhesiveness of the printing part with respect to the structural member (base material) of the semiconductor mounting substrate can be further improved.

The first ink may contain an oligomer in addition to the monomer as the polymerizable compound. In particular, those containing polyfunctional oligomers are preferred. Thereby, the adhesiveness of the printing part with respect to the structural member (base material) of the semiconductor mounting substrate can be made particularly excellent while making the storage stability of the first ink excellent. In the present invention, among polymerizable compounds, those having a repeating structure in the molecular skeleton and having a molecular weight of 600 or more are called oligomers. As the oligomer, a urethane oligomer whose repeating structure is urethane, an epoxy oligomer whose repeating structure is epoxy, and the like are preferably used.
The first ink may have a chemical structure containing a bromine atom or a phosphorus atom as a polymerizable compound. Thereby, the flame retardance of a printing part can be made especially excellent, and the reliability of the structural member of the semiconductor mounting substrate in which the printing part was provided can be made especially excellent.

  The content of the polymerizable compound in the first ink is preferably 70% by mass or more and 99% by mass or less, and more preferably 80% by mass or more and 98% by mass or less. As a result, the storage stability, ejection stability, and curability of the first ink can be further improved, and the adhesion of the printed portion to the component (base material) of the semiconductor mounting substrate is further improved. Can be. The first ink may include two or more compounds as the polymerizable compound. In this case, it is preferable that the total content of these compounds is a value within the above range.

(Other ingredients)
The first ink may contain components other than those described above (other components). Examples of such components include a dispersant, a photopolymerization initiator, a slip agent (leveling agent), a polymerization accelerator, a polymerization inhibitor, a penetration accelerator, a wetting agent (humectant), a colorant, a fixing agent, an anti-blocking agent. Examples include glazes, preservatives, antioxidants, chelating agents, thickeners, and sensitizers (sensitizing dyes).

  The photopolymerization initiator is not particularly limited as long as it generates active species such as radicals and cations by ultraviolet irradiation and initiates the polymerization reaction of the polymerizable compound. As the photopolymerization initiator, a radical photopolymerization initiator or a cationic photopolymerization initiator can be used, but it is preferable to use a radical photopolymerization initiator. When using a photopolymerization initiator, the photopolymerization initiator preferably has an absorption peak in the ultraviolet region.

Examples of the photo radical polymerization initiator include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, Examples thereof include ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and alkylamine compounds.
Among these, at least one selected from an acylphosphine oxide compound and a thioxanthone compound is preferable from the viewpoint of solubility in a polymerizable compound and curability, and it is more preferable to use an acylphosphine oxide compound and a thioxanthone compound in combination.

  Specific examples of the photo radical polymerization initiator include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine. , Carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) ) -2-Hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethyl Oxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, bis (2,4,6-trimethylbenzoyl) -phenyl Phosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,4-diethylthioxanthone, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, etc. 1 type or 2 types or more selected from these can be used in combination.

The content of the photopolymerization initiator in the first ink is preferably 0.5% by mass or more and 10% by mass or less. When the content of the photopolymerization initiator is within the above range, the ultraviolet curing rate is sufficiently high, and the photopolymerization initiator is hardly dissolved or colored due to the photopolymerization initiator.
When the first ink contains a slip agent, the surface of the printing portion becomes smooth due to the leveling action, and the abrasion resistance is improved. As a result, the durability of the printing part is improved.

Although it does not specifically limit as a slip agent, For example, silicone type surfactants, such as polyester modified silicone and polyether modified silicone, can be used, It is preferable to use polyether modified polydimethylsiloxane or polyester modified polydimethylsiloxane. .
The first ink may contain a polymerization inhibitor, but even when it contains a polymerization inhibitor, the content of the polymerization inhibitor in the first ink is 0.6 mass. % Or less is preferable, and 0.2% by mass or less is more preferable. Thereby, since the content rate of the polymerizable compound in the first ink can be relatively increased, the durability of the printed portion can be particularly improved.

Moreover, it is preferable that the first ink does not contain a solvent (volatile solvent) that is removed (evaporated) in the formation process of the printing portion. As a result, it is possible to more reliably prevent an adverse effect (for example, a short circuit) from occurring on the constituent members of the semiconductor mounting substrate on which the printed portion is formed. Moreover, generation | occurrence | production of the problem of a volatile organic compound (VOC) can be prevented effectively. In the present specification, the volatile solvent means a solvent having a vapor pressure of 0.3 Pa or more at room temperature (20 ° C.).
The viscosity of the first ink at room temperature (20 ° C.) is preferably 20 mPa · s or less, and more preferably 3 mPa · s or more and 15 mPa · s or less. Thereby, the droplet discharge by an inkjet method can be performed suitably.

<Second ink>
(Powder)
As described above, the second ink includes a powder composed of an electromagnetic wave suppression material.
By providing such a second ink together with the first ink as described above, a printed portion having excellent visibility can be formed on the constituent member of the semiconductor mounting substrate, and the configuration of the semiconductor mounting substrate. It is possible to reliably prevent adverse effects on the electronic equipment and the like due to the electromagnetic waves generated by the members.
In the present invention, the electromagnetic wave suppression material refers to a material that cuts unnecessary electromagnetic noise.

Examples of the electromagnetic wave suppressing material constituting the powder include metal materials, metal oxides (ceramics, etc.), and more specifically, Fe-based amorphous, Co-based amorphous, Mn—Zn based ferrite, Ni—Zn. iron; system ferrite, Mn-Mg-Zn ferrite, _Zn 2 -W type ferrite, Ni-Fe alloy, Fe-Cr-Si-Al alloy, Fe-Al-Si alloy, permalloy, soft magnetic material of silicon steel -Sintered carbon; Micro-expanded metal; Ceramics such as titanium oxide and silicon carbide; Nanocomposite particles composed of soft magnetic material (metal) and ceramics; Carbon / carbon microcoil; Composite of carbon and polyethylene foam A composite of carbon and GFRP (glass fiber reinforced composite); rare earth magnet compound; Bi-based superconductor, etc. However, the second ink is composed of a powder composed of a material including a Ni—Fe alloy and / or a material including a Fe—Al—Si alloy as a powder composed of an electromagnetic wave suppressing material. It is preferable that the powder contains a powder. Thereby, the electromagnetic wave shielding effect by the printing part formed using an ink set can be made especially excellent. In addition, the storage stability and ejection stability of the second ink can be made particularly excellent. Moreover, the visibility of the printing part formed using an ink set can be made especially excellent.

When the second ink contains a powder composed of a material containing a Ni—Fe alloy, the Ni content in the Ni—Fe alloy is represented by X _Ni [mass%], and the Fe in the Ni—Fe alloy. Is preferably X _Fe [mass%], the relationship 0.5 ≦ X _Ni / X _Fe ≦ 1.5 is preferably satisfied, and 0.6 ≦ X _Ni / X _Fe ≦ 1.4 It is more preferable to satisfy the relationship, and it is even more preferable to satisfy the relationship of 0.9 ≦ X _Ni / X _Fe ≦ 1.2. Thereby, the electromagnetic wave shielding effect by the printing part formed using the ink set of the present invention can be further improved. In addition, the storage stability and ejection stability of the second ink can be further improved.

  When the second ink contains powder composed of a material containing a Ni—Fe alloy, the Ni—Fe alloy is not particularly limited, but the Ni content is 48.0% by mass or more and 55.0%. It is preferable that the content of Fe is 4% by mass or less and 52.0% by mass or less. Thereby, the electromagnetic wave shielding effect by the printing part formed using the ink set of the present invention can be further improved. In addition, the storage stability and ejection stability of the second ink can be further improved.

As described above, the Ni content in the Ni-Fe alloy is preferably 48.0% by mass or more and 55.0% by mass or less, but is 49.0% by mass or more and 53.0% by mass or less. More preferably, it is 49.5 mass% or more and 50.5 mass% or less. Thereby, the effects as described above can be exhibited more remarkably.
As described above, the content of Fe in the Ni-Fe alloy is preferably 40.0% by mass or more and 52.0% by mass or less, but 45.0% by mass or more and 51.0% by mass or less. More preferably, it is 48.0 mass% or more and 50.5 mass% or less. Thereby, the effects as described above can be exhibited more remarkably.

  The Ni—Fe alloy may contain components other than Ni and Fe, but the sum of the contents of components other than Ni and Fe is preferably 2.0% by mass or less. More preferably, it is 0.0 mass% or less, and further preferably 0.6 mass% or less. Thereby, the electromagnetic wave shielding effect by the printing part formed using the ink set of the present invention can be further improved. In addition, the storage stability and ejection stability of the second ink can be further improved.

  When the second ink contains a powder composed of a material containing an Fe—Al—Si alloy, the Fe—Al—Si alloy contains Fe as a main component and is 8.2 wt% or more and 11.2 wt%. It is preferable to contain the following Si and Al of 4.0 wt% or more and 7.0 wt% or less. Thereby, the electromagnetic wave shielding effect by the printing part formed using an ink set can be made especially excellent. In addition, the storage stability and ejection stability of the second ink can be made particularly excellent. Moreover, the visibility of the printing part formed using an ink set can be made especially excellent.

  When the second ink contains a powder composed of a material containing an Fe—Al—Si alloy, the Fe content in the Fe—Al—Si alloy is 80.0 wt% or more and 87.8 wt%. The content is preferably 81.3 wt% or more and 86.8 wt% or less, more preferably 82.5 wt% or more and 85.8 wt% or less. Thereby, the effects as described above can be exhibited more remarkably.

  When the second ink contains a powder composed of a material containing an Fe—Al—Si alloy, the Si content in the Fe—Al—Si alloy is 8.2 wt% or more and 11.2 wt%. The content is preferably 8.7 wt% or more, more preferably 8.7 wt% or more and 10.7 wt% or less, and further preferably 9.2 wt% or more and 10.2 wt% or less. Thereby, the effects as described above can be exhibited more remarkably.

  When the second ink contains a powder composed of a material containing an Fe—Al—Si alloy, the Al content in the Fe—Al—Si alloy is 4.0 wt% or more and 7.0 wt%. Although it is preferable that it is below, it is more preferable that it is 4.5 wt% or more and 6.5 wt% or less, and it is further more preferable that it is 5.0 wt% or more and 6.0 wt% or less. Thereby, the effects as described above can be exhibited more remarkably.

  When the second ink contains a powder composed of a material containing an Fe—Al—Si alloy, the Fe—Al—Si alloy may contain components other than Fe, Si and Al. The sum of the contents of components other than Fe, Si and Al is preferably 2.0 wt% or less, more preferably 1.0 wt% or less, and 0.6 wt% or less. More preferably. Thereby, the electromagnetic wave shielding effect by the printing part formed using an ink set can be made especially excellent. In addition, the storage stability and ejection stability of the second ink can be made particularly excellent. Moreover, the visibility of the printing part formed using an ink set can be made especially excellent.

  Further, the powder (particles) constituting the second ink may be subjected to surface treatment. Thereby, the storage stability, ejection stability, etc. of the second ink can be made particularly excellent. In addition, by including the surface-treated powder (particles), the affinity of the powder (particles) for the polymerizable compound can be made suitable, and the printed part (electromagnetic wave) formed using the ink set In the shield film), it is possible to reliably prevent the particles constituting the powder from coming into contact with each other and to ensure insulation, and in the printed part to be formed, the powder can be suitably arranged, and the printed part The electromagnetic wave shielding effect by can be made particularly excellent.

  Although the surface treating agent used for the said surface treatment is not specifically limited, It is preferable that it is a fluorine-type phosphate ester. Thereby, the storage stability and ejection stability of the second ink can be made particularly excellent. Moreover, the electromagnetic shielding effect of the printing part formed using the ink set of this invention, the adhesiveness with respect to the structural member (base material) of a semiconductor mounting board, etc. can be made especially excellent.

Hereinafter, the fluorine-based phosphate ester as the surface treatment agent will be described in detail.
As the fluorine-based phosphate ester, a phosphate ester having at least one fluorine atom in the molecule can be used.
In particular, the fluorine-based phosphate ester preferably has a chemical structure represented by the following formula (2).
POR _n (OH) _3-n (2)
(In the formula (2), R _{is, CF 3 (CF 2) m} -, CF 3 (CF 2) m (CH 2) l -, CF 3 (CF 2) m (CH 2 O) l -, CF 3 (CF ₂ ) _m (CH ₂ CH ₂ O) ₁ —, CF ₃ (CF ₂ ) _m O—, or CF ₃ (CF ₂ ) _m (CH ₂ ) ₁ O—, and n is 1 or more and 3 or less. M is an integer from 5 to 17, and l is an integer from 1 to 12.)

Thereby, the storage stability and ejection stability of the second ink can be made particularly excellent. Moreover, the electromagnetic shielding effect of the printing part formed using the ink set of this invention, the adhesiveness with respect to the structural member (base material) of a semiconductor mounting board, etc. can be made especially excellent.
In formula (2), m is preferably an integer of 5 to 17, more preferably an integer of 5 to 12. Thereby, the effects as described above are more remarkably exhibited.

In formula (2), l is preferably an integer of 1 to 12, but more preferably an integer of 1 to 10. Thereby, the effects as described above are more remarkably exhibited.
Further, fluorine-based phosphate ester (surface treatment agent) is preferably one having a perfluoroalkyl structure _{(C n F 2n + 1)} . Thereby, the storage stability and ejection stability of the second ink can be further improved. Moreover, the electromagnetic wave shielding effect of the printing part formed using the ink set of this invention, the adhesiveness with respect to the structural member (base material) of a semiconductor mounting board | substrate, etc. can be made further excellent.

  The surface treatment agent as described above may be directly treated on the mother particles. However, after the mother particles are treated with an acid or a base, the mother particles are treated with the surface treatment agent. It is preferred to do so. As a result, the surface of the mother particles can be more reliably modified by chemical bonding with the surface treatment agent, and the effects of using the surface treatment agent as described above can be more effectively exhibited. Examples of the acid include hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid, carbonic acid, formic acid, benzoic acid, chlorous acid, hypochlorous acid, sulfurous acid, hyposulfite, nitrous acid, hyponitrous acid, phosphorous acid, and the following. Protic acids such as phosphorous acid can be used. Of these, hydrochloric acid, phosphoric acid, and acetic acid are preferable. On the other hand, as the base, for example, sodium hydroxide, potassium hydroxide, calcium hydroxide or the like can be used. Of these, sodium hydroxide and potassium hydroxide are preferred.

  The powder (particles) constituting the second ink may have any shape such as a spherical shape, a spindle shape, or a needle shape, but preferably has a scaly shape. Thereby, the electromagnetic wave shielding effect by the printing part formed using an ink set can be made especially excellent. Further, since the amount of ink necessary to obtain a sufficient electromagnetic wave shielding effect can be reduced, it is advantageous from the viewpoint of cost and the efficiency (productivity) of forming the printing portion. Moreover, the adhesiveness of the printing part with respect to the structural member (base material) of the semiconductor mounting substrate can be made particularly excellent.

In the present invention, the scale shape is an area when the area when observed from a predetermined angle (when viewed in plan) is observed from an angle orthogonal to the observation direction, such as a flat plate shape or a curved plate shape. In particular, the area S ₁ [μm ² ] when observed from the direction in which the projected area is maximum (when viewed in plan) and the direction orthogonal to the observation direction are observed. The ratio (S ₁ / S ₀ ) with respect to the area S ₀ [μm ² ] when observed from the direction in which the area of the area becomes maximum is preferably 2 or more, more preferably 5 or more, and still more preferably 8 or more. It is. As this value, for example, it is possible to observe an arbitrary 10 particles and adopt an average value of values calculated for these particles.

The average particle diameter of the powder (particles) constituting the second ink is preferably 500 nm or more and 3.0 μm or less, and more preferably 800 nm or more and 1.8 μm or less. Thereby, the electromagnetic wave shielding effect by the printing part formed using an ink set can be made especially excellent. In addition, the storage stability and ejection stability of the second ink can be made particularly excellent.
The content of the powder in the second ink is preferably 0.5% by mass or more and 10.0% by mass or less, and more preferably 1.0% by mass or more and 5.0% by mass or less.

(Polymerizable compound)
The second ink only needs to include a powder composed of the electromagnetic wave suppressing material as described above, but preferably includes a polymerizable compound that is polymerized by irradiation with ultraviolet rays in addition to the powder as described above. . Thereby, the efficiency (productivity) of formation of a printing part can be made especially excellent. Moreover, the adhesiveness of the printing part with respect to the structural member (base material) of the semiconductor mounting substrate can be made particularly excellent. Moreover, the selection range of the material on the surface of the constituent member of the semiconductor mounting substrate on which the printing part is to be formed can be made wider.

In the following description, the case where the second ink contains a polymerizable compound that is polymerized by irradiation with ultraviolet rays will be mainly described.
The polymerizable compound is in a liquid state and preferably functions as a dispersion medium for dispersing the powder in the second ink. Accordingly, it is not necessary to use a dispersion medium that is removed (evaporated) separately in the formation process of the printing part, and it is not necessary to provide a process for removing the dispersion medium in the formation of the printing part. Efficiency (productivity) can be made particularly excellent. Moreover, since it is not necessary to use what is generally used as an organic solvent as a dispersion medium, generation | occurrence | production of the problem of a volatile organic compound (VOC) can be prevented.

  The polymerizable compound may be any component that can be polymerized by irradiation with ultraviolet rays. For example, various monomers and various oligomers (including dimers and trimers) can be used. The second ink is a polymerizable compound. It is preferable that at least a monomer component is included. Since the monomer is generally a component having a low viscosity as compared with the oligomer component or the like, it is advantageous for making the ejection stability of the second ink particularly excellent.

  As the monomer as the polymerizable compound constituting the second ink, for example, those exemplified as the constituent component (monomer as the polymerizable compound) of the first ink can be used. Among them, 4-hydroxybutyl acrylate, phenoxyethyl acrylate, phenoxyethyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, dipropylene glycol diacrylate, trimethylolpropane tri Preferred are acrylate, trimethylolpropane EO-modified triacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, and 2- (2-vinyloxyethoxy) ethyl acrylate.

  In particular, the second ink preferably contains phenoxyethyl acrylate as the polymerizable compound. As a result, the storage stability and ejection stability of the second ink are excellent, and the reactivity of the second ink after ejection by the ink jet method is particularly excellent, and the efficiency of forming the printing portion (production) Property) can be made particularly excellent. Moreover, the adhesiveness of the printing part with respect to the structural member (base material) of the semiconductor mounting substrate can be made particularly excellent.

  In addition to the phenoxyethyl acrylate, the second ink includes 2- (2-vinyloxyethoxy) ethyl acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 2-hydroxy 3-phenoxy as a polymerizable compound. It is preferable that it contains at least one selected from the group consisting of propyl acrylate and 4-hydroxybutyl acrylate. As a result, the storage stability and ejection stability of the second ink are improved, and the reactivity of the second ink after ejection by the ink jet method is further improved, and the efficiency of forming the printed portion (production) Property) can be further improved. Moreover, the adhesiveness of the printing part with respect to the structural member (base material) of the semiconductor mounting substrate can be further improved.

  In addition, the second ink contains dimethylol tricyclodecane diacrylate, dimethylol dicyclopentane diacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, isobornyl acrylate, acryloyl morpholine, tetrahydrofluoro as a polymerizable compound. It is preferable that it contains at least one selected from the group consisting of furyl acrylate, ethyl carbitol acrylate, and methoxytriethylene glycol acrylate. Thereby, while making the storage stability and ejection stability of the second ink more excellent, the reactivity of the second ink after ejection by the ink jet method is further improved, and the efficiency of forming the printing portion ( (Productivity) can be further improved. Moreover, the adhesiveness of the printing part with respect to the structural member (base material) of the semiconductor mounting substrate can be further improved.

The second ink may contain an oligomer in addition to the monomer as the polymerizable compound. In particular, those containing polyfunctional oligomers are preferred. Thereby, the adhesiveness of the printing part with respect to the structural member (base material) of the semiconductor mounting substrate can be made particularly excellent while making the storage stability of the second ink excellent. As the oligomer, a urethane oligomer whose repeating structure is urethane, an epoxy oligomer whose repeating structure is epoxy, and the like are preferably used.
The second ink may have a chemical structure containing a bromine atom or a phosphorus atom as the polymerizable compound. Thereby, the flame retardance of a printing part can be made especially excellent, and the reliability of the structural member of the semiconductor mounting substrate in which the printing part was provided can be made especially excellent.

  The content of the polymerizable compound in the second ink is preferably 70% by mass or more and 99% by mass or less, and more preferably 80% by mass or more and 98% by mass or less. As a result, the storage stability, ejection stability, and curability of the second ink can be further improved, and the electromagnetic wave shielding effect by the printing unit manufactured using the ink set of the present invention, semiconductor mounting The adhesiveness of the printing part with respect to the structural member (base material) of the substrate can be further improved. The second ink may include two or more compounds as the polymerizable compound. In this case, it is preferable that the total content of these compounds is a value within the above range.

(Dispersant)
The second ink preferably contains a basic dispersant having a polymer structure (hereinafter also referred to as “basic polymer dispersant”). Thereby, the durability of the printed portion can be further improved. In addition, the storage stability and ejection stability of the second ink can be made particularly excellent.

In the present invention, the basic polymer dispersant is not particularly limited as long as it shows basicity and has a polymer structure.
The polymer structure constituting the basic polymer dispersant is not particularly limited. For example, an acrylic polymer structure (including a copolymer), a methacrylic polymer structure (including a copolymer), and polyurethane. Examples thereof include a polymer structure, a hydroxyl group-containing carboxylic acid ester structure, a polyether polymer structure, and a silicone polymer structure.

The amine value of the basic polymer dispersant is not particularly limited, but is preferably 3 mgKOH / g or more and 80 mgKOH / g or less, more preferably 10 mgKOH / g or more and 70 mgKOH / g or less.
Specific examples of the basic polymer dispersant include DISPERBYK-116 (manufactured by BYK Chemie), DISPERBYK-182 (manufactured by BYK Chemy), DISPERBYK-183 (manufactured by BYK Chemy), DISPERBYK-184 (manufactured by BYK Chemy), DISPERBYK- 2155 (manufactured by Big Chemie), DISPERBYK-2164 (manufactured by Big Chemie), DISPERBYK-108 (manufactured by Big Chemie), DISPERBYK-112 (manufactured by Big Chemie), DISPERBYK-198 (manufactured by BYK Chemie), DISPERBYK-2150 (manufactured by Big Chemie) ), PAA-1112 (manufactured by Nittobo Co., Ltd.) and the like.

  The content of the basic polymer dispersant in the second ink is preferably 0.01% by mass or more and 5.0% by mass or less, and more preferably 0.1% by mass or more and 2.0% by mass or less. Is more preferable. As a result, the storage stability, ejection stability, and curability of the second ink can be further improved, and the durability of the printed portion can be further improved. The second ink may contain two or more compounds as a basic polymer dispersant. In this case, it is preferable that the total content of these compounds is a value within the above range.

(Substance A)
The second ink preferably contains a substance A having a partial structure represented by the following formula (6).

  The second ink contains the substance A having such a chemical structure (particularly, together with the powder subjected to the surface treatment as described above and the basic polymer dispersant), so that the second ink Storage stability and curability can be made particularly excellent. Moreover, in a printing part, powder can be arranged suitably and the electromagnetic wave shielding effect can be made especially excellent. Further, the durability of the printed part can be made particularly excellent.

In the formula (6), R ¹ may be a hydrogen atom, a hydrocarbon group or an alkoxyl group (a chain or alicyclic hydrocarbon group bonded to an oxygen atom), particularly a hydrogen atom, methyl It is preferably a group or an octyloxy group. As a result, the storage stability and ejection stability of the second ink can be further improved, and the durability of the printed portion, the electromagnetic shielding effect, and the like can be further improved.

In Formula (6), R ^{2 to} R ⁵ may be independently a hydrogen atom or a hydrocarbon group, but are preferably an alkyl group having 1 to 3 carbon atoms, and is a methyl group. Is more preferable. As a result, the storage stability and ejection stability of the second ink can be further improved, and the durability of the printed portion, the electromagnetic shielding effect, and the like can be further improved.

  The content of the substance A in the second ink is preferably 0.1% by mass or more and 5.0% by mass or less, and more preferably 0.5% by mass or more and 3.0% by mass or less. As a result, the storage stability, ejection stability, and curability of the second ink can be further improved, and the durability of the printed portion, the electromagnetic shielding effect, and the like can be further improved. . Note that the second ink may include two or more compounds as the substance A. In this case, it is preferable that the total content of these compounds is a value within the above range.

When the content of the substance A is X _A [mass%] and the content of the powder is X _M [mass%], it is preferable that the relationship of 0.01 ≦ X _A / X _M ≦ 0.8 is satisfied. More preferably, the relationship 0.05 ≦ X _A / X _M ≦ 0.4 is satisfied. By satisfying such a relationship, the storage stability and ejection stability of the second ink can be further improved, and the durability of the printing portion, the electromagnetic shielding effect, etc. can be further improved. can do.

(Other ingredients)
The second ink may contain components other than those described above (other components). Examples of such components include dispersants other than basic polymer dispersants, photopolymerization initiators, slip agents (leveling agents), polymerization accelerators, polymerization inhibitors, penetration enhancers, wetting agents (humectants). , Colorants, fixing agents, antifungal agents, antiseptics, antioxidants, chelating agents, thickeners, sensitizers (sensitizing dyes) and the like.

  The photopolymerization initiator is not particularly limited as long as it generates active species such as radicals and cations by ultraviolet irradiation and initiates the polymerization reaction of the polymerizable compound. As the photopolymerization initiator, a radical photopolymerization initiator or a cationic photopolymerization initiator can be used, but it is preferable to use a radical photopolymerization initiator. When using a photopolymerization initiator, the photopolymerization initiator preferably has an absorption peak in the ultraviolet region.

As the radical photopolymerization initiator, for example, those exemplified as the constituent of the first ink (photoradical polymerization initiator) can be used.
Among these, at least one selected from an acylphosphine oxide compound and a thioxanthone compound is preferable from the viewpoint of solubility in a polymerizable compound and curability, and it is more preferable to use an acylphosphine oxide compound and a thioxanthone compound in combination.

As specific examples of the photo radical polymerization initiator, those exemplified as the constituent components (photo radical polymerization initiator) of the first ink can be used.
The content of the photopolymerization initiator in the second ink is preferably 0.5% by mass or more and 10% by mass or less. When the content of the photopolymerization initiator is within the above range, the ultraviolet curing rate is sufficiently high, and the photopolymerization initiator is hardly dissolved or colored due to the photopolymerization initiator.

When the second ink contains a slip agent, the surface of the printing portion becomes smooth due to the leveling action, and the abrasion resistance is improved. As a result, the durability of the printing part is improved.
As the slip agent, for example, those exemplified as the constituent component (slip agent) of the first ink can be used, but it is preferable to use polyether-modified polydimethylsiloxane or polyester-modified polydimethylsiloxane.

  The second ink may contain a polymerization inhibitor, but even when it contains a polymerization inhibitor, the content of the polymerization inhibitor in the second ink is 0.6 mass. % Or less is preferable, and 0.2% by mass or less is more preferable. Thereby, since the content rate of the polymerizable compound in the second ink can be made relatively high, the durability of the printed portion can be made particularly excellent.

  The second ink preferably does not contain a solvent (a volatile solvent) that is removed (evaporated) in the printing portion forming step. As a result, it is possible to more reliably prevent an adverse effect (for example, a short circuit) from occurring on the constituent members of the semiconductor mounting substrate on which the printed portion is formed. Moreover, generation | occurrence | production of the problem of a volatile organic compound (VOC) can be prevented effectively.

The viscosity of the second ink at room temperature (20 ° C.) is preferably 20 mPa · s or less, and more preferably 3 mPa · s or more and 15 mPa · s or less. Thereby, the droplet discharge by an inkjet method can be performed suitably.
The ink set of the present invention only needs to include at least one kind of each of the first ink and the second ink, and may include a plurality of kinds of inks as the second ink.

<Semiconductor mounting substrate>
Next, the semiconductor mounting substrate of the present invention will be described.
The semiconductor mounting substrate of the present invention is provided with a member having a printing portion formed using the ink set as described above. Thereby, the semiconductor mounting board provided with the member which has the printing part excellent in visibility can be provided. In addition, it is possible to reliably prevent adverse effects on electronic devices and the like due to electromagnetic waves generated by the constituent member (base material) of the semiconductor mounting substrate.

  The printing unit only needs to be formed using an ink set including a first ink and a second ink. For example, a region formed by applying the first ink, May have a region formed by applying the second ink, or may have a region formed by applying the first ink and the second ink so as to overlap each other. It may be. When the printing unit has a region formed by applying the first ink and the second ink so as to overlap each other, the first ink for the constituent member of the semiconductor mounting substrate as the base material and The order of application of the second ink may be any first, but it is preferable to apply the first ink after the application of the second ink. Thereby, the visibility of a printing part can be made especially excellent. Further, after one ink is solidified (polymerized / cured) on the component of the semiconductor mounting substrate, the other ink may be applied, or one ink is solidified (polymerized / cured) on the component of the semiconductor mounted substrate. ), The other ink may be applied. That is, the first ink having fluidity and the second ink may be mixed on the constituent member (base material) of the semiconductor mounting substrate, or on the constituent member (base material) of the semiconductor mounting substrate. Thus, a layer made of the first ink and a layer made of the second ink may be formed so as not to mix the first ink and the second ink.

Although the thickness of the printing part formed using an ink set is not specifically limited, It is preferable that they are 5.0 micrometers or more and 800 micrometers or less, and it is more preferable that they are 10.0 micrometers or more and 300 micrometers or less. As a result, the electromagnetic wave shielding effect can be made particularly excellent, and it is advantageous for reducing the size and thickness of an electronic device as a final product.
Examples of the component (base material) of the semiconductor mounting substrate on which the printing unit is formed include, for example, mounting parts such as a semiconductor device (for example, an IC chip), wiring in the semiconductor mounting substrate (for example, Cu wiring, Ag wiring, etc.) ), A substrate on which a semiconductor device or the like is mounted.

In the case where the first ink and the second ink are ejected by an inkjet method, a known droplet ejecting apparatus can be used.
As a droplet discharge method (inkjet method), a piezo method, a method in which ink is discharged by bubbles generated by heating ink, or the like can be used. Ink (first ink, first ink) The piezo method is preferable from the viewpoint of the difficulty of alteration of the second ink).

  The method of solidifying the ink (first ink, second ink) is performed by a method according to the composition of the ink. For example, when the ink (first ink, second ink) contains a polymerizable compound that is polymerized by irradiation with ultraviolet rays, the ink (first ink, second ink) is solidified by irradiation with ultraviolet rays. be able to. Thereby, the efficiency (productivity) of formation of a printing part can be made especially excellent. Further, the durability of the printed part can be made particularly excellent. Moreover, the selection range of the material on the surface of the constituent member (base material) of the semiconductor mounting substrate on which the printing part is formed can be made wider.

In this case, as the ultraviolet ray source, for example, a mercury lamp, a metal halide lamp, an ultraviolet light emitting diode (UV-LED), an ultraviolet laser diode (UV-LD), or the like can be used. Among these, ultraviolet light emitting diodes (UV-LED) and ultraviolet laser diodes (UV-LD) are preferable from the viewpoints of small size, long life, high efficiency, and low cost.
Further, when the ink (first ink, second ink) contains a thermosetting component, the ink (first ink, second ink) is solidified by performing a heating process. Can do.
When the ink (first ink, second ink) contains a volatile solvent, the ink (first ink, second ink) is solidified by heating and / or decompression. Can be performed.

"Electronics"
Next, the electronic apparatus of the present invention will be described.
The electronic apparatus of the present invention includes the semiconductor mounting substrate of the present invention. Thereby, the electronic device provided with the structural member of the semiconductor mounting board | substrate which has a printing part excellent in visibility can be provided. In addition, it is possible to provide an electronic device in which adverse effects due to electromagnetic waves generated by the constituent member (base material) of the semiconductor mounting substrate are reliably prevented.

The electronic apparatus of the present invention may be used for any application, for example, a mobile phone, an ink jet type ejection device (for example, an ink jet printer), a television, a digital still camera, a video camera, a viewfinder type, and a monitor direct view type. Video tape recorders, personal computers, car navigation systems, pagers, electronic notebooks (including those with communication functions), electronic dictionaries, calculators, electronic game machines, electronic newspapers, word processors, workstations, videophones, security TV monitors, electronic binoculars , POS terminals, devices equipped with touch panels (for example, cash dispensers of financial institutions, automatic ticket vending machines), medical devices (for example, electronic thermometers, blood pressure monitors, blood glucose meters, electrocardiogram display devices, ultrasonic diagnostic devices, endoscope displays) Equipment), fish finder, various Constant devices, gauges (e.g., gages for vehicles, aircraft, and ships), a flight simulator, various monitors, may be mentioned a projection type display device such as a projector.
As mentioned above, although this invention was demonstrated based on suitable embodiment, this invention is not limited to these.
For example, in the method for forming a printed part of a semiconductor mounting substrate according to the present invention, in addition to the steps described above, the method may further include other steps (a pretreatment step, an intermediate treatment step, a post treatment step). .

Next, specific examples of the present invention will be described.
[1] Manufacture of ink set (Example 1)
<Production of first ink>
C. as a colorant (pigment) I. Pigment Blue 15: 6, phenoxyethyl acrylate as a polymerizable compound, Irgacure 819 (manufactured by Ciba Japan) as a photopolymerization initiator, Speedcure TPO (manufactured by ACETO) as a photopolymerization initiator, and a photopolymerization initiator The first ink of blue-violet (cyan) was obtained by mixing Speedcure DETX (manufactured by Lambson).

The type of colorant (pigment) is C.I. I. Pigment Blue 15: 6, C.I. I. Pigment red 122, C.I. I. Except for the change to Pigment Yellow 150, TiO ₂ , and Carbon Black, the same as above, the first ink of magenta (magenta), the first ink of yellow (yellow), the first ink of white, and A first black ink was obtained.

<Manufacture of second ink>
First, a powder having a spherical shape and an average particle size of 9.9 μm was produced by a water atomization method using a molten Ni—Fe alloy. The produced powder had a composition of Ni: 50.1% by mass, Fe: 49.6% by mass, and Si: 0.3% by mass.
Next, CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ O (P) (OH) ₂ and CF ₃ (CF ₂ ) are used as the fluorine-based phosphate ester for the substantially spherical powder obtained as described above. ) ₅ (CH ₂ ) ₂ O (P) (OH) (OCH ₂ CH ₃ ) in a 1% by mass propanol solution of a mixture (mass ratio 5:95) and stirred for 10 seconds to give fluorine. Surface treatment with a phosphoric acid ester was performed.

Next, the substantially spherical powder subjected to the surface treatment with the fluorine-based phosphate ester was deformed (scaled) into a scale shape by a planetary ball mill using zirconia beads (diameter: 5 mm). This treatment was performed in phenoxyethyl acrylate.
Next, the mixture obtained by the above treatment is introduced into an ultrasonic disperser, finely processed, and then filtered through a 3 μm membrane filter to remove zirconia beads and coarse particles of powder. Cut. The powder thus obtained had an average particle size of 0.8 μm and an average thickness of 60 nm.

  Next, the scaled powder is separated, and then DISPERBYK-183 (manufactured by Big Chemie) as a basic dispersant having a polymer structure (basic polymer dispersant), phenoxyethyl acrylate, a photopolymerization initiator. Irgacure 819 (manufactured by Ciba Japan), Speedcure TPO (manufactured by ACETO) as a photopolymerization initiator, Speedcure DETX (manufactured by Lambson) as a photopolymerization initiator, and the following formula (7) The second ink was obtained by mixing with the substance A having a chemical structure.

  As described above, an ink set including five types of first ink and one type of second ink was obtained.

(Examples 2 to 11)
Except for the composition shown in Tables 1 to 4 by changing the type and ratio of the raw materials used for the preparation of the first ink and the second ink, the same as in Example 1 above. An ink set was manufactured.
(Comparative Example 1)
In this comparative example, the first ink was manufactured in the same manner as in Example 1, but the second ink was not manufactured. That is, the ink set of this comparative example is composed of five types of first ink.
(Comparative Example 2)
In this comparative example, the second ink was manufactured in the same manner as in Example 1, but the first ink was not manufactured. That is, in this comparative example, only one type of second ink was manufactured.

For each of the above Examples and Comparative Examples 1 and 2, the composition of the ink constituting the ink set is summarized in Tables 1 to 4. In the table, phenoxyethyl acrylate is “PEA”, 2- (2-hydroxyethoxy) ethyl acrylate is “VEEA”, tripropylene glycol diacrylate is “TPGDA”, dipropylene glycol diacrylate is “DPGDA”, N -Vinylcaprolactam "VC", benzyl methacrylate "BM", dimethylol tricyclodecane diacrylate "DMTCDDA", urethane acrylate "UA", Irgacure 819 (manufactured by Ciba Japan) "ic819", Speedcure TPO (Lambson) is “scTPO”, Speedcure DETX (Lambson) is “scDETX”, UV-3500 (Bicchemy) is “UV3500”, 4-hydroxybutyl alcohol. The rate is “HBA”, 2-hydroxy 3-phenoxypropyl acrylate is “HPPA”, dimethylol dicyclopentane diacrylate is “DMDCPTA”, dicyclopentenyl acrylate is “DCPTeA”, dicyclopentanyl acrylate is “DCPTaA”, Isobornyl acrylate "IBA", acryloylmorpholine "AM", tetrahydrofurfuryl acrylate "THFA", ethyl carbitol acrylate "ECA", methoxytriethylene glycol acrylate "MTEGA", hydroquinone monomethyl ether "MEHQ"", C.I. I. Pigment Blue 15: 6 is changed to “PB15: 6”, C.I. I. Pigment Red 122 is “PR122”, C.I. I. Pigment Yellow 150 is “PY150”, TiO ₂ is “TiO ₂ ”, carbon black is “CB”, C.I. I. Pigment Violet 19 is “PV19”, C.I. I. Pigment Yellow 73 is “PY73”, C.I. I. Pigment Yellow 185 is "PY185", C.I. I. Pigment Yellow 155 is changed to “PY155”, C.I. I. Pigment Yellow 138 is changed to “PY138”, C.I. I. Pigment Green 7 is “PG7”, Metal Aluminum is “Al”, Duralumin is “AlS”, CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ O (P) (OH) ₂ and CF ₃ (CF ₂ ) ₅ ( CH ₂ ) ₂ O (P) (OH) (OCH ₂ CH ₃ ) and a mixture (mass ratio 5:95) were designated as “S1”, CF ₃ (CF ₂ ) ₄ (CH ₂ ) ₂ O—PO (OH ) ₂ for “S2”, CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ O (P) (OH) ₂ for “S3”, CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ O (P) (OH) ) (OCH ₂ CH ₃ ) as “S4”, CF ₃ (CF ₂ ) ₁ (CH ₂ ) ₃ P (O) (OCH ₂ CH ₃ ) as “S5”, CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ O-PO a _{(OH) (OC 2 H 5} ) _{"S6", CF 3 (CF 2) 14} ( _{H 2) 4 P (O)} (OH) (OCH 2 CH 3) The "S7", the zircon hydrofluoric acid _"S8", "S9" and H 3 PO _4, peroxide containing 30% by weight hydrogen peroxide A solution obtained by adding 1.5 parts by mass of metal molybdenum powder to 10 parts by mass of hydrogen water and causing the reaction to dissolve in 175 parts by mass of isopropyl alcohol was obtained as “S10”, DISPERBYK-183 (BIC Chemie) Manufactured, amine value: 17 mgKOH / g) “D1”, DISPERBYK-182 (manufactured by Big Chemie, amine value: 13 mgKOH / g) “D2”, DISPERBYK-184 (manufactured by Big Chemie, amine value: 15 mgKOH / g) “D3”, DISPERBYK-116 (by Big Chemie, amine value: 65 mgKOH / g) is replaced with “D4”, DISP RBYK-2155 (by Big Chemie, amine value: 48 mgKOH / g) is “D5”, DISPERBYK-2164 (by Big Chemie, amine value: 14 mgKOH / g) is “D6”, PAA-1112 (manufactured by Nittobo) “D7”, Emanon 4110 (dispersant having a polymer structure but not basic, manufactured by Kao Corporation) “D′ 1”, Nonion P-208 (dispersant having no polymer structure, NOF Corporation) "D'2" made by the company, the compound (substance A) represented by the above formula (7) is "A1", the compound represented by the following formula (8) (substance A) is "A2", the following formula The compound (substance A) represented by (9) is represented by “A3”, and the substance A represented by the following formula (10) is represented by “A4”. In Tables 1 to 3, for the first ink, cyan is “C”, magenta is “M”, yellow is “Y”, and black is “K”. The white color is indicated by “W”. In Table 4, the composition of the mother particles indicates the content of the constituent elements in parts by weight. In addition, when 10 arbitrary metal particles included in the inks (second ink) according to each of the examples and the comparative example 2 are observed and observed from the direction in which the projected area is maximized (plan view) the area S ₁ of the time) _[μm ^2], the ratio to the area when the area at the time when observations were observed from the direction of maximum of a direction orthogonal to the viewing direction ^{_{S 0 [μm 2] (S}} 1 / S ₀ ) was determined, and the average value of these was also shown in Table 4. Also, in the column of “Viscosity” in the table, the viscosity at 20 ° C. of the ink measured according to JIS Z8809 using a vibration viscometer was shown. D1 to D7 are all basic and have a polymer structure (basic polymer dispersant). In addition, the inks according to the respective examples and comparative examples 1 and 2 did not contain a volatile solvent.

[2] Droplet discharge stability evaluation (discharge stability evaluation)
Using the inks according to the respective Examples and Comparative Examples 1 and 2, evaluations by the following tests were performed.
First, a droplet discharge device installed in a chamber (thermal chamber) and inks according to the above examples and comparative examples 1 and 2 were prepared, and the drive waveform of the piezo element was optimized. Under the RH environment, 2 million droplets (2000000 droplets) of each ink were continuously ejected from each nozzle of the droplet ejection head. Thereafter, the operation of the droplet discharge device was stopped, and the droplet discharge device was left in an environment of 25 ° C. and 55% RH for 240 hours in a state where each flow path was filled with each ink.

  Thereafter, 4 million droplets (4000000 droplets) were continuously discharged from each nozzle of the droplet discharge head in an environment of 25 ° C. and 55% RH. The average deviation amount d from the center target position of the center position of each landed droplet for the 4000000 droplets discharged from the designated nozzle near the center of the droplet discharge head after being left for 150 hours. Values were obtained and evaluated according to the following five-step criteria. It can be said that the smaller the value is, the more effectively the occurrence of flight bending is prevented.

A: The average value of the shift amount d is less than 0.07 μm.
B: The average value of the shift amount d is 0.07 μm or more and less than 0.14 μm.
C: The average value of the shift amount d is 0.14 μm or more and less than 0.17 μm.
D: The average value of the shift amount d is 0.17 μm or more and less than 0.21 μm.
E: The average value of the shift amounts d is 0.21 μm or more.

[3] Frequency characteristics of the ink In the state where the droplet discharge device installed in the chamber (thermal chamber) and the ink according to each of the examples and comparative examples 1 and 2 are prepared and the drive waveform of the piezoelectric element is optimized, In an environment of 25 ° C. and 55% RH, for each ink, droplet ejection was performed while changing the frequency (frequency) of the piezo element from all nozzles of the droplet ejection head. The droplet discharge time at each frequency was 10 minutes. The frequency range that can be actually used was evaluated according to the following four-stage criteria, with the number of undischarged nozzles being less than 1% of the total number of nozzles at the time point after 10 minutes of discharge as the highest frequency that can be actually used. It can be said that the larger this value, the better the frequency characteristics.
A: 15 kHz or more.
B: 10 kHz or more and less than 15 kHz.
C: 5 kHz or more and less than 10 kHz.
D: Less than 5 kHz.

[4] Ink storage stability evaluation (long-term stability evaluation)
About the ink according to each of the above Examples and Comparative Examples 1 and 2, after being allowed to stand for 40 days in an environment of 40 ° C., each of the above Examples and the Examples measured according to JIS Z8809 using a vibration viscometer The viscosity at 20 ° C. of the inks according to Comparative Examples 1 and 2 was measured, and the rate of increase in viscosity immediately after production was determined and evaluated according to the following criteria.

A: Increase rate of viscosity is less than 5%.
B: Increase rate of viscosity is 5% or more and less than 10%.
C: Increase rate of viscosity is 10% or more and less than 18%.
D: Increase rate of viscosity is 18% or more and less than 23%.
E: The rate of increase in viscosity is 23% or more, or generation of foreign matter is observed.

[5] Curability About the ink according to each of the above Examples and Comparative Examples 1 and 2, the ink jet printer manufactured by Epson; Then, solid printing was performed at an ink amount of 9 g / m ² , and immediately after printing, an LED-UV lamp; Foseon's RX firefly (gap 6 mm, peak wavelength 365 nm, 1000 mW / cm ² ) was irradiated. Whether the ink was cured or not was evaluated and evaluated according to the following five criteria. Whether or not the ink was cured was determined by rubbing the surface with a cotton swab and not adhering uncured ink. In addition, whether it corresponds to the irradiation amount of the following AE can be calculated by how many seconds the lamp is irradiated.

A: Cured with an ultraviolet irradiation dose of less than 100 mJ / cm ² .
B: It hardened | cured with the ultraviolet irradiation amount of 100 mJ / cm < ² > or more and less than 200 mJ / cm < ² >.
C: Cured with an ultraviolet irradiation amount of 200 mJ / cm ² or more and less than 500 mJ / cm ² .
D: It hardened | cured with the ultraviolet irradiation amount of 500 mJ / cm < ² > or more and less than 1000 mJ / cm < ² >.
E: It hardens | cures by the ultraviolet irradiation amount of 1000 mJ / cm < ² > or more. Or it does not cure at all.

[6] Formation of printing part (electromagnetic wave shielding film), manufacture of semiconductor mounting substrate / electronic device Semiconductor device provided with printing part (electromagnetic wave shielding film) using ink set of each example as follows A mobile phone as an electronic device provided with (a component of a semiconductor mounting substrate) was manufactured.
First, a mobile phone without a printing part (electromagnetic wave shielding film) was prepared.

Next, the cover of the cellular phone was removed, and the second ink was applied in a predetermined pattern to the surface of the IC chip as a semiconductor device by an ink jet method.
Thereafter, ultraviolet rays having a spectrum having maximum values at wavelengths of 365 nm, 380 nm, and 395 nm were irradiated for 15 seconds at an irradiation intensity of 180 mW / cm ² to cure the second ink, thereby forming a printing portion (electromagnetic wave shielding film).

Thereafter, the first ink was applied in a predetermined pattern to a part of the surface of the printing portion using the second ink by an inkjet method.
Thereafter, ultraviolet rays having a spectrum having maximum values at wavelengths of 365 nm, 380 nm, and 395 nm were irradiated at an irradiation intensity of 180 mW / cm ² for 15 seconds to cure the first ink, thereby forming a printing portion.

The thickness of the printed part formed using the ink set was 30 μm.
Then, a cover was attached and a mobile phone provided with a printing unit was obtained.
In Comparative Example 1, a cellular phone provided with a printing unit was manufactured in the same manner as described above except that the step of applying the second ink and the step of curing the second ink were omitted.
In Comparative Example 2, a mobile phone provided with a printing unit was manufactured in the same manner as described above except that the step of applying the first ink and the step of curing the first ink were omitted.

Further, in Comparative Example 3, instead of forming the printing part using the ink set, the laser marking device was used to carry the marking process on the part where the printing part was formed in the same manner as described above. A telephone (a mobile phone provided with a printing part) was manufactured.
Further, in Comparative Example 4, instead of forming a printing portion using an ink set, a bust raid R4N (manufactured by NEC TOKIN) as an electromagnetic wave suppression sheet (noise suppression sheet) was prepared and cut into a predetermined pattern. Thereafter, a mobile phone (a mobile phone provided with an electromagnetic wave shielding film) was manufactured in the same manner as described above except that it was attached to the site where the printing part was formed.

[7] Productivity (efficiency of forming printed part) evaluation of electronic equipment Productivity of mobile phone (electronic equipment) provided with semiconductor device provided with printed part (electromagnetic wave shielding film) manufactured in [6] above (Efficiency of forming the printed part) was evaluated according to the following criteria.
A: The productivity of the mobile phone provided with the semiconductor device provided with the printing part (electromagnetic wave shielding film) is very excellent.
B: Productivity of a mobile phone provided with a semiconductor device provided with a printing part (electromagnetic wave shielding film) is excellent.
C: The productivity of the mobile phone provided with the semiconductor device provided with the printing part (electromagnetic wave shielding film) is slightly inferior.
D: The productivity of the mobile phone provided with the semiconductor device provided with the printing part (electromagnetic wave shielding film) is inferior.
E: Productivity of a mobile phone provided with a semiconductor device provided with a printing part (electromagnetic wave shielding film) is very inferior.

[8] Visibility evaluation About the semiconductor device provided with the printing part (electromagnetic wave shielding film) manufactured by said [6], the site | part in which the printing part (electromagnetic wave shielding film) was provided is observed visually, and a printing part ( The visibility (ease of recognition) of the electromagnetic wave shielding film was evaluated according to the following criteria.
A: The visibility of the printed part (electromagnetic wave shielding film) is very excellent.
B: The visibility of the printed part (electromagnetic wave shielding film) is excellent.
C: The visibility of the printed part (electromagnetic wave shielding film) is slightly inferior.
D: The visibility of the printed part (electromagnetic wave shielding film) is inferior.
E: The visibility of the printed part (electromagnetic wave shielding film) is very poor.

[9] Evaluation of aesthetics (aesthetic appearance) The semiconductor device provided with the printing part (electromagnetic wave shielding film) produced in [6] above is visually observed, and the aesthetics (aesthetic appearance) are determined according to the following criteria. evaluated.
A: The aesthetics (aesthetic appearance) of the semiconductor device is very excellent.
B: The aesthetics (aesthetic appearance) of the semiconductor device is excellent.
C: The aesthetics (aesthetic appearance) of the semiconductor device is slightly inferior.
D: The aesthetics (aesthetic appearance) of the semiconductor device is inferior.
E: The aesthetics (aesthetic appearance) of the semiconductor device is very poor.

[10] Electromagnetic wave suppression effect On the surface of a PET film (length 10.0 cm × width 5 mm), each ink constituting the ink set of each of the examples and comparative examples 1 and 2 has a line width of 25 μm, a thickness of 20 μm, 200 lines having a length of 10.0 cm were sequentially drawn at intervals of 0. Thereafter, ultraviolet rays having a spectrum having maximum values at wavelengths of 365 nm, 380 nm, and 395 nm were irradiated for 15 seconds at an irradiation intensity of 180 mW / cm ² to cure the ink and form a printing portion.

Moreover, about the comparative example 4, the sheet material was cut out to length 10.0cm x width 5mm, and this was stuck on the surface of PET film (length 10.0cm x width 5mm), and it was set as the electromagnetic wave shielding film.
About the PET film provided with the printing part (electromagnetic wave shielding film) of the Example and Comparative Examples 1, 2, and 4 formed as described above, the printing part is placed on the microstrip line so that the printing part faces upward. It was installed and pressed from above with a load of 500 gf. In this state, the transmission loss of the microstrip line was measured at a frequency of 3 GHz using a network analyzer, and evaluated according to the following criteria.

A: Attenuation characteristics with a transmission loss of −8 dB or more.
B: Shows attenuation characteristics with a transmission loss of -8 dB or more and less than -6 dB.
C: Attenuation characteristics with a transmission loss of -6 dB or more and less than -4 dB.
D: Shows attenuation characteristics with a transmission loss of -4 dB or more and less than -2 dB.
E: Transmission loss is less than −2 dB and hardly exhibits attenuation characteristics.

[11] Adhesion evaluation The ink constituting the ink set of each of the above Examples and Comparative Examples 1 and 2 was applied to the surface of a plate-like member made of a mold resin for IC (manufactured by Dow Corning, 307) 200 lines having a width of 25 μm, a thickness of 20 μm, and a length of 10.0 cm were sequentially drawn at an interval of 0. Thereafter, ultraviolet rays having a spectrum having maximum values at wavelengths of 365 nm, 380 nm, and 395 nm were irradiated for 15 seconds at an irradiation intensity of 180 mW / cm ² to cure the ink and form a printing portion.

For Comparative Example 4, the sheet material was cut into a length of 10.0 cm × a width of 5 mm, and this was adhered to the surface of a plate-like member made of a mold resin for IC (307 manufactured by Dow Corning). An electromagnetic shielding film was obtained.
About the printing part (electromagnetic wave shielding film) of the Example and Comparative Examples 1, 2, and 4 formed as described above, in accordance with JIS K5600, evaluated by the cross-cut method according to the following four-stage criteria, It was set as evaluation of the adhesiveness of a printing part (electromagnetic wave shielding film) and a plate-shaped member.

A: Peeling is not recognized.
B: The portion where the blade is inserted is notched.
C: Slight peeling occurs.
D: Peeling is clearly recognized.
These results are shown in Table 5.

As is apparent from Table 5, in the present invention, a printed part (electromagnetic wave shielding film) excellent in visibility could be efficiently formed. Moreover, the semiconductor device (component member of the semiconductor mounting substrate) provided with the printing part (electromagnetic wave shielding film) was also excellent in aesthetics (aesthetic appearance). Moreover, the printing part as a sufficiently thin electromagnetic wave shielding film could be suitably formed, and a sufficient electromagnetic wave shielding effect was obtained. Moreover, in this invention, the printing part (electromagnetic wave shielding film) of arbitrary shapes can be formed suitably, and it was excellent in on-demand property. In addition, the ink constituting the ink set of the present invention was excellent in ejection stability, storage stability, and the like.
On the other hand, in the comparative example, a satisfactory result was not obtained.

Claims (15)

An ink set comprising a plurality of types of ink applied to the constituent members of the semiconductor mounting substrate,
A first ink containing a colorant;
An ink set comprising: a second ink containing powder composed of an electromagnetic wave suppressing material.   The ink set according to claim 1, wherein the first ink and the second ink are ejected by an inkjet method.   The ink set according to claim 1 or 2, wherein the powder composed of the electromagnetic wave suppressing material has a scaly shape.   The second ink includes a powder composed of a material including a Ni—Fe alloy and / or a powder composed of a material including a Fe—Al—Si alloy as a powder composed of the electromagnetic wave suppressing material. The ink set according to any one of claims 1 to 3, wherein the ink set is contained.   The ink set according to any one of claims 1 to 4, wherein the first ink and the second ink contain a polymerizable compound that is polymerized by irradiation with ultraviolet rays.   The ink set according to claim 5, wherein the first ink and the second ink do not contain a volatile solvent.   The ink set according to claim 5 or 6, wherein the first ink and the second ink contain phenoxyethyl acrylate as the polymerizable compound.   In addition to the phenoxyethyl acrylate, the first ink and the second ink may include N-vinylcaprolactam, N-vinylpyrrolidone, 2- (2-vinyloxyethoxy) ethyl acrylate, di-acid as the polymerizable compound. The ink set according to claim 7, comprising at least one selected from the group consisting of propylene glycol diacrylate, tripropylene glycol diacrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 4-hydroxybutyl acrylate.   The first ink and the second ink are dimethylol tricyclodecane diacrylate, dimethylol dicyclopentane diacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, isobornyl acrylate as the polymerizable compound. The ink set according to any one of claims 5 to 8, which comprises at least one selected from the group consisting of acryloylmorpholine, tetrahydrofurfuryl acrylate, ethyl carbitol acrylate, and methoxytriethylene glycol acrylate.   The ink set according to claim 1, comprising a plurality of types of ink as the first ink.   The ink set according to claim 10, wherein the first ink includes a cyan-purple (cyan) ink, a magenta ink, and a yellow (yellow) ink.   The ink set according to claim 1, comprising white or black ink as the first ink.   The ink set according to any one of claims 1 to 12, wherein an average particle size of the powder composed of the electromagnetic wave suppressing material is 500 nm or more and 3.0 µm or less.   A semiconductor mounting board comprising a member having a printing portion formed using the ink set according to claim 1.   An electronic apparatus comprising the semiconductor mounting substrate according to claim 14.