WO2006038262A1

WO2006038262A1 - Solder resist coating, cured product therefrom and printed wiring board having coating film therefrom

Info

Publication number: WO2006038262A1
Application number: PCT/JP2004/014369
Authority: WO
Inventors: Masakazu Takemoto; Takashi Naito; Ryuzo Kaneko
Original assignee: Ceramission Co., Ltd.
Priority date: 2004-09-30
Filing date: 2004-09-30
Publication date: 2006-04-13
Also published as: JPWO2006038262A1; JP3928136B2

Abstract

A two component solder resist coating wherein a first component comprising a partial hydrolyzate of an alkoxysilane compound and an organic solvent and a second component comprising a titanium alkoxide and an organic solvent are mixed and cured, characterized in that the first component and/or the second component contain a potassium titanate fiber; a solder resist cured product formed from the coating; and a printed wiring board having a coating film prepared by forming a pattern using the coating and then curing the pattern. Said solder resist coating may further contain, in the first component and/or the second component, at least one selected from among a kaolin powder, an alumina powder and an aluminum hydroxide powder having been treated with a coupling agent, a fumed silica powder having been subjected to a surface treatment for imparting hydrophobicity, an ethyl cellulose powder, a blue pigment containing no halogen atom and/or a yellow pigment containing no halogen atom.

Description

Specification

Solder resist paint, cured product and printed wiring board with coating

Technical field

TECHNICAL FIELD [0001] The present invention relates to a two-component type solder resist paint, a cured product thereof, and a printed wiring board provided with a film that is one form of the cured product. More specifically, a first liquid containing a partial hydrolyzate of an alkoxysilane compound and a second liquid solder resist paint composed of a second liquid containing alkoxy titanium, and then the first liquid. And two-component solder resist paints containing potassium titanate fibers in Z or the second liquid, cured products formed from these two-component solder resist paints, and cured products formed from solder resist paints It is related with the printed wiring board provided with the film which is one form. The cured product and the coating have high heat resistance to withstand component mounting with lead-free solder. Further, it does not contain antimony compounds, halogen compounds and phosphorus compounds, but also exhibits flame retardancy.

Background art

[0002] Currently, an alkaline development type liquid solder resist is often used as a solder resist for some consumer printed wiring boards and most industrial printed wiring boards. Alkali development type liquid solder resists such as these photosensitive / thermosetting resin compositions are disclosed in JP-A-61-243869, JP-A-3-253093, JP-A-4-281454. The composition is disclosed in Japanese Patent Laid-Open No. 8-335767 and the like.

[0003] In addition, in order to impart flame retardancy to a solder resist, halogen flame retardants and combinations of halogen flame retardants and antimony compounds are widely used. As an alkali developing type solder resist using such a halogen-based flame retardant, a composition is disclosed in, for example, JP-A-2-88615. Recently, however, there has been an increasing demand for dehalogenation and deantimony for flame retardancy due to global environmental problems and safety issues for human bodies. For example, JP 2003-277470 A In the publication, no halogen compound is used. A composition containing an organophosphorus compound is disclosed! Speak. [0004] On the other hand, apart from the alkali developing type liquid solder resist, as another solder resist, a thermosetting type liquid solder resist has been used for a long time. Japanese Patent Publication No. 57-49588, Japanese Patent Application Laid-Open No. 56- No. 15741, JP-B-5-75032 and JP-A-11-158252 disclose the composition. As the composition, epoxy resin is mainly used. Recently, these liquid solder resists for thermosetting are mainly used for flexible printed wiring boards and printed wiring boards for IC packages.

[0005] By the way, various electronic components are mounted on the printed wiring board, and most of them are joined by solder. Due to environmental issues, this solder is also being switched to the current eutectic soldering power of tin and lead with lead-free solder, which requires a higher soldering temperature, resulting in improved heat resistance of the solder resist. I have to go. For the purpose of improving the heat resistance, a method of adding a filler having a radius of several tens of nm power / zm to the solder resist has been proposed, but it is insufficient in terms of quality and productivity. Thus, in order to solve environmental problems, solder resists that do not contain halogen compounds, phosphorus compounds, and antimony compounds, and that have high heat resistance that can withstand component mounting with lead-free solder, are available. The current situation has led to practical application.

[0006] Regardless of whether it is an alkali development type or a thermosetting type, conventional solder resists are mainly organic polymers, and thus have limited heat resistance and flame retardancy. In many cases, after a solder resist is applied to the entire surface of the substrate, a film is formed on the substrate and the like through complicated operations such as drying, exposure, development and curing. In addition, there are very few cases where a solder resist is applied only to the necessary locations according to the pattern, and then a film is formed only by a thermosetting operation. Furthermore, as mentioned above, organic solder resists are the mainstream, and inorganic solder resists are very few. If an inorganic solder resist appears, it can withstand high temperatures during soldering, and can form a solder resist film with high heat resistance. Even without using a flame retardant such as an antimony compound or phosphorus compound, the effect of ensuring flame retardancy can be expected. In addition, solder resist is applied only to the necessary locations in accordance with Noturn, and then a film is formed only by a thermal curing operation, so there is no need for equipment for exposure and development, and there are few processes. From the viewpoint of manufacturing cost Is also advantageous.

[0007] While researching a coating agent having excellent heat resistance, the present inventors have obtained a coating film having excellent heat resistance by a composition having an alkoxy compound, alkoxy titanium, colloidal silica aqueous dispersion, silica powder and the like. As a result, the inventors filed a patent application as a composition and film having excellent heat dissipation and heat shielding properties (Japanese Patent Application No. 2003-159589 (Patent Document 1)). The present inventor has been studying solder-resist paints by paying attention to the application of such a composition having excellent heat dissipation and heat shielding properties to a solder resist.

[0008] As an application of an alkoxysilane compound to a solder resist composition, JP-A-200 1-40663 (Patent Document 2) discloses a partially dealcoholized condensation of a novolac phenol resin and an alkoxysilane partial condensate. The use of an alkoxy group-containing silane-modified phenolic resin obtained by reaction with an epoxy resin is described. However, this alkoxy group-containing silane-modified phenolic resin requires the precise control of the partial condensation degree of alkoxysilane and the degree of condensation by dealcoholization, and there is a problem that its production becomes complicated. Since it is a composition based on phenolic resin and epoxy resin, there is a limit to heat resistance as soon as warpage and cracks occur in the cured film.

It has already been known that an inorganic coating agent can be obtained by reacting a partially hydrolyzed silane compound with alkoxytitanium (Japanese Patent Laid-Open No. 63-12671 (Patent Document). 3)). Patent Document 3 describes that a compound in which silica fine powder is added to an inorganic coating agent is used for a tile joint material or a filled cement. However, when these mixtures are used in a solder resist, as shown in the comparative examples, a good film with a low hardness of the film cannot be obtained.

[0010] Patent Document 1: Japanese Patent Application 2003-159589 Specification

Patent Document 2: Japanese Patent Laid-Open No. 2001-40663

Patent Document 3: JP-A 63-12671

Disclosure of the invention

Problems to be solved by the invention

[0011] The present invention has been made in view of the circumstances related to the organic solder resist described above. Focusing on the solder resist of the machine system, it has high heat resistance, so it can withstand high temperature mounting by lead-free solder when mounting components, and it has high flame resistance without using any flame retardant. In addition, the process is simpler and less costly than the conventional ones, and it is equipped with an inorganic solder resist paint that has reduced costs, a cured product that also has the solder resist paint power, and a film that also has the solder resist paint power. Intends to provide printed wiring boards

Means for solving the problem

[0012] The gist of the present invention is that the first liquid and the second liquid are composed of a partially hydrolyzed product of an alkoxysilane compound and a first liquid that also has an organic solvent power, and an alkoxy titanium and an organic solvent power. This is a two-part solder resist paint characterized by containing potassium titanate fibers in the first and / or second liquid in a two-part solder resist paint that is mixed and cured. .

[0013] The first liquid and Z or the second liquid may contain at least one selected from the group consisting of kaolin powder, alumina powder, and coupling agent-treated aluminum hydroxide powder, The first liquid and Z or the second liquid can contain a surface-hydrophobized fumed silica powder, and the first liquid and the Z or the second liquid can contain an ethyl cellulose powder. The first liquid and Z or the second liquid may be blended with a blue pigment that does not contain a halogen atom and a yellow pigment that does not contain Z or a halogen atom.

[0014] A solder resist cured product can be obtained by mixing the first and second liquids of the solder resist coating. Furthermore, a film which is one form of the cured product can be obtained in the same manner. This coating can be patterned on a printed wiring board. At this time, the thickness of the coating is preferably 7 μm-40 μm at the edge of the circuit.

[0015] The present inventor has intensively studied, focusing on the heat resistance, flame retardancy, and the like of an inorganic polymer obtained by the reaction of a partially hydrolyzed alkoxysilane compound and alkoxy titanium. Is completed. In other words, potassium titanate fiber is added to the partially hydrolyzed product of alkoxysilane compound, and kaolin powder, alumina powder, coupling agent treated aluminum hydroxide powder, pigment, etc. are added as necessary. In addition, fumed silica powder or ethyl cellulose powder that has been surface-hydrophobized is added and reacted with alkoxy titanium. Accordingly, the present invention provides a solder-resisted paint having excellent performance, a cured product made of the paint, and a printed wiring board provided with a film which is one form of the cured product also having the paint power. At this time, potassium titanate fiber, kaolin powder, alumina powder, aluminum hydroxide-hydroxide powder treated with a coupling agent, fumed silica powder, cellulose cellulose powder, pigment, and the like subjected to surface hydrophobization treatment, It can be mixed with a liquid containing an alkoxy titanium, or can be mixed with both a liquid containing a partially hydrolyzed product of an alkoxysilane compound and a liquid containing an alkoxy titanium.

The invention's effect

The solder resist paint of the present invention forms a solder resist cured product and a film, and these cured product and film are used when various electronic components are mounted on a printed wiring board having high heat resistance. It exhibits high heat resistance that can withstand the high mounting temperatures associated with lead-free soldering, and has great practical advantages. In addition, since it is virtually antimony-free, halogen-free, and phosphorus-free, it is associated with the disposal of printed wiring boards that do not adversely affect the human body and the natural environment due to incineration of waste compared to conventional yarns and products. The burden can be reduced. However, the solder resist paint can be easily manufactured, and the cured product and film formation do not require complicated equipment, and the process is simplified, resulting in low manufacturing costs.

BEST MODE FOR CARRYING OUT THE INVENTION

[0017] The basis of the present invention is a first liquid composed of a first liquid composed of a partially hydrolyzed alkoxysilane compound and an organic solvent, and a second liquid composed of an alkoxytitanium and an organic solvent. Two-component type solder resist paint that mixes and cures with the second solution, and then the two-component type solder resist resist paint that contains potassium titanate fiber etc. in the first and / or second solution It is in. The first liquid and the second liquid are mixed, and the mixed liquid (this mixed solution is referred to as a solder resist solution) is applied to the coated body, for example, and heated as necessary. An inorganic cured product is formed on top. When applied in the form of a film, a film is formed. Here, the potassium titanate fiber can be added to the first liquid, or can be added to the second liquid. It can also be added to both the first liquid and the second liquid. In the first liquid and Z or the second liquid, in addition to potassium titanate fiber, kaolin powder, alumina powder, coupling agent-treated aluminum hydroxide-powder powder, and a surface hydrophobized fume A dosilica powder, an ethyl cellulose powder, a pigment, etc. can be added suitably. Hereinafter, the power for explaining the present invention centering on mixing potassium titanate fiber and the like into the first liquid containing the partial hydrolyzate of alkoxysilane compound, potassium titanate fiber, kaolin powder, alumina powder, Coupling agent-treated aluminum hydroxide powder, and fumed silica powder and ethyl cellulose powder that have been subjected to surface hydrophobization treatment, pigments, etc. can also be used by mixing them in a second liquid containing alkoxy titanium. it can. In addition, kaolin powder, alumina powder, coupling agent-treated aluminum hydroxide powder, hydrophobized fumed silica powder, ethyl cellulose powder, and pigments are mixed in the first and second liquids. Can be used together.

For example, potassium titanate fiber is added to the first liquid, kaolin powder, alumina powder, coupling agent-treated aluminum hydroxide powder is added to the second liquid, and fumed silica powder that has been surface-hydrophobized. Ethylcellulose powder, pigment, etc. may be added, and potassium titanate fiber, kaolin powder, alumina powder, coupling agent-treated hydroxide, aluminum-umium powder, pigment, etc. are added to the first liquid. Fumed silica powder or ethyl cellulose powder that has been surface-hydrophobized to the two liquids may be added, potassium titanate fibers are added to the second liquid, and potassium titanate fibers are added to the first liquid. Kaolin powder, alumina powder, aluminum hydroxide powder treated with coupling agent, fumed silica powder, ethyl cellulose powder, pigments, etc. that have been surface-hydrophobized. It is possible to add potassium titanate fiber, kaolin powder, alumina powder, coupling agent-treated aluminum hydroxide powder to the second liquid, and add potassium titanate fiber to the first liquid and surface. Hydrophobized fumed silica powder, ethyl cellulose powder, pigments and the like may be added. In addition, strong powder, alumina powder, coupling agent-treated hydroxide-aluminum-umum powder, and fumed silica powder, ethyl cellulose powder, pigments, etc. that have been subjected to surface hydrophobization treatment are the first and second liquids. For example, 80% of these inorganic substances to be added can be added to the first liquid and the remaining 20% can be added to the second liquid. In any case, in a solder resist solution obtained by mixing the first solution and the second solution, a predetermined amount of potassium titanate fiber, kaolin powder, alumina powder, coupling agent-treated hydroxyaluminum-aluminum powder. , Fumed silica powder with hydrophobized surface, ethyl cellulose powder, pigments, etc. It may be contained.

[0019] Alkoxytitanium may be used alone or diluted with an organic solvent. That is, the second liquid is used in a state where at least alkoxy titanium and an organic solvent are mixed. In order to achieve uniform mixing with the first liquid, potassium titanate fiber, kaolin powder, alumina powder, coupling agent-treated aluminum hydroxide-powder powder, and surface hydrophobization treatment were also performed. It is also preferable for uniformly mixing fumed silica powder, ethyl cellulose powder, pigments and the like. As the organic solvent for alkoxytitanium, any organic solvent that can keep alkoxytitanium stable can be used. Needless to say, the same solvent as the first solvent can be used.

[0020] The partially hydrolyzed product of the alkoxysilane compound of the first liquid and the alkoxytitanium of the second liquid start to react immediately after mixing and start to cure. It is good to use it after mixing. After mixing the first and second liquids, it is recommended that they be used up and not left in a mixed state for a long time. Moreover, after mixing the first liquid and the second liquid, it is preferable to keep the temperature as low as possible without exposing it to a high temperature.

[0021] When the first liquid and the second liquid are mixed, the partially hydrolyzed product of the alkoxysilane compound and alkoxy titanium react and cure. This is because when a partially hydrolyzed product of an alkoxysilane compound and alkoxytitanium react with each other, dealcoholization results in formation of a Si—O—Ti bond or Si—O—Si bond, resulting in a polymer having a three-dimensional network structure. Because it becomes. The formed polymer, that is, the cured product or film, is substantially composed of an inorganic substance. The cured product or film is composed of inorganic material at 80% or more by weight. The organic group in the solder resist paint of the present invention is an organic group such as an alkoxy group (alcohol component) bonded to a silicon atom and a titanium atom and an alkyl group directly bonded to the silicon atom. When the partial hydrolyzate of the alkoxysilane compound reacts with the alkoxytitanium, a Si—O—Ti bond or Si—O—Si bond is generated, and the alcohol component of the alkoxy group is eliminated. However, organic groups such as alkyl groups directly bonded to silicon atoms remain as they are.

[0022] The first liquid and / or the second liquid of the solder resist paint of the present invention includes potassium titanate. The reason for using the fiber is described below. A printed wiring board consists of a circuit part and a board part, and the unevenness of the surface is generally a 30-100 m step. Therefore, the solder resist for circuit coating needs to have a thickness of 20-30 / zm at the concave part and 20-80 / zm at the convex part. In addition, since electronic components are mounted on the printed wiring board, the solder resist must withstand, for example, 260 ° C solder. It is difficult to form a thick film only with a partially hydrolyzed product of an alkoxysilane compound and an alkoxytitanium power, and cracks are likely to occur, for example, with 260 ° C solder. By adding potassium titanate fiber to these paints, the thickness of the coating can be ensured and, for example, a coating that can withstand solder at 260 ° C. can be formed.

[0023] In addition to the potassium titanate fiber, at least one selected from the group consisting of kaolin powder, alumina powder, and coupling agent-treated aluminum hydroxide powder is added to the first liquid and Z or the second liquid. Can do. By adding these compounds, it is possible to form a film with a thickness and thickness on the uneven surface of the cover, and to form a film with no unevenness. On the other hand, when the partially hydrolyzed silane compound and alkoxytitanium are reacted, the ability to mix silica powder is described in Patent Document 3 (Japanese Laid-Open Patent Publication No. 63-12671). Although various studies including various coupling agent-treated silica powders were made, it was found that the pencil hardness after heat curing was extremely low and a cured product or a film that could be put to practical use could not be obtained.

[0024] In addition, the viscosity of the solder resist liquid after mixing the first liquid and the second liquid is increased by adding the hydrophobized fumed silica powder to the first liquid and the Z or second liquid. It can increase the viscosity and improve the printability of screen printing and flexographic printing of solder resist solution. In addition, the effect of preventing the precipitation of potassium titanate fibers contained in the first liquid and / or the second liquid, as well as kaolin powder, alumina powder, coupling agent-treated hydroxide, aluminum, and the like was recognized. . Further, by adding ethylcellulose powder to these paints, it is possible to improve the external punchability from the work board at the time of manufacturing the printed wiring board.

[0025] The blending ratio of the organic solvent constituting the solder resist paint, that is, the solder resist liquid obtained by mixing the first liquid and the second liquid will be described below. A mixture of the first and second liquids The amount of the organic solvent in the rudder resist solution is not particularly limited, but it is very small.For example, when the total amount of the solder resist solution is 30% or less, the first solution and the second solution When this is mixed, the curing time of the mixed solution is shortened, which is not preferable for use. In addition, when the amount is very large, for example, 55% or more by weight with respect to the total amount of the solder resist solution, the film becomes thin and it becomes difficult to form a stable film.

[0026] The potassium titanate fiber is preferably used in an amount of 80 parts by weight of 18 parts by weight with respect to 100 parts by weight of the partially hydrolyzed alkoxysilane compound. A good film can be obtained with an amount of additive in this range. If it is less than 18 parts by weight, it is difficult to ensure the thickness of the coating, and for example, resistance to soldering at 260 ° C becomes poor. On the other hand, when it exceeds 80 parts by weight, for example, when a film is formed by screen printing, the printability is deteriorated, and it is difficult to obtain a uniform and non-uniform film.

[0027] The amount of the alkoxytitanium used as the main component of the second liquid is 5 to 30 parts by weight based on 100 parts by weight of the partially hydrolyzed alkoxysilane compound. Obtainable. If it is less than 5 parts by weight, the pencil hardness etc. of the film will be low and it will not be practically used, and if it exceeds 30 parts by weight, for example, a crack will easily occur in the film in a float test in a 260 ° C solder bath. It will not be practical. The amount used here is based on alkoxytitanium, a partial hydrolyzate of an alkoxysilane compound, which does not contain an organic solvent. The actual amount of alkoxy titanium added depends on the type of alkoxy titanium compound used (for example, whether titanium tetrabutoxide or titanium tetrapropoxide), the type of alkoxysilane compound, and the like. It depends on the amount used (especially the amount of trialkoxysilane or tetraalkoxysilane). Of the alkoxysilanes, if the amount of trialkoxysilane or tetraalkoxysilane used is large, the amount of alkoxytitanium added may be small. In addition, since titanium tetrabutoxide has a large molecular weight, it should be added in a larger amount than titanium tetrapropoxide.

[0028] The addition amount of alkoxytitanium is preferably in the range of 0.0 10-0.15, expressed as a ratio of titanium element to silicon element. If the amount of titanium added is less than 0.001 for silicon, it will be difficult to form a cured product or film having a network structure, while the amount of titanium added will be greater than 0.15 for silicon. And the curing speed of the solder resist solution is too fast, For example, the formed cured product or film has insufficient performance. For example, cracks are likely to occur during soldering.

[0029] Next, the addition amount of kaolin powder, alumina powder, coupling agent-treated aluminum hydroxide powder, etc., the upper limit of the addition amount is the coating choking (a phenomenon in which the powder is exposed to the coating surface) ) Does not occur.

[0030] The fumed silica powder subjected to the surface hydrophobization treatment is preferably 19 parts by weight or less with respect to 100 parts by weight of partially hydrolyzed alkoxysilane compound. If the amount exceeds this amount, the viscosity of the mixed solution mixed with the second solution will increase rapidly during storage, and small-diameter grains will be generated in the coating, which is not preferable in practice. The ethyl cellulose powder is preferably 13 parts by weight or less based on 100 parts by weight of the partially hydrolyzed alkoxysilane compound. This is because if the amount exceeds this amount, the flame retardancy of the coating decreases, and for the pigment, a blue pigment containing no halogen atom and a yellow pigment containing no halogen atom are used. The proportion of blue and yellow pigments in the amount that looks green.

[0031] Next, a partial hydrolyzate of an alkoxysilane compound, which is a central component of the solder resist paint of the present invention, will be described. The partial hydrolyzate of the alkoxysilane compound is an oligomer obtained by partially hydrolyzing and condensing the alkoxysilane compound expressed by the general formula 1. In R ¹ , R ¹ is a methyl group, an ethyl group, a propyl group, an isopropyl group, an aminoethyl group, a glycidylpropyl group (see Chemical Formula 2) or the like, and R ² is a methyl group, an ethyl group, or the like. It can be illustrated. Here, n is an integer of 0-3.

[0032] [Chemical 1]

R ^ S i (OR ² ) 4- [0033] [Chemical 2]

_{_{CH 2 - CH- CH 2 - 0}} - (CH 2) 3 - O

[0034] As the alkoxysilane compound, at least one selected from the substances represented by the above formula 1 is appropriately used. Usually, two to three compounds are mixed and used. Less than the amount of water (calculated value) required to completely hydrolyze these alkoxysilane compounds in the presence of an acid catalyst! A partial hydrolyzate can be obtained by reacting with an amount of water. When trialkoxysilane or tetraalkoxysilane is present, the coating obtained by curing the coating has a three-dimensional structure.

[0035] As the organic solvent used in the first liquid or the second liquid, the following solvents can be used. Methyl alcohol, ethyl alcohol, isopropyl alcohol, 1-butanol, 2-butanol, diacetone alcohol, butyl acetate, butyl butyrate, propylene darcol monomethyl ether, diacetone alcohol, butyl carbitol, butyl carbitol acetate, butyl lactate, ethyl Carbitol, Ethyl carbitol acetate, Isophorone, Dipropylene glycol methyl ether, Dipropylene glycol n-propyl ether, Propylene glycol n-butyl ether, Dipropylene glycol dimethyl ether, Propylene glycol noresate acetate, Ethylene glycol monobuty Nore Iter, ethylene glycol monobutyl ether acetate, 3-methoxybutanol, 3-methoxybutyl acetate It is a solvent. However, the solvent is not limited to these solvents, and one kind or a mixture of two or more kinds of solvents may be used.

[0036] The potassium titanate fiber is a fiber of potassium hexatitanate. The diameter of the fiber is 1 μm or less, the average length of the fiber is preferably 20 m or less, and the maximum length is preferably 100 m or less. If the diameter, average length, and maximum length of the fiber are greater than these values, the coating will become uneven during screen printing or flexographic printing, and stable printing will not be possible, making it unsuitable.

[0037] The alkoxytitanium is represented by Formula 3. In the formula, R represents a methyl group, Examples thereof include a til group, a propyl group, and a butyl group. From the reaction rate, a propyl group or a butyl group can be suitably used as R.

[0038] [Chemical 3]

T i (OR) 4

[0039] The kaolin powder is preferably a powder having an average particle size of 5 µm or less and a maximum particle size of 25 µm or less, and having a moisture content of 0.8 wt% or less. If the particle size is larger than these values, spots are likely to occur on the film, and it is not suitable because it becomes less uniform. If the adhering moisture exceeds 0.8% by weight, the pencil hardness of the coating becomes extremely small, which is not suitable. As the alumina powder, a powder having an average particle size of 5 μm or less and a maximum particle size of 25 μm or less is preferred, and a powder of 0.06 wt% or less of sodium oxide (N a O) can be suitably used. Particle size force greater than these numbers

2

In this case, spots are likely to occur in the coating, and a uniform coating cannot be obtained, which is not suitable. If the amount of sodium oxide (Na 2 O) exceeds 0.06% by weight, curing of the solder resist solution will be inhibited.

2

So not suitable.

[0040] The coupling agent-treated aluminum hydroxide powder preferably has an average particle size of 3 µm or less and a maximum particle size force of S25 µm or less. The soluble acid sodium salt is preferably 0.06 wt% or less. . Furthermore, those whose surface is coated with an epoxysilane or titanate coupling agent can be suitably used. The surface coated with an epoxysilane coupling agent is excellent in adhesion to printed circuit board copper. The numerical limits on particle size and soluble sodium oxide (Na 2 O) are the same reasons as for alumina powder. Also force

2

If the surface is not coated with a pulling treatment agent, the film will shed and is not suitable.

[0041] The surface hydrophobized fumed silica powder preferably has an average primary particle diameter of 20 nm or less. Those whose surfaces have been subjected to a hydrophobic treatment with dimethyldichlorosilane or hexamethyldisilazane can be suitably used. In particular, the hexamethyldisilazane-treated product is effective in increasing the viscosity of the solder resist solution (the mixed solution of the first and second solutions is called the solder resist solution). It is not suitable because the surface is not hydrophobized! And the thickening effect of the solder resist solution is not present. On the other hand, when the average diameter of the primary particles exceeds 20 nm, circular protrusions are generated on the cured film, which is not preferable. Ethylcellulose powder is available from, for example, Hercules N-type (with an ethoxy group substitution degree per anhydroglucose unit of 2.41 to 2.51) can be preferably used. Among the N-types, N-50 and N-100 are particularly preferable from the viewpoint of the balance between solubility and film quality, depending on the grade according to viscosity. As for the blue pigment containing no halogen atom and the yellow pigment containing no halogen atom, examples of the blue pigment include copper phthalocyanine blue, iron phthalocyanine blue, and indigo. As the yellow pigment, anthraquinone yellow, benzimidazolone yellow, iron oxide and the like can be suitably used.

[0042] Next, the first liquid and the second liquid are mixed to prepare a solder resist solution, and this solder resist solution is applied to a printed wiring board or the like to form a cured product and form a film. I will explain. Add potassium titanate fiber to an organic solvent in which a partially hydrolyzed alkoxysilane compound is dissolved, and mix. If necessary, kaolin powder, alumina powder, coupling agent-treated aluminum hydroxide powder, fumed silica powder with hydrophobized surface, ethyl cellulose powder, and blue pigments and halogens that do not contain halogen atoms. Add a yellow pigment that does not contain atoms, and stir and mix in a stirring tank having a propeller-type or saddle-type rotary blade until these fibers and powder are sufficiently kneaded into the liquid. Naturally, a stirring method other than this method can also be used. The mixing temperature at this time is preferably 40 ° C or less. Exceeding 40 ° C is not preferred because it tends to cause skinning of the mixed solution (thin film formed on the surface of the solder resist solution). Furthermore, if necessary, the mixed solution is transferred to a ball mill, a three-roller or the like, and mixed and kneaded until the powder and fibers are sufficiently dispersed. At this time, the liquid temperature during mixing and kneading is preferably 40 ° C. or lower for the same reason as described above. In this way, the first liquid is obtained.

On the other hand, a second liquid in which alkoxytitanium is dissolved in an organic solvent is prepared. The first liquid and the second liquid are generally stirred for 10 minutes or more in a stirring tank having a propeller-type or saddle-type rotary blade until both liquids are sufficiently mixed. The stirring liquid temperature at this time is preferably 30 ° C or less. If the temperature exceeds 30 ° C, non-uniform spots will appear on the film appearance!

[0044] In preparing the solder resist solution, it is preferable that the viscosities of the first solution and the second solution are substantially the same as each other immediately before mixing. In addition, when preparing the solder resist solution, in order to prevent the local reaction from proceeding due to insufficient mixing, a part of the alkoxysilane compound is required. Potassium titanate fiber, kaolin powder, alumina powder, aluminum hydroxide powder with coupling agent treatment, fumed silica powder with hydrophobized surface, ethyl cellulose powder, pigment, etc., added to the organic solvent solution of hydrolyzate A part of this may be added to an organic solvent solution of alkoxy titanium, and mixed and kneaded thoroughly with a ball mill or a three-roll. In this case, the liquid temperature during mixing and kneading is preferably 40 ° C. or lower for the same reason as described above. In addition, when the first and second liquids are mixed, they immediately react and begin to cure. Therefore, after mixing the first and second liquids, the first liquid and the second liquid should be applied immediately to the object without leaving them for a long time. Good. Also, the solder resist solution obtained by mixing the first solution and the second solution should be used up without leaving any residue. If the solder resist solution remains, it is recommended that it be discarded and not reused. The solder resist solution can be obtained by preparing the first solution and the second solution separately and mixing them together, or by adding titanic acid to the organic solvent solution of the partially hydrolyzed alkoxysilane compound. Mixing potassium fiber, kaolin powder, alumina powder, coupling agent-treated aluminum hydroxide powder, surface hydrophobized fumed silica powder, ethyl cellulose powder, pigment, etc. It can also be obtained by mixing the solutions

[0045] In order to form a film on the substrate, a solder-one resist solution, which is a mixed solution of the first solution and the second solution prepared above, is applied to the substrate, dried and heat-treated. The substrate is a printed wiring board or the like whose circuit is formed by a subtractive method, a semi-additive method, an additive method, or the like. As a method for forming a pattern by applying a solder resist solution on the surface of a printed wiring board, a screen printing method or a flexographic printing method can be applied.

[0046] The coating applied to the circuit surface is dried and cured with a profile in which the temperature is gradually raised in the range of 200 ° C at the maximum and 100 ° C at the minimum. Cool to room temperature after curing with a profile that cools gradually, avoiding rapid cooling. The temperature rise and cooling profiles are determined by considering the quality and productivity according to the printed circuit board thickness and circuit thickness. If the maximum temperature exceeds 200 ° C, it is not preferable due to thermal degradation of the printed wiring board and generation of internal stress. Further, if the maximum temperature is less than 100 ° C, the curing (drying) of the solder resist coating of the present invention is not completed in a practically necessary time, which is preferable! /.

[0047] The thickness of the coating after curing must be 7 μm or more at the edge of the circuit on the printed wiring board. is there. 7 If it is less than 111, it causes deterioration of circuit protection during long-term use.

Example 1

[0048] 2000 g of dimethyldimethoxysilane, 4000 g of methyltrimethoxysilane and an alkoxysilane containing an epoxy group represented by the formula 4 (see formula 4) An alkoxysilane mixture composed of lOOOg is mixed with a mixture of pure water lOOOg and acetic acid 100 g. The mixture was added dropwise and reacted at room temperature. The reaction proceeded with exotherm and was completed in tens of minutes. To this was added propylene glycol monomethyl ether to obtain a hydrolyzate solution of an alkoxysilane compound. The amount of propylene glycol monomethyl ether added was 45% by weight based on the solid content after the alkoxysilane compound hydrolyzate solution was dried at 105 ° C for 120 minutes.

[0049] [Chemical 4]

CH 2-CH-C H2-O-(CH ₂ ) ₃ -S i (OCH 3) 3

O

[0050] Next, to the above partially hydrolyzed solution of alkoxysilane compound lOOOg, potassium hexatitanate fiber (with an average fiber diameter of 0.5 μm and an average length of 15 m) Things) 240 g was added and stirred at a liquid temperature of 20 ° C. to 30 ° C. for 30 minutes in a stirring tank having a propeller rotor. Next, this mixed solution was transferred to a ball mill and mixed for 120 minutes. The liquid temperature during mixing was controlled to be 20 ° C to 30 ° C. Defoaming was easy during the ball mill. In this way, the first liquid was prepared. As a second liquid, a 50 wt% solution of propylene glycol monomethyl ether of tetrabutoxytitanium was prepared. The second liquid is added to the first liquid at a ratio of 36 parts by weight with respect to 100 parts by weight of the solid after the solution of the hydrolyzate of alkoxysilane compound is dried at 105 ° C for 120 minutes. The mixture was mixed with a mold stirrer at 25 ° C. for 15 minutes to obtain a liquid solder resist solution.

Example 2

[0051] Partial hydrolyzate solution of alkoxysilane compound of Example 1 1 Those average grain size of the powder is 3. 0 m, the average particle size of the deposited water 0.6 weight ^_0/0 ones) 100 g and alumina powder (powder those 2. 0 m, the sodium oxide 0.03% by weight) 460g and potassium hexatitanate fiber (with an average fiber diameter of 0. and an average length of 15 m) The mixture was stirred in a stirring tank having a propeller rotor for 30 minutes at ° C. Next, this mixed solution was transferred to a ball mill and mixed for 120 minutes. The liquid temperature during mixing was controlled to be 20 ° C to 30 ° C. Easily defoamed in the middle of the ball mill. In this way, the first liquid is obtained. As a second liquid, a 50 wt% solution of propylene glycol monomethyl ether of tetrabutoxytitanium was prepared. The second liquid is added to the first liquid, and the solution of the partially hydrolyzed product of alkoxysilane compound is dried at 105 ° C for 120 minutes at a rate of 36 parts by weight with respect to 100 parts by weight of the solid. The mixture was mixed with a propeller type stirrer at 25 ° C for 15 minutes to obtain a liquid solder resist solution.

Example 3

[0052] To 1000 g of the partial hydrolyzate solution of the alkoxysilane compound of Example 1, kaolin powder (with an average particle diameter of 3.0 m and a moisture content of 0.6% by weight) ) but the average particle size of 100g and § alumina powder (powder 2., Sani匕sodium 0.03 wt ^_0/0 ones) 460 g of potassium hexatitanate fibers (fiber average diameter of 0.5 120g and fumed silica powder with hydrophobized surface (average particle size of primary particles 7nm, surface-treated with hexamethyldisilazane) 50g The mixture was stirred at a liquid temperature of 20 ° C. to 30 ° C. for 30 minutes in a stirring tank having a propeller rotor. Next, this mixed solution was transferred to a ball mill and mixed for 120 minutes. The liquid temperature during mixing was controlled from 20 ° C to 30 ° C. The first liquid was obtained by simply defoaming during the ball mill. As a second solution was prepared of 50 weight ^_0/0 solution of propylene glycol monomethyl ether Te trub butoxy titanium. The second liquid is added to the first liquid, and the solution of the hydrolyzate of the alkoxysilane compound is dried at 105 ° C for 120 minutes at a rate of 36 parts by weight with respect to 100 parts by weight of the solid. Then, the mixture was mixed with a propeller-type stirrer at 25 ° C for 15 minutes to obtain a liquid solder resist solution.

Example 4

[0053] To 1000 g of the partial hydrolyzate solution of the alkoxysilane compound of Example 1, kaolin powder (with an average particle size of 3.0 m and a moisture content of 0.6% by weight) ) 100g and a Alumina powder (average particle size of the powder 2. intended O / zm, Sani匕sodium 0.03 wt ^_0/0 ones) 460 g and the average diameter of the potassium fiber (hexatitanate those 0.5 With an average length of 15 μm) and fumed silica powder with surface hydrophobization treatment (average particle size of primary particles 7 nm and surface treatment with hexamethyldisilazane) 50 g 30 g of N-50 type ethylcellulose powder made by Churres was added and stirred at a liquid temperature of 20 ° C. to 30 ° C. for 30 minutes in a stirring tank having a propeller-type rotor blade. The mixture was then transferred to a ball mill and mixed for 120 minutes. The liquid temperature during mixing was controlled from 20 ° C to 30 ° C. The first liquid was obtained by simply defoaming during the ball mill. As a second solution was prepared of 50 weight ^_0/0 solution of propylene glycol monomethyl ether Tetorabutoki Shichitan. The second liquid is added to the first liquid at a ratio of 36 parts by weight with respect to 100 parts by weight of the solid after the solution of the hydrolyzate of the alkoxysilane compound is dried at 105 ° C for 120 minutes. It mixed for 15 minutes at 25 degreeC with the type | mold stirrer, and it was set as the liquid soldering resist liquid.

Example 5

To the partially hydrolyzed solution of alkoxysilane compound of Example 1 lOOOOg, potassium hexatitanate fiber (fiber having an average diameter of 0.5 m and an average length of 15 m) 240 g, Aluminum hydroxide powder treated with coupling agent (Since the average particle size of the powder is 2, soluble sodium hydroxide is 0.05% by weight, and the surface is coated with an epoxysilane coupling agent. 550g, fumed silica powder with surface hydrophobization treatment (average particle size of primary particles 7nm, surface treatment with hexamethyldisilazane) 60g, yellow pigment (anthraquinone yellow) 4g, 4 g of a blue pigment (copper lid mouth-cyan blue) was added and stirred at a liquid temperature of 20 ° C. to 30 ° C. for 30 minutes in a stirring tank having a propeller rotor. The mixture was then transferred to a ball mill and mixed for 180 minutes. The liquid temperature during mixing was controlled from 20 ° C to 30 ° C. In this way, a first liquid was prepared. As a second solution, a 50% by weight solution of tetrabutoxytitanium butyl butyrate was prepared. Add the second liquid to the first liquid and add 40 parts by weight to the 100 parts by weight of the solid after the hydrolyzate solution of the alkoxysilane compound is dried at 105 ° C for 120 minutes. The mixture was mixed with a stirrer at 25 ° C for 15 minutes to obtain a liquid solder resist solution.

Example 6 [0055] Example 1-1 Three solder resist solutions of FR-4 graded copper-laminated FR-4 graded copper foil and patterned on the entire surface by a conventional subtractive method. The applicator was coated on the substrate, heated gradually with a temperature profile of maximum temperature 180 ° C, dried with hot air for 120 minutes in total drying time, and then gradually cooled to room temperature in 60 minutes. For the solder resist solutions of Examples 4 and 5, the applicator was coated on a FR-4 grade copper circuit board patterned by a conventional subtractive method, and the temperature profile was 180 ° C. The temperature was gradually raised and hot air drying was performed for 120 minutes in the total drying time, and then gradually cooled to room temperature in 60 minutes. The film thickness after curing (drying) was set to 10 μm at the edge of the copper circuit.

Example 1 A performance test as a printed wiring board was performed on the cured solder resist (coating film) obtained in 1-5. The results are shown in Table 1 for Examples 1, 2 and 3, and Table 2 for Examples 4 and 5. The evaluation method for each performance test in the table is as shown separately.

[0057] [Table 1]

[0058] [Table 2]

Characteristics Example 4 Example 5 Appearance of coating Good Good

On copper circuit 6Η 6Η

Pencil hardness

On substrate 6Η 6Η

Solder heat resistance (260 to 20 seconds float) No crack, no peeling Crack, no peeling Pencil hardness 6Η 6Η

Acid resistance on copper circuit

Appearance No cracks, no peeling Cracks, no peeling

(0.5% sulfuric acid aqueous solution

30 minutes for 10 minutes soaked on the substrate Pencil hardness 6Η 6Η

溴)

Appearance No crack or flaking Crack or no peeling Electrical insulation 1O0O0M Ω 10000M Ω Electrical withstand voltage

By visual inspection by visual inspection

Salt water ¹ crack, no peeling Crack, no peeling

(Spray with 5% saline for 35 hours)

No flaking with tape No flaking with tape Flame resistance (according to UL vertical method) V-0 pass V-0 pass Antimony content in the cured solder resist 1mm or less 1mm or less

Chlorine 12 ΡΡΜ 12 ハロゲン Halogen content in the cured solder resist

Bromine 5% or less 5% or less Phosphorus content in solder resist cured product 80% or less 80% or less Example 7

240 g of potassium hexatitanate fiber (with an average fiber diameter of 0.5 m and an average length of 15 m) is added to lOOOOg, a partially hydrolyzed solution of the alkoxysilane compound of Example 1. The mixture was stirred at a liquid temperature of 20 ° C. to 30 ° C. for 30 minutes in a stirring tank having a propeller rotor. Next, this mixed solution was transferred to a ball mill and mixed for 180 minutes. The liquid temperature during mixing was controlled to be 20 ° C to 30 ° C. In this way, a first liquid was obtained. Separately, as the second liquid was prepared 50 weight ^_0/0 solution of propylene glycol monomethyl ether tetrabutoxytitanium. The second liquid is added to the first liquid, and the solution of the partially hydrolyzed alkoxysilane compound is dried at 105 ° C for 120 minutes, to 100 parts by weight of the solid, 10, 16, 30, 40, 48 Blended in proportions of 60, 60 parts by weight, mixed with propeller-type stirrer for 15 minutes at 25 ° C, and this solution was mixed with FR-4 grade copper patterned by conventional subtractive method Applicator coating is applied on copper foil of stretched laminate and FR-4 grade substrate that has been etched on the entire surface, then heated gradually with a temperature profile of maximum temperature of 180 ° C and dried with hot air for 120 minutes in total drying time. Then, it was gradually cooled to room temperature in 60 minutes. Hardened (dried) The thickness of the subsequent coating was set to 10 m on the etching substrate. Table 3 shows the physical properties of the cured product. From Table 3, the relationship between the alkoxysilane compound and the alkoxytitanium compound, which is useful in this example, is determined based on 100 parts by weight of the solid content of the partial hydrolyzate of the alkoxysilane compound. It can be seen that 8-24 parts by weight of the net amount of titanium gives the preferred coating. When this is expressed as an element ratio of titanium element to silicon element, a value of 0.029−0.087 is obtained.

[0060] [Table 3]

Comparative Example 1

[0061] Partially hydrolyzate solution of alkoxysilane compound of Example 1 Fumed silica powder hydrophobized to 470 g of silica powder (with an average particle size of 4.8 μm) in lOOOOg (The average particle size of the primary particles was 7nm and was surface-treated with hexamethyldisilazane) 60g was added, and the mixture was stirred in a stirring vessel with a propeller rotor for 30 minutes at a liquid temperature of 20 ° C to 30 ° C. . Next, this mixed solution was transferred to a ball mill and mixed for 180 minutes. The liquid temperature during mixing was controlled to be 20 ° C to 30 ° C. In this way, the first liquid was prepared. On the other hand, a 50% by weight solution of tetrabutoxytitanium butyl butyrate was prepared as the second liquid. The second liquid is added to the first liquid, and the partially hydrolyzed solution of the alkoxysilane compound is dried at 105 ° C for 120 minutes at a ratio of 40 parts by weight with respect to 100 parts by weight of the solid, and propeller type stirring is performed. The mixture was mixed for 15 minutes at 25 ° C. to obtain a liquid solder resist solution. Solder resist solution is applied on the copper foil of FR—4 grade copper clad laminate patterned by the conventional subtractive method and on the FR—4 grade substrate that has been fully etched. The temperature was gradually raised with a temperature profile of 180 ° C., hot air drying was performed for 120 minutes for the total drying time, and then gradually cooled to room temperature in 60 minutes. The film thickness after curing (drying) was set to 10 μm at the edge of the copper circuit. Comparative Example 2

[0062] Hydrophobized silica powder instead of 470 g of silica powder of Comparative Example 1 (with an average particle diameter of 5. O / zm, chemically bonded with an organic key compound in hydrous key acid The surface was covered with an organic group (470 g), and the same treatment as in Comparative Example 2 was performed.

Comparative Example 3

[0063] Instead of 470 g of the silica powder of Comparative Example 1, 360 g of kaolin powder (with an average particle diameter of 2.3 m and an attached water content of 0.9% by weight) was blended, and Comparative Example 1 Comparative Example 4 treated in the same manner as

[0064] In place of 60 g of the surface-hydrophobized fumed silica powder of Example 3, 60 g of fumed silica powder (having an average primary particle size of 12 nm) that was surface-hydrophobized was included. Then, the same treatment as in Comparative Example 2 was performed.

[0065] Example 1 is a system in which potassium hexatitanate fiber is added as an additive, Example 2 is a system in which kaolin powder and alumina powder are added in addition to potassium hexatitanate fiber as an additive, Example 3 Is a system in which, in addition to potassium hexatitanate fibers, kaolin powder, alumina powder and fumed silica powder surface-hydrophobized with hexamethyldisilazane are added. As shown in Table 2, both systems have a good coating appearance, a coating hardness of 6H, sufficient hardness, and heat resistance with solder heat resistance of 260 ° C for 20 seconds float. Sex was also a problem!

[0066] Example 4 is a system in which, in addition to potassium hexatitanate fiber, kaolin powder, alumina powder, fumed silica powder subjected to surface hydrophobization treatment and ethyl cellulose powder are added. Example 5 is hexatitanate. In addition to potassium fiber, a hydroxide-aluminum powder treated with a coupling agent, fumed silica powder treated with a hydrophobic surface, yellow pigment (anthraquinone yellow) and blue pigment (copper lid-cyan blue) is there. As shown in Table 3, the V and misaligned coatings also have problems with surface appearance, surface hardness, solder heat resistance, acid resistance, electrical insulation, electrical voltage resistance, acid resistance, flame resistance, etc. , Halogen, Antimony and Phosphorus content was low! Comparative Example 1 A performance test as a printed wiring board was performed on the cured solder resist (coating film) obtained in 1-14. The results are shown in Table 4. The evaluation methods for each performance test in the table are as described separately.

[0068] [Table 4]

[0069] Comparative Example 1 is a system in which silica powder and a surface-hydrophobized fumed silica powder are added. Comparative Example 2 is a system in which a hydrophobized silica powder is added instead of the silica powder in Comparative Example 1, a comparison. Example 3 is a system in which kaolin powder is added instead of silica powder in Comparative Example 1, and Comparative Example 4 is a fumed silica powder that has not been surface hydrophobized in place of the surface hydrophobized fumed silica powder of Example 3. It is a system that is attached. Both systems do not contain potassium titanate fibers and contain silica powder. In particular, Comparative Example 4 is a system containing fumed silica powder not subjected to surface hydrophobization treatment. From Table 4, it can be seen that a system that does not include potassium titanate fiber, that simply contains silica particles, and a system that contains fumed silica powder that has not been subjected to surface hydrophobization treatment can provide a good coating with low hardness. I can't do it.

[0070] Test methods in each performance test in the table are as follows.

Pencil hardness: According to the test method of JISK5600, the evaluation is based on the tearing of the film. The locations to be evaluated are on the copper circuit and on the copper circuit board.

Solder heat resistance: JISC5012 test method. Float in a solder bath at 260 ° C for 20 seconds, and visually observe the presence or absence of cracks in the coating, and the presence or absence of peeling between the coating and the substrate and copper circuit.

Acid resistance: Immerse the specimen in 0.5% sulfuric acid solution at 30 ° C for 10 minutes, wash with water, dry at 120 ° C for 120 minutes, allow to cool to room temperature, and then test the pencil hardness test and Observe peeling. Salt spray resistance: JISK5600 test method, spray with 5% saline solution at 35 ° C for 96 hours, rinse with water, and observe visually for cracks and peeling of the film. Also, observe the peeling of the film with cello tape (registered trademark).

Electrical insulation: JISC5012 test method is used. Measure the insulation resistance between circuits after processing the test piece for 60 hours at 60 ° CZ90% ZDC30VZ500. The circuit of the test piece was line Z space = 125 μm / 125 μm.

Electric withstand voltage: JISC5012 test method. Circuit line Z space = 125 μm Ζΐ 25 / ζ πι Apply 250V for 1 minute between circuits, and let leakage current 0.5mA or less pass. Flame resistance: Tested in accordance with the UL94 flame retardant test standard. 1. 6mm thick FR-4 grade glass epoxy copper clad laminate (V94 grade approved by UL94), thickness after curing (drying) on both sides of the whole etched substrate A film with a thickness of approximately 20 μm is formed, and a flame resistance test is performed by the vertical method to determine whether it passes V-0. Antimony, halogen, and phosphorus contents: Antimony is measured by atomic absorption, halogen is ion chromatographed, and phosphorus is measured by spectrophotometry.

Industrial applicability

As described in detail above, the present invention relates to a two-component type solder resist paint, a cured product such as the solder-resist paint coating, and a printed wiring board provided with a film that is the cured product. Cured products and coatings are characterized in that more than 80% of the components are inorganic. Therefore, it can sufficiently withstand the high temperature of the mounting temperature associated with lead-free solder used when mounting various electronic components on a printed wiring board with high heat resistance. Because it contains virtually no compound or phosphorus compound, it has high flame retardancy per se and has a negative impact on the human body and the natural environment due to incineration of waste compared to conventional solder resist cured products and coatings. It has the feature of not giving. Further, since no exposure and development processes are required, the process is simplified and the manufacturing cost is reduced. The present invention having such a feature can be effectively used in a wide industrial field using a printed wiring board.

Claims

The scope of the claims

[1] A first liquid composed of a partial hydrolyzate of an alkoxysilane compound and an organic solvent, and a first liquid composed of alkoxy titanium and a second liquid composed of an organic solvent and a second liquid are mixed and cured. A two-component type solder resist paint, wherein the first liquid and / or the second liquid contain potassium titanate fibers.

[2] The first liquid and Z or the second liquid contain kaolin powder, alumina powder, and coupling agent treatment. Item 1. The solder resist paint according to Item 1.

[3] The solder resist paint according to claim 1 or 2, wherein the first liquid and the Z or second liquid contain fumed silica powder subjected to surface hydrophobization treatment.

[4] The solder resist paint according to any one of claims 1 to 3, wherein the first liquid and Z or the second liquid contain ethyl cellulose powder.

[5] The first liquid and Z or the second liquid are blended with a halogen atom-free! Blue pigment and a Z / halogen atom-free / yellowish pigment. Item 4 ヽ Displacement force Solder resist paint according to item 1.

[6] The two-component type solder resist coating material according to claim 1, wherein the misalignment force is a cured solder resist.

[7] A printed wiring board provided with a film obtained by pattern-forming and curing the two-component type solder resist paint according to claim 1, wherein the displacement force is 1.

8. The printed wiring board according to claim 7, wherein the thickness of the film is 7 m to 40 m at the edge of the circuit.