KR101526065B1 - Board coating agent - Google Patents

Abstract

An object of the present invention is to provide a substrate coating agent which is easy to form a coating film thinly and uniformly on a substrate, has good peelability between coats after curing, and is excellent in resistance to chemicals such as acid and alkali, The coating agent contains a urethane resin, a styrene resin and a thickener for the solvent. The substrate coating agent according to the present invention is excellent in resistance to chemicals and hardly causes coating film defects and makes it easy to form a coating film thinly and uniformly on a substrate and has excellent peelability between coats after curing, So that the handling of the substrate after coating becomes better.

Description

{Board coating agent}

 BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate coating agent, and more particularly, to a substrate coating agent, which comprises an end face of a circuit board (hereinafter referred to as a substrate) such as a metal substrate or a copper-clad laminate substrate, And the like, and is capable of protecting a portion coated on a substrate from various agents used in circuit processing.

A substrate (metal substrate) based on a metal plate such as an aluminum plate is excellent in heat dissipation and mechanical strength, and can be mounted with heavy parts, thereby making it possible to increase current capacity. As circuit processing for performing etching treatment or the like on such a metal substrate, acid or alkali agents are used. In order to prevent erosion of the end surface portion of the metal substrate by these medicines, conventionally, an erosion preventing tape is manually attached to the end surface of the metal substrate, and after etching treatment, the erosion preventing tape is manually . In this method, the cost of the anti-erosion tape is high, and labor costs are also high because of manual work. Also, there was a problem that the working efficiency was low.

A printed board using a glass epoxy member other than the above-described metal substrate (so-called glass epoxy substrate is widely used.) A glass epoxy substrate is made by impregnating a glass fiber cloth with an epoxy resin. , And when the glass epoxy substrate is cut, fine dust composed of an epoxy resin or glass fiber is generated. Such a fine dust may cause poor contact or quality deterioration of the substrate circuit. The dust that has occurred in the city needs to be removed.

Patent Document 1 below discloses a technique of coating ultraviolet ray hardening resin on the end face of a substrate and curing the coated resin by ultraviolet ray irradiation in order to prevent scattering of cutting powder generated on the end face of the substrate.

In order to prevent erosion of the metal plate due to acid or alkali used at the time of circuit processing, the following Patent Document 2 discloses a method in which an ultraviolet curable resin is applied to the end face of a metal plate-based substrate, Discloses a technique of increasing the efficiency of cross-section sealing (shortening the curing time rather than a thermosetting type) by curing.

On the other hand, demand for a thin copper-clad laminate substrate (also referred to as a package substrate) having a thickness of several tens of microns to several hundreds of microns has been increasing in recent years in order to cope with the thinning and downsizing of electronic devices. With respect to such a thin substrate, it is not easy to apply the resin for protecting the end face of the substrate to only the end face of the substrate as described above, but it is also possible to apply the resin to the periphery including the end face of the substrate in a liquid- The same form can be considered.

In the case where the substrate itself is very thin, the thickness of the coating film should be sufficiently thin so as not to bulge or bend when the substrate on which the coating film is formed is superposed. Further, in order to facilitate the handling of the coated substrate, the peelability of the coated films must be good. Even a thin coating film must have sufficient chemical resistance to acids and alkalis used in circuit processing. However, there has been a problem in that a substrate coating agent which simultaneously satisfies such characteristics that the coating film is easily formed thinly and uniformly, the peelability of the coating films after curing is good, and the drug resistance is excellent also has not been developed.

Japanese Patent Application Laid-Open No. 2005-197443 Japanese Patent Laid-Open No. 5-152729

Disclosure of the Invention The present invention has been conceived in view of the problems described above, and it is an object of the present invention to provide a coating composition which is easy to form a coating film thinly and uniformly on a substrate, has excellent releasability between coats after curing, And to provide a substrate coating agent.

 In order to achieve the above object, the inventors of the present invention have conducted intensive studies and, as a result, have found that a substrate coating liquid containing a urethane resin, a styrene resin, and a thickening agent is excellent in resistance to chemicals such as acid and alkali, And it is easy to form the coating film thinly and uniformly on the substrate, and the peelability of the coated film after curing is good. Thus, the present invention has been completed.

In other words, the substrate coating agent (1) according to the present invention is characterized in that it contains a urethane resin, a styrene resin and a thickening agent for a solvent.

The substrate coating agent (1) is excellent in resistance to chemicals such as strong acidity and strong alkalinity, and it is easy to form a coating film thinly and uniformly on a substrate, The substrates do not stick to each other, and the handling of the substrate after coating can be made good.

Therefore, when the substrate coating agent is applied to the end face of the substrate or a peripheral edge portion including the end face thereof, a phenomenon that a foreign substance (dust or the like) is generated at the end of the substrate at the time of subsequent circuit processing It is possible to increase the strength of the substrate. In addition, it is possible to protect the end portion of the substrate from an etching solution or a plating solution (to prevent erosion of the substrate), so that there is no need to use a conventional erosion prevention tape or the like, and the processing cost can be reduced. Further, the peelability of the coating films after curing is good, and even when the substrates on which the coating films are formed are superimposed, the substrates can be prevented from sticking to each other at the coating film portions, and the handling property of the substrates can be improved.

The substrate coating agent (2) according to the present invention is characterized in that in the substrate coating agent (1), the urethane resin contains a urethane resin having a polycarbonate structure.

According to the above-mentioned substrate coating agent (2), since the urethane resin contains a urethane resin having a polycarbonate structure, it is possible to increase the durability of the coating film and to provide a coating agent having excellent resistance to strong acidity and strong alkalinity .

The substrate coating agent (3) according to the present invention is characterized in that in the substrate coating agent (1) or the substrate coating agent (2), the urethane resin is contained in an amount of 5 to 35 mass%, the styrene resin is contained in an amount of 1 to 10 mass% And 0.1 to 3% by mass of an acrylic resin.

According to the above-mentioned substrate coating agent (3), the effect of the above-mentioned substrate coating agent (1) can be exerted even if the viscosity is low and the viscosity is low. Further, by including the acrylic resin as the thickening agent, have.

The substrate coating agent (4) according to the present invention is any one of the substrate coating agents (1) to (3), wherein the solvent is an aqueous medium, and the urethane resin, the styrene resin and the thickener are water- .

According to the substrate coating agent (4), the urethane resin, the styrene resin and the thickener are water-soluble resins (for example, water-soluble emulsion resins Etc.), it is easy to handle, and can be made excellent in terms of safety and environment.

The substrate coating agent (5) according to the present invention is characterized in that it contains at least one of a moisturizing agent, a wettability improving agent and a defoaming agent as an additive in any one of the substrate coating agent (1) to the substrate coating agent (4) .

According to the substrate coating agent (5), the performance of the substrate coating agent can be further improved by the additive. By including the above-described moisturizing agent, it is possible to enhance the effect of preventing cracks and the like of the coating film during drying and after drying of the coating film. In addition, since the wettability improver is included, the wettability of the substrate surface can be increased, and the coating unevenness on the substrate at the time of coating can be prevented, and the coatability can be improved. Further, it is possible to prevent bubbles from being formed on the surface of the coating film by including the above-mentioned defoaming agent, to prevent the occurrence of bubble marks on the coating film, and to improve the smoothness of the film surface.

Further, the substrate coating agent (6) according to the present invention is characterized by containing a colorant in any one of the substrate coating agent (1) to the substrate coating agent (5).

According to the substrate coating agent (6), since the colorant is contained in the substrate coating agent (6), the goodness and the badness of the state coated on the substrate can be visually confirmed easily.

Hereinafter, embodiments of the substrate coating agent according to the present invention will be described, but the scope of the present invention is not limited to these embodiments. The substrate coating agent according to the present invention contains a urethane resin, a styrene resin and a thickener for a solvent.

The urethane resin used as the substrate coating agent according to the present invention is a generic name of a polymer having a plurality of urethane bonds in its main chain and is usually obtained by a reaction between a polyol and a compound having a plurality of isocyanate groups in the molecule. As the polyol, a polycarbonate polyol or a polyester polyol is used.

The polycarbonate polyol can be obtained, for example, by reacting a carbonate compound with a diol. Examples of the carbonate compound include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, diethylene carbonate and the like. Examples of diols include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, , Aliphatic diols such as octanediol, nonanediol, decanediol and dodecanediol, alicyclic diols such as cyclohexanediol and hydrogenated xylylene glycol, and aromatic diols such as xylylene glycol.

The polyesterpolyol can be obtained by condensing a low-molecular diol and a dicarboxylic acid. Examples of the low-molecular diol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and 1,4-butanediol. Of these, ethylene glycol, propylene glycol and 1,4-butanediol are most suitably used. Examples of the dicarboxylic acid include aromatic dibasic acids such as aliphatic dibasic acids such as succinic acid, glutaric acid, adipic acid, pimeric acid, suberic acid, azelaic acid and sebacic acid, isophthalic acid, terephthalic acid and naphthalenedicarboxylic acid Can be used.

There is no particular limitation on the molecular weight of the polycarbonate polyol or polyester polyol, but the number average molecular weight is usually from 700 to 4000, and more preferably from 1000 to 2500.

Examples of the polyisocyanate compound include aromatic, aliphatic and alicyclic polyisocyanate compounds. Examples of the aromatic diisocyanate compound include tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, toluidine diisocyanate, phenylene diisocyanate, Diisocyanate diisocyanate, 4,4-diphenyl ether diisocyanate, triphenylmethane triisocyanate, tris (isocyanate phenyl) thiophosphate, tetramethylxylylene diisocyanate, and the like. Examples of the aliphatic diisocyanate compound include trimethyl hexamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated 4,4-diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, lysine diisocyanate, lysine ester triisocyanate , 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate. Examples of the alicyclic diisocyanate include cyclohexane diisocyanate and methylcyclohexane diisocyanate. These may be used alone, or a plurality of species may be used in combination.

The reaction product of the polyol and the diisocyanate can further increase the molecular weight by using a chain extender if necessary. As the make-up agent, a compound containing at least two functional groups containing an active hydrogen atom reactive with an isocyanate group can be used.

Examples thereof include aliphatic diols such as ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl- Examples of the aliphatic diol include aliphatic diols such as diol, octanediol, nonanediol, decanediol and dodecanediol, cyclohexanediol, alicyclic diol, aromatic diol, ethylenediamine, propylenediamine, hexamethylenediamine, tolylenediamine, Diamines such as phenyldiamine and diaminodiphenylmethane, and the like.

In the urethane resin having a polycarbonate structure in the substrate coating agent according to the present invention, an organic solvent may be used as a solvent as a solvent, but water is preferably used as a medium. In order to disperse or dissolve the urethane resin in water, there are a forced emulsification type using an emulsifying agent, a self-emulsifying type in which a hydrophilic group is introduced into a urethane resin, or a receiving type. In particular, a self-emulsifying type in which an ionic group is introduced into the skeleton of a urethane resin is preferable because it is excellent in storage stability of a liquid and adhesion of a coat which can be obtained. The ionic group to be introduced may be various ones such as a carboxyl group, a sulfonic acid, a phosphoric acid, a phosphonic acid and a quaternary ammonium salt, but a carboxyl group is preferable.

As the method of introducing the carboxyl group into the urethane resin, various methods can be employed in each step of the polymerization reaction. For example, there is a method in which a resin having a carboxyl group is used as a copolymerization component in the synthesis of a prepolymer, and a method in which a component having a carboxyl group is used as a component such as polyol, polyisocyanate or chain extender.

The urethane resin used in the present invention is preferably a resin composed of a polycarbonate polyol, a polyisocyanate, a chain extender having a reactive hydrogen atom, a group reacting with an isocyanate group, and a compound having at least one anionic group.

The amount of the anionic group in the urethane resin is preferably 0.1 wt% to 8 wt%. With respect to the amount of the anionic group, the urethane resin has poor water solubility or water dispersibility, and the amount of the anionic group is likely to be hygroscopic and stick to each other.

The content of the polycarbonate component in the urethane resin is usually 10 to 90% by weight, preferably 20 to 70% by weight. If the content is less than 10% by weight, the effect of improving the adhesiveness of the urethane resin may be insufficient. If the content is more than 90% by weight, the coating property may be deteriorated.

Furthermore, the urethane resin in the present invention preferably has a glass transition point (hereinafter referred to as Tg) of 10 占 폚 or lower, preferably -10 占 폚 or lower. If the Tg is higher than 10 占 폚, the adhesion may be insufficient.

As the urethane resin in the present invention, a commercially available polyurethane resin can be used. As the urethane resin emulsion, for example, "HYDRAN" (trade name) manufactured by DIC Co., Ltd. and the like can be mentioned.

As the thickening agent used as the substrate coating agent according to the present invention, an acrylic resin, a gellant (solubilizer), a polymer solution or the like may be employed. These are added to adjust the viscosity to a suitable level for the application device or application method. Of these thickeners, an acrylic resin is preferable in that the strength of the coating film can be increased.

The acrylic resin is a polymer composed of acrylic acid, methacrylic acid, and derivatives thereof. Specific examples thereof include acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylamide, acrylonitrile, hydroxyl acrylate, A copolymerizable monomer (for example, styrene, divinylbenzene, etc.).

As the acrylic resin, it is preferable to use a water-dispersed acrylic resin obtained by emulsion polymerization using an acrylic monomer. As the acrylic monomer to be a raw material of the water-dispersed acrylic resin, acrylic acid monomers such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, Isobornyl, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, methacryl (Meth) acrylic acid alkyl ester monomers such as benzyl acrylate, benzyl methacrylate and isobornyl methacrylate, carboxyl group-containing acrylic monomers such as acrylic acid and methacrylic acid, 2-hydroxyethyl acrylate, hydroxypropyl acrylate , 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, poly Acrylic acid-containing acrylates such as acrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, A tertiary amino group such as a monomer, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, Containing acrylic monomer, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine Acrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, hydroxymethylacrylamide, hydroxyethyl acrylamide, N, N- N-methoxymethylacrylamide, N-butoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N- Methacrylamide, ethylethylene urea, and the like; urea group-containing acrylic monomers such as 2-methacryloyloxyethyl-ethylene urea, glycidyl acrylate, methyl glycidyl acrylate, glycidyl methacrylate , Epoxy group-containing acrylic monomers such as methyl glycidyl methacrylate, and vinyl benzyl glycidyl ether. The water-dispersed acrylic resin may be composed of these acrylic monomers alone, or may be composed of two or more kinds of mixtures.

It is preferable to use an aqueous dispersion acrylic resin obtained by emulsion-polymerizing the monomer as described above. The most suitable water-dispersed acrylic resin has a number average molecular weight of, for example, 5,000 to 200,000.

Specific examples of the acrylic resin used in the present invention include a copolymer of an ethylenically unsaturated monomer containing a carboxyl group such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid with an ethylenically unsaturated monomer having a carboxyl group such as methyl (meth) acrylate, ethyl , Copolymers with other ethylenically unsaturated monomers such as styrene, and the like, and they are used as polycarboxylic acid thickeners.

The properties of the acrylic resin used in the present invention are not particularly limited, and examples thereof include an emulsion and an aqueous solution. The acrylic resin used in the present invention is used to improve the coating workability by thickening the coating solution to a desired viscosity, and is used to adjust viscosity to a viscosity that is easy to use in response to the resin, additives, and concentration of the coating agent.

In the present invention, a commercially available acrylic resin can be used for the above-mentioned acrylic resin. For example, "VONCOAT" (trade name) manufactured by DIC Co., Ltd. and the like can be mentioned as the water-dispersed acrylic resin.

The styrene resin to be used for the substrate coating agent according to the present invention may be a copolymer of styrene homopolymer or styrene containing? -Methylstyrene, vinyltoluene or divinylbenzene monomer units, or other monomer capable of copolymerizing with styrene And the like.

Examples of the monomer copolymerizable with styrene include vinyl esters having 2 to 18 carbon atoms such as vinyl acetate and vinyl caprate; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and fumaric acid; unsaturated carboxylic acids such as monomethyl maleate and dimethyl fumarate; Vinyl ethers such as isobutyl vinyl ether and octyl vinyl ether; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride and the like; acrylic acid esters such as methyl methacrylate, ethyl methacrylate, Ronitril, vinylidene chloride, and the like.

In the present invention, it is preferable to use an acrylic styrene resin. The acrylic styrene resin is a resin obtained by polymerizing a styrene monomer and an acrylic ester monomer. As the styrene monomer, styrene,? -Methylstyrene and the like can be used. Examples of the acrylic acid ester monomer include monomers such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, Etc. may be used. Examples of the most suitable acrylic styrene resin include styrene-methyl methacrylate copolymer, styrene-butyl acrylate copolymer, styrene-methyl methacrylate-butyl acrylate copolymer, and styrene-methacrylate butyl.

In the present invention, a commercially available styrene resin can be used for the styrene resin. For example, "VONCOAT" (trade name) manufactured by DIC Corporation can be used as the acrylic styrene resin.

Other additives added to the substrate coating agent according to the present invention include humectants, wettability improvers, antifoaming agents, preservatives and coloring agents.

Examples of the moisturizing agent include glycerin, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (molecular weight: 100 to 2000), propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propylene glycol, isopropylene glycol, Glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, mesoerythritol, pentaerythritol and the like.

In the present invention, polyethylene glycol is preferably used in order to suppress the addition amount. For example, POLYETHLYLENE GLYCOL 200 manufactured by Showa Kagaku Co., Ltd. and the like can be used.

Examples of the wettability improver include ethylene glycol, polyethylene glycol alkyl ether (the number of carbon atoms of the alkylene group is 2 to 3), polyethylene glycol (molecular weight of 100 to 800), alkylsulfonic acid (the number of carbon atoms of the alkylene group is 2 to 3) Based copolymer, an aliphatic alcohol (having 1 to 3 carbon atoms), an anionic surfactant, a fluorine-based surfactant, and the like. The acrylic copolymer includes a copolymer of an ether group-containing alkyl (meth) acrylate monomer and an alkyl (meth) acrylate monomer, and the copolymer preferably has a weight average molecular weight of 3000 to 200000, Is 5000 to 50000. The weight average molecular weight can be determined by polystyrene conversion, for example, by gel permeation chromatography.

As the antiseptic agent (fungicide agent), an organic preservative or a preparation containing silver ion may be used. Organic nitrogen-sulfur compounds, organic aromatic compounds or organic nitrogen compounds can be used as the organic preservative.

As the colorant, inorganic pigments, organic pigments, aqueous dyes (organic), oily dyes (organic), extender pigments and the like can be used. Specific examples thereof include mica, iron oxide, titanium oxide, CI Pigment Black 7, CI Pigment Red 122, CI Pigment Orange 16, CI Pigment Green 7, CI Pigment Violet 23, Basic Green 4, Basic Violet 1, Basic Orenge 2 , Direct Blue 87, Acid Blue 90, CIAcid Yellow 23, CIFood Yellow 3, and the like.

Examples of the solvent of the substrate coating agent according to the present invention include water and an organic solvent. Considering safety and environmental aspects, it is preferable to use water as a solvent.

Examples of the water-soluble organic solvent include alkyl alcohols having 1 to 4 carbon atoms such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol and tert- Alkylene glycols having an alkylene group having 2 to 6 carbon atoms such as propylene glycol, butylene glycol, diethylene glycol and triethylene glycol, polyhydric alcohols such as glycerin, polyalkylene glycols, amides and ethers And the like.

Next, a method for preparing the substrate coating agent according to the embodiment will be described. A predetermined amount of a urethane resin, a styrene resin and, if necessary, a solvent (for example, water) are put in predetermined containers, respectively, and mixed by a stirrer. While mixing at low speed (1 to 100 rpm), a predetermined amount of moisturizing agent, wettability improving agent and preservative are added thereto and mixed. Subsequently, a predetermined amount of colorant is added, and then a predetermined amount of acrylic resin, for example, is added as a thickening agent. Thereafter, the agitation speed of the agitator is increased and high-speed agitation (200 to 500 rpm) of about 1 hour is carried out. After the high-speed stirring, a predetermined amount of the defoaming agent is added, and the stirring speed of the stirrer is set at a low speed (1 to 100 rpm) and stirred for about 30 minutes to prepare a substrate coating agent.

In addition, the preferred viscosity of the substrate coating agent according to the embodiment is 50 to 120 Pa · S, and more preferably 0.01 to 1.0 Pa · S from the viewpoint of thinning the film.

When the viscosity of the substrate coating agent is lowered, the content of the urethane resin or the styrene resin is decreased according to the set viscosity by appropriately increasing the content of the solvent (water) or the wettability improver, and a small amount of a thickener (acrylic resin or the like) A substrate coating agent capable of obtaining a desired effect can be prepared.

[Example]

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

[Example 1]

(Containing HYDRAN WLS-213, average particle size: 120 nm, elongation percentage: 400%, Tg: -30 캜, urethane resin concentration: about 35%, water: about 65%, skeleton derived from polycarbonate) And 10.0 parts by weight of a styrene resin (VONCOAT SK-105-E, a product of DIC Co., Ltd., solids content (acrylic styrene resin concentration: about 55%, water: about 45%)) were mixed and mixed with a stirrer.

0.5 parts by weight of a moisturizer (POLYETHLYLENE GLYCOL 200, manufactured by Showa Kagaku Co., Ltd.), 0.5 parts by weight of a wettability improving agent and 0.2 parts by weight of an antiseptic are added while mixing at a low speed (0 to 100 rpm). Then, 2.0 parts by weight of a colorant is added, and then 1.5 parts by weight of an acrylic resin (VONCOAT 3750-E manufactured by DIC Co., Ltd., acrylic resin concentration: about 25%, water: about 75%) is added. Thereafter, the stirring speed of the stirrer is increased (200 to 5.00 rpm), and high-speed stirring is performed for about 1 hour. The wettability improver and the preservative may be appropriately selected from those described above.

0.5 parts by weight of an antifoaming agent (AQUALEN SB-630, manufactured by Kyoeisha Kagaku Co., Ltd.) was charged, stirring was carried out at a low speed (0 to 100 rpm) for 30 minutes, Was prepared.

[Example 2]

93.0 parts by weight of a urethane resin (HYDRAN WLS-213, manufactured by DIC Co., Ltd.) and 6.0 parts by weight of a styrene resin (VONCOAT SK-105-E manufactured by DIC Co., Ltd.) were put in a vessel.

0.5 parts by weight of a moisturizing agent (POLYETHLYLENE GLYCOL 200 manufactured by Showa Kagaku Co., Ltd.), 0.5 parts by weight of a wettability improving agent and 0.2 parts by weight of an antiseptic are added while mixing at a low speed (1 to 100 rpm). Then, 2.0 parts by weight of a colorant is added, and then 1.0 part by weight of an acrylic resin (VONCOAT 3750-E manufactured by DIC Co., Ltd.) is added. Thereafter, the stirrer speed of the stirrer is increased (200 to 500 rpm) and high-speed stirring is performed for about 1 hour.

0.5 parts by weight of an antifoaming agent (AQUALEN SB-630 manufactured by Kyoeisha Kakaku Co., Ltd.) was charged, and the stirring speed of the stirrer was set to low speed (0 to 100 rpm), followed by stirring for about 30 minutes. Was prepared.

[Example 3]

41.0 parts by weight of a solvent (water) was put into the vessel, and then 45.0 parts by weight of a urethane resin (HYDRAN WLS-213 manufactured by DIC Co., Ltd.) and 5.0 parts by weight of styrene resin (VONCOAT SK-105- Mix with a stirrer.

0.5 parts by weight of a humectant (POLYETHLYLENE GLYCOL 200, manufactured by Showa Kagaku Co., Ltd.), 4.0 parts by weight of a wettability improving agent and 0.2 parts by weight of an antiseptic are added while mixing at a low speed (1 to 100 rpm). Then, 2.0 parts by weight of a colorant is added, and then 2.0 parts by weight of an acrylic resin (VONCOAT 3750-E manufactured by DIC Co., Ltd.) is added. Thereafter, the stirrer speed of the stirrer is increased (200 to 500 rpm) and high-speed stirring is performed for about 1 hour.

0.5 parts by weight of an antifoaming agent (AQUALEN SB-630 manufactured by Kyoeisha Kagaku Co., Ltd.) was added, and the stirring speed of the stirrer was set to a low speed (0 to 100 rpm), followed by stirring for about 30 minutes. Was prepared.

[Example 4]

(HYDRAN WLS-213 manufactured by DIC Co., Ltd.) and 4.0 parts by weight of styrene resin (VONCOAT SK-105-E manufactured by DIC Co., Ltd.) were added to the vessel, , And mixed with a stirrer.

0.5 parts by weight of a humectant (POLYETHLYLENE GLYCOL 200, manufactured by Showa Kagaku Co., Ltd.), 4.0 parts by weight of a wettability improving agent and 0.2 parts by weight of an antiseptic are added while mixing at a low speed (1 to 100 rpm). Then, 2.0 parts by weight of a colorant is added, and then 1.0 part by weight of an acrylic resin (VONCOAT 3750-E manufactured by DIC Co., Ltd.) is added. Thereafter, the stirrer speed of the stirrer is increased (200 to 500 rpm) and high-speed stirring is performed for about 1 hour.

0.5 parts by weight of an antifoaming agent (AQUALEN SB-630 manufactured by Kyoeisha Kagaku Co., Ltd.) was added, and the stirring speed of the stirrer was set to a low speed (0 to 100 rpm), followed by stirring for about 30 minutes. Was prepared.

[Comparative Example 1]

96.6 parts by weight of a urethane resin (HYDRAN WLS-213, manufactured by DIC Co., Ltd.) was added to the vessel and mixed with a stirrer. 0.1 part by weight of a preservative and 0.1 part by weight of a silane coupling agent are added while mixing at a low speed (1 to 100 rpm). Subsequently, 2.0 parts by weight of a colorant is added, and then 0.8 parts by weight of an acrylic resin (VONCOAT 3750-E manufactured by DIC Co., Ltd.) is added. Thereafter, the stirrer speed of the stirrer is increased (200 to 500 rpm) and high-speed stirring is performed for about 1 hour.

0.5 parts by weight of an antifoaming agent (AQUALEN SB-630 manufactured by Kyoeisha Kagaku Co., Ltd.) was added and the stirring speed of the stirrer was set to a low speed (0 to 100 rpm) and stirred for about 30 minutes, Was prepared.

[Comparative Example 2]

87.4 parts by weight of a urethane resin (HYDRAN WLS-213, a product of DIC Co., Ltd.) and 10.0 parts by weight of a hot-melt adhesive were put into a container and mixed with a stirrer. While mixing at low speed (1 to 100 rpm), 0.1 part by weight of preservative is added. Then, 2.0 parts by weight of a colorant is added. Thereafter, the stirrer speed of the stirrer is increased (200 to 500 rpm) and high-speed stirring is performed for about 1 hour.

0.5 parts by weight of an antifoaming agent (AQUALEN SB-630, manufactured by Kyoeisha Kakaku KK) was added, and the stirring speed of the stirrer was set to a low speed (0 to 100 rpm), followed by stirring for about 30 minutes. Was prepared.

[Comparative Example 3]

93.4 parts by weight of an acrylic resin (JONCRYL PDX-7100 manufactured by BASF Japan Co., Ltd., acrylic resin concentration: about 30%, water: about 70%) was charged into a container and mixed with a stirrer. 0.1 part by weight of a preservative and 0.1 part by weight of a silane coupling agent are added while mixing at a low speed (1 to 100 rpm). Then, 2.0 parts by weight of a colorant is added, and then 4.0 parts by weight of an acrylic resin (VONCOAT 3750-E manufactured by DIC Co., Ltd.) is added. Thereafter, the stirrer speed of the stirrer is increased (200 to 500 rpm) and high-speed stirring is performed for about 1 hour.

0.5 parts by weight of an antifoaming agent (AQUALEN SB-630, manufactured by Kyoeisha Kakaku Co., Ltd.) was added, stirring was carried out at a low speed (0 to 100 rpm) for 30 minutes, Was prepared.

[Comparative Example 4]

54.0 parts by weight of a urethane resin (HYDRAN WLS-213, manufactured by DIC Co., Ltd.), 40.0 parts by weight of a thermosetting resin (DICFINE EN-0274 manufactured by DIC Co., Ltd., solids content (epoxy resin concentration: about 25%, water: about 75% And the mixture is mixed with a stirrer.

0.2 parts by weight of the preservative and 1.5 parts by weight of the pH adjuster are added while mixing at low speed (0 to 100 rpm). Then, 2.0 parts by weight of a colorant is added, and then 1.8 parts by weight of an acrylic resin (VONCOAT 3750-E manufactured by DIC Co., Ltd.) is added. Thereafter, the stirrer speed of the stirrer is increased (200 to 500 rpm) and high-speed stirring is performed for about 1 hour.

0.5 parts by weight of an antifoaming agent (AQUALEN SB-630, manufactured by Kyoeisha Kakaku KK) was added and the stirring speed of the stirrer was set to a low speed (0 to 100 rpm) and stirred for about 30 minutes, Was prepared.

[Comparative Example 5]

96.3 parts by weight of a vinyl acetate resin (SUMIKAFLEX 520HQ, a concentration of a vinyl acetate resin: about 45%, water: about 55%) manufactured by Sumika CAM TEX Co., Ltd. was added to the vessel and mixed with a stirrer. While mixing at low speed (0 to 100 rpm), 0.2 part by weight of preservative is added. Then, 2.0 parts by weight of a colorant is added, and then 1.0 part by weight of an acrylic resin (VONCOAT 3750-E manufactured by DIC Co., Ltd.) is added. Thereafter, the stirrer speed of the stirrer is increased (200 to 500 rpm) and high-speed stirring is performed for about 1 hour.

0.5 parts by weight of an antifoaming agent (AQUALEN SB-630, manufactured by Kyoeisha Kagaku Co., Ltd.) was added, stirring was carried out at a low speed (0 to 100 rpm) for 30 minutes, Was prepared.

(Acid resistance and alkali resistance test)

In order to confirm the acid resistance and alkali resistance of the substrate coating agent, an etching process test and a plating process test were carried out.

The etching process test was conducted by coating (after film thickness about 30 to 50 占 퐉) a substrate coating agent according to Examples 1 to 4 and Comparative Examples 1 to 5 on the end face of a metal substrate (aluminum substrate having a thickness of about 2 mm) The metal substrate after coating film curing was etched in the following order (1) to (4), and the state of the coated film portion before and after the etching treatment was confirmed by a microscope.

(1) 3% sodium carbonate solution: treated at 50 DEG C for 0.5 minute

(2) Cupric chloride solution: treatment at 50 占 폚 for 15 minutes

(3) Sodium hydroxide solution: treated at 50 DEG C for 1 minute

(4) Washing (washing)

The results are shown in Table 1. The evaluation was made in three stages, that is, the case where the coating film was not peeled off, the case where the coating film was partially peeled off, and the case where the coating film was mostly peeled off.

The plating process test was carried out in such a manner that the substrate coating material according to the above-described Examples 1 to 4 and Comparative Examples 1 to 5 was subjected to liquid-phase transfer (hereinafter referred to as " liquid transfer ") on the periphery including a cross section of a copper- (About 30 to 50 mu m after film formation) to coat the copper-clad laminate after coating film curing in the order of the following (1) to (7) to form a coating film portion before and after the plating treatment Was confirmed by a microscope.

(1) Cleansing solution (ACL-007: manufactured by Kamimura Kogyo Co., Ltd.): treated at 50 ° C for 5 minutes

(2) Acid treatment (sulfuric acid): treatment at room temperature for 1 minute

(3) Soft etching solution (sodium persulfate 100 g / L, sulfuric acid 10 ml / L): treatment at room temperature for 1 minute

(4) Free dip solution (sulfuric acid 18 mL / L): treated at room temperature for 1 minute

(5) Activator solution (KAT-450, manufactured by Kamimura Kogyo Co., Ltd., 100 ml / L, sulfuric acid 18 ml / L)

(6) Electroless nickel plating (NIMUDEN NPR-4): treatment at 80 ° C, pH 4.6, 50 minutes

(7) Electroless gold plating (GOBRIGHT TSB-72): A nickel plating film (7 μm or more) and a gold-plated film (0.4 μm or more) were formed at 80 ° C. for 5 minutes, Were confirmed with a microscope.

The results are shown in Table 1. The evaluation was made in three stages, that is, the case where the coating film was not peeled off, the case where the coating film was partially peeled off, and the case where the coating film was mostly peeled off.

The evaluation of the wettability when applied to the above-mentioned copper-clad laminate was visually observed for the coating condition of the substrate coating agent according to Examples 1 to 4 and Comparative Examples 1 to 5 on the substrate.

The results are shown in Table 1. The results are shown in Table 1. The results are shown in Table 1. The results are shown in Table 1. The results are shown in Table 1.

In addition, the coating film surface was rubbed and observed for the presence or absence of peeling of the coating film after the application and curing of the substrate coating agent to the copper clad laminate according to Examples 1 to 4 and Comparative Examples 1 to 5.

The results are shown in Table 1. The evaluation was carried out in three stages, that is, the case where no peeling of the coating film was observed, the case where peeling occurred a little, the case where peeling occurred a little, and the case where peeling occurred a lot.

The peelability of the coating films after curing was evaluated by superimposing the substrate coating agent according to Examples 1 to 4 and Comparative Examples 1 to 5 on the periphery of the above-mentioned copper-clad laminate, And the peelability (sticking state) was observed.

The results are shown in Table 1. A case in which the coating films were peeled off without peeling off was evaluated as?, A case in which the coating films were slightly peeled off but a peel was simply peeled, and a case in which the coating films were stuck to each other and were not easily peeled off.

As shown in Table 1, the substrate coating agents according to Examples 1 to 4 were excellent in etching resistance and plating resistance, and excellent in resistance to strong acid and strong alkaline chemicals. In particular, the results of Example 1 were good. Therefore, it is possible to protect the coated portion of the substrate from the etching solution or the plating solution (prevent the substrate from being molten), and it is not necessary to use the conventionally used anti-erosion tape, and the processing cost can be reduced.

In addition, the substrate coating agents according to Examples 1 to 4 were less prone to paint film defects such as unevenness, and were easily formed thinly and uniformly on a substrate (metal substrate or a copper-clad laminate). In addition, the coating film after curing was not easily peeled off, the peeling property between the coating films was good, and the substrates did not stick to each other, and the handling of the substrate after coating was good.

Further, by applying the above-mentioned substrate coating agent to the peripheral portion including the end face or cross section of the substrate using a coating device or a brush, it is possible to prevent foreign matter (dust or the like) from being generated at the end of the substrate at the time of the subsequent circuit processing And the strength of the substrate can be increased by the coating film of the substrate coating agent.

On the other hand, according to the substrate coating materials of Comparative Examples 1 to 5, the resistance to chemicals with strong acidity and strong alkalinity was low, and coating film defects were generated, so that the coating film could not be formed thinly and uniformly. In addition, the coated film after curing was liable to be peeled off and the peeling property was low, and the substrates adhered to each other and the handling of the substrate after coating was bad.

Claims (6)

1. A substrate coating agent for application to a cross section of a circuit board or a periphery portion including said cross section,
Wherein the solvent contains a urethane resin, a styrene resin and an acrylic resin,
Wherein the solvent is an aqueous medium, and the urethane resin, the styrene resin and the acrylic resin are aqueous resins,
Wherein the urethane resin is contained in an amount of 5 to 35 mass%, the styrene resin is contained in an amount of 1 to 10 mass%, and the acrylic resin is contained in an amount of 0.1 to 3 mass%. The method according to claim 1,
Wherein the urethane resin contains a urethane resin having a polycarbonate structure into which an ionic group is introduced. The method according to claim 1,
Wherein the styrene resin contains an acryl-styrene resin. The method according to claim 1,
A substrate coating agent characterized by further comprising a wettability improving agent as an additive. 5. The method of claim 4,
Wherein the wettability improver is at least one selected from the group consisting of ethylene glycol, polyethylene glycol alkyl ether having 2 to 3 carbon atoms in the alkyl group, polyethylene glycol having a molecular weight of 100 to 800, alkyl sulfonic acid having 2 to 3 carbon atoms in the alkyl group, Wherein the coating liquid contains at least one selected from the group consisting of a copolymer, an aliphatic alcohol having 1 to 3 carbon atoms, an anionic surfactant, and a fluorinated surfactant. 6. The method according to any one of claims 1 to 5,
And a viscosity of 0.01 to 1.0 Pa · S.