CN101407636A - Resin composition for appearance inspection of printed circuit board - Google Patents
Resin composition for appearance inspection of printed circuit board Download PDFInfo
- Publication number
- CN101407636A CN101407636A CNA200710182014XA CN200710182014A CN101407636A CN 101407636 A CN101407636 A CN 101407636A CN A200710182014X A CNA200710182014X A CN A200710182014XA CN 200710182014 A CN200710182014 A CN 200710182014A CN 101407636 A CN101407636 A CN 101407636A
- Authority
- CN
- China
- Prior art keywords
- resin combination
- resin
- intensity level
- circuit board
- printed circuit
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
The invention provides a resin composition used for visual examination of a printed circuit board. The invention is characterized in that the resin composition contains (A) colorant and (B) components with curing property. The luminance level of a curative capsule of the resin composition ranges 30 to 120.
Description
Technical field
The present invention relates in the visual inspection of printed circuit board (PCB), improve the resin combination and the cured article thereof of electronic component recognition rate and the printed circuit board (PCB) that possesses the curing tunicle of described resin combination.
Background technology
The real of printed circuit board (PCB) at densification, diversified development adorned in the operation, the real dress state of electronic component, the quality of soldering portion meeting left and right sides reliability of products, therefore, in order to improve operating efficiency, to guarantee that the automatization of the visual inspection of operation quality, mechanize are popularized.
As the real appearance inspection method that installs to the electronic component of printed circuit board (PCB), just like patent documentation 1 proposed like that, for example take and check object elements and welding zone contacted and solder resist with it with ccd video camera, obtain intensity level separately, whether the difference by judging this intensity level is in the quality of certain certain difference with the decision element installment state of coming up.
In addition, patent documentation 2 discloses the inspection method of positions of electronic parts skew, according to this method, obtain and be set at from the only briliancy distribution of the offset detection line of the position of deviation position skew permissible value of electrode, in the briliancy of being tried to achieve distributes if any or it more than bright part bright on an equal basis with terminal, then check the zone in the terminals of electronic components set positions, obtain the distribution of checking the part that becomes clear on an equal basis with terminal or become clear more than it in the zone, can judge that thus at the detected light of offset detection line be terminals of electronic components or noise, reduce the false judgment that noise causes, improve and judge precision.
Yet when judging quality by intensity level, according to the kind of the solder resist that is applied to printed circuit board (PCB), the substrate (on the copper circuit pattern or on the base material) of coating solder resist, there is difference in intensity level and deviation is arranged easily.
For example, intensity level is in the situation of 80 solder resist, the real dress of element is normal shown in Fig. 1 (a-1), and element is real shown in Fig. 1 (a-2) adorns when unusual, check and measure the position: (a) is big with the difference of the intensity level at element electrode position (b) on the solder mask, can discern on the solder mask and element electrode portion, can carry out whether qualified judgement.
In addition, when element comes off shown in Fig. 1 (a-3), check and measure the position: (a) is big with the difference of the intensity level of component body portion (c) on the solder mask, therefore can carry out whether qualified judgement.
Intensity level is in the situation of 150 solder resist, even if the real dress of element just often shown in Fig. 1 (a-1), because check and measure the position: the difference of the intensity level of the intensity level of (a) and element electrode position (b) is little on the solder mask, therefore feature difference that can't extraction and determination portion is difficult to carry out the whether qualified judgement of the real dress of element.
In addition, element is real shown in Fig. 1 (a-2) adorns under the unusual situation, because check to measure the position: the difference of the intensity level of the intensity level of (a) and element electrode position (b) is little on the solder mask, feature difference that therefore can't extraction and determination portion is difficult to carry out the real whether qualified judgement of adorning of element.
Intensity level is in the situation of 20 solder resist, even if the real dress of element just often shown in Fig. 1 (a-1), because check and measure the position: the difference of the intensity level of the intensity level of (a) and component body (c) is little on the solder mask, therefore feature difference that can't extraction and determination portion is difficult to carry out the whether qualified judgement of the real dress of element.
In addition, shown in Fig. 1 (a-3) the real dress of element unusual, when element comes off, because the intensity level of (a) is little with the difference of the intensity level of component body (c) on the solder mask, feature difference that therefore can't extraction and determination portion is difficult to carry out the real whether qualified judgement of adorning of element.
Patent documentation 1: Japanese kokai publication hei 5-249045 communique
Patent documentation 2: Japanese kokai publication hei 11-63924 communique
Summary of the invention
The problem that invention will solve
The present invention carries out for the problem that solves above-mentioned prior art existence, its main purpose is to provide a kind of resin combination, said composition can form the certain resin layer of intensity level on substrate or solder mask, eliminate the difference of the intensity level that the solder resist difference caused thus.
The means that are used to deal with problems
The result of people's further investigation of the present invention, find by layer at the resin combination of formation intensity level between scolder and element on substrate or the solder mask, recognition rate in the time of can significantly improving the difference of utilizing intensity level and check the real dress of element, thus the present invention finished.
Promptly, a form of the present invention is a kind of resin combination that is used for the visual inspection of printed circuit board (PCB), it is characterized in that described resin combination contains (A) tinting material, (B) solidified nature composition, the intensity level of the curing tunicle of this resin combination is 30～120.
Another form of the present invention is a kind of cured article, and its resin combination by the invention described above solidifies and obtains.
A form more of the present invention is a kind of printed circuit board (PCB), and its resin combination that is provided with the invention described above solidifies the curing tunicle that obtains.
The invention effect
The resin combination that is used for the visual inspection of printed circuit board (PCB) of the present invention, because its intensity level that solidifies tunicle is 30～120, intensity level is between scolder and element, therefore, by on substrate or solder mask, forming the layer of resin combination of the present invention, the recognition rate in the time of can significantly improving the difference of utilizing intensity level and check the real dress of element.
Description of drawings
Fig. 1 is solder mask, the circuit pad (scolder) when the real dress of element schematically is shown, the explanatory view of element.Fig. 1 (a-1) illustrates the sketch of the visual inspection of printed circuit board (PCB) and the real dress of element.Fig. 1 (a-2) illustrates the unusual sketch of position of components skew.In addition, Fig. 1 (a-3) illustrates the element unusual sketch that comes off.Fig. 1 (a-4) illustrates the sketch of the intensity level of real dress element.In Fig. 1, (d) expression printed circuit board (PCB), (e) indication circuit pad, B1 represent that the component body intensity level is 15, B2 represents that the element electrode intensity level is 200.
Fig. 2 is the figure of expression intensity level.
Fig. 3 is for schematically illustrating the explanatory view that resin combination of the present invention is applied to the inspection when going forward side by side the real dress of units on the printed circuit board (PCB).In Fig. 3, (a) expression is formed with the printed circuit board (PCB) of circuit, (b) coating of expression solder resist is solidified, (c) expression resin combination coating of the present invention is solidified, (d) expression solder paste coating, (e) the real dress of expression element, (f-1) expression does not have the visual inspection under the situation of resin combination of the present invention, in the judgement of the real dress of element, the difference of the briliancy rate between solder mask (circuit pattern) and element electrode is few, can not carry out whether qualifiedly judging, (f-2) expression has the visual inspection under the situation of resin combination of the present invention, in the judgement of the real dress of element, the difference of the briliancy rate between resin combination of the present invention (briliancy rate 30～120) and element electrode is big, can carry out whether qualifiedly judging.In Fig. 3,1 expression base material, 2 expression copper circuits, 3 expression solder resists, 4 expressions resin combination of the present invention, 5 expression solder paste coatings, the real dress of 6 expressions element, B3 represents that solder mask (on the copper circuit) brightness value is 150, B4 indication circuit pad brightness value is about 200, B5 represents that the element electrode brightness value is about 200, and B6 represents that resin combination brightness value of the present invention is 30～120, and B7 represents that the element electrode brightness value is about 200.
Fig. 4 represents the visual inspection treatment scheme.
Embodiment
Below specify the present invention.
The intensity level of the curing tunicle of resin combination of the present invention is 30～120 scope, more preferably 60～100.Intensity level is lower than at 30 o'clock, might be difficult to distinguish solder resist and element, and intensity level is higher than at 120 o'clock and might be difficult to distinguish solder resist and scolder.
Intensity level among the present invention is meant that the image transitions of the object that will take with ccd video camera becomes numerary signal and carries out various calculations and handle, thereby makes the shading image that object deep or light is divided into 0～255 256 tones.The level that this is deep or light is called intensity level, and as shown in Figure 2, intensity level 0 expression black, intensity level 255 are represented pure white.Poor according to intensity level carries out the shape recognition of object and carries out position detection with high accuracy.
Among the present invention,, use tinting material as the method that is used to adjust intensity level.More particularly, by (A) tinting material is cooperated with (B) solidified nature composition (Thermocurable composition, light solidified composition) etc., and the intensity level that obtains curing tunicle of the present invention is 30～120 resin combination.
In the present invention, (A) tinting material can use known material commonly used, and pigment, dyestuff, pigment all can.Wherein, from reducing carrying capacity of environment and, preferably not containing halogen to the viewpoint of the influence of human body.
The object lesson of (A) used in the present invention tinting material, can list carbon black system, phthalocyanine system, azo system, tetrazo system, quinacridone, anthraquinone system, flavanthrene Xi, piceneketone Xi, perylene is the various organic system tinting materials of, dioxazine system, condensation azo system, azomethine system, methyne system, titanium oxide, zinc oxide, iron oxide black, chrome yellow, zinc yellow, chrome vermilion, colcother, lead sulfate, cobalt violet, ultramarine, dark purple, chrome green, chromic oxide, cobalt green etc. are inorganic to be tinting material.Preferred especially carbon black.These tinting materials can use separately or mix more than 2 kinds and use.
Resin combination of the present invention, by cooperating tinting material to adjust the intensity level of the curing tunicle of resin combination, its use level is to make the intensity level of the curing tunicle of resulting composition become 30～120, preferred 60～100 ratio as mentioned above.0.1 quality % of the common complexing compositions total amount of tinting material～10.0 quality %.
As mentioned above, be the curing tunicle of 30～120 resin combination by being formed with on the substrate of circuit or on the solder mask at this substrate, intensity level of the present invention being set, distinguish this three of scolder, element and solder mask.Yet, sometimes because of the influence of substrate that resin combination of the present invention is set, and the intensity level of resin combination of the present invention is changed, can not distinguish exactly.According to the inventor's research, by improving the hidden power of resin combination of the present invention, intensity level does not change because of the influence of substrate, the identification error in the time of can further eliminating self-verifying.
That is, resin combination of the present invention is preferably the high resin combination of hidden power, and (C) masking agent as giving the hidden power of resin combination can use weighting agent or above-mentioned tinting material.In the present invention, filling agent can use known material commonly used.These weighting agents can use separately or mix more than 2 kinds and use.
The object lesson of the filling agent that the present invention is used can list titanium oxide, zinc oxide, subcarbonate, basic zinc sulfate, silicate, zinc sulphide, weisspiessglanz, talcum, aluminum oxide, clay, magnesium oxide, aluminium hydroxide, silica, magnesium hydroxide, barium sulfate etc.Wherein, from hidden power and avirulent viewpoint, preferred titanium oxide.
Hidden power among the present invention is meant and covers and cover the color of substrate and can not see the performance of substrate color, during with the thickness coating resin composition of 10～20 μ m, and the measured color value L of resin combination
*Value not because of the measured color value L of substrate
*Value and when big difference is arranged, think that this resin combination has hidden power.In addition, measured color value L
*Being meant the numerical value of expression lightness=concentration, is that from 0 to 100,0 expression black, 100 expressions are pure white.Measuring method is specified in JIS JIS-K5600-4-4, JIS-K5600-4-5, JIS-K5600-4-6.
In the composition of the present invention, be used to give the masking agent of the hidden power of resin combination, its content is preferably 10～50 quality % of total composition.When content is lower than 10 quality %, can not give sufficient hidden power, when content is higher than 50 quality %, might bring detrimentally affect the characteristic that gained solidifies tunicle.
As previously mentioned, by aforementioned (A) tinting material is cooperated with (B) solidified nature composition, further cooperate (C) masking agent, and obtain resin combination of the present invention.In addition, resin combination of the present invention can be set directly on the substrate that is formed with circuit and play the function of solder mask simultaneously, or also can be arranged on the printing ink that serves as a mark on the solder mask.
As above-mentioned (B) solidified nature composition, can use (B-1) photo-curable resin and (B-2) side or the both sides of thermosetting resin.According to the kind of employed curable resin, resulting composition becomes thermoset composition, light thermosetting composition or light solidity thermoset composition.
(B-1) used in the present invention photo-curable resin is as the known material of ultraviolet curing resin, and the resin of radical polymerization mould assembly, cationic polymerization type is arranged.
As the radical polymerization mould assembly, can list polyvalent alcohol system, polyethers system, unsaturated polyester system, urethane system, epoxy system, polyester/urethane system, polyacetal system, polyhutadiene system, contain various acrylate monomers, methacrylate monomer and the oligopolymer thereof of carboxylic acid photo-curable resin system.
Photo-curable resin of the present invention is contained contains the carboxylic acid resin, can use the resin compound known commonly used that contains carboxylic acid in the molecule.From light solidity, alkaline-resisting development aspect, what more preferably also have ethylenical unsaturated double bonds in molecule contains the carboxylic acid photoresist.
As cationic polymerization type, use Resins, epoxy, be preferably especially and contain carboxylic acid photo-curable resin system.
Resin combination of the present invention is to be set directly to be formed with on the circuit substrate and when using as solder mask, as (B-1) photo-curable resin, from utilizing alkaline aqueous solution to develop, and the viewpoint that can obtain the welding resistance tunicle of the tunicle excellent such as adaptation, thermotolerance, chemical proofing, electrical insulating property, hardness to substrate is set out, and is preferably the photosensitivity prepolymer (oligopolymer or polymkeric substance) that has carboxyl and at least two ethylenical unsaturated double bonds in 1 molecule.
As described photosensitivity prepolymer, can list:
Have multi-group epoxy compound's the epoxy group(ing) of at least two epoxy group(ing) and the carboxyl of unsaturated monocarboxylic in (1) 1 molecule and carry out esterification (full esterification or partial esterification reaction, be preferably full esterification), the material that the hydroxyl that generated is further obtained with saturated or unsaturated multi-anhydride reaction;
(2) after the multipolymer that forms by (methyl) alkyl acrylate and (methyl) glycidyl acrylate and the reaction of (methyl) vinylformic acid, further react and the material that obtains with saturated or unsaturated multi-anhydride;
(3) make the multipolymer of (methyl) acrylic acid hydroxy alkyl ester and (methyl) alkyl acrylate and (methyl) glycidyl acrylate, after the reaction of (methyl) vinylformic acid, the further material that obtains with saturated or unsaturated multi-anhydride reaction;
(4) make (methyl) alkyl acrylate and (methyl) acrylic acid multipolymer, the material that obtains with (methyl) glycidyl acrylate partial reaction;
(5) make have in the multi-group epoxy compound that has at least two epoxy group(ing) in 1 molecule, unsaturated monocarboxylic, 1 molecule at least two hydroxyls and 1 can with the compound reaction of other reactive group beyond the hydroxyl of epoxy reaction, the material that gained reaction product (I) is obtained with saturated or unsaturated multi-anhydride reaction;
(6) make unsaturated multi-anhydride such as maleic anhydride and vinylbenzene etc. have the multipolymer of the aromatic hydrocarbons of vinyl, the material that obtains with the reaction of (methyl) acrylic acid hydroxy alkyl ester
Deng the poly carboxylic acid resin that contains unsaturated group;
(7) above-mentioned reaction product (I) and saturated or unsaturated multi-anhydride and the reaction product that contains the unsaturated group monoisocyanates
Deng poly carboxylic acid urethane resin that contains unsaturated group etc.
Aforesaid photosensitivity prepolymer, owing to be the material of having given a plurality of free carboxies at the side chain of trunk polymer, therefore, the composition that contains this photosensitivity prepolymer can develop by the diluted alkaline aqueous solution, simultaneously, can obtain the photo-resist tunicle of predetermined pattern by exposure, development.In addition, cooperate thermoset composition (B-2) simultaneously, for example during epoxy compounds, film by post-heating, between the epoxy group(ing) of the epoxy compounds of thermoset composition and the free carboxy of above-mentioned side chain addition reaction takes place, the curing tunicle of every excellents such as the thermotolerance that can obtain filming, solvent resistance, acid resistance, adaptation, electroless plating tolerance, electrical characteristic, hardness.
In addition, the preferable range of the acid number of above-mentioned photosensitivity prepolymer need be the scope of 30～200mgKOH/g usually according to its kind and different, and preferred range is 30～120mgKOH/g.Acid number is during less than 30mgKOH/g, to the solvability variation of alkaline aqueous solution, if instead during excessively greater than 200mgKOH/g, can become the major cause as the characteristic of solder resist such as the alkali resistance that reduces cured film, electrical characteristic, and is neither preferred.
The resin of aforementioned (1), as described later, (for example be by multi-group epoxy compound and unsaturated monocarboxylic, vinylformic acid, methacrylic acid, β-styrene acrylic, β-furfuryl group vinylformic acid, Ba Dousuan, the alpha-cyano styracin, styracin etc.) reaction product, with saturated or unsaturated multi-anhydride (for example, maleic anhydride, succinyl oxide, itaconic anhydride, Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, carbic anhydride, the methyl carbic anhydride, dibasic acid anhydrides such as hexachloroendomethylene-tetrahvdrophthalic anhydride, perhaps, trimellitic acid 1,2-anhydride, aromatic series polybasic acid anhydride classes such as pyromellitic acid acid anhydride) reaction obtains.At this moment, what be suitable for is: each hydroxyl that reaction product had of multi-group epoxy compound and unsaturated monocarboxylic, react multi-anhydride more than 0.15 mole and the resin that obtains.
On the other hand, multipolymer as the base polymer of aforementioned (2) and (3) resin, can be by using foregoing (methyl) alkyl acrylate and (methyl) glycidyl acrylate or further using (methyl) acrylic acid hydroxy alkyl ester as monomer, pass through known method, solution polymerization process etc. for example makes these monomers carry out copolymerization and obtains.
Aforementioned (methyl) alkyl acrylate has: alkyl esters such as the methyl esters of acrylic or methacrylic acid, ethyl ester, propyl ester, isopropyl ester, butyl ester, own ester, here, alkyl is the aliphatic group of charcoal atomicity 1～6.In addition, (methyl) acrylic acid hydroxy alkyl ester is the hydroxy alkyl ester of acrylic or methacrylic acid, and here, hydroxyalkyl is preferably the aliphatic group of the charcoal atomicity 1～6 with primary hydroxyl.
In the resin of aforementioned (2)～(4), the polymerization degree of the multipolymer that obtains by each monomer of copolymerization counts 10000～70000 with weight-average molecular weight, is preferably 20000～60000 scope.During weight-average molecular weight less than 10000, the touch dry reduction of filming, on the other hand, weight-average molecular weight surpasses at 70000 o'clock, and development reduces easily, so not preferred.
In addition, except aforementioned each monomer, in the scope that characteristic is not had influence, can also use vinyl compounds such as vinylbenzene, vinyl toluene.
The building-up reactions of the resin of aforementioned (5) has: first method, make multi-group epoxy compound and foregoing unsaturated monocarboxylic (perhaps, have at least two hydroxyls and 1 can with the compound of other reactive group beyond the hydroxyl of epoxy reaction, for example, dimethylol propionic acid, dihydroxymethyl acetate, dimethylolpropionic acid, dihydroxymethyl valeric acid, dihydroxymethyl caproic acid etc. contain polyhydric monocarboxylic acid; Dialkanol such as diethanolamine, diisopropanolamine (DIPA) amine etc.) method with above-claimed cpd (perhaps unsaturated monocarboxylic) reaction is followed in reaction; Second method, the method that multi-group epoxy compound, unsaturated monocarboxylic and above-claimed cpd are reacted simultaneously.Two kinds of methods all can, preferred second method.
The reaction product (I) that obtains by above-mentioned reaction and the reaction of multi-anhydride, preferably with respect to the hydroxyl in the described reaction product (I), per 1 equivalent hydroxyl reaction, 0.1～0.9 equivalent multi-anhydride.
On the other hand; in the building-up reactions of the poly carboxylic acid urethane resin that contains unsaturated group of aforementioned (7); preferably make previous reaction product (I) and multi-anhydride reaction; then; with the monoisocyanates that contains unsaturated group (for example; the methacryloyl based isocyanate; the methylacryoyloxyethyl isocyanic ester; perhaps; organic diisocyanate (for example, tolylene diisocyanate; Xylene Diisocyanate; isophorone diisocyanate; hexamethylene diisocyanate etc.) with 1 molecule in have 1 hydroxyl (methyl) esters of acrylic acid with the reaction product that waits molar ratio reaction approximately and obtain etc.) react.
As other (B-1) photo-curable resin; can use existing known various photosensitivity prepolymers; as, have the photosensitivity prepolymer of at least 2 acryls or methacryloyl etc. in 1 molecule of being put down in writing in Japanese kokai publication sho 51-131706 number, Japanese Patent Publication 63-46791 number, the Japan special fair 1-32868 number etc.
As the object lesson of (B-2) used in the present invention thermosetting resin, can list existing known various thermosetting resins, be not subjected to special qualification.For example can enumerate: Resins, epoxy, guanamine resin, benzoguanamine resin, silicone resin, diallyl phthalate resin, resol, melamine resin, urea resin, unsaturated polyester resin, urethane resin, polyimide resin etc.From the aspects such as characteristic of thermofixation characteristic, curing tunicle, special preferred epoxy.
Resin combination of the present invention is set directly on the substrate that is formed with circuit and when using as solder mask, (B-2) thermosetting resin is preferably: have the multi-group epoxy compound of at least two epoxy group(ing) in (B-2-1) 1 molecule as above-mentioned Resins, epoxy and/or (B-2-2) have the polyfunctional group oxetane compound of at least two oxetanyls in 1 molecule.
The object lesson that has the multi-group epoxy compound of at least two epoxy group(ing) in aforementioned (B-2-1) 1 molecule, can use or make up two or more uses separately with having known Resins, epoxy now, for example, phenolic resin varnish type epoxy resin (for example, phenol, cresols, phenols such as alkylphenol and formaldehyde react under an acidic catalyst and obtain the phenolic varnish class, the reaction of this phenolic varnish class and epoxy chloropropane and/or methyl epichlorohydrin and the material that obtains etc.), bisphenol-type epoxy resin (for example, dihydroxyphenyl propane, Bisphenol F, bisphenols such as bisphenol S and epoxy chloropropane and/or methyl epichlorohydrin reaction and the material that obtains, the condenses that the diglycidylether of dihydroxyphenyl propane and aforementioned bisphenols form reacts with epoxy chloropropane and/or methyl epichlorohydrin and the material that obtains etc.), tris-phenol type Resins, epoxy (for example, tris-phenol, three cresols methane etc. and epoxy chloropropane and/or methyl epichlorohydrin reaction and the material that obtains etc.), three (2, the 3-epoxypropyl) isocyanuric acid ester, biphenyldiglycid ether, and ester ring type, contain aminoepoxy resin, copoly type Resins, epoxy (for example, glycidyl methacrylate and cinnamic multipolymer, the multipolymer of glycidyl methacrylate and vinylbenzene and methyl methacrylate, perhaps multipolymer of glycidyl methacrylate and cyclohexyl maleimide etc. etc.), perhaps other has the Resins, epoxy of special construction etc.
In addition, as the polyfunctional group oxetane compound that has two above oxetanyls in (B-2-2) 1 molecule, can enumerate the ether compound etc. that polyfunctional group trimethylene oxide classes such as dioxygen heterocycle butanes, trioxa cyclobutane, phenolic varnish type trimethylene oxide, calixarene type trimethylene oxide, cardo type trimethylene oxide, polycarboxylated styrene type trimethylene oxide or silicone resin classes such as these compounds and silsesquioxane etc. have the resin formation of hydroxyl.
In addition, in the above-mentioned thermosetting resin (B-2),, can realize a liquefaction of curable resin composition by using the polyfunctional group oxetane compound.This is because the polyfunctional group oxetane compound is compared reactive slow with the multi-group epoxy compound, the cause that ageing stability is extremely excellent.According to the characteristic of this ageing stability excellence, above-mentioned curable resin composition also helps dry filmization.
Addition about above-mentioned solidified nature composition (B) is not particularly limited.Can form suitably according to target and select.Constitute under the situation of light solidity thermoset composition, for example, with respect to 100 mass parts photo-curable resins (B-1), the addition of thermosetting resin (B-2) is preferably the scope of 1～100 mass parts.This is because during thermosetting resin (B-2) less than 1 mass parts, the thermosetting performance significantly reduces, and perhaps causes the increase at uncured position; On the other hand, when the addition of thermosetting resin (B-2) surpassed 100 mass parts, ageing stability might extremely reduce.Therefore, from the viewpoint of curing performance and ageing stability, with respect to 100 mass parts photo-curable resins (B-1), the addition of thermosetting resin (B-2) is preferably 2～70 mass parts, more preferably in the scope of 5～50 mass parts.
Further, resin combination of the present invention can add additive etc. as required.As additive, can list (D) curing catalyst, (E) light trigger, (F) organic solvent.These additives can use separately or mix more than 2 kinds and use.
As (D) curing catalyst, can use known promotor, as amine, imidazoles, four substituted boracic acid salt, triphenylphosphine class, annular aliphatic amine etc.
As (E) light trigger used among the present invention, can use the compound that produces free radical by the irradiation active energy beam, for example photic radical polymerization initiator, photo-induced cationic polymerization initiator etc.
As (E-1) radical polymerization mould assembly light trigger, can enumerate for example anthraquinone class, as 2-methylanthraquinone, 2-amyl anthraquinone, 2-tertiary butyl anthraquinone, 1-chloroanthraquinone etc.; Bitter almond oil camphor and benzoin ethers are as bitter almond oil camphor, benzoin methylether, ethoxybenzoin etc.; Benzophenone, as benzophenone, 4-(1-tertiary butyl dioxy-1-methylethyl) benzophenone, 3,3 ', 4,4 '-four (tertiary butyl dioxy carbonyl) benzophenone etc.; Acetophenones, as methyl phenyl ketone, 2,2-dimethoxy-2-phenyl methyl phenyl ketone, 4-(1-tertiary butyl dioxy-1-methylethyl) methyl phenyl ketone etc.; The thioxanthene ketone, as 2,4-dimethyl thioxanthone, 2,4-di-isopropyl thioxanthone, 2-clopenthixal ketone etc.
As (E-2) cationic polymerization type light trigger, can use known light triggers such as aromatic series diazonium salt, aromatic series halogen, aromatic series sulfosalt, metallocene compound.
As (F) organic solvent, can list ketone, aromatic hydrocarbon based, glycol ethers, glycol ether acetates, ester class, alcohols, aliphatic hydrocarbon, oil series solvent etc.For example, can enumerate ketones such as methylethylketone, pimelinketone; Toluene, dimethylbenzene, tetramethyl-benzene etc. are aromatic hydrocarbon based; Glycol ethers such as cellosolve, methylcyclohexane, ethylene glycol butyl ether, Trivalin SF, methyl carbitol, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, Triethylene glycol ethyl ether; Acetate esters such as ethyl acetate, butylacetate, cellosolve acetic ester, butyl cellosolve acetate, Trivalin SF acetic ester, acetate of butyl carbitol, propylene glycol methyl ether acetate, dipropylene glycol monomethyl ether acetic ester; Alcohols such as ethanol, propyl alcohol, ethylene glycol, propylene glycol; Aliphatic hydrocarbon such as octane, decane; Petroleum-type solvents such as sherwood oil, petroleum naphtha, hydrotreated naphtha, solvent naphtha etc.Can be used alone or make up two or more uses.
Resin combination of the present invention can also cooperate following known additive kind commonly used as required, as, known hot stoppers commonly used such as quinhydrones, hydroquinone monomethyl ether, tert-butyl catechol, pyrogallol, thiodiphenylamine, known thickening materials commonly used such as fine particle silica, organobentonite, polynite, the defoamer and/or the flow agent of silicone, fluorine class, high score subclass etc., the silane coupling agent of imidazoles, thiazoles, triazole species etc., antioxidant, rust-preventive agent etc.
After materials such as resin combination of the present invention is the resin combination more than a kind or 2 kinds that will comprise aforementioned hot thermosetting resin or photo-curable resin, be used to adjust the tinting material of intensity level and hidden power and weighting agent, the curing catalyst that cooperates as required, light trigger, organic solvent evenly cooperate, mixing rolls such as use roller mill are mixing, make aqueous resin combination of the present invention then.
In addition, resin combination of the present invention is when containing the carboxylic acid photo-curable resin, be will comprise the aforementioned hot thermosetting resin or contain materials such as the resin combination more than a kind or 2 kinds of carboxylic acid photo-curable resin, the tinting material that is used to adjust intensity level and hidden power and weighting agent, the curing catalyst that cooperates as required, light trigger, organic solvent evenly cooperate after, mixing rolls such as use roller mill are mixing, make aqueous resin combination of the present invention then.
The following describes the using method of the resin combination that obtains thus.(with reference to Fig. 3) is being formed with (Fig. 3 it (a)) on the printed circuit board (PCB) of circuit, by known method coating solder resist and after solidifying, obtains forming figuratum printed circuit board (PCB).
For example, thermofixation or UV solidify under the situation of solder resist, carry out the pattern printing by silk screen print method after, thermofixation (heated air circulation type drying oven, IR stove etc.) or UV solidify (UV travelling belt).
In addition, contain under the situation of carboxylic acid photo-curable resin, after the silk screen print method printing,, form pattern, carry out thermofixation (Fig. 3 it (b)) with the heated air circulation type drying oven then with photomask exposure, alkali development with the heated air circulation type kiln dried.
Then, on above-mentioned printed circuit board (PCB), be coated with resin combination of the present invention and curing, obtain being formed with the curing of resin combination of the present invention by the printed circuit board (PCB) of rete.
For example, when resin combination of the present invention is under thermofixation or the UV solidified situation, after known method (silk screen print method, spraying method, curtain are coated with method, rolling method, dip coating, spin-coating method, photopolymer layer platen press etc.) coating, carry out thermofixation (heated air circulation type drying oven, IR stove etc.) or UV and solidify (UV travelling belt etc.), obtain being formed with the printed circuit board (PCB) of the curing tunicle of resin combination of the present invention.
In addition, when resin combination of the present invention is to contain under the situation of carboxylic acid photo-curable resin, be applied on the printed circuit board (PCB) that is formed with copper circuit and is coated with solder resist by known method, under about 60～100 ℃ temperature, with organic solvent volatile dry contained in the composition (interim dry), by forming figuratum photomask, utilize active energy beam that resulting filming carried out the selectivity exposure.By the diluted alkaline aqueous solution (for example 0.3～3% aqueous sodium carbonate) unexposed development formed pattern.Further contain under the situation of light solidity thermoset composition of thermoset composition heating and carry out thermofixation (heated air circulation type drying oven, IR stove etc.) and obtain being formed with the curing of resin combination of the present invention under about 140～200 ℃ temperature again by the printed circuit board (PCB) of rete.
The thickness of cured article is generally 5～100 μ m, more preferably 10～50 μ m (Fig. 3 it (c)).
And then have: the curing of making in above-mentioned operation that is formed with resin combination of the present invention is by the solder paste painting process by printing such as silk screen print method soldering paste on the copper pad that is used for soldered elements on the printed circuit board (PCB) of rete.(Fig. 3 it (d))
After this operation, have the real dress of element operation, carry element being printed with on the copper pad of soldering paste, put in the reflow ovens, make the soldering paste fusion, cool off then and weld.(Fig. 3 it (e))
Further, the substrate behind the real dress carries out shape recognition according to the difference of intensity level and carries out the judgement of correcting errors of real dress in visual inspection.(Fig. 3 it (f-1), (f-2))
Fig. 4 is the synoptic diagram of structure of the appearance inspection device of expression embodiment of the present invention.Illustrated appearance inspection device is by the visual inspection portion that possesses pick up camera and perform calculations, the image processing part of feature extraction, judgement constitutes.Visual inspection portion will be formed with circuit pattern and the real printed circuit board (PCB) of having adorned element carries out visual inspection as the inspection object.Image processing part reads the picture signal of the substrate that is obtained by the shooting of visual inspection portion and uses this picture signal to judge.
Particularly, the illumination light of ejaculation is reflected by substrate, and pick up camera for example is to use ccd sensor to constitute, by ccd sensor photographic substrate surface.In this pick up camera, be subjected to light by ccd sensor, form and this light income image signals corresponding (electrical signal).The picture signal that is generated by this pick up camera is sent to image processing part.
Image processing part possesses signal conversion part, feature extraction portion, detection unit.The picture signal that the letter converter section will be sent by the pick up camera of visual inspection portion converts luminance signal to.In this signal conversion part, the pixel unit that reads with the ccd sensor of further saying so in detail corresponding to the pixel unit of the shooting resolution of pick up camera converts picture signal to luminance signal.The briliancy rate (gray-scale value) that this luminance signal for example is represented as the darkest dark portion is made as " 0 ", and the briliancy rate of the brightest bright portion is made as 256 gray scales of " 255 ".Feature extraction portion extracts the difference of the intensity level separately of checking object elements and welding zone contacted with it and solder resist.At detection unit, whether the difference of the intensity level that inquiry agency extracts is more than certain difference, if more than certain difference, it is normal then to be judged to be real dress, if below certain difference, it is unusual then to be judged to be real dress.
Embodiment
Below, embodiment being shown and comparative example is specifically described the present invention, the present invention is not limited to following embodiment.In addition, following " part " all represents " mass parts " unless otherwise specified.
＜contain the synthetic of carboxylic acid resin 〉
Prepare the carboxylic acid photo-curable resin that contains of the present invention according to following synthesis example.
Add 220 parts of cresols phenolic resin varnish type epoxy resins (Dainippon Ink. ﹠ Chemicals Inc's manufacturing, " EPICLON " (registered trademark) N-695, epoxy equivalent (weight)s: 220) in the four-hole boiling flask of belt stirrer and reflux exchanger, add 214 parts of Trivalin SF acetic ester, heating for dissolving.Then, add 0.46 part of quinhydrones as stopper, as 1.38 parts of the triphenylphosphines of catalysts.With this mixture heating up to 95～105 ℃, slowly drip 72 parts of vinylformic acid, reacted 16 hours.This reaction product is cooled to 80～90 ℃, adds 106 parts of Tetra Hydro Phthalic Anhydrides, reacted 8 hours, after the cooling, take out reaction soln (being called varnish (A-1)).The acid number of the solid matter that contains the carboxylic acid resin that obtains like this is that 100mgKOH/g, nonvolatile component are 65%.
Example 1～5 and comparative group precedent 1,2 are formed in＜enforcement 〉
With each components matching of prescription shown in the following table 1, and use three roller rollers mill mixing, obtain resin combination.
Table 1
Resins, epoxy: EPIKOTE828 (manufacturing of japan epoxy resin Co., Ltd.)
Resol: HOCN581-EC65 (bright chemical (Huzhou) company limited makes)
Carbon black: carbon black M-50 (Mitsubishi chemical Co., Ltd's manufacturing)
Titanium oxide: KA-15 (manufacturing of titanium Industrial Co., Ltd)
Phthalocyanine blue: Fastogen Blue 5380 (Dainippon Ink. ﹠ Chemicals Inc's manufacturing)
Defoamer: KS-66 (Shin-Etsu Chemial Co., Ltd's manufacturing)
Curing catalysts: 2, (Shikoku Chem makes 4-diamino-6-(2 '-methylimidazolyl-(1 '))-ethyl-S-triazine, CUREZOL2MZA-PW)
Photoepolymerizationinitiater initiater: IRGACURE 907 Ciba Specialty Chemicals Holding Inc make)
Barium sulfate: B-30 (Sakai Chemical Industry Co., Ltd.'s manufacturing)
DPM: diethylene glycol monomethyl ether (manufacturing of DOW Chemical Amada Co., Ltd.)
The manufacturing of＜real dress substrate 〉
Behind the solder resist that is formed with on the printed circuit board (PCB) of circuit by silk screen print method printing comparative group precedent 3, with the heated air circulation type drying oven in 80 ℃ of dryings 30 minutes, across photomask with exposure 500mJ/cm
2Conditions of exposure expose, press the 1wt%Na of 0.2MPa with spray
2CO
3The aqueous solution carries out 1 minute development, in 150 ℃ of thermofixations of carrying out 60 minutes, obtains the printed circuit board (PCB) of comparative example 3 at the heated air circulation type drying oven.
Further, on above-mentioned solidified solder mask, print the thermally curable resin composition that example 1,2 (enforcement is formed except the example 3,4) and comparative group precedent 1,2 are formed in above-mentioned enforcement by silk screen print method, then at the heated air circulation type drying oven in 150 ℃ of thermofixations of carrying out 60 minutes, obtain the printed circuit board (PCB) of embodiments of the invention 1, embodiment 2 and comparative example 1, comparative example 2.
Implement to form example 3,4 contain the carboxylic acid photo-curable resin (below, be called photo-curable resin) situation under, on the above-mentioned solidified solder mask by silk screen print method printing photo-curable resin after, in the heated air circulation type drying oven in 80 ℃ of dryings 30 minutes, across photomask with exposure 500mJ/cm
2Conditions of exposure expose, press the 1wt%Na of 0.2MPa with spray
2CO
3The aqueous solution carries out 1 minute development, in 150 ℃ of thermofixations of carrying out 60 minutes, obtains the printed circuit board (PCB) of embodiments of the invention 3, embodiment 4 with the heated air circulation type drying oven.
After being formed with the thermally curable resin composition that passes through silk screen print method pattern printing enforcement composition example 1 on the printed circuit board (PCB) of circuit, in 150 ℃ of thermofixations of carrying out 60 minutes, obtain the printed circuit board (PCB) of embodiments of the invention 5 at the heated air circulation type drying oven.
＜by whether qualifiedly judging that visual inspection is carried out 〉
Use appearance inspection machine VARIR (manufacturing of ソ ニ one マ ニ ユ Off ア Network チ ヤ リ Application グ シ ス テ system (strain)), gained test substrate is carried out visual inspection, and estimate according to following standard.Evaluation result is as shown in table 2.
Zero: identification error does not take place.
*: identification error takes place.
＜thermotolerance 〉
Coating rosin series solder flux on resulting test substrate, dipping is 10 seconds in being redefined for 260 ℃ solder bath, behind the washed with isopropyl alcohol solder flux, utilizes the glassine paper adhesive tape to carry out stripping test, with following benchmark variable color evaluation is peeled off in the expansion of resist layer, evaluation result is shown in table 2.
Zero: can't see variation fully
△: only a little variation such as variable color
*: have resist layer expansion, peel off
＜electrical characteristic 〉
Use the comb-type electrode B print of IPC B-25 test pattern, similarly make the evaluation substrate with the making of above-mentioned real dress substrate, this comb-type electrode is applied the bias voltage of DC100V, insulating resistance value after placing 1000 hours at the constant temperature and humidity cabinet of 85%R.H. is measured, and measurement result is shown in table 2.
By the result of above-mentioned table 2 as can be known, the embodiment 1～4 of resin combination layer of the present invention is set on the solder mask that is formed with on the tellite of circuit, the intensity level of solder mask+resin combination curing tunicle of the present invention and element electrode part intensity level and component body part intensity level have difference, the intensity level of solder mask is more than 30 120 when following, be judged as certain difference, position of components when decision element is adorned in fact well departs from, the recognition rate height of the visual inspection of real dress substrate.
In addition, the printed circuit board (PCB) that is formed with circuit is provided with the embodiment 5 of the layer of resin combination of the present invention, the intensity level of the resin combination curing tunicle of the present invention on the circuit pattern and element electrode part intensity level and component body part intensity level have difference, the intensity level of solder mask is more than 30 120 when following, be judged as certain difference, position of components when decision element is adorned in fact well departs from, the recognition rate height of the visual inspection of real dress substrate.
Relative with it, comparative example 1,2,3, the difference of the intensity level of solder mask and element portion of terminal or component body is little, and judgement makes a mistake.
Industrial utilizability
According to the present invention, certain by at substrate or solder mask intensity level being set Resin bed, the scolder in the time of can distinguishing well the element actual load, element, solder resist this three The person, the identification in the time of can significantly improving the element actual load that the difference of utilizing intensity level carries out Rate. And then, according to the present invention, by the hidden power of raising resin combination of the present invention, Intensity level does not change because of substrat, further eliminates the knowledge in the automatic inspection Not other mistake.
Claims (12)
1. a resin combination that is used for the visual inspection of printed circuit board (PCB) is characterized in that, described resin combination contains (A) tinting material, (B) solidified nature composition, and the intensity level of the curing tunicle of this resin combination is 30～120.
2. resin combination according to claim 1 is characterized in that, the intensity level of the curing tunicle of described resin combination is 60～100.
3. resin combination according to claim 1 and 2 is characterized in that, the content of described (A) tinting material is 0.1 quality % of resin combination total amount～10.0 quality %.
4. according to each described resin combination of claim 1～3, it is characterized in that described (A) tinting material is that to be selected from carbon black system, phthalocyanine system, azo system, tetrazo system, quinacridone, anthraquinone system, flavanthrene Xi, piceneketone Xi, perylene be at least a of, dioxazine system, condensation azo system, azomethine system, methyne system, titanium oxide, zinc oxide, iron oxide black, chrome yellow, zinc yellow, chrome vermilion, colcother, lead sulfate, cobalt violet, ultramarine, dark purple, chrome green, chromic oxide, cobalt green.
5. resin combination according to claim 4 is characterized in that, described (A) tinting material is a carbon black.
6. according to each described resin combination of claim 1～5, it is characterized in that described (B) solidified nature composition is (B-1) photo-curable resin and/or (B-2) thermosetting resin.
7. according to each described resin combination of claim 1～6, it is characterized in that, also contain (C) masking agent.
8. resin combination according to claim 7, it is characterized in that described (C) masking agent is at least a weighting agent that is selected from titanium oxide, zinc oxide, subcarbonate, basic zinc sulfate, silicate, zinc sulphide, weisspiessglanz, talcum, aluminum oxide, clay, magnesium oxide, aluminium hydroxide, silica, magnesium hydroxide, barium sulfate.
9. resin combination according to claim 8 is characterized in that, described (C) masking agent is a titanium oxide.
10. cured article, it is solidified by each described resin combination of claim 1～9 and obtains.
11. a printed circuit board (PCB), it is provided with each described resin combination of claim 1～9 and solidifies the curing tunicle that obtains.
12. the appearance inspection method of a printed circuit board (PCB), it comprises: the curing tunicle that each described resin combination of claim 1～9 is set on substrate that is formed with circuit or the solder mask at this substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200710182014XA CN100554335C (en) | 2007-10-17 | 2007-10-17 | The resin combination that is used for the visual inspection of printed circuit board (PCB) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200710182014XA CN100554335C (en) | 2007-10-17 | 2007-10-17 | The resin combination that is used for the visual inspection of printed circuit board (PCB) |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101407636A true CN101407636A (en) | 2009-04-15 |
| CN100554335C CN100554335C (en) | 2009-10-28 |
Family
ID=40570856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200710182014XA Active CN100554335C (en) | 2007-10-17 | 2007-10-17 | The resin combination that is used for the visual inspection of printed circuit board (PCB) |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100554335C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102483571A (en) * | 2009-09-10 | 2012-05-30 | 积水化学工业株式会社 | Photosensitive composition and printed wiring board |
| CN102906867A (en) * | 2010-05-20 | 2013-01-30 | 株式会社Lg化学 | Printed circuit board including a dam for underfills, and method for manufacturing same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4087650B2 (en) * | 2002-07-12 | 2008-05-21 | 太陽インキ製造株式会社 | Photocurable / thermosetting resin composition and cured product thereof |
| TW200417294A (en) * | 2002-11-28 | 2004-09-01 | Taiyo Ink Mfg Co Ltd | Photo- and thermo-setting resin composition and printed wiring boards made by using the same |
| JP4328645B2 (en) * | 2004-02-26 | 2009-09-09 | 太陽インキ製造株式会社 | Photocurable / thermosetting resin composition and printed wiring board using the same |
| JP4809006B2 (en) * | 2005-07-05 | 2011-11-02 | 太陽ホールディングス株式会社 | Colored photosensitive resin composition and cured product thereof |
-
2007
- 2007-10-17 CN CNB200710182014XA patent/CN100554335C/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102483571A (en) * | 2009-09-10 | 2012-05-30 | 积水化学工业株式会社 | Photosensitive composition and printed wiring board |
| CN102483571B (en) * | 2009-09-10 | 2013-10-23 | 积水化学工业株式会社 | Photosensitive composition and printed wiring board |
| CN102906867A (en) * | 2010-05-20 | 2013-01-30 | 株式会社Lg化学 | Printed circuit board including a dam for underfills, and method for manufacturing same |
| CN102906867B (en) * | 2010-05-20 | 2016-04-27 | 株式会社Lg化学 | Comprise the Printed circuit board and manufacturing methods in underfill cofferdam |
| US9865480B2 (en) | 2010-05-20 | 2018-01-09 | Lg Chem, Ltd. | Printed circuit board including under-fill dam and fabrication method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100554335C (en) | 2009-10-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102385244B (en) | Black curable resin composition | |
| CN100566540C (en) | The appearance inspection method of printed circuit board (PCB) | |
| CN103224609B (en) | Reactive epoxy carboxylic acids's ester cpds, reactive polycarboxylic compounds, active energy ray-curable resin composition and article | |
| KR102167483B1 (en) | Photocurable thermosetting resin composition, cured product, and printed wiring board | |
| CN103554433B (en) | Curable resin composition | |
| KR102046341B1 (en) | Black curable resin composition and printed circuit board using the same | |
| JP5583091B2 (en) | Black curable resin composition | |
| CN101105629B (en) | Light solidifying/heat solidifying one-part welding resistant agent composition and printing circuit plate | |
| CN100469843C (en) | Liquid photosensitive ink and applied in printing circuit board | |
| JP4257786B2 (en) | Active energy ray-curable alkali-soluble imide resin, active energy ray-curable alkali-soluble imide resin composition, solder resist composition, printed wiring board, and photosensitive dry film | |
| KR20200139632A (en) | Curable resin composition, dry film, cured product and printed wiring board | |
| TW201833162A (en) | Photocurable resin composition, dry film, cured product, and printed wiring board | |
| CN104470962A (en) | Alkali development type resin, and photosensitive resin composition using same | |
| CN100554335C (en) | The resin combination that is used for the visual inspection of printed circuit board (PCB) | |
| CN101784577B (en) | Reactive carbonate, the curable resin composition using this reactive carbonate and uses thereof | |
| CN107561858A (en) | polyimide dry film and use thereof | |
| CN106604947A (en) | Reactive polyester compound and active energy ray-curable resin composition using same | |
| CN103524711A (en) | Novel epoxy carboxylate compound, derivative thereof, active energy ray curable resin composition containing them, and cured product thereof | |
| CN105733352B (en) | Photosensitive solder resist ink composition and circuit board | |
| CN105086605B (en) | A kind of photocuring heat-curing composition ink, purposes and the wiring board containing it | |
| JP6542285B2 (en) | Photosensitive resin composition and printed wiring board | |
| CN103869615A (en) | Photocurable composition, solder resist layer and printed circuit board | |
| JP2009249607A (en) | Photosensitive resin composition and cured product of the same | |
| JP6114799B2 (en) | Photosensitive resin composition, printed wiring board having cured film of photosensitive resin composition, and method for producing reflection sheet | |
| JP2020025092A (en) | Black curable resin composition and printed wiring board |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |