TW200827413A - Resist ink, printed circuit board and method for producing resist ink - Google Patents

Abstract

To provide a color resist ink such as a green resist ink, which has good dispersion stability not only in the case of a low viscosity product of ink using a pigment such as a green pigment by itself or ink using a plurality of pigments at the same time but also in the case of a low viscosity product using a mixture of blue and yellow colorants each having no halogen atom in its molecular formula, and in which both the colorants do not separate, a method for producing the resist ink, and a printed wiring board having a cured film of the resist ink. The resist ink comprises (A) a colorant, (B) a curable resin, c a reactive diluent, (D) a polymerization initiator and (E) a filler, wherein the colorant (A) has an average particle diameter of 0.01 to 1 μm measured by a laser diffraction scattering method and a standard deviation of particle size distribution of 0.1-0.2 μm.

Description

200827413 IX. Description of the Invention: [Technical Disclosure of the Invention] The present invention relates to a solder resist ink (s 〇1 de Γ resjstink), which is used to protect a circuit pattern such as a printed circuit board from a circuit that does not require soldering. The solder resist/ink making method and the printed circuit board having the coated cured film.

[Prior Art] A circuit board is formed by forming a pattern of circuit wiring on a base layer of a copper-clad laminate, for example, and can carry an electronic component such as a valley or a resistor thereon to form an electrical and electronic circuit. When the unit 〇7 η is small on the circuit board, it is performed by soldering the electronic component to a predetermined portion (welding::) of the circuit composed of the conductor; as the soldering method, there is a reflow The method of rod connection or the method of welding by jetting; when welding, ± if it is composed of a resin, that is, the solder resist oil (4), is covered by a portion of the circuit other than the solder joint where it is desired to == solder contact. The solder resist ink film also has the function of being a permanent material and a crucible to prevent the metal material constituting the conductor of the circuit portion from being exposed to the air, causing corrosion due to oxidation or humidity. Since most of the materials are soldered to the printed circuit board to test the apricot, it is visually observed whether the solder is defective or not. As a result of this, the eye is comfortable. Earth tone. In order to color the green, the stable color from the ink 5

200827413 In terms of adjustment, it is better to use green copper. However, if the electronic components are disposed of after being discarded, such as the use of the atomic atoms, if the industry is to be incinerated, In recent years, it has been particularly regarded as a problem of toxic problems. In order to avoid this problem, a non-primary atomic pigment is used in combination, for example, copper indigo blue and non-halogen raw materials are used (refer to Japanese Laid-Open Patent Publication No. 2000-7974); The pigment having a yellow pigment is eluted due to acid rain or the like, and since it is toxic, there is also a possibility that the coating film is eluted without the yellow color of the azo group. 2000-290564 Bulletin). [Patent Document 1] JP-A-2000-290564 [Patent Document 2] JP-A-2000-290564 SUMMARY OF INVENTION [Problems to be Solved by the Invention] However, the use of copper phthalocyanine or copper enamel A solder resist ink in the case of any of the pigment and the yellow pigment, having an average particle diameter of 8 to 10 μm (by a grind meter (grind particle size) (converted to be measured by laser diffraction scattering method) : If it is not previously notified, it means 1~8 micrometers as determined by this method. Because the particle size is large, there is pigment dispersibility; I, the color development of the coating film is deteriorated. Or the color tone is not the case. The solder resist ink film composed of such a coating film cannot have a halogen printed circuit board waste, and the yellow azo group of the blue color of the dioxin of the dioxin is likely to be In the case where the particle size (particle size) of the house is not measured from the material (refer to the gauge of the pigment such as cyan or the like), the knot is stable and the r is sharp and 6 200827413 is uniform. Hue, not just for the above-mentioned visual inspection It is a problem that there is a decline in the value of printed circuit boards.

When the solder resist ink described in the above-mentioned JP-A-2000-290564 is used, the coating film is formed by screen printing, and since the viscosity at the time of printing is sufficient at about 200 dPa*s, the above-mentioned cyan pigment is used. Indigo blue is stably dispersed without being separated from the yellow pigment, but is carried out while moving the coated body in a manner such as a curtain flow method in which the ink is continuously flowed in a curtain flow to traverse it. When the coating method is applied, or the spraying method (the method of applying the ink to the coated body by spraying), the viscosity at the time of use must be about 2 dPa*s. The solvent must be used to dilute the ink. For example, when diluted to 50 dPa or less, the indigo blue is easily separated and floated on the surface, that is, color separation occurs, so that the coating film easily becomes unsatisfactory and uniform green. A first object of the present invention is to provide a colorant resist ink of various colors such as a green color, and the resist ink is not limited to an ink using a green pigment alone or a low viscosity ink obtained by using a plurality of pigments, even if When it is an ink of a low-viscosity product in which a cyan system and a yellow-based agent which do not have a halogen atom in the molecular formula are mixed, the dispersibility stability is good, the two coloring agents are not separated, and the resistance is provided. A method of preparing a toner and a printed circuit board having a cured film of the resist ink. A second object of the present invention is to provide a resist ink which can obtain a uniform and stable color tone coating film even by a curtain flow method or a spray method, and a printed circuit for providing a cured film having the resist ink. board. [Means for Solving the Problem] 7 200827413 In order to solve the lesson, the inventor, etc., focused on the research, and found that the basic components of the resist ink, that is, the resin into the eight-solvent component, and the coloring were first discovered by mechanical means. The agent is pulverized to form a colorant dispersion, and when the colorant dispersion is used to produce a resist ink, the use ratio of each component in the composition of the toner dispersion can be produced by woven. A low-viscosity colorant dispersion' is also a mechanical means for crushing (or pulverizing) a coloring agent such as a pigment for a coloring agent.

When a pulverizer for a fine powder such as a milling and dispersion method of a medium such as a sphere or a bead is used, the toner particles of the colorant can be more micronized, and if the granules (average particle diameter) are less than 1 μm, When the standard deviation of the particle size distribution is micrometer, the above problems can be solved, and the present invention has been completed. · The important factors that determine the dispersion and aggregation of pigments are the zeta potential, pH, particle size, and specific gravity of the material. The copper phthalocyanine itself contains the copper phthalocyanine itself, which does not contain halogen, because of the zeta potential. Low, specific gravity is small, if it is contained in a low-viscosity composition that is easy to flow, it is easy to float on the liquid/surface relative, and it has been found that the particle diameter (average particle diameter) of each pigment is less than 1 μm. When the standard deviation of the particle size distribution is 〇1 to 〇·2 μm, when compared with the average particle size of only 1 to 8 μm, it is possible to reduce floating or no floating, especially for low-viscosity inks. . Therefore, the present invention (1) provides a resist ink comprising (Α) a coloring (curing) resin, (C) a reactive diluent, (D) a polymerization initiator, and a resist ink of a (Ε) filler. Wherein the average particle diameter of the above (a) colorant is 〇·〇5 μm or more smaller than that measured by the field diffraction scattering method! The standard deviation of the micron and the particle size distribution is 0. 02 microns. 8 200827413 Further, the present invention (2) provides a printed circuit board having a coating film of a resist ink thereon. ( ', ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( a toner thick dispersion, (B) a curable resin, (6) a reactive dilute (D) polymerization initiator, and (8) a filler; the average particle size of the colorant determined by a laser-' & method The diameter is 〇〇5 μm or more and less than 1 μm′ and the standard deviation of the particle size distribution is οι 〇·2 μm. (4) The method for producing a resist ink is used at least when it is contained in an amount of 1 相对 relative to the whole. , for 1~5 〇 蚤々 认 认 认 认 认 认 认 认 认 认 认 认 、 、 、 、 、 、 、 、 、 、 、 、 、 、 认 认 认 认 认 认 认 认 认 认 认 认 认 认 认 认 认 认 认 认To produce a thick dispersion of the colorant which is densely dispersed by the colorant 9; then, σ (Α) the toner thick dispersion, (Β) hardening resin, (C) reactive diluent, (D) polymerization Initiator, and (8) filler; the above-mentioned colorant, the particle size determined by the field shot and the 7-shot government method, and the average thereof The diameter is ^5 μm or more and less than 1 μm, and the standard deviation of the particle size distribution is 胄〇1 to 2 μm. () The resist ink of the above (1), wherein the (Α) coloring agent is contained in (Α-1) a cyan coloring agent which does not have a halogen atom in the molecular formula, and a yellow coloring agent which does not have a halogen atom in the (A 2) knife type, and the cyan coloring agent and the yellow coloring agent form a green color tone (12) The resist ink according to the above (11), wherein the (B) curable resin is photocurable, and the (C) reactive diluent is a photopolymerizable reactive diluent, (D) a polymerization initiator is a photopolymerization initiator; (13) a resist ink comprising a (A) colorant, (F) a thermosetting resin, and (E) a filler green-type solder resist 9 200827413 Resist ink, Wherein the (A) coloring agent contains a cyan coloring agent which does not have a halogen atom in the formula (A-), and a yellow coloring agent which does not have a halogen atom in the formula (A-2), and is colored by the cyan coloring system. And the yellow coloring agent to form a green color tone; (14) as (11) to (13) A resist ink comprising (G) a thermosetting compound; (15) a resist ink according to any one of (11) to (14), which contains (H) a solvent and/or (1) an additive (16) The resist ink according to any one of (11) to (15), wherein the yellow coloring agent of the (A_2) component is a coloring agent having no azo group in the formula; (17) 6) The resist ink, wherein the yellow coloring agent of the component (A-2) is at least one of an isoindane coloring agent and an anthraquinone coloring agent; (1 8 ) such as (1 1 ) to ( The resist ink according to any one of the preceding claims, wherein the cyan coloring agent of the bismuth-bismuth component is indigo blue; (19) providing a printed circuit board, for example, a printed circuit before or after carrying the electronic component A printed circuit board having a cured film of a coating film of a resist ink according to any one of (11) to (18). In the above inventions, "resist ink" may be referred to as "solder resist ink", and "colorant" may be referred to as "pigment". [Effects of the Invention] According to the present invention, it is possible to provide a resist ink which is colored by using a coloring agent having an average particle diameter of less than 1 μm and a standard deviation of a particle size distribution of from 0.1 to 0.2 μm. The agent particles are uniformly dispersed in the ink, have good color development and color tone stability, and in particular, can provide a resist ink such as a solder resist ink which does not easily impair the performance of the particles even if the viscosity is low. 10 200827413 In addition, since A can provide a printed circuit board with or without a hardened film of a film and an ink film, the coated lanthanum has good color development and color tone stability. Not only is it excellent in visibility, 'and: it can increase the value of goods. Further, since the coloring agent is dispersed by using a fine particle mill or the like, the average particle diameter of the dispersed particles can be made smaller than 丨, and the standard deviation of the particle size distribution can be 0.1 to 0.2 μm, which can be made, for example, by lowering the resin. It is easier to increase the ratio of pigments and solvents by the ratio. Further, even if the curtain flow method or the spray coating method is performed, or the production line is temporarily stopped or the coating device is enlarged, a resist ink capable of obtaining a coating film having a uniform stable color tone can be provided, and the agent can be provided. A printed circuit board of a cured film of ink. [Embodiment] The "(A) coloring agent" used in the present invention may be exemplified by gasification enthalpy, chrome green, green recording, oxidized chlorination, desertification, chloroplast, chlorophyll, strontium- A pigment such as nickel-cobalt-zinc-based green. Further, examples of the cyan-based coloring agent include copper indigo blue (C·!•Pigment Blue 15) and metal-free indigo blue (C I. Pigment Blue 1 6) which do not contain a south atom in the structure. ), oxy titanium (tit any 1) indigo blue, iron blue, nickel blue, Ming blue, tin blue, alkaline blue (CI pigment blue 1, 2, 3, 1 〇, 14, 18, 19, 24, 56, 57, 61), sulfonated CuPc (CI·Pigment Blue 17), Sweet Green (CI·Pigment Blue 27), Ultramarine (CI·Pigment Blue 29), Cobalt Blue (CI· Pigment Blue 28), Sky Blue - (CI · Pigment Blue 35), Co (Al, Cr) 204 (CI · Pigment Blue 36), Diazo (CI · Pigment Blue 25, 26), Standard Reduction Blue (CI· Pigment blue 11 200827413 60), indigo (CI Pigment Blue 63, 66), cobalt indigo (CI · Pigment Blue 75) and other pigments.

Further, examples of the yellow-based coloring agent include monoazo yellow (C.I. Pigment Yellow 1, 4, 5, 9, 65, 74) which does not contain a halogen atom, and a benzo-flavored surface! Yellow (CI Pigment Yellow 120, 151, 175, 180, 181, 194), Xanthone (CI Pigment Yellow 24), Azomethyl Yellow (CI·Pig Yellow 117, 129), Yellow (CI·Pigment) Yellow 123, 147), different sputum full yellow (€: 丄 pigment yellow 139, 185), diazo yellow (CI pigment yellow 155), condensed polycyclic system (CI pigment yellow 148, 182, 192), iron oxide (CI·Pigment Yellow 42), Zwitterazomethine (CI·Pigment Yellow 101), Soluble Azo (CI Pigment Yellow 61, 62, 100, 104, 133, 168, 169), Metal Complex (CI·Pigment) Yellow 150, 153, 177, 179) and other pigments. Among these, as the yellow coloring agent which is halogen-free and does not have an azo group in the molecular formula, an organic system of at least one of a yellow system isoindane coloring agent and an anthraquinone coloring agent is mentioned. The coloring agent, the iso-SI c-full coloring agent has the property of being economical, solvent-resistant, and heat-resistant, and can be used for high-grade paints, plastic coloring, and the like. Specifically, there may be mentioned anthraquinones such as full yellow, xanthine yellow, anthrapyrimidine yellow, titanium yellow, and the like. As the green coloring agent, one or a plurality of the above-mentioned halogen-free blue coloring agents and one or a plurality of yellow coloring agents may be used in combination; and as a yellow coloring agent, a yellow system is used. It is also preferable to use at least one organic coloring agent of the full coloring agent and the lanthanoid coloring agent. In order to make such a halogen-free coloring agent have the same color tone as the conventional indigo blue solder resist ink, 0.1 to 10 parts of a blue coloring agent is added to 1 part of the yellow coloring agent to add 1 to 5 parts. Blue colorants are preferred. 12 200827413 Colorant u ^ μ u pigment is preferred. The present invention is a resisting ink, which contains a ruthenium scattering method, which is based on a laser, and has an average particle diameter of 〇η Ί at 1 μm to .1. The standard 偬M wood is more than micrometers and smaller than 0 · 0 5 micrometers and less than 1 micro-abundance distribution, and the particle size leisure is 0.1 to 0.2 micrometers, and the particle size of the suede is 1 to 8 The pigment (mean Wenmi) is small and the particle size distribution is narrow. In order to make the particle size of the pigment smaller, the particle size of the pigment is narrower than that of the pressed cake, for example, when the crucible or the dried pigment is dispersed in water to f 1 # π &> In the water suspension with pigments, the disperser, the high-speed mixer, the homogenization-笙, 畐# from the μ mix, the mixing through the spoon, the benefit of the usual stirring, or the use of a particle mill, sanding, smashing Α (attritor) and so on ι your machine ultra-fine grinding machine., this is enough to give a kind of mechanical energy disperser, for A to make micro-powder _ m 1 . ▲ machine; fruit as - device to enter, - when performing a series of processing ' can use concentric j can also be done by changing the device. Making an aqueous suspension of pigments _, at #1 ^ ^ _ at a temperature higher than room temperature or at a temperature lower than room temperature, when using a pigment slurry or pressed cake, by imparting mechanical energy, The aggregation of the pigment is solved to the size of the primary particle size kle size). Further, when a dry pigment is used, it is made to have a larger particle size by giving it a larger amount. The average primary particle size can be from 0. 02 to 1 μm (refer to JP-A-2002-35655), and the standard deviation of the particle size distribution is 〇·1 to 〇 2 μm. Further, as the pulverizer for producing a fine powder, in addition to the above, a bead mill, a ball mill, a jet pulverizer or the like may be mentioned. Further, the resin can be used together with the solvent. To use a commercially available pigment to make it smaller in particle size, and to make the particle size fine 13 200827413, use a colorant to make a colorant concentrate 8.4 dispersion, and then use it with other resist inks. The components are mixed together to obtain a resist ink, wherein in the process of preparing the thick dispersion of the colorant, the pulverization method of the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Grinding machine, ball mill, jet mill, sand mill, ultrafine grinder, etc. These pulverizers are capable of diffusing a large amount of medium (a medium of a granular material) by rotating energy = by rubbing them into contact with each other and colliding with each other to grind the pulverized material, thereby improving the moving speed (pulverizing energy) ) 'and increase the degree of smashing. In this case, the coloring agent is treated with a pulverizer at least together with a solvent, preferably with a solvent and a resin, wherein a coloring agent containing Γ 5 5 parts by weight, 20 to 60 parts by weight is used with respect to 100 parts by weight of the whole. The solvent is preferably a material of 10 to 50 parts by weight of the resin. This also includes the case where the total weight of the colorant, the solvent, and the resin is less than 100 parts by weight. That is, it is also possible to contain other additives such as a dispersant. When the right bismuth two sticks are used for dispersion into the yf ,, for example, in the composition of 1 Q by weight of the toner, 80 parts by weight of the resin, and 1 part by weight of the solvent, the fine dispersion of the colorant is less likely to occur. Further, a solvent or a resin to be described later can also be used as the solvent or the resin. When a mechanical energy is to be imparted by a dispersing machine, a dispersing agent may be used in combination, and the dispersing agent may be an acrylic polymer dispersing agent (manufactured by EFCA Co., Ltd.) and 0.5 to 30% by weight of a polymer dispersing agent ( Colorant derivative) (SOLSPERSE 32000/ 36000/39000 (made by AVECIA)), modified acrylic copolymer (DOPA-15B/-1 7/-33/-44 (manufactured by Kyoeisha Co., Ltd.), used with respect to colorants 1. 1 to 5 wt% is preferred. 14 200827413 In this manner, the average particle diameter of the particles capable of obtaining the colorant is determined to be 0.01 μm or more and less than 1 μm in accordance with the laser diffraction scattering method, and is 〇·〇5. Preferably, the micrometer is less than 1 micrometer, and the standard deviation is 〇〇5 μm or more and 0.5 μm or less, and more preferably, a particle size distribution having 〇1 to 〇2 μm can be obtained; and mixing with other components can produce a resist. When the average particle diameter is larger than 1 μm or the standard deviation value is too large, it is difficult to suppress the above-described deterioration of color developability or color tone instability, etc. (B) hardenability used in the present invention. Resin", there are rings An epoxy resin (ep〇xy acrylate resin) such as a phenolic type (n〇v〇lac type) epoxy acrylate, and a carboxylic acid adduct thereof (water-soluble) At least one of the above-mentioned resins may be a photocurable photocurable type which is photopolymerizable by ultraviolet rays or the like, or may be a thermosetting type, or may contain a fluorene (F) thermosetting resin. The "(F) thermosetting resin" may be another epoxy resin. The "(C) reactive diluent" used in the present invention is used for the purpose of the above (B) component. The curable property such as photocurability of the reaction product is more sufficient, and a coating film having acidity, solvent resistance, heat resistance and the like is obtained. Representative examples thereof include, for example, a hydroxyl group. Dilute vinegar, 1,4-butanediol di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, neopentyl glycol di(meth) acrylate, polyethylene glycol Di(indenyl) acrylate, neopentyl glycol adipate di(meth)acrylate, hydroxy three Neopentyl glycol di(meth)acrylate, dicyclopentyl di(meth)acrylate, caprolactone modified dicyclopentene di(meth)acrylate, E〇 modified phosphoric acid II Methyl) acrylate, bis(indenyl) acrylate allylate cyclohexane 15 200827413

Ester, trimeric isocyanate di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol (mercapto) acrylate, propionic acid modified diterpene tetraol (Meth) acrylate, neodecyl alcohol tri(meth) acrylate, P 0 modified trimethylolpropane tri (meth) acrylate, ginseng (propylene decyl ethyl) trimeric isocyanate, propionic acid Reactive dilution of modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(meth) acrylate, caprolactone modified dinonosmeol hexa(nonyl) acrylate Agent. These reactive diluents can be used in a single type or in a mixture of two or more types. As the "(D) polymerization initiator" used in the present invention, a photopolymerizable composition is generally used as a photopolymerization initiator. Representative examples thereof include benzoin, benzoin thiol ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin and butyl Base ester, acetophenone, dinonylaminoacetophenone, 2,2-dimethoxyoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-mercapto-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-flavor Morpholino - propan-1-one, diphenyl ketone, 4,4'-diethylaminodiphenyl ketone, dichlorodiphenyl ketone, 2-mercaptopurine, 2-ethyl Bismuth, 2-t-butyl sulfonium S-Kun, 2-amino-based broth, 2-mercapto-oxygen sulphate, Yamaguchi, 2-ethyl oxysulfanyl sulphate, 2-chlorosulfur sulphate, 2 , 4-dimethyloxosulfanyl Yamaguchi, 2,4-diethyloxysulfanyl Yamaguchi, benzyldimethylketal, acetophenone dimethyl ketal, p-didecylaminobenzoquinone Ethyl acetate or the like, these may be used singly or in combination. The "(E) filler used in the present invention may, for example, be cerium oxide, talc, clay, magnesium carbonate, calcium carbonate, natural mica, synthetic cloud 16 200827413 mother, aluminum hydroxide, sedimentary barium sulfate Inorganic pigments such as barium titanate, iron oxide, non-fibrous glass, asbestos, slag wool, dream acid, crushed sour dance, zinc white, and acidified titanium. The above-mentioned fillers may be used alone or in a mixture of two or more.

In the present invention, "(G) thermosetting compound" may be used, and examples thereof include (propylidene, polypropyl) diol diepoxypropyl ether and polytetramethylene glycol (polytetramethylene glycol). Di-epoxypropyl ether, 2-ethylhexylepoxypropyl ether, phenylepoxypropyl ether, p-tert-butylphenylepoxypropyl ether, lauryl alcohol oxide propyl ether, glycerol poly Epoxypropyl ether, trimethylolpropane polyepoxypropyl ether, resorcinol diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, (extended ethyl, extended C Glycol diglycidyl ether, sorbitol polyepoxypropyl ether, sorbitan polyepoxypropyl ether, neotetraol polyepoxypropyl ether, ginseng (2,3-epoxy a melamine compound such as propyl)trimeric isocyanate or triepoxypropyl ginseng (2-hydroxyethyl)trimeric isocyanate; melamine compound such as thiolated melamine, butylated melamine or hexamethyleneoxymethylol melamine; Other phenol compounds, polyester compounds, and the like. These can be used singly or in combination. In the present invention, "(H) solvent" may be used, and such as ethylene glycol monoalkyl ether or its acetate, diethylene glycol mono- or dialkyl ether, propylene glycol monoalkane may be mentioned. Ether or its acetate, dipropylene glycol mono or dialkyl ether, methyl carbitol, butyl carbitol, butyl succinate acetate, carbitol acetate, ethyl decyl Ketone, cyclohexanone, toluene, xylene, tetradecylbenzene, petroleum ether, petroleum brain, mineral spirits, etc., which may be used singly or in combination. 17 200827413 In the present invention, "(I) additive" can be used, and examples thereof include an antifoaming agent such as an anthraquinone, a hydrocarbon or an acrylic, a decane system, a titanate system, and an alumina system. a dispersant such as a coupling agent, a boron trifluoride-amine complex, dicyanodiamine (DICY) and a derivative thereof, an organic acid hydrazine, a diamine maleimonitrile (DAMN; diaxnino maleonitrile) And its derivatives, melamine and its derivatives, guanamine and its derivatives, amine quinone imine (AI), polyamine salts and other potential hardeners, acetyl acetonate zinc salt (acetyl

Acetonate Zn), metal salt of acetylpyruvate such as acetyl acetonate Cr, enamine, tin octylate, sulfonium salt of the fourth grade, trimethylphosphine, 1,8-nitrogen Heterobicyclo (5,4,0) eleven -7 and its 2-ethylhexanoate and thermal hardening accelerators such as bismuth, sputum, η rice sulphate, triethanolamine borate, etc. Used alone or in combination. The resist ink of the present invention obtained by mixing the above components can have a halogen content of less than 1000 ppm, more preferably less than 5 〇〇 ppm, and an amine elution amount of the cured product of less than 100 ρρπι, more preferably less than 1 〇. Ppm. When the resist ink of the present invention is to be used as a solder resist ink to obtain a solder resist ink film, three methods can be applied. When the photopolymerizable resin composition is used for photocuring such as ultraviolet light, the coating liquid film pattern is formed in a portion where the welding circuit pattern is not required by a coating means such as a screen printing method. Then, for example, an ultraviolet curing furnace is used to sensitize the film, and a cured film of the coating film of the target solder resist ink can be formed. In the second method, the photopolymerizable resin composition is used for photocuring such as ultraviolet light. However, after the exposure to the lamp development process, the solder resist ink is applied to the substrate, and 18 200827413 After heating at 60 to 80 ° C for 15 to 60 minutes, the organic solvent is volatilized, and the negative film of the desired pattern is brought into contact with the dried coating film, and then ultraviolet rays are irradiated thereon, and then diluted. A method in which an aqueous alkali solution removes a non-exposed area to perform development. The diluted aqueous solution used herein is usually a 0.5 to 5 · 0% by weight aqueous solution of sodium carbonate, but other aqueous solutions may also be used. The coating film after development is, for example, a hot air circulation type dryer at 150 ° C, for example, post-baking for about 30 minutes, whereby a cured film of the target solder resist coating film can be formed. In the third method, when the resin composition for thermosetting is used for thermal curing, the pattern is formed by a coating means such as a screen printing method, and then heated by a far infrared ray hardening furnace or a hot air drying furnace. It is hardened to form a cured film of the target solder resist ink coating film. The above is a negative type of a negative film pattern, but the resist ink of the present invention can also be applied to a positive type using a positive film pattern. [Example 1] The "parts" in the examples mean "parts by weight", and the same applies hereinafter. (Cyan color, manufacture of toner thick dispersion) 250 parts of epoxy acrylate resin (THpA and gma (glycidyl methacrylate) addition resin) (manufactured by Dainippon Ink Chemical Industry Co., Ltd.) LK)N〇L Blue FG_735 1 (Toyo Ink Co., Ltd. made copper sapphire blue) 5 parts propylene glycol monodecyl ether acetic acid MPMA) (made by Sanyo Chemicals Co., Ltd.) metered in 'by dissolver (TARB0 industry) Company system) Into (four) mix and mix (revolution number earn 5 rpm, mixing time: 2 minutes ± 1 minute, content temperature is 10~35. 〇, preparative dispersion, (4) division preparation dispersion. 19 200827413 Subsequently, The pre-dispersion liquid was placed in a 1 mm zirconium bead, and a horizontal wet sand mill (manufactured by SHINMARU-ENTERPRISES Co., Ltd.) was used, and the dispersion treatment was carried out six times at a peripheral speed of 20 m/sec. Cyan colorant thick dispersion.

The cyan colorant thick dispersion is measured by a laser diffraction scattering particle size distribution measuring device (product name: BECKMAN COUNTER type: LS230), and the measured particle diameter (average particle diameter) is less than 1 micrometer, and the standard deviation is 0.182 microns. (Production of a thick yellow colorant dispersion) The above is carried out in the same manner as in the case of using a compound of the above [Chemical Formula 1] (CI·Pigment Yellow 24) instead of LIONOL Blue FG-73 5 1 . And 1 000 parts of a thick dispersion of a yellow colorant is obtained. The particle size distribution of the yellow colorant thick dispersion measured by the above measuring apparatus is as shown in Fig. 1, and the particle diameter (average particle diameter) is less than 0.118 μm. The standard deviation is 0.016 microns. [Chemical Formula 1]

〇

(Manufacturing of solder resist ink) 20 200827413 In 100 parts of tartare acid addition type ^novolac) epoxy resin,

8.0 parts of diterpene tetraol hexaacrylate, 8.0 parts of 2-methyl-1-[4-(indolyl)phenyl]-2-2- morpholino-propyl-1-one, 8.0 parts of triethoxypropyl ginseng (2-carbylethyl)isocyanurate (thermosetting resin), 1.2 parts of the above-mentioned cyan colorant thick dispersion, 1.2 parts of the above yellow colorant Thick dispersion, 0.3 parts of dicyanodiamine, 0.5 parts of polymer defoamer, 20 parts of molten cerium oxide, and 30 parts of settling barium sulphate. After mixing by three rolls, propylene glycol monoterpene was used. The base ether acetate adjusted the viscosity to 2 dPa.s. (Coated on printed circuit board) The obtained light and thermosetting solder resist ink were applied to the entire surface of the printed circuit board which had been previously processed by a bar coater (the thickness of the undried coating film was 80). Micron), and then, after preliminary drying (80 ° C, 20 minutes), the negative film formed with the pattern was brought into contact and exposed (500 mJ/cm 2 ). Subsequent development (immersion in 1% sodium carbonate aqueous solution) 60 seconds), and post-baking (1501, 30 minutes) to thermally harden it to form a coating film pattern which is cured by light and heat, thereby obtaining a cured film formed with a green solder resist coating film. Printed circuit board. [Comparative Example 1] The production of the cyan colorant thick dispersion of Example 1 and the production of the yellow colorant thick dispersion were changed to 800 parts of THPA and GMA (glycidyl methacrylate-addition resin). , LIONOL Blue-FG· 7351 was changed to 1 part, propylene glycol monoterpene ether acetate (PMA) was 100 parts, and iron three rolls were used instead of the particle mill to disperse, and 2 times 21 200827413 In the first time, the maximum particle diameter is 19 μί μm. The second largest film has a maximum particle diameter of 12 μm 3 μm. (The particle size measured by the measurement of the fineness of the polishing is performed in the same manner as in Example 1 to produce cyan. In the same manner as in the case of measuring the particle size of the dispersion using the above-mentioned measuring device, the cyan colorant was thickly dispersed at 1 μm, and its standard deviation was more than 0.2 μm and 'except for the use of xanthone yellow (the above [Chemical Formula Pigment Yellow 24] Instead of LIONOL Blue-FG-735 1 to obtain 1000 parts of a thick dispersion of yellow colorant. The yellow coloring k' was determined using the above measuring apparatus to have a particle diameter (average particle diameter) of 〇2 〇 5 μm at 0.249 μm. Do this The coloring agent corresponding to the obtained blue coloring coloring agent thick dispersion liquid was applied in the same manner as in Example 1 to produce a solder resist oil. The printed circuit board was applied in the same manner as in Example 1 and Comparative Example 1. The obtained printed circuit board and the solder resist ink were subjected to the following (1) heat resistance: the solder resist film of each printed circuit board obtained was immersed in 260 C molten solder for 30 seconds according to the test method of JIS C6481, and then A transparent dispersion was placed on the cured film, and the thick dispersion was used except that the average particle size was 15 min and the average particle diameter was 1 〇 to 2 5 μm. The average particle diameter of the concentrated liquid of the cyan colorant is larger than that of the compound shown in 1] (the same applies to the ci, the particle of the thick dispersion of the agent is the standard deviation of the thickener thick dispersion, the thick dispersion) In addition, the ink is used before the pre-loading of the electronic component to be carried out. The film of the ink is filmed in the solder bath (the cellophane is peeled off, and then peeled off in 22,274,274, that is, peeling off In the test, one test was performed as one cycle, and the same process was carried out for up to three cycles. The degree of peeling of the cured film was visually observed and evaluated according to the following criteria. The results are shown in Table 1. ◎ : No film after 3 cycles Change 〇: There is only a slight change in the coating film after 3 cycles △ : 2 After the cycle, the coating film changes. X : 1 After the cycle, the film is peeled off.

(2) Chemical resistance The cured film of the coating film of the solder resist ink of each printed circuit board was immersed in a 10% hydrochloric acid aqueous solution for 30 minutes, and then the state of the cured film was visually observed. The following benchmarks were evaluated and the results are shown in Table 1. ◎: There is no change at all 〇: only a slight change △: There is a significant change X: The coating film is expanded and peeled off (3) Solvent resistance The cured film of the coating film of the solder resist ink of each printed circuit board is obtained, and impregnated After 3 minutes of dichloromethane, the state of the cured film was visually observed, and evaluation was performed based on the following criteria. The results are shown in Table 1. ◎: No change at all 〇: Only a little change △: There is a significant change X: The film is expanded and peeled off 23 200827413 (4) Electrical characteristics

On the cured film of the coating film of the solder resist ink of each printed circuit board, a comb type electrode of IPC-SM-840B B-25 test coupon was placed at 60 ° C, 90 % RH. DC (direct current) 100 V was applied to the constant temperature and humidity chamber (relative humidity), and the degree of discoloration of the insulation resistance and the copper foil of the circuit pattern after 500 hours was investigated. The measured values of the insulation resistance were as shown in Table 1, and the degree of discoloration of the copper foil was visually observed and evaluated according to the following criteria. The results are shown in Table 1. ◎: Completely no discoloration 〇: only slight discoloration △: significant discoloration X: change to coke black (5) Amount of amine elution The filmed film of the coating film of the solder resist ink of each printed circuit board was cut and finely pulverized The measurement sample was prepared and measured by an ion chromatograph, and the measured values thereof are shown in Table 1. (6) Viscosity stability of the solder resist ink The obtained solder resist ink was filled in a polypropylene container and sealed, and after being stored in a hot air circulation tester at 70 ° C, the viscosity was measured using a viscometer. The evaluation was performed based on the following criteria, and the results are shown in Table 1. ◎: No increase in viscosity was observed for more than 7 days. 〇: The viscosity increased by more than 2 times or gelation in 5 to 6 days. △: The viscosity increased by more than 2 times or gelled in 3 to 4 days. 200827413 x : The viscosity increased more than 2 times or gelled in 1 to 2 days. (7) Lifting of blue pigment The obtained solder resist ink was placed in a beaker and sealed, and allowed to stand at 25 ° C for 72 hours. The state was visually observed and evaluated according to the following criteria. Table 1 shows. ◎: There is no cyan paint floating at all. 〇: I can see a little cyan paint floating up.

X: Cyan pigment floated on the surface (8) Color separation test PMA (propylene glycol monomethyl ether ethylene glycol) was added to 300 g of the solder resist of the examples and the comparative examples in a beaker at a concentration of 25%. The viscosity was adjusted so that the viscosity was 70S (measured by Iwata CUP NK_2). The ink was stirred at a low speed using a stirrer (8 ft. 31111, manufactured by ADVANTEC Co., Ltd.), and observed after 12 hours and 24 hours, and evaluated according to the following criteria. Table 1 shows the results. ◎: No color separation was observed. Color separation was observed. X: The color separation was severe. As shown in Table 1, the evaluation was also "〇" after 24 hours, and the pigment was not separated to maintain the dispersibility of the pigment. The color tone and color developability were also good. In contrast, the solder resist ink of the comparative example was "Δ" after 12 hours, and was "X" after 24 hours, and the dispersibility of the pigment deteriorated over time (more details) In other words, the color separation occurs, the cyan floats after 24 hours, and the centrifugal force makes the large grain 25 200827413

On the outer side, the small particles are concentrated on the inner side, and become a double concentric shape with a diameter ratio of about 1:5 (the inner circle is a circle in which the inner circle is concentrated without gaps, and the outer circular particles are concentrated on the outer diameter 1) /5, which becomes a ring-shaped circle that gradually becomes thinner on the inner side, and this tendency can be clearly observed after 12 hours.) Both the color tone and the color developability are deteriorated. As a result, it has been found that the particle size of the pigment of the present invention is smaller than that of the prior art, and the particle size distribution is also set to be narrow, and the pigment dispersion using the resist ink is good, and the dispersibility can be maintained, and as a result, the color tone and Hair color is not easy to get worse. (9) Coating test using a curtain flow applicator Fig. 3 is a schematic view of a known curtain flow applicator 10. As shown in Fig. 3, the conveyor belt 1 is wound around the shaft-supporting cylindrical rollers 8A and 8B by a motor (not shown), linearly moved in the direction of the arrow A, and the previously processed surface is sequentially transported. The printed circuit board 2 is coated by the ink jet head 3 by flowing down the obtained photo-thermosetting solder resist ink. The ink jet head 3 circulates, replenishes, and reuses the ink from the ink tank 4, which passes through the ink receiving tank 5 and is transferred by the pump 6, through the solder resist ink of the filter 7. In this manner, the printed circuit board is entirely coated, and then treated by the same conditions as in the application of the applicator described above, whereby a cured film formed with a green solder resist coating film is obtained. Printed circuit board. When the curtain coater 10 is applied, the light and the thermosetting solder resist ink can be improved and maintained in dispersibility, and stable color developability can be obtained, so that uniform color tone can be obtained. Coating film; at the time of manufacture of 2008 200827413 (at the time of mass production), since the color separation does not occur in the ink tank, the ink receiving groove 5 can also be enlarged, and the entire apparatus of the curtain flow applicator 10 can also be large. Therefore, the production efficiency of the printed circuit board of the coating film having the more stable color tone resist ink can be improved, and not only the cost of the product can be reduced, but also the color tone can be prevented from being prevented.

27 200827413 [Table i]

Example 1 Comparative Example 1 Solder heat resistance ◎ ◎ Chemical resistance ◎ ◎ Good solvent property ◎ ◎ Electrical property Insulation resistance X 1012 (Ω ) 2.5 2.5 Discoloration ◎ ○ Viscosity stability ◎ ◎ Amount of amine elution (ppm) <5 <;5 The floating color of the cyan pigment 〇 X color separation test 〇 X

[Industrial Applicability] The resist ink of the present invention can be used as a resist ink applied to a solder resist ink (s ο 1 d e r r e s i s t i n k ) such as a printed circuit board.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing the particle size distribution of a yellow pigment of a yellow thick dispersion used for a solder resist ink according to an embodiment of the present invention. Fig. 2 is a graph showing the particle size distribution of the yellow pigment of the yellow thick dispersion of the comparative example. Fig. 3 is a schematic perspective view showing a curtain flow applicator which is coated with a solder resist ink according to an embodiment of the present invention. [Main component symbol description] 28 200827413 1 Conveyor belt 2 Pre-processed printed circuit board 3 Ink nozzle 4 Ink tank 5 Ink receiving tank 6 Pump 7 Filter 8 A, 8B Shaft support cylindrical roller 9 Resist ink 10 Curtain Applicator

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Claims (1)

200827413 X. Patent application scope: 1. A resist ink comprising (A) a colorant, (B) a curable (C) reactive diluent, (D) a polymerization initiator, and (E) a filler ink. Wherein the average particle diameter of the (A) colorant, the particle diameter measured by laser diffraction is 0.01 μm or more and less than 1 μm, and the particle size registration deviation is 0.1 to 0.2 μm. 2. A printed circuit board comprising a coating film of a resist ink as claimed in claim 1. 3. A method for preparing a resist ink by using at least a coloring agent and a pulverizer for producing a fine powder to produce a thick dispersion of a coloring agent thick; and then mixing (A') the coloring agent And the average particle diameter of the particles measured by the laser diffraction scattering method is 0. 0 1 or more and less than or less than (1) less than 0.1 micron or less. 1 micron, and the particle size distribution deviation is 0.; 1~0.2 micron. 4. A method for producing a resist ink, which comprises at least 1 to 50 parts by weight of a coloring agent, 20 to 60 heavy solvents, and 10 to 50 parts by weight of a resin in an amount of 100 parts by weight or more. A micro-powder crusher for producing a thickener for dispersing a colorant thickly, and then mixing (A') the thick dispersion of the colorant, (B) hardening the cation (C) reactive diluent, and (D) polymerizing And the average particle size of the particle size is less than 1 μm, and the standard deviation of the particle size distribution is 0. 1~0. Resin, The agent mentioned in the standard of the resisting oil spray method, and scattered with the 'dispersion, and (E) diameter, which is based on the whole amount of powder dispersion; resin, f color agent, 05 microns 2 microns. 30