KR20210153328A - Solder resist resin composition, solder resist structure, dry film, and printed wiring board - Google Patents

Abstract

The present invention relates to a resin composition having excellent dispersity, sedimentation stability, and agglomeration stability. Furthermore, the present invention relates to a solder resist structure, a dry film, and a printed wiring board. The solder resist structure is formed of the resin composition and exhibits high average reflectance and reflectance at a wavelength of 450 nm before and after a reflow process without requiring a reflector. According to the present invention, a photosensitive resin composition and a thermosetting resin composition comprise: (B) rutile titanium oxide; (C) a phosphor; and (D) a colorant, wherein the (C) a phosphor is coated with the (D) a colorant.

Description

Solder resist resin composition, solder resist structure, dry film, and printed wiring board {SOLDER RESIST RESIN COMPOSITION, SOLDER RESIST STRUCTURE, DRY FILM, AND PRINTED WIRING BOARD}

The present invention relates to a solder resist resin composition having excellent dispersion, sedimentation stability, and cohesive stability. In addition, the present invention relates to a solder resist structure formed from the above solder resist resin composition and exhibiting high average reflectance before and after a reflow process and a high reflectance at a wavelength of 450 nm without a reflector, a dry film, and a printed wiring board.

Conventionally, in a printed wiring board, as a protective film for preventing the adhesion of solder to a necessary part and for preventing the conductor of the circuit from being exposed and corroded by oxidation or moisture, except for the connection hole on the board on which the circuit pattern is formed. In the region, a solder resist structure was formed. Since a soldering resist structure also functions as a permanent protective film of a circuit board, it was calculated|required by a soldering resist composition to be equipped with various performances, such as alkali developability and solder heat resistance. In addition, dry to touch properties (non-tackiness) were also required for the dry coating film formed from the solder resist composition.

Moreover, in the case of a white soldering resist structure, while having a high reflectance in addition to the required characteristic as a soldering resist structure, it becomes important that yellowing of hardened|cured material does not generate|occur|produce by exposure to heat or light.

Patent Document 1 discloses a printed wiring board comprising a layer made of a white alkali developing type photosensitive resin composition and a layer made of a white thermosetting resin composition provided so as to overlap this layer as an invention for providing a printed wiring board having a high reflectance. are doing However, in spite of using a coating film having a thickness of 60 µm (30 µm for each layer), the average reflectance is only 91%. In addition, since it is necessary to manufacture a thick coating film, it is not economical and has a problem in that it may be vulnerable to crack resistance in a post-process.

Patent Document 2 uses a curable resin composition including a white colorant and a light excitable inorganic filler and attempts to implement a high reflectance coating film by optimizing the pH of the resin composition. However, since the photo-excitable inorganic filler has ^{a light emission lifetime of 10 -7} seconds to several minutes, there is a problem that an afterglow may remain, and it is inconvenient to have to treat the surface with an acidic liquid. In addition, the photo-excitable inorganic filler is highly likely to be decomposed during the reflow process, thereby reducing the reflectance.

Patent Document 3 intends to form a solder resist structure having high light reflectivity by providing a solder resist composition containing a photosensitive resin, a white pigment, a photopolymerization initiator activated by light having a wavelength of 400 nm or more, and a fluorescent dye. However, it is unclear whether the average reflectance and reflectance at a wavelength of 450 nm can be maintained high even after the solder resist structure undergoes a reflow process.

Since the conventional solder resist structure including a layer made of a photosensitive resin composition and a layer made of a thermosetting composition has a low reflectance at a wavelength of 450 nm, it was necessary to use a reflector when applied to a backlight unit of an OLED display. However, due to the inclusion of the reflector, the manufacturing process of the OLED display is complicated and there is a problem that a lot of cost is consumed.

Laid-Open Patent Publication No. 10-2011-0023798 Laid-open Patent Publication No. 10-2016-0042151 Japanese Patent Publication No. 5513965

An object of the present invention is a solder resist resin composition having excellent dispersion, sedimentation stability, and cohesive stability, and a solder resist formed from the resin composition and exhibiting high average reflectance before and after the reflow process and reflectance at 450 nm wavelength without a reflector To provide a structure, a dry film, and a printed wiring board.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said subject could be solved with the following soldering resist resin composition, a soldering resist structure, a dry film, and a printed wiring board.

<1> (A-1) photosensitive resin, (B) rutile-type titanium oxide, (C) a phosphor, and (D) a colorant are included, The resin composition characterized by the above-mentioned.

<2> (A-2) A resin composition comprising a thermosetting resin, (B) rutile titanium oxide, (C) a phosphor, and (D) a colorant.

<3> The resin composition of the phosphor (C) having an absorption peak of 440 nm or less and an emission peak of 445 to 455 nm.

<4> The (C) phosphor is 1,4-bis(2-benzooxazolyl)naphthalene and 4,4'-bis[2-(2-methoxyphenyl)ethenyl]-1,1'-biphenyl A resin composition comprising at least one of.

<5> A resin composition comprising 0.01 to 3% by mass of the phosphor (C) based on the total composition.

<6> the (D) colorant is 1,4-bis(butylamino)anthracene-9,10-dione, 2,2'-bis(2,3-dihydro-3-oxoindolyldene) and 3; A resin composition comprising at least one of 7-bis(dimethylamino)phenothiazine-5-ium chloride.

<7> A resin composition comprising 0.001 to 1 mass % of the (D) colorant based on the total composition.

<8> A solder resist structure including one or more layers, the solder resist structure comprising at least one photosensitive resin layer made of the photosensitive resin composition.

<9> When the solder resist structure including at least one photosensitive resin layer is a single layer, the thickness of the solder resist structure is 10 to 60 µm.

<10> When the solder resist structure including at least one photosensitive resin layer is a multilayer, each layer has a thickness of 10 to 60 µm independently.

<11> A solder resist structure comprising one or more layers, the solder resist structure comprising at least one thermosetting resin layer made of the thermosetting resin composition.

<12> When the solder resist structure including at least one thermosetting resin layer is a single layer, the thickness of the solder resist structure is 10 to 60 µm.

<13> When the solder resist structure including at least one thermosetting resin layer is a multilayer, the upper layer is a thermosetting resin layer, and the thickness of each layer is independently 10 to 60 μm.

<14> A solder resist structure comprising a photosensitive resin layer made of the photosensitive resin composition and a thermosetting resin layer made of the thermosetting resin composition, wherein the thermosetting resin layer is positioned above the photosensitive resin layer.

<15> The thickness of the photosensitive resin layer is 10 to 60 µm, and the thickness of the thermosetting resin layer is 10 to 60 µm, the solder resist structure.

<16> A dry film obtained by coating and drying any one of the above resin compositions.

<17> A printed wiring board comprising any one of the above solder resist structures.

The solder resist resin composition of the present invention has excellent dispersion, sedimentation stability and cohesive stability, and the solder resist structure, dry film and printed wiring board formed from the resin composition have average reflectance before and after the reflow process and at a wavelength of 450 nm. Since the reflectance is high, when applied to the backlight unit of an OLED display, it is possible to efficiently reflect the LED light without a reflector.

1 shows UV-VIS absorption spectra of a phosphor and a fluorescent particle.
2 shows fluorescence spectra of a phosphor and a fluorescent particle.
3 schematically shows the structure of a single-layer coating film formed from a photosensitive resin composition ink or a thermosetting resin composition ink (thickness of the coating film after drying: 25 µm).
4 schematically shows the structure of a multilayer coating film including a resin layer formed from a photosensitive resin composition ink and/or a resin layer formed from a thermosetting resin composition ink (thickness of the coating film after drying: upper layer 25 μm, lower layer 25 μm) .
5 shows the results of measurement of fluorescence images of the multilayer coating films of Comparative Example 1 and Examples 1 to 3 of the present invention before and after the reflow process.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

In the present invention, a resin composition comprising (A-1) photosensitive resin, (B) rutile titanium oxide, (C) phosphor, and (D) colorant is described as “photosensitive resin composition”. In the present invention, the resin composition comprising (A-2) thermosetting resin, (B) rutile titanium oxide, (C) phosphor, and (D) colorant is described as “thermosetting resin composition”. In the present invention, a resin composition including the photosensitive resin composition and the thermosetting resin composition is referred to as a "solder resist resin composition".

photosensitive resin

The photosensitive resin composition of this invention may contain (A-1) photosensitive resin.

(A-1) As photosensitive resin, what is necessary is just resin which hardens|cures by active energy ray irradiation and shows electrical insulation, In particular, in this invention, the compound which has one or more ethylenically unsaturated bond in a molecule|numerator is used preferably.

As a compound which has an ethylenically unsaturated bond, a well-known and usual photopolymerizable oligomer, a photopolymerizable vinyl monomer, etc. are used. Among these, as a photopolymerizable oligomer, an unsaturated polyester type oligomer, a (meth)acrylate type oligomer, etc. are mentioned. Examples of the (meth)acrylate oligomer include epoxy (meth)acrylates such as phenol novolac epoxy (meth)acrylate, cresol novolac epoxy (meth)acrylate, and bisphenol type epoxy (meth)acrylate, urethane (meth) Acrylate, epoxy urethane (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polybutadiene modified (meth)acrylate, etc. are mentioned.

As a photopolymerizable vinyl monomer, A well-known and usual thing, For example, Styrene derivatives, such as styrene, chlorostyrene, (alpha)-methylstyrene; vinyl esters such as vinyl acetate, vinyl butyrate, or vinyl benzoate; Vinyl isobutyl ether, vinyl-n-butyl ether, vinyl-t-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl vinyl ethers such as ether and triethylene glycol monomethyl vinyl ether; (acrylamide, methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-butoxymethylacrylamide, etc.) meth)acrylamides; allyl compounds such as triallyl isocyanurate, diallyl phthalate, and diallyl isophthalate; 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) esters of (meth)acrylic acid such as acrylates; hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and pentaerythritol tri(meth)acrylate; Alkoxyalkylene glycol mono(meth)acrylates, such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate; Ethylene glycol di(meth)acrylate, butanediol di(meth)acrylates, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate , pentaerythritol tetra(meth)acrylate, and alkylene polyol poly(meth)acrylates such as dipentaerythritol hexa(meth)acrylate; Polyoxyalkylene glycol poly(es) such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated trimethylolpropane tri(meth)acrylate meth) acrylates; poly(meth)acrylates such as hydroxypivalic acid neopentyl glycol ester di(meth)acrylate; Isocyanurate-type poly(meth)acrylates, such as tris[(meth)acryloxyethyl] isocyanurate, etc. are mentioned. These can be used individually or in combination of 2 or more types according to a required characteristic.

The solder resist resin composition of the present invention may include, for example, a photosensitive resin of the following structural formula, but is not limited thereto.

thermosetting resin

The thermosetting resin composition of this invention may contain (A-2) thermosetting resin.

(A-2) As thermosetting resin, what is necessary is just resin which hardens|cures by heating and shows electrical insulation, For example, an epoxy compound, an oxetane compound, a melamine resin, a silicone resin, etc. are mentioned. In particular, in this invention, an epoxy compound and an oxetane compound can be used suitably, These may be used together.

As said epoxy compound, the well-known and usual compound which has one or more epoxy groups can be used, Especially, the compound which has two or more epoxy groups is preferable. For example, mono epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, glycidyl (meth) acrylate, bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, phenol furnace Volak type epoxy resin, cresol novolak type epoxy resin, alicyclic epoxy resin, trimethylolpropane polyglycidyl ether, phenyl-1,3-diglycidyl ether, biphenyl-4,4'-diglycidyl Ether, 1,6-hexanediol diglycidyl ether, diglycidyl ether of ethylene glycol or propylene glycol, sorbitol polyglycidyl ether, tris(2,3-epoxypropyl) isocyanurate, triglycidyl The compound which has 2 or more epoxy groups in 1 molecule, such as tris (2-hydroxyethyl) isocyanurate, is mentioned. These can be used individually or in combination of 2 or more types according to a required characteristic.

As said oxetane compound, the following general formula

Specific examples of the oxetane compound containing the oxetane ring represented by (wherein, R ³ represents a hydrogen atom or an alkyl group having 1 to 6 atoms) include 3-ethyl-3-hydroxymethyloxetane (Toagosei Co., Ltd. product, brand name OXT-101), 3-ethyl-3-(phenoxymethyl)oxetane (Toagosei Co., Ltd. product, brand name OXT-211), 3-ethyl-3-(2-ethylhexyloxy) Methyl) oxetane (manufactured by Toagosei Co., Ltd., trade name OXT-212), 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene (manufactured by Toagosei Co., Ltd.; trade name OXT-121), bis(3-ethyl-3-oxetanylmethyl) ether (Toagosei Co., Ltd. product, trade name OXT-221) etc. are mentioned. Moreover, the oxetane compound of a phenol novolak type, etc. are mentioned. These oxetane compounds may be used together with the said epoxy compound, and may be used independently.

The solder resist resin composition of the present invention may include, for example, an epoxy compound, an oxetane compound, a melamine resin, and a styrene/acrylic acid/acrylic acid ester compound together with a silicone resin, but is not limited thereto.

Rutile Titanium Oxide

The solder resist resin composition of this invention may contain (B) rutile type titanium oxide. (B) When rutile-type titanium oxide is used, while heat resistance can be improved more, it becomes difficult to raise|generate the discoloration resulting from light irradiation, and it can make it difficult to reduce quality also under severe use environment.

In particular, heat resistance can be further improved by using rutile-type titanium oxide surface-treated with aluminum oxide such as alumina. As rutile-type titanium oxide surface-treated with the said aluminum oxide, Ishihara Sangyo Co., Ltd. product CR-58 which is a rutile-type chlorine method titanium oxide, R-630 manufactured by the company which is a rutile type sulfuric acid method titanium oxide, etc. are, for example. can be heard Moreover, it is also preferable to use the rutile-type titanium oxide surface-treated with silicon oxide, and also in this case, heat resistance can be improved further. It is also preferable to use rutile-type titanium oxide surface-treated with both aluminum oxide and silicon oxide, for example, CR-90 manufactured by Ishihara Sangyo Co., Ltd. which is a rutile-type chlorine-method titanium oxide. .

The soldering resist resin composition of this invention can contain such (B) rutile type titanium oxide with respect to the total composition, Preferably it is 5-80 mass %, More preferably, it can contain it in 10-70 mass %.

phosphor

The soldering resist resin composition of this invention can contain (C) fluorescent substance.

The phosphor (C) of the present invention absorbs light having a wavelength of 200 to 400 nm and emits light having a wavelength of 400 to 500 nm. More preferably, in the phosphor (C) of the present invention, an absorption peak may have a wavelength of 440 nm or less, and an emission peak may be 445 to 455 nm. Since the phosphor (C) of the present invention absorbs light in the ultraviolet region and emits light in the blue wavelength region, the reflectance in the blue wavelength region of the solder resist structure formed from the solder resist composition including the same is improved.

(C) as such a phosphor, a benzooxazoyl derivative having naphthalene as a substituent, a benzooxazoyl derivative having thiophene as a substituent, a benzooxazoyl derivative having stilbene as a substituent, a coumarin derivative, a styrene biphenyl derivative, a pyrazolone derivative; A bis(triazinylamino) stilbendisulfonic acid derivative etc. are mentioned. The phosphor (C) of the present invention is, for example, 1,4-bis(2-benzooxazolyl)naphthalene, 4,4'-bis[2-(2-methoxyphenyl)ethenyl]-1,1 '-Biphenyl, 7-hydroxycoumarin-3-carboxylic acid, 4-bromomethyl-7-methoxycoumarin, 5-dimethylaminonaphthalene-1-sulfonyl hydrazine (Dansyl hydrazine), N,N'- Di-naphthyl-N,N'-diphenylbenzidine, 4,4'-bis(2,2-diphenylvinyl)biphenyl, Alexa fluor 405, DAPI, bisbenzimide (Hoechst 33258), bisbenzimide ( Hoechst 33342), SYTOX Blue, and the like, but are not limited thereto.

The solder resist resin composition of this invention may contain (C) a phosphor and (D) a colorant. In an embodiment of the present invention, the solder resist resin composition may include (C) a phosphor and (D) a colorant uniformly mixed. The solder resist resin composition of this invention can be used for manufacture of an ink with favorable dispersion degree, sedimentation stability, and cohesion stability by including (C) a phosphor and (D) a colorant.

The solder resist resin composition of the present invention may include (D) a phosphor coated with a colorant (C). In one embodiment of the present invention, the (C) phosphor coated with (D) the colorant may include (C) a core including the phosphor, and (D) the colorant attached to the surface of the core. In another embodiment of the present invention, the (C) phosphor coated with (D) a colorant may include a core including (C) the phosphor, and a layer structure surrounding the core, and the layer structure surrounding the core is ( D) may include a colorant. By coating (C) the phosphor of the present invention with the (D) colorant, the absorption rate of the wavelength in the range of 500 nm or more can be increased, and the amount of light emitted in the range of 400 to 500 nm can be increased.

The solder resist resin composition of the present invention contains (C) a phosphor and (D) a colorant, or (D) contains a (C) phosphor coated with a colorant. It can be used, and it can be used for manufacturing a solder resist structure, a dry film, and a printed wiring board, in which both the average reflectance before and after the reflow process and the reflectance at 450 nm wavelength are high, even without a reflector.

(C) The amount of the phosphor is preferably in the range of 0.01 to 3 mass%, more preferably in the range of 0.05 to 3 mass%, based on the total composition. When the content of (C) phosphor of the solder resist resin composition of the present invention is within the above range, it is advantageous in that 100% reflectance can be exhibited without affecting ink properties. However, (C) if the content of the phosphor is less than the above range, the effect of increasing the reflectance is insignificant, and if it is larger than the above range, the b value among the color values of the coating film produced from the resin composition is too low, which will negatively affect the color expression of the display in the future. In addition, as the content of the (C) phosphor in the resin composition is increased, the content of the resin included in the resin composition is reduced, and problems such as cracks and poor adhesion may occur.

(C) phosphor of the present invention may be used in the form of powder or dissolved in a solvent. (C) When the phosphor is used in powder form, the particle size is in the range of 0.1 to 10 μm, preferably in the range of 0.1 to 5 μm. When the particle size is within the above range, it is advantageous in terms of dispersion degree, sedimentation stability, and surface leveling of the solder resist resin composition. can

coloring agent

The soldering resist resin composition of this invention can contain the (D) coloring agent, and can contain coloring agents other than white. In the present invention, "colorant" means a colorant other than white, unless otherwise defined. (D) The colorant includes commonly known colorants such as red, blue, green, yellow, and black, and any of a pigment, dye, and dye may be used. Specifically, a color index (C.I.; issued by The Society of Dyers and Colorists) numbered can be mentioned.

Examples of the red colorant include monoazo, disazo, azolake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. As the blue colorant, there are metal-substituted or unsubstituted phthalocyanine-based, anthraquinone-based, and indolylidene-based compounds, and pigment-based compounds classified as pigments. As a green colorant, there exist a metal-substituted or unsubstituted phthalocyanine type, anthraquinone type, and a perylene type similarly. Examples of the yellow colorant include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone. Examples of the black colorant include titanium black, carbon black, graphite, iron oxide, anthraquinone, cobalt oxide, copper oxide, manganese, antimony oxide, nickel oxide, perylene and aniline pigments, molybdenum sulfide. , and bismuth sulfide. In addition, you may add colorants, such as purple, orange, and brown, for the purpose of adjusting a color tone.

The colorant (D) of the present invention may include a blue colorant. (D) the colorant included in the resin composition of the present invention can absorb a wavelength in the range of 500 nm or more, preferably can absorb a wavelength in the range of 600 nm or more. (D) The resin composition of the present invention comprising a colorant may be used to prepare a solder resist structure having improved average reflectance.

The colorant (D) of the present invention is, for example, 1,4-bis(butylamino)anthracene-9,10-dione, 2,2'-bis(2,3-dihydro-3-oxoindolyldene) ), 3,7-bis(dimethylamino)phenothiazine-5-ium chloride, phthalocyanine blue, alcyan blue, cresyl blue BBS, phenylene blue, victoria blue B/FBR/BO/FGA/4R/R, etc. may include, but is not limited thereto.

The amount of the colorant (D) of the present invention is preferably 0.001 to 1 mass%, more preferably 0.001 to 0.5 mass%, based on the total composition. When the content of (D) colorant in the resin composition of the present invention is less than the above range, the light emitting effect at a wavelength of 450 nm is insufficient, and when it is larger than the above range, absorption in the visible light region increases and the average reflectance decreases. .

Etc

The photosensitive resin composition of the present invention may include a photoinitiator. As a photoinitiator, if it is a well-known photoinitiator as a photoinitiator and a photoradical generator, any can also be used.

The thermosetting resin composition of the present invention may further contain a curing agent and/or a curing catalyst. Examples of the curing agent include polyfunctional phenol compounds, polycarboxylic acids and acid anhydrides thereof, aliphatic or aromatic primary or secondary amines, polyamide resins, and polymercapto compounds. Among these, polyfunctional phenol compounds, polycarboxylic acids, and acid anhydrides thereof are preferably used in view of workability and insulating properties. Further, the curing catalyst is a compound that can serve as a curing catalyst in reaction with an epoxy compound and/or an oxetane compound and the like with a curing agent, or a compound that becomes a polymerization catalyst when a curing agent is not used. Specific examples of the curing catalyst include tertiary amines, tertiary amine salts, quaternary onium salts, tertiary phosphines, crown ether complexes, phosphonium ylide, and the like. Or it can be used in combination of 2 or more types. In one embodiment of the present invention, the solder resist resin composition may include a photopolymerization initiator and an amine curing agent.

The soldering resist resin composition of this invention can contain the organic solvent for the purpose of manufacture of a composition, viscosity adjustment at the time of apply|coating to a board|substrate or a carrier film, etc. Examples of the organic solvent include esters; aliphatic hydrocarbons such as octane and decane; A well-known and usual organic solvent, such as petroleum solvents, such as petroleum ether, petroleum naphtha, and solvent naphtha, can be used. These organic solvents can be used individually or in combination of 2 or more types.

The solder resist resin composition of this invention may contain antioxidant. By containing antioxidant, oxidative deterioration of curable resin etc. is normally prevented, there exists an effect of suppressing discoloration, while heat resistance improves, there exists an effect that resolution (line width reproducibility) becomes favorable. That is, depending on the kind of the white colorant, the resolution may be deteriorated by reflecting and absorbing light. However, by containing the antioxidant, good resolution can be obtained regardless of the kind of the white colorant.

Antioxidants include radical scavengers that invalidate generated radicals, peroxide decomposers that decompose generated peroxides into harmless substances to prevent new radicals from being generated, and the like, and may be used alone or in combination of two or more you can use it.

Moreover, since antioxidant, especially a phenolic antioxidant, may exhibit a further effect by using together with a heat-resistant stabilizer, you may mix|blend a heat-resistant stabilizer with the soldering resist resin composition of this invention.

Examples of the heat-resistant stabilizer include phosphorus-based, hydroxylamine-based, and sulfur-based heat-resistant stabilizers. The said heat-resistant stabilizer may be used individually by 1 type, and may use 2 or more types together.

Moreover, you may mix|blend another well-known and usual additive with the soldering resist resin composition of this invention in the field|area of an electronic material. Examples of the other additives include a thermal polymerization inhibitor, an ultraviolet absorber, a silane coupling agent, a plasticizer, a flame retardant, an antistatic agent, an anti-aging agent, an antibacterial/mildew inhibitor, an antifoaming agent, a leveling agent, a filler, a thickener, an adhesion imparting agent, a thixotropic imparting agent, A photoinitiation auxiliary agent, a sensitizer, a hardening accelerator, a mold release agent, a surface treatment agent, a dispersing agent, a dispersion auxiliary agent, a surface modifier, a stabilizer, etc. are mentioned.

Solder resist structure

In the solder resist structure of the present invention, the resin composition may include one or more layers.

The solder resist structure of the present invention may include at least one layer made of the photosensitive resin composition, that is, the photosensitive resin layer. Alternatively, the solder resist structure of the present invention may include at least one layer made of a thermosetting resin composition, that is, a thermosetting resin layer.

The thickness of each layer included in the solder resist structure of the present invention is in the range of 10 to 60 μm, preferably in the range of 10 to 40 μm. When the thickness of the layer is thin, there is a problem in that the reflectance of the structure of the solder resist is lowered, and when the thickness of the layer is thick, the manufacturing cost of the structure of the solder resist increases, which is not economical and the crack resistance may be weak.

In one embodiment of the present invention, the solder resist structure may be a single-layer structure including one layer. The single-layered solder resist structure may be formed of a photosensitive resin layer or a thermosetting resin layer. In this case, the thickness of the layer is in the range from 10 to 60 μm, preferably in the range from 10 to 40 μm.

In one embodiment of the present invention, the solder resist structure may be a multi-layer structure including an upper layer and a lower layer. The multi-layered solder resist structure may include a photosensitive resin layer, and the photosensitive resin layer may be positioned on an upper layer or a lower layer of the structure. The multi-layered solder resist structure may include a thermosetting resin layer, and the thermosetting resin layer is preferably located on the upper layer. In this case, the thickness of each layer is in the range of 10 to 60 μm, preferably in the range of 10 to 40 μm.

In an embodiment of the present invention, the solder resist structure may include a photosensitive resin layer and a thermosetting resin layer, and the thermosetting resin layer is preferably located on an upper layer of the photosensitive resin layer. In this case, the thickness of the photosensitive resin layer is in the range of 10 to 60 µm, preferably 10 to 40 µm, and the thickness of the thermosetting resin layer is in the range of 10 to 60 µm, preferably 10 to 40 µm.

When the solder resist structure of the present invention is white, light generated from a light emitting diode (LED) or electroluminescence (EL) used as the light source in the backlight of a liquid crystal display such as a lighting fixture, a portable terminal, a personal computer, or a television. can be used to reflect

Dry Film and Printed Wiring Boards

The dry film of the present invention can be obtained by coating and drying the solder resist resin composition.

When forming a dry film, first, the composition of the present invention is diluted with the organic solvent and adjusted to an appropriate viscosity, and then a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll coater, a gravure It is apply|coated with a uniform thickness on a carrier film with a coater, a spray coater, etc. Thereafter, by drying the applied composition at ^{a temperature of 50 to 130 o} C for 1 to 30 minutes, a resin layer can be formed. Although there is no restriction|limiting in particular about the coating film thickness, Generally, the film thickness after drying is suitably selected from 10-150 micrometers, Preferably it is 10-60 micrometers, More preferably, it is 10-40 micrometers.

As a carrier film, a plastic film is used, For example, polyester films, such as a polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, etc. can be used. Although there is no restriction|limiting in particular about the thickness of a carrier film, Generally, it selects suitably in the range of 10-150 micrometers.

After forming the resin layer containing the soldering resist resin composition of this invention on a carrier film, it is preferable to laminate|stack a peelable cover film on the surface of a film|membrane for the purpose of preventing dust from adhering to the surface of a film|membrane. do. As a peelable cover film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, the surface-treated paper etc. can be used, for example. As a cover film, when peeling a cover film, what is necessary is just to be smaller than the adhesive force of a resin layer and a carrier film.

Moreover, in this invention, a soldering resist resin layer is formed by apply|coating and drying the soldering resist resin composition of this invention on the said cover film, and you may laminate|stack a carrier film on the surface. That is, when manufacturing a dry film in this invention, you may use any of a carrier film and a cover film as a film which apply|coats the soldering resist resin composition of this invention.

The printed wiring board of the present invention may include a solder resist structure including one or more layers formed from the solder resist resin composition.

Example

Hereinafter, the present invention will be described in detail using examples.

Preparation of Fluorescent Particles Containing Phosphor and Colorant

90 to 92 mass% of the phosphor 1,4-bis(2-benzooxazolyl)naphthalene, 7 to 8 mass% of 4,4'-bis[2-(2-methoxyphenyl)ethenyl]-1,1 Phosphor Blue440, a phosphor mixture in the form of particles containing '-biphenyl, was prepared.

The phosphor mixture Phosphor Blue440 was coated with a colorant 1,4-bis(butylamino)anthracene-9,10-dione to prepare fluorescent particles Phosphor Blue OEF-BTS. The mass ratio of the phosphor mixture Phosphor Blue440 to the colorant coating the same was 100:0.2.

Phosphor and Fluorescent Particle Size

The size or diameter of the phosphor (Phosphor Blue440) and the phosphor particles (Phosphor Blue OEF-BTS) can be measured using a particle size analyzer or a grinder gauge. The result of measuring the size of the phosphor Phosphor Blue440 was 5 μm. And the result of measuring the size of the prepared fluorescent particles Phosphor Blue OEF-BTS was 5 μm.

Comparison of optical properties of phosphors and fluorescent particles

In order to compare the optical properties of the phosphor and the fluorescent particles, the UV-VIS absorption spectrum and the fluorescence spectrum were measured.

FIG. 1 shows UV-VIS absorption spectra of a phosphor and a fluorescent particle, and FIG. 2 shows a fluorescence spectrum of a phosphor and a fluorescent particle.

As shown in the absorption spectrum of FIG. 1 , both the fluorescent material and the fluorescent particle have absorption peaks at a wavelength of about 400 nm, but the fluorescent particle exhibited significantly higher absorption than the fluorescent material in a wavelength region of 500 nm or more.

The fluorescence spectra of the phosphor and the fluorescent particles were measured with absorption wavelengths set to 415 nm and 409 nm, respectively. As shown in FIG. 2 , both the phosphor and the fluorescent particles exhibited maximum fluorescence at a wavelength of 452 nm, but the fluorescent particles exhibited much stronger fluorescence.

From FIGS. 1 and 2 , it can be confirmed that by using the colorant together with the phosphor, light absorption is possible in a wider wavelength region than when the phosphor alone is used, and the fluorescence efficiency is improved and the fluorescence intensity is increased.

Preparation of photosensitive resin composition ink

The raw materials were put in a container and stirred to visually confirm that the filler was evenly dispersed, and then stretched on 3 rolls to prepare photosensitive resin composition inks A-1-1 to A-1-8. The content of each component is as described in Table 1 below.

Table 1: Contents of each component of the photosensitive resin composition ink (unit: mass %)

Details of each component shown in Table 1 are as follows.

Photosensitive resin: (1) CYCLOMER-P(ACA)Z250 (Daicel Corporation)

(2) CYCLOMER-P(ACA)Z254F (Daicel allnex)

Defoamer: KS-66 (Shin-Etsu CHEMICAL CO., LTD.), BYK-1791 (BYK)

Dispersant: DISPERBYK-111 (BYK)

Leveling agent: BYK-405 (BYK)

Thinner: DOWANOL DPM (Dow chem)

Thermosetting agent: KH-1600 (NINGXIA DARONG CHEMICALS), MELAMIN FUNSAI (JingShan Ink Material Manufacturing (Huai))

Photoinitiators: OMNIRAD 819 (IGM Resins B.V.), MOSAPHOTO 348 (UFC Corporation), OMNIRAD 907 (IGM Resins B.V.), Shoufu ITX (Zhejiang Shou&Fu Chemtrade Co., Ltd.)

Titanium oxide: Ti Pure R-706 (CHEMOURS)

Filler: NIPSIL L-300 (Tosoh Silica Corporation)

Phosphor: Phosphor Blue440 (Timerich)

Colorant: 1,4-bis(butylamino)anthracene-9,10-dione

A-1-1 of Table 1 is a photosensitive resin composition ink that does not contain both a phosphor and a colorant, and A-1-7 and A-1-8 are a photosensitive ink that contains a phosphor (Phosphor Blue440) but does not contain a colorant. It is a resin composition ink. And A-1-2 to A-1-6 are fluorescent particles (Phosphor Blue OEF-BTS) in which a phosphor (Phosphor Blue440) is coated with a colorant (1,4-bis(butylamino)anthracene-9,10-dione) It is a photosensitive resin composition ink comprising a.

Preparation of thermosetting resin composition ink

The raw material was put in a container and stirred to visually confirm that the filler was evenly dispersed, and then spread on three rolls to prepare thermosetting resin composition inks A-2-1 to A-2-5. The content of each component is as described in Table 2 below.

Table 2: Contents of each component of the thermosetting resin composition ink (unit: mass %)

Details of each component shown in Table 2 are as follows.

Thermosetting resin: VB-5305DPM50 (Nihon Cima Co., Ltd.)

Defoamer: KS-66

Dispersant: DISPERBYK-111

Thermosetting agent: KH-1600, MELAMINE FUNSAI

Thinner: DOWANOL TPM GLYCOL ETHER (DOW CHEM)

Titanium Oxide: TiONA 595 (TRONOX LLC)

Filler: KHP-25 (KOCH), AEROSIL R974 (Evonik Resource Efficiency GmbH)

Phosphor: Phosphor Blue440 (Timerich)

Colorant: 1,4-bis(butylamino)anthracene-9,10-dione

A-2-1 of Table 2 is a thermosetting resin composition ink that does not contain both a phosphor and a colorant, and A-2-5 is a thermosetting resin composition ink that includes a phosphor (Phosphor Blue440) but does not contain a colorant. . And A-2-2 to A-2-4 are fluorescent particles (Phosphor Blue OEF-BTS) in which a phosphor (Phosphor Blue440) is coated with a colorant (1,4-bis(butylamino)anthracene-9,10-dione) It is a thermosetting resin composition ink comprising a.

Ink evaluation

The dispersion degree, sedimentation stability, and cohesive stability of the prepared ink were evaluated.

(Ink dispersion evaluation method using grinder gauge)

The measurement sample was mixed with a diluent in a 1:1 ratio, and 2-3 drops of an antifoaming agent were added. Then, the sample, diluent and antifoaming agent were rubbed with Hera. After that, the measurement sample was filled on the top plate of the grinder meter, and the blade was drawn perpendicular to the top surface of the grinder gauge with a scraper, and the sample was pulled from top to bottom. Thereafter, the lines of the grinder gauge were counted according to the following method.

Ink dispersion was evaluated based on the following criteria.

O: less than 10

△: 10 or more and less than 15

X: 15 or more

(Method for evaluating sedimentation stability)

Sedimentation stability was visually evaluated 2 weeks after the ink was diluted and dispersed.

Sedimentation stability was evaluated according to the following criteria.

O: good sedimentation state

△: Normal sedimentation

X: poor sedimentation

(Method for Assessing Aggregation Stability)

The ink was measured with a Malvern particle sizer (Model: Mastersizer 3000 by Malvern Panalytical Ltd, Principle: Laser light scattering, Analysis: Mie and Fraunhofer scattering, Data acquisition rate: 10 kHz) two weeks after dilution and dispersion.

Aggregation stability was evaluated as follows based on D50.

O: less than 0.3 μm

△: 0.3 µm or more and less than 0.4 µm

X: 0.4 µm or more

The results of checking the dispersion degree, sedimentation stability, and cohesive stability of the ink according to the above evaluation method are as shown in Tables 3 and 4.

Table 3: Evaluation of photosensitive resin composition ink (A-1-1, A-1-3, A-1-5, A-1-6 and A-1-7)

Table 4: Evaluation of thermosetting resin composition ink (A-2-1 to A-2-5)

The solder resist resin composition ink of the present invention containing both a phosphor and a colorant exhibits good ink dispersibility, sedimentation stability and cohesive stability.

film manufacturing

The resin composition ink of Table 1 or Table 2 was prepared in the form of a film on a PET film and bonded to a substrate, and then treated in the following manner.

After 80 mesh screen printing of the photosensitive resin composition inks A-1-1 to A-1-8 of Table 1 ^{, precured at 90 o} C for 15 minutes, and irradiated with ultraviolet rays under the condition of an energy density of 600 mJ/cm 2 , 150 ^By final curing at o C for 30 minutes, photosensitive coating films PSR1 to PSR8 were prepared (thickness of the coating film after drying: 25 μm).

After 80mesh screen printing of the thermosetting resin composition inks A-2-1 to A-2-5 in Table 2 ^{, final curing at 150 o} C for 60 minutes to prepare thermosetting coating films IR1 to IR5 (coating after drying) thickness: 25 μm).

The dry film substrate application method is as follows.

(1) After grinding and cleaning the test board, remove the water and dry it.

(2) After placing White DFSR on the test board, vacuum lamination (Nichiko Molton) equipment is used for vacuum lamination to transfer the dry film onto the test board (vacuum lamination conditions: 1st chamber - 60 ^o C, 3.0 hpa, 10sec. / 0.2Mpa, 10sec, 2nd chamber - 70 ^o C).

(4) The substrate onto which the dry film has been transferred is UV-exposed using a DI exposure machine (DI UV exposure conditions: SCREEN LEDIA5, 300 mJ/cm 2 ).

(5) After UV exposure, the substrate is cooled at room temperature, and then placed in a developer for development (development conditions: 1 wt% Na ₂ CO ₃ , 30 ^o C, 2 kgf/cm 2 , 60 sec.).

(6) ^{Final curing (Post Cure) the developed substrate in an oven at 150 o} C for 1 hour to complete the substrate production.

Reflectance of the coating film - 1 layer (single layer)

The structure of a single-layer coating film formed from the photosensitive resin composition ink of Table 1 or the thermosetting resin composition ink of Table 2 is schematically shown in FIG. 3 (thickness of the coating film after drying: 25 µm). Here, PSR1 to PSR8 mean a coating film formed from the photosensitive resin composition inks A-1-1 to A-1-8 of Table 1, and IR1 to IR5 are the thermosetting resin composition inks A-2-1 to A- of Table 2 It means the coating film formed from 2-5.

The average reflectance (average) and the reflectance (450 nm) of 450 nm wavelength were measured and evaluated for the single-layer coating film of FIG. 3 before and after the reflow process was performed three times. Tables 5 and 6 show the results.

The average reflectance was evaluated based on the following criteria.

◎: 87% or more

O: 86% or more and less than 87%

△: 85% or more and less than 86%

X: less than 85%

The reflectance of the 450 nm wavelength was evaluated according to the following criteria.

◎: 89% or more

O: 88% or more and less than 89%

△: 87% or more and less than 88%

X: less than 86%

Table 5: Average reflectance before and after reflow process of PSR1, 3, 5, 6 and 7 monolayers and reflectance at 450 nm wavelength

Table 6: Average reflectance and reflectance of 450 nm wavelength before and after reflow process of IR1 ~ IR5 monolayer

The single-layer coating film prepared using the solder resist resin composition ink of the present invention including both a phosphor and a colorant showed high average reflectance before and after the reflow process and high reflectance at a wavelength of 450 nm.

However, the single-layer coating films PSR1 and IR1 containing neither a phosphor nor a colorant had poor average reflectance before and after the reflow process and poor reflectance at a wavelength of 450 nm. The single-layer coating films PSR7 and IR5 containing a phosphor but not containing a colorant had remarkably low average reflectance and reflectance at a wavelength of 450 nm after the reflow process.

Reflectance and fluorescence image of coating film - 2 layers (double layer)

A coating film having a multilayer structure, which is a coating film formed from the solder resist resin composition of the present invention, wherein at least one of the upper layer or the lower layer contains fluorescent particles, is shown in Examples 1 to 12 of Table 7 (thickness of the coating film after drying: upper layer 25 µm, lower layer 25 μm).

Examples 1 to 6 of Table 7 are multilayer coating films including a photosensitive coating film as a lower layer and a thermosetting coating film as an upper layer. Examples 7 to 12 are multilayer coating films in which both the upper and lower layers are photosensitive coating films.

Comparative Examples 1 and 2 are multilayer coating films formed from a resin composition containing no phosphor and no colorant. Comparative Example 3 is a commercial reflector used to increase the reflectance of a conventional 450 nm wavelength.

The structures of the multilayer coating films of Examples 1 to 12 and Comparative Examples 1 and 2 in Table 7 are schematically shown in FIG. 4 .

Table 7: Composition of multilayer coating film

For the multilayer coating film of Table 7, the average reflectance and the reflectance of 450 nm wavelength were measured and evaluated before and after the reflow process 3 times, and the average reflectance of the commercial reflector and the reflectance of the 450 nm wavelength were measured and evaluated The results are shown in Table 8.

The average reflectance was evaluated based on the following criteria.

◎: 94% or more

O: 93% or more and less than 94%

△: 92% or more and less than 93%

X: More than 90% and less than 92%

XX: less than 90%

The reflectance of the 450 nm wavelength was evaluated according to the following criteria.

◎◎: 100% or more

◎: 98% or more and less than 100%

OO: 97% or more and less than 98%

O: 96% or more and less than 97%

△: 93% or more and less than 96%

X: less than 93%

Table 8: Average reflectance before and after reflow process and reflectance at 450 nm wavelength

The multilayer coating films of Examples 1 to 12 including an upper layer and/or a lower layer formed from the solder resist resin composition of the present invention containing both a phosphor and a colorant had better initial average reflectance than the commercial reflector of Comparative Example 3. , the average reflectance before and after the reflow process was superior to that of the multilayer coating films of Comparative Examples 1 and 2.

In addition, when the photosensitive resin composition of the present invention is used for the lower layer when manufacturing a multilayer coating film, it is advantageous for oxidation prevention than when used for the upper layer, and thus the reflectance after the reflow process is higher.

In addition, the multilayer coating films of Examples 1 to 12 comprising an upper layer and/or a lower layer formed from the solder resist resin composition of the present invention exhibited superior initial reflectance at 450 nm wavelength than the commercial reflector of Comparative Example 3, The reflectance at a wavelength of 450 nm before and after the reflow process was superior to that of the multilayer coating films of Comparative Examples 1 and 2. In this regard, the results obtained by measuring the fluorescence images of the multilayer coating films of Examples 1 to 3 of Table 8 and Comparative Example 1 before and after the reflow process are shown in FIG. 5 .

As shown in FIG. 5 , in the multilayer coating film including a layer formed from the solder resist resin composition ink of the present invention including both a phosphor and a colorant, the fluorescence intensity after the reflow process is greatly reduced compared to the fluorescence intensity before the reflow process I never do that. However, the multilayer coating film of Comparative Example 1 showed very inferior fluorescence intensity before and after the reflow process compared to Examples 1 to 3.

Therefore, by using the solder resist resin composition of the present invention, it is possible to provide a solder resist structure, a dry film, and a printed wiring board having excellent average reflectance and reflectance at a wavelength of 450 nm before and after reflow revolution without using a reflector.

Claims (17)

(A-1) A photosensitive resin, (B) rutile titanium oxide, (C) a phosphor, and (D) a colorant. A resin composition comprising: (A-2) A resin composition comprising a thermosetting resin, (B) rutile titanium oxide, (C) a phosphor, and (D) a colorant. The resin composition according to claim 1 or 2, wherein (C) the phosphor has an absorption peak of 440 nm or less and an emission peak of 445 to 455 nm. 4. The phosphor according to claim 3, wherein (C) the phosphor is 1,4-bis(2-benzooxazolyl)naphthalene and 4,4'-bis[2-(2-methoxyphenyl)ethenyl]-1,1'- A resin composition comprising at least one of biphenyls. The resin composition according to claim 1 or 2, wherein (C) the phosphor is contained in an amount of 0.01 to 3 mass% based on the total composition. 3. The colorant according to claim 1 or 2, wherein (D) the colorant is 1,4-bis(butylamino)anthracene-9,10-dione, 2,2'-bis(2,3-dihydro-3-oxo) dolylden) and 3,7-bis(dimethylamino)phenothiazine-5-ium chloride. The resin composition according to claim 1 or 2, wherein the (D) colorant is contained in an amount of 0.001 to 1 mass % with respect to the total composition. A solder resist structure comprising one or more layers, the solder resist structure comprising at least one photosensitive resin layer made of the resin composition of claim 1 . The solder resist structure according to claim 8, wherein, when the solder resist structure is a single layer, the thickness of the layer is 10 to 60 μm. The solder resist structure according to claim 8, wherein when the solder resist structure is a multi-layer, the thickness of each layer is independently 10 to 60 µm. A solder resist structure comprising one or more layers, the solder resist structure comprising at least one thermosetting resin layer made of the resin composition of claim 2 . The solder resist structure according to claim 11, wherein, when the solder resist structure is a single layer, the thickness of the layer is 10 to 60 μm. The soldering resist structure according to claim 11, wherein when the solder resist structure is a multilayer, the upper layer is a thermosetting resin layer, and the thickness of each layer is independently 10 to 60 µm. A solder resist structure comprising a photosensitive resin layer made of the resin composition of claim 1 and a thermosetting resin layer made of the resin composition of claim 2, wherein the thermosetting resin layer is located above the photosensitive resin layer. 15. The solder resist structure according to claim 14, wherein the thickness of the photosensitive resin layer is 10 to 60 μm, and the thickness of the thermosetting resin layer is 10 to 60 μm. The dry film obtained by apply|coating and drying the resin composition of Claim 1 or 2. A printed wiring board comprising the solder resist structure according to any one of claims 8 to 13.

Images