JP2016184159A - First and second liquids for two-liquid mixing system and method for manufacturing printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide first and second liquids for a two-liquid mixing system, which have excellent storage stability and can suppress variation in a reflectance of a resist film.SOLUTION: The first and second liquids for a two-liquid mixing system of the present invention are first and second liquids for a two-liquid mixing system to obtain a photosensitive composition as a mixture. The first liquid comprises a polymerizable polymer having a carboxyl group, a photopolymerization initiator, titanium oxide, an inorganic filler, and an organic solvent; and the second liquid comprises a compound having a cyclic ether group, titanium oxide, and an inorganic filler. The second liquid contains no organic solvent or contains an organic solvent by 10 wt.% or less with respect to the whole 100 wt.% of organic solvents included in the photosensitive composition.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a two-liquid mixed type first and second liquid for obtaining a photosensitive composition which is a mixture. In more detail, the present invention is a two-liquid mixture suitably 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. Moreover, this invention relates to the manufacturing method of the printed wiring board using the said 1st, 2nd liquid of the said 2 liquid mixture type.

  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 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 light directly irradiated from the surface of the LED chip to the opposite side of the printed wiring board but also reflected light that reaches the upper surface side of the printed wiring board and is reflected by the white solder resist film can be used. . Therefore, the utilization efficiency of the light generated from the LED can be increased.

  As an example of a material for forming the white solder resist film, the following Patent Document 1 contains an alkoxy group-containing silane-modified epoxy resin obtained by a dealcoholization reaction between an epoxy resin and a hydrolyzable alkoxysilane. A resist material further containing an unsaturated group-containing polycarboxylic acid resin, a diluent, a photopolymerization initiator, and a cured adhesion-imparting agent is disclosed. This 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, a rutile titanium oxide, and a diluent. Yes.

  The following Patent Document 3 discloses a two-liquid mixed type first and second liquid used by mixing. The photosensitive composition which is a mixture of the first and second liquids as a whole, a polymerizable polymer having a carboxyl group, a photopolymerization initiator, a compound having a cyclic ether group, titanium oxide, an organic solvent, The 1st and 2nd liquid is prepared so that it may contain. The photosensitive composition is, as the organic solvent, dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and a group of naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point of 290 ° C. or less in distillation properties. Includes at least two selected. The first liquid contains the polymerizable polymer, and as part of the organic solvent, dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and an initial boiling point in distillation properties of 150 ° C. or higher, in 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 a compound having the cyclic ether group, and as 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 includes 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 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 of poor storage stability. Furthermore, when a conventional resist material as described in Patent Documents 1 and 2 is applied onto a substrate to produce a resist film, the reflectance of the resist film may vary.

  Further, compared with the two-liquid mixed type first and second liquids described in Patent Document 3, the resist material is more excellent in storage stability, and the resist film is less likely to cause variations in the reflectance of the resist film. 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 that is excellent in storage stability and can suppress variations in the reflectance of a resist film. Moreover, the objective of this invention is providing the manufacturing method of the printed wiring board using the said 1st, 2nd liquid of the said 2 liquid mixture type.

  According to a wide aspect of the present invention, there are two-liquid mixed type first and second liquids for obtaining a photosensitive composition which is a mixture, and the two-liquid mixed type first and second liquids are The photosensitive composition which is a liquid before the first and second liquids are mixed and is a mixture in which the first and second liquids are mixed as a whole, 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, wherein the second liquid is a compound having the cyclic ether group, the titanium oxide, and the inorganic filler. And the second liquid does not contain the organic solvent, or Two-component mixed type first and second liquids (hereinafter referred to as first and second liquids) containing 10% by weight or less of the total amount of the organic solvent in 100% by weight of the organic solvent contained in the photosensitive composition. May be described as liquid).

  On the specific situation with the 1st, 2nd liquid which concerns on this invention, the said 2nd liquid does not contain the said organic solvent.

  On the specific situation with the 1st, 2nd liquid which concerns on this invention, the said organic solvent contained in the said photosensitive composition contains dibasic acid ester.

  On the specific situation with the 1st, 2nd liquid which concerns on this invention, the average particle diameter of the said inorganic filler is 0.1 micrometer or more and 10 micrometers or less.

  In a 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: 80-80: 20.

  On the specific situation with the 1st, 2nd liquid which concerns on this invention, the photosensitive composition which is a mixture with which the said 1st, 2nd liquid was mixed contains a polymerizable monomer as a whole.

  On the specific situation with the 1st, 2nd liquid which concerns on this invention, the said 1st, 2nd liquid is used in order to form a soldering resist film.

  According to a wide aspect of the present invention, there is provided a printed wiring board manufacturing method comprising a printed wiring board body having a circuit on a surface and a solder resist film laminated on the surface of the printed wiring board body on which a circuit is provided. A step of obtaining a photosensitive composition which is a solder resist composition in which the first and second liquids of the two-liquid mixed type described above are mixed, and the first and second liquids are mixed; On the surface of the printed wiring board body having a circuit, a photosensitive composition that is a solder resist composition in which the first and second liquids are mixed is applied to the printed wiring board body. And a step of forming a solder resist film laminated on the surface provided with the circuit.

  The photosensitive composition which is a mixture in which the first and second liquids of the two liquid mixture type according to the present invention are mixed is a whole, a polymerizable polymer having a carboxyl group, a photopolymerization initiator, and a cyclic ether group The first liquid is a polymerizable polymer having the carboxyl group, the photopolymerization initiator, and the above-mentioned photopolymerization initiator, the titanium oxide, an inorganic filler different from titanium oxide, and an organic solvent. The second liquid contains titanium oxide, the inorganic filler, and the organic solvent. The second liquid contains the compound having the cyclic ether group, the titanium oxide, and the inorganic filler. 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 mixed type first and second liquid according to an embodiment of the present invention.

  Hereinafter, the present invention will be described in detail.

  The two-component mixed type first and second solutions according to the present invention are used to obtain a photosensitive composition which is a mixture. The two-liquid mixed type first and second liquids according to the present invention are kits used for obtaining a photosensitive composition as a mixture. The two-liquid mixed type first and second liquids according to the present invention are mixed and used. The two-liquid mixed type 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 the photosensitive compositions before being mixed. The photosensitive composition which is a mixture in which the first and second liquids of the two liquid mixture type according to the present invention are mixed as a whole is 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 in which the first and second liquids are mixed is a photosensitive composition, and the mixed photosensitive composition as a whole includes the components (A) to (F).

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

  The second liquid comprises 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). And a part of the inorganic filler (E).

  The second liquid may or may not contain an 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 in 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 two-liquid mixed type first and second liquids according to the present invention contain a polymerizable monomer described later or an antioxidant described later, the polymerizable monomer And the antioxidant 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. .

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

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

  Hereinafter, the detail of each component contained in the photosensitive composition after mixing of the 1st, 2nd liquid of 2 liquid mixing type which concerns on this invention, and mixing is demonstrated.

(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 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, and includes a liquid resin and an oligomer.

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

  (A) 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 a 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) Reaction of an unsaturated monocarboxylic acid with a copolymer of a compound having one epoxy group and a polymerizable unsaturated double bond in each molecule and a compound having a polymerizable unsaturated double bond A carboxyl group-containing resin obtained by reacting the secondary hydroxyl group of the resulting reaction product with a saturated or unsaturated polybasic acid anhydride

  (D) After reacting a hydroxyl group-containing polymer with a saturated or unsaturated polybasic acid anhydride, the resulting polymer having a carboxyl group has one epoxy group and one polymerizable unsaturated double bond in each molecule. Hydroxyl 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 an epoxy compound having an aromatic ring and at least one unsaturated double bond Resin obtained by further reacting with saturated polybasic acid anhydride or unsaturated polybasic acid anhydride after reacting with carboxyl group-containing compound

  In 100% by weight of the photosensitive composition, the content of the polymerizable polymer (A) having a carboxyl group is preferably 3% by weight or more, more preferably 5% by weight or more, and preferably 50% by weight or less. Preferably it is 40 weight% or less. When the content of the polymerizable polymer (A) having a carboxyl group is not less than the above lower limit and not more than the above upper limit, the curability of the photosensitive composition is improved.

(Photopolymerization initiator (B))
Since the said photosensitive composition contains a photoinitiator (B), a photosensitive composition can be hardened by irradiation of light. The photopolymerization initiator (B) is not particularly limited. As for a photoinitiator (B), only 1 type may be used and 2 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, benzanthrone, benzophenone, acetophenone, thioxanthone, and benzoic acid ester. , Acridine, phenazine, titanocene, α-aminoalkylphenone, oxime, and derivatives thereof. As for the said photoinitiator (B), only 1 type may be used and 2 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 the stickiness of the resist film surface, an acylphosphine oxide photopolymerization initiator is preferred.

  In the photosensitive composition, the content of the photopolymerization initiator (B) is preferably 0.1 parts by weight or more, more preferably 100 parts by weight of the polymerizable polymer (A) having a carboxyl group. 1 part by weight or more, preferably 30 parts by weight or less, more preferably 15 parts by weight or less. When the content of the photopolymerization initiator (B) is not less than the above lower limit and not more than the above upper limit, the photosensitivity of the photosensitive composition can be further enhanced.

(Compound having a cyclic ether group (C))
For the purpose of improving the cutting processability of the resist film, the photosensitive composition contains a compound (C) having a cyclic ether group. Moreover, sclerosis | hardenability of a photosensitive composition becomes favorable by use of the compound (C) which has the said cyclic ether group.

  Examples of the compound (C) having a cyclic ether group include heterocyclic epoxy resins such as bisphenol S type epoxy resin, diglycidyl phthalate resin, triglycidyl isocyanurate, bixylenol type epoxy resin, biphenol type epoxy resin, tetra 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 novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy Resin, bisphenol A novolak epoxy resin, chelate epoxy resin, glyoxal epoxy resin, amino group-containing epoxy resin, rubber-modified epoxy resin, dicyclopentadiene phenol Click type epoxy resins, silicone-modified epoxy resin and ε- caprolactone-modified epoxy resin. As for the compound (C) which has the said cyclic ether group, only 1 type may be used and 2 or more types may be used together.

  The compound (C) having the cyclic ether group acts to react with the carboxyl group of the polymerizable polymer (A) having the carboxyl group 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 0.1 parts by weight or more with respect to 100 parts by weight of the polymerizable polymer (A) having a carboxyl group. The amount is preferably 1 part by weight or more, preferably 50 parts by weight or less, more preferably 30 parts by weight or less. When the content of the compound (C) having a cyclic ether group is not less than the above lower limit and not more than the above 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 said photosensitive composition is not specifically limited. As for titanium oxide (D), only 1 type may be used and 2 or more types may be used together.

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

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

  Further, 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 preferably contains titanium oxide.

  It is preferable that the said titanium oxide (D) contains the rutile type titanium oxide surface-treated with the silicon oxide or the silicone compound. In 100% by weight of the titanium oxide (D), the content of the rutile 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 rutile titanium oxide surface-treated with the silicon oxide or the silicone compound. By using rutile type titanium oxide surface-treated with the silicon oxide or silicone compound, the heat-resistant 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, for example, a product number: CR-90 manufactured by Ishihara Sangyo Co., Ltd., which is a rutile chlorine-based titanium oxide, and a product manufactured by Ishihara Sangyo Co., Ltd., which is a rutile sulfate titanium oxide Product number: R-550 etc. are mentioned.

  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, 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 the 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 commercial product of the laser beam type particle size distribution analyzer, “LS 13 320” manufactured by Beckman Coulter, Inc. can be cited.

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

  Further, the content of titanium oxide (D) in the first liquid and the content of titanium oxide (D) in the second liquid are in a weight ratio (titanium oxide (D in the first liquid). ) Content: 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 for the said inorganic filler (E), only 1 type may be used and 2 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, calcium carbonate, magnesium carbonate, aluminum carbonate, calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, calcium sulfate, barium sulfate, silicon nitride, boron nitride, clays such as calcined clay, talc, silicon carbide and silicone Particles and the like. As for the said inorganic filler (E), only 1 type may be used and 2 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 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 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, more preferably 5 μm or less.

  The average particle size in the inorganic filler (E) is a particle size 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 beam type particle size distribution meter. As a commercial product of the laser beam type particle size distribution analyzer, “LS 13 320” manufactured by Beckman Coulter, Inc. can be cited.

  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, More preferably, it is 3% by weight or more, preferably 50% by weight or less, more preferably 30% by weight or less, and still more preferably 10% by weight or less. When the content of the inorganic filler (E) and the total content of talc and silica are not less than the above lower limit and not more than the above upper limit, the heat resistance and light resistance of the resist film are further enhanced, and the surface is not sticky. It 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 still more preferably. It is 20% by weight or more, preferably 80% by weight or less, more preferably 60% by weight or less, and still more preferably 40% by weight or less. When the total content of the titanium oxide (D) and the inorganic filler (E) is not less than the above lower limit and not more than the above upper limit, the heat resistance and light resistance of the resist film are further enhanced, and the surface is more sticky. It 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 It is 0.1: 99.9-99.9: 0.1, More preferably, it is 1: 99-99: 1, More preferably, it is 10: 90-90: 10.

  Moreover, content of the inorganic filler (E) in said 1st liquid and content of the inorganic filler (E) in said 2nd liquid are weight ratio (inorganic filler (E in 1st liquid (E ) Content: 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 in which the first and second liquids are mixed contains an organic solvent (F). The photosensitive composition preferably contains at least two kinds of organic solvents. As for an organic solvent (F), only 1 type may be used and 2 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, methyl carbitol, butyl Carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, glycol ethers such as 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, as the organic solvent (F), a dibasic acid ester, dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, or an initial distillation point in distillation properties of 150 ° C. or higher, and an end point in distillation properties of 290 ° C. 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 enhanced, and the reflection of the resist film using the two-liquid mixed type first and second liquids can be further 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 of 150 ° C. or more in distillation properties and an end point of 290 ° C. in distillation properties 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). The content of the organic solvent (F) in the second liquid is preferably 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 distilled as the organic solvent (F). It is preferable to include naphtha having an initial boiling point of 150 ° C. or more in properties and an end point of 290 ° C. or less in distillation properties. The organic solvent (F) contained in the second liquid may contain a dibasic acid ester.

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

  The “initial boiling point in distillation properties” and the “end point in distillation properties” mean values measured by 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 in 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 whole of the first and second liquids of the two-component mixed type and 100% by weight of the photosensitive composition after mixing. % Or more, preferably 50% by weight or less, more preferably 30% by weight or less.

(Other ingredients)
In order to further improve 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 is polymerizable and can be polymerized. The polymerizable monomer is not particularly limited. As for the said polymerizable monomer, only 1 type may be used and 2 or more types may be used together.

  The polymerizable monomer is preferably a polymerizable unsaturated group-containing monomer. 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 preferred because the crosslinking 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 the (meth) acryloyl group include a di (meth) acrylate modified product of glycol such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol or propylene glycol, polyhydric alcohol, and ethylene oxide adduct of polyhydric alcohol. Or a polyhydric (meth) acrylate modified product of a propylene oxide adduct of a polyhydric alcohol, a (meth) acrylate modified product of phenol, an ethylene oxide adduct of phenol or a propylene oxide adduct of phenol, glycerin diglycidyl ether or (Meth) acrylate modified products of glycidyl ether such as trimethylolpropane triglycidyl ether and melamine (meth) acrylate are exemplified.

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

  “(Meth) acryloyl” means acryloyl and methacryloyl. “(Meth) acryl” means acrylic and methacrylic. “(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. Preferably it is 5 weight% or more, Preferably it is 50 weight% or less. A photosensitive composition can fully be hardened as content of the said polymerizable monomer is more than the said minimum and below the said upper limit. Furthermore, the crosslink density of the resist film becomes appropriate, sufficient resolution can be obtained, and the resist film is hardly yellowed.

  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 high temperatures. 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 phenolic antioxidants, phosphorus antioxidants, and amine antioxidants. Is preferred. From the viewpoint of further suppressing the yellowing of the resist film, the antioxidant is preferably a phenolic antioxidant. That is, the photosensitive composition preferably contains a phenolic antioxidant.

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

  Examples of the phosphorus antioxidant include cyclohexylphosphine and triphenylphosphine. Examples of commercially available phosphoric antioxidants include ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260, ADK STAB 522A, ADK STAB 1178, and ADK STAB. 1500, ADK STAB C, ADK STAB 135A, ADK STAB 3010, and ADK STAB TPP (all of which are manufactured by ADEKA), Sandstub P-EPQ, and Hostanox PAR24 (all of which are 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 antioxidant include triethylamine, dicyandiamide, melamine, ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-tolyl-S-triazine, 2,4- And diamino-6-xylyl-S-triazine and quaternary ammonium salt derivatives.

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

  In addition, the photosensitive composition includes a colorant, a filler, an antifoaming agent, a curing agent, a curing accelerator, a mold release agent, a surface treatment agent, a flame retardant, a viscosity modifier, a dispersant, a dispersion aid, a surface modification agent. A quality agent, a plasticizer, an antibacterial agent, an antifungal agent, a leveling agent, a stabilizer, a coupling agent, an anti-sagging agent, or a phosphor may be included.

  The said photosensitive composition can be prepared by, for example, stirring and mixing each compounding component and then uniformly mixing with three rolls.

Examples of the light source used for curing the photosensitive composition include an irradiation device that emits active energy rays such as ultraviolet rays or visible rays. Examples of the light source include an ultrahigh 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 wavelength of the constituent components of the photosensitive composition. The irradiation energy of light is appropriately selected depending on a desired film thickness or a constituent of the photosensitive composition. The irradiation energy of light is generally in the range of 10 to 3000 mJ / cm ² .

(LED device)
The two-liquid mixed type 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 type first and second liquids according to the present invention are preferably resist compositions, and are preferably solder resist compositions.

  A method for manufacturing a printed wiring board according to the present invention is a method for manufacturing 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 provided with the circuit. Is the method. The resist film is formed of a two-liquid mixed type first and second liquid according to the present invention.

  FIG. 1 is a partially cutaway front sectional view schematically showing an example of an LED device having a resist film formed using a two-liquid mixed type first and second liquid 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 2 a 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. The substrate 2 is preferably a printed wiring board body.

  The LED chip 7 is laminated on the upper surface 3 a of the resist film 3. An LED chip 7 is laminated on the substrate 2 via the resist film 3. Terminals 8 a and 8 b are provided on the outer peripheral edge of the lower surface 7 a of the LED chip 7. The terminals 8a and 8b are electrically connected to the electrodes 4a and 4b by the solder 9a and 9b. By 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)
A flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser is charged with ethyl carbitol acetate as a solvent and azobisisobutyronitrile as a catalyst, heated to 80 ° C. in a nitrogen atmosphere, and methacrylic. A monomer in which acid and methyl methacrylate were mixed at a molar ratio of 30:70 was added dropwise over 2 hours. After dropping, the mixture was stirred for 1 hour, and the temperature was raised to 120 ° C. Then it was cooled. Glycidyl acrylate was added in such an amount that the molar ratio of the total amount of all the monomer units of the obtained resin was 10 and then heated at 100 ° C. for 30 hours using tetrabutylammonium bromide as a catalyst. The group was subjected to an addition reaction. After cooling, it was taken out from the flask to obtain a solution containing 50 wt% (nonvolatile content) of a carboxyl group-containing resin having a solid content acid value of 60 mg KOH / g, a weight average molecular weight of 15000, and a double bond equivalent 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 which is a photo radical generator, manufactured by BASF Japan)
5) CR-50 (titanium oxide, manufactured by Ishihara Sangyo Co., Ltd., rutile titanium oxide manufactured by the 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 (Nippon Emulsifier Co., Ltd.)
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 (a photopolymerization initiator that is a photoradical generator, manufactured by BASF Japan), 30 g of CR-50 (titanium oxide, manufactured by Ishihara Sangyo Co., Ltd.), 30 g of ethyl carbitol acetate (diethylene glycol monoethyl ether acetate, manufactured by Daicel), 5 g of FH105 (manufactured by talc, 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 (Nertaro ARE-310, manufactured by Shinky Corporation), and then mixed with 3 rolls to obtain a mixture. Then, the 1st liquid was obtained by degassing the obtained mixture for 3 minutes using ARE-310.

  828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation) 5 g, DPHA (dipentaerythritol hexaacrylate) 5 g, FH105 (talc, manufactured by Fuji Talc) 5 g, CR-50 (titanium oxide, manufactured by Ishihara Sangyo Co., Ltd.) 10 g Were mixed for 3 minutes with a mixer (Nertaro ARE-310, manufactured by Shinky Corporation), and then mixed with 3 rolls to obtain a mixture. Then, the 2nd liquid was obtained by defoaming the obtained mixture for 3 minutes using ARE-310.

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

(Examples 2 to 9 and Comparative Examples 1 and 2)
It has 1st, 2nd liquid like Example 1 except having changed the kind and compounding quantity of the material which were used with the 1st liquid and the 2nd liquid as shown in the following table 1. Two-component mixed type first and second liquids (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, fired at 550 ° C. for 2 hours, and the ash content was calculated from the following formula.

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

  From the difference between the ash content of the supernatant obtained from the above formula and the liquid at the bottom of the container, 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 are placed in a 1 L round plastic container (BHS-1200, manufactured by Kinki Container Co., Ltd.), and manufactured by Mesh Corporation. A resist material (photosensitive composition after mixing) stirred for 10 seconds at 50 rpm was prepared with an automatic ink kneader.

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 with 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 is 400 mJ / cm ^2. Irradiated for 2 seconds. Thereafter, in order to remove the resist material layer in the unexposed area and form a pattern, the resist material layer was dipped 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 post-cured by heating in an oven at 150 ° C. for 1 hour to obtain 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 (CR-400, manufactured by Konica Minolta Co., Ltd.) at a total of five locations including the four corners and the center of the 510 mm × 610 mm measurement sample.

[Criteria for variations in resist film reflectance]
○: 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 ... Board | 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 (8)

Two-liquid mixed type first and second liquids for obtaining a photosensitive composition as a mixture, and the two-liquid mixed type first and second liquids are mixed by the first and second liquids. The liquid before being
The photosensitive composition which is a mixture in which the first and second liquids are mixed as a whole, a polymerizable polymer having a carboxyl group, a photopolymerization initiator, a compound having a cyclic ether group, titanium oxide, , Including an inorganic filler different from titanium oxide, and an organic solvent,
The first liquid includes a polymerizable polymer having the carboxyl group, the photopolymerization initiator, the titanium oxide, the inorganic filler, and the organic solvent.
The second liquid contains the compound having the cyclic ether group, the titanium oxide, and the inorganic filler,
The second liquid does not contain the organic solvent, or contains the organic solvent in 10 wt% or less of the total 100 wt% of the organic solvent contained in the photosensitive composition. First and second liquids.   The two-liquid mixed type first and second liquid according to claim 1, wherein the second liquid does not contain the organic solvent.   The two-component mixed type first and second solutions according to claim 1 or 2, wherein the organic solvent contained in the photosensitive composition contains a dibasic acid ester.   The two-liquid mixed type first and second liquids 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 titanium oxide content in the first liquid and the titanium oxide content in the second liquid are 20:80 to 80:20 by weight ratio,
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 in weight ratio. The two-liquid mixed type first and second liquids according to any one of the above.   6. The two-component mixed type first according to claim 1, wherein the photosensitive composition which is a mixture in which the first and second liquids are mixed contains a polymerizable monomer as a whole. 1, 2nd liquid.   The two-liquid mixed type first and second liquids according to any one of claims 1 to 6, which are used to form a solder resist film. A printed wiring board main body having a circuit on its surface, and a printed wiring board manufacturing method comprising a solder resist film laminated on the surface on which the circuit of the printed wiring board main body is provided,
The photosensitive composition which is the soldering resist composition which mixed the 1st, 2nd liquid of the 2 liquid mixture type of any one of Claims 1-7, and the said 1st, 2nd liquid was mixed. Obtaining a product;
Applying a photosensitive composition, which is a solder resist composition in which the first and second liquids are mixed, on the surface of the printed wiring board body having the circuit on the surface, the printed wiring And a step of forming a solder resist film laminated on the surface of the board body on which the circuit is provided.

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