JP2012212039A - Photosensitive composition and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition which can enhance glossiness of a cured product after curing, and reliability in moisture resistance, and to provide a printed wiring board using the photosensitive composition.SOLUTION: The photosensitive composition includes a polymerizable compound having a polymerizable group, a photoinitiator, titanium oxide, and a first antioxidant having both a phenolic hydroxyl group and a sulfur atom. In the printed wiring board which includes a printed wiring board body having a circuit provided thereon, and a solder resist film stacked on the surface provided with the circuit of the printed wiring board body, the solder resist film is formed by using the photosensitive composition.

Description

  The present invention relates to a photosensitive composition 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, and the photosensitive composition. The present invention relates to a printed wiring board using an adhesive composition.

  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.

  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.

JP 2007-249148 A JP 2007-322546 A

  When a resist film is formed on a substrate using a conventional resist material as described in Patent Documents 1 and 2, the glossiness of the resist film may be low. Further, when the resist film is exposed to high humidity conditions, the resist film may be altered, and the resist film may be peeled off from the substrate or may be easily peeled off. That is, with conventional resist materials, the moisture resistance reliability of the cured product may be low.

  The objective of this invention is providing the photosensitive composition which can improve the glossiness of a hardened | cured material after hardening, and moisture-proof reliability, and the printed wiring board using this photosensitive composition.

  According to a wide aspect of the present invention, a polymerizable compound having a polymerizable group, a photopolymerization initiator, titanium oxide, and a first antioxidant having both a phenolic hydroxyl group and a sulfur atom are included. A photosensitive composition is provided.

  On the specific situation with the photosensitive composition concerning this invention, the 2nd antioxidant which does not have a sulfur atom is further contained.

  In another specific aspect of the photosensitive composition according to the present invention, silica is further included.

  In another specific aspect of the photosensitive composition according to the present invention, a silane coupling agent having an unsaturated double bond is further included.

  In still another specific aspect of the photosensitive composition according to the present invention, the silane coupling agent having an unsaturated double bond is a silane coupling agent having a (meth) acryloyl group.

  In another specific aspect of the photosensitive composition according to the present invention, the polymerizable compound having a polymerizable group has an aromatic ring.

  In still another specific aspect of the photosensitive composition according to the present invention, the polymerizable compound having a polymerizable group has a carboxyl group.

  The photosensitive composition according to the present invention is suitably used as a solder resist composition. The photosensitive composition according to the present invention is preferably a solder resist composition.

  The printed wiring board according to the present invention includes a printed wiring board main body having a circuit on the surface, and a solder resist film laminated on the surface of the printed wiring board main body on which the circuit is provided. It is formed using a photosensitive composition constructed according to the present invention.

  The photosensitive composition according to the present invention includes a polymerizable compound having a polymerizable group, a photopolymerization initiator, titanium oxide, and a first antioxidant having both a phenolic hydroxyl group and a sulfur atom. Therefore, the glossiness and moisture resistance reliability of the cured product after curing can be improved.

FIG. 1 is a partially cutaway front sectional view schematically showing an example of an LED device having a resist film using a photosensitive composition according to an embodiment of the present invention.

  Hereinafter, the present invention will be described in detail.

  The photosensitive composition concerning this invention contains the polymeric compound (A) which has a polymeric group, a photoinitiator (B), a titanium oxide (C), and antioxidant (D). The photosensitive composition which concerns on this invention contains the 1st antioxidant (D1) which has both a phenolic hydroxyl group and a sulfur atom as said antioxidant (D) essential.

  Since the photosensitive composition which concerns on this invention has the said composition, the glossiness of the hardened | cured material after hardening can be raised. Furthermore, since the photosensitive composition which concerns on this invention has the said composition, it can improve the moisture resistance reliability of the hardened | cured material after hardening. For example, when the cured product is exposed to high humidity conditions, the cured product is less likely to be altered, and the cured product is less likely to be peeled off from a member to be laminated such as a substrate. As a result, the reliability of various electronic components such as a printed wiring board using the photosensitive composition according to the present invention can be enhanced.

  The photosensitive composition according to the present invention preferably further contains a second antioxidant (D2) having no sulfur atom. The photosensitive composition according to the present invention preferably further contains silica (E). The photosensitive composition according to the present invention preferably further contains a silane coupling agent (F1) having an unsaturated double bond.

  Hereinafter, the detail of each component contained in the photosensitive composition concerning this invention is demonstrated.

(Polymerizable compound having a polymerizable group (A))
The polymerizable compound (A) having a polymerizable group is not particularly limited as long as it is a polymerizable compound having a polymerizable group. The polymerizable compound (A) having a polymerizable group may be a polymerizable monomer or a polymerizable polymer. Only one of the polymerizable monomer and the polymerizable polymer may be used, or both the polymerizable monomer and the polymerizable polymer may be used. As for the polymeric compound (A) which has the said polymeric group, only 1 type may be used and 2 or more types may be used together.

  Examples of the polymerizable monomer include a polymerizable unsaturated group-containing monomer or a polymerizable cyclic ether group-containing monomer.

  Examples of the polymerizable unsaturated group include functional groups having a polymerizable unsaturated double bond such as a (meth) acryloyl group and a vinyl ether group. Among these, a (meth) acryloyl group is preferable 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 the polyhydric (meth) acrylate modified product of the propylene oxide adduct of polyhydric alcohol, the (meth) acrylate modified product of phenol, the ethylene oxide adduct of phenol or the propylene oxide adduct of phenol, glycerin diglycidyl ether or tri (Meth) acrylate modified products of glycidyl ether such as methylolpropane 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.

  Examples of the polymerizable polymer include acrylic resins, epoxy resins, and olefin resins. The “resin” is not limited to a solid resin, and includes a liquid resin and an oligomer.

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

(A) carboxyl group-containing resin obtained by copolymerization of unsaturated carboxylic acid and compound having polymerizable unsaturated double bond (b) carboxyl group-containing (meth) acrylic copolymer resin (b1) and in one molecule A carboxyl group-containing resin obtained by reaction with a compound (b2) having an oxirane ring and an ethylenically polymerizable unsaturated double bond (c) one epoxy group and a polymerizable unsaturated double bond each in one molecule After reacting an unsaturated monocarboxylic acid with a copolymer of a compound having a polymerizable compound and a compound having a polymerizable unsaturated double bond, the secondary hydroxyl group of the resulting reaction product is saturated or unsaturated polybasic. Carboxyl group-containing resin obtained by reacting an acid anhydride (d) After reacting a hydroxyl group-containing polymer with a saturated or unsaturated polybasic acid anhydride, a polymer having a carboxyl group is formed. Hydroxyl and carboxyl group-containing resins obtained by reacting a compound with one epoxy group and a compound having a polymerizable unsaturated double bond in each molecule (e) an epoxy compound having an aromatic ring and a saturated polybasic acid Resin obtained by reacting anhydride or unsaturated polybasic acid anhydride, or epoxy compound having aromatic ring and carboxyl group-containing compound having at least one unsaturated double bond, and then saturated polybasic Resin obtained by further reacting acid anhydride or unsaturated polybasic acid anhydride

  In 100% by weight of the polymerizable compound (A), the content of the polymerizable monomer is preferably 5% by weight or more and 50% by weight or less. Moreover, it is preferable that content of the said polymerizable monomer is 5 to 50 weight% in the total of 100 weight% of the said polymerizable monomer and the said polymerizable polymer. When the content of the polymerizable monomer is within the above range, the photosensitive composition can be sufficiently cured. Furthermore, the crosslink density of the resist film becomes appropriate, sufficient resolution can be obtained, and the resist film is hardly yellowed.

  The polymerizable compound (A) preferably has an aromatic ring. When the polymerizable compound (A) has an aromatic ring, the moisture resistance reliability of the cured product is further improved.

  The polymerizable compound (A) preferably has a carboxyl group. The developability of the photosensitive composition is improved when the polymerizable compound (A) has a carboxyl group. Examples of the polymerizable compound having a polymerizable group and a carboxyl group include a (meth) 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.

  In 100% by weight of the photosensitive composition, the content of the polymerizable compound (A) is preferably 5% by weight or more, more preferably 10% by weight or more, preferably 50% by weight or less, more preferably 40% by weight or less. It is. When the content of the polymerizable compound (A) 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 photosensitive composition concerning this invention contains a photoinitiator (B), it can harden a photosensitive composition 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.

  The content of the photopolymerization initiator (B) with respect to 100 parts by weight of the polymerizable compound (A) is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, preferably 30 parts by weight or less. More preferably, it is 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 is further increased.

(Titanium oxide (C))
Since the photosensitive composition according to the present invention contains titanium oxide, a cured product film such as a resist film having a high reflectance can be formed. The titanium oxide (C) contained in the photosensitive composition according to the present invention is not particularly limited. As for titanium oxide (C), only 1 type may be used and 2 or more types may be used together.

  By using the titanium oxide (C), 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 (C) is used.

  The titanium oxide (C) 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 increases the processability of the resist film.

  It is preferable that the said titanium oxide (C) contains the rutile type titanium oxide surface-treated with the silicon oxide or the silicone compound. In 100% by weight of the titanium oxide (C), 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, preferably 100% by weight. % Or less. The total amount of the titanium oxide (C) may be rutile titanium oxide surface-treated with the silicon oxide or the silicone compound. By using the rutile type titanium oxide surface-treated with the silicon oxide or the silicone compound, the heat-resistant yellowing of the resist film is further increased.

  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.

  In 100% by weight of the photosensitive composition according to the present invention, the content of titanium oxide (C) is preferably 3% by weight or more, more preferably 10% by weight or more, still more preferably 15% by weight or more, preferably 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 (C) is not less than the above lower limit and not more than the above upper limit, it is difficult to yellow when the resist film is exposed to a high temperature. Furthermore, a photosensitive composition having a viscosity suitable for coating can be easily prepared.

(Antioxidant (D))
The photosensitive composition concerning this invention contains antioxidant (D). By using the antioxidant (D), yellowing of the solder resist film can be suppressed when exposed to a high temperature.

  The antioxidant (D) preferably has a Lewis basic site. In addition, the antioxidant (D) is used to reduce yellowing of the resist film by using at least one selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, and amine antioxidants. It can be further suppressed. From the viewpoint of further suppressing the yellowing of the resist film, the antioxidant (D) is preferably a phenolic antioxidant.

  Moreover, the photosensitive composition which concerns on this invention essentially contains the 1st antioxidant (D1) which has both a phenolic hydroxyl group and a sulfur atom as said antioxidant (D). The first antioxidant (D1) is a phenolic antioxidant having a sulfur atom. By using this specific first antioxidant (D1), it is possible to effectively increase both the glossiness and the moisture resistance reliability of the cured product. Furthermore, by using this specific first antioxidant (D1), the heat-resistant yellowing of the cured product can be enhanced, and the yellowing of the resist film can be suppressed.

  Moreover, it is preferable that the photosensitive composition concerning this invention further contains the 2nd antioxidant (D2) which does not have a sulfur atom as said antioxidant (D). By using the second antioxidant (D2), the heat-resistant yellowing of the cured product can be further increased, and the yellowing of the resist film can be effectively suppressed. The second antioxidant (D2) preferably has a phenolic hydroxyl group, and is preferably a phenolic antioxidant having no sulfur atom. However, the second antioxidant (D2) does not necessarily have a phenolic hydroxyl group. When said 2nd antioxidant (D2) has a phenolic hydroxyl group, the heat-resistant yellowing of hardened | cured material will become still higher.

  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 BASF), ADK STAB AO-30, and 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, and Sumizer MDP -S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F), and Sumilizer G (All are manufactured by Sumitomo Chemical Co., Ltd.), HOSTANOX O10, HOSTANOX O16, HOSTANOX O14, and HOSTANOX O3 (all are manufactured by Clariant), Antage BHT, Antage W-300, Antage W-400, and Antage W500 (All as described above, manufactured by Kawaguchi Chemical Industry Co., Ltd.), SEENOX 224M, and SEENOX 326M (all as described above, manufactured by Sipro Kasei Co., Ltd.).

  Among the phenolic antioxidants, examples of the antioxidant corresponding to the first antioxidant (D1) include IRGANOX 1035 (manufactured by BASF). The first antioxidant (D1) is preferably a thioether.

  Examples of the phosphorus antioxidant include cyclohexylphosphine and triphenylphosphine. Commercially available products of the above phosphorus antioxidants include Adeastab PEP-4C, Adeastab PEP-8, Adeastab PEP-24G, Adeastab PEP-36, Adeastab HP-10, Adeastab 2112, Adeastab 260, Adeastab 522A, Adeastab 1178, Adeastab 1500, Adeastab C, Adeastab 135A, Adeastab 3010, and Adeastab 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 (D) is preferably 0.1 parts by weight or more, more preferably 5 parts by weight or more, preferably 30 parts by weight or less, based on 100 parts by weight of the polymerizable compound (A). The amount is preferably 15 parts by weight or less. Further, the content of the first antioxidant (D1) is preferably 0.1 parts by weight or more, more preferably 5 parts by weight or more, and preferably 30 parts with respect to 100 parts by weight of the polymerizable compound (A). It is 15 parts by weight or less, more preferably 15 parts by weight or less. When the content of the antioxidant (D) and the first antioxidant (D1) is not less than the above lower limit and not more than the above upper limit, a more excellent resist film can be formed by heat yellowing. Moreover, the glossiness and moisture resistance reliability of hardened | cured material can be further improved as content of the said 1st antioxidant (D1) is more than the said minimum and below an upper limit. The “content of the antioxidant (D)” means that the antioxidant (D) includes both the first antioxidant (D1) and the second antioxidant (D2). In the case, “the total content of the first antioxidant (D1) and the second antioxidant (D2)” is indicated.

  When the antioxidant (D) contains both the first antioxidant (D1) and the second antioxidant (D2), the first antioxidant (D1) and the above The content ratio with the second antioxidant (D2) is not particularly limited. The photosensitive composition according to the present invention has a weight ratio of the first antioxidant (D1) and the second antioxidant (D2) of 0.01: 99.99 to 99.99: 0. .01, preferably 1:99 to 99: 1, more preferably 10:90 to 90:10, still more preferably 20 to 80:80:20. When the photosensitive composition according to the present invention contains the first antioxidant (D1) and the second antioxidant (D2) in a preferable weight ratio, the polymerizable compound (A) 100 The content of the first antioxidant (D1) is preferably 0.1 parts by weight or more, more preferably 5 parts by weight or more with respect to parts by weight.

(Silica (E))
The photosensitive composition according to the present invention preferably contains silica (E). By using silica (E), the moisture resistance reliability of the cured product can be further enhanced.

  In 100% by weight of the photosensitive composition according to the present invention, the content of the silica (E) is preferably 0.1% by weight or more, more preferably 1% by weight or more, still more preferably 3% by weight or more, particularly preferably. Is 5% by weight or more, preferably 50% by weight or less, more preferably 40% by weight or less. When the content of the silica (E) is not less than the above lower limit and not more than the above upper limit, the moisture resistance reliability of the cured product is further enhanced.

(Coupling agent (F))
The photosensitive composition according to the present invention according to the present invention preferably contains a coupling agent (F). Examples of the coupling agent (F) include a silane coupling agent, a titanium coupling agent, a zircon coupling agent, and an aluminum coupling agent. As for the said coupling agent (F), only 1 type may be used and 2 or more types may be used together.

  The coupling agent (F) is preferably a silane coupling agent. Furthermore, the coupling agent (F) is preferably a silane coupling agent (F1) having an unsaturated double bond. That is, it is preferable that the photosensitive composition according to the present invention further includes a silane coupling agent (F1) having an unsaturated double bond. The silane coupling agent (F1) having an unsaturated double bond is a compound different from the polymerizable compound (A) having a polymerizable group. By using the silane coupling agent (F1) having an unsaturated double bond, the moisture resistance reliability of the cured product can be further enhanced.

  The silane coupling agent (F1) having an unsaturated double bond is preferably a silane coupling agent having a (meth) acryloyl group. In this case, the moisture resistance reliability of the cured product becomes even better.

  Examples of the group having an unsaturated double bond in the silane coupling agent (F1) having an unsaturated double bond include an alkenyl group and a (meth) acryloyl group. Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group.

  Commercially available silane coupling agents (F1) having an unsaturated double bond include KBM-1003 (having a vinyl group), KBM-503 (having a methacryloyl group), and KBM-5103 (having an acryloyl group). (All of which are manufactured by Shin-Etsu Chemical Co., Ltd.).

  The content of the coupling agent (F) is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, preferably 10 parts by weight or less with respect to 100 parts by weight of the polymerizable compound (A). More preferably, it is 5 parts by weight or less, and still more preferably 3 parts by weight or less. Furthermore, the content of the silane coupling agent (F1) having an unsaturated double bond is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight with respect to 100 parts by weight of the polymerizable compound (A). Part by weight or more, preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and still more preferably 3 parts by weight or less. When the content of the coupling agent (F) and the silane coupling agent (F1) having an unsaturated double bond is not less than the above lower limit and not more than the above upper limit, a more excellent resist film can be formed by heat yellowing. . Moreover, the glossiness and moisture resistance reliability of hardened | cured material can be improved further as content of the silane coupling agent (F1) which has an unsaturated double bond is more than the said minimum and below the said upper limit.

(Other ingredients)
In order to improve the cutting processability of the resist film, the photosensitive composition preferably contains a compound having a cyclic ether skeleton. Further, the use of the compound having the cyclic ether skeleton also improves the curability of the photosensitive composition.

  Examples of the compound having a cyclic ether skeleton include heterocyclic epoxy resins such as bisphenol S type epoxy resin, diglycidyl phthalate resin, triglycidyl isocyanurate, bixylenol type epoxy resin, biphenol type epoxy resin, and tetraglycidyl xyleno. Irethane 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 novolac type epoxy resin, chelate type epoxy resin, glyoxal type epoxy resin, amino group-containing epoxy resin, rubber-modified epoxy resin, dicyclopentadiene phenolic Type epoxy resins, silicone-modified epoxy resin and ε- caprolactone-modified epoxy resin. As for the compound which has the said cyclic ether frame | skeleton, only 1 type may be used and 2 or more types may be used together.

  When the polymerizable compound (A) has a carboxyl group, the compound having a cyclic ether skeleton reacts with the carboxyl group and acts to cure the photosensitive composition.

  The content of the compound having a cyclic ether skeleton with respect to 100 parts by weight of the polymerizable compound (A) is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, preferably 50 parts by weight or less. The amount is preferably 30 parts by weight or less. When the content of the compound having a cyclic ether skeleton 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.

  The photosensitive composition according to the present invention may contain a solvent. The dipole moment of the solvent is preferably 1 Debye or more. By using a solvent having a dipole moment of 1 Debye or more, a photosensitive composition excellent in pot life can be provided.

  The photosensitive composition according to the present invention includes a colorant, a filler, a curing agent, a curing accelerator, a release agent, a surface treatment agent, a flame retardant, a viscosity modifier, a dispersant, a dispersion aid, and a surface modification. An agent, a plasticizer, an antibacterial agent, an antifungal agent, a leveling agent, a stabilizer, an anti-sagging agent or a phosphor may be included.

  Furthermore, the photosensitive composition according to the present invention has a first liquid and a second liquid, and the two-liquid mixed photosensitive composition used by mixing the first and second liquids. It may be. In the case of a two-component mixed photosensitive composition, the progress of polymerization or curing reaction before use can be suppressed. For this reason, the pot life of each of the two liquids can be improved. Further, the photosensitive composition according to the present invention may be a one-component type photosensitive composition having only the first liquid. The photosensitive composition according to the present invention includes a one-component type photosensitive composition and a multi-component mixed type photosensitive composition such as a two-component mixed type.

  In the case of a two-component mixed photosensitive composition, the polymerizable compound (A), the photopolymerization initiator (B), the titanium oxide (C), and the first antioxidant (D1) are: Each is contained in at least one of the first liquid and the second liquid. When the second antioxidant (D2), the silica (E), the silane coupling agent (F1) having the unsaturated double bond, and the compound having the cyclic ether skeleton are included, The second antioxidant (D2), the silica (E), the silane coupling agent (F1) having an unsaturated double bond, and the compound having the cyclic ether skeleton are respectively the first liquid and the above It is contained in at least one of the second liquids.

  The mixture in which the first and second liquids are mixed is a photosensitive composition, and the polymerizable compound (A), the photopolymerization initiator (B), the titanium oxide (C), and the first mixture. Antioxidant (D1) is essential.

  The photosensitive composition according to the present invention 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 the desired film thickness or the constituent components of the photosensitive composition. The irradiation energy of light is generally in the range of 10 to 3000 mJ / cm ² .

(LED device)
The photosensitive composition concerning this invention is used suitably in order to form the resist film of an LED device, and is used more suitably in order to form a soldering resist film. The photosensitive composition according to the present invention is preferably a resist composition, and is preferably a solder resist composition.

  The printed wiring board according to the present invention includes a printed wiring board body having a circuit on the surface, and a solder resist film laminated on the surface of the printed wiring board body on which the circuit is provided. The solder resist film is formed of the photosensitive composition according to the present invention.

  In FIG. 1, an example of the LED device which has a resist film formed using the photosensitive composition which concerns on one Embodiment of this invention is typically shown with a partial notch front sectional drawing.

  In the LED device 1 shown in FIG. 1, a resist film 3 formed of a photosensitive composition is laminated on an upper surface 2 a of a substrate 2. The resist film 3 is a solder resist film and 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. The present invention is not limited to the following examples.

  In the examples and comparative examples, the following materials 1) to 15) were used.

1) Acrylic polymer 1 (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% by weight (nonvolatile content) of a carboxyl group-containing resin having a solid content acid value of 60 mgKOH / g, a weight average molecular weight of 15,000, and a double bond equivalent of 1,000. Hereinafter, this solution is referred to as acrylic polymer 1.

2) Acrylic polymer 2 (acrylic polymer 2 obtained in Synthesis Example 2 below)
(Synthesis Example 2)
In 139 parts by weight of ethyl carbitol acetate, 0.5 part by weight of dimethylbenzylamine as a catalyst and 0.1 part by weight of hydroquinone as a polymerization inhibitor were used, and the cresol novolac type having an epoxy equivalent of 210 and a softening point of 80 ° C. 210 parts by weight of an epoxy resin (“Epototo YDCN-704”, manufactured by Tohto Kasei Co., Ltd.), 50 parts by weight of acrylic acid and 18 parts by weight of acetic acid were reacted to obtain an epoxy acrylate. 278 parts by weight of the obtained epoxy acrylate and 46 parts by weight of tetrahydrophthalic anhydride (0.3 mole with respect to 1.0 mole of hydroxyl group of epoxy acrylate) are reacted to form an aromatic ring having a solid content acid value of 52 mgKOH / g. As a result, a solution containing 65% by weight of a carboxyl group-containing resin was obtained. Hereinafter, this solution is called acrylic polymer 2.

3) DPHA (acrylic monomer, dipentaerythritol hexaacrylate, specific gravity 1.1)
4) TPO (photopolymerization initiator which is a photo radical generator, manufactured by BASF Japan)
5) 828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation, specific gravity 1.2)
6) Ethyl carbitol acetate (solvent, dipole moment 1 Debye or more, specific gravity 1.0)
7) CR-50 (titanium oxide, manufactured by Ishihara Sangyo Co., Ltd., rutile titanium oxide manufactured by the chlorine method)
8) SO-C5 (silica, manufactured by Admatechs)
9) KBM-1003 (silane coupling agent having a vinyl group, manufactured by Shin-Etsu Chemical Co., Ltd.)
10) KBM-503 (silane coupling agent having a methacryloyl group, manufactured by Shin-Etsu Chemical Co., Ltd.)
11) KBM-5103 (a silane coupling agent having an acryloyl group, manufactured by Shin-Etsu Chemical Co., Ltd.)
12) KBM-803 (silane coupling agent having a thiol group, manufactured by Shin-Etsu Chemical Co., Ltd.)
13) IRGANOX 1010 (phenolic antioxidant, manufactured by BASF)
14) IRGANOX 1035 (phenolic antioxidant having a sulfur atom, manufactured by BASF)
15) IRGANOX 1330 (phenolic antioxidant, manufactured by BASF)

Example 1
15 parts by weight of the acrylic polymer 1 obtained in Synthesis Example 1, 5 parts by weight of DPHA (dipentaerythritol hexaacrylate), and 2 parts by weight of TPO (a photopolymerization initiator that is a photoradical generator, manufactured by BASF Japan) 8 parts by weight of 828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation), 20 parts by weight of CR-50 (titanium oxide, manufactured by Ishihara Sangyo Co., Ltd.), IRGANOX 1035 (phenolic antioxidant having a sulfur atom, BASF) 0.5 parts by weight) and 30 parts by weight of ethyl carbitol acetate were mixed, mixed for 3 minutes with a mixer (Nentaro SP-500, manufactured by Shinky Corporation), and then mixed with 3 rolls. A mixture was obtained. Then, the resist material which is a photosensitive composition was obtained by defoaming the obtained mixture for 3 minutes using SP-500.

(Examples 2 to 13 and Comparative Examples 1 to 4)
A resist material was obtained in the same manner as in Example 1 except that the type and blending amount of the material used were changed as shown in Table 1 below.

(Evaluation)
(1) Preparation of measurement sample A substrate of FR-4 having a size of 80 mm x 90 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 an evaluation sample. The thickness of the obtained resist film was 20 μm.

(2) Heat-resistant yellowing The evaluation sample was put in a heating oven and heated at 270 ° C. for 10 minutes.

  Using a color / color difference meter (CR-400, manufactured by Konica Minolta Co., Ltd.), L *, a *, and b * of the evaluation sample before heat treatment were measured. Further, L *, a *, and b * of the evaluation sample after the heat treatment were measured, and ΔE * ab was obtained from these two measured values. When ΔE * ab of the evaluation sample after the heat treatment is 2 or less, “◯◯” is greater than 2, and when it is 3 or less, “◯” is greater than 3, and when 6 or less is “Δ”, 6 The case of exceeding “×” was defined as “×”.

(3) Glossiness Using a gloss meter (IG-410, manufactured by Horiba, Ltd.), the gloss value of 60 degrees of the obtained evaluation sample was measured. The case where it exceeded 80 was designated as “◯”, the case where it exceeded 70, and the case where it was 79 or less was designated as “Δ”, and the case where it was 70 or less was designated as “X”.

(4) Moisture resistance reliability A pressure cooker test (PCT) of the obtained evaluation sample (sample in which a resist film is formed on the substrate) is performed, and the obtained evaluation sample is treated at a temperature of 130 ° C. and a humidity of 100% for 100 hours. did.

  The resist film that had been treated at a temperature of 130 ° C. and a humidity of 100% for 100 hours was cut with a grid of 100 squares at 1 mm intervals. Next, a cellophane tape (JIS Z1522) was sufficiently applied to the resist film having the cut portion, and one end of the tape was strongly peeled off at an angle of 45 degrees to confirm the peeled state of the resist film.

  The moisture resistance reliability was judged according to the following criteria.

[Judgment criteria for moisture resistance reliability]
XX: No change in appearance of resist film after peeling of tape, no peeling of resist film XX: No change in appearance of resist film after peeling of tape, but partial peeling of resist film (width less than 0.3 mm) ○: Although there was no change in the appearance of the resist film after peeling of the tape, the resist film was partially peeled (width 0.3 mm or more, less than 1 mm in width) Δ: Although there was no change in appearance of the resist film after peeling of the tape, A lot of resist film was peeled x: The resist film was lifted after the tape was peeled off, and a lot of resist film was peeled off

  The 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 (9)

A polymerizable compound having a polymerizable group;
A photopolymerization initiator;
Titanium oxide,
A photosensitive composition comprising a first antioxidant having both a phenolic hydroxyl group and a sulfur atom.   The photosensitive composition of Claim 1 which further contains the 2nd antioxidant which does not have a sulfur atom.   The photosensitive composition of Claim 1 or 2 which further contains a silica.   The photosensitive composition of any one of Claims 1-3 which further contains the silane coupling agent which has an unsaturated double bond.   The photosensitive composition of any one of Claims 1-4 whose silane coupling agent which has the said unsaturated double bond is a silane coupling agent which has a (meth) acryloyl group.   The photosensitive composition of any one of Claims 1-5 in which the polymeric compound which has the said polymeric group has an aromatic ring.   The photosensitive composition of any one of Claims 1-6 in which the polymeric compound which has the said polymeric group has a carboxyl group.   The photosensitive composition of any one of Claims 1-7 which is a soldering resist composition. A printed wiring board body having a circuit on the surface, and a solder resist film laminated on the surface of the printed wiring board body on which the circuit is provided,
The printed wiring board with which the said soldering resist film is formed using the photosensitive composition of any one of Claims 1-8.

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