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WO2006038262A1 - Revêtement de résist pour brasage, produit vulcanisé réalisé à partir de celui-ci et carte à circuit imprimé ayant un film de revêtement réalisé à partir dudit revêtement - Google Patents

Revêtement de résist pour brasage, produit vulcanisé réalisé à partir de celui-ci et carte à circuit imprimé ayant un film de revêtement réalisé à partir dudit revêtement Download PDF

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Publication number
WO2006038262A1
WO2006038262A1 PCT/JP2004/014369 JP2004014369W WO2006038262A1 WO 2006038262 A1 WO2006038262 A1 WO 2006038262A1 JP 2004014369 W JP2004014369 W JP 2004014369W WO 2006038262 A1 WO2006038262 A1 WO 2006038262A1
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WO
WIPO (PCT)
Prior art keywords
liquid
solder resist
powder
coating
solution
Prior art date
Application number
PCT/JP2004/014369
Other languages
English (en)
Japanese (ja)
Inventor
Masakazu Takemoto
Takashi Naito
Ryuzo Kaneko
Original Assignee
Ceramission Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ceramission Co., Ltd. filed Critical Ceramission Co., Ltd.
Priority to JP2005509258A priority Critical patent/JP3928136B2/ja
Priority to PCT/JP2004/014369 priority patent/WO2006038262A1/fr
Publication of WO2006038262A1 publication Critical patent/WO2006038262A1/fr

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0239—Coupling agent for particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0242—Shape of an individual particle
    • H05K2201/0251—Non-conductive microfibers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/16—Inspection; Monitoring; Aligning
    • H05K2203/161—Using chemical substances, e.g. colored or fluorescent, for facilitating optical or visual inspection

Definitions

  • 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.
  • 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.
  • halogen flame retardants and combinations of halogen flame retardants and antimony compounds are widely used.
  • a composition is disclosed in, for example, JP-A-2-88615.
  • JP 2003-277470 A In the publication, no halogen compound is used.
  • a composition containing an organophosphorus compound is disclosed! Speak.
  • 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.
  • epoxy resin is mainly used.
  • these liquid solder resists for thermosetting are mainly used for flexible printed wiring boards and printed wiring boards for IC packages.
  • 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.
  • solder resists are mainly organic polymers, and thus have limited heat resistance and flame retardancy.
  • 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.
  • 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.
  • organic solder resists are the mainstream, and inorganic solder resists are very few.
  • solder resist 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.
  • 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.
  • Patent Document 2 JP-A-200 1-40663 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.
  • 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.
  • Patent Document 3 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.
  • a good film with a low hardness of the film cannot be obtained.
  • 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
  • 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
  • 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. .
  • 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.
  • 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 ⁇ m-40 ⁇ m at the edge of the circuit.
  • 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.
  • 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.
  • fumed silica powder or ethyl cellulose powder that has been surface-hydrophobized is added and reacted with alkoxy titanium.
  • 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.
  • 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 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • first and second liquids that have been subjected to surface hydrophobization treatment are the first and second liquids.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the partially hydrolyzed product of the alkoxysilane compound and alkoxy titanium react and cure.
  • 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.
  • an alkoxy group alcohol component
  • a Si—O—Ti bond or Si—O—Si bond is generated, and the alcohol component of the alkoxy group is eliminated.
  • organic groups such as alkyl groups directly bonded to silicon atoms remain as they are.
  • 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.
  • the solder resist since electronic components are mounted on the printed wiring board, the solder resist must withstand, for example, 260 ° C solder.
  • 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.
  • Patent Document 3 Japanese Laid-Open Patent Publication No. 63-12671.
  • 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.
  • 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. .
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • R 2 is a methyl group, an ethyl group, or the like. It can be illustrated.
  • n is an integer of 0-3.
  • 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.
  • the coating obtained by curing the coating has a three-dimensional structure.
  • the organic solvent used in the first liquid or the second liquid the following solvents can be used.
  • the potassium titanate fiber is a fiber of potassium hexatitanate.
  • the diameter of the fiber is 1 ⁇ m 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.
  • the alkoxytitanium is represented by Formula 3.
  • 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.
  • the kaolin powder is preferably a powder having an average particle size of 5 ⁇ m or less and a maximum particle size of 25 ⁇ m 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 ⁇ m or less and a maximum particle size of 25 ⁇ m 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
  • the coupling agent-treated aluminum hydroxide powder preferably has an average particle size of 3 ⁇ m or less and a maximum particle size force of S25 ⁇ m or less.
  • the soluble acid sodium salt is preferably 0.06 wt% or less.
  • 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
  • the film will shed and is not suitable.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the yellow pigment anthraquinone yellow, benzimidazolone yellow, iron oxide and the like can be suitably used.
  • 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.
  • a solder resist solution is applied to a printed wiring board or the like to form a cured product and form a film.
  • potassium titanate fiber to an organic solvent in which a partially hydrolyzed alkoxysilane compound is dissolved, and mix.
  • 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.
  • 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!
  • the viscosities of the first solution and the second solution are substantially the same as each other immediately before 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.
  • the liquid temperature during mixing and kneading is preferably 40 ° C. or lower for the same reason as described above.
  • the first and second liquids when they 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.
  • 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
  • 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.
  • a screen printing method or a flexographic printing method can be applied as a method for forming a pattern by applying a solder resist solution on the surface of a printed wiring board.
  • 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! /.
  • the thickness of the coating after curing must be 7 ⁇ m 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.
  • 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.
  • 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.
  • the first liquid is obtained.
  • 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.
  • 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.
  • the average diameter of the potassium fiber (hexatitanate those 0.5 With an average length of 15 ⁇ m) 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.
  • 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 ⁇ m at the edge of the copper circuit.
  • Solder heat resistance (260 to 20 seconds float) No crack, no peeling Crack, no peeling Pencil hardness 6 ⁇ 6 ⁇
  • 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).

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Paints Or Removers (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Materials For Photolithography (AREA)

Abstract

L’invention concerne un revêtement de résist pour brasage à deux composants où un premier composant comprenant un hydrolysat partiel d’un composé d’alcoxysilane et un solvant organique et un second composant comprenant un alcoxyde de titane et un solvant organique sont mélangés et vulcanisés, caractérisé en ce que le premier composant et/ou le second composant contiennent une fibre de titanate de potassium ; un produit vulcanisé de résist pour brasage réalisé à partir du revêtement ; et une carte à circuit imprimé possédant un film de revêtement élaboré en formant un motif en utilisant le revêtement, avant cuisson du motif. Ledit revêtement de résist pour brasage peut comprendre en outre, dans le premier composant et/ou le second composant, au moins un élément sélectionné parmi une poudre de kaolin, une poudre d’alumine et une poudre d’hydroxyde d’aluminium ayant été traitées avec un agent de couplage, une poudre de silice fumée ayant subi un traitement de surface pour conférer une hydrophobicité, une poudre de cellulose d’éthyle, un pigment bleu ne contenant pas d’atome d’halogène et/ou un pigment jaune ne contenant pas d’atome d’halogène.
PCT/JP2004/014369 2004-09-30 2004-09-30 Revêtement de résist pour brasage, produit vulcanisé réalisé à partir de celui-ci et carte à circuit imprimé ayant un film de revêtement réalisé à partir dudit revêtement WO2006038262A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2005509258A JP3928136B2 (ja) 2004-09-30 2004-09-30 ソルダーレジスト塗料、その硬化物及びその被膜を備えたプリント配線板
PCT/JP2004/014369 WO2006038262A1 (fr) 2004-09-30 2004-09-30 Revêtement de résist pour brasage, produit vulcanisé réalisé à partir de celui-ci et carte à circuit imprimé ayant un film de revêtement réalisé à partir dudit revêtement

Applications Claiming Priority (1)

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PCT/JP2004/014369 WO2006038262A1 (fr) 2004-09-30 2004-09-30 Revêtement de résist pour brasage, produit vulcanisé réalisé à partir de celui-ci et carte à circuit imprimé ayant un film de revêtement réalisé à partir dudit revêtement

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008142794A1 (fr) * 2007-05-24 2008-11-27 Ceramission Hanbai Co., Ltd. Composition de revêtement, produits de durcissement, revêtements pour l'isolation électrique, revêtements pour la dissipation de chaleur et cartes de câblage imprimé flexibles
JP4968257B2 (ja) * 2006-04-28 2012-07-04 住友ベークライト株式会社 ソルダーレジスト材料及びそれを用いた配線板並びに半導体パッケージ
JP2016125144A (ja) * 2014-12-29 2016-07-11 四国化成工業株式会社 表面処理剤、樹脂組成物及びそれらの利用
CN110204915A (zh) * 2019-02-25 2019-09-06 王成 一种防水型纳米纤维素的制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6312671A (ja) * 1986-07-02 1988-01-20 T S B:Kk 無機系コーティング剤の製造方法
JPS6330578A (ja) * 1986-07-24 1988-02-09 Shikoku Chem Corp エポキシ樹脂系レジストインク組成物
JPH11158252A (ja) * 1997-09-08 1999-06-15 Taiyo Ink Mfg Ltd 熱硬化性樹脂組成物、並びにその硬化物からなる保護膜及びその形成方法
JP2002040663A (ja) * 2000-07-26 2002-02-06 Taiyo Ink Mfg Ltd ソルダーレジスト組成物及びその硬化物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6312671A (ja) * 1986-07-02 1988-01-20 T S B:Kk 無機系コーティング剤の製造方法
JPS6330578A (ja) * 1986-07-24 1988-02-09 Shikoku Chem Corp エポキシ樹脂系レジストインク組成物
JPH11158252A (ja) * 1997-09-08 1999-06-15 Taiyo Ink Mfg Ltd 熱硬化性樹脂組成物、並びにその硬化物からなる保護膜及びその形成方法
JP2002040663A (ja) * 2000-07-26 2002-02-06 Taiyo Ink Mfg Ltd ソルダーレジスト組成物及びその硬化物

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4968257B2 (ja) * 2006-04-28 2012-07-04 住友ベークライト株式会社 ソルダーレジスト材料及びそれを用いた配線板並びに半導体パッケージ
WO2008142794A1 (fr) * 2007-05-24 2008-11-27 Ceramission Hanbai Co., Ltd. Composition de revêtement, produits de durcissement, revêtements pour l'isolation électrique, revêtements pour la dissipation de chaleur et cartes de câblage imprimé flexibles
JPWO2008142794A1 (ja) * 2007-05-24 2010-08-05 セラミッション販売株式会社 コーティング用組成物、硬化物、電気絶縁用コーティング膜、放熱用コーティング膜、およびフレキシブルプリント配線板
JP2016125144A (ja) * 2014-12-29 2016-07-11 四国化成工業株式会社 表面処理剤、樹脂組成物及びそれらの利用
CN110204915A (zh) * 2019-02-25 2019-09-06 王成 一种防水型纳米纤维素的制备方法

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