WO2005027601A1 - Insulating pattern and method of forming the same - Google Patents

Abstract

A method of forming an insulating pattern, comprising the steps of (1) on a substrate with a circuit formed thereon, effecting application and bonding of cissing agent (A) to a pattern being in negative relationship reverse to a pattern of insulating layer, (2) coating the whole surface of substrate obtained in step (1) with liquid insulating resin composition (B) having a surface tension that is higher than that of the bonded cissing agent (A) but lower than that of the substrate and (3) by irradiation with active energy rays and/or heat curing, or heat drying, effecting bonding of the coating film of liquid insulating resin composition (B) obtained in the step (2) onto the substrate to thereby provide an insulating layer, characterized in that through the steps (2) to (3), the liquid insulating resin composition (B) is repelled by the matter resulting from bonding of the cissing agent (A), thereby enabling obtaining an insulating pattern.

Description

 Specification

 Insulating pattern and method for forming the same

 Technical field

 The present invention relates to an insulating pattern and a method for forming the same, and more particularly, to a technique for forming an insulating pattern such as a solder resist using a repellent.

 Background art

 [0002] Solder resist ink is intended to prevent solder bridges and protect circuits when soldering components to a printed wiring board, and to selectively protect circuits to be protected by screen printing or the like. Coating and impart protective properties by light curing and heat curing. On the other hand, solder the mounted components to the parts that are selectively exposed without being covered. In general, the area of the part that selectively exposes the leads of the mounted components to the printed wiring board by soldering without covering with solder resist is generally smaller than the area covered by solder resist.

 [0003] A liquid composition generally called an ink is diluted with a diluent such as water or an organic solvent, and adjusted to have a viscosity corresponding to a printing method. The ink is applied by printing to a desired pattern to be coated by various methods, and is used for forming a desired pattern having good touch properties through a drying step and the like. It is also widely known to use an organic substance having a reactive functional group as a diluent to obtain finger touch through a curing step using light or heat. These inks are selectively applied only to the portions to be applied, for example, in the case of pattern printing using a screen.

 In recent years, in the printed wiring board manufacturing industry, there has been a demand for lightweight printed wiring boards and high-density conductor circuits. As the size of parts has become smaller, fine pattern drawing has been required. Accordingly, a solder resist composition of a photo-developing method, especially a composition developable with an aqueous alkali solution, has been developed and widely used as a liquid resist method (see, for example, JP-A-1-141904).

[0005] In this pattern forming method, first, the entire surface of a printed wiring board on which a conductive circuit is formed is A liquid photosensitive resin composition is applied by any method such as screen printing, curtain coating, spray coating and the like so as to fill the conductive circuit, and dried, and then the dried film is coated with a negative film having a predetermined exposure pattern. The laminated film is exposed by irradiating ultraviolet rays, and then the negative film is removed, and the unexposed portion is removed by developing with an aqueous alkali solution, thereby forming a cured resin insulating layer having a predetermined pattern. After that, heat curing is performed to form a solder resist layer that becomes a protective film of the circuit.

 [0006] The viscosity of such a solder resist of a photo-developing method is adjusted with an organic solvent so as to have a viscosity suitably used for various coating methods, and is then printed on a printed wiring board by a screen printing method, a curtain coating method, or the like. A coating step of applying a resist over the entire surface by a spray coating method, a roll coating method, a die coating method, etc., a temporary drying step for volatilizing an organic solvent used for viscosity adjustment, an exposure step of curing only a desired pattern so as not to be developed, It requires a development step to remove unexposed areas by image development, and a thermosetting step to obtain sufficient coating film properties.

 [0007] Among these processes, the exposure process is an extremely complicated process of aligning a negative film with a dry coating film, and then exposing the film to vacuum contact. It lowers the yield, such as the occurrence of tack marks during vacuum. In addition, negative films must be made by the photographic method for each pattern on the printed wiring board!

 [0008] In recent years, with the aim of improving productivity and reducing the cost of producing negative films, which are the problems of pattern formation methods by exposure through negative films, only necessary parts are directly illuminated from design data without using negative films. A direct imaging method using a UV laser that irradiates and draws is being studied.However, since the integrated exposure amount is lower than the light energy of exposure through a negative film, undercutting due to lack of deep curability is considered. Occurrence is remarkable, and the rise in component costs associated with the higher sensitivity of the composition has become a problem.

[0009] In the case of a photographic developing solder resist composition that has been used so far, in the exposure step, light is hardened in the deep part of the coating film compared to the surface layer of the coating film due to the attenuation of light due to UV absorption of the coating film. Is insufficient, so that a phenomenon called undercut occurs, in which the cross-sectional shape of the pattern edge portion after development is overhanged from the deep portion to the surface, which makes it difficult to obtain development resistance. Undercuts that occur in the solder resist on copper circuits are caused by external stress in the direction of lifting the paint film from its shape during the soldering or plating of the underlying copper. As a result, a defect phenomenon occurs in which the solder resist does not withstand the stress and becomes defective.

 [0010] When the same thread is formed and a pattern is formed by screen printing to form a pattern without undercuts, the solder resist defect at the time of soldering and plating is improved. In pattern printing, a high-definition pattern is formed. I can not cope.

 [0011] In order to obtain a high-definition pattern free from undercutting, it is effective to improve the deep curability of the solder resist composition of the photo-developing method. Therefore, the workability is reduced, and an increase in the amount of the photopolymerization initiator causes an increase in the material cost.

 Disclosure of the invention

 [0012] The present invention has been made under the above-described background. The main object of the present invention is to provide a method for forming an insulating pattern having excellent undercoating and excellent film properties by a simple process without using a photomask at low cost and with high productivity.

 [0013] The inventors of the present invention have made intensive studies for realizing the above object, and as a result, have conceived the following invention.

 [0014] That is, in order to realize the above object, as a first aspect of the present invention, there is provided a method for forming an insulating pattern, wherein (1) a repellent agent (A) is provided on an insulating layer (2) A liquid insulating resin that has a higher surface tension than the fixed repellent (A) and a lower surface tension than that of the substrate. A step of applying the composition (B) to the entire surface of the substrate obtained in the step (1), and (3) a coating film of the liquid insulating resin composition (B) obtained in the step (2), A step of irradiating with an active energy ray and curing with Z or heat, or drying with heat to fix the film on the substrate to form an insulating layer. In the steps (2) to (3), the liquid Wherein the insulating resin composition (B) is repelled by the adhered substance of the repellent (A) to obtain an insulating pattern. An edge pattern forming method is provided.

 [0015] Further, as a second aspect of the present invention, there is provided an insulating pattern formed using the method for forming an insulating pattern.

[0016] Further, as a third aspect of the present invention, there is provided a printed wiring board having an insulating pattern formed by using the method for forming an insulating pattern. Brief Description of Drawings

 FIG. 1 is an explanatory diagram schematically showing tension acting on a droplet on a solid surface.

 FIG. 2 is an explanatory diagram schematically showing the stable tension of a droplet on a solid surface.

 FIG. 3 is an explanatory view schematically showing tension acting on a droplet on a repellent (A).

 FIG. 4A is an explanatory view schematically showing a repellent applying step in one embodiment of the method for forming an insulating pattern according to the present invention.

 FIG. 4B is an explanatory view schematically showing a step of fixing a repellent by photocuring in one embodiment of the method of forming an insulating pattern according to the present invention.

 FIG. 4C is an explanatory view schematically showing a step of applying an insulating resin composition in one embodiment of the method for forming an insulating pattern according to the present invention.

 FIG. 4D is an explanatory view schematically showing an insulating pattern formed into a desired pattern by being repelled by a repellent in one embodiment of the method for forming an insulating pattern according to the present invention.

 BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, a method for forming an insulating pattern according to the present invention will be described in detail.

 First, (1) a repelling agent (A) is applied and fixed on a circuit-formed substrate in a pattern having a negative relationship opposite to the desired pattern of the insulating layer.

 [0020] The "repellent agent" referred to in this specification is a material for repelling the liquid insulating resin composition (B), and the surface of the liquid insulating resin composition (B) This shows a composition having a surface tension lower than the tension and capable of forming a fixed layer insoluble in the liquid insulating resin composition (B).

 In this step, as a method of applying the repellent (A) onto the substrate, any method that can selectively apply the repellent (A) onto the substrate, such as ink jet printing, letterpress printing, or screen printing, can be used. Either may be used. In particular, it is preferable to form a pattern by ink jet printing, in which non-contact coating is desired, since it is possible to directly draw a high-definition pattern with the design data power, since it is desirable to prevent non-contact application of the repelling agent to unnecessary portions. The application temperature may be room temperature or may be heated to improve fluidity.

According to the composition of the repellent (A), the coating film of the repellent (A) thus obtained may be dried by heat, irradiated with photoactive energy rays, cured by Z or heat, or hot-coated. Place by melt In the case of solidification by cooling, it can be fixed on the substrate by any one method

Specifically, the repellent composition fixed by drying with heat contains a diluent such as an organic solvent or moisture, and the repellent is solidified by drying to remove the diluent by heat. It can be fixed on the substrate.

 [0024] The repellent composition fixed by irradiation with photoactive energy rays and curing with Z or heat contains a liquid compound having a functional group that reacts with irradiation with photoactive energy rays and Z or heat. The repelling agent can be solidified and fixed on the substrate by irradiation with radiation and curing by Z or heat.

 [0025] The repellent agent thread which solidifies by cooling and solidifying after hot melt contains a compound which is solid at room temperature and liquefies by raising the temperature, and the composition liquefied at a high temperature remains at a high temperature. After the application, by cooling, the repelling agent can be solidified and fixed on the substrate.

 The reason for fixing the repellent (A) in this manner is as follows. In other words, when the repellent (A) exhibits fluidity, during the formation of an insulating pattern due to the repelling phenomenon of the liquid insulating resin composition (B), which also exhibits fluidity, pattern deformation due to flow or insulation This is because the repellent (A) diffuses into the composition (B). Also, if the repellent (A) is not fixed, the repellent (A) becomes contaminated during transportation in the subsequent process and adheres to unnecessary parts. I need. This fixation is performed for the purpose of preventing the repellent (A) from flowing, so that there is no need to completely solidify the liquid insulating resin composition (B) unless a problem occurs during the application process. The drying property may be poor.

 [0027] Next, (2) a liquid insulating resin composition (B) having a higher surface tension than the fixed repellent (A) and a lower surface tension than the substrate is added to the repellent (A). Apply to the entire surface of the substrate on which the pattern consisting of the fixed film is formed.

[0028] As a method of applying the liquid insulating resin composition (B) to the entire surface of the substrate, any method can be used as long as it can be applied uniformly on the substrate on which the pattern of the repellent agent (A) is formed. Any method is acceptable. For example, dip coating, flow coating, curtain coating, spray coating, etc. can apply the insulating resin composition (B), which is a low-viscosity composition with excellent fluidity. Since the insulating resin composition (B) is applied after application, it is easily repelled by the fixed film of the repellent (A), which is preferable. In particular, curtain coats and spray coats are non-contact coatings, and are preferred because there is no risk of adhering pieces of the repellent (A) to the insulating resin composition (B).

 [0029] The viscosity of the insulating resin composition (B) is usually preferably 500 dPa or less, more preferably 300 dPa or less, measured with an E-type viscometer at 25 ° C.

 When the insulating resin composition (B) applied to the entire surface of the substrate as described above is applied to the substrate, as shown in FIG. 1, when the contact angle between the solid 1 and the liquid 2 is set to 0, Surface tension γ of solid 1,

 S

 There are three tensions, the surface tension γ of liquid 2 and the interfacial tension γ of solid 1 and liquid 2.

 S S

 Each tension when the droplet is stabilized on the substrate surface operates in an equilibrium state as shown in FIG. 2, and the relational expression of each tension at that time is known as Young's equation (Equation 1). Have been.

 y — y cos θ + y · · (Equation 1)

 s then s

 The interfacial tension γ between solid and liquid is approximated by Girifalco-Good equation (Equation 2).

 s

 You can ask. Φ is a material-specific correction coefficient.

Ύ = Ύ + Ύ -2Φ (γ γ) ^1/2

 S then S then S

 On the other hand, as shown in Fig. 3, the liquid insulating resin composition (B) is repelled by the fixed film of the repellent agent (A). Zhang trying

 S

 The force (γ cos θ + γ) is required to be large and can be expressed as (Equation 3).

 S S

 y ^ y cos Θ + y

 S then S

 In addition, since the contact angle く is 0 and cos Θ 1 and the (Equation 1) force is a smaller value of the interface tension γ between the solid and the liquid than the surface tension γ of the solid, 3) is established

S then S

 In order to achieve this, the surface tension of the liquid γ 1S must be at least larger than the surface tension of the solid γ

 Don't be. (Surface tension of solid γ) <(Surface tension of liquid γ) needs to be satisfied.

 S

 Become. That is, in the surface tension,

 (Surface tension of adhered repellent (Α)) <(surface tension of liquid insulating resin composition (Β)) is a necessary condition.

 In the liquid insulating resin composition (榭), since the purpose is to coat the substrate, (solid surface tension γ)> (liquid surface tension γ) is satisfied based on the surface tension. .

 S

[0033] That is, in terms of surface tension, (Surface tension of substrate)> (Surface tension of liquid insulating resin composition (B)) is a necessary condition.

[0034] When the above conditions are satisfied, the repellent agent (A) in the insulating resin composition (B) on the top of the adhered substance has the inside of the droplet (in the γ cos θ + γ direction in FIG. 3). Pulled. On the other hand,

 Insulating resin composition (張力) spreads on the substrate due to wetting. From these two phenomena, the insulating resin composition (Β) on the top of the repellent (Α) adheres to the substrate, and is repelled from the repellent (Α) adherent onto the substrate, It comes into contact with the side of the repellent (Α). Thus, the insulating resin composition (組成) is positioned in a desired insulating pattern.

 [0035] The surface tension of the fixed repellent (は) must be smaller than the surface tension of the liquid insulating resin composition (Β), and the difference is the difference between the surface tension of the liquid insulating resin composition (Β). Preferably, the surface tension is lower than 2.5 mNZm, more preferably lower than 5 mNZm.

 (3) The coating film of the liquid insulating resin composition (B) is fixed on a substrate by irradiation with active energy rays and curing with Z or heat, or drying with heat to form an insulating layer. .

 [0037] In this step, the method of fixing the insulating resin composition on the substrate may be selected according to the composition of the liquid insulating resin composition (B). For example, the UV-curable insulating resin composition (B) is irradiated with active energy rays, and the thermosetting insulating resin composition (B) is heated by the alkali-imaging insulating resin composition (B). Can be fixed on the substrate by curing with active energy ray irradiation and Z or heat, and can be fixed on the substrate by thermal drying in the case of a dry insulating resin composition (B).

 [0038] In the method of forming an insulating pattern according to the present invention as described above, the repellent (A) may be a surface of a fixed substance which is formed of a yarn and a material satisfying the following formula. The tension may be adjusted by an additive or by changing the surface energy during fixing.

(Surface tension of fixed repellent (A)) <(Surface tension of liquid insulating resin composition (B)) Here, the surface tension of the fixed substance of repellent (A) is adjusted by an additive. To this end, a silicone compound or a fluorine compound may be added, and in particular, the silicone conjugate can reduce the surface tension and can suitably impart repelling properties. Such silicone compounds include low molecular weight silicone oil, high molecular weight silicone resin, and silicone resin. Corn graft acrylic copolymer resin or their fluorides can be used

[0040] It is desirable that this silicone conjugate is added to the repellent (A) in an amount of 1% by mass or more, preferably 5% or more, and more preferably 10% or more.

 [0041] The reactivity can be used for fixing the repellent (A), which may be provided with a reactive functional group, to the silicone conjugate. The silicone conjugate having a silanol group and an alkoxysilane can be cured by condensation. In the case of a silicone conjugate having a (meth) atalyloyl group, the photo-curing property is improved in combination with a photo-radical polymerization initiator, and in the case of a silicone conjugate having an epoxy group, a photo-induced thione polymerization initiator is used. Can be granted. In the case of a silicone conjugate having a carboxyl group, alkali developability or alkali releasability can be imparted. Further, thermosetting can be imparted by mixing a silicone conjugate having a carboxyl group, an epoxy resin and a curing accelerator such as amines, azines and imidazoles.

 [0042] These silicone conjugates can be used by mixing with other organic compounds.

As a composition of the repellent (A), for example, in a composition which is fixed by drying with heat, it is necessary that the composition contains an organic solvent or a diluent such as moisture. The composition that cures with (meth) atariloyl group contains a polymer, an oligomer, and a monomer, and a photo-radical polymerization initiator or a polymer, an oligomer, and a monomer that contains an epoxy group, and a photo-thione polymerization initiator. Is preferred.

[0044] In a composition which is fixed by heat, a compound having a heat-reactive group such as an alkoxysilane having an epoxy group, a carboxyl group, a phenolic hydroxyl group, a silanol group, a methoxy group and an ethoxy group, and maleic anhydride Succinic anhydride, itaconic anhydride, citraconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendomethylenetetrahydroanhydride Phthalic acid, endomethylenetetrahydrophthalic anhydride, dodece-succinic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene 1,2-dicarboxylic anhydride, benzophene Anhydride-based curing agents such as non-tetracarboxylic anhydrides, and triethylamine, triptynoleamine, DBU (1,8-diazabicyclo [5,4,0] indene-7-ene), DBN (1,5- Amines such as diazabicyclo [4,3,0] nonane-5-ene), DABCO (l, 4-diazabicyclo [2,2,2] otatan), pyridine, N, N dimethyl-4-aminopyridine, dicyandiamide and melamine It is preferable to contain a hardening accelerator such as a hardening accelerator such as a compound; an azine; and an imidazole.

 [0045] Furthermore, in the repellent composition which solidifies by cooling and solidifying after hot melt, it is a repellent containing a compound which solidifies at room temperature and liquefies at high temperature, and has a low viscosity under high application temperature conditions. It is preferred that it be rapidly solidified by rapid cooling. For example, wax and the like can be mentioned.

 [0046] The liquid insulating resin composition (B) is (the surface tension of the fixed repellent (A)) <(the surface tension of the liquid insulating resin composition (B)), and (the surface of the substrate). Tension)> (Surface tension of the liquid insulating resin composition (B)) and UV curable if it shows a fluidity of 500 dPa or less under the working atmosphere where the entire surface is coated on the substrate. The present invention can be applied to any of known and commonly used solder resist compositions such as a mold solder resist, a thermosetting solder resist, an alkali development solder resist, and a heat drying solder resist.

 [0047] In a printed wiring board having an insulating pattern formed by the method for forming an insulating pattern according to the present invention, the repellent (A) adjacent to the insulating pattern may be dissolved, if necessary. , Peeling, or decomposition. For example, in the case of a repellent (A) using an alkali-soluble fatty alkali-soluble monofunctional monomer, it can be removed by dissolution or swelling with an alkaline aqueous solution, and similarly, a repellent using a tertiary amine-containing resin ( A) can be removed with an acid such as hydrochloric acid. In the case of the heat-repellent repellent (A) using a solvent-soluble resin, it can be removed by dissolving it in an organic solvent. Since the repellent (A) using rosin-based resin has a flux effect, it can be melted or decomposed by the heat of solder at the time of component mounting, and can be removed with a solvent after mounting. it can.

[0048] As described above, by selecting the composition of the repellent agent (A), the cured resin of the insulating resin composition (B) can be dissolved by a solvent, an acid or an alkali, swelled and peeled, or activated so as not to attack the coating film. It can also be removed by energy irradiation or decomposition by heat during soldering. [0049] When the repellent (A) is removed with an aqueous alkali solution, a compound having a carboxyl group is contained in order to increase the solubility in the aqueous alkali solution. It is important that the carboxyl groups be present without reaction.

 [0050] The repelling agent (A) may be provided with a function other than the repelling function, for example, a function as a flux for soldering, a function of inhibiting the hardening of the insulating resin composition (B), and an anti-etching function. .

 For example, by providing the repelling agent (A) with a function as a flux for soldering, mounting can be performed without the step of removing the repelling agent (A) adhered matter.

 [0052] A cationic curing system is used for the insulating resin composition (B), an amine or the like that inhibits cationic polymerization is added to the repellent agent (A), and the insulating resin composition (B) is irradiated with active energy rays, or Selectively inhibits cationic polymerization when cured by heat. As a result, it is possible to inhibit and remove the interface between the repellent (A) and the insulating resin composition (B) and the hardening of the insulating resin composition (B) adhering to the repellent fixed substance. .

 [0053] Further, by imparting etching resistance and photodegradability to the repellent agent (A), it is possible to perform from circuit formation to formation of an insulating pattern. Specifically, first, a repelling agent is fixed on the entire copper-clad substrate in a circuit pattern, a copper etchant is used to remove copper other than the repelling agent pattern to form a circuit, and then an insulating layer is formed on the copper circuit. After removing the repelling agent (A) at the required site by photolysis, apply a liquid insulating resin composition (B) over the entire surface and perform patterning by repelling to improve the circuit forming power. It is possible to perform up to formation.

An example of the insulating pattern forming method of the present invention will be specifically described with reference to FIGS. 4A to 4D. First, as shown in FIG. 4A, a repellent (A) 11 is applied from a print head 10 to a pattern having a negative relationship opposite to the pattern of the insulating layer by an ink jet or the like. Next, as shown in FIG. 4B, the repelling agent (A) 11 is light-cured by light irradiation, and is fixed on the substrate 12. As shown in FIG.4C, the entire surface of the substrate 12 on which the pattern 13 composed of the repellent fixing film (B) having a negative relationship opposite to the pattern of the insulating layer thus obtained was formed, as shown in FIG. The entire surface of the insulating resin composition (B) 14 is applied from a printing head or a nozzle 15 by screen printing or the like. Liquid insulating resin group coated on the whole surface in this way The composition (B) 14 is repelled by a repellent fixed to a pattern having a negative relationship opposite to the pattern of the insulating layer, and an insulating pattern 16 is formed as shown in FIG. 4D. After that, the insulating layer can be fixed on the substrate by irradiation with active energy rays and curing with Z or heat, or drying with heat.

(Example)

 Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Example 1

 100 parts by mass of a copolymer resin containing a carboxyl group (trade name: Cyclomer P250) manufactured by Daicel Chemical Industries, Ltd., 75 parts by mass of propylene glycol monomethyl ether, Silicone conjugate (trade name: KS) manufactured by Shin-Etsu Chemical Co., Ltd. — 66) Two parts by mass were thoroughly mixed to obtain an alkali-soluble repellent (A-1).

 [0057] The obtained repellent agent (A-1) was applied on a circuit-formed FR-4 substrate using an ink jet printer in a pattern opposite to that of the solder resist, and was applied at 80 ° C. It dried and solidified in 10 minutes.

 Example 2

 100 parts by mass of a copolymer resin containing a carboxyl group (trade name: Cyclomer P250) manufactured by Daicel Chemical Industries, Ltd., 75 parts by mass of propylene glycol monomethyl ether, a silicone compound manufactured by Toray Dawko Silicone Co., Ltd. (trade name: FS) — 1265—1000) 2 parts by mass were thoroughly mixed to obtain an alkali-soluble repellent (A-2).

 [0059] The obtained repellent (A-2) was applied on an FR-4 substrate on which a circuit was formed, using an ink jet printer, in a pattern opposite to the solder resist pattern. It dried and solidified in 10 minutes.

 Example 3

100 parts by mass of a copolymer resin containing a carboxyl group (trade name: Cyclomer P250) manufactured by Daicel Chemical Industries, 75 parts by mass of propylene glycol monomethyl ether, silicone-grafted acrylic resin manufactured by Shin-Etsu Chemical Co., Ltd. (trade name: X — 22— 8195) 100 parts by mass were sufficiently mixed to obtain an alkali-soluble repellent (A-3). [0061] The obtained repellent (A-3) was applied onto a circuit-formed FR-4 substrate using an ink jet printer in a pattern opposite to that of the solder resist, and then applied at 80 ° C. It dried and solidified in 10 minutes.

 Example 4

 Silicone-based reactive oligomer manufactured by Shin-Nakamura-Danigakusha Co., Ltd. (Product name: Resin SA-200) 1

00 parts by mass and 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide (5 parts by mass) were sufficiently mixed to obtain a photocurable repellent (A-4).

[0063] The obtained repellent (A-4) was applied on an FR-4 substrate having a circuit formed thereon, using an ink jet printer, in a pattern opposite to the solder resist pattern. cured at LOOOmjZcm ² at (a high pressure mercury lamp).

Example 5

 100 parts by mass of silicone-based reactive oligomer (trade name: Resin SA-200) manufactured by Shin-Nakamura-Danigaku Co., Ltd. 100 parts by mass of 2-ataryloy quichetyl succinic acid, 2,4,6-trimethylbenzoyl Five parts by mass of enylethoxyphosphine oxide were sufficiently mixed to obtain a photo-curable and alkali-soluble repellent (A-5).

[0065] The obtained repellent (A-5) was applied on an FR-4 substrate on which a circuit was formed, using an ink jet printer, in a pattern opposite to the solder resist pattern. cured at LOOOmjZcm ² at (a high pressure mercury lamp).

 Example 6

 20 parts by mass of a modified silicone oil (trade name: SF8418) manufactured by Toray Dow Corning Silicone Co., Ltd. The mixture was thoroughly mixed to obtain a photocurable and alkali-soluble repellent (A-6).

[0067] The obtained repellent (A-6) was applied on a circuit-formed FR-4 substrate in a pattern opposite to that of the solder resist using an ink jet printer, and a UV conveyor furnace was used. cured at LOOOmjZcm ² at (a high pressure mercury lamp).

 Example 7

20 parts by mass of silicone monoatarylate (trade name: X-24-8201) manufactured by Shin-Etsu Danigaku Kogyo Co., Ltd. , 2 Atariloi mouth xicetyl succinic acid 100 parts by mass, 2,4,6-trimethylbenzoylfe

-Luethoxyphosphine oxide (5 parts by mass) was sufficiently mixed to obtain a photo-curable and alkali-soluble repellent (A-7).

[0069] The obtained repellent (A-7) was applied on an FR-4 substrate on which a circuit was formed, using an ink jet printer, in a pattern opposite to that of the solder resist, and a UV conveyor furnace was used. cured at LOOOmjZcm ² at (a high pressure mercury lamp).

Example 8

 20 parts by mass of rosin-based monoatalylate manufactured by Arakawa Chemical Industry Co., Ltd. (trade name: Beam Set 101) After thorough mixing, a light-curing and flux-repelling repellent (A-8) was obtained.

[0071] The obtained repellent agent (A-8) was applied on a circuit-formed FR-4 substrate using an ink jet printer in a pattern opposite to that of the solder resist, and the UV conveyor furnace was used. cured at LOOOmjZcm ² at (a high pressure mercury lamp).

 Comparative Example 1

 100 parts by mass of a copolymer resin containing a carboxyl group (trade name: Cyclomer P250) manufactured by Daicel Chemical Industries, Ltd. and 75 parts by mass of propylene glycol monomethyl ether were sufficiently mixed, and the repellent of Examples 13 to 13 was used. A comparative composition (C1) excluding the silicone compound was obtained.

 [0073] The obtained comparative composition (C-1) was applied on a FR-4 substrate having a circuit formed thereon, using an ink jet printer, in a pattern opposite to that of the solder resist, and then applied at 80 ° C. CX dried and solidified for 10 minutes.

 [0074] Comparative Example 2

 (2) 100 parts by mass of xylethyl succinic acid with atarilo mouth and 5 parts by mass of 2,4,6-trimethylbenzoylphenyl-ethoxyphosphine oxide were sufficiently mixed, and the silicone compound was removed from the repellent of Examples 5-7. A comparative composition (C2) was obtained.

[0075] The obtained comparative composition (C-2) was applied on an FR-4 substrate on which a circuit was formed, using an ink jet printer, in a pattern opposite to that of the solder resist, and a UV competition was performed. Cured in a furnace (high pressure mercury lamp) with lOOOOmjZcm ² .

As a liquid insulating resin composition (B), an alkali-developed photo-solder resist (manufactured by Taiyo Ink Mfg. Co., Ltd.) was applied on each of the substrates obtained in Examples 1 to 8 and Comparative Examples 1 and 2. Product name;

PSR-4000 CC02) was applied over the entire surface with a curtain coater, and after standing at room temperature for 5 minutes, the repellency (pattern forming property) was visually evaluated.

Further, the substrate used in Examples 1 to 8 and Comparative Examples 1 and 2 and the repellent agent (A-1) 1 (A

-8) and comparative compositions (C-1) and (C-2) surface tension, and a liquid insulating resin composition, an alkali-developed photosolder resist (trade name: PSR) manufactured by Taiyo Ink Manufacturing Co., Ltd. - Four

000 CC02) was determined as follows, and the results are shown in Table 1.

[0078] Surface tension of solid surface (substrate, repellent after fixation, and comparative composition after fixation)

 Based on JIS K 6768 "Wetting tension test method", each standard wetting tension test solution was applied linearly with a cotton swab, and the area where the line was not broken by repelling was measured.

[0079] The minimum wetting tension standard solution used this time was 22.6 mNZm.

[0080] Surface tension of liquid (insulating resin composition)

 The surface tension was measured using a surface tensiometer dynometer (manufactured by BYK Japan KK) using a platinum ring.

[table 1]

table 1

As described above, in each of the substrates obtained in Examples 18 to 18, the liquid insulating resin composition (B) was repelled by the repellent ((A-1) -1 (A-8) ) And was arranged in the desired pattern. After that, the strong liquid insulating resin composition (B) is dried at 80 ° C. for 30 minutes, and then exposed and cured at 500 mJZcm ^{2 in} a UV comparator furnace to obtain a solder resist having good coating characteristics. A pattern was obtained.

 Further, each of the substrates obtained in Comparative Examples 1 and 2, the liquid insulating resin composition (B) is repelled by the fixed film of the comparative composition (Cl, C 2). It was impossible to cover the entire surface of the substrate without obtaining the desired solder resist pattern.

 Industrial applicability

According to the method for forming an insulating pattern according to the present invention, an insulating pattern without undercut and excellent in coating characteristics can be formed at low cost and with high productivity by a simple process without using a photomask. .

According to the present invention, as the liquid insulating resin composition to be used, a light-curing and Z- or thermosetting or heat-drying simple composition can be used according to the present invention. Compared with the complex photosensitive resin composition of the development type used for dying or the like, the composition has a higher degree of freedom and a lower price can be achieved.

[0085] Therefore, according to the present invention, it is possible to easily achieve the improvement in productivity and low price required for forming a solder resist on a printed wiring board.

Claims

Claims [1] A method for forming an insulating pattern,  (1) a step of applying a repellent agent (A) on a circuit-formed substrate in a pattern having a negative relationship opposite to the pattern of the insulating layer and fixing the same;  (2) Apply a liquid insulating resin composition (B), which has a higher surface tension than the fixed repellent (A) and a lower surface tension than the substrate, over the entire surface of the substrate obtained in step (1). The process and  (3) The coating of the liquid insulating resin composition (B) obtained in the step (2) is fixed on the substrate by irradiation with active energy rays and curing with Z or heat, or drying with heat to insulate the resin. Process of forming layers  In the steps (2) to (3), the liquid insulating resin composition (B) is repelled by the fixed substance of the repellent (A) to obtain an insulating pattern. A method for forming an insulating pattern, comprising:  [2] In step (1), the coating film of the repellent agent (A) may be dried by heat, irradiated with active energy rays and cured by Z or heat, or solidified by cooling in the case of hot melt. 2. The method for forming an insulating pattern according to claim 1, wherein the insulating pattern is fixed on the substrate by a method.  3. The method for forming an insulating pattern according to claim 1, wherein a composition containing at least a silicone adhesive is used as the repellent (A). [4] The silicone ligated product according to claim 3, wherein the silicone ligated product has at least one functional group in a molecule which reacts by irradiation with active energy rays and Z or heat. The method for forming an insulating pattern according to the above. [5] The method for forming an insulating pattern according to any one of claims 14 to 14, wherein in the step (1), the repellent agent (A) is applied on a substrate by an ink jet method. . [6] An insulating pattern formed by using the insulating pattern forming method according to any one of claims 115.  [7] A printed wiring board having an insulating pattern formed using the method for forming an insulating pattern according to any one of claims 115.