JP5964608B2 - UV curable transparent resin composition - Google Patents

Description

  The present invention is, for example, a flame retardant ultraviolet curable transparent resin composition suitable for a coating material, in particular, a difficulty suitable for a coating material for coating a conductor circuit pattern formed on a wiring board such as a flexible wiring board. The present invention relates to a flammable ultraviolet curable transparent resin composition.

  Conventionally, the curable resin composition may be used as, for example, a solder resist film of a flexible wiring board. The flexible wiring board may be used as a mounting substrate for a light emitting diode element (LED) or the like. In this case, the solder resist film formed on the mounting surface has a function of improving the reflectance of light from the light source. It has been demanded. And in order to raise the reflectance of the cured film of curable resin composition, mix | blending inorganic white pigments, such as a titanium oxide, is known.

  On the other hand, the solder resist film formed on the mounting surface may require not only mechanical properties such as bending resistance (flexibility) but also transparency depending on the use of the flexible wiring board. Moreover, since it is strongly desired that the electrode substrate for a touch panel incorporated in the front surface of a display body such as a liquid crystal display does not deteriorate its visibility, a highly transparent electrode protective film material is required. Therefore, Patent Document 1 discloses a reactive epoxycarboxylate compound and a reactivity that give a cured product having high transparency, little deterioration with respect to light, and excellent balance of toughness, heat resistance, and moisture resistance. Polycarboxylic acid compounds have been proposed.

  However, the reactive epoxycarboxylate compound and the reactive polycarboxylic acid compound of Patent Document 1 have a problem that the discoloration resistance and transparency are not sufficient.

  On the other hand, since the wiring board is mounted on an electronic device, it not only has excellent transparency but also requires flame retardancy. However, when a flame retardant such as a phosphorus compound is added to the curable resin composition, the cured coating film of the curable resin composition has a problem that transparency and bending resistance (flexibility) are impaired. .

WO2006 / 109572

  In view of the above circumstances, an object of the present invention is to provide an ultraviolet curable transparent resin composition capable of forming a cured product having excellent transparency and flame retardancy without impairing various properties such as bending resistance and resolution. It is to provide. Furthermore, the objective of this invention provides the wiring board provided with the insulating film which has a bending resistance, resolution, transparency, and a flame retardance obtained by using the said ultraviolet curable transparent resin composition. There is.

  The aspect of the present invention is a compound having an oxirane ring and an ethylenically unsaturated bond in a part of the carboxyl group of a copolymer obtained by reacting (A) (meth) acrylic acid and (meth) acrylic ester And a carboxyl group-containing (meth) acrylic resin obtained by adding a phosphorus compound containing at least one aromatic ring to a part of the ethylenically unsaturated bond, and (B) light. An ultraviolet curable transparent resin composition comprising a polymerization initiator, (C) a diluent, and (D) an epoxy resin.

  In this embodiment, the structural unit containing at least one aromatic ring and at least one phosphorus element is incorporated in part of the side chain of the (A) carboxyl group-containing (meth) acrylic resin. The structural unit containing at least one aromatic ring and at least one phosphorus element imparts flame retardancy to the ultraviolet curable transparent resin composition. In addition, unless this invention mix | blends the coloring agent (for example, white pigment) which loses transparency, it is a transparent resin composition, As a result, the hardened | cured material has transparency.

  In an aspect of the present invention, the phosphorus compound containing at least one aromatic ring is represented by the general formula (i) or the general formula (ii).

（式中、Ｚは置換基を表し、ｌは０〜５の整数、ｍは０〜４の整数である。）であることを特徴とする紫外線硬化性透明樹脂組成物である。

(Wherein Z represents a substituent, l is an integer of 0 to 5, and m is an integer of 0 to 4).

  An aspect of the present invention is the ultraviolet curable transparent resin composition in which the (A) carboxyl group-containing (meth) acrylic resin contains 0.5 to 10% by mass of a phosphorus element in a solid content. . This phosphorus element is derived from a phosphorus compound containing at least one aromatic ring.

  An aspect of the present invention is the ultraviolet curable transparent resin composition, wherein the (A) carboxyl group-containing (meth) acrylic resin has a solid content acid value of 30 to 140 mgKOH / g.

  An aspect of the present invention is the ultraviolet curable transparent resin composition, wherein the double bond equivalent of the (A) carboxyl group-containing (meth) acrylic resin is 400 to 2500 g / mol.

  An embodiment of the present invention is an ultraviolet curable transparent resin composition further comprising (E) (meth) acrylated epoxy resin.

  An embodiment of the present invention is an ultraviolet curable transparent resin composition further comprising (F) (meth) acrylated urethane resin.

  An aspect of the present invention is a wiring board having an insulating film obtained by curing the ultraviolet curable transparent resin composition.

  In the embodiment of the present invention, the (A) carboxyl group-containing (meth) acrylic resin has a structural unit containing at least one aromatic ring and at least one phosphorus element in a part of its side chain. The group-containing (meth) acrylic resin is excellent in flame retardancy and resolution is not impaired. Further, in the embodiment of the present invention, in order to impart flame retardancy to the ultraviolet curable transparent resin composition, it is not necessary to add a flame retardant separately, so the haze of the cured product is increased and the bending resistance is decreased. As a result, excellent transparency can be obtained without impairing the bending resistance. That is, the cured product of the ultraviolet curable transparent resin composition containing a carboxyl group-containing (meth) acrylic resin has excellent flame resistance without impairing mechanical properties such as bending resistance and resolution. And has transparency.

  Next, the ultraviolet curable transparent resin composition of the present invention will be described. The ultraviolet curable transparent resin composition of the present invention comprises (A) (meth) acrylic acid and (meth) acrylic acid ester reacted with a part of the carboxyl group of the copolymer, an oxirane ring and an ethylenic group. A carboxyl group-containing (meth) acrylic resin obtained by adding a compound having an unsaturated bond, and further adding a phosphorus compound containing at least one aromatic ring to a part of the ethylenically unsaturated bond And (B) a photopolymerization initiator, (C) a diluent, and (D) an epoxy resin.

(A) Carboxyl group-containing (meth) acrylic resin Carboxyl group-containing (meth) acrylic resin is obtained by reacting (a-1) (meth) acrylic acid with (a-2) (meth) acrylic acid ester. (A-3) A compound having an oxirane ring and an ethylenically unsaturated bond is added to a part of the carboxyl group of the resulting copolymer, and further, (a -4) Obtained by adding a phosphorus compound containing at least one aromatic ring.

  In the carboxyl group-containing (meth) acrylic resin, (a-4) a structural unit containing at least one aromatic ring and at least one phosphorus element derived from a phosphorus compound containing at least one aromatic ring is a side chain. Therefore, the carboxyl group-containing (meth) acrylic resin has flame retardancy even if a flame retardant is not separately added. As a result, the ultraviolet curable transparent resin composition of the present invention has flame retardancy and transparency.

  (A-1) (Meth) acrylic acid means at least one of acrylic acid and methacrylic acid.

  (A-2) The (meth) acrylic acid ester is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, butyl (meth) acrylate, hydroxybutyl (meth) Acrylate, propyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate and isobornyl (meth) ) Aromatic (meth) acrylates such as alkyl (meth) acrylates such as acrylate, phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acrylate, dimethylaminoethyl Examples thereof include dialkylaminoalkyl (meth) acrylates such as (meth) acrylate and diethylaminoethyl (meth) acrylate, and N-acryloyloxyethyl hexahydrophthalimide. Among these, alkyl (meth) acrylate and phenoxyethyl (meth) acrylate are preferable from the viewpoint of imparting good bending resistance to the cured product of the ultraviolet curable transparent resin composition. These compounds may be used alone or in combination of two or more.

  Among the copolymers obtained by reacting (a-1) (meth) acrylic acid and (a-2) (meth) acrylic acid ester, the content of (a-1) (meth) acrylic acid (charging) The amount) is not particularly limited, but is preferably 20 to 70% by mass and particularly preferably 30 to 60% by mass from the viewpoint of imparting good bending resistance to the cured product of the ultraviolet curable transparent resin composition.

  (A-3) The compound having an oxirane ring and an ethylenically unsaturated bond is not particularly limited, but from the viewpoint of reactivity, the following general formulas (iiia), (iiib) and (iiic)

(Wherein R ¹ , R ³ , R ⁴ , R ⁷ and R ⁸ each independently represents a hydrogen atom or a methyl group, and R ² , R ⁵ , R ⁶ and R ⁹ are each independently Represents an alkylene group having 1 to 20 carbon atoms, R ² , R ⁶ and R ⁹ are preferably methylene groups, and R ⁵ is preferably an alkylene group having 2 to 10 carbon atoms, particularly preferably a butylene group. At least one selected is preferred.

  The content (preparation amount) of the compound having an oxirane ring and an ethylenically unsaturated bond is not particularly limited, but the lower limit is 10 in the carboxyl group-containing (meth) acrylic resin from the viewpoint of improving photosensitivity. % By mass is preferred, and 20% by mass is particularly preferred. On the other hand, the upper limit is preferably 50% by mass and particularly preferably 40% by mass in the carboxyl group-containing (meth) acrylic resin from the viewpoint of preventing sticking to the film during exposure.

  (A-4) The phosphorus compound containing at least one aromatic ring is not particularly limited as long as it contains at least one aromatic ring and at least one phosphorus element, but it contains a carboxyl group-containing (meth) acrylic resin. The above phosphorus compound having a plurality of aromatic rings is preferable, in that the ultraviolet curable transparent resin composition applied to the film is reliably prevented from sticking to the film during exposure, while imparting flame retardancy to the film. The above phosphorus compounds having two are particularly preferred. Examples of the phosphorus compound include the following general formula (i) and general formula (ii).

  (Wherein Z represents a substituent, l is an integer of 0 to 5, and m is an integer of 0 to 4).

  Z as a substituent is not particularly limited, but a group selected from an alkyl group, an alkoxy group, a phenyl group, and a halogen atom is preferable. When a plurality of Z are present, these may be the same as or different from each other. Regardless of the quantity and type of Z, the phosphorus compound having at least one aromatic ring is added to the side chain of the carboxyl group-containing (meth) acrylic resin, making it difficult for the carboxyl group-containing (meth) acrylic resin. While imparting flammability, the ultraviolet curable transparent resin composition applied during exposure can be prevented from sticking to the film.

  Examples of phosphorus compounds containing at least one aromatic ring include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (corresponding to m = 0 in general formula (i)), diphenylphosphine. Examples thereof include phosphine oxide compounds having active hydrogen such as fin oxide (corresponding to 1 = 0 in the general formula (ii)). These may be used alone or in combination of two or more.

  The content (preparation amount) of the phosphorus compound containing at least one aromatic ring is not particularly limited, but the lower limit value is that the carboxyl group-containing (metathesis) from the viewpoint of imparting flame retardancy to the ultraviolet curable transparent resin composition. ) 10% by mass is preferable in the acrylic resin, and 20% by mass is particularly preferable from the viewpoint of further improving flame retardancy. On the other hand, the upper limit value is preferably 40% by mass in the carboxyl group-containing (meth) acrylic resin from the viewpoint of suppressing the decrease in mechanical strength of the cured product of the ultraviolet curable transparent resin composition, and is soluble. Therefore, 30% by mass is particularly preferable.

  The phosphorus element content in the solid content of the carboxyl group-containing (meth) acrylic resin is selected according to the use conditions of the ultraviolet curable transparent resin composition. For example, the lower limit is 0.5% by mass from the viewpoint of reliably imparting flame retardancy to the carboxyl group-containing (meth) acrylic resin, and ensures sufficient flame retardancy for the ultraviolet curable transparent resin composition. 1.0 mass% is preferable from the point which performs, and 2.0 mass% is especially preferable from the point which satisfies VTM-0 which is a flame-retardant UL specification to an ultraviolet curable transparent resin composition reliably. Moreover, the upper limit is 10 mass% from the point which suppresses the fall of mechanical strength about the hardened | cured material of an ultraviolet curable transparent resin composition, for example, and 5.0 mass from the point which suppresses the fall of mechanical strength reliably. % Is preferable, and 4.0% by mass is particularly preferable from the viewpoint of compatibility in the ultraviolet curable transparent resin composition.

  The solid content acid value of the carboxyl group-containing (meth) acrylic resin is preferably from 30 to 140 mgKOH / g, particularly preferably from 60 to 130 mgKOH / g, from the viewpoint of completing the reaction with the epoxy resin. The double bond equivalent of the carboxyl group-containing (meth) acrylic resin is preferably from 400 to 2500 g / mol, particularly preferably from 500 to 1600 g / mol, from the viewpoints of ultraviolet curability and flexibility.

  The number average molecular weight of the carboxyl group-containing (meth) acrylic resin is preferably from 2,000 to 50,000, particularly preferably from 5,000 to 20,000, from the viewpoint of viscosity and coatability. Further, the weight average molecular weight is preferably from 5,000 to 100,000, particularly preferably from 14,000 to 50,000.

(B) Photopolymerization initiator The photopolymerization initiator is not particularly limited as long as it is generally used. For example, oxime initiators, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin -N-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane- 1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy -2-propyl) Ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2- Examples include ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4 diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, and P-dimethylaminobenzoic acid ethyl ester. These may be used alone or in combination of two or more.

  When ultraviolet light having a wavelength of 300 to 400 nm is irradiated to the ultraviolet curable transparent resin composition of the present invention, the photopolymerization initiator promotes photocuring of the ultraviolet curable transparent resin composition. The compounding quantity of a photoinitiator can be selected suitably, for example, 5-20 mass parts is preferable with respect to 100 mass parts of carboxyl group-containing (meth) acrylic-type resin, and 6-15 mass parts is especially preferable.

(C) Diluent diluent is, for example, a photopolymerizable monomer and a compound having at least two polymerizable double bonds per molecule. (A) It is used for obtaining a cured coating film having sufficient acid resistance, heat resistance, alkali resistance, etc. by sufficiently photocuring the carboxyl group-containing (meth) acrylic resin of the component.

  The diluent is not particularly limited as long as it is the above compound. For example, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol Di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene Oxide-modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol Rutri (meth) acrylate, dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol Examples include penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate. These may be used alone or in combination of two or more.

  The compounding quantity of a diluent can be suitably selected according to use conditions, for example, is 2-100 mass parts with respect to 100 mass parts of carboxyl group-containing (meth) acrylic-type resin, and 10-90 mass parts is. preferable.

( D) Epoxy resin Epoxy resin is used to increase the crosslink density of the cured product. The (D) component epoxy resin means an epoxy resin that is not (meth) acrylated, unlike the (E) component (meth) acrylated epoxy resin described later. Examples of the epoxy resin include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, novolak type epoxy resin (phenol novolak type epoxy resin, o-cresol novolak type epoxy resin, p-tert-butylphenol novolak type, etc.). Bisphenol F and bisphenol S epoxy resins obtained by reacting bisphenol F and bisphenol S with epichlorohydrin, alicyclic epoxy resins having a cyclohexene oxide group, a tricyclodecane oxide group, a cyclopentene oxide group, tris ( 2,3-epoxypropyl) isocyanurate, triglycidyl isocyanurate having a triazine ring such as triglycidyltris (2-hydroxyethyl) isocyanurate, Ropentajien type epoxy resins, adamantane type epoxy resin.

  The compounding quantity of an epoxy resin can be suitably selected according to use conditions, for example, is 10-50 mass parts with respect to 100 mass parts of carboxyl group containing (meth) acrylic-type resin.

  In the ultraviolet curable transparent resin composition of the present invention, in addition to the components (A) to (D), (E) (meth) acrylated epoxy resin, (F) (meth) acrylated urethane resin May be blended.

(E) (Meth) acrylated epoxy resin (Meth) acrylated epoxy resin is obtained by esterifying (meth) acrylic acid to an epoxy resin having two or more epoxy groups in one molecule. Partially esterified epoxy (meth) acrylate. The (meth) acrylated epoxy resin has a (meth) acryl group that can be radically polymerized by ultraviolet irradiation. Therefore, when a (meth) acrylated epoxy resin is blended with the ultraviolet curable transparent resin composition of the present invention, (meth) acrylated epoxy resins undergo a crosslinking reaction by ultraviolet irradiation, and the crosslinking density of the cured product is increased and the curability is increased. Can be further improved, and the flexibility of the cured product can be improved to give better bending resistance.

  The (meth) acrylated epoxy resin is not particularly limited, but is 50 to 100% equivalent of (meta) to the epoxy group of the epoxy resin with respect to the epoxy resin having at least two epoxy groups in one molecule. ) A (meth) acrylated epoxy resin obtained by esterifying acrylic acid is preferred, and a (meth) acrylated epoxy resin obtained by esterifying 80 to 100% equivalent of (meth) acrylic acid is particularly preferred. .

  Examples of the epoxy resin that is a synthetic raw material for the (meth) acrylated epoxy resin include bisphenol A type epoxy resins (bisphenol A type liquid epoxy resin, bisphenol A type modified flexible epoxy resin, nuclear hydrogenated bisphenol A type liquid epoxy resin). ), Novolak type epoxy resins (phenol novolak type epoxy resins, o-cresol novolak type epoxy resins, p-tert-butylphenol novolak type, etc.), bisphenol F type obtained by reacting bisphenol F or bisphenol S with epichlorohydrin, Bisphenol S type epoxy resin, cycloaliphatic epoxy resin having cyclohexene oxide group, tricyclodecane oxide group, cyclopentene oxide group, tris (2,3-epoxypropyl) iso Cyanurate, may be mentioned triglycidyl tris (2-hydroxyethyl) triglycidyl isocyanurate having a triazine ring such as isocyanurate, dicyclopentadiene type epoxy resins, adamantane type epoxy resin. Among these, bisphenol A type epoxy resin is preferable from the viewpoint of bending resistance. These compounds may be used alone or in combination of two or more.

  The blending amount of the (meth) acrylated epoxy resin can be appropriately selected depending on the use conditions, and imparts sufficient curability and bending resistance to 100 parts by mass of the carboxyl group-containing (meth) acrylic resin. For example, 1 to 75 parts by mass is preferable, and 3 to 50 parts by mass is particularly preferable.

(F) (Meth) acrylated urethane resin (F) (Meth) acrylated urethane resin may be urethane (meth) acrylate obtained by reacting (meth) acrylic acid with urethane resin. It is not limited. When a (meth) acrylated urethane resin is contained in an ultraviolet curable transparent resin composition, a cured coating film excellent in extensibility and bending resistance can be formed. For example, to a wiring board, particularly a flexible wiring board. Effective for application.

  The urethane resin is obtained by reacting a compound having two or more isocyanate groups in one molecule with a polyol compound having two or more hydroxyl groups in one molecule.

  The compound having two or more isocyanate groups in one molecule is not particularly limited, and examples thereof include hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), methylenebiscyclohexyl isocyanate, and trimethyl. Examples of the diisocyanate include hexamethyl diisocyanate, hexamethylamine diisocyanate, methylenebiscyclohexyl isocyanate, toluene diisocyanate, 1,2-diphenylethane diisocyanate, 1,3-diphenylpropane diisocyanate, diphenylmethane diisocyanate, and dicyclohexylmethyl diisocyanate. These compounds may be used alone or in combination of two or more.

The polyol compound having two or more hydroxyl groups in one molecule is not particularly limited. For example, ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2 -Butylene glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, neopentyl glycol, 1,6-hexanediol, 2,2- C ₂ − such as diethyl-1,3-propanediol, 3,3-dimethylolheptane, 2-ethyl-2-butyl-1,3-propanediol, 1,12-dodecanediol, 1,18-octadecanediol, etc. C ₂₂ or alkane diol, 2-butene-1,4-diol, 2,6-dimethyl-1-o Aliphatic diols such as alkene diols such as ten-3,8-diol; alicyclic diols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol; glycerin, 2-methyl-2-hydroxymethyl-1 , 3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, trimethylolethane, trimethylolpropane, 2-methyl-2-hydroxymethyl-1,3-propanediol Aliphatic triols such as 2,4-dihydroxy-3- (hydroxymethyl) pentane and 2,2-bis (hydroxymethyl) -3-butanol; and hydroxyl groups such as tetramethylolmethane, pentaerythritol, dipentaerythritol and xylitol Such as polyols with 4 or more It is. These compounds may be used alone or in combination of two or more.

  Examples of commercially available (meth) acrylated urethane resins include “purple light UV-1400B”, “purple light UV-1700B”, “purple light UV-6300B”, “purple light UV-” of Nippon Synthetic Chemical Co., Ltd. "7510B", "purple light UV-7600B", "purple light UV-7605B", "purple light UV-7610B", "purple light UV-7620EA", "purple light UV-7630B" and "purple light UV-7640B", Negami Kogyo "Art Resin UN-9000H", "Art Resin UN-3320HA", "Art Resin UN-3320HC", "Art Resin UN-3320HS" and "Art Resin UN-901T", Shin Nakamura Chemical Co., Ltd. NK Oligo U-4HA, NK Oligo U-6HA, NK Oligo U-6LPA, NK Oligo U-15 “A”, “NK Oligo UA-32P”, “NK Oligo U-324A” and “NK Oligo U-6H”, “EBECRYL1204”, “EBECRYL1205”, “EBECRYL215”, “EBECRYL230” from Daicel Cytec Co., Ltd. "EBECRYL244", "EBECRYL245", "EBECRYL264", "EBECRYL965", "EBECRYL845Y", "EBECRYL8405", "EBECRYL8405" ”,“ EBECRYL1290 ”,“ EBECRYL1290K ”,“ EBECRYL5129 ”,“ EBECRYL 10 ”,“ EBECRYL220 ”,“ EBECRYL284 ”,“ EBECRYL8210 ”,“ EBECRYL8402 ”and“ EBECRYL9260 ”, Nippon Kayaku Co., Ltd.“ UX-2201 ”,“ UX-2301 ”,“ UX-3204 ”,“ UX ” -3301 "," UX-4101 "," UX-0937 "," UX-5000 "," UX-5001 "," UX-5002 "," Beamset 575 "from Arakawa Chemical Industries, Toagosei ( "M-313", "M-315" and "M-1200" of Kyoeisha Chemical Co., Ltd.

  The skeleton of the (meth) acrylated urethane resin is not particularly limited, but those having a large number of (meth) acryl functional groups may cure and shrink and the elongation may decrease, so the number of (meth) acryl functional groups in one molecule Is preferably 2-4. Moreover, since the weight average molecular weight tends to easily adhere to the substrate of the artwork film at the time of exposure when the value is small, it becomes difficult to obtain the intended cured coating film, so the lower limit is preferably 1500, Since the bending resistance tends to decrease when the weight average molecular weight is large, the upper limit is preferably 3000.

  The blending amount of the (meth) acrylated urethane resin can be appropriately selected depending on the use conditions, and is, for example, 1 to 40 parts by mass with respect to 100 parts by mass of the carboxyl group-containing (meth) acrylic resin, and high elongation. 2 to 25 parts by mass is preferable from the viewpoint of excellent balance between resistance and bending resistance. In addition, in order to obtain the cured coating film excellent in bending resistance, you may mix | blend (meth) acrylate urethane resin with the said (meth) acrylate epoxy resin.

  In addition to the components (A) to (F) described above, the ultraviolet curable transparent resin composition of the present invention may further include a phosphorus compound and various additive components, for example, various additives, as necessary. Further, a solvent or the like can be contained. In addition, the ultraviolet curable transparent resin composition of the present invention does not contain a colorant in order to prevent the transparency from being impaired, but when coloring in a desired color, a coloring pigment is appropriately used. You may mix | blend coloring agents, such as.

  As described above, the ultraviolet curable transparent resin composition of the present invention is imparted with flame retardancy. However, in order to supplement the flame retardancy and improve the flame retardancy, transparency and folding resistance are improved. You may add a phosphorus compound in the range of the compounding quantity which does not impair a curvature.

  Examples of phosphorus compounds include tris (chloroethyl) phosphate, tris (2,3-dichloropropyl) phosphate, tris (2-chloropropyl) phosphate, tris (2,3-bromopropyl) phosphate, tris (bromochloropropyl) Halogen-containing phosphates such as phosphate, 2,3-dibromopropyl-2,3-chloropropyl phosphate, tris (tribromophenyl) phosphate, tris (dibromophenyl) phosphate, tris (tribromoneopentyl) phosphate; trimethyl Non-halogen aliphatic phosphates such as phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triallyl phosphine; Sulfate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, tricresyl phosphate, trixylenyl phosphate, xylenyl diphenyl phosphate, tris (isopropylphenyl) phosphate, isopropylphenyl diphenyl phosphate, diisopropylphenylphenyl phosphate, tris (trimethylphenyl) Phosphate, tris (t-butylphenyl) phosphate, hydroxyphenyl diphenyl phosphate, octyl diphenyl phosphate, 3-glycidyloxypropylene diphenylphosphine oxide, 3-glycidyloxydiphenylphosphine oxide, diphenylvinylphosphine oxide, 2- (9,10-dihydro -9-oxa-10-oxide-10-fo Non-halogen aromatic phosphoric acid ester such as phaphenanthrene-10-yl) methyl succinic acid bis- (2-hydroxyethyl) -ester polymer; aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, Zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, zinc bisdiphenylphosphinate, titanyl bisdiethylphosphinate, titanium tetrakisdiethylphosphinate, titanyl bismethylethylphosphinate, titanium tetrakismethylethylphosphinate, titanyl bisdiphenylphosphinate And metal salts of phosphinic acid such as titanium tetrakisdiphenylphosphinate.

  When using phosphoric acid ester as a phosphorus compound, the upper limit of the compounding quantity of a phosphorus compound is 12 mass parts from the point which prevents transparency being impaired with respect to 100 mass parts of carboxyl group-containing (meth) acrylic resins. And 10 parts by mass is preferable from the viewpoint of surely suppressing deterioration of transparency and bending resistance. On the other hand, when a metal salt of phosphinic acid is used as the phosphorus compound, the upper limit of the blending amount is 10 from the viewpoint of preventing transparency from being impaired with respect to 100 parts by mass of the carboxyl group-containing (meth) acrylic resin. 8 parts by mass is preferable because it is a part by mass and reliably suppresses the decrease in transparency and bending resistance.

  Various additives include an antifoaming agent mainly composed of a vinyl polymer, an antifoaming agent mainly composed of an acrylic polymer, and a leveling agent composed mainly of a mixture of polyether-modified polydimethylsiloxane and polyether. .

  The solvent is used to adjust the viscosity and drying property of the ultraviolet curable transparent resin composition. Examples of the solvent include ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, isopropanol and cyclohexanol, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, Petroleum solvents such as petroleum ether and petroleum naphtha, cellosolves such as cellosolve and butylcellosolve, carbitols such as carbitol and butylcarbitol, ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, diethylene glycol mono Examples thereof include acetates such as ethyl ether acetate and butyl carbitol acetate. The amount of the solvent used is preferably 1 to 500 parts by weight with respect to 100 parts by weight of the carboxyl group-containing (meth) acrylic resin.

  The colorant is not particularly limited as long as it does not lose transparency, and when it is colored white, black, blue, yellow, etc., the white colorant, black colorant, blue You may mix | blend a coloring agent, a yellow coloring agent, etc.

  Although the manufacturing method of the above-mentioned ultraviolet curable transparent resin composition of the present invention is not limited to a specific method, for example, after blending the above components (A) to (D) and other components at a predetermined ratio as necessary. It can be produced by kneading or mixing at room temperature with a kneading means such as a three-roll, ball mill or sand mill, or a stirring means such as a super mixer or a planetary mixer. Further, prior to the kneading or mixing, if necessary, preliminary kneading or premixing may be performed.

  Next, the coating method of the above-mentioned ultraviolet curable transparent resin composition of the present invention will be described. Here, a method of forming a film by coating the ultraviolet curable transparent resin composition of the present invention on a flexible substrate, more specifically, on a flexible wiring board having a circuit pattern formed by etching a copper foil Next, a method for forming the insulating film by applying the ultraviolet curable transparent resin composition of the present invention will be described as an example. On a flexible wiring board having a circuit pattern formed by etching a copper foil, the ultraviolet curable transparent resin composition produced as described above is formed to a desired thickness using a method such as a screen printing method or a spray coating method. Apply. Next, when a solvent is blended in the ultraviolet curable transparent resin composition, preliminary drying is performed by heating at a temperature of about 60 to 80 ° C. for about 15 to 60 minutes in order to volatilize the solvent. The solvent is volatilized from the transparent resin composition to make the surface of the coating film tack-free.

  Then, the negative film which has the pattern which made translucent except the land of the said circuit pattern is closely_contact | adhered on the apply | coated ultraviolet curable transparent resin composition, and an ultraviolet-ray is irradiated from it. Then, the coating film is developed by removing a non-exposed area corresponding to the land with a dilute alkaline aqueous solution. As the developing method, for example, a known method such as a spray method or a shower method can be appropriately used. Examples of the diluted alkaline aqueous solution used include 0.5 to 5% sodium carbonate aqueous solution. After the development, the target insulating film can be formed on the flexible wiring board by curing for 20 to 80 minutes with a hot air circulating dryer or the like at 130 to 170 ° C.

  Next, examples of the present invention will be described. However, the present invention is not limited to these examples as long as the gist thereof is not exceeded.

(A) Carboxyl group-containing (meth) acrylic resin Physical property measurement conditions The phosphorus element content in the solid content was calculated from the theoretical value of the amount of each component as a raw material. The solid content acid value is determined by first measuring the solid content acid value of (A) carboxyl group-containing (meth) acrylic resin by the phenolphthalein discoloration method based on alkali neutralization titration, and then (A) carboxyl group content It calculated by drying (meth) acrylic-type resin at 150 degreeC for 2 hours, and multiplying the solid content ratio calculated | required from the mass ratio before and behind drying. The double bond equivalent was calculated by (A) the solid content mass (g) of the carboxyl group-containing (meth) acrylic resin / the number of moles of the compound having an oxirane ring and an ethylenically unsaturated bond (g / mol).
2. The weight average molecular weight was measured as follows.
It measured using the Tosoh GPC apparatus. The measurement conditions are as follows.
Column: TSK gel (manufactured by Tosoh Corporation, "SuperH4000", "SuperHZ2500")
Detector: Differential refraction Solvent: Tetrahydrofuran Solute concentration: 10 mg / ml
Standard material: Standard polystyrene (manufactured by VARIAN, "EASICAL PS-2" (monodisperse sample))
Flow rate: 0.3 ml / min
Temperature: 40 ° C

  Synthesis of (A) carboxyl group-containing (meth) acrylic resin synthesis examples (A-1) to (A-3) and comparative synthesis example (A-4) of the comparative resin will be described with reference to Table 1.

Synthesis example 1
Into a 1 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, nitrogen or air introduction tube, 550 g of dipropylene glycol monomethyl ether (DPM manufactured by Sanyo Chemicals Co., Ltd.) was charged, and 100 ° C. under a nitrogen atmosphere. , Methacrylic acid (corresponding to “a-1” component) 120 g, phenoxyethyl methacrylate (corresponding to “a-2” component) 20 g, 2-hydroxyethyl methacrylate “corresponding to“ a-2 ”component) 30 g, A solution in which 30 g of isobornyl methacrylate (corresponding to “a-2” component) and 20 g of dimethyl 2,2′-azobis (2-methylpropionate) (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) was mixed for 3 hours The reaction was continued and aged in a nitrogen atmosphere for 3 hours after the addition. Next, 150 g of 4-hydroxybutyl acrylate glycidyl ether (corresponding to “a-3” component) (manufactured by Nippon Kasei Co., Ltd. (4HBAGE)), 1.0 g of triphenylphosphine, and 0.3 g of methoxyphenol in an air atmosphere. In addition, the reaction was carried out at 110 ° C. for 8 hours. Further, 100 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (corresponding to “a-4” component) (manufactured by Sanko Co., Ltd. (HCA)) was added and reacted at 110 ° C. for 3 hours. It was. Thus, a solution of a carboxyl group-containing (meth) acrylic resin having a solid content acid value of 80.5 mgKOH / g, a double bond equivalent of 1567.7 g / mol, a phosphorus element content of 3.2 mass%, and a weight average molecular weight of 18,000 ( A-1) was obtained.

Synthesis example 2
Into a 1 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, nitrogen or air introduction tube, 550 g of dipropylene glycol monomethyl ether (DPM manufactured by Sanyo Chemicals Co., Ltd.) was charged, and 100 ° C. under a nitrogen atmosphere. After raising the temperature, acrylic acid (corresponding to “a-1” component) 130 g, phenoxyethyl methacrylate (corresponding to “a-2” component) 20 g, 4-hydroxybutyl acrylate (corresponding to “a-2” component) 20 g 3 solutions of 20 g of isobornyl methacrylate (corresponding to “a-2” component) and 20 g of dimethyl 2,2′-azobis (2-methylpropionate) (V-601 manufactured by Wako Pure Chemical Industries, Ltd.) The solution was added dropwise over a period of time, and after the addition, the reaction was continued and aged for 3 hours in a nitrogen atmosphere. Next, 150 g of 4-hydroxybutyl acrylate glycidyl ether (corresponding to “a-3” component) (manufactured by Nippon Kasei Co., Ltd. (4HBAGE)), 1.0 g of triphenylphosphine, and 0.3 g of methoxyphenol in an air atmosphere. In addition, the reaction was carried out at 110 ° C. for 8 hours. Furthermore, 110 g of diphenylphosphine oxide (corresponding to “a-4” component) (manufactured by Katayama Chemical Co., Ltd. (OX-2)) was added and reacted at 110 ° C. for 3 hours. Thus, a solution of a carboxyl group-containing (meth) acrylic resin having a solid content acid value of 131.6 mgKOH / g, a double bond equivalent of 2190.4 g / mol, a phosphorus element content of 3.7% by mass, and a weight average molecular weight of 14,000 ( A-2) was obtained.

Synthesis example 3
Into a 1 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, nitrogen or air introduction tube, 550 g of dipropylene glycol monomethyl ether (DPM manufactured by Sanyo Chemicals Co., Ltd.) was charged, and 100 ° C. under a nitrogen atmosphere. After the temperature rises, 130 g of methacrylic acid (corresponding to “a-1” component), 10 g of phenoxyethyl methacrylate (corresponding to “a-2” component), 20 g of 2-hydroxyethyl methacrylate (corresponding to “a-2” component) N-acryloyloxyethylhexahydrophthalimide (corresponding to “a-2” component) (M-140 manufactured by Toa Gosei Co., Ltd.) and dimethyl 2,2′-azobis (2-methylpropionate) ( A solution in which 20 g of Wako Pure Chemical Industries, Ltd. (V-601) was mixed was added dropwise over 3 hours, and after the dropwise addition, the reaction was continued and aged in a nitrogen atmosphere for 3 hours. Next, glycidyl methacrylate (corresponding to “a-3” component) (Blenmer GH manufactured by NOF Corporation) 80 g, 4-hydroxybutyl acrylate glycidyl ether (corresponding to “a-3” component) in an air atmosphere ( Nippon Kasei Co., Ltd. 4HBAGE) 90g, triphenylphosphine 1.0g, and methoxyphenol 0.3g were added, and it was made to react at 110 degreeC for 8 hours. Furthermore, 95 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (corresponding to “a-4” component) (HCA manufactured by Sanko) was added and reacted at 110 ° C. for 3 hours. Thus, a solution of a carboxyl group-containing (meth) acrylic resin having a solid content acid value of 62.1 mg KOH / g, a double bond equivalent of 784.6 g / mol, a phosphorus element content of 3.0 mass%, and a weight average molecular weight of 24,000 ( A-3) was obtained.

Comparative Synthesis Example A 1 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, nitrogen or air introduction tube was charged with 550 g of dipropylene glycol monomethyl ether (DPM manufactured by Sanyo Chemicals), and a nitrogen atmosphere After raising the temperature to 100 ° C., a solution in which 110 g of methacrylic acid, 250 g of butyl methacrylate, and 20 g of dimethyl 2,2′-azobis (2-methylpropionate) (V-601 manufactured by Wako Pure Chemical Industries, Ltd.) was mixed for 3 hours. The reaction was continued and aged in a nitrogen atmosphere for 3 hours after the addition. Next, 90 g of glycidyl methacrylate, 1.0 g of triphenylphosphine, and 0.3 g of methoxyphenol were added in an air atmosphere and reacted at 110 ° C. for 8 hours. As a result, a solution (A-4) of a carboxyl group-containing (meth) acrylic resin having a solid content acid value of 80.4 mgKOH / g, a double bond equivalent of 710.0 g / mol, and a weight average molecular weight of 21,000 was obtained.

Examples 1 to 23, Comparative Examples 1 to 4
Ultraviolet rays used in Examples 1 to 23 and Comparative Examples 1 to 4 by mixing the components shown in Table 2 below at the mixing ratios shown in Table 2 below and mixing and dispersing at room temperature using three rolls. A curable transparent resin composition was prepared. In addition, the compounding quantity shown in following Table 2 represents a mass part.

In Table 2, the carboxyl group-containing ultraviolet curable resin having no phosphorus element used in the comparative example is as follows.
Cyclomer P-ACA-Z251: Daicel-Cytec Co., Ltd., unsaturated group-containing acrylic resin.
ZFR-1122: Nippon Kayaku Co., Ltd. product, acrylic ester oligomer (epoxy acrylate anhydride modified product), diethylene glycol monoethyl ether acetate, methyl hydroquinone mixture.

Each component in Table 2 other than the above is as follows.
(B) Photopolymerization initiator, Irgacure 184: 1-hydroxy-cyclohexyl-phenyl-ketone manufactured by Ciba Specialty Chemicals.
Irgacure 1173: 2-hydroxy-2-methyl-1-phenyl-propan-1-one manufactured by Ciba Specialty Chemicals.
Irgacure 2529: 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one manufactured by Ciba Specialty Chemicals Co., Ltd.
(C) Diluent / light ester 2EG: manufactured by Kyoeisha Chemical Co., Ltd., diethylene glycol dimethacrylate.
M-306: manufactured by Toagosei Co., Ltd., pentaerythritol triacrylate.
DPHA: Nippon Kayaku Co., Ltd. product, reaction product of dipentaerythritol and acrylic acid.
(D) Epoxy resin / JER828: manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin.
-JER837: manufactured by Mitsubishi Chemical Corporation, bisphenol F type epoxy resin.
-JER1003: Mitsubishi Chemical Corporation, bisphenol A type solid epoxy resin.

(E) (Meth) acrylated epoxy resin / EBECRYL 3708: manufactured by Daicel-Cytec Co., Ltd., a mixture of epoxy acrylate and 2-hydroxyethyl acrylate.
-Miramer PE110: manufactured by MIWON, phenyl epoxy acrylate.
-Miramer PE250: manufactured by MIWON, bisphenol A type epoxy dimethacrylate.
(F) (Meth) acrylated urethane resin. EBECRYL 8405: Urethane acrylate, manufactured by Daicel-Cytec.
* M-1200: Toagosei Co., Ltd. urethane acrylate.
AH-600: Phenylglycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer manufactured by Kyoeisha Chemical Co., Ltd.

Phosphorus compound (flame retardant)
Diphenyl vinyl phosphine oxide: manufactured by Katayama Chemical Co., Ltd.
ME-P8: manufactured by Sanko Co., Ltd., 2- (9,10-dihydro-9-oxa-10-oxide-10-phosphaphenanthrene-10-yl) methylsuccinic acid bis- (2-hydroxyethyl) -ester Polymer.
Exolit OP 935: manufactured by Clariant Japan Co., Ltd., organophosphate.
Additive: UVX-189: A vinyl polymer produced by Enomoto Chemical Co., Ltd.
・ Polyflow No. 90: Acrylic polymer manufactured by Kyoeisha Chemical Co., Ltd.
BYK-361N: manufactured by Big Chemie Japan Co., Ltd., acrylic polymer.
BYK-307: A mixture of polyether-modified polydimethylsiloxane and polyether, manufactured by Big Chemie Japan Co., Ltd.
Colored pigment, Lionol Blue FG-7351: a phthalocyanine compound manufactured by Toyo Ink Co., Ltd.
Chromophthal yellow AGR: Anthraquinone compound manufactured by Ciba Specialty Chemicals.
Solvent / diethylene glycol monoethyl ether acetate: manufactured by Shinko Organic Chemical Industry Co., Ltd.

Test piece preparation process After the surface of the transparent polyimide film (Mitsubishi Gas Chemical Co., Ltd., thickness 30 μm) was degreased with isopropyl alcohol, the UV-cured surface was prepared as described above by screen printing on the degreased surface. The transparent resin composition was applied. After coating, preliminary drying was performed in a BOX furnace at 80 ° C. for 20 minutes (25 minutes in the BOX furnace). After pre-drying, a photomask having a pattern in which a part other than a predetermined land is made to be translucent is brought into intimate contact with the coating film, and ultraviolet rays (wavelength 300 to 450 nm) are applied thereon with an exposure device (HMW-680GW manufactured by Oak Co.). The exposure was performed up to 1000 mJ / cm ² . Then, after developing under a condition of 0.1 MPa for 60 seconds using a 1% sodium carbonate developer at 30 ° C., post-cure was performed at 150 ° C. for 60 minutes (70 minutes in the BOX furnace) in a BOX furnace. A cured coating film of an ultraviolet curable transparent resin composition was formed on a PET film. The DRY film thickness of the cured coating film was 20 to 23 μm.

Evaluation (1) Haze (cloudiness value) (%)
In place of the transparent polyimide film, a cured coating film was formed on the surface of a quartz glass substrate (50 mm × 50 mm, thickness 1 mm) by the same method as in the test piece preparation step to obtain a test piece. The haze of the test piece was measured using a U-3310 spectrophotometer manufactured by Hitachi High-Tech, in accordance with JIS-K-7105 and JIS-K-7136.
(2) Resolution With respect to the cured coating film prepared as described above using a photomask having a pattern with a line width of 30 to 150 μm, the minimum line width completely remaining on the substrate as a line is visually observed. Confirmed and evaluated.
(3) Bending resistance
For the test piece created in the above-mentioned test piece creation step, 180 ° bending is repeated several times by goby folding, and the crack occurrence state in the transparent cured coating at that time is observed visually and with a × 200 optical microscope, The number of times that no crack occurred was measured.
(4) Flame retardancy Instead of a transparent polyimide film, a cured coating film having a DRY film thickness of 20 μm is formed on both surfaces of a polyimide substrate (15 mm × 25 mm, thickness 25 μm) in the same manner as in the above test piece preparation step. To form a test piece. A vertical combustion test based on the UL94 standard was performed on this test piece. Evaluation was expressed as VTM-0 to combustion based on the UL94 standard.
(5) Insulation resistance (Ω)
Instead of the PET film, a comb-like test pattern (line width: 100 μm, line spacing: 100 μm) was applied by the same method as in the test piece preparation step to form a cured coating film, which was used as a test piece. The test piece was applied with a direct current of 50 V in a tank having a temperature of 85 ° C. and a humidity of 85% and allowed to stand for 1000 hours, and then the test piece was taken out of the tank and the insulation resistance value was measured.

  The evaluation results are shown in Table 3.

  As shown in the results of Examples and Comparative Examples in Table 3 above, when a carboxyl group-containing (meth) acrylic resin obtained by adding a phosphorus compound containing at least one aromatic ring is used, bending resistance is achieved. A cured coating film having good transparency with reduced haze was obtained while having flame retardancy without impairing properties, resolution, and insulation. When (meth) acrylated epoxy resin was blended from Examples 13 to 15 and (meth) acrylated urethane resin was blended from Examples 16 to 18, the bending resistance was further improved without impairing transparency. Moreover, by not adding the phosphorus compound which is a flame retardant from Examples 1-9 and 13-23, the fall of bending resistance could be prevented reliably and the bending resistance and transparency improved with good balance.

  On the other hand, from Comparative Examples 2 to 4, when a carboxyl group-containing ultraviolet curable resin having no phosphorus element is used and a phosphorus compound that is a flame retardant is blended, the flame haze is improved, but the haze is increased and good. Transparency could not be obtained. From Comparative Example 1, a carboxyl group-containing ultraviolet curable resin that does not have a phosphorus element is used, and if a phosphorus compound that is a flame retardant is not blended, it has transparency and can prevent a decrease in bending resistance. Could not get flame retardant.

  Since the ultraviolet curable transparent resin composition of the present invention can form a cured product excellent in transparency and flame retardancy without impairing various properties such as bending resistance and resolution, for example, a wiring board High utility value in the field of insulating films and protective films for touch panels.

Claims (8)

(A) After adding a compound having an oxirane ring and an ethylenically unsaturated bond to a part of the carboxyl group of the copolymer obtained by reacting (meth) acrylic acid and (meth) acrylic acid ester, A carboxyl group-containing (meth) acrylic resin obtained by adding a phosphorus compound containing at least one aromatic ring to a part of the ethylenically unsaturated bond;
(B) a photopolymerization initiator;
(C) a diluent,
(D) An ultraviolet curable transparent resin composition comprising an epoxy resin. The phosphorus compound containing at least one aromatic ring is represented by the general formula (i) or the general formula (ii).

The ultraviolet curable transparent resin composition according to claim 1, wherein Z represents a substituent, l is an integer of 0 to 5, and m is an integer of 0 to 4. .   The ultraviolet curable transparent resin composition according to claim 1 or 2, wherein the (A) carboxyl group-containing (meth) acrylic resin contains 0.5 to 10% by mass of a phosphorus element in a solid content. .   4. The ultraviolet curable transparent resin according to claim 1, wherein the (A) carboxyl group-containing (meth) acrylic resin has a solid content acid value of 30 to 140 mgKOH / g. 5. Composition.   5. The ultraviolet curable transparent resin according to claim 1, wherein the (A) carboxyl group-containing (meth) acrylic resin has a double bond equivalent of 400 to 2500 g / mol. Composition.   The ultraviolet curable transparent resin composition according to any one of claims 1 to 5, further comprising (E) (meth) acrylated epoxy resin.   Furthermore, (F) (meth) acrylation urethane resin is contained, The ultraviolet curable transparent resin composition of any one of the Claims 1 thru | or 6 characterized by the above-mentioned.   The wiring board which has an insulating film obtained by hardening | curing the ultraviolet curable transparent resin composition of any one of Claims 1 thru | or 7.