KR102625987B1 - First liquid and second liquid of two-liquid mixing type, and method for manufacturing printed wiring board - Google Patents

Abstract

The object of the present invention is to provide a first and second liquid of a two-liquid mixing type that has excellent dispersibility of titanium oxide and inorganic filler and can easily recognize the mixed state of the first and second liquid.
The first and second two-liquid mixed liquids according to the present invention are the first and second two-liquid mixed liquids for obtaining a photosensitive composition as a mixture, and the first liquid contains a polymerizable polymer having a carboxyl group and a photopolymerization initiator. and titanium oxide, an inorganic filler, and an organic solvent, and the second liquid contains a compound having a cyclic ether group, and the second liquid does not contain titanium oxide, an inorganic filler, and an organic solvent, respectively. , or titanium oxide, an inorganic filler, and an organic solvent are each contained in an amount of 10% by weight or less based on a total of 100% by weight of the titanium oxide, inorganic filler, and organic solvent contained in the photosensitive composition.

Description

Manufacturing method of the first and second two-liquid mixing liquid and printed wiring board {FIRST LIQUID AND SECOND LIQUID OF TWO-LIQUID MIXING TYPE, AND METHOD FOR MANUFACTURING PRINTED WIRING BOARD}

The present invention relates to first and second two-liquid mixed liquids for obtaining a photosensitive composition as a mixture. The present invention, more specifically, relates to the first and second liquids of a two-liquid mixing type that are appropriately used to form a solder resist film on a substrate or to form a resist film that reflects light on a substrate on which a light emitting diode chip is mounted. Additionally, the present invention relates to a method of manufacturing a printed wiring board using the first and second liquids of the above two-liquid mixing type.

Solder resist films are widely used as protective films to protect printed wiring boards from high-temperature solder.

Additionally, in various electronic device applications, a light emitting diode (hereinafter abbreviated as LED) chip is mounted on the upper surface of a printed wiring board. In order to utilize the light emitted from the LED that reaches the upper surface of the printed wiring board, a white solder resist film may be formed on the upper surface of the printed wiring board. In this case, not only the light directly irradiated from the surface of the LED chip to the side opposite to the printed wiring board, but also the reflected light that reaches the upper surface of the printed wiring board and is reflected by the white solder resist film can be used. Therefore, the efficiency of using light generated from the LED can be increased.

As an example of a material for forming the white solder resist film, Patent Document 1 below contains a silane-modified epoxy resin containing an alkoxy group obtained by a dealcoholization reaction between an epoxy resin and a hydrolyzable alkoxysilane, and also contains a polycarboxylic acid containing an unsaturated group. A resist material further containing a boxylic acid resin, a diluent, a photopolymerization initiator, and a curing adhesion imparting agent is disclosed. A filler such as titanium oxide can also be added to this resist material.

Patent Document 2 below discloses a white solder resist material containing a carboxyl group-containing resin without an aromatic ring, a photopolymerization initiator, an epoxy compound, rutile-type titanium oxide, and a diluent.

Patent Document 3 below discloses the first and second liquids of a two-liquid mixing type that are used by mixing. The first and second liquids are used so that the photosensitive composition, which is a mixture of the first and second liquids, contains as a whole a polymerizable polymer having a carboxyl group, a photopolymerization initiator, a compound having a cyclic ether group, titanium oxide, and an organic solvent. This is manufactured. The photosensitive composition is selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and naphtha having an initial distillation point of 150°C or higher and an end point of distillation properties of 290°C or lower as the organic solvent. Includes at least two selected species. The first liquid contains the polymerizable polymer, and as a part of the organic solvent, dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and an initial boiling point of 150°C or higher in distillation properties. It contains at least one type selected from the group consisting of naphtha whose end point is 290°C or lower. The second liquid contains the compound having the cyclic ether group, and as a part of the organic solvent, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, and distillation properties having an initial point of 150°C or higher. It contains at least one type selected from the group consisting of naphtha whose end point in properties is 220°C or lower. The first liquid contains the photopolymerization initiator, the titanium oxide, or both the photopolymerization initiator and the titanium oxide.

When the first liquid does not contain the photopolymerization initiator, the second liquid contains the photopolymerization initiator, and when the first liquid does not contain the titanium oxide, the second liquid contains the titanium oxide. do.

Japanese Patent Publication No. 2007-249148 Japanese Patent Publication No. 2007-322546 WO2012/111356A1

Conventional resist materials such as those described in Patent Documents 1 and 2 have a problem in that the dispersibility of fillers is low. Additionally, in the case of the first and second two-liquid mixing liquids as described in Patent Document 3, it may be difficult to recognize whether they have been mixed well.

The purpose of the present invention is to provide a first and second two-liquid mixed liquid that has excellent dispersibility of titanium oxide and inorganic filler and allows the mixing state of the first and second liquids to be easily recognized. Additionally, an object of the present invention is to provide a method for manufacturing a printed wiring board using the first and second liquids of the two-liquid mixing type.

According to a broad aspect of the present invention, the first and second two-liquid mixed liquids are used to obtain a photosensitive composition as a mixture, and the first and second two-liquid mixed liquids are used before the first and second liquids are mixed. The photosensitive composition, which is a liquid and is a mixture of the first and second liquids, contains as a whole a polymerizable polymer having a carboxyl group, a photopolymerization initiator, a compound having a cyclic ether group, titanium oxide, and an inorganic substance different from titanium oxide. Containing a filler and an organic solvent, the first liquid contains the polymerizable polymer having the carboxyl group, the photopolymerization initiator, the titanium oxide, the inorganic filler, and the organic solvent, and the second liquid This includes a compound having the cyclic ether group, and the second liquid does not contain the titanium oxide, or the titanium oxide is contained in an amount of 10% by weight or less based on a total of 100% by weight of the titanium oxide contained in the photosensitive composition. wherein the second liquid does not contain the inorganic filler, or contains the inorganic filler in an amount of 10% by weight or less based on a total of 100% by weight of the inorganic filler contained in the photosensitive composition, and the second liquid The first and second two-liquid mixed liquids (hereinafter referred to as: , may be described as the first and second liquids) are provided.

In certain aspects of the first and second liquids according to the present invention, the second liquid does not contain the titanium oxide.

In certain aspects of the first and second liquids according to the present invention, the second liquid does not contain the inorganic filler.

In certain aspects of the first and second liquids according to the present invention, the second liquid does not contain the organic solvent.

In a specific aspect of the first and second liquids according to the present invention, the photosensitive composition, which is a mixture of the first and second liquids, contains a polymerizable monomer as a whole, and the second liquid contains the polymerizable monomer. It contains a monomer, and the first liquid does not contain the polymerizable monomer, or contains the polymerizable monomer in an amount of 10% by weight or less based on a total of 100% by weight of the polymerizable monomer included in the photosensitive composition.

In certain aspects of the first and second liquids according to the present invention, the organic solvent contained in the photosensitive composition contains a dibasic acid ester.

In certain aspects of the first and second liquids according to the present invention, the average particle diameter of the inorganic filler is 0.1 μm or more and 10 μm or less.

In certain aspects of the first and second liquids according to the present invention, the first and second liquids are used to form a solder resist film.

According to a broad aspect of the present invention, there is a method of manufacturing a printed wiring board comprising a printed wiring board main body having a circuit on the surface, and a solder resist film laminated on the surface of the printed wiring board main body on which the circuit is installed, comprising the first two-liquid mixing type described above. , a step of mixing a second liquid, and obtaining a photosensitive composition, which is a solder resist composition mixed with the first and second liquids, and placing the first and second liquids on the surface on which the circuit of a printed wiring board main body having a circuit on the surface is installed. A method for manufacturing a printed wiring board is provided, comprising the steps of coating a photosensitive composition, which is a solder resist composition mixed with a liquid, and forming a solder resist film laminated on the surface of the printed wiring board main body on which the circuit is installed.

The photosensitive composition, which is a mixture of the first and second two-liquid mixed liquids according to the present invention, is comprised as a whole of a polymerizable polymer having a carboxyl group, a photopolymerization initiator, a compound having a cyclic ether group, titanium oxide, and titanium oxide. It contains an inorganic filler different from the above and an organic solvent, and the first liquid contains the polymerizable polymer having the carboxyl group, the photopolymerization initiator, the titanium oxide, the inorganic filler, and the organic solvent, The second liquid contains a compound having the cyclic ether group, and the second liquid does not contain the titanium oxide, or the titanium oxide is included in the total 100% by weight of the titanium oxide contained in the photosensitive composition. 10% by weight or less, and the second liquid does not contain the inorganic filler, or contains the inorganic filler in an amount of 10% by weight or less based on a total of 100% by weight of the inorganic filler contained in the photosensitive composition, Since the second liquid does not contain the organic solvent or contains the organic solvent in an amount of 10% by weight or less based on the total 100% by weight of the organic solvent contained in the photosensitive composition, the dispersibility of titanium oxide and the inorganic filler This is excellent, and the mixed state of the first and second liquids can be easily recognized.

1 is a partially cut front cross-sectional view schematically showing an example of an LED device having a resist film using first and second two-liquid mixed liquids according to one embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

The first and second two-liquid mixed liquids according to the present invention are used to obtain a photosensitive composition as a mixture. The first and second two-liquid mixed liquids according to the present invention are a kit used to obtain a photosensitive composition as a mixture. The first and second liquids of the two-liquid mixing type according to the present invention are mixed and used. The first and second liquids of the two-liquid mixing type according to the present invention are the liquids before the first and second liquids are mixed. The first and second liquids before mixing are the photosensitive composition before mixing. The photosensitive composition, which is a mixture of the first and second two-liquid mixtures according to the present invention, consists as a whole of a polymerizable polymer having a carboxyl group (A), a photopolymerization initiator (B), and a compound having a cyclic ether group (C). ), titanium oxide (D), an inorganic filler (E) different from titanium oxide, and an organic solvent (F). The mixture of the first and second liquids is a photosensitive composition, and the mixed photosensitive composition includes the components (A) to (F) as a whole.

The first liquid contains the polymerizable polymer (A), a photopolymerization initiator (B), titanium oxide (D), an inorganic filler (E), and an organic solvent (F).

The second liquid contains compound (C) having a cyclic ether group.

The second liquid may or may not contain titanium oxide (D). The second liquid does not contain titanium oxide (D), or contains titanium oxide (D) in an amount of 10% by weight or less based on 100% by weight of the total titanium oxide (D) contained in the photosensitive composition. The second liquid may contain titanium oxide (D), but when the second liquid contains titanium oxide (D), the content of titanium oxide (D) is small.

The second liquid may or may not contain an inorganic filler (E). The second liquid does not contain the inorganic filler (E), or contains 10% by weight or less of the inorganic filler (E) based on the total 100% by weight of the inorganic filler (E) contained in the photosensitive composition. The second liquid may contain the inorganic filler (E), but when the second liquid contains the inorganic filler (E), the content of the inorganic filler (E) is small.

The second liquid may or may not contain the organic solvent (F). The second liquid does not contain the organic solvent (F), or contains 10% by weight or less of the organic solvent (F) based on the total 100% by weight of the organic solvent (F) contained in the photosensitive composition. The second liquid may contain the organic solvent (F), but when the second liquid contains the organic solvent (F), the content of the organic solvent (F) is small.

In addition, when the first and second liquids of the two-liquid mixing type according to the present invention contain the polymerizable monomer described later or contain the antioxidant described later, the polymerizable monomer and the antioxidant are each added to the first liquid. It may be contained in, may be contained in the second liquid, or may be contained in both the first liquid and the second liquid.

By employing the above structure in the first and second liquids of the two-liquid mixing type according to the present invention, the dispersibility of titanium oxide (D) and the inorganic filler (E) can be improved. In particular, the dispersibility of the inorganic filler (E) increases. Additionally, by employing the above configuration, the mixed state of the first and second liquids can be easily recognized.

On the other hand, when the second liquid contains titanium oxide (D) in more than 10% by weight of the total 100% by weight of titanium oxide (D) contained in the photosensitive composition, the titanium oxide (D) in the photosensitive composition ) and the dispersibility of the inorganic filler (E) is greatly reduced. In addition, even when the second liquid contains more than 10% by weight of the inorganic filler (E) in the total 100% by weight of the inorganic filler (E) contained in the photosensitive composition, the inorganic filler (E) in the photosensitive composition ) dispersibility is greatly reduced. Moreover, even when the second liquid contains the organic solvent (F) in more than 10% by weight of the total 100% by weight of the organic solvent (F) contained in the photosensitive composition, the inorganic filler (E) in the photosensitive composition ) dispersibility is greatly reduced.

In the present invention, which essentially uses an inorganic filler (E), titanium oxide (D), an inorganic filler (E), and an organic solvent (F) are selectively mixed into the first liquid to obtain the effect of the present invention. plays a big role for

Hereinafter, details of each component contained in the first and second two-liquid mixed liquids according to the present invention and the mixed photosensitive composition will be described.

(polymerizable polymer (A))

The polymerizable polymer (A) has a carboxyl group. The polymerizable polymer (A) having a carboxyl group has polymerizability and can be polymerized. When the polymerizable polymer (A) has a carboxyl group, the developability of the photosensitive composition becomes good. Examples of the polymerizable polymer (A) include acrylic resins having a carboxyl group, epoxy resins having a carboxyl group, and olefin resins having a carboxyl group. In addition, “resin” is not limited to solid resin, but also includes liquid resin and oligomers.

The polymerizable polymer (A) is preferably one of the following carboxyl group-containing resins (a) to (e).

(a) Carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid and a compound having a polymerizable unsaturated double bond

(b) Carboxyl group-containing resin obtained by reaction between a carboxyl group-containing (meth)acrylic copolymer resin (b1) and a compound (b2) having an oxirane ring and an ethylenically polymerizable unsaturated double bond in one molecule.

(c) After reacting an unsaturated monocarboxylic acid with a copolymer of a compound each having one epoxy group and one polymerizable unsaturated double bond in one molecule and a compound having a polymerizable unsaturated double bond, the second reactant produced A carboxyl group-containing resin obtained by reacting a saturated or unsaturated polybasic acid anhydride with a hydroxyl group.

(d) Containing hydroxyl and carboxyl groups obtained by reacting a saturated or unsaturated polybasic acid anhydride with a hydroxyl group-containing polymer and then reacting the resulting polymer with a carboxyl group with a compound each having one epoxy group and one polymerizable unsaturated double bond per molecule. profit

(e) a resin obtained by reacting an epoxy compound having an aromatic ring with a saturated polybasic acid anhydride or an unsaturated polybasic acid anhydride, or reacting an epoxy compound having an aromatic ring with a carboxyl group-containing compound having at least one unsaturated double bond, followed by reacting a saturated polybasic acid anhydride or A resin obtained by further reacting an unsaturated polybasic acid anhydride.

The content of the polymerizable polymer (A) having a carboxyl group in 100% by weight of the photosensitive composition is preferably 3% by weight or more, more preferably 5% by weight or more, preferably 50% by weight or less, more preferably is 40% by weight or less. When the content of the polymerizable polymer (A) having a carboxyl group is equal to or greater than the lower limit and equal to or lower than the upper limit, the curability of the photosensitive composition becomes good.

(Photopolymerization initiator (B))

Since the photosensitive composition includes a photopolymerization initiator (B), the photosensitive composition can be cured by irradiation of light. The photopolymerization initiator (B) is not particularly limited. Only one type of photopolymerization initiator (B) may be used, or two or more types may be used together.

Examples of the photopolymerization initiator (B) include acylphosphine oxide, halomethylated triazine, halomethylated oxadiazole, imidazole, benzoin, benzoin alkyl ether, anthraquinone, benzantrone, benzophenone, and acetophenone. , thioxanthone, benzoic acid ester, acridine, phenazine, titanocene, α-aminoalkylphenone, oxime, and derivatives thereof. Only one type of the photopolymerization initiator (B) may be used, or two or more types may be used together.

From the viewpoint of further increasing the heat resistance and light resistance of the resist film and further suppressing stickiness of the surface of the resist film, an acylphosphine oxide-based photopolymerization initiator is preferable.

In the photosensitive composition, the content of the photopolymerization initiator (B) is preferably 0.1 part by weight or more, more preferably 1 part by weight or more, based on 100 parts by weight of the polymerizable polymer (A) having a carboxyl group. is 30 parts by weight or less, more preferably 15 parts by weight or less. If the content of the photopolymerization initiator (B) is more than the above lower limit and below the above upper limit, the photosensitivity of the photosensitive composition can be further improved.

(Compound (C) having a cyclic ether group)

For the purpose of improving the cutting processability of the resist film, etc., the photosensitive composition contains a compound (C) having a cyclic ether group. In addition, the use of the compound (C) having the cyclic ether group improves the curability of the photosensitive composition.

Examples of the compound (C) having the cyclic ether group include heterocyclic epoxy resins such as bisphenol S-type epoxy resin, diglycidyl phthalate resin, triglycidyl isocyanurate, bixylenol-type epoxy resin, and biphenol-type epoxy resin. Epoxy resin, tetraglycidyl xylenoylethane resin, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type resin, brominated bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy. Resin, alicyclic epoxy resin, novolak-type epoxy resin of bisphenol A, chelate-type epoxy resin, glyoxal-type epoxy resin, amino group-containing epoxy resin, rubber-modified epoxy resin, dicyclopentadiene phenolic-type epoxy resin, silicone-modified epoxy resin. and ε-caprolactone modified epoxy resin. As for the compound (C) having the cyclic ether group, only one type may be used, or two or more types may be used in combination.

The compound (C) having the cyclic ether group reacts with the carboxyl group of the polymerizable polymer (A) having the carboxyl group, and acts to cure the photosensitive composition. The compound (C) having the cyclic ether group is preferably an epoxy compound.

In the photosensitive composition, the content of the compound (C) having a cyclic ether group relative to 100 parts by weight of the polymerizable polymer (A) having a carboxyl group is preferably 0.1 part by weight or more, more preferably 1 part by weight. or more, preferably 50 parts by weight or less, more preferably 30 parts by weight or less. If the content of the compound (C) having the cyclic ether group is more than the lower limit and less than the upper limit, the electrical insulation of the resist film can be further improved.

(Titanium oxide (D))

Since the photosensitive composition contains titanium oxide (D), a resist film such as a solder resist film with high reflectance can be formed. Titanium oxide (D) contained in the photosensitive composition is not particularly limited. Only one type of titanium oxide (D) may be used, or two or more types may be used together.

By using the titanium oxide (D), it is possible to form a resist film with a high reflectance compared to the case where an inorganic filler other than titanium oxide (D) is used.

The titanium oxide (D) is preferably rutile-type titanium oxide or anatase-type titanium oxide. By using rutile-type titanium oxide, a resist film with even more excellent heat yellowing resistance can be formed. The anatase type titanium oxide has lower hardness than rutile type titanium oxide. For this reason, the processability of the resist film can be improved by using anatase-type titanium oxide.

In addition, from the viewpoint of effectively increasing the dispersibility of titanium oxide (D) and the inorganic filler (E) and more easily recognizing the mixed state of the first and second liquids, the titanium oxide (D) is rutile-type oxidation. It is preferred that it contains titanium.

The titanium oxide (D) preferably includes rutile-type titanium oxide surface-treated with silicon oxide or a silicon compound. Among 100% by weight of the titanium oxide (D), the content of rutile-type titanium oxide surface-treated with the silicon oxide or silicon compound is preferably 10% by weight or more, more preferably 30% by weight or more, and 100% by weight. It is as follows. The entire amount of the titanium oxide (D) may be rutile-type titanium oxide surface-treated with the silicon oxide or silicon compound. By using rutile-type titanium oxide surface-treated with the silicon oxide or silicon compound, the heat yellowing resistance of the resist film can be further improved.

Examples of rutile-type titanium oxide surface-treated with silicon oxide or a silicon compound include rutile chlorine-processed titanium oxide manufactured by Ishihara Sangyo Co., Ltd., product number: CR-90, and rutile sulfate-processed titanium manufactured by Ishihara Sangyo Co., Ltd., product number: R. -550, etc.

The average particle diameter of the titanium oxide (D) is preferably 0.1 μm or more, more preferably 0.15 μm or more, preferably 1.0 μm or less, and more preferably 0.5 μm or less.

The average particle diameter of the titanium oxide (D) is the particle diameter value when the integrated value is 50% in the volume-based particle size distribution curve. The average particle diameter can be measured using, for example, a laser light type particle size distribution meter. Commercially available products of the laser light type particle size distribution meter include "LS 13 320" manufactured by Beckman Coulter.

The content of titanium oxide (D) in the second liquid is preferably 5% by weight or less, more preferably 1% by weight or less, based on the total 100% by weight of titanium oxide (D) contained in the photosensitive composition.

In 100% by weight of the photosensitive composition, the content of titanium (D) and rutile-type titanium oxide is each preferably 3% by weight or more, more preferably 10% by weight or more, further preferably 15% by weight or more. Preferably it is 80% by weight or less, more preferably 75% by weight or less, and even more preferably 70% by weight or less. If the content of titanium oxide (D) and rutile-type titanium oxide is more than the above lower limit and less than the above upper limit, it becomes difficult to yellow the resist film when exposed to high temperature. Additionally, a photosensitive composition having a viscosity suitable for coating can be easily manufactured.

(Inorganic Filler (E))

The inorganic filler (E) is an inorganic filler different from titanium oxide. Only one type of the inorganic filler (E) may be used, or two or more types may be used together.

Specific examples of the inorganic filler (E) include silica, alumina, mica, beryllia, potassium titanate, barium titanate, strontium titanate, calcium titanate, zirconium oxide, antimony oxide, aluminum borate, aluminum hydroxide, magnesium oxide, Examples include calcium carbonate, magnesium carbonate, aluminum carbonate, calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, calcium sulfate, barium sulfate, silicon nitride, boron nitride, clay such as calcined clay, talc, silicon carbide, and silicon particles. . Only one type of the inorganic filler (E) may be used, or two or more types may be used together.

From the viewpoint of further increasing the heat resistance and light resistance of the resist film and further suppressing stickiness of the surface of the resist film, the photosensitive composition preferably contains talc or silica, and more preferably contains silica. The photosensitive composition may contain talc.

The average particle diameter of the inorganic filler (E) is preferably 0.1 μm or more, more preferably 0.2 μm or more, preferably 10 μm or less, and more preferably 5 μm or less.

The average particle diameter of the inorganic filler (E) is the particle diameter value when the integrated value is 50% in the volume-based particle size distribution curve. The average particle diameter can be measured using, for example, a laser light type particle size distribution meter. Commercially available products of the laser light type particle size distribution meter include "LS 13 320" manufactured by Beckman Coulter.

The content of the inorganic filler (E) in the second liquid is preferably 5% by weight or less, more preferably 1% by weight or less, based on the total 100% by weight of the inorganic filler (E) contained in the photosensitive composition.

In 100% by weight of the photosensitive composition, the content of the inorganic filler (E) and the total content of talc and silica are each preferably 0.1% by weight or more, more preferably 1% by weight or more, and even more preferably 3% by weight. % or more, preferably 50% by weight or less, more preferably 30% by weight or less, and even more preferably 10% by weight or less. If the content of the inorganic filler (E) and the total content of talc and silica are more than the above lower limit and less than the above upper limit, the heat resistance and light resistance of the resist film are further improved, and surface stickiness is further suppressed.

In 100% by weight of the photosensitive composition, the total content of the titanium oxide (D) and the inorganic filler (E) is preferably 5% by weight or more, more preferably 10% by weight or more, and even more preferably 20% by weight. % or more, preferably 80% by weight or less, more preferably 60% by weight or less, and even more preferably 40% by weight or less. If the total content of the titanium oxide (D) and the inorganic filler (E) is more than the lower limit and less than the upper limit, the heat resistance and light resistance of the resist film are further improved, and surface stickiness is further suppressed.

In the photosensitive composition, the weight ratio of the content of the titanium oxide (D) and the inorganic filler (E) (content of titanium oxide (D):content of inorganic filler (E)) is preferably 0.1:99.9 to 99.9. :0.1, more preferably 1:99 to 99:1, even more preferably 1:9 to 9:1.

(Organic solvent (F))

The photosensitive composition includes an organic solvent (F). The photosensitive composition obtained by mixing the first and second liquids includes an organic solvent (F). Only one type of organic solvent (F) may be used, or two or more types may be used together.

Commonly known organic solvents include ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, cellosolve, methyl cellosolve, butyl cellosolve, carbitol, and methyl carboxylate. Glycol ethers such as bitol, butylcarbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, and tripropylene glycol monomethyl ether, ethyl acetate, butyl acetate, butyl lactate, and cellosolve acetate. , butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, esters such as propylene carbonate, octane, decane, etc. aliphatic hydrocarbons, petroleum solvents such as petroleum ether and naphtha, and dibasic acid esters. The dibasic acid ester is a solvent called DBE.

The photosensitive composition is the organic solvent (F), which is dibasic acid ester, dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, or an initial distillation point of 150°C or higher and a distillation end point of 290°C. It is preferable to include naphtha with a temperature of ℃ or lower. In this case, the dispersibility of titanium oxide (D) and the inorganic filler (E) can be effectively increased, and the mixed state of the first and second liquids can be recognized more easily. It is preferable that the organic solvent (F) contained in the photosensitive composition contains a dibasic acid ester.

The first liquid is the organic solvent (F), which is dibasic acid ester, dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, or an initial point in distillation properties of 150°C or higher and an end point in distillation properties. It is preferable to include naphtha at a temperature of 290°C or lower. It is preferable that the organic solvent (F) contained in the first liquid contains a dibasic acid ester.

The second liquid may contain the organic solvent (F) or may not contain the organic solvent (F). It is preferable that the content of the organic solvent (F) in the second liquid is small. When the second liquid contains the organic solvent (F), the second liquid is dibasic acid ester, dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, or distillation. It is preferable to include naphtha with an initial boiling point of 150°C or higher in properties and an end point in distillation properties of 290°C or lower. The organic solvent (F) contained in the second liquid may contain dibasic acid ester.

As the organic solvent (F), dibasic acid ester, dipropylene glycol monomethyl ether, or diethylene glycol monoethyl ether acetate may be used, and the initial distillation point is 150° C. or higher, Naphtha whose distillation end point is 290°C or lower can also be used.

The above “initial point in distillation properties” and the above “end point in distillation properties” mean values measured according to JIS K2254 “Petroleum products - Distillation test methods”.

The content of the organic solvent (F) in the second liquid is preferably 5% by weight or less, more preferably 1% by weight or less, based on the total 100% by weight of the organic solvent (F) contained in the photosensitive composition.

The content of the organic solvent (F) in 100% by weight of the first and second liquids of the two-liquid mixing type and in 100% by weight of the photosensitive composition after mixing is preferably 5% by weight or more, more preferably 10% by weight or more. , Preferably it is 50% by weight or less, more preferably 30% by weight or less.

(other ingredients)

In order to further improve curability, the photosensitive composition preferably contains components different from the polymerizable polymer (A) having a carboxyl group and a polymerizable monomer. The photosensitive composition preferably contains both a polymerizable polymer (A) having a carboxyl group and a polymerizable monomer. The polymerizable monomer has polymerizability and can be polymerized. The polymerizable monomer is not particularly limited. Only one type of the polymerizable monomer may be used, or two or more types may be used in combination.

The polymerizable monomer is preferably a monomer containing a polymerizable unsaturated group. Examples of the polymerizable unsaturated group in the polymerizable monomer include functional groups having a polymerizable unsaturated double bond, such as a (meth)acryloyl group and a vinyl ether group. A (meth)acryloyl group is preferable because it can increase the crosslinking density of the resist film.

The polymerizable unsaturated group-containing monomer is preferably a compound having a (meth)acryloyl group. Examples of the compounds having the (meth)acryloyl group include di(meth)acrylate modified products of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, or propylene glycol, polyhydric alcohols, and ethylene oxide additions to polyhydric alcohols. Polyhydric (meth)acrylate modified product of water or propylene oxide adduct of polyhydric alcohol, (meth)acrylate modified product of phenol, ethylene oxide adduct of phenol, or propylene oxide adduct of phenol, or glycerin diglycy. Examples include (meth)acrylate modified products of glycidyl ether such as dil ether or trimethylolpropane triglycidyl ether, and melamine (meth)acrylate.

Examples of the polyhydric alcohol include hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tris-hydroxyethyl isocyanurate. Examples of the (meth)acrylate of the phenol include phenoxy (meth)acrylate and di(meth)acrylate modified product of bisphenol A.

“(meth)acryloyl” means acryloyl and methacryloyl. “(Meth)acrylic” means acrylic and methacrylic. “(Meth)acrylate” means acrylate and methacrylate.

When the polymerizable monomer is included, the content of the polymerizable monomer is preferably 5% by weight or more, based on a total of 100% by weight of the polymerizable monomer and the polymerizable polymer (A) having a carboxyl group. It is 50% by weight or less. If the content of the polymerizable monomer is equal to or greater than the lower limit and equal to or lower than the upper limit, the photosensitive composition can be sufficiently cured. Additionally, the crosslinking density of the resist film becomes appropriate, sufficient resolution can be obtained, and yellowing of the resist film becomes difficult.

The polymerizable monomer may be contained in the first liquid, may be contained in the second liquid, or may be contained in both the first liquid and the second liquid. From the viewpoint of further improving dispersibility and recognition of the mixed state, it is preferable that the second liquid contains the polymerizable monomer. From the viewpoint of further improving stability under UV exposure, the first liquid does not contain the polymerizable monomer, or contains the polymerizable monomer in an amount of 10% by weight based on a total of 100% by weight of the polymerizable monomer contained in the photosensitive composition. It is preferable to include it at % or less. The first liquid may contain the titanium oxide, but when the first liquid contains a polymerizable monomer, it is preferable that the content of the polymerizable monomer is small. From the viewpoint of further improving stability under UV exposure, it is preferable that the first liquid does not contain a polymerizable monomer.

To reduce the risk of yellowing of the resist film when exposed to high temperatures, the photosensitive composition preferably contains an antioxidant. The antioxidant preferably has a Lewis basic moiety. From the viewpoint of further suppressing yellowing of the resist film, the antioxidant is preferably at least one selected from the group consisting of phenol-based antioxidants, phosphorus-based antioxidants, and amine-based antioxidants. From the viewpoint of further suppressing yellowing of the resist film, the antioxidant is preferably a phenol-based antioxidant. That is, the photosensitive composition preferably contains a phenol-based antioxidant.

Commercially available products of the phenolic antioxidant include IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, and IRGANOX 295 (all manufactured by Chiba Japan), Adeka Step AO-30, Adeka Step AO- 40, Adeka Step AO-50, Adeka Step AO-60, Adeka Step AO-70, Adeka Step AO-80, Adeka Step AO-90 and Adeka Step AO-330 (above, all Adeka Step ADEKA), Sumilizer GA-80, Sumilizer MDP-S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS(F) and Sumilizer GP (all manufactured by Sumitomo Chemical Industries, Ltd.), HOSTANOX O10, HOSTANOX O16, HOSTANOX O14 and HOSTANOX O3 (all manufactured by Clariant Corporation), Antenna BHT, Antenna W-300, W-400 and Antenna W500 (all manufactured by Kawaguchi Chemical Industries), and SEENOX 224M and SEENOX 326M (all manufactured by Kawaguchi Chemical Industries, Ltd.) , all manufactured by Siplo Kasei), etc.

Examples of the phosphorus-based antioxidant include cyclohexyl phosphine and triphenylphosphine. Commercially available products of the phosphorus-based antioxidant include Adekastep PEP-4C, Adekastep PEP-8, Adekastep PEP-24G, Adekastep PEP-36, Adekastep HP-10, Adekastep 2112, Adekastep Step 260, Adeka Step 522A, Adeka Step 1178, Adeka Step 1500, Adeka Step C, Adeka Step 135A, Adeka Step 3010 and Adeka Step TPP (all made by ADEKA), sand Staff P-EPQ and Hostanox PAR24 (all made by Clariant), and JP-312L, JP-318-0, JPM-308, JPM-313, JPP-613M, JPP-31, JPP-2000PT and JPH. -3800 (above, all made by Johoku Kagaku High School), etc.

Examples of the amine-based antioxidants include triethylamine, dicyandiamide, melamine, ethyldiamino-S-triazine, 2,4-diamino-S-triazine, and 2,4-diamino-6-tolyl-S. -Triazine, 2,4-diamino-6-xylyl-S-triazine, and quaternary ammonium salt derivatives.

The content of the antioxidant relative to 100 parts by weight of the polymerizable polymer (A) having a carboxyl group is preferably 0.1 parts by weight or more, more preferably 5 parts by weight or more, preferably 30 parts by weight or less, more preferably Typically, it is 15 parts by weight or less. If the content of the antioxidant is more than the lower limit and less than the upper limit, a resist film with even more excellent heat yellowing resistance can be formed.

In addition, the photosensitive composition includes colorants, fillers, anti-foaming agents, curing agents, curing accelerators, mold release agents, surface treatment agents, flame retardants, viscosity modifiers, dispersants, dispersion aids, surface modifiers, plasticizers, antibacterial agents, anti-mold agents, leveling agents, stabilizers, coupling agents, It may contain a flow prevention agent or a phosphor.

The photosensitive composition can be produced, for example, by stirring and mixing each of the ingredients and then uniformly mixing them with a three-axis roll.

The light source used to cure the photosensitive composition includes an irradiation device that emits active energy rays such as ultraviolet rays or visible rays. Examples of the light source include ultra-high pressure mercury lamps, deep UV lamps, high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, and excimer lasers. These light sources are appropriately selected depending on the photosensitive wavelengths of the components of the photosensitive composition. The irradiation energy of light is appropriately selected depending on the desired film thickness or the constituents of the photosensitive composition. The irradiation energy of light is generally in the range of 10 to 3000 mJ/cm2.

(LED device)

The first and second two-liquid mixed liquids according to the present invention are suitably used to form a resist film of an LED device, and are more suitably used to form a solder resist film. The first and second liquids of the two-liquid mixing type according to the present invention are preferably resist compositions, and are preferably solder resist compositions.

The manufacturing method of a printed wiring board according to the present invention is a manufacturing method of a printed wiring board comprising a printed wiring board main body having a circuit on its surface, and a resist film laminated on the surface of the printed wiring board main body on which the circuit is installed. The resist film is formed by the first and second two-liquid mixed liquid according to the present invention.

In Fig. 1, an example of an LED device having a resist film formed using the first and second two-liquid mixed liquids according to one embodiment of the present invention is schematically shown in a partially cut front cross-sectional view.

In the LED device 1 shown in FIG. 1, a resist film 3 formed of a first and second two-liquid mixed liquid is laminated on the upper surface 2a of the substrate 2. The resist film 3 is a pattern film. Accordingly, the resist film 3 is not formed in some areas of the upper surface 2a of the substrate 2. Electrodes 4a and 4b are provided on the upper surface 2a of the substrate 2 in the portion where the resist film 3 is not formed. The board 2 is preferably a printed wiring board main body.

LED chips 7 are stacked on the upper surface 3a of the resist film 3. LED chips 7 are stacked on a substrate 2 with a resist film 3 interposed therebetween. Terminals 8a and 8b are provided on the outer periphery of the lower surface 7a of the LED chip 7. Terminals 8a and 8b are electrically connected to electrodes 4a and 4b by solder 9a and 9b. Through this electrical connection, power can be supplied to the LED chip 7.

Hereinafter, the present invention will be clarified by giving specific examples and comparative examples of the present invention.

In the examples and comparative examples, the following materials 1) to 11) were used.

1) Acrylic polymer 1 (polymerizable polymer having a carboxyl group, acrylic polymer 1 obtained in Synthesis Example 1 below)

(Synthesis Example 1)

In a flask equipped with a thermometer, stirrer, dropping funnel, and reflux condenser, ethylcarbitol acetate as a solvent and azobisisobutyronitrile as a catalyst were added, heated to 80°C under a nitrogen atmosphere, and methacrylic acid and methyl methacrylate were added. Monomers mixed at a molar ratio of 30:70 were added dropwise over 2 hours. After dropping, the mixture was stirred for 1 hour and the temperature was raised to 120°C. After that, it was cooled. Glycidyl acrylate was added in an amount such that the molar ratio of 10 to the total molar amount of all monomer units of the obtained resin was heated at 100°C for 30 hours using tetrabutylammonium bromide as a catalyst, and glycidyl acrylate and Carboxyl group addition reaction was carried out. After cooling, it was taken out from the flask to obtain a solution containing 50% by weight (non-volatile matter) of carboxyl group-containing resin with a solid acid value of 60 mgKOH/g, a weight average molecular weight of 15000, and a double bond equivalent weight of 1000. Hereinafter, this solution is referred to as acrylic polymer 1.

2) DPHA (acrylic monomer, dipentaerythritol hexaacrylate)

3) 828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation)

4) TPO (photopolymerization initiator, a photo-radical generator, manufactured by BASF Japan)

5) CR-50 (titanium oxide, Ishihara Sangyo Co., Ltd., rutile-type titanium oxide manufactured by the chlorine method)

6) FH105 (talc, manufactured by Fuji Talc Co., Ltd.)

7) 5X (silica, manufactured by Tatsumori)

8) KS-7710 (compound silicone oil, polydimethylsiloxane, manufactured by Shinetsu Chemical Co., Ltd.)

9) Ethyl carbitol acetate (diethylene glycol monoethyl ether acetate, manufactured by Daicel)

10) Dipropylene glycol monomethyl ether (manufactured by Nippon New Gazai Co., Ltd.)

11) DBE (dibasic acid ester, manufactured by Sankyo Chemical Co., Ltd.)

(Example 1)

15 g of acrylic polymer 1 obtained in Synthesis Example 1, 2 g of TPO (photopolymerization initiator as a photo radical generator, manufactured by BASF Japan), 40 g of CR-50 (titanium oxide, manufactured by Ishihara Sangyo Corporation), and ethyl carbitol acetate (di 30 g of ethylene glycol monoethyl ether acetate, manufactured by Daicel Corporation, 10 g of FH105 (talc, manufactured by Fuji Talc Corporation), and 1 g of KS-7710 (compound type silicone oil, polydimethylsiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed, and placed in a mixer. After mixing for 3 minutes (Neritaro ARE-310, manufactured by Shinki Corporation), the mixture was mixed with a three-axis roll to obtain a mixture. After that, the obtained mixture was defoamed for 3 minutes using ARE-310 to obtain the first liquid.

8 g of 828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation) and 5 g of DPHA (dipentaerythritol hexaacrylate) were mixed and mixed for 3 minutes in a mixer (Neritaro ARE-310, manufactured by Shinki Corporation). By mixing with a three-axis roll, a mixture was obtained. After that, the obtained mixture was defoamed for 3 minutes using ARE-310 to obtain a second liquid.

As described above, the first and second liquids (photosensitive composition before mixing) of a two-liquid mixture containing the first and second liquids were prepared.

(Examples 2 to 5 and Comparative Examples 1 and 3)

Except that the types and mixing amounts of the materials used in the first and second liquids were changed as shown in Table 1 below, in the same manner as in Example 1, the first two-liquid mixed type having the first and second liquids was prepared. , a second liquid (photosensitive composition before mixing) was obtained.

(evaluation)

(1) Dispersibility of titanium oxide and inorganic fillers different from titanium oxide

With respect to the first and second liquids obtained as described above, the dispersibility of titanium oxide and an inorganic filler different from titanium oxide was evaluated using a grind meter (100 μm) manufactured by Daiyuki Gigi Corporation. It was judged based on the following criteria.

[Criteria for judging the dispersibility of inorganic fillers different from titanium oxide and titanium oxide]

○: No streaks.

△: Length exceeds 0㎛, and stripes occur below 50㎛

×: Length exceeds 50㎛, and stripes occur at less than 100㎛

(2) Mixability of the first and second liquids

The first and second liquids were placed in a 1L circular plastic container (BHS-1200, manufactured by Kinki Yoki Co., Ltd.), and the resist material (photosensitive composition after mixing) was stirred for 10 seconds at 50 rpm using an automatic ink machine manufactured by Mesh Co., Ltd. Produced. The first and second liquids were placed in a 1L round plastic container (BHS-1200, manufactured by Kinki Yoki Co., Ltd.), and the resist material (photosensitive composition after mixing) was stirred for 20 seconds at 50 rpm using an automatic ink machine manufactured by Mesh Co., Ltd. Produced. Additionally, in the following judgment criteria, the mixed state could be easily recognized in the order of ○>Δ>×.

The miscibility of the first and second liquids was determined based on the following criteria.

[Criteria for judging the miscibility of the first and second liquids]

○: Regardless of whether a resist material stirred for 10 seconds or a resist material stirred for 20 seconds was used, the resist material after stirring was uniformly mixed.

△: When a resist material stirred for 10 seconds was used, slightly striped irregularities were seen in the resist material after stirring, but when a resist material stirred for 20 seconds was used, the resist material after stirring was uniform.

×: Regardless of whether a resist material stirred for 10 seconds or a resist material stirred for 20 seconds was used, slightly striped unevenness was observed in the resist material after stirring.

(3) Stability of the first and second liquids under UV exposure

The first liquid and the second liquid were each placed in a plastic container (BHR-150, manufactured by Kinki Yoki Co., Ltd.), and ultraviolet rays with a wavelength of 365 nm were applied to the surface of the liquid at an ultraviolet irradiance of 100 mW/cm2 so that the irradiation energy was 1000 mJ/cm2. investigated. The stability of the first and second liquids under UV exposure was determined based on the following criteria.

[Criteria for determining the stability of the first and second liquids under UV exposure]

○: A slight cured film is formed on the surface layer of the liquid, stickiness remains, and the liquid maintains fluidity.

△: A cured film is slightly formed on the surface layer of the liquid, and although stickiness remains, the liquid has lost its fluidity.

×: A cured product is formed on the surface layer of the liquid, but the adhesiveness is lost and the liquid has lost its fluidity.

The composition and results are shown in Table 1 below.

1: LED device
2: substrate
2a: top surface
3: Resist film
3a: top surface
4a, 4b: electrodes
7: LED chip
7a: If you do
8a, 8b: terminal
9a, 9b: solder

Claims (9)

They are the first and second liquids of a two-liquid mixing type to obtain a photosensitive composition as a mixture, and the first and second liquids of the two-liquid mixing type are the liquids before the first and second liquids are mixed,
The photosensitive composition, which is a mixture of the first and second liquids, consists as a whole of a polymerizable polymer having a carboxyl group, a monomer containing a polymerizable unsaturated group, a photopolymerization initiator, a compound having a cyclic ether group, titanium oxide, and oxidation. Contains an inorganic filler different from titanium and an organic solvent,
The first liquid contains the polymerizable polymer having the carboxyl group, the photopolymerization initiator, the titanium oxide, the inorganic filler, and the organic solvent,
The second liquid contains the polymerizable unsaturated group-containing monomer and the compound having the cyclic ether group,
The second liquid does not contain the titanium oxide, or contains 10% by weight or less of the titanium oxide based on the total 100% by weight of the titanium oxide contained in the photosensitive composition,
The second liquid does not contain the inorganic filler,
The first and second liquids of a two-liquid mixing type, wherein the second liquid does not contain the organic solvent or contains the organic solvent in an amount of 10% by weight or less based on a total of 100% by weight of the organic solvent contained in the photosensitive composition. 2 liquid. The first and second two-liquid mixed liquid according to claim 1, wherein the second liquid does not contain the titanium oxide. The first and second two-liquid mixed liquid according to claim 1, wherein the second liquid does not contain the organic solvent. The method according to any one of claims 1 to 3, wherein the first liquid does not contain a polymerizable monomer, or contains 10% by weight of the polymerizable monomer based on a total of 100% by weight of the polymerizable monomer contained in the photosensitive composition. The first and second two-liquid mixed liquids containing % or less. The first and second two-liquid mixed liquid according to any one of claims 1 to 3, wherein the organic solvent contained in the photosensitive composition contains a dibasic acid ester. The first and second two-liquid mixing liquid according to any one of claims 1 to 3, wherein the inorganic filler has an average particle diameter of 0.1 μm or more and 10 μm or less. The first and second liquids of a two-liquid mixing type according to any one of claims 1 to 3, which are used to form a solder resist film. A method of manufacturing a printed wiring board comprising a printed wiring board main body having a circuit on the surface, and a solder resist film laminated on the surface of the printed wiring board main body on which the circuit is installed,
A process of mixing the first and second liquids of the two-liquid mixing type according to any one of claims 1 to 3 to obtain a photosensitive composition, which is a solder resist composition in which the first and second liquids are mixed;
A photosensitive composition, which is a solder resist composition mixed with the first and second liquids, is coated on the surface of a printed wiring board main body having a circuit on its surface, where the circuit is installed, and the solder resist is laminated on the surface of the printed wiring board main body where the circuit is installed. A method of manufacturing a printed wiring board, comprising a film forming process. delete

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