TWI506358B - And a method for producing the printed circuit board of the first liquid and the second liquid - Google Patents

Description

Combination of first liquid and second liquid of two-liquid mixing type and method for manufacturing printed wiring board

The present invention relates to a first liquid and a second liquid for obtaining a two-liquid mixing type as a photosensitive composition of a mixture. More specifically, the present invention relates to a two-liquid mixing type which can be preferably used for forming a solder resist film on a substrate or forming a photoresist film for reflecting light on a substrate on which a light-emitting diode wafer is mounted. A second liquid, and a method of producing a printed wiring board using the first and second liquids of the two-liquid mixing type.

As a protective film for protecting a printed wiring board from high-temperature solder damage, a solder resist film is widely used.

Further, in various electronic device applications, a light-emitting diode (hereinafter abbreviated as an LED, Light Emitting Diode) wafer is mounted on the upper surface of the printed wiring board. In order to obtain light from the LED, light reaching the upper surface side of the printed wiring board is also utilized, and a white solder resist film may be formed on the upper surface of the printed wiring board. In this case, not only light that is directly irradiated from the surface of the LED chip to the side opposite to the printed wiring board but also reflected light that is reflected by the white solder resist film may be used to reach the upper surface side of the printed wiring board. Therefore, the utilization efficiency of light generated from the LED can be improved.

As an example of a material for forming the white solder resist film, Patent Document 1 below discloses a photoresist material containing an alkoxy group obtained by a dealcoholization reaction of an epoxy resin and a hydrolyzable alkane. The base decane-modified epoxy resin further contains a polycarboxylic acid resin containing an unsaturated group, a diluent, a photopolymerization initiator, and a hardening adhesion imparting agent.

Patent Document 2 listed 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-type titanium oxide, and a diluent.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-249148

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-322546

When a photoresist film is formed on a substrate, when the prior photoresist material described in Patent Documents 1 to 2 is applied to the substrate, the photoresist may not be uniformly applied to cause coating unevenness. In the case where the previous photoresist material is applied to the substrate by screen printing, for example, unevenness in the strip shape can be seen in the applied photoresist material layer.

An object of the present invention is to provide a two-liquid mixing type first and second liquid, and a method of manufacturing a printed wiring board using the two-liquid mixing type first and second liquids, the first and second liquid mixing When the photosensitive composition which is a mixture which is a mixture of the first and second liquids is applied to the member to be coated, the coating can be uniformly applied to suppress unevenness.

According to a broad aspect of the present invention, the first and second liquids of the two-liquid mixing type may be provided, which are used to obtain a photosensitive composition as a mixture, and the first and second liquids of the two-liquid mixing type are Mixing the liquid before the first and second liquids, and the mixture of the first and second liquids is photosensitive The composition as a whole contains a polymerizable polymer having a carboxyl group, a photopolymerization initiator, a compound having a cyclic ether group, titanium oxide, and an organic solvent, and the photosensitive composition contains a solvent selected from the group consisting of dipropylene glycol monomethyl ether and diethylene glycol. At least two of the group consisting of monoethyl ether acetate and a group of naphtha having a boiling point of 150 ° C or higher and a boiling point of 290 ° C or less as the above-mentioned organic solvent, the first liquid The polymerizable polymer is contained and is selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and an initial boiling point of 150 ° C or higher in a distillation property and a final boiling point of 290 ° C or lower in a distillation property. At least one of the group consisting of naphtha as part of the organic solvent, the second liquid containing the above compound having a cyclic ether group, and containing a monomer selected from the group consisting of diethylene glycol monoethyl ether acetate and dipropylene glycol At least one of a group consisting of an ether and a naphtha having a boiling point of 150 ° C or higher and a boiling point of 220 ° C or less at the beginning of the distillation property is used as the organic In one part of the agent, the first liquid contains the photopolymerization initiator or contains the titanium oxide, or both the photopolymerization initiator and the titanium oxide, and the first liquid does not contain the photopolymerization initiator. In the case where the second liquid contains the photopolymerization initiator, the second liquid contains the titanium oxide when the first liquid does not contain the titanium oxide.

A method of manufacturing a printed wiring board according to the present invention is a method of manufacturing a printed wiring board including a circuit board having a circuit on a surface thereof and a solder resist film laminated on a surface of the printed wiring board body provided with a circuit, the manufacturing method The method includes the steps of: mixing the first and second liquids, and obtaining a solder resist composition which is a mixture of the first and second liquids; that is, a photosensitive composition; a photosensitive composition which is a solder resist composition obtained by mixing the first and second liquids on a surface of a circuit board having a circuit having a circuit, and a layer formed on the printed wiring board body The solder resist film on the surface of the circuit, the photosensitive composition which is a solder resist composition obtained by mixing the first and second liquids as a whole contains a polymerizable polymer having a carboxyl group, a photopolymerization initiator, and a cyclic ether group. a compound, titanium oxide, and an organic solvent, wherein the photosensitive composition contains a solvent selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and a boiling point of 150 ° C or higher at the beginning of the distillation property, and is at the end of the distillation property. At least two of the group consisting of naphtha having a boiling point of 290 ° C or less are used as the organic solvent, and the first liquid contains the polymerizable polymer and contains a solvent selected from the group consisting of dipropylene glycol monomethyl ether and diethylene glycol monoethyl ether. At least one of a group consisting of an acetate and a naphtha having a boiling point of 150 ° C or higher and a boiling point of 290 ° C or less; a part of the organic solvent, wherein the second liquid contains the compound having a cyclic ether group, and is selected from the group consisting of diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, and an initial boiling point of 150 ° C or higher in a distillation property. And at least one of the group consisting of naphtha having a boiling point of 220 ° C or less as a part of the organic solvent, wherein the first liquid contains the photopolymerization initiator or contains the titanium oxide or contains the above a photopolymerization initiator and the titanium oxide, wherein the second liquid contains the photopolymerization initiator when the first liquid does not contain the photopolymerization initiator, and the first liquid does not contain the titanium oxide In the case of the above, the second liquid contains the titanium oxide.

The first and second liquids of the two-liquid mixing type of the present invention and the printing of the present invention In a specific aspect of the method for producing a wiring board, the first liquid contains a solvent selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and a boiling point of 150 ° C or higher and a distillation property. At least two of the group consisting of naphtha having a final boiling point of 290 ° C or less are part of the above organic solvent.

In other specific aspects of the first and second liquids of the two-liquid mixing type of the present invention and the method for producing a printed wiring board of the present invention, the first liquid contains at least dipropylene glycol monomethyl ether and diethylene glycol monoethyl ether. The acetate, or at least diethylene glycol monoethyl ether acetate, and naphtha having a boiling point of 150 ° C or higher and a distillation boiling point of 290 ° C or less are included as part of the organic solvent.

In other specific aspects of the first and second liquids of the two-liquid mixing type of the present invention and the method for producing a printed wiring board of the present invention, the first liquid contains at least dipropylene glycol monomethyl ether and an initial boiling point in a distillation property. A naphtha having a boiling point of 290 ° C or lower at 150 ° C or higher is used as a part of the above organic solvent.

In another specific aspect of the method for producing a first liquid and a second liquid of the present invention, and the method for producing a printed wiring board of the present invention, the photosensitive composition contains a monomer selected from the group consisting of dipropylene glycol monomethyl ether and diethylene glycol. At least two of the group consisting of monoethyl ether acetate and a group of naphtha having a boiling point of 150 ° C or higher and a boiling point of 220 ° C or lower, wherein the first liquid is the organic solvent, the first liquid Among the above, the naphtha having a boiling point of 150 ° C or higher and a boiling point of 290 ° C or lower is a boiling point of 150 ° C or higher and a distillation property. A naphtha with a final boiling point of 220 ° C or less.

In another specific aspect of the first and second liquids of the two-liquid mixing type of the present invention and the method of producing a printed wiring board of the present invention, the first liquid contains the photopolymerization initiator.

In another specific aspect of the first and second liquids of the two-liquid mixing type of the present invention and the method of producing a printed wiring board of the present invention, the first liquid contains the titanium oxide.

In still another specific aspect of the first and second liquids of the two-liquid mixing type of the present invention and the method for producing a printed wiring board of the present invention, the first liquid contains the photopolymerization initiator and the titanium oxide. By.

In the first and second liquids of the two-liquid mixing type of the present invention, the photosensitive composition obtained by mixing the first and second liquids can be preferably used as a solder resist composition. In the first and second liquids of the two-liquid mixing type of the present invention, it is preferred that the photosensitive composition obtained by mixing the first and second liquids is a solder resist composition.

The first liquid and the second liquid of the two-liquid mixing type of the present invention are used to obtain a first liquid and a second liquid of a two-liquid mixing type as a photosensitive composition of a mixture, and the first liquid and the second liquid of the two liquid mixing type. a liquid before mixing the first and second liquids, wherein the photosensitive composition having a mixture of the first and second liquids as a whole comprises a polymerizable polymer having a carboxyl group, a photopolymerization initiator, and a ring The ether group-containing compound, titanium oxide, and an organic solvent, wherein the photosensitive composition contains a solvent selected from the group consisting of dipropylene glycol monomethyl ether and diethylene glycol monoethyl ether acetate, and has a boiling point of 150 ° C or higher and a distillation property. At least two of the group consisting of naphtha having a final boiling point of 290 ° C or less are used as the organic solvent, and the first liquid contains the polymerizable polymer and contains a solvent selected from the group consisting of dipropylene glycol monomethyl ether and diethylene glycol. At least one of a group consisting of monoethyl ether acetate and a naphtha having a boiling point of 150 ° C or higher and a boiling point of 290 ° C or less as a part of the organic solvent, the second The liquid contains the above-mentioned compound having a cyclic ether group, and contains a terminal boiling point selected from the group consisting of diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, and the boiling point of the distillation property of 150 ° C or more and the distillation property. At least one of the group consisting of naphtha below 220 ° C as part of the organic solvent, the first liquid containing the photopolymerization initiator or containing the titanium oxide, or containing the photopolymerization initiator and the oxidation In the case of the titanium, the first and second liquids are excellent in the miscibility, and when the photosensitive composition after the application is applied to the member to be coated, the unevenness can be suppressed. Coated.

The invention is described in detail below.

The first and second liquids of the two-liquid mixing type of the present invention can be used to obtain a photosensitive composition as a mixture. The first and second liquids of the two-liquid mixing type of the present invention are used to obtain a kit of photosensitive compositions as a mixture. The first liquid and the second liquid of the two-liquid mixing type of the present invention are used in combination. The first liquid and the second liquid of the two-liquid mixing type of the present invention are liquids before the first and second liquids are mixed. The first and second liquids before mixing are photosensitive compositions before mixing. The photosensitive composition which is a mixture of the first and second liquids of the two-liquid mixing type of the present invention as a whole contains a polymerizable polymer (A) having a carboxyl group, and light. The polymerization initiator (B), the compound (C) having a cyclic ether group, the titanium oxide (D), and the organic solvent (E) (hereinafter, the organic solvent contained in the entire photosensitive composition may be referred to as an organic solvent (E) )). The mixture obtained by mixing the first and second liquids is a photosensitive composition, and the photosensitive composition as a whole comprises a polymerizable polymer (A) having a carboxyl group and a photopolymerization initiator (B). a cyclic ether group compound (C), titanium oxide (D), and an organic solvent (E).

The photosensitive composition contains naphtha selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and a boiling point of 150 ° C or higher and a distillation boiling point of 290 ° C or lower. At least two of the group consisting of are the above-mentioned organic solvent (E).

The first liquid contains the polymerizable polymer (A) and is selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and a boiling point of 150 ° C or higher in a distillation property, and is in a distillation property. At least one of the group consisting of naphtha having a final boiling point of 290 ° C or less is part of the above organic solvent (E). The second liquid contains the compound (C) having a cyclic ether group, and is selected from the group consisting of diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, and an initial boiling point of 150 ° C or higher in a distillation property. At least one of the group consisting of naphtha having a boiling point of 220 ° C or less has a part of the organic solvent (E).

The first liquid contains the photopolymerization initiator (B) or the titanium oxide (D), or both the photopolymerization initiator (B) and the titanium oxide (D). In the case where the first liquid does not contain the photopolymerization initiator (B), the second liquid contains the photopolymerization initiator (B). In the case where the first liquid does not contain the titanium oxide (D), the second liquid contains the titanium oxide (D). The photopolymerization initiator (B) and the titanium oxide (D) may be contained in the first liquid, or may be included in the second liquid, or may be included in both the first liquid and the second liquid.

Further, when the first liquid and the second liquid of the two-liquid mixing type of the present invention contain the following polymerizable monomer or contain the following antioxidant, the polymerizable monomer and the antioxidant may be contained in the first liquid, respectively. It may also be included in the second liquid, or may be included in both the first liquid and the second liquid.

By using the above-described configuration of the first and second liquids of the two-liquid mixing type of the present invention, the mixing property of the first and second liquids can be improved. Further, when the photosensitive composition after the application is applied to a member to be coated such as a substrate, unevenness mainly due to titanium oxide can be suppressed, and uniform coating can be performed. In particular, when the photosensitive composition after mixing is applied by screen printing, unevenness in strip shape can be suppressed. Preferably, the first and second liquids of the two-liquid mixing type of the present invention are the first and second liquids of the two-liquid mixing type applied by screen printing.

The photopolymerization initiator (B) is preferably contained in the first liquid and not included in the second liquid. At this time, the miscibility of the first and second liquids described above becomes higher, and the photosensitive composition can be applied more uniformly.

The above titanium oxide (D) is preferably contained in the first liquid and not included in the second liquid. At this time, the dispersibility of the titanium oxide (D) is increased, and the miscibility of the first and second liquids is further increased, and the photosensitive composition can be applied more uniformly.

It is preferred that both the photopolymerization initiator (B) and the titanium oxide (D) described above are contained in the first liquid instead of being contained in the second liquid. At this time, the dispersibility of the titanium oxide (D) becomes higher, and the miscibility of the first and second liquids becomes higher. Further, the photosensitive composition can be applied more uniformly.

Hereinafter, the first and second liquids of the two-liquid mixing type of the present invention and the respective components contained in the photosensitive composition after mixing will be described in detail.

(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 can be 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. Further, the "resin" is not limited to a solid resin, and includes a liquid resin and an oligomer.

The polymerizable polymer (A) is preferably a carboxyl group-containing resin (a) to (e): (a) a carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid with a compound having a polymerizable unsaturated double bond. (b) a carboxyl group-containing resin obtained by reacting a carboxyl group-containing (formic acid) acrylic copolymer resin (b1) with a compound (b2) having an oxirane ring and an ethylenically polymerizable unsaturated double bond in one molecule; c) saturating or unsaturated after reacting an unsaturated monocarboxylic acid and a compound having one epoxy group and a polymerizable unsaturated double bond in one molecule with a copolymer having a polymerizable unsaturated double bond a carboxyl group-containing resin obtained by reacting a polybasic acid anhydride with a secondary hydroxyl group of the resulting reactant; (d) reacting a saturated or unsaturated polybasic acid anhydride with a hydroxyl group-containing polymer to have one epoxy group and polymerization in one molecule a hydroxyl group-containing and carboxyl group-containing resin obtained by reacting a compound of an unsaturated double bond with a polymer having a carboxyl group; (e) reacting a resin obtained by reacting an epoxy compound having an aromatic ring with a saturated polybasic acid anhydride or an unsaturated polybasic acid anhydride, or reacting an epoxy compound having an aromatic ring with a carboxyl group-containing compound having at least one unsaturated double bond, and further A resin obtained by reacting with a saturated polybasic acid anhydride or an unsaturated polybasic acid anhydride.

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 most preferably 50% by weight or less, more preferably 40% by weight or less. When the content of the polymerizable polymer (A) having a carboxyl group is at least the above lower limit and not more than the above upper limit, the curability of the photosensitive composition is good.

(Photopolymerization initiator (B))

Since the photosensitive composition contains the photopolymerization initiator (B), the photosensitive composition can be cured by irradiation of light. The photopolymerization initiator (B) is not particularly limited. The photopolymerization initiator (B) may be used alone or in combination of two or more.

Examples of the photopolymerization initiator (B) include mercaptophosphine oxide and halomethylation III. Halomethylation Diazole, imidazole, benzoin, benzoin alkyl ether, hydrazine, benzoxanthone, benzophenone, acetophenone, 9-oxosulfur Benzoate, acridine, brown , ferrocene, alpha-aminoalkyl benzophenone, hydrazine and derivatives thereof. The photopolymerization initiator (B) may be used alone or in combination of two or more.

The content of the photopolymerization initiator (B) is preferably 0.1 part by weight or more, more preferably 1 part by weight or more, and preferably 30 parts by weight, based on 100 parts by weight of the polymerizable polymer (A) having a carboxyl group. Hereinafter, it is more preferably 15 parts by weight or less. When the content of the photopolymerization initiator (B) is at least the above lower limit and above Below the limit, the photosensitivity of the photosensitive composition can be further improved.

(Compound (C) having a cyclic ether group)

The photosensitive composition contains a compound (C) having a cyclic ether skeleton for the purpose of improving the cutting processability of the photoresist film. Further, by using the above compound (C) having a cyclic ether skeleton, the curability of the photosensitive composition can be improved.

Examples of the compound (C) having a cyclic ether skeleton include a heterocyclic epoxy resin such as a bisphenol S-type epoxy resin, a diglycidyl phthalate resin, or a triglycidyl isocyanurate. Dixylenol type epoxy resin, biphenol type epoxy resin, tetraglycidyl xylene decyl ethane resin, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type ring Oxygen resin, brominated bisphenol A epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, alicyclic epoxy resin, phenolic phenolic epoxy resin of bisphenol A, chelation Epoxy resin, glyoxal epoxy resin, amine-based epoxy resin, rubber modified epoxy resin, dicyclopentadiene phenol epoxy resin, polyfluorene modified epoxy resin and ε- Ester modified epoxy resin. The compound (C) having a cyclic ether skeleton may be used alone or in combination of two or more.

The compound (C) having a cyclic ether skeleton functions by reacting with a carboxyl group of the carboxyl group-containing polymerizable polymer (A) to cure the photosensitive composition.

The content of the compound (C) having a cyclic ether skeleton is preferably 0.1 part by weight or more, more preferably 1 part by weight or more, and more preferably 50% by weight based on 100 parts by weight of the polymerizable polymer (A) having a carboxyl group. Below the weight, more preferably 30 Parts by weight or less. When the content of the compound (C) having a cyclic ether skeleton is at least the above lower limit and not more than the above upper limit, the electrical insulating properties of the resist film can be further improved.

(titanium oxide (D))

Since the photosensitive composition contains titanium oxide (D), a cured film such as a photoresist film having a high reflectance can be formed. The titanium oxide (D) contained in the photosensitive composition is not particularly limited. The titanium oxide (D) may be used alone or in combination of two or more.

A photoresist film having a high reflectance can be formed by using the above titanium oxide (D) as compared with the case of using an inorganic filler other than titanium oxide (D).

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

The titanium oxide (D) is preferably a rutile-type titanium oxide which is surface-treated with a cerium oxide or an anthrone compound. The content of the rutile-type titanium oxide surface-treated with the cerium oxide or the fluorenone compound in 100% by weight of the titanium oxide (D) is preferably 10% by weight or more, more preferably 30% by weight or more, and 100% by weight. Below weight%. The titanium oxide (D) may be all rutile-type titanium oxide surface-treated with a cerium oxide or an anthrone compound. The heat-resistant yellowing of the photoresist film can be further improved by using the above-described rutile-type titanium oxide surface-treated with a cerium oxide or an anthrone compound.

Rutile as a surface treatment using cerium oxide or an oxime compound Examples of the titanium oxides include chlorinated rutile-type titanium oxide, product number: CR-90 manufactured by Ishihara Sangyo Co., Ltd., or rutile-type titanium oxide, which is manufactured by Ishihara Sangyo Co., Ltd., product number: R-550.

The content of the titanium oxide (D) in 100% by weight of the photosensitive composition is preferably 3% by weight or more, more preferably 10% by weight or more, still more preferably 15% by weight or more, and most preferably 80% by weight or less. More preferably, it is 75% by weight or less, and still more preferably 70% by weight or less. When the content of the titanium oxide (D) is at least the above lower limit and not more than the above upper limit, yellowing is less likely to occur when the photoresist film is exposed to a high temperature. Further, a photosensitive composition having a viscosity suitable for coating can be easily prepared.

(Organic solvent (E))

The photosensitive composition contains an organic solvent (E). The photosensitive composition obtained by mixing the above first and second liquids contains an organic solvent (E). The above photosensitive composition contains at least two organic solvents. It is preferable that the organic solvent (E1) contained in the first liquid (hereinafter, the organic solvent contained in the first liquid is referred to as an organic solvent (E1)) and the organic solvent contained in the second liquid (hereinafter) E2) (hereinafter, the organic solvent contained in the second liquid may be referred to as an organic solvent (E2)).

Examples of the known organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, and butyl cellosolve. , carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether and other glycol ethers, ethyl acetate, acetic acid Ester, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Acetate, dipropylene glycol monomethyl ether acetate, propylene carbonate, etc. An ester, an aliphatic hydrocarbon such as octane or decane, or a petroleum solvent such as petroleum ether or naphtha.

In the above organic solvent, the first liquid must contain a solvent selected from the group consisting of dipropylene glycol monomethyl ether and diethylene glycol monoethyl ether acetate, and has a boiling point of 150 ° C or higher and a distillation boiling point of 290 ° C. At least one of the group consisting of the following naphtha is part of the above organic solvent (E). At least one of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and naphtha having a boiling point of 150 ° C or higher and a distillation boiling point of 290 ° C or less is an organic solvent ( E1).

Further, in the organic solvent, the second liquid contains a solvent selected from the group consisting of diethylene glycol monoethyl ether acetate and dipropylene glycol monomethyl ether, and has a boiling point of 150 ° C or higher and a distillation boiling point of 220. At least one of the group consisting of naphtha below °C is part of the above organic solvent (E). It is selected from the group consisting of diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, and naphtha having a boiling point of 150 ° C or higher and a boiling point of 220 ° C or less. At least one is an organic solvent (E2).

By allowing the organic solvents (E1) and (E2) to be contained in the first and second liquids, respectively, the mixing property of the first and second liquids can be remarkably improved. The use of the specific organic solvents (E1) and (E2), and the specific use of the specific organic solvents (E1) and (E2) in the first liquid and the second liquid, respectively, contributes greatly to the improvement of the first and second The miscibility of the liquid suppresses unevenness after application of the photosensitive composition to be mixed.

The above "in the initial boiling point of the distillation property" and the above "in the distillation property" The final boiling point refers to a value measured by JIS K2254 "Petroleum Products - Distillation Test Method".

The first liquid is preferably at least one of dipropylene glycol monomethyl ether and naphtha having a boiling point of 150 ° C or higher and a distillation boiling point of 220 ° C or lower as the organic solvent ( E) One part. The first liquid contains dipropylene glycol monomethyl ether, and naphtha having a boiling point of 150 ° C or higher and a boiling point of 220 ° C or less as a part of the organic solvent (E). In this case, the first liquid may contain titanium oxide or may not contain titanium oxide.

The first liquid may contain dipropylene glycol monomethyl ether, may also contain diethylene glycol monoethyl ether acetate, or may have a boiling point of 150 ° C or higher in the distillation property and a final boiling point of 290 ° C or less in the distillation property. The naphtha may also contain, as a part of the organic solvent (E), a naphtha having a boiling point of 150 ° C or higher and a boiling point of 220 ° C or lower.

Further, the second liquid may contain diethylene glycol monoethyl ether acetate, may also contain dipropylene glycol monomethyl ether, or may have a boiling point of 150 ° C or higher in the distillation property and a boiling point of 220 ° C in the distillation property. The following naphtha is part of the above organic solvent (E).

The photosensitive composition contains naphtha selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and a boiling point of 150 ° C or higher and a distillation boiling point of 290 ° C or lower. At least two of the group formed.

The above photosensitive composition may also contain dipropylene glycol monomethyl ether, diethylene glycol Monoethyl ether acetate and naphtha having a boiling point of 150 ° C or higher and a boiling point of 290 ° C or lower.

The photosensitive composition preferably contains at least dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, or at least diethylene glycol alone, from the viewpoint of more uniformly applying the photosensitive composition. Ethyl acetate and naphtha having a boiling point of 150 ° C or higher and a boiling point of 290 ° C or lower.

The photosensitive composition preferably contains at least dipropylene glycol monomethyl ether and diethylene glycol monoethyl ether acetate from the viewpoint of more uniformly applying the photosensitive composition. In this case, the photosensitive composition may contain naphtha having a boiling point of 150 ° C or higher and a boiling point of 290 ° C or lower.

From the viewpoint of applying the photosensitive composition more uniformly, the photosensitive composition preferably contains at least diethylene glycol monoethyl ether acetate, and has a boiling point of 150 ° C or higher and a distillation property. The naphtha with a final boiling point of 290 ° C or less. In this case, the first liquid preferably contains dipropylene glycol monomethyl ether.

In view of applying the photosensitive composition more uniformly, the photosensitive composition preferably contains at least dipropylene glycol monomethyl ether, and has a boiling point of 150 ° C or higher at the initial boiling point and a final boiling point of the distillation property. Naphtha below 290 °C. In this case, the first liquid may also contain diethylene glycol monoethyl ether acetate.

From the viewpoint of applying the photosensitive composition more uniformly, the photosensitive composition has a boiling point of at least 150 ° C in the form of a distillation property and is steamed. The naphtha having a final boiling point of 290 ° C or less is preferably a naphtha having a boiling point of 150 ° C or higher and a boiling point of 220 ° C or lower.

Preferably, the first liquid contains a stone selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and a boiling point of 150 ° C or higher and a distillation boiling point of 290 ° C or lower. At least two of the groups consisting of brain oil are part of the above organic solvent (E). In this case, the miscibility of the first and second liquids can be further improved, and the photosensitive composition can be applied more uniformly.

The first liquid may further contain dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and naphtha having a boiling point of 150 ° C or higher and a distillation boiling point of 290 ° C or lower. As a part of the above organic solvent (E).

Preferably, the first liquid contains at least dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, or at least diethylene glycol monoethyl ether acetate, and has a boiling point of 150 ° C or higher. The naphtha having a boiling point of 290 ° C or less at the end of the distillation property is a part of the organic solvent (E). In this case, the miscibility of the first and second liquids can be further improved, and the photosensitive composition can be applied more uniformly.

The first liquid preferably contains at least dipropylene glycol monomethyl ether and diethylene glycol monoethyl ether from the viewpoint of further improving the miscibility of the first and second liquids and applying the photosensitive composition more uniformly. Acetate is part of the above organic solvent (E). In this case, the first liquid may also contain a boiling point of 150 ° C or higher at the beginning of the distillation property, and the final boiling point of the distillation property is Naphtha below 290 °C.

The first liquid preferably contains at least diethylene glycol monoethyl ether acetate from the viewpoint of further improving the miscibility of the first and second liquids and applying the photosensitive composition more uniformly. The naphtha having an initial boiling point of the distillation property of 150 ° C or higher and a boiling point of 290 ° C or less is a part of the organic solvent (E). In this case, the first liquid preferably contains dipropylene glycol monomethyl ether.

The first liquid preferably contains at least dipropylene glycol monomethyl ether and is at the beginning of distillation characteristics from the viewpoint of further improving the miscibility of the first and second liquids and applying the photosensitive composition more uniformly. The naphtha having a boiling point of 150 ° C or higher and a boiling point of 290 ° C or lower is a part of the organic solvent (E). In this case, the first liquid may also contain diethylene glycol monoethyl ether acetate.

The photosensitive composition preferably contains a selected from the group consisting of dipropylene glycol monomethyl ether and diethylene glycol, from the viewpoint of further improving the miscibility of the first and second liquids and applying the photosensitive composition more uniformly. At least two of the group consisting of monoethyl ether acetate and a group of naphtha having a boiling point of 150 ° C or higher and a boiling point of 220 ° C or less at the end of the distillation property are used as the organic solvent, and the first The naphtha in the liquid having a boiling point of 150 ° C or higher and having a boiling point of 290 ° C or less is preferably at a boiling point of 150 ° C or higher at the beginning of the distillation property and 220 at a final boiling point of the distillation property. Naphtha below °C.

The first liquid may also be free of diethylene glycol monoethyl ether acetate.

The second liquid may also contain a solvent selected from the group consisting of dipropylene glycol monomethyl ether and diethylene glycol. At least two of the group consisting of monoethyl ether acetate and naphtha having a boiling point of 150 ° C or higher and a boiling point of 220 ° C or less at the end of the distillation property are part of the organic solvent (E). .

The second liquid may further comprise diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, and naphtha having a boiling point of 150 ° C or higher and a boiling point of 220 ° C or less. As a part of the above organic solvent (E).

In view of further improving the miscibility of the first and second liquids and applying the photosensitive composition more uniformly, the second liquid preferably contains at least diethylene glycol monoethyl ether acetate, and Propylene glycol monomethyl ether is part of the above organic solvent (E). In this case, the second liquid may contain naphtha having a boiling point of 150 ° C or higher and a boiling point of 220 ° C or lower.

The second liquid preferably contains at least diethylene glycol monoethyl ether acetate from the viewpoint of further improving the miscibility of the first and second liquids and applying the photosensitive composition more uniformly. The naphtha having an initial boiling point of the distillation property of 150 ° C or higher and a boiling point of 220 ° C or less is a part of the organic solvent (E). In this case, the second liquid preferably contains dipropylene glycol monomethyl ether.

The second liquid preferably contains at least dipropylene glycol monomethyl ether and is at the beginning of distillation characteristics from the viewpoint of further improving the miscibility of the first and second liquids and applying the photosensitive composition more uniformly. A naphtha having a boiling point of 150 ° C or higher and a boiling point of 220 ° C or lower is a part of the organic solvent (E). At this time, the second liquid may also contain diethyl Alcohol monoethyl ether acetate.

The second liquid may also be free of diethylene glycol monoethyl ether acetate.

The content of the organic solvent (E) is not particularly limited. The organic solvent (E) can be used in an appropriate amount in view of the coatability of the photosensitive composition. In 100% by weight of the photosensitive composition after mixing, the total content of the organic solvent (E) (the total content of the organic solvent (E1) and the organic solvent (E2)) is preferably 10% by weight or more, and more preferably 15% by weight or more, preferably 60% by weight or less, more preferably 50% by weight or less.

In view of further improving the miscibility of the first and second liquids and applying the photosensitive composition more uniformly, the first and second liquids of the two-liquid mixing type are included in the first The content of the organic solvent (E1) in the liquid and the content of the organic solvent (E2) contained in the second liquid are preferably from 1:99 to 99:1, more preferably from 1:9 to 9:1 by weight. More preferably, it is 2:8~8:2, and the best is 3:7~7:3. In other words, in the photosensitive composition after mixing, the content of the organic solvent (E1) contained in the first liquid is 100% by weight based on the total content of the organic solvent (E) contained in the photosensitive composition. The content of the organic solvent (E2) contained in the second liquid is preferably 1:99 to 99:1, more preferably 1:9 to 9:1, and still more preferably 2:8 by weight. 8:2, especially good for 3:7~7:3.

The content of diethylene glycol monoethyl ether acetate may be 30% by weight or more in 100% by weight of the first and second liquids of the two-liquid mixing type and 100% by weight of the photosensitive composition after mixing. The content of diethylene glycol monoethyl ether acetate in 100% by weight of the first liquid may be 50% by weight or less, or may be 55% by weight or more.

In the case where the first liquid contains two kinds of organic solvents, and when the second liquid contains two organic solvents, the content and content of the organic solvent having a larger content in the first liquid and the second liquid The content of the organic solvent of the lesser side is preferably from 1:99 to 99:1, more preferably from 1:9 to 9:1, still more preferably from 2:8 to 8:2, and particularly preferably from 3: 7~7:3.

In the case where the first liquid contains three kinds of organic solvents, and the second liquid contains three kinds of organic solvents, the content of the organic solvent having the highest content in the first liquid and the second liquid is the next organic solvent. The content is preferably from 1:99 to 99:1, more preferably from 1:9 to 9:1, more preferably from 2:8 to 8:2, and particularly preferably from 3:7 to 7:3. At this time, the lower limit of the content of the organic solvent having the lowest content is not particularly limited.

(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 above polymerizable monomer has polymerizability and can be polymerized. The polymerizable monomer is not particularly limited. These polymerizable monomers may be used alone or in combination of two or more.

The polymerizable monomer is preferably a monomer having a polymerizable unsaturated group. The polymerizable unsaturated group in the above-mentioned polymerizable monomer is, for example, a functional group having a polymerizable unsaturated double bond such as a (meth)acryl fluorenyl group or a vinyl ether group. Among them, in order to increase the crosslinking density of the photoresist film, a (meth)acryl fluorenyl group is preferred.

The above monomer having a polymerizable unsaturated group preferably has (meth) propylene. a compound of thiol. Examples of the compound having a (meth)acryl fluorenyl group include a di(meth)acrylate modified product of a glycol such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol or propylene glycol, or a plurality of compounds. a poly (meth) acrylate modification of an oxirane adduct of an alcohol, a polyol, or a propylene oxide adduct of a polyol, or an oxirane of phenol, phenol, or an epoxy of phenol a (meth) acrylate modification of a propane adduct, or a (meth) acrylate modification of a glycidyl ether such as glycerol diglycidyl ether or trimethylolpropane triglycidyl ether, or melamine (methyl) Acrylate.

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

"(Meth)acryloyl fluorenyl" means propylene fluorenyl and methacryl fluorenyl. "(Meth)acrylic acid" means acrylic acid and methacrylic acid. "(Meth)acrylate" means acrylate and methacrylate.

In the case where the polymerizable monomer is contained, the content of the polymerizable monomer is preferably 5% by weight or more based on 100% by weight of the total of the polymerizable polymer (A) having a carboxyl group. It is preferably 50% by weight or less. When the content of the polymerizable monomer is at least the above lower limit and not more than the above upper limit, the photosensitive composition can be sufficiently cured. Further, the crosslinking density of the photoresist film is moderate, and sufficient resolution can be obtained, and the photoresist film becomes less likely to yellow.

In order to reduce yellowing of the solder resist film when exposed to high temperatures, the photosensitive composition preferably contains an antioxidant. The above antioxidant preferably has Lewis alkaline part. The antioxidant is preferably at least one selected from the group consisting of a phenolic antioxidant, a phosphorus antioxidant, and an amine antioxidant, from the viewpoint of further suppressing yellowing of the photoresist film. The antioxidant is preferably a phenolic antioxidant from the viewpoint of further suppressing yellowing of the photoresist film. That is, the photosensitive composition preferably contains a phenolic antioxidant.

As a commercial item of the phenolic antioxidant, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, and IRGANOX 295 (all of which are manufactured by Ciba Japan Co., Ltd.), Adekastab AO-30, Adekastab 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 Industries, 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 W-500 (all of which are manufactured by Kawaguchi Chemical Industry Co., Ltd.), and SEENOX 224M and SEENOX 326M (all of which are manufactured by Shipro Kasei Co., Ltd.).

Examples of the phosphorus-based antioxidant include cyclohexylphosphine and triphenylphosphine. Commercial products of the above phosphorus-based antioxidants include Adekastab PEP-4C, Adekastab PEP-8, Adekastab PEP-24G, and Adekastab. PEP-36, Adekastab HP-10, Adekastab 2112, Adekastab 260, Adekastab 522A, Adekastab 1178, Adekastab 1500, Adekastab C, Adekastab 135A, Adekastab 3010, and Adekastab TPP (all manufactured by ADEKA), Sandostab 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 the above) For the manufacture of Chengbei Chemical Industry Co., Ltd.).

Examples of the amine-based antioxidant include triethylamine, dicyandiamide, melamine, and ethyldiamine-all three. 2,4-diamino--three , 2,4-diamino-6-tolyl-all three 2,4-diamino-6-dimethylphenyl-all three And quaternary ammonium salt derivatives and the like.

The content of the antioxidant is preferably 0.1 part by weight or more, more preferably 5 parts by weight or more, more preferably 30 parts by weight or less, and even more preferably 15 parts by weight based on 100 parts by weight of the polymerizable polymer (A) having a carboxyl group. 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 photoresist film having more excellent heat yellowing resistance can be formed.

Further, the photosensitive composition may further contain a coloring agent, a filler, an antifoaming agent, a hardening agent, a hardening accelerator, a releasing agent, a surface treating agent, a flame retardant, a viscosity adjusting agent, a dispersing agent, a dispersing aid, Surface modifiers, plasticizers, antibacterial agents, antifungal agents, leveling agents, stabilizers, coupling agents, anti-sagging agents or phosphors.

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

Examples of the light source for curing the photosensitive composition include an irradiation device that emits an active energy ray such as ultraviolet rays or visible rays. Examples of the light source include an ultrahigh pressure mercury lamp, a Deep UV lamp (Deep Ultraviolet lamp), a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, and an excimer laser. These light sources can be appropriately selected depending on the light-sensing wavelength of the constituent components of the photosensitive composition. The irradiation energy of light can be appropriately selected depending on the desired film thickness or the constituent components of the photosensitive composition. The light irradiation energy is generally in the range of 10 to 3000 mJ/cm ² .

(LED device)

The first liquid and the second liquid of the two-liquid mixing type of the present invention are suitably used for forming a photoresist film of an LED device, and are more suitable for forming a solder resist film. The first and second liquids of the two-liquid mixing type of the present invention are preferably a photoresist composition, more preferably a solder resist composition.

A method of manufacturing a printed wiring board according to the present invention is a method of manufacturing a printed wiring board comprising a printed wiring board body having a circuit on a surface thereof, and a photoresist laminated on a surface of the printed wiring board main body on which the circuit is provided membrane. The photoresist film is formed by the first liquid and the second liquid of the two-liquid mixing type of the present invention.

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

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

An LED wafer 7 is laminated on the upper surface 3a of the photoresist film 3. The LED chip 7 is laminated on the substrate 2 via the photoresist film 3. Terminals 8a, 8b are provided on the outer periphery of the lower surface 7a of the LED wafer 7. The terminals 8a and 8b are electrically connected to the electrodes 4a and 4b by the solders 9a and 9b. By this electrical connection, electric power can be supplied to the LED chip 7.

The invention will be readily understood by the following detailed description of the preferred embodiments and comparative examples. The invention is not limited to the following examples.

The following materials 1) to 18) were used in the examples and comparative examples:

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

(Synthesis Example 1)

To a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, ethyl carbitol acetate as a solvent and azobisisobutyronitrile as a catalyst were heated and heated to 80 ° C under a nitrogen atmosphere. The monomer obtained by mixing methacrylic acid with methyl methacrylate at a molar ratio of 30:70 was added over two hours. After the dropwise addition, the mixture was stirred for one hour and heated to 120 °C. Thereafter, it is cooled. Glycidyl acrylate was added in an amount of 10 with respect to the total molar amount of all the monomer units of the obtained resin, and tetrabutylammonium bromide was used as a catalyst, and heated at 100 ° C for 30 hours to obtain acrylic acid. The glycidyl ester is subjected to an addition reaction with a carboxyl group. After cooling, it was taken out from the flask to obtain an acid value of 60 mg KOH/g and a weight average molecular weight of 15,000. A solution of 50% by weight (nonvolatile) of a carboxyl group-containing resin having a bond equivalent of 1000. Hereinafter, this solution is referred to as an acrylic polymer 1.

2) Acrylic polymer 2 (polymerizable polymer having a carboxyl group, the acrylic polymer 2 obtained in Synthesis Example 2 below)

(Synthesis Example 2)

In 139 parts by weight of ethyl carbitol acetate, 0.5 parts by weight of dimethylbenzylamine as a catalyst and 0.1 parts by weight of hydroquinone as a polymerization inhibitor were used to have an epoxy equivalent of 210 and softened. 210 parts by weight of a cresol novolac type epoxy resin ("Epotohto YDCN-704", manufactured by Nippon Steel Chemical Co., Ltd.) at 80 ° C was reacted with 50 parts by weight of acrylic acid and 18 parts by weight of acetic acid to obtain an epoxy acrylate. 278 parts by weight of the obtained epoxy acrylate was reacted with 46 parts by weight of tetrahydrophthalic anhydride (1.0 mol per hydroxy group of epoxy acrylate) to obtain an acid value of 52 containing a solid component. A solution of 65 wt% (nonvolatile) of a carboxyl group-containing resin having an aromatic ring of mg KOH/g. Hereinafter, this solution is referred to as an acrylic polymer 2.

3) DPHA (acrylic monomer, dipentaerythritol hexaacrylate, specific gravity 1.1)

4) TMPTA (acrylic monomer, trimethylolpropane triacrylate, specific gravity 1.1)

5) TPO (photopolymerization initiator, photopolymerization initiator, manufactured by BASF Japan)

6) Irgacure 819 (photopolymerization initiator, photopolymerization initiator, manufactured by BASF Japan)

7) 828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation, specific gravity 1.2)

8) 806 (bisphenol F type epoxy resin, manufactured by Mitsubishi Chemical Corporation, specific gravity 1.2)

9) CR-50 (titanium oxide, manufactured by Ishihara Sangyo Co., Ltd., rutile-type titanium oxide produced by the chlorination method)

10) R-830 (titanium oxide, manufactured by Ishihara Sangyo Co., Ltd., rutile-type titanium oxide produced by sulfuric acid method)

11) Ethyl carbitol acetate (diethylene glycol monoethyl ether acetate, manufactured by Daicel Chemical Co., Ltd., dipole moment 1 Debye (above), specific gravity 1.0)

12) Solvesso 150 (naphtha, manufactured by Exxon Mobil, at a boiling point of 189 ° C at the beginning of the distillation trait and 210 ° C at the final boiling point of the distillation trait)

13) Solvesso 100 (naphtha, manufactured by Exxon Mobil, at a boiling point of 165 ° C at the beginning of the distillation, and at a final boiling point of 174 ° C in the form of a distillation)

14) Dipropylene glycol monomethyl ether (manufactured by Nippon Emulsifier Co., Ltd.);

15) Dipropylene glycol dimethyl ether (manufactured by Japan Emulsifier Co., Ltd.)

16) Diethylene glycol diethyl ether (manufactured by Japan Emulsifier)

17) Solvesso 200 (naphtha, manufactured by Exxon Mobil, at a boiling point of 230 ° C at the beginning of the distillation trait and at a final boiling point of 283 ° C in the form of distillation)

18) Toluene (manufactured by Exxon Mobil Co., Ltd.).

(Example 1)

The acrylic polymer 1 obtained by the synthesis example 1, 5 g of DPHA (dipentaerythritol hexaacrylate), TPO (photopolymerization initiator which is a photo-radical generator, the BASF Japan company) 2 g, CR-50 ( Titanium oxide, manufactured by Ishihara Sangyo Co., Ltd.) 40 g, and Solvesso 150 (naphtha, manufactured by Exxon Mobil Co., Ltd.) 25 g, mixed in a mixer (Kyotaro SP-500, manufactured by Thinky Co., Ltd.) for 3 minutes, in three rolls Mix in a grinder to obtain a mixture. Thereafter, The resulting mixture was subjected to defoaming treatment for 3 minutes using SP-500, whereby a first liquid was obtained.

828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation) 8 g, and ethyl carbitol acetate (diethylene glycol monoethyl ether acetate, manufactured by Daicel Chemical Co., Ltd.) 5 g in a mixer (Lintaro SP-500, manufactured by Thinky Co., Ltd.) was mixed for 3 minutes, and then mixed in a three-roll mill to obtain a mixture. Thereafter, the obtained mixture was subjected to defoaming treatment for 3 minutes using SP-500, whereby a second liquid was obtained.

A photosensitive composition containing a two-liquid mixing type of the first and second liquids was prepared by the method described above.

(Examples 2 to 49, Reference Examples 1 to 11 and Comparative Examples 1 to 19)

The first and second liquids were obtained in the same manner as in Example 1 except that the types and the amounts of the materials used in the first liquid and the second liquid were changed as shown in the following Tables 1 to 8. The first and second liquids of the two-liquid mixing type (photosensitive composition before mixing).

(Evaluation) Mixture of two liquids:

The first liquid and the second liquid were placed in a 1 L round plastic container (manufactured by Kinki Container Co., Ltd., BHS-1200), and the light was stirred at 50 rpm for 10 seconds by an automatic ink agitator manufactured by Mesh Corporation. Resistive material (photosensitive composition after mixing). The first liquid and the second liquid were placed in a 1 L round plastic container (manufactured by Kinki Container Co., Ltd., BHS-1200), and the light was stirred at 50 rpm for 20 seconds by an automatic ink agitator manufactured by Mesh Corporation. Resistive material (photosensitive composition after mixing). Add the first liquid and the second liquid to the circle of 1 L A plastic container (manufactured by Kinki U.S.A., BHS-1200) was used to prepare a photoresist material (mixed photosensitive composition) which was stirred at 50 rpm for 1 minute by an automatic ink agitator manufactured by Mesh Corporation. Further, the first liquid and the second liquid were placed in a 1 L round plastic container (manufactured by Kinki Container Co., Ltd., BHS-1200), and prepared by stirring at 50 rpm for 5 minutes by an automatic ink agitator manufactured by Mesh Corporation. Photoresist material (photosensitive composition after mixing).

Further, a 100 × 100 mm FR-4 substrate on which copper foil was attached was prepared. The photoresist material immediately after the completion of the agitation was applied to the surface of the FR-4 substrate to which the copper foil was attached by screen printing to form a photoresist material layer. The appearance of the photoresist layer on the substrate was visually observed.

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

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

A: When using a photoresist material obtained by stirring for 10 seconds, a photoresist material obtained by stirring for 20 seconds, a photoresist material obtained by stirring for 1 minute, and a photoresist material obtained by stirring for 5 minutes, Uniform photoresist layer

B: When a photoresist material which was stirred for 10 seconds was used, a small amount of stripe unevenness was observed on the photoresist layer, but it was formed by stirring for 20 minutes using a photoresist material which was stirred for 20 seconds. When the photoresist material and the photoresist material which is stirred for 5 minutes, the photoresist layer is uniform

C: When a photoresist material which was stirred for 10 seconds and a photoresist material which was stirred for 20 seconds was used, a small amount of unevenness was observed on the photoresist layer, but it was stirred for 1 minute. When the photoresist material and the photoresist material which is stirred for 5 minutes, the photoresist layer is uniform

D: When using a photoresist material which was stirred for 10 seconds, a photoresist material which was stirred for 20 seconds, and a photoresist material which was stirred for 1 minute, a small amount of strip was observed on the photoresist layer. In the case of using a photoresist material which is stirred for 5 minutes, the photoresist layer is uniform.

E: When using a photoresist material obtained by stirring for 10 seconds, a photoresist material obtained by stirring for 20 seconds, a photoresist material obtained by stirring for 1 minute, and a photoresist material obtained by stirring for 5 minutes, Uneven strips are seen on the photoresist layer

The results are shown in Tables 1 to 8 below. In the following Tables 1 to 8, "(1)" in the category of the liquid to be dispensed indicates the first liquid, and "(2)" indicates the second liquid. Further, after evaluating the miscibility of the first and second liquids, a photoresist film can be obtained by curing the photoresist layer on the substrate.

Further, although the evaluation results of the two liquid mixing properties of Example 5, Example 29, and Example 33 were both "A", Example 5 and Example 29 were shorter than Example 33 in a shorter period of time. The photosensitive composition was uniformly mixed. Although the evaluation results of the two liquid mixing properties of Example 30, Example 31, and Example 34 were both "A", Example 30 and Example 31 were uniformly mixed in a shorter period of time than in Example 34. Photosensitive composition. Although the evaluation results of the two liquid mixing properties of Example 35, Example 37, and Example 39 were both "A", Example 35 and Example 37 were uniformly mixed in a shorter period of time than in Example 39. Photosensitive composition.

1‧‧‧LED device

2‧‧‧Substrate

2a‧‧‧Upper surface

3‧‧‧Photoresist film

3a‧‧‧Upper surface

4a, 4b‧‧‧ electrodes

7‧‧‧LED chip

7a‧‧‧lower surface

8a, 8b‧‧‧ terminals

9a, 9b‧‧‧ solder

Fig. 1 is a partially cutaway front cross-sectional view showing an example of an LED device including a solder resist film using the two-liquid mixing type first and second liquids according to an embodiment of the present invention.

Claims (21)

A combination of a first liquid and a second liquid of a two-liquid mixing type, which is used to obtain a photosensitive composition as a mixture, wherein a combination of the first liquid and the second liquid of the two-liquid mixing type is mixed The liquid before the first liquid and the second liquid, the mixture of the first liquid and the second liquid, that is, the photosensitive composition as a whole contains a polymerizable polymer having a carboxyl group, a photopolymerization initiator, and a cyclic ether. The base compound, titanium oxide, and an organic solvent, wherein the photosensitive composition contains a solvent selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and a boiling point of 150 ° C or higher in a distillation property. At least two of the group consisting of naphtha having a final boiling point of 290 ° C or less are used as the organic solvent, and the first liquid contains the polymerizable polymer and contains a monomer selected from the group consisting of dipropylene glycol monomethyl ether and diethylene glycol. At least one of a group consisting of diethyl ether acetate and a naphtha having a boiling point of 150 ° C or higher and a boiling point of 290 ° C or less as a part of the organic solvent; The second liquid contains the above-mentioned compound having a cyclic ether group, and contains a compound selected from the group consisting of diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, and the boiling point of the distillation property of 150 ° C or higher and at the end of the distillation property. At least one of the group consisting of naphtha having a boiling point of 220 ° C or less is a part of the organic solvent, and the first liquid contains the photopolymerization initiator or contains the titanium oxide or contains the photopolymerization initiator Both of the above titanium oxides, In the case where the first liquid does not contain the photopolymerization initiator, the second liquid contains the photopolymerization initiator, and when the first liquid does not contain the titanium oxide, the second liquid contains the oxidation. In the titanium, the polymerizable polymer having a carboxyl group is an acrylic polymer having a carboxyl group, and the compound having a cyclic ether group is an epoxy compound, and the polymerization of the carboxyl group is 100% by weight of the photosensitive composition after mixing. The content of the photopolymerization initiator is 3% by weight or more and 50% by weight or less, and the content of the photopolymerization initiator is 100 parts by weight based on 100 parts by weight of the polymerizable polymer having a carboxyl group in the photosensitive composition after mixing. 0.1 parts by weight or more and 30 parts by weight or less, and the content of the compound having a cyclic ether group is 0.1 part by weight or more based on 100 parts by weight of the polymerizable polymer having a carboxyl group in the photosensitive composition after mixing. 50 parts by weight or less, in the 100% by weight of the photosensitive composition after mixing, the content of the titanium oxide is 3% by weight or more and 80% by weight or less, and the above-mentioned after mixing 100% by weight of the photosensitive composition, the total content of the organic solvent is 10% by weight or more and 60% by weight or less, and the first of the first liquid and the second liquid of the two-liquid mixing type is the first The content of the organic solvent contained in the liquid and the content of the organic solvent contained in the second liquid are 1:99 to 99:1 by weight, the initial boiling point in the distillation property, and the above-described distillation property. in The final boiling point is based on the value determined by JlS K2254 "Petroleum Products - Distillation Test Method". The combination solution of the first liquid and the second liquid of the two-liquid mixing type of claim 1, wherein the first liquid contains a solvent selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and a distillation property. At least two of the group consisting of naphtha having an initial boiling point of 150 ° C or higher and a boiling point of 290 ° C or less have a part of the organic solvent. The combination solution of the first liquid and the second liquid of the two-liquid mixing type of claim 1, wherein the first liquid contains at least dipropylene glycol monomethyl ether and diethylene glycol monoethyl ether acetate, or at least two ethylene Alcohol monoethyl ether acetate is a part of the above organic solvent, which is a naphtha having a boiling point of 150 ° C or higher and a boiling point of 290 ° C or lower. The combination solution of the first liquid and the second liquid of the two-liquid mixing type of claim 1, wherein the first liquid contains at least dipropylene glycol monomethyl ether and is at the end of the distillation property at a boiling point of 150 ° C or higher. Naphtha having a boiling point of 290 ° C or less is used as a part of the above organic solvent. The combination solution of the first liquid and the second liquid of the two-liquid mixing type of claim 1, wherein the photosensitive composition contains a solvent selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and a distillation property. At least two of the group consisting of naphtha having a boiling point of 150 ° C or higher and a boiling point of 220 ° C or less are used as the organic solvent, and the first liquid contains a solvent selected from the group consisting of dipropylene glycol monomethyl ether and Ethylene glycol monoethyl ether acetate and a group of naphtha having a boiling point of 150 ° C or higher and a boiling point of 220 ° C or lower At least two of them are part of the above organic solvent. The combination solution of the first liquid and the second liquid of the two-liquid mixing type of claim 1, wherein the photosensitive composition contains a solvent selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and a distillation property. At least two of the group consisting of naphtha having a boiling point of 150 ° C or higher and a boiling point of 220 ° C or less as the above-mentioned organic solvent, the first liquid containing dipropylene glycol monomethyl ether and diethylene glycol Alcohol monoethyl ether acetate, or at least diethylene glycol monoethyl ether acetate and naphtha having a boiling point of 150 ° C or more and a boiling point of 220 ° C or less as the above organic solvent portion. The combination solution of the first liquid and the second liquid of the two-liquid mixing type of claim 1, wherein the photosensitive composition contains a solvent selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and a distillation property. At least two of the group consisting of naphtha having a boiling point of 150 ° C or higher and a boiling point of 220 ° C or less as the above-mentioned organic solvent, the first liquid containing at least dipropylene glycol monomethyl ether and being distilled A naphtha having a boiling point of 150 ° C or higher at the beginning of the character and a boiling point of 220 ° C or less in the distillation property is a part of the organic solvent. The combination of the first liquid and the second liquid of the two-liquid mixing type according to any one of claims 1 to 7, wherein the first liquid contains the photopolymerization initiator. The combination of the first liquid and the second liquid of the two-liquid mixing type according to any one of claims 1 to 7, wherein the first liquid contains the titanium oxide. The combination of the first liquid and the second liquid of the two-liquid mixing type according to any one of claims 1 to 7, wherein the first liquid contains the photopolymerization initiator and the upper liquid Both titanium oxides are described. The combination of the first liquid and the second liquid of the two-liquid mixing type according to any one of claims 1 to 7, wherein the photosensitive composition obtained by mixing the first liquid and the second liquid is a solder resist composition . A method of manufacturing a printed wiring board, which is a method of manufacturing a printed wiring board including a circuit board having a circuit on a surface thereof and a solder resist film laminated on a surface of the printed wiring board body provided with a circuit, the manufacturing method The method includes the steps of: mixing a first liquid and a second liquid to obtain a photosensitive composition which is a solder resist composition obtained by mixing the first liquid and the second liquid, and the printed wiring board body having a circuit on the surface thereof is provided a photosensitive composition which is a solder resist composition obtained by mixing the first liquid and the second liquid, is applied to the surface of the circuit, and a solder resist film laminated on the surface of the printed wiring board body on which the circuit is provided is formed by The photosensitive composition which is a solder resist composition in which the first liquid and the second liquid are mixed as a whole contains a polymerizable polymer having a carboxyl group, a photopolymerization initiator, a compound having a cyclic ether group, titanium oxide, and an organic solvent. The photosensitive composition contains a solvent selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and a boiling point of 150 ° C or higher. At least two of the group consisting of naphtha having a boiling point of 290 ° C or less as the above-mentioned organic solvent, the first liquid containing the polymerizable polymer and containing a dipropylene glycol monomethyl ether, two Ethylene glycol monoethyl ether acetate, and the boiling point of the distillation property is 150 ° C or more, and the final boiling point of the distillation property is At least one of the group consisting of naphtha of 290 ° C or less is part of the organic solvent, and the second liquid contains the compound having a cyclic ether group and is selected from the group consisting of diethylene glycol monoethyl ether acetate. At least one of dipropylene glycol monomethyl ether and a group of naphtha having a boiling point of 150 ° C or higher and a boiling point of 220 ° C or less as a part of the organic solvent, the first The liquid contains the photopolymerization initiator or the titanium oxide, or both the photopolymerization initiator and the titanium oxide, and when the first liquid does not contain the photopolymerization initiator, the second liquid In the case where the first liquid contains no titanium oxide, the second liquid contains the titanium oxide, and the polymerizable polymer having a carboxyl group is an acrylic polymer having a carboxyl group, and the ring has the above-mentioned photopolymerization initiator. The compound of the ether group is an epoxy compound, and the content of the polymerizable polymer having a carboxyl group is 3% by weight in 100% by weight of the photosensitive composition after mixing. In the above-mentioned photosensitive composition after mixing, the content of the photopolymerization initiator is 0.1 part by weight or more and 30 parts by weight or less based on 100 parts by weight of the polymerizable polymer having a carboxyl group. In the photosensitive composition after the mixing, the content of the compound having a cyclic ether group is 0.1 part by weight or more and 50 parts by weight or less based on 100 parts by weight of the polymerizable polymer having a carboxyl group. The content of the titanium oxide is 3% by weight or more and 80% by weight or less based on 100% by weight of the photosensitive composition after mixing, and the total content of the organic solvent is 100% by weight of the photosensitive composition after mixing. 10% by weight or more and 60% by weight or less, the content of the organic solvent contained in the first liquid and the second liquid in the entire liquid mixture of the first liquid and the second liquid of the two-liquid mixing type The content of the above organic solvent contained in the weight ratio is 1:99 to 99:1, the initial boiling point in the distillation property and the final boiling point in the distillation property according to JlS K2254 "Petroleum Products - Distillation Test Method The measured value. The method for producing a printed wiring board according to claim 12, wherein the first liquid contains a solvent selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and an initial boiling point of 150 ° C or higher in distillation. At least two of the group consisting of naphtha having a final boiling point of 290 ° C or less are part of the above organic solvent. The method of manufacturing a printed wiring board according to claim 12, wherein the first liquid contains at least dipropylene glycol monomethyl ether and diethylene glycol monoethyl ether acetate, or at least diethylene glycol monoethyl ether acetate and is in a distillation A naphtha having a boiling point of 150 ° C or higher at the beginning of the property and a boiling point of 290 ° C or less in the distillation property is a part of the organic solvent. The method of producing a printed wiring board according to claim 12, wherein the first liquid contains at least dipropylene glycol monomethyl ether and a stone brain having a boiling point of 150 ° C or more and a boiling point of 290 ° C or less. The oil is part of the above organic solvent. The method for producing a printed wiring board according to claim 12, wherein the photosensitive composition contains a solvent selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and a boiling point of 150 ° C or higher. At least two of the group consisting of naphtha having a boiling point of 220 ° C or less are used as the organic solvent, and the first liquid contains a solvent selected from the group consisting of dipropylene glycol monomethyl ether and diethylene glycol monoethyl ether acetate. At least two of the group consisting of naphtha having a boiling point of 150 ° C or higher and a boiling point of 220 ° C or less at the beginning of the distillation property are part of the organic solvent. The method for producing a printed wiring board according to claim 12, wherein the photosensitive composition contains a solvent selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and a boiling point of 150 ° C or higher. At least two of the group consisting of naphtha having a boiling point of 220 ° C or less as the above organic solvent, the first liquid containing at least dipropylene glycol monomethyl ether and diethylene glycol monoethyl ether acetate, or At least diethylene glycol monoethyl ether acetate and naphtha having a boiling point of 150 ° C or higher and a boiling point of 220 ° C or less are included as part of the organic solvent. The method for producing a printed wiring board according to claim 12, wherein the photosensitive composition contains a solvent selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and a boiling point of 150 ° C or higher. At least two of the group consisting of naphtha having a boiling point of 220 ° C or less as the above organic solvent, The first liquid contains at least dipropylene glycol monomethyl ether and naphtha having a boiling point of 150 ° C or higher and a boiling point of 220 ° C or lower as a part of the organic solvent. The method of producing a printed wiring board according to any one of claims 12 to 18, wherein the first liquid contains the photopolymerization initiator. The method of producing a printed wiring board according to any one of claims 12 to 18, wherein the first liquid contains the titanium oxide. The method of producing a printed wiring board according to any one of claims 12 to 18, wherein the first liquid contains both the photopolymerization initiator and the titanium oxide.