CN1088526C - Photosensitive ink inhibitor composition - Google Patents
Photosensitive ink inhibitor composition Download PDFInfo
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- CN1088526C CN1088526C CN 99105797 CN99105797A CN1088526C CN 1088526 C CN1088526 C CN 1088526C CN 99105797 CN99105797 CN 99105797 CN 99105797 A CN99105797 A CN 99105797A CN 1088526 C CN1088526 C CN 1088526C
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Abstract
The present invention relates to a novel photosensitive ink inhibitor composition which comprises prepolymers which can be polymerized by light, a single carboxylic acid functional basic monomer containing at least three vinyls, a light starting agent, an organic solvent, an epoxide whose self molecule unit contains at least one vinyl and one epoxy group, a stiffening agent which makes the prepolymers carry out thermal crosslinking, and clay soil. The composition has excellent characteristics of adhesiveness, voltinism resistance, anti insulating property and electroplating proof property, and especially, the composition has the advantages of heat resistance, developing property, chemical gold plating proof property, coated film transparent property and satisfactory analysis degree.
Description
The present invention relates to a kind of photosensitive ink inhibitor composition.This photosensitive ink inhibitor is in the printed circuit board (PCB) manufacturing, all have special purposes to soldering resistance and the gold-plated property of chemically-resistant, this photosensitive ink inhibitor utilizes ultraviolet light photopolymerization to have the characteristic of high sensitive, resolution (can reach 50 μ m) and quick-hardening, and its formed cured film is also excellent in the extreme on electrical properties and physical strength after the sclerosis film forming, and can use weak caustic solution to develop, its development character is very good, the photoresistance film that forms has gloss and transparent outward appearance, is convenient to inspect.
In recent years, electronic product is towards light, thin, short and small, densification development, the electronics package technique is then towards development of demand such as extensive aggregationization, high pin number, granulars, therefore to the demand of anti-solder ink more towards higher resolution and fiduciary level, so the improvement of anti-solder ink is a research topic in the industry always.
Anti-solder ink is by low-res, the high pollution sexual type attitude of early stage plate-making wire mark and heat curing, progressive high-res and low contaminative kenel to liquid photodevelopment alkali cleaning, but liquid photodevelopment alkali cleaning anti-solder ink, still have many shortcomings, for example, Taiwan patent case numbers 140202, it is the reaction that improves photosensitivity and minimizing and rigidizer with the particle epoxy compound of slightly solubility, but for making its photosensitivity prepolymer can be soluble in the weak lye, need higher acid value, therefore cause the gold-plated ability drop of chemically-resistant; And the slightly solubility epoxy compound is limited by in the reticulate texture after light reaction, even heating makes it to fuse fully, also reduces with the chance of rigidizer complete reaction, causes thermotolerance to descend.
The objective of the invention is in order to overcome the defective of the anti-welding photoresistance printing ink of above-mentioned liquid state, a kind of novel photosensitive ink inhibitor composition is provided, can be used for liquid anti-welding photoresistance printing ink, have remarkable ultraviolet light photopolymerization ability, soldering resistance, endurance, pliability, adhesiveness, electrical properties, weak base aqueous solution development and the gold-plated ability of chemically-resistant, and have gloss and transparent appearance.
Research of the present invention be about a kind of can be developed by weak base aqueous solution and have high analytic ability the photopolymerizable composition, comprise: (A) photopolymerizable prepolymer (I), its preparation can be by containing two epoxy resin (a) more than the epoxy radicals, with the monocarboxylic acid that contains a vinyl (b) reaction, get with saturated or unsaturated multi-anhydride (c) reaction again; (B) contain the monocarboxylic acid functional group monomer (II) of at least three vinyl; (C) light initiator; (D) organic solvent; (E) contain the epoxy compound (III) of at least one vinyl and an epoxy radicals; (F) make prepolymer (A) carry out the thermoinitiators of thermal response; (G) clay.
The ratio of above-mentioned composition is (a parts by weight meter) in the present composition:
(A) photopolymerizable prepolymer (formula I): 10～80;
(B) contain the monocarboxylic acid functional group monomer (formula II) of at least three vinyl: 1～40;
(C) light initiator: 0.5～10;
(D) organic solvent: 15～60;
(E) contain the epoxy compound (formula III) of at least one vinyl and an epoxy radicals: 1～60;
(F) make prepolymer (A) carry out the thermoinitiators of thermal response: 0.1～15;
(G) nanoscale intercalation clay: 0.001～12.5;
Characteristics of the present invention: the compound that in liquid photopolymerizable prepolymer (A), contains vinyl and low acid value in the framework unit formula, make liquid photoresistance printing ink have photosensitivity, and low acid value compound more can increase the gold-plated property of chemically-resistant except that the weak base development is provided.In addition the present invention also in photoreactive monomer (B) the hydrophilic carboxylic-acid functional base of framework improve its development and resolution to increase the difference of exposure area and unexposed area solubleness.Moreover the epoxy compound (E) that molecular cell of the present invention contains at least one vinyl and an epoxy radicals provides steric hindrance to prevent rigidizer and the reaction of photosensitivity prepolymer; Have vinyl can be when light reaction and the photosensitivity prepolymer build bridge, thermal response probability when increasing thermmohardening is strengthened thermotolerance; Dissolve in organic solvent and alkali lye, make bright and translucent in appearance and be easy to and develop.
Liquid photopolymerizable prepolymer (A) among the present invention, its preparation can be by containing two epoxy resin (a) more than the epoxy radicals, with the monocarboxylic acid that contains a vinyl (b) reaction, again with saturated or unsaturated multi-anhydride (c) reaction and get, its structural formula is as shown in the formula expression:
Wherein: R
1:-H '-CH
3
Can be used for the above epoxy resin (a) of at least two epoxy radicals that contains of the present invention, comprise: phenolic resin varnish, toluene phenolic resin varnish, halophenol varnish epoxy resin, connection phenol A epoxy resin, connection phenol F epoxy resin, connection phenol S epoxy resin, triphenol methane epoxy or tetrabromo connection phenol A epoxy resin etc. wherein are preferably phenolic resin varnish or toluene phenolic resin varnish.
The monocarboxylic acid (b) that contains at least one vinyl is acrylic acid, methacrylic acid, crotonic acid, cinnamic acid etc., and wherein preferred embodiment is an acrylic acid.
As for saturated or unsaturated acid anhydride (c) is succinic anhydride, hexahydrobenzene dimethyl acid anhydrides, methyl hexahydrobenzene dimethyl acid anhydrides, tetrahydrochysene xylylene acid anhydrides, maleic anhydride etc., and wherein Zui Jia example is a tetrahydrochysene xylylene acid anhydrides.
According to above-mentioned amount and the ratio that each composition is discussed, in following scope, can obtain best effect: the consumption that contains the monocarboxylic acid (b) of a vinyl, with epoxy resin (a) is benchmark, whenever 0.5 to 1.2 mole of amount epoxy radicals use is preferable, is preferably 0.9～1.1 mole; The consumption of multi-anhydride (c) is a benchmark with the hydroxyl that aforementioned carboxyl and epoxy reaction produced then, generates whenever the amount hydroxyl need use 0.1～1.0 mole of multi-anhydride, is preferably 0.3～0.5 mole.
Liquid photopolymerizable prepolymer (A) among the present invention, by containing two epoxy resin (a) more than the epoxy radicals, in the monocarboxylic acid that contains a vinyl (b) reaction, dilution with an organic solvent, the catalyzer of use can be triphenyl phosphorus, triethylamine, methyl triethyl ammonium chloride etc.Wherein with triphenyl phosphorus the best.This catalyst consumption is that 0.1～10% (weight %) of reaction mixture total amount is than preferable, in the reaction for preventing that two keys from producing free radical polymerizations, can add thermal polymerization inhibitor such as p-dihydroxy-benzene, hydroquinone dimethyl ether, the consumption of this polymerization inhibitor is preferable with 0.01～1% (weight %) of reaction mixture.Temperature of reaction is preferably 80～120 ℃, and the reaction time is 6～24 hours.This reaction product and saturated or unsaturated multi-anhydride (c) reaction, temperature of reaction is preferably 80～130 ℃, 4～16 hours reaction time.
With the photopolymerizable prepolymer (A) that above-mentioned course of reaction obtains, its acid number is preferably 20～120 (milligram KOH/g), and the best is 30～80 milligrams of KOH/g.
Photopolymerizable prepolymer (A) is preferably 10～80 (parts by weight) at the content of the present composition, and the best is 30～50 parts.
At least the monocarboxylic acid functional group monomer (B) who contains three vinyl of the present invention is the commercial commodity that can't buy, can be obtained by the prepared in reaction of diisoamyl tetrol five acrylate or isoamyl tetrol triacrylate and unsaturated multi-anhydride.Use therein multi-anhydride can be succinic anhydride, hexahydrobenzene dimethyl acid anhydrides, methyl hexahydrobenzene dimethyl acid anhydrides, tetrahydrochysene xylylene acid anhydrides or maleic anhydride, reactant ratio is the hydroxyl that contains in diisoamyl tetrol five acrylate or the isoamyl tetrol triacrylate, with the equivalent proportion of unsaturated multi-anhydride be 1: 0.5～1.1, be preferably 1: 0.7～0.9, the catalyzer that reaction is used can be triphenyl phosphorus, triethylamine, methyl triethyl ammonium chloride etc., and is wherein preferred with triphenyl phosphorus.This catalyst consumption is that 0.1～10% (percentage by weight) of reaction mixture total amount is preferable.Produce free radical polymerizations in when reaction in order to prevent two keys, can add use thermal polymerization inhibitor such as p-dihydroxy-benzene, hydroquinone dimethyl ether, the consumption of this polymerization inhibitor is reaction-ure mixture 0.01～1% (percentage by weight), temperature of reaction is preferably 80～120 ℃, in 24～48 hours reaction time, so can get reaction product (II).Reaction equation is as follows:
Wherein:
The above-mentioned content of monocarboxylic acid functional group monomer (B) in the present composition that contains at least three vinyl is 1～40 part (parts by weight), is preferably 5～20 parts.
Can comprise any known light initiator as for light initiator (C), as benzoin methyl ether, benzoin isopropyl ether, 2,2-dimethyl-2-phenyl acetophenone, 1, the 1-dichloroacetophenone, the 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-[4-(methyl sulphur) phenyl]-2-morpholine third-1-ketone, N, N-dimethyl amine benzoylformaldoxime, 2,4-dimethyl 9-oxygen dibenzo sulphur piperazine is muttered, 2,4-diethyl 9-oxygen dibenzo sulphur piperazine is muttered, 2-chlorine 9 oxygen dibenzo sulphur piperazines are muttered, 2,4-diisopropyl 9-oxygen dibenzo sulphur piperazine is muttered, the acetophenone dimethyl ketal, diphenylketone, methyldiphenyl base ketone, 4,4-dichloro diphenylketone, 4,4-diethyl amido phenyl ketone, Michler's keton, 4-benzyl sulfydryl diphenyl phosphate oxidation etc.These compounds can use or mix use separately, preferred compositions is that the 2-methyl isophthalic acid-[4-(methyl sulphur) phenyl]-(Irgacure 907 for 2-morpholine third-1-ketone, Ciba-Geigy is made) with 2,4-diisopropyl 9-oxygen dibenzo sulphur piperazine mutter (Kayacure ITX, Japanese chemical drug corporate system is made).
Above-mentioned light initiator (C) use amount in the present invention is 0.5～10 part (parts by weight), is preferably 1～5 part.
The used organic solvent of the present invention (D) can comprise: carbonic allyl ester (propylene carbonate), butyl cellosolve, butoxy acetic acid ethyl ester, toluene, dimethylbenzene, acetic acid butyl carbitol, cyclohexanone, propylene glycol monomethyl ether, dipropylene glycol diethyl ether and acetic acid methyl carbitol etc.Wherein preferable example is propylene carbonate and butoxy acetic acid ethyl ester, and use amount in the present invention is 15～60 parts (parts by weight), is preferably 25～50 parts.
The epoxy compound (E) that contains at least one vinyl and an epoxy radicals, be one of feature of the present invention, this epoxy compound does not have crystallinity, exist with transparent liquid under the normal temperature, dissolve in organic solvent, after vinylated, can increase photosensitivity, and molecular weight Xiao Yi washes out when being developed by weak base aqueous solution; This epoxy compound (E) has steric hindrance because of this body structure of molecule, be difficult for and rigidizer or the reaction of photosensitivity prepolymer, but molecule contain a vinyl can with photosensitivity prepolymer generation photo-crosslinking, dwindle intermolecular distance, during heat curing, can fully react completely, not reduce thermotolerance; And do not cause photoresistance film transparency variation because of crystallinity.
The above-mentioned preparation feedback that contains the epoxy compound (E) of at least one vinyl and an epoxy radicals is the reaction with crystalline epoxy compound and unsaturated monocarboxylic, structure is shown in formula III, and the epoxy compound that satisfies above-mentioned condition comprises: bisphenol-s epoxy resin, heterocyclic ring epoxy resins, two diformazan phenol-type epoxy resin, diphenol type epoxy resin, the Fourth Ring oxygen third xylenol ethane resin.Wherein preferably two diformazan phenol-type epoxy resins.
This reaction mol ratio be the carboxylic acid equivalents epoxide equivalent is counted ratio is 0.05～1.1, optimal proportion is 0.1～0.5.The catalyzer that uses can be triphenyl phosphorus, triethylamine, methyl triethyl ammonium chloride etc., wherein with triphenyl phosphorus the best.Effect was preferable when this catalyst consumption was 0.1～10% (percentage by weight) of reaction mixture total amount.For the polymerization that prevents that two keys produce free radicals when reacting, can use thermal polymerization inhibitor such as p-dihydroxy-benzene, hydroquinone dimethyl ether etc., the consumption of this polymerization inhibitor is 0.01～1% (percentage by weight) of reaction mixture, temperature of reaction is preferably 80～120 ℃, and the reaction time is 6～12 hours.
The above-mentioned epoxy compound (E) that contains at least one vinyl and an epoxy radicals, the content in the present composition is preferably 1～60 part (parts by weight), is preferably 5～20.
As for making prepolymer (A) carry out the thermoinitiators (F) of heat cross-linking, requirement be the known epoxide that contains two epoxy radicals all can, wherein preferable three-glycidyl based isocyanate, phenolic resin varnish, toluene phenolic resin varnish, halophenol varnish epoxy resin, connection phenol A epoxy resin, connection phenol F epoxy resin, connection phenol S epoxy resin, triphenol methane epoxy or the tetrabromo connection phenol A epoxy resin etc. of being chosen as.
The above-mentioned consumption that makes prepolymer (A) carry out the thermoinitiators (F) of heat cross-linking, for the above-mentioned photopolymerizable prepolymer (A) of per 100 weight portions with 0.1～15 weight portion, be preferably 0.5～5 weight portion.
Also use an amount of filling material in the present composition, be mainly widely used inorganic fillings, as talcum powder, barium sulphate, magnesium carbonate, lime carbonate, aluminium oxide, silica powder etc., use amount is that 20～40% (percentage by weights) are preferable, is preferably 25～35% (percentage by weights).Other is added with the clay of quarternary ammonium salt intercalation (G), but blending or use intercalation instead after utilize the reaction of epoxy resin and rigidizer again and nanoscale (nano-meter, 10
-9M) clay, wherein quarternary ammonium salt is CH
3(CH
2)
nNR
3 +, wherein n=3～17 are preferable, are preferably n=11～17, and R is H or CH
3Or a part is that H, a part are CH
3, wherein preferred R is H.Epoxy resin be phenolic resin varnish, toluene phenolic resin varnish, halophenol varnish epoxy resin, connection phenol A epoxy resin, connection phenol F epoxy resin, connection phenol S epoxy resin, triphenol methane epoxy or tetrabromo connection phenol A epoxy resin etc. all can, with connection phenol A epoxy resin, connection phenol F epoxy resin the best.Rigidizer with 1,2,3 grade of amine, polymercaptan, polyprotonic acid, acid anhydrides all can, wherein preferable with 1 grade of amine.Since this reactant after reacting with the particle size dispersion of nanometer in the printing ink epithelium, except that the interpolation that can reduce inorganic filler, more can increase thermotolerance, scratch resistance, resistance to water soak, the resistance to impact of this composition, and not influence the transparency and the glossiness of composition.The use amount of this nanoscale clay is that 0.001～12.5 part (parts by weight) are more suitable, is preferably 0.05～2 part.
In addition, composition of the present invention contains as the widely used additive of known technology, for example: at least a in coloring pigment or dyestuff, polymerization inhibitor, defoamer, levelling agent and thickening agent or the now promoter.The pigment of Shi Yonging wherein can be xylylene indigo plant, xylylene is green, iodine is green, azophosphine (diazoyellow), crystal violet, titania, carbon black, how black, phthalein viridescent etc.; Polymerization inhibitor can be p-dihydroxy-benzene, hydroquinone dimethyl ether; Defoamer, levelling agent can be organic silicone (Silicone), fluorine element; Thickening agent can be colloidal clay, shakes modification silicon dioxide; Optionally can add melamine in addition, purpose is to increase bridge formation density, and its consumption is good with 0～3% (percentage by weight).
Removing the above is, composition of the present invention further also can comprise and contain the above reaction monomers of a vinyl at least.
Synthetic example
Below to photosensitive ink inhibitor composition of the present invention, the synthetic method of the epoxy compound (E) of monocarboxylic acid functional group monomer (B), at least one vinyl and an epoxy radicals of photopolymerizable prepolymer (A), at least three vinyl, with the embodiment explanation, but it is not limited by these synthesis examples.
One, the synthetic example of photopolymerizable prepolymer (A)
Synthetic embodiment 1
(Japanese Dongdu changes into the YDCN-704 that company makes to the cresols novolaks of 210 parts (1 equivalents), softening point: 92 ℃, 210), 72 parts of (1 mole) acrylic acid, 0.72 part of benzene xylenol, 90 parts of carbonic allyl esters, 90 parts of carbitol acetic acid esters epoxide equivalent:, pan feeding is to reactive tank, heated and stirred to 80 ℃ solubilizing reaction potpourri, after the question response potpourri dissolves fully, add 1.05 parts of triphenyl phosphorus, be heated to 110 ℃, and after reacting about 24 hours, obtain the reaction product that acid number is 3 milligrams of potassium hydroxide/gram.Add 52 parts of tetrahydrochysene xylylene acid anhydrides in this reaction product, continue to react 5 hours in 100 ℃, obtain the solid concentration 65% of reaction product, the solid content acid value is 57 milligrams of potassium hydroxide/gram, (A-1).
Synthetic embodiment 2～3
Repeat the reaction of synthetic embodiment 1, but replace carbonic allyl ester and change partly reactant with the carbitol acetic acid esters.So can get solid concentration 65%, the unsaturated polyester carboxylic acid resin listed as table 1.
| Synthetic embodiment | 2 | 3 |
| The product numbering | A-2 | A-3 |
| With dihydromethyl propionic acid (0.1 mole) substitutional crylic acid | 13.4 | - |
| Tetrahydrochysene xylylene acid anhydrides | 35.25 | 74.8 |
| The carbitol acetic acid esters | 85.12 | 103.08 |
| Solid content acid value (mg KOH/g) | 40 | 77 |
Two, the synthetic embodiment that contains the monocarboxylic acid functional group monomer (B) (formula II) of at least three vinyl
Synthetic embodiment 4
Diisoamyl tetrol five acrylate of 524 parts (1 equivalents) and the tetrahydrochysene xylylene acid anhydrides of 152 parts (1 moles), 0.6 part benzene xylenol, 2.6 parts triphenyl phosphorus, pan feeding is to reactive tank, stirring is warming up to 80 ℃, pre-molten reaction mixture 1 hour, be warming up to 105 ℃, react again after 32 hours and obtain having the reaction product (B-1) of 83 milligrams of potassium hydroxide/gram of acid value
Synthetic embodiment 5
As the reaction of synthetic embodiment 4, but diisoamyl tetrol five acrylate are replaced with 292 parts of isoamyl tetrol triacrylates, and must have the reaction product (B-2) of 126 milligrams of potassium hydroxide/gram of acid value.
Three, the synthetic embodiment that contains the epoxy compound (E) of at least one vinyl and an epoxy radicals
Synthesis example 6
Two xylenol epoxy resin of 184 parts (1 equivalents) (YX-4000 that Yuka-Shell makes), 0.1 part of benzene xylenol, 36.38 portions of carbitol acetate vinegar are to reactive tank, and in stirring, be heated to 90 ℃ and make reaction mixture dissolving, then under 100 ℃, with the acrylic acid mixture dropwise reaction of 0.48 part of triphenyl phosphorus and 21.6 parts (0.3 moles) 1 hour, be heated to 105 ℃, after reacting about 4.5 hours, obtain the reaction product (E-1) of 1 milligram of potassium hydroxide/gram of acid number.
Four, embodiment and comparative example
Following examples will more clearly illustrate the present invention, yet application of the present invention is not limited in these examples.According to the composition of table 2, use amount wherein after fully grinding by three roller grinders, obtains the photoresistance ink composite by weight.The photoresistance ink component that so obtains by the screen painting method, is coated the printed circuit board (PCB) of figure, obtains the thick film of 20～30mm thickness, or coats the naked copper substrate with rubber squeegee, gets the film of 1～3mm thickness.Respectively film again with air drier at 80 ℃ of dry special times down, with the negative film close ground with photoresistance figure adhere to film on, and by using ultraviolet photoetching device (the HMW-680GW type of ORC company manufacturing), and at 25mW/cm
2Dosage with UV-irradiation it, secondly, under 2.0 kilograms/square centimeter spray pressure, developed 60 seconds with 1% aqueous solution of sodium carbonate, dissolving and elimination be the part of exposure not.Certainly the weak base aqueous solution of other kinds also can use.At last, can increase,, and get filming of sclerosis fully again in 100～200 ℃ of bakings 0.5～1 hour in order to make its thermotolerance.
Comparative example uses the solid-state fine powder epoxy resin of slightly solubility, causes being limited by reticulate texture behind the photo-hardening, even heating makes it to fuse fully, also reduces the density deficiency that causes building bridge, thermotolerance thereby reduction with the chance of prepolymer complete reaction; Chemically-resistant gold plating property does not also descend with the epoxy resin complete reaction because of the carboxylic acid of high acid value prepolymer.The present invention adds solubility and has the epoxy compound of sensitization polymerizing power (E), can be dispersed in the ink composite, increase itself and prepolymer chance in back baking reaction, when in addition this epoxy compound also has steric hindrance and can reduce prebake conditions and prepolymer react, therefore except that increasing the thermotolerance, development is also quite superior.The present invention adds nanoscale intercalation clay (G) in addition, effectively increases the surface area of inorganic material in the ink composite, thereby can increase the thermotolerance of this composition again; And because of it can be dispersed to nanoscale, can make the epithelium of printing ink more sturdy, thereby increase the golden ability of its anti-ization.
Table 2 prescription is formed reference example
Annotate: Ingacure 907: Switzerland vapour Ba-Jia Ji makes, light initiator, 2-methyl isophthalic acid-[4 (methyl sulphur) phenyl]-2-morpholine third-1-ketone.
| Embodiment | Comparative example | |||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 1 | 2 | 3 | ||
| (A) photonasty prepolymer | 57 milligrams of potassium hydroxide/gram of solid content acid value (A-1) | 48 | 48 | 48 | ||||||
| 40 milligrams of potassium hydroxide/gram of solid content acid number (A-2) | 48 | 48 | 48 | |||||||
| 77 milligrams of potassium hydroxide/gram of solid content acid value (A-3) | 48 | 48 | 48 | |||||||
| (B) photoreactive monomer | B-1 | 11.25 | 11.75 | 10.05 | 11.55 | 7 | 7 | |||
| B-2 | 10.75 | 10.55 | 7 | |||||||
| (C) light initiator | Iragacure907 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
| Kayacure ITX | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | |
| (D) organic solvent | White spirit | 6.25 | 6.25 | 6.25 | 6.25 | 6.25 | 6.25 | 6.25 | 6.25 | 6.25 |
| The carbitol acetic acid esters | 6.5 | 6.5 | 6.5 | 6.5 | 6.5 | 6.5 | 6.5 | 6.5 | 6.5 | |
| (E) | E-1 | 10 | 6 | 3 | 10 | 6 | 3 | |||
| (F) thermoinitiators | YX-4000 | 8.5 | 8.5 | 8.5 | ||||||
| NPCN-702 | 3 | 6 | 3 | 6 | ||||||
| (G) nanoscale clay | 4 grades of ammonium intercalations | 0.25 | 0.25 | 0.25 | ||||||
| Add the reaction of epoxy resin and rigidizer behind the intercalation again | 0.45 | 0.45 | 0.45 | |||||||
| Other | Melamine | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
| Barium sulphate | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | |
| Silicon dioxide powder | 5 | 5 | 5 | |||||||
| The phthalein viridescent | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | |
| KS-66 (defoamer) | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | |
| Statistics | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | |
Kayacure ITX: Japanese chemical drug corporate system is made, light initiator, and isopropyl-9-oxygen dibenzo sulphur group mutters.
YX-4000: Japanese YuKa Shell company makes, bis-xylene phenol epoxy.
NPCN 702: the epoxy resin that Nan Ya Plastics company makes.
Experiment
In the sample of the foregoing description 1 to 6 and comparative example 1 to 3 gained, film sample is only accepted the test of development property, and the thick film sample before developing accepts to refer to touch the dry test of the universe.Development sample before the thermmohardening is accepted development test, photonasty test and photosensitivity test.And the sample after the thermmohardening is accepted adhesiveness, soldering resistance, the gold-plated property of chemically-resistant, acid resistance, alkali resistance, solvent resistance, pencil hardness test.
1, dry to touch (Tackiness after drying)
After the prebake conditions, the surface of filming is by the contiguous sense of hand, and the degree of its sticking hand is represented by following mark:
Zero: tack-free
△: slightly sticking hand
*: partly sticking hand
2, development (Developability)
Thick, thin coating film with dry 70,80,90 minutes developed 60 seconds under 2.0 kilograms/square centimeter spray pressure with 1% aqueous solution of sodium carbonate, dissolving and elimination unexposed portion.The ability of its development is by following symbolic representation:
◎: develop fully
Zero: trace can't develop partly
△: partly can't develop fully
*: all can't develop
3, adhesiveness (Adhesion)
According to the test method of JIS D 0202 appointment, cured film has grid partly, after use cellophane adhesive tape carries out spalling test, peels off situation with visual assessment:
◎: 100/100, promptly 100 parts all do not have and peel off
Zero: 100/100, few partly system fell
△: 50～90/100, promptly 100 50 to 90 partly keep not peeling off
*: 0～50/100, promptly 100 0 to 50 partly keep not peeling off
4, soldering resistance (Solder Heat Resistance)
According to the test method of JIS C 6481 appointments, scribble each 10 seconds of melting tin bath of immersing 260 ℃ of sample of solder flux, the variation of the assessment outward appearance that causes.The melting welding heat impedance is assessed based on following benchmark:
Zero: outward appearance and no change
△: the change color of observing hardened coating film
*: hardened coating film carries out projection, peel off and melting welding wrinkling
5, the gold-plated property of chemically-resistant (Electroless Plating Resistance)
The method of chemical gilding:
Test film is by being dipped in acid degreasant solution 3 minutes and taking off ester at 30 ℃, be dipped in then in the water and cleaned with water in 3 minutes, secondly, test film is dipped in 14.3% (weight %) aqueous solution 3 minutes of ammonium persulfate and carries out soft etching in room temperature, and then be dipped in the water and cleaned with water in 3 minutes, be dipped in 10% (volume %) aqueous solution of sulfuric acid after 1 minute in room temperature, this test film is dipped in the water again and cleaned with water to 1 minute in 30 seconds, be dipped in catalyst solution 7 minutes and add catalyzer at 30 ℃ then, be dipped in again in the water 3 minutes and clean with water.This test film with catalyzer is by being dipped in nickel plating solution 20 minutes and carrying out chemical nickel plating at 85 ℃.Room temperature was dipped in 10% (volume %) aqueous solution of sulfuric acid after 1 minute, was dipped in the mobile water 30 seconds to 1 minute and with water washing test sheet.Secondly, test film is by being dipped in nickel plating solution 10 minutes and carrying out chemical gilding at 95 ℃, be dipped in then in the mobile water 3 minutes and clean with water, and in 60 ℃ of hot water 3 minutes and clean with hot water, so clean fully, and behind the bone dry, obtain the chemical gilding test film with water, test film uses the cellophane adhesive tape to carry out spalling test then, and the situation of peeling off of assessment photoresist.
Zero: outward appearance or photoresist peel off and all do not observe any variation.
△: though observe peeling off a little of photoresist, outward appearance is not observed any variation.
*: photoresist projection and plate are wrinkling, and observe great peeling off in spalling test.
6, photosensitivity (Sensitivity)
A test board that contains ladder wedge type energy rank, the difference on every lattice energy rank was 0.15 (representing with Δ Log E), in process with after testing the same step of development, lattice number with visual ladder wedge type energy rank, judge it, ladder energy rank are high more, and representative has higher light sensitivity.
7, pencil hardness (Pencil Hardness)
With the method for adhesiveness, make test pieces after, with the pencil of the 2B-9H hardness of Mitsubishi's system, nib polishes (meeting at right angles), scrapes it with miter angle in test piece again, till the meeting scratch is filmed.
8, acid resistance (Acid resistance)
With the method for adhesiveness, make test pieces after, impregnated in 10% (volume percent) aqueous sulfuric acid, 20 ℃ are taken out after 30 minutes, judge it according to the state and the close outstanding property summation of filming.
◎: do not change fully.
Zero: surperficial microvariations.
△: surperficial marked change.
*: hardened coating film comes off.
9, alkali resistance (Base resistance)
With the method for adhesiveness, make test pieces after, impregnated in 10% (volume percent) sodium hydrate aqueous solution, 20 ℃ are taken out after 30 minutes, judge it according to the state and the close outstanding property summation of filming.
◎: do not change fully.
Zero: surperficial microvariations.
△: surperficial marked change.
*: hardened coating film comes off.
10, solvent resistance (Solvent resistance)
With the method for adhesiveness, make test pieces after, impregnated in respectively in methenyl choloride and the acetone, 20 ℃ are taken out after 30 minutes, judge it according to the state and the close outstanding property summation of filming.
◎: do not change fully.
Zero: surperficial microvariations.
△: surperficial marked change.
*: hardened coating film comes off.
11, resolution (Resolution)
With the method for adhesiveness, make test pieces after, judge that with 100 times of magnifieres the live width of each photoresistance, the numerical value liquid photoresistance resolution of little representative of healing is higher, the circuit that can form is thin more, the scope of application heals extensively.
Table 3 embodiment, the materialization of ratio example are relatively
| Embodiment | Comparative example | ||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 1 | 2 | 3 | |||
| Dry to touch (1) | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ||
| Development (2) | 70 minutes | Thick film | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ |
| Film | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ||
| 80 minutes | Thick film | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | |
| Film | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | △ | ||
| 90 minutes | Thick film | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | × | × | |
| Film | ◎ | ◎ | ◎ | ◎ | ○ | × | × | × | |||
| Adhesiveness (3) | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ||
| Soldering resistance (4) | ○ | ○ | ○ | ◎ | ◎ | ◎ | △ | △ | △ | ||
| The gold-plated property of chemically-resistant (5) | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | ○ | ||
| Photosensitivity (6) | 13 | 12 | 13 | 13 | 12 | 13 | 14 | 13 | 13 | ||
| Pencil hardness (7) | 6H | 6H | 6H | 6H | 6H | 6H | 6H | 6H | 6H | ||
| Acid resistance (8) | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ||
| Alkali resistance (9) | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | ○ | ||
| Solvent resistance (10) | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ||
| Analyticity (11) | 50μm | 50μm | 50μm | 50μm | 50μn | 50μn | 50μm | 50μm | 50μn | ||
By above-mentioned result as can be known, the monocarboxylic acid functional group monomer (B) who contains at least three vinyl, photopolymerizable prepolymer (A), sensitization epoxy compound (E) and nanoscale intercalation clay (G) among the present invention, in a liquid photopolymerizable composition, play the part of very important role, they have improved development, make exposure area and unexposed area strengthen because contain acidic group (II) in the monomer to the compatibility difference of weak base aqueous solution, and epoxy compound with steric hindrance, reduced the chance of reacting, can make development more complete with rigidizer; Low acid number photopolymerizable resin, sensitization epoxy compound and nanoscale intercalation clay have then increased gold-plated ability of chemically-resistant and soldering resistance.
Claims (8)
1, a kind of photosensitive ink inhibitor composition is characterized in that, said composition comprises the following component in parts by weight:
(A) structural formula is suc as formula the photopolymerizable prepolymer shown in the I: 10～80,
The acid number of this photopolymerizable prepolymer is 20～120 milligrams of KOH/g, be by containing two epoxy resin (a) more than the epoxy radicals, with after the monocarboxylic acid that contains a vinyl (b) reaction again with saturated or unsaturated multi-anhydride (c) reaction and make, wherein, the consumption that contains the monocarboxylic acid (b) of a vinyl, with epoxy resin (a) is benchmark, whenever the amount epoxy radicals is used monocarboxylic acid (b) 0.5～1.2 mole, the consumption of multi-anhydride (c) is a benchmark with the hydroxyl that aforementioned carboxylic acid and epoxy reaction produced then, generates whenever the amount hydroxyl need use 0.1～1.0 mole of multi-anhydride;
(B) structural formula is suc as formula the monocarboxylic acid functional group monomer who contains at least three vinyl shown in the II: 1～40,
This monocarboxylic acid functional group monomer is obtained by the reaction II ' of diisoamyl tetrol five acrylate or isoamyl tetrol triacrylate and unsaturated multi-anhydride, wherein, the equivalents of the hydroxyl that contains in diisoamyl tetrol five acrylate or the isoamyl tetrol triacrylate is 1: 0.5～1.1 with the ratio of the mole of unsaturated multi-anhydride;
(C) light initiator: 0.5～10;
(D) organic solvent: 15～60;
(E) epoxy compound that contain at least one vinyl and an epoxy radicals of structural formula shown in formula III: 1～60,
This compound is obtained by the reaction with crystalline epoxy compound and unsaturated monocarboxylic, and wherein epoxide equivalent is counted ratio is 0.05～1.1: 1 to the reactant carboxylic acid equivalents
(F) make prepolymer (A) carry out the thermoinitiators of thermal response: 0.1～15;
(G) nanoscale intercalation clay: 0.001～12.5;
Wherein
R
1:-H ,-CH
3 
Wherein
2, photosensitive ink inhibitor composition according to claim 1, it is characterized in that, be used to prepare the epoxide (a) that contains at least containing of photopolymerizable prepolymer (A) more than two epoxy radicals, can be: phenolic resin varnish, toluene phenolic resin varnish, halophenol varnish epoxy resin, connection phenol A epoxy resin, connection phenol F epoxy resin, connection phenol S epoxy resin, triphenol methane epoxy or tetrabromo connection phenol A epoxy resin; At least the monocarboxylic acid (b) that contains a vinyl is acrylic acid, methacrylic acid, crotonic acid or cinnamic acid; Saturated or unsaturated acid anhydride (c) then is succinic anhydride, hexahydrobenzene dimethyl acid anhydrides, methyl hexahydrobenzene dimethyl acid anhydrides, tetrahydrochysene xylylene acid anhydrides or maleic anhydride.
3, photosensitive ink inhibitor composition according to claim 1, it is characterized in that, being used to prepare the described multi-anhydride that contains the monocarboxylic acid functional group monomer (B) of three vinyl at least, can be succinic anhydride, hexahydrobenzene dimethyl acid anhydrides, methyl hexahydrobenzene dimethyl acid anhydrides, tetrahydrochysene xylylene acid anhydrides or maleic anhydride.
4, photosensitive ink inhibitor composition according to claim 1, it is characterized in that the oxygen compound of going back that is used to prepare the described epoxy compound of epoxy compound (E) that contains a vinyl and an epoxy radicals at least comprises: bisphenol-s epoxy resin, heterocyclic ring epoxy resins, two diformazan phenol-type epoxy resin, diphenol type epoxy resin or the Fourth Ring oxygen third xylenol ethane resin.
5, photosensitive ink inhibitor composition according to claim 1, it is characterized in that, the described thermoinitiators (F) that makes prepolymer (A) carry out thermal response can be the epoxide that contains two epoxy radicals, comprising: three-glycidyl based isocyanate, phenolic resin varnish, toluene phenolic resin varnish, halophenol varnish epoxy resin, connection phenol A epoxy resin, connection phenol F epoxy resin, connection phenol S epoxy resin, triphenol methane epoxy or tetrabromo connection phenol A epoxy resin.
6, photosensitive ink inhibitor composition according to claim 1 is characterized in that, said composition further comprises inorganic fillings talcum powder, magnesium carbonate, lime carbonate, barium sulphate, aluminium oxide or silicon dioxide powder.
7, photosensitive ink inhibitor composition according to claim 1 is characterized in that, said composition further comprises coloring pigment or dyestuff, polymerization inhibitor, defoamer, levelling agent, and is at least a in thickening agent or the now promoter.
8, photosensitive ink inhibitor composition according to claim 1 is characterized in that, said composition further can comprise and contain the above reaction monomers of a vinyl at least.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99105797 CN1088526C (en) | 1999-04-16 | 1999-04-16 | Photosensitive ink inhibitor composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99105797 CN1088526C (en) | 1999-04-16 | 1999-04-16 | Photosensitive ink inhibitor composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1236115A CN1236115A (en) | 1999-11-24 |
| CN1088526C true CN1088526C (en) | 2002-07-31 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99105797 Expired - Fee Related CN1088526C (en) | 1999-04-16 | 1999-04-16 | Photosensitive ink inhibitor composition |
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| CN (1) | CN1088526C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5027458B2 (en) * | 2006-07-12 | 2012-09-19 | 太陽ホールディングス株式会社 | Photo-curable and thermosetting one-component solder resist composition and printed wiring board using the same |
| JP5425360B2 (en) * | 2006-07-12 | 2014-02-26 | 太陽ホールディングス株式会社 | Photo-curable and thermosetting one-component solder resist composition and printed wiring board using the same |
| CN106318019B (en) * | 2015-07-06 | 2020-03-17 | 南亚塑胶工业股份有限公司 | Low dielectric solder resist ink composition for printed circuit board |
| US10527936B2 (en) | 2016-06-17 | 2020-01-07 | Nan Ya Plastics Corporation | Low Dk/Df solder resistant composition use for printed circuit board |
| US11174217B2 (en) | 2017-06-12 | 2021-11-16 | Dic Corporation | Polymerizable compound and liquid crystal composition |
| CN111194305B (en) | 2017-11-17 | 2023-01-03 | Dic株式会社 | Polymerizable compound, and liquid crystal composition and liquid crystal display element using same |
| JP6729815B2 (en) | 2018-03-01 | 2020-07-22 | Dic株式会社 | Polymerizable compound, liquid crystal composition using the same, and liquid crystal display device |
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1999
- 1999-04-16 CN CN 99105797 patent/CN1088526C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1236115A (en) | 1999-11-24 |
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