JP2020030433A - Two-liquid mixed type first and second liquids, second liquid and first liquid - Google Patents

Abstract

To provide two-liquid mixed type first and second liquids which are excellent in storage stability and can suppress variations in reflectances of a resist film.SOLUTION: Two-liquid mixed type first and second liquids include a first liquid containing a polymerizable polymer having a carboxyl group, a photopolymerization initiator, titanium oxide, an inorganic filler different from the titanium oxide, and an organic solvent, and a second liquid including a compound having a cyclic ether group, titanium oxide, and an inorganic filler different from the titanium oxide, in which the first and second liquids are two-liquid mixed type liquids for obtaining a photosensitive composition by mixing, and the second liquid contains no organic solvent or contains 10 wt.% or less of the organic solvent in 100 wt.% of the whole organic solvent contained in the photosensitive composition.SELECTED DRAWING: Figure 1

Description

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

  A solder resist film is widely used as a protective film for protecting a printed wiring board from high-temperature solder.

  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. A white solder resist film may be formed on the upper surface of the printed wiring board in order to use the light that has reached the upper surface side of the printed wiring board among the light emitted from the LEDs. In this case, not only the light directly irradiated from the surface of the LED chip to the opposite side to the printed wiring board but also the reflected light reaching the upper surface side of the printed wiring board and reflected by the white solder resist film can be used. . Therefore, it is possible to increase the use efficiency of light generated from the LED.

  As an example of a material for forming the white solder resist film, Patent Literature 1 below contains an alkoxy group-containing silane-modified epoxy resin obtained by a dealcoholation reaction between an epoxy resin and a hydrolyzable alkoxysilane. A resist material further comprising an unsaturated group-containing polycarboxylic acid resin, a diluent, a photopolymerization initiator, and a curing adhesion imparting agent is disclosed. The resist material may contain a filler such as titanium oxide.

  Patent Document 2 below discloses a white solder resist material containing a carboxyl group-containing resin having no aromatic ring, a photopolymerization initiator, an epoxy compound, rutile-type titanium oxide, and a diluent. I have.

  Patent Literature 3 below discloses two-liquid mixed-type first and second liquids used by mixing. The entire photosensitive composition as a mixture of the first and second liquids is a polymerizable polymer having a carboxyl group, a photopolymerization initiator, a compound having a cyclic ether group, titanium oxide, and an organic solvent. The first and second liquids are prepared so as to include The photosensitive composition, as the organic solvent, from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate and naphtha whose initial boiling point in distillation properties is 150 ° C. or more and the end point in distillation properties is 290 ° C. or less. Including at least two selected. The first liquid contains the polymerizable polymer, and as a part of the organic solvent, has an initial boiling point in dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate and distillation properties of 150 ° C. or higher, and in the distillation properties. It includes at least one selected from the group consisting of naphtha having an end point of 290 ° C. or lower. The second liquid contains the compound having a cyclic ether group, and as a part of the organic solvent, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, and an initial boiling point in distillation properties of 150 ° C. or higher, It contains at least one selected from the group consisting of naphtha whose end point in distillation properties is 220 ° C. or lower. The first liquid contains the photopolymerization initiator, contains the titanium oxide, or contains 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 The liquid contains the above titanium oxide.

JP 2007-249148 A JP 2007-322546 A WO2012 / 111356A1

  Conventional resist materials as described in Patent Documents 1 and 2 have a problem that storage stability is poor. Furthermore, when a conventional resist material as described in Patent Documents 1 and 2 is applied on a substrate to form a resist film, the reflectivity of the resist film may vary.

  Further, as compared with the two-liquid type first and second liquids described in Patent Document 3, a resist material which is more excellent in storage stability and in which the variation in the reflectance of the resist film is less likely to occur is a resist material. Improve the performance of printed wiring boards with membranes.

  An object of the present invention is to provide a two-liquid mixed-type first and second liquid which have excellent storage stability and can suppress variations in the reflectance of a resist film. Another object of the present invention is to provide a method for manufacturing a printed wiring board using the two-liquid mixed type first and second liquids.

  According to a broad aspect of the present invention, a two-liquid mixture type first and second liquids for obtaining a photosensitive composition that is a mixture, wherein the two-liquid mixture type first and second liquids are The first and second liquids are liquids before being mixed, and the entire photosensitive composition, which is a mixture of the first and second liquids, is a polymerizable polymer having a carboxyl group; A photopolymerization initiator, a compound having a cyclic ether group, titanium oxide, an inorganic filler different from titanium oxide, and an organic solvent, wherein the first liquid is a polymerizable polymer having the carboxyl group. The photopolymerization initiator, the titanium oxide, the inorganic filler, and the organic solvent, the second liquid, the compound having a cyclic ether group, the titanium oxide, and the inorganic filler Containing, the second liquid does not contain the organic solvent, or A two-liquid mixed type first and second liquid (hereinafter, first and second liquids) containing the organic solvent in an amount of 10% by weight or less based on 100% by weight of the whole organic solvent contained in the photosensitive composition. (Sometimes referred to as a liquid).

  In a specific aspect of the first and second liquids according to the present invention, the second liquid does not contain the organic solvent.

  In one specific aspect 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 one specific aspect of the first and second liquids according to the present invention, the inorganic filler has an average particle diameter of 0.1 μm or more and 10 μm or less.

  In one specific aspect of the first and second liquids according to the present invention, the content of the titanium oxide in the first liquid and the content of the titanium oxide in the second liquid are weights. The ratio is 20:80 to 80:20, and the content of the inorganic filler in the first liquid and the content of the inorganic filler in the second liquid are 20:80 by weight. 80-80: 20.

  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.

  In a specific aspect of the first and second liquids according to the present invention, the first and second liquids are used for forming a solder resist film.

  According to a broad aspect of the present invention, there is provided a method for manufacturing a printed wiring board comprising: a printed wiring board main body having a circuit on a surface; and a solder resist film laminated on a surface of the printed wiring board main body on which the circuit is provided. Mixing the first and second liquids of the two-liquid mixing type described above 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 in which the first and second liquids are mixed, is applied on the surface of the printed wiring board main body provided with the circuit, and the printed wiring board main body is Forming a solder resist film laminated on the surface on which the circuit is provided.

  The photosensitive composition, which is a mixture of the first and second liquids of the two-liquid mixture type according to the present invention, is a polymerizable polymer having a carboxyl group, a photopolymerization initiator, and a cyclic ether group. And a titanium oxide, an inorganic filler different from titanium oxide, and an organic solvent, wherein the first liquid, the polymerizable polymer having a carboxyl group, the photopolymerization initiator, and The second liquid includes the titanium oxide, the inorganic filler, and the organic solvent, and the second liquid includes the compound having the cyclic ether group, the titanium oxide, and the inorganic filler, and the second liquid includes The organic solvent is not contained, or the organic solvent is contained in 10% by weight or less of the total 100% by weight of the organic solvent contained in the photosensitive composition. Excellent storage stability of liquid 2 Ri, and it is possible to suppress the resist variations in the reflectance of the film using the first, second liquid two-liquid mixing type.

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

  Hereinafter, the present invention will be described in detail.

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

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

  The second liquid contains a compound (C) having a cyclic ether group, titanium oxide (D) (a part of titanium oxide (D) in the photosensitive composition), and an inorganic filler (E) (photosensitive composition (Part of the inorganic filler (E)).

  The second liquid may or may not contain the organic solvent (F). The second liquid does not contain the organic solvent (F) or contains the organic solvent (F) in an amount of 10% by weight or less based on 100% by weight of the whole 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 the case where the two-liquid mixed first and second liquids according to the present invention contain a polymerizable monomer described below or contain an antioxidant described later, the polymerizable monomer is used. And the antioxidant may each be contained in the first liquid, may be contained in the second liquid, and may be contained in both the first liquid and the second liquid. .

  By employing the above-described configuration in the two-liquid mixed type first and second liquids according to the present invention, the mixing property of the first and second liquids can be improved. Furthermore, the storage stability of the two-liquid mixed type first and second liquids can be improved by adopting the above configuration. Further, by adopting the above configuration, it is possible to suppress the variation in the reflectance of the resist film using the first and second liquids of the two-liquid mixture type.

  In the present invention in which the inorganic filler (E) is used indispensably, setting the composition in the first and second liquids as described above plays a large role in obtaining the effects of the present invention.

  Hereinafter, the details of the components contained in the photosensitive composition after mixing and the two-liquid mixing type first and second liquids according to the present invention 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 is polymerizable. When the polymerizable polymer (A) has a carboxyl group, the developability of the photosensitive composition is improved. Examples of the polymerizable polymer (A) include an acrylic resin having a carboxyl group, an epoxy resin having a carboxyl group, and an olefin resin having a carboxyl group. The “resin” is not limited to a solid resin but includes a liquid resin and an oligomer.

  The polymerizable polymer (A) is preferably 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) a carboxyl group-containing resin obtained by reacting a carboxyl group-containing (meth) acrylic copolymer resin (b1) with a compound (b2) having an oxirane ring and an ethylenically polymerizable unsaturated double bond in one molecule

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

  (D) After reacting a hydroxyl-containing polymer with a saturated or unsaturated polybasic anhydride, the resulting polymer having a carboxyl group has one epoxy group and one polymerizable unsaturated double bond in each molecule. And carboxyl group-containing resin obtained by reacting a compound having

  (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 having an epoxy compound having an aromatic ring and at least one unsaturated double bond After reacting with a carboxyl group-containing compound, a resin obtained by further reacting a saturated polybasic acid anhydride or 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, and preferably 50% by weight or less. It is preferably at most 40% by weight. When the content of the polymerizable polymer (A) having a carboxyl group is at least the lower limit and at most the upper limit, the curability of the photosensitive composition will be good.

(Photopolymerization initiator (B))
Since the photosensitive composition contains the photopolymerization initiator (B), the photosensitive composition can be cured by light irradiation. The photopolymerization initiator (B) is not particularly limited. As the photopolymerization initiator (B), only one type may be used, or two or more types may be used in combination.

  Examples of the photopolymerization initiator (B) include acylphosphine oxide, halomethylated triazine, halomethylated oxadiazole, imidazole, benzoin, benzoin alkyl ether, anthraquinone, benzuanthrone, benzophenone, acetophenone, thioxanthone, and benzoate. , Acridine, phenazine, titanocene, α-aminoalkylphenone, oximes, and derivatives thereof. As the photopolymerization initiator (B), only one type may be used, or two or more types may be used in combination.

  From the viewpoint of further increasing the heat resistance and light resistance of the resist film and further suppressing the 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 at least 0.1 part by weight, more preferably at least 100 parts by weight, based on 100 parts by weight of the polymerizable polymer (A) having a carboxyl group. It is at least 1 part by weight, preferably at most 30 parts by weight, more preferably at most 15 parts by weight. When the content of the photopolymerization initiator (B) is at least the lower limit and at most the upper limit, the photosensitivity of the photosensitive composition can be further enhanced.

(Compound (C) having cyclic ether group)
The photosensitive composition contains a compound (C) having a cyclic ether group for the purpose of enhancing the processability of cutting out the resist film. Further, by using the compound (C) having a cyclic ether group, the curability of the photosensitive composition is improved.

  Examples of the compound having a cyclic ether group (C) include heterocyclic epoxy resins such as bisphenol S type epoxy resin, diglycidyl phthalate resin, and triglycidyl isocyanurate, bixylenol type epoxy resin, biphenol type epoxy resin, tetraphenol Glycidyl xylenoyl ethane 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 pheno Click type epoxy resins, silicone-modified epoxy resin and ε- caprolactone-modified epoxy resin. As the compound (C) having a cyclic ether group, only one type may be used, or two or more types may be used in combination.

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

  In the photosensitive composition, the content of the compound (C) having a cyclic ether group is preferably at least 0.1 part by weight, based on 100 parts by weight of the polymerizable polymer (A) having a carboxyl group. It is preferably at least 1 part by weight, preferably at most 50 parts by weight, more preferably at most 30 parts by weight. When the content of the compound (C) having a cyclic ether group is not less than the lower limit and not more than the upper limit, the electrical insulation of the resist film can be further enhanced.

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

  By using the titanium oxide (D), a resist film having a higher reflectance can be formed as compared with the case where an inorganic filler other than the titanium oxide (D) is used.

  The titanium oxide (D) is preferably rutile-type titanium oxide or anatase-type titanium oxide. By using the rutile type titanium oxide, a more excellent resist film due to heat-resistant yellowing can be formed. The anatase type titanium oxide has a lower hardness than the rutile type titanium oxide. Therefore, by using anatase type titanium oxide, the processability of the resist film can be improved.

  From the viewpoint of further improving the storage stability of the two-liquid mixed type first and second liquids and further suppressing the variation in the reflectance of the resist film, the titanium oxide (D) is a rutile type. It is preferable to include titanium oxide.

  The titanium oxide (D) preferably contains rutile-type titanium oxide surface-treated with a silicon oxide or a silicone compound. In 100% by weight of the titanium oxide (D), the content of the rutile type titanium oxide surface-treated with the silicon oxide or the silicone compound is preferably 10% by weight or more, more preferably 30% by weight or more and 100% by weight or less. It is. The total amount of the titanium oxide (D) may be a rutile type titanium oxide surface-treated with the silicon oxide or the silicone compound. By using the rutile-type titanium oxide surface-treated with the silicon oxide or the silicone compound, the heat resistance yellowing of the resist film can be further enhanced.

  Examples of the rutile-type titanium oxide surface-treated with a silicon oxide or a silicone compound include rutile chlorine method titanium oxide manufactured by Ishihara Sangyo Co., Ltd .: CR-90, and rutile sulfuric acid method titanium oxide manufactured by Ishihara Sangyo Co., Ltd. No .: R-550.

  The average particle size 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, more preferably 0.5 μm or less.

  The average particle diameter in the titanium oxide (D) is a particle diameter value when the integrated value is 50% in a volume-based particle size distribution curve. The average particle diameter can be measured using, for example, a laser beam type particle size distribution meter. As a commercially available product of the laser beam type particle size distribution analyzer, “LS 13 320” manufactured by Beckman Coulter and the like can be mentioned.

  In the photosensitive composition of 100% by weight, the content of titanium oxide (D) and rutile type titanium oxide is preferably 3% by weight or more, more preferably 10% by weight or more, and further preferably 15% by weight or more, respectively. Is at most 80% by weight, more preferably at most 75% by weight, further preferably at most 70% by weight. When the content of the titanium oxide (D) and the content of the rutile-type titanium oxide are not less than the lower limit and not more than the upper limit, the resist film is not easily yellowed when exposed to a high temperature. Further, a photosensitive composition having a viscosity suitable for coating can be easily prepared.

  The content of the titanium oxide (D) in the first liquid and the content of the titanium oxide (D) in the second liquid are represented by the weight ratio (titanium oxide (D) in the first liquid). )): The content of titanium oxide (D) in the second liquid), preferably 20:80 to 80:20, more preferably 50:50 to 75:25.

(Inorganic filler (E))
The inorganic filler (E) is an inorganic filler different from titanium oxide. As the inorganic filler (E), only one type may be used, or two or more types may be used in combination.

  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, aluminum hydroxide, Clays such as magnesium oxide, calcium carbonate, magnesium carbonate, aluminum carbonate, calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, calcium sulfate, barium sulfate, silicon nitride, boron nitride, calcined clay, talc, silicon carbide and silicone And the like. As the inorganic filler (E), only one type may be used, or two or more types may be used in combination.

  From the viewpoint of further increasing the heat resistance and light resistance of the resist film and further suppressing the stickiness of the surface of the resist film, the photosensitive composition preferably contains talc or silica, and preferably contains silica. More preferred. The photosensitive composition may include 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, more preferably 5 μm or less.

  The average particle diameter in the inorganic filler (E) is a particle diameter value when the integrated value is 50% in a volume-based particle size distribution curve. The average particle diameter can be measured using, for example, a laser beam type particle size distribution meter. As a commercially available product of the laser beam type particle size distribution analyzer, “LS 13 320” manufactured by Beckman Coulter and the like can be mentioned.

  In 100% by weight of the photosensitive composition, the content of the inorganic filler (E) and the total content of talc and silica are preferably 0.1% by weight or more, more preferably 1% by weight or more, respectively. It is more preferably at least 3% by weight, preferably at most 50% by weight, more preferably at most 30% by weight, further preferably at most 10% by weight. When the content of the inorganic filler (E) and the total content of talc and silica are equal to or greater than the lower limit and equal to or less than the upper limit, the heat resistance and light resistance of the resist film are further increased, and the surface becomes sticky. It can be further suppressed.

  The total content of the titanium oxide (D) and the inorganic filler (E) in 100% by weight of the photosensitive composition is preferably 5% by weight or more, more preferably 10% by weight or more, and still more preferably. It is at least 20% by weight, preferably at most 80% by weight, more preferably at most 60% by weight, further preferably at most 40% by weight. When the total content of the titanium oxide (D) and the inorganic filler (E) is equal to or more than the lower limit and equal to or less than the upper limit, the heat resistance and light resistance of the resist film are further increased, and the surface is more sticky. It can be further suppressed.

  In the photosensitive composition, the weight ratio of the content of the titanium oxide (D) to the content of the inorganic filler (E) (content of the titanium oxide (D): content of the inorganic filler (E)) is preferably 0.1: 99.9 to 99.9: 0.1, more preferably 1:99 to 99: 1, and still more preferably 10:90 to 90:10.

  The content of the inorganic filler (E) in the first liquid and the content of the inorganic filler (E) in the second liquid are expressed by a weight ratio (inorganic filler (E) in the first liquid). ): Content of the inorganic filler (E) in the second liquid), preferably 20:80 to 80:20, more preferably 30:70 to 50:50.

(Organic solvent (F))
The photosensitive composition contains an organic solvent (F). The photosensitive composition obtained by mixing the first and second liquids contains an organic solvent (F). The photosensitive composition preferably contains at least two kinds of organic solvents. As the organic solvent (F), only one type may be used, or two or more types may be used in combination.

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

  The photosensitive composition has a dibasic acid ester, dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate or an initial boiling point in distillation properties of 150 ° C. or more and an end point in distillation properties of 290 ° C. as the organic solvent (F). It is preferable to include the following naphtha. In this case, the storage stability of the two-liquid mixed type first and second liquids can be further improved, and the reflection of the resist film using the two-liquid mixed type first and second liquids can be improved. Variation in rate can be further suppressed. It is preferable that the organic solvent (F) contained in the photosensitive composition contains a dibasic acid ester.

  The first liquid has a dibasic acid ester, dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate or an initial boiling point in distillation properties of 150 ° C. or more and an end point in distillation properties of 290 ° C. as the organic solvent (F). It is preferable to include the following naphtha. The organic solvent (F) contained in the first liquid preferably 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 may be a dibasic acid ester, dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate or a distillate as the organic solvent (F). It is preferable to include naphtha whose initial boiling point in properties is 150 ° C. or higher and whose end point in distillation properties is 290 ° C. or lower. The organic solvent (F) contained in the second liquid may contain a dibasic acid ester.

  As the organic solvent (F), a dibasic acid ester may be used, dipropylene glycol monomethyl ether may be used, or diethylene glycol monoethyl ether acetate may be used. The initial boiling point in the distillation properties is 150 ° C. or higher. Alternatively, naphtha having an end point of 290 ° C. or less in distillation properties may be used.

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

  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, of the total 100% by weight of the organic solvent (F) contained in the photosensitive composition. is there.

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

(Other ingredients)
In order to further enhance the curability, the photosensitive composition preferably contains a polymerizable monomer as a component different from the polymerizable polymer (A) having a carboxyl group. The photosensitive composition preferably contains both a polymerizable polymer (A) having a carboxyl group and a polymerizable monomer. The polymerizable monomer has polymerizability and is polymerizable. The polymerizable monomer is not particularly limited. One of the above polymerizable monomers may be used alone, or two or more thereof may be used in combination.

  The polymerizable monomer is preferably a polymerizable unsaturated group-containing monomer. Examples of the polymerizable unsaturated group in the polymerizable monomer include a functional group having a polymerizable unsaturated double bond such as a (meth) acryloyl group and a vinyl ether group. (Meth) acryloyl groups are preferred because the crosslink density of the resist film can be increased.

  The polymerizable unsaturated group-containing monomer is preferably a compound having a (meth) acryloyl group. Examples of the compound having a (meth) acryloyl group include modified di (meth) acrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol, polyhydric alcohols, and ethylene oxide adducts of polyhydric alcohols. Alternatively, a polyhydric (meth) acrylate modified product of a propylene oxide adduct of a polyhydric alcohol, a phenol, a (meth) acrylate modified product of an ethylene oxide adduct of phenol or a propylene oxide adduct, glycerin diglycidyl ether or Examples thereof include (meth) acrylate-modified glycidyl ethers such as trimethylolpropane triglycidyl ether and melamine (meth) acrylate.

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

  "(Meth) acryloyl" means acryloyl and methacryloyl. “(Meth) acryl” means acryl and methacryl. "(Meth) acrylate" means acrylate and methacrylate.

  When the polymerizable monomer is contained, the content of the polymerizable monomer is 100% by weight in total of the polymerizable monomer and the polymerizable polymer (A) having a carboxyl group. It is preferably at least 5% by weight, preferably at most 50% by weight. When the content of the polymerizable monomer is not less than the lower limit and not more than the upper limit, the photosensitive composition can be sufficiently cured. Further, the crosslink density of the resist film becomes appropriate, sufficient resolution can be obtained, and the resist film is less likely to yellow.

  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. Good.

  The photosensitive composition preferably contains an antioxidant in order to reduce the risk of yellowing of the resist film when exposed to a high temperature. The antioxidant preferably has a Lewis basic site. From the viewpoint of further suppressing yellowing of the resist film, the antioxidant is at least one selected from the group consisting of a phenolic antioxidant, a phosphorus antioxidant, and an amine antioxidant. Is preferred. From the viewpoint of further suppressing yellowing of the resist film, the antioxidant is preferably a phenolic antioxidant. That is, the photosensitive composition preferably contains a phenolic antioxidant.

  Commercially available phenolic antioxidants include IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, and IRGANOX 295 (all manufactured by Ciba Japan Co., Ltd.), ADK STAB AO-30, ADK STAB AO-40, Adekastab AO-50, Adekastab AO-60, Adekastab AO-70, Adekastab AO-80, Adekastab AO-90, and Adekastab AO-330 (all manufactured by ADEKA), Sumilizer GA-80, Sumilizer MDP-S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F), and Sumilizer GP (all, manufactured by Sumitomo Chemical Co., Ltd.), HOSTANOX O10, HOSTANOX O16, HOSTANOX O14, and HOSTANOX O3 (all, manufactured by Clariant), Antage BHT, Antage W-300, Antage W-400, and Antage W500 (all, manufactured by Kawaguchi Chemical Co., Ltd.), SEENOX 224M, and SEENOX 326M (all, manufactured by Cipro Kasei Corporation), and the like.

  Examples of the phosphorus antioxidant include cyclohexylphosphine and triphenylphosphine. Commercial products of the above-mentioned phosphorus-based antioxidants include Adekastab PEP-4C, Adekastab PEP-8, Adekastab PEP-24G, Adekastab PEP-36, Adekastab HP-10, Adekastab 2112, Adekastab 260, Adekastab 522A, Adekastab 1178, Adekastab 1500, ADK STAB C, ADK STAB 135A, ADK STAB 3010, and ADK STAB TPP (all, manufactured by ADEKA), Sandstub P-EPQ, and Hostanox PAR24 (all, manufactured by Clariant), and JP-312L, JP -318-0, JPM-308, JPM-313, JPP-613M, JPP-31, JPP-2000PT, and JPH-3800 (all of which are Johoku Manabu Kogyo Co., Ltd.), and the like.

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

  The content of the antioxidant is preferably at least 0.1 part by weight, more preferably at least 5 parts by weight, and preferably at most 30 parts by weight, based on 100 parts by weight of the polymerizable polymer (A) having a carboxyl group. , More preferably 15 parts by weight or less. When the content of the antioxidant is not less than the lower limit and not more than the upper limit, a more excellent resist film due to heat yellowing can be formed.

  Further, the photosensitive composition includes a coloring agent, a filler, an antifoaming agent, a curing agent, a curing accelerator, a release agent, a surface treatment agent, a flame retardant, a viscosity modifier, a dispersant, a dispersion aid, a surface modification It may contain a filler, a plasticizer, an antibacterial agent, an antifungal agent, a leveling agent, a stabilizer, a coupling agent, an anti-sagging agent or a phosphor.

  The above-mentioned photosensitive composition can be prepared, for example, by stirring and mixing the components, and then uniformly mixing them with a three-roll mill.

Examples of the light source used for curing the photosensitive composition include an irradiation device that emits an active energy ray such as ultraviolet light or visible light. Examples of the light source include an ultra-high pressure mercury lamp, a Deep UV lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, and an excimer laser. These light sources are appropriately selected according to the photosensitive wavelengths of the components of the photosensitive composition. The irradiation energy of light is appropriately selected depending on a desired film thickness or a component of the photosensitive composition. Light irradiation energy is generally in the range of 10 to 3000 mJ / cm ² .

(LED device)
The two-liquid mixed first and second liquids according to the present invention are preferably used for forming a resist film of an LED device, and more preferably used for forming a solder resist film. The two-liquid mixed first and second liquids according to the present invention are preferably a resist composition, and more preferably a solder resist composition.

  A method of manufacturing a printed wiring board according to the present invention is directed to a method of manufacturing a printed wiring board including: a printed wiring board main body having a circuit on a surface; and a resist film laminated on a surface of the printed wiring board main body on which the circuit is provided. Is the way. The resist film is formed of the two-liquid mixed type first and second liquids according to the present invention.

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

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

  The LED chip 7 is stacked on the upper surface 3a of the resist film 3. The LED chip 7 is stacked on the substrate 2 via the resist film 3. Terminals 8a and 8b are provided on the outer peripheral edge of the lower surface 7a of the LED chip 7. The terminals 8a and 8b are electrically connected to the electrodes 4a and 4b by the solders 9a and 9b. With 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)
Ethyl carbitol acetate as a solvent and azobisisobutyronitrile as a catalyst were placed in a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, and heated to 80 ° C. under a nitrogen atmosphere to obtain methacrylic acid. A monomer obtained by mixing the acid and methyl methacrylate at a molar ratio of 30:70 was dropped over 2 hours. After the dropwise addition, the mixture was stirred for 1 hour, and the temperature was increased to 120 ° C. Then, it cooled. Glycidyl acrylate was added in an amount such that the molar ratio to the molar amount of the total amount of all monomer units of the obtained resin was 10 and heated at 100 ° C. for 30 hours using tetrabutylammonium bromide as a catalyst. The group was subjected to an addition reaction. After cooling, the solution was taken out of the flask to obtain a solution containing a carboxyl group-containing resin having an acid value of 60 mgKOH / g, a weight-average molecular weight of 15,000, and a double bond equivalent of 50% by weight (nonvolatile content). 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 which is a photoradical generator, manufactured by BASF Japan)
5) CR-50 (titanium oxide, manufactured by Ishihara Sangyo Co., Ltd., rutile type titanium oxide manufactured by a chlorine method)
6) FH105 (talc, manufactured by Fuji Talc)
7) 5X (silica, manufactured by Tatsumori)
8) KS-7710 (compound type silicone oil, polydimethylsiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.)
9) Ethyl carbitol acetate (diethylene glycol monoethyl ether acetate, manufactured by Daicel)
10) Dipropylene glycol monomethyl ether (manufactured by Nippon Emulsifier)
11) DBE (dibasic acid ester, manufactured by Sankyo Chemical Co., Ltd.)

(Example 1)
15 g of the acrylic polymer 1 obtained in Synthesis Example 1, 2 g of TPO (photopolymerization initiator which is a photoradical generator, manufactured by BASF Japan), and 30 g of CR-50 (titanium oxide, manufactured by Ishihara Sangyo). 30 g of ethyl carbitol acetate (diethylene glycol monoethyl ether acetate, manufactured by Daicel), 5 g of FH105 (talc, manufactured by Fuji Talc), and 1 g of KS-7710 (compound type silicone oil, polydimethylsiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.) Were mixed for 3 minutes with a mixer (Nerita ARE-310, manufactured by Sinky), and then mixed with three rolls to obtain a mixture. Then, the obtained mixture was defoamed for 3 minutes using ARE-310 to obtain a first liquid.

  828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation), 8 g, DPHA (dipentaerythritol hexaacrylate), 5 g, FH105 (talc, manufactured by Fuji Talc), 5 g, CR-50 (titanium oxide, manufactured by Ishihara Sangyo), 10 g Were mixed for 3 minutes with a mixer (Nerita ARE-310, manufactured by Sinky), and then mixed with three rolls to obtain a mixture. Then, the obtained mixture was degassed for 3 minutes using ARE-310 to obtain a second liquid.

  As described above, two-liquid mixed first and second liquids (the photosensitive composition before mixing) having the first and second liquids were prepared.

(Examples 2 to 9, and Comparative Examples 1 and 2)
Except having changed the kind and compounding amount of the materials used in the first liquid and the second liquid as shown in Table 1 below, in the same manner as in Example 1 and having the first and second liquids Thus, a two-liquid mixed type first and second liquids (the photosensitive composition before mixing) were obtained.

(Evaluation)
(1) Storage stability The first and second liquids obtained as described above are placed in a plastics container (BHR-150, manufactured by Kinki Container Co., Ltd.), and allowed to stand at room temperature for 6 months. From each of the first and second liquids, 2 g of the supernatant liquid and the liquid at the bottom of the container were collected in a crucible, and calcined at 550 ° C. for 2 hours, and the ash content was calculated from the following equation.

  Ash content (%) = liquid weight after firing / liquid weight before firing × 100

  From the difference in the ash content between the supernatant liquid and the liquid at the bottom of the container determined by the above equation, the storage stability was determined according to the following criteria.

[Criteria for storage stability]
：: Difference in ash content is less than 0.1% △: Difference in ash content is 0.1% or more and less than 0.5% ×: Difference in ash content is 0.5% or more

(2) Variation in reflectance of resist film Preparation of measurement sample The first liquid and the second liquid were put into a 1 L round plastic container (BHS-1200, manufactured by Kinki Container Co., Ltd.) and manufactured by Mesh Co., Ltd. A resist material (photosensitive composition after mixing) was stirred with an automatic ink kneader at 50 rpm for 10 seconds.

An FR-4 substrate having a size of 510 mm × 610 mm and a thickness of 0.8 mm was prepared. On this substrate, a resist material was printed in a solid pattern using a 100-mesh polyester bias plate by a screen printing method. After printing, it was dried in an oven at 80 ° C. for 20 minutes to form a resist material layer on the substrate. Next, using a UV irradiation device through a photomask having a predetermined pattern, UV light having a wavelength of 365 nm is applied to the resist material layer at a UV intensity of 100 mW / cm ² so that the irradiation energy becomes 400 mJ / cm ^2. Irradiated for seconds. Thereafter, in order to form a pattern by removing the unexposed portion of the resist material layer, the resist material layer was immersed in a 1% by weight aqueous solution of sodium carbonate and developed to form a resist film on the substrate. Thereafter, the resist film was heated in an oven at 150 ° C. for one hour to post-cure the resist film, thereby obtaining a resist film as a measurement sample. The thickness of the obtained resist film was 20 μm.

  The reflectance value was measured using a color / color difference meter (manufactured by Konica Minolta, CR-400) at a total of five places at the four corners and the central part of the measurement sample of 510 mm × 610 mm.

[Judgment Criteria for Variation in Reflectance of Resist Film]
：: Standard deviation σ is less than 0.5 Δ: Standard deviation σ is 0.5 or more and less than 1.0 ×: Standard deviation σ is 1.0 or more

  The composition and results are shown in Table 1 below.

DESCRIPTION OF SYMBOLS 1 ... LED device 2 ... Substrate 2a ... Upper surface 3 ... Resist film 3a ... Upper surface 4a, 4b ... Electrode 7 ... LED chip 7a ... Lower surface 8a, 8b ... Terminal 9a, 9b ... Solder

Claims (9)

A first liquid containing a polymerizable polymer having a carboxyl group, a photopolymerization initiator, titanium oxide, an inorganic filler different from titanium oxide, and an organic solvent,
A second liquid containing a compound having a cyclic ether group, titanium oxide, and an inorganic filler different from titanium oxide,
The first liquid and the second liquid are a two-liquid mixture type liquid for obtaining a photosensitive composition by mixing,
The two-liquid mixed type first liquid containing no organic solvent or containing the organic solvent in an amount of 10% by weight or less based on 100% by weight of the total organic solvent contained in the photosensitive composition. , The second liquid. A second liquid for obtaining a photosensitive composition by mixing with the first liquid described below,
A compound having a cyclic ether group,
Titanium oxide,
Including an inorganic filler different from titanium oxide,
A second liquid containing no organic solvent or containing the organic solvent in an amount of 10% by weight or less based on 100% by weight of the total organic solvent contained in the photosensitive composition.
First liquid: including a polymerizable polymer having a carboxyl group, a photopolymerization initiator, titanium oxide, an inorganic filler different from titanium oxide, and an organic solvent.   3. The second liquid according to claim 2, which does not contain an organic solvent.   4. The second liquid according to claim 2, wherein the organic solvent contained in the photosensitive composition contains a dibasic acid ester. 5.   The second liquid according to any one of claims 2 to 4, wherein the average particle diameter of the inorganic filler is 0.1 m or more and 10 m or less. The content of the titanium oxide in the first liquid and the content of the titanium oxide in the second liquid are in a weight ratio of 20:80 to 80:20,
The content of the inorganic filler in the first liquid and the content of the inorganic filler in the second liquid are 20:80 to 80:20 by weight. The second liquid according to any one of the above.   The second liquid according to claim 2, wherein the photosensitive composition entirely contains a polymerizable monomer.   The second liquid according to any one of claims 2 to 7, which is used for forming a solder resist film. A first liquid for obtaining a photosensitive composition by mixing with a second liquid described below,
A polymerizable polymer having a carboxyl group,
A photopolymerization initiator,
Titanium oxide,
An inorganic filler different from titanium oxide,
A first liquid containing an organic solvent;
Second liquid: contains a compound having a cyclic ether group, titanium oxide, and an inorganic filler different from titanium oxide, and contains no organic solvent or contains an organic solvent in the photosensitive composition. Contains up to 10% by weight of the total 100% by weight of organic solvent

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