CN103713470A - Active energy-ray curable resin composition for print resist, method for resist patterning using the same, print resist laminate, and printed circuit board - Google Patents

Active energy-ray curable resin composition for print resist, method for resist patterning using the same, print resist laminate, and printed circuit board Download PDF

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Publication number
CN103713470A
CN103713470A CN201310272330.1A CN201310272330A CN103713470A CN 103713470 A CN103713470 A CN 103713470A CN 201310272330 A CN201310272330 A CN 201310272330A CN 103713470 A CN103713470 A CN 103713470A
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composition
acid
resist
printing
resin composition
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CN103713470B (en
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山口贵史
辻雅之
福田猛
合田秀树
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Arakawa Chemical Industries Ltd
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Arakawa Chemical Industries Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • G03F7/0043—Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits

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  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Metallurgy (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Materials For Photolithography (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Silicon Polymers (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)

Abstract

The purpose of the invention is to provide a print resist layer that can form pattern by printing without fired curing and drying, has adhesion to conductors like copper or aluminum after UV curing, can bear etching tolerance and electroless plating, and can be peeled off simply thereafter. The purpose can be realized through the following procedures: the resin composite is characterized in comprising a condensate (A) and a chemical (B), wherein the condensate (A) can be obtained by performing hydrolysis (not when all are hydrogen atoms except R2) and condensation to alkoxysilane (a1) containing sulfhydryl that can be expressed by formula (1) R1Si(OR2)3; in the formula (1), R1 represents alkyl that has at least one sulfhydryl with 1-4 carbon atoms, R2 represents alkyl that has 1-4 hydrogen atoms or carbon atoms, and the chemical (B) has at least one alkyl and at least one carbon-carbon double bond in the molecule.

Description

Formation method, layered product and the printed circuit board (PCB) of printing activity energy-line solidifying type resin composition, corrosion-resisting pattern for resist
Technical field
The present invention relates to corrosion-resisting pattern formation method, printing resist layer laminate and the printed circuit board (PCB) of a kind of printing activity energy-line solidifying type resin composition (described composition is for being printed in substrate or conductor layer by having solidify to form the resist layer of pattern), use said composition for resist.
Background technology
The resist layer that forms pattern is generally used for the industrial fields such as printed circuit board (PCB), lead frame, LCD.Conventionally, resist layer at least forms pattern by 3 treatment steps through photoetching process.; must through by the resist-coating of solution type in the step of substrate, coating layer is carried out to the step of the photomask exposure step of pattern transferring and tediously long complexity such as development step of resist layer on resist layer, aspect production efficiency and cost, all having problems.Further, in the situation that there is no permanent resist, that is, in the situations such as printed base plate and lead frame, the etching step of substrate, plating step and strip step against corrosion are necessary.In addition, it is cambial dry and fire that the lithography step of using due to LCD must pass through photomask exposure, development and common pattern, therefore, increased the manufacturing cost of LCD display.
On the other hand, someone has reported and has not used photoetching process, forms the method (with reference to patent documentation 1) of corrosion-resisting pattern by letterpress reverse printing method.But, because this etching contains solvent with ink, in forming step, etching can not fully fire, can cause tunicle remitted its fury against corrosion, so must spend more time-consumingly firing step, therefore, from the viewpoint of production efficiency, be less desirable.
Patent documentation 1: JP 2010-116525 communique
Summary of the invention
The object of this invention is to provide a kind of printing resist layer, described printing resist layer can form pattern through mode of printing, through ultraviolet curing, form resist layer, do not need to fire, drying steps, the conductors such as copper, aluminium are had to tack, can tolerate etching step and metallide step, can also peel off simply afterwards.
The result that the present inventors further investigate for solving above-mentioned problem, in the hydrolytic condensate of discovery by the alkoxy silane by containing sulfydryl and molecule, there is composition and the solidfied material thereof that the compound of at least one carboxyl and at least one carbon-carbon double bond forms and can solve above-mentioned problem, thereby complete the present invention.
; the present invention is that a kind of printing activity energy-line solidifying type resin composition for resist is (following; there is the situation that is called " resist resin combination "); it is characterized in that; described resin combination contains condensation product (A) and compound (B) as neccessary composition; described condensation product (A) (following, to be called composition (A)) is general formula (1) R 1si (OR 2) 3(in formula, R 1expression has the alkyl of the carbon number 1～4 of at least one sulfydryl, R 2the alkyl that represents hydrogen atom or carbon number 1～4) alkoxy silane that contains sulfydryl (a1) hydrolysis shown in is (except R 2the situation that is all hydrogen atom is outer), condensation obtains, described compound (B) (following, to be called composition (B)) has at least one carboxyl and at least one carbon-carbon double bond in molecule; A formation method for corrosion-resisting pattern, described method is characterised in that: after aforementioned resist is printed on substrate with resin combination, more described composition is solidified; A kind of printing resist layer laminate obtaining by the formation method of aforementioned corrosion-resisting pattern; A kind of by after the etching of aforementioned printing resist layer laminate, further peel off the printed circuit board (PCB) that obtains of printing resist.
Because printing resist of the present invention can form pattern with resin combination by mode of printing, through ultraviolet curing, form resist layer, do not need to fire curing, drying steps, therefore can provide a kind of production efficiency high, the conductors such as copper, aluminium are had to tack, can tolerate etching step and metallide step, the printing resist layer that can also peel off simply afterwards.In addition,, when the metal substrate of printing resist layer is carried out after etching, can further peel off printing resist and obtain printed circuit board (PCB).
Embodiment
The composition using in the present invention (A) is for the alkoxy silane that contains sulfydryl (a1) hydrolysis shown in general formula (1) is (except R 2the situation that is all hydrogen atom is outer), the compound that obtains of condensation, described general formula (1) is shown below:
R 1Si(OR 2) 3
(in formula, R 1expression has the alkyl of the carbon number 1～4 of at least one sulfydryl, R 2the alkyl that represents hydrogen atom or carbon number 1～4).Wherein, the R of general formula (1) 2be all in the situation of hydrogen atom, do not need hydrolysis only by condensation reaction, to obtain composition (A).As the object lesson of the alkoxy silane that contains sulfydryl (a1) (following, to be called composition (a1)), can enumerate 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl-triethoxysilicane, 3-sulfydryl propyl group tripropoxy silane, 3-sulfydryl propyl group three butoxy silanes, Isosorbide-5-Nitrae-dimercapto-2-(trimethoxysilyl) butane, Isosorbide-5-Nitrae-dimercapto-2-(triethoxysilyl) butane, Isosorbide-5-Nitrae-dimercapto-2-(tripropoxy-silicane base) butane, Isosorbide-5-Nitrae-dimercapto-2-(three butoxy silicyls) butane, 2-mercapto methyl-3-sulfydryl propyl trimethoxy silicane, 2-mercapto methyl-3-sulfydryl propyl-triethoxysilicane, 2-mercapto methyl-3-sulfydryl propyl group tripropoxy silane, 2-mercapto methyl-3-sulfydryl propyl group three butoxy silanes, 1,2-dimercapto ethyl trimethoxy silane, 1,2-dimercapto ethyl triethoxysilane, 1,2-dimercapto ethyl tripropoxy silane, 1,2-dimercapto ethyl, three butoxy silanes etc., this example compound can be used alone, and also can be used in combination aptly.In this example compound, because the reactivity of the hydrolysis reaction of 3-sulfydryl propyl trimethoxy silicane is high, easily obtain, therefore particularly preferably simultaneously.
In addition, except composition (a1), also can use (a2) (following, be called composition (a2)), for example, the trialkyl alkoxyl silicone alkanes such as trimethyl methoxy silane, trimethylethoxysilane, triethyl methoxy silane, triethyl-ethoxy-silicane alkane, triphenyl methoxy silane, triphenyl Ethoxysilane; Dialkyl group (or two aromatic radicals) the dialkoxy silicane classes such as dimethyldimethoxysil,ne, dimethyldiethoxysilane, diethyl dimethoxy silane, diethyl diethoxy silane, dimethoxydiphenylsilane, diphenyl diethoxy silane, aminomethyl phenyl dimethoxy silane, aminomethyl phenyl diethoxy silane, 3-sulfydryl propyl group methyl dimethoxysilane; Alkyl (or aromatic radical) trialkoxysilanes such as methyltrimethoxy silane, methyl triethoxysilane, ethyl trimethoxy silane, ethyl triethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane; The tetraalkoxysilane classes such as tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes; And the four alkoxytitanium classes such as tetramethoxy titanium, purity titanium tetraethoxide, four titanium propanolates, four titanium butoxide, the four zirconium alkoxide classes such as tetraethoxy zirconium, zirconium-n-propylate, tetrabutyl zirconate these containing the metal alkoxide of sulfydryl.Composition (a2) can be used alone, and also can be used in combination.Wherein, by using the cross-linking density of trialkyl alkoxyl silicone alkanes, dialkyl dialkoxy silicane class, tetraalkoxysilane class capable of regulating composition (A).By using the amount of the sulfydryl that alkyltrialkoxysilaneand class contains in can adjusting component (A).
In the situation that composition (a1) and composition (a2) are used in combination, [molal quantity of the sulfydryl containing in composition (a1)]/[total mole number of composition (a1) and composition (a2)] (mol ratio) is preferably more than 0.2.If this ratio is more than 0.2, can guarantees to give in (A) composition of active energy ray-curable and contain enough sulfydryl quantity, from improving the viewpoint of the physical propertys such as hardness of solidfied material, therefore preferably.
In addition, [total mole number of the alkoxy containing separately in composition (a1) and composition (a2)]/[total mole number of composition (a1) and composition (a2)] (mol ratio) is preferably more than 2.5, below 3.5, more preferably more than 2.7, below 3.2.By making, in the scope of mol ratio in aforementioned molar ratio, when preventing gelation, can to obtain the cured film of high crosslink density.
The composition using in the present invention (A) is used separately composition (a1) or is used in combination composition (a1) and composition (a2), is hydrolyzed after condensation and obtains.By hydrolysis reaction, can change contained alkoxy in composition (a1) and composition (a2) into hydroxyl, accessory substance is alcohol.In hydrolysis reaction, the necessary water yield is that [molal quantity of institute's water in hydrolysis reaction]/[in composition (a1) and composition (a2) separately the total mole number of contained alkoxy] (mol ratio) is preferably more than 0.4, below 10, more preferably 1.By making in the scope of mol ratio in aforementioned molar ratio, the negligible amounts of unhydrolysed residual alkoxy, meanwhile, the water yield that should remove during condensation reaction (dehydration) is less, can manufacture efficiently.
In addition R in general formula (1) only, 2(a1) composition that is all hydrogen atom obtains in the situation of composition (A), due to can be without hydrolysis only by condensation reaction, so unnecessary interpolation water.
In addition, in the situation that be used in combination with the high metal alkoxide of four alkoxytitanium classes as composition (a2), four zirconium alkoxide classes etc., particularly water-disintegrable and condensation reaction, hydrolysis rapidly and the carrying out of condensation reaction may have the situation that causes system gelation.In above-mentioned situation, stop the hydrolysis reaction of composition (a1), after the used up in fact state by whole water, by adding this composition (a2), can avoid gelation.
Catalyzer as using in hydrolysis reaction, is not particularly limited, and can use arbitrarily known hydrolyst.As hydrolyst, can enumerate organic acid, mineral acid, organic base, inorganic base.As organic acid, can enumerate acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, ethane diacid (oxalic acid), maleic acid, methylmalonic acid, hexane diacid, decanedioic acid, gallic acid, butyric acid, mellitic acid, arachidonic acid, 2 ethyl hexanoic acid, oleic acid, stearic acid, linoleic acid, leukotrienes (linoleinic acid), salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzene sulfonic acid, monochloro acetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartrate etc.As mineral acid, can enumerate hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid etc.As organic base, can enumerate pyridine, pyrroles, piperazine, pyrrolidine, piperidines, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethyl monoethanolamine, monomethyl diethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicyclo undecylene, Tetramethylammonium hydroxide, 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene etc.As inorganic base, can enumerate ammonia, NaOH, potassium hydroxide, baryta hydrate, calcium hydroxide etc.In above-mentioned catalyzer,, the viewpoint of easily removing high from catalytic activity, is preferably formic acid.With respect to composition (a1) and composition (a2), amount to 100 weight portions, the addition of catalyzer is preferably 0.1～25 weight portion, more preferably 1～10 weight portion.When the addition of catalyzer is during more than 25 weight portion, the printing resist obtaining has the tendency of reduction by the stability of resin combination, and in addition, although because later step can be removed catalyzer, the amount of removing is more, from the viewpoint of production efficiency, is disadvantageous.On the other hand, when the addition of catalyzer is less than 0.1 weight portion, although can make reaction carry out in fact, there is the tendency that the reaction time is extended.Although can set arbitrarily temperature of reaction and reaction time according to the reactivity of composition (a1) and composition (a2), temperature of reaction is generally 0～100 ℃ of left and right, is preferably 20～60 ℃, the reaction time is about 1 minute～2 hours.This hydrolysis reaction can carry out under solvent existence or non-existent condition.Kind to solvent is not particularly limited, can select more than one arbitrarily solvent use, preferably with condensation reaction described later in the solvent phase that uses with.In the situation that composition (a1) and composition (a2) are reactive lower, preferred solvent-free reaction.
Reaction under the following conditions is preferably hydrolyzed: while using separately composition (a1), [in composition (a1) in the molal quantity/composition (a1) of contained hydroxyl the molal quantity of contained alkoxy] (mol ratio) reaches more than 0.5, is further preferably adjusted into more than 0.8; In the situation that being used in combination composition (a1) and composition (a2), [total mole number of contained hydroxyl in composition (a1) and composition (a2)]/[in composition (a1) and composition (a2) separately the total mole number of contained alkoxy] (mol ratio) reaches more than 0.5, is further preferably adjusted into more than 0.8.Because the follow-up condensation reaction of hydrolysis reaction does not occur over just between the hydroxyl that hydrolysis generates, also occur between this hydroxyl and residual alkoxy, therefore, there is no need alkoxy complete hydrolysis to become hydroxyl.Make hydrolysis proceed to aforementioned molar ratio and reach 0.5 left and right, can obtain simply further stable printing resin combination against corrosion.
In condensation reaction, between aforementioned hydroxyl, accessory substance generates water, and in addition, between hydroxyl and alkoxy, accessory substance generates alcohol, produces vitrification phenomenon.In condensation reaction, can use arbitrarily current known dehydrating condensation catalyzer.As dehydrating condensation catalyzer, in aforementioned hydrolyst, illustrative those are enumerated.As previously mentioned,, the viewpoint of easily removing high from catalytic activity, is preferably formic acid.Although can set arbitrarily temperature of reaction and reaction time according to the reactivity of composition (a1) and composition (a2), temperature of reaction is generally 40～150 ℃ of left and right, is preferably 60～100 ℃, the reaction time is about 30 minutes～12 hours.
Pass through said method, preferably carry out under the following conditions condensation reaction: [total mole number of unreacted hydroxyl and unreacted alkoxy]/[in composition (a1) and composition (a2) separately the total mole number of contained alkoxy] (mol ratio) reaches below 0.3, be further preferably adjusted into below 0.2.By making in the scope of mol ratio in aforementioned molar ratio, can prevent that unreacted hydroxyl and alkoxy from producing gelation at resist with carrying out condensation reaction in the preservation of resin combination, can obtain the product that storage stability is higher.In addition, prevent the condensation reaction after solidifying, also do not have volatile ingredient to produce, in the printing resist layer that makes to obtain, the generation of crackle reduces.
Preferably composition (a1) is carried out to solvent dilution (in situation about being used in combination with composition (a2), by composition (a1) and composition (a2), both carry out solvent dilution), adjusting its concentration is 2～80 % by weight left and right, more preferably 15～60 % by weight are carried out above-mentioned condensation reaction.If use, there is the solvent higher than the boiling point of the water being generated by condensation reaction and alcohol, owing to distilling, remove above-mentioned product in reaction system, therefore preferably.As solvent, can choice for use more than one solvents arbitrarily, but due in the reaction system of low-boiling solvent below easily distillation remove, therefore preferred low-boiling solvent.
If remove solvent for use after above-mentioned condensation reaction completes,, before the printing resist by finally obtaining forms the step of pattern with resin combination, do not need to carry out drying steps, therefore preferably remove solvent for use after above-mentioned condensation reaction completes.In addition,, in the situation that forming pattern by printing, because viscosity is to a certain degree being necessary in some cases, from this starting point, viscosity is to a certain degree desired.
If remove used catalyst after above-mentioned condensation reaction completes, make the resist finally obtaining improve by the stability of resin combination, therefore preferably remove used catalyst after above-mentioned condensation reaction completes.The method of removing can be carried out suitable selection according to catalyzer used from various known methods.For example,, in the situation that using formic acid, after condensation reaction completes, by being heated on formic acid boiling point, the method such as decompression can easily remove formic acid removal, from the above point of view, preferably uses formic acid.
For the composition using in the present invention (B), so long as there is the compound of at least one carboxyl and at least one carbon-carbon double bond in molecule, be just not particularly limited, carboxyl equivalent is preferably 50～2000g/mol, more preferably 70～600g/mol.Carboxyl equivalent, more than 50g/mol, suppresses polarity and reduces, and improves the etch resistance of resulting resist solidfied material, simultaneously, carboxyl equivalent, below 2000g/mol, can make by the alkali lye of resist solidfied material to peel off and becomes easily, and metal adhesion is further improved.As composition as above (B), can enumerate and in commercially available unsaturated carboxylic acid, molecule, there is the compound of a hydroxyl and a carbon-carbon double bond and the partial esterification thing of polyprotonic acid, only there is the compound of an epoxy radicals and a carbon-carbon double bond and the partial esterification thing of polybasic carboxylic acid.
As unsaturated carboxylic acid, can enumerate the carboxylic acid that (methyl) acrylic acid, 2-butenoic acid, 3-butenoic acid, 4-penetenoic acid, 3-penetenoic acid, 2-penetenoic acid, 5-hexenoic acid, 4-hexenoic acid, 3-hexenoic acid, 2-hexenoic acid etc. have straight chain unsaturated alkyl, monomethyl maleate, ethyl maleate, crotonic acid, myristic acid, palmitoleic acid, oleic acid, elaidic acid, octadecenoic acid, gadoleic acid (gadoleic acid), eicosenoic acid, erucic acid, nervonic acid, linoleic acid, eicosadienoic acid (eicosadienoic acid), two dodecadienoic acids, leukotrienes, pinolenic acid (pinolenic acid), eleostearic acid (eleostearic acid), Mead acid, dihomo-gamma-linolenic acid, eicosatrienoic acid, parinaric acid, arachidonic acid, 18 carbon 5 alkene acids (bosseopentaenoic acid), eicosapentaenoic acid, clupanodonic acid (osbond acid), clupanodonic acid (clupanodonic acid), the acid of tetracosa carbon pentaene, DHA, nisioic acid (nisinic acid), colophonic acid, neoabietic acid, palustric acid (palustric acid), pimaric acid, isodextropimaric acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, 2-penetenoic acid (2-ペ Application テ Application ニ acid), methene succinic acid, allyl malonic acid, isopropylidene succinic acid, 2,4-hexadiene dicarboxylic acid, acetylenedicarboxylic acid, aconitic acid etc.In addition, also can use polycaprolactone list (methyl) acrylate etc.Wherein, acrylic acid, methacrylic acid, 3-butenoic acid are little molecule, and silicon rubber blanket has good absorbability to it.Therefore, owing to can there being more volume to remain in blanket, therefore from excellent transferability, can high-precision refinement viewpoint, preferred these molecules.
In the situation that the compound in using molecule with a hydroxyl and a carbon-carbon double bond and polybasic carboxylic acid partly become the compound of ester, its manufacture method is known, for example, the compound in the acid anhydrides such as dibasic acid, ternary acid and molecule with a hydroxyl and a carbon-carbon double bond, use as required catalyzer, by adding thermal response, obtain.In the situation of above-mentioned reaction, wish to stay monoesters compound.As the object lesson of above-mentioned acid anhydrides, can enumerate for example succinic acid, phthalic acid, maleic acid, trimellitic acid, pyromellitic acid, Na Dike acid (nadic acid), methyl Na Dike acid, dodecyl succinic acid, HET acid (chlorendic acid), benzophenone tetrabasic carboxylic acid, ethylene glycol bis trimellitic anhydride ester (ethylene glycol bis (anhydrotrimellitic acid)), poly-azelaic acid, tetrahydrophthalic acid, 3-methyl tetrahydrophthalic acid, 4-methyl tetrahydrophthalic acid, 3-ethyl tetrahydrophthalic acid, 4-ethyl tetrahydrophthalic acid, 3-propyl group tetrahydrophthalic acid, 4-propyl group tetrahydrophthalic acid, 3-butyl tetrahydrophthalic acid, 4-butyl tetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthaacid acid, 4-methylhexahydrophthaacid acid, 3-ethyl hexahydrophthalic acid, 4-ethyl hexahydrophthalic acid, 3-propyl group hexahydrophthalic acid, 4-propyl group hexahydrophthalic acid, 3-butyl hexahydrophthalic acid, the corresponding acid anhydrides of polybasic carboxylic acid such as 4-butyl hexahydrophthalic acid.Above-mentioned acid anhydrides can be used alone, also can the two or more uses of proper combination.
In addition, can enumerate with molecule in there is the reactant of the compound of a hydroxyl and a carbon-carbon double bond, these materials can be independent or two or more proper combinations use.As the object lesson in molecule with the compound of a hydroxyl and a carbon-carbon double bond, such as 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 2-hydroxyl butyl (methyl) acrylate, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, polytetramethylene glycol list (methyl) acrylate, acryloxy ethyl hexahydrophthalic acid etc.
In the situation that use, only there is the compound of an epoxy radicals and a carbon-carbon double bond and the partial esterification thing of polybasic carboxylic acid, the manufacture method of above-claimed cpd is known, for example, the acid anhydrides only with the alefinically unsaturated compounds of an epoxy radicals and a carbon-carbon double bond and dibasic acid, ternary acid etc., as required, use catalyzer, by adding thermal response, obtain above-mentioned partial esterification thing.The in the situation that of above-mentioned reaction, wish to stay monoesters compound.
As the object lesson only with the compound of an epoxy radicals and a carbon-carbon double bond and the partial esterification thing of polybasic carboxylic acid, can enumerate (methyl) glycidyl acrylate classes such as (methyl) glycidyl acrylate, (methyl) acrylic acid-2-methyl ethylene oxidic ester; (methyl) acrylic acid epoxycyclohexyl derivant classes such as (3,4-epoxycyclohexyl) methyl (methyl) acrylate etc.Above-mentioned substance can be used alone or the two or more uses of proper combination.In addition,, as polybasic carboxylic acid, can use the corresponding material of above-mentioned acid anhydrides.
In the present invention, as required, can use the compound (C) (following, to be called composition (C)) that does not there is carboxyl but there are at least two carbon-carbon double bonds.As composition (C), so long as do not there is carboxyl but there is the compound of at least two carbon-carbon double bonds, be just not particularly limited.As composition (C), can enumerate allyl compound and (methyl) esters of acrylic acid.
As the allyl compound in composition (C), can enumerate diallyl phthalate, properties of diallyl isophathalate, diallyl cyanurate, diallyl isocyanuric acid ester, pentaerythritol diallyl ether, trimethylolpropane allyl ether, glycerine diallyl ether, tetrabutyl ammonium bromide, Bisphenol F diallyl ether, ethylene glycol bisthioglycolate allyl ether, diethylene glycol diallyl ether, triethylene glycol diallyl ether, propylene glycol list diallyl ether, dipropylene glycol diallyl ether, tripropylene glycol diallyl ether etc. contains two allylic compounds, cyanacrylate, pentaerythritol triallyl ether, pentae-rythritol tetraallyl ether, trimethylolpropane tris allyl ether etc. contain three above allylic compounds.Above-claimed cpd can be used alone, also use capable of being combined.
As (methyl) esters of acrylic acid in composition (C), can enumerate nonanediol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, three (2-hydroxyethyl) isocyanuric acid ester three (methyl) acrylate, pentaerythrite three (methyl) acrylate, BDO two (methyl) acrylate, neopentyl glycol two (methyl) acrylate etc.Above-claimed cpd can be used alone, also use capable of being combined.
Because composition (C) is so that composition (A) is cross-linked as object, the functional group of containing carbon-carbon double bond reacts more preferably with sulfydryl, in order not cause the adverse effect of polymerization between the functional group of containing carbon-carbon double bond, preferably uses free-radical polymerised low material.From the above point of view, preferred aforementioned allyl compound, further preferred cyanacrylate, diallyl phthalate, pentaerythritol triallyl ether wherein.
Composition as above (C), can obtain the product as commercially available product.Trade name " Gechron " etc.), allyl end polyisobutylene polymkeric substance ((strain) カ ネ カ: trade name " エ ピ オ Application "), urethane acrylate (waste river chemical industry (strain) system: trade name “ ビ ー system セ ッ ト 550B ") etc. for example can enumerate the multipolymer that the multipolymer that methacrylic siloxane and dimethyl siloxane are made, epichlorokydrin and allyl glycidyl ether are made (ダ イ ソ ー (strain): trade name " エ ピ Network ロ マ ー ", Japanese ゼ オ Application (strain):.From free-radical polymerised low, simultaneously can guarantee resist by the viscosity of resin combination, can improve the flexible viewpoint of solidfied material, preferred above-mentioned commercially available product.Above-mentioned commercially available product can be used alone, and also can be used in combination.
, in the time of due to alkene-thiol reactant, can cause the polyreaction between composition (B) and (C) herein, with respect to the sulfydryl in (A), the carbon-carbon double bond ratio (mol ratio) (B) and (C) is preferably more than 1.
From the above point of view, composition (A) and usage ratio (B) when printing resist of the present invention is prepared with activity energy-line solidifying type resin composition, being preferably and making [molal quantity of the carbon-carbon double bond containing in composition (B)]/[molal quantity of the sulfydryl containing in composition (A)] (mol ratio) is 0.9～100.In the situation that surpassing 100, because the amount of the composition (A) using is very few, there is the tendency that is difficult to realize the desired effect of the present invention.In addition, in the situation that not reaching 0.9, sulfydryl is residual, has because of it and decomposes the situation that produces stink.In addition,, because the carboxyl equivalent in said composition increases, there is the tendency that is difficult to realize the desired effect of the present invention.
While using composition (C), with respect to the whole amount of composition (B), the amount being preferably below 50 % by weight coordinates.In the situation that surpassing 50 % by weight, owing to too having increased the cross-linking density of solidfied material, there is the alkali-soluble tendency of reduction.In addition, be used in combination in the situation of composition (C), it is 0.9～100 that the usage ratio of composition (A), composition (B) and composition (C) preferably makes [molal quantity of the carbon-carbon double bond containing in composition (B) and composition (C)]/[molal quantity of the sulfydryl containing in composition (A)] (mol ratio).In the situation that aforementioned molar ratio surpasses 100, because the amount of composition used (A) is very few, there is the tendency that is difficult to realize the desired effect of the present invention.In addition, in the situation that not reaching 0.9, sulfydryl is residual, has because of it and decomposes the situation that produces stink.In addition,, because the mol ratio of carboxyl too reduces, therefore there is the tendency that is difficult to realize the desired effect of the present invention.
As spendable polymerization initiator in activity energy-line solidifying type resin composition for printing resist of the present invention, be not particularly limited, can select arbitrarily known smooth cationic initiator, optical free radical initiating agent etc. at present.As light cationic initiator, can enumerate by ultraviolet ray and irradiate acidic compound sulfosalt, salt compounded of iodine, metallocene compound, toluenesulfonic acid benzoin ester (benzoin tosylate) etc., as above-mentioned commercially available product, have such as サ イ ラ キ ュ ア UVI-6970, same UVI-6974, with the UVI-6990(Union Carbide Corporation(U.S.) trade name processed), イ Le ガ キ ュ ア 264(チバ ジャパン Co., Ltd.), CIT-1682(this Cao of day Da (strain) system) etc.With respect to the said composition of 100 weight portions, the consumption of light cationic initiator is generally below 10 weight portion left and right, is preferably 1～5 weight portion.As optical free radical initiating agent, can enumerate ダ ロ キ ュ ア 1173, イ Le ガ キ ュ ア 651, イ Le ガ キ ュ ア 184, イ Le ガ キ ュ ア 907(チバ ジャパン Co., Ltd.), benzophenone etc., with respect to said composition 100 weight portions, the consumption of optical free radical initiating agent is generally below 15 weight portion left and right, is preferably 1～15 weight portion.In addition,, in the situation that the weatherability of the solidfied material that concern obtains reduces, use weatherability, the transparency are required in the situation of extra high optical material etc., inapplicable photoreaction initiator and photosensitizer.
In addition,, for further improving the keeping stability in activity energy-line solidifying type resin composition keeping for printing resist, can coordinate the compound of inhibition alkene-thiol reactant.As compound as above, can enumerate triphenylphosphine, triphenyl phosphite etc.Wherein, because triphenyl phosphite suppresses the effective of alkene-thiol reactant, under room temperature, be liquid simultaneously, easily process, therefore be preferred.With respect to the composition of 100 weight portions, printing resist is preferably 0.1～10 weight portion left and right by the amount that coordinates this compound in resin combination.By using in above-mentioned scope, when fully suppressing alkene-thiol reactant, can reduce residual sulfydryl amount, described residual sulfydryl amount is the principal element that makes the physical property reduction of gained solidfied material.
In addition, printing resist of the present invention, with in activity energy-line solidifying type resin composition, can be used in conjunction with solvent as required.As solvent, can use known any solvent at present, for after forming at pattern, do not produce volatile ingredient, make solvent easily volatilization before pattern forms, preferably use and hold volatile solvent.Printing resist is used in situation about being coated with resin combination, and useable solvents dilution obtains desired viscosity.Printing resist can carry out suitable setting according to mode of printing and purposes by the viscosity of activity energy-line solidifying type resin composition, is generally 0.5PaS～5000PaS, is preferably 2PaS～1000PaS.In viscosity, lower than 0.5PaS in the situation that, owing to oozing out, may when printing, can not carry out the printing that pattern precision is high; In viscosity, higher than 5000PaS in the situation that, may not make composition flow in pattern plate efficiently.
In addition,, while forming pattern, the volatilization due to solvent after formation produces bubble, can cause the confusion of pattern, therefore, printing is more than for resist, the total concentration of composition in resin combination (A), composition (B) and composition (C) is preferably 90 % by weight, more preferably more than 95 % by weight.The quantity of solvent calculating that described total concentration adds while not needing total concentration by composition (A), composition (B) and composition (C) and printing resist with the preparation of resin combination is tried to achieve, can more than the boiling point with the solvent containing in resin combination heat about 2 hours at printing resist, by the weight change before and after heating, try to achieve.In addition, the in the situation that of using solvent, after having reacted, make solvent evaporates when synthetic ingredient (A), it is more than 90 % by weight reaching nonvolatile component content.In addition, preparation printing resist, with after resin combination, makes solvent evaporates used, can improve the total concentration of composition (A), composition (B) and composition (C).
In addition, as further another embodiment of activity energy-line solidifying type resin composition for printing resist of the present invention, at composition (a1) and optional member (a2) after there is lower hydrolysis in catalyzer, under solvent and composition (B) and existence (C), by condensation reaction, obtain.The conditions such as temperature of reaction, reaction time, solvent species are identical with the situation in aforementioned composition (A).
Further, printing resist of the present invention is with in activity energy-line solidifying type resin composition, according to purposes, can coordinate aforementioned composition (a1) and/or its hydrolysate (note, this condensation product except) (D) [following, to merge and be called composition (D)].The composition (a1) using when composition (D) can directly be used synthetic ingredient (A), also can be used its hydrolysate, also they can be used in combination.By using composition (D), there is the tack of can further improve.The printing resist of 100 weight portions is with in activity energy-line solidifying type resin composition, and the use level of composition (D) preferably contains 0.1～20 weight portion with solid component meter.By making use level more than 0.1 weight portion, owing to can fully improving the effect by the tack of the substrate of resin combination to printing resist, therefore be preferred.In addition, by making use level below 20 weight portions, because composition (D) reduces at hydrolysis, volatile quantity during condensation reaction, can make to print resin combination film thickening for resist, in addition, the solidfied material obtaining is non-friable, therefore be preferred.As composition as above (D), from the viewpoint of above-mentioned raising tack, 3-sulfydryl propyl trimethoxy silicane particularly preferably.
In addition,, according to purposes (against corrosion etc.), printing resist of the present invention can coordinate aforementioned composition (a2) and/or its hydrolysate (note, this condensation product except) (E) (following, to merge and be called composition (E)) with activity energy-line solidifying type resin composition.The composition (a2) using when composition (E) can directly be used synthetic ingredient (A), also can be used its hydrolysate, also two kinds can be used in combination.The printing resist resin combination that contains composition (E) by use, the refractive index of capable of regulating gained solidfied material.In the situation that printing resist is used as high refractive index coating agent with resin combination, as composition (E), suitable use four alkoxytitanium classes, four zirconium alkoxide classes.With respect to the activity energy-line solidifying type resin composition of 100 weight portions, the use level of composition (E) preferably contains 0.1～20 weight portion left and right with solid component meter.By making content more than 0.1 weight portion, below 20 weight portions, the foaming in the time of can suppressing to solidify and crackle produce, therefore be preferred.
In addition, printing resist of the present invention is with in activity energy-line solidifying type resin composition, transfer printing when making to print improves, can coordinate the component of polymer (F) (following, to be called composition (F)) making containing the monomer polymerization of ethylenically unsaturated group (ethylenically unsaturated group).By gradation composition (F), can improve transfer printing.As long as component of polymer (F) is the material that can dissolve in composition (B), composition (C), be just not particularly limited.(F) weight-average molecular weight of composition (by the polystyrene conversion value of gel permeation chromatography) is 1000～50000 left and right, is preferably 5000～20000 left and right.Weight-average molecular weight is below 1000, can make the effect that viscosity improves reduce; Weight-average molecular weight surpasses more than 50000, can make it can not be dissolved in composition (B), composition (C).
As composition as above (F), be not particularly limited (methyl) alkyl acrylate or (methyl) acrylic acid cycloalkyl esters such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) cyclohexyl acrylate, (methyl) polyalkylene glycol acrylate alkyl ethers such as (methyl) acrylic acid ethylene glycol monomethyl ether, (methyl) acrylic acid diethylene glycol dimethyl ether, (methyl) polyalkylene glycol acrylate methyl ether, (methyl) acrylic-amino methyl esters, (methyl) acrylic acid N-methylamino methyl esters, (methyl) acrylic acid N, (methyl) acrylic-amino Arrcostabs such as N-lignocaine ethyl ester, (methyl) glycidyl acrylate, low polyethylene oxide (methyl) acrylate, low polypropyleneoxide (methyl) acrylate, (methyl) acrylic acid methoxyl polypropylene glycol ester, (methyl) acrylic acid methoxy poly (ethylene glycol) ester, methacrylic acid, acrylic acid, N-methylamino ethyl (methyl) acrylate, N-ethylamino ethyl (methyl) acrylate, N-tert-butyl group amino-ethyl (methyl) acrylate, N, N-dimethyl aminoethyl (methyl) acrylate, N, N-diethylamino ethyl (methyl) acrylate, N, (methyl) acrylic polymer of the homopolymerizations such as N-dimethylaminopropyl (methyl) acrylate or copolymerization, is used in combination styrene in the monomer component of aforementioned (methyl) acrylic polymer, α-methyl styrene, vinyltoluene, polymkeric substance to chlorostyrene etc., further, as long as meet above-mentioned weight-average molecular weight, does not have the restriction of aforementioned monomer composition and polymkeric substance, can be homopolymer or the multipolymer of the monomer that contains unsaturated alkyl yet.Above-mentioned (F) composition can be used alone, and also can be used in combination.
With respect to the activity energy-line solidifying type resin composition of 100 weight portions, the use level of composition (F), with solid component meter, preferably contains 0.1～70 weight portion left and right.By making content more than 0.1 weight portion, below 70 weight portions, owing to can increasing viscosity, the raising transfer printing of activity energy-line solidifying type resin composition, therefore be preferred.More than 70 weight portions, because the amount of activity energy-line solidifying type resin composition used is very few, there is the tendency that is difficult to realize the desired effect of the present invention.
Further, in not damaging the scope of effect of the present invention, according to the necessity of various uses, printing resist of the present invention can coordinate plastifier, weather resisting agent, antioxidant, thermal stabilizer, lubricant, antistatic agent, whitening agent, colorant, conductive agent, release agent, surface conditioning agent, viscosity modifier, filler etc. with activity energy-line solidifying type resin composition.
For example, according to purposes, printing resist of the present invention is with dispersibling the silica filler that makes viscosity rise in activity energy-line solidifying type resin composition.
The silica filler adding for above-mentioned purpose, is not particularly limited, and preferably specific surface area is 50～400m 2/ g, average primary particle diameter is the product of 7～40nm scope.In addition, as silicon dioxide granule, so long as the silicon dioxide of manufacturing by so-called pyrolysismethod (vapor phase method) or sol-gal process can preferably obtain.In addition, from improving dispersed viewpoint, preferably the surface of silicon dioxide granule is carried out the product of hydrophobization by surface conditioning agent, particularly by dimethyldichlorosilane, carry out surface-treated product.With respect to the printing resist activity energy-line solidifying type resin composition of the present invention of 100 weight portions, as the use level of silicon dioxide granule, with solid constituent, count 0.1～5 weight portion, more preferably the scope of 1～3 weight portion.In situation less than 0.1 weight portion, do not demonstrate and put forward full-bodied effect; In addition, surpass in the situation of 5 weight portions, have the tendency of the physical property that reduces solidfied material.
As the object lesson of water wettability aerosil, can enumerate AEROSIL90, AEROSIL130, AEROSIL150, AEROSIL200, AEROSIL300, AEROSIL380, AEROSIL OX50, AEROSIL EG50, AEROSIL TT600, the レ オ ロ シ ー Le QS-09 of (strain) ト Network ヤ マ system, QS-10L, QS-10, QS-102, CP-102, QS-20L, QS-20, QS-25C, QS-30, QS-30C, the QS-40 etc. of Japanese ア エ ロ ジ Le (strain) system.In addition, object lesson as hydrophobicity aerosil, can enumerate the AEROSIL R972 of Japanese ア エ ロ ジ Le (strain) system, AEROSIL R974, AEROSIL R104, AEROSIL R106, AEROSIL R202, AEROSIL R805, AEROSIL R812, AEROSIL R816, AEROSIL R7200, AEROSIL R8200, AEROSIL R9200, AEROSIL RY50, AEROSIL NY50, AEROSIL RY200, AEROSIL RY200S, AEROSIL RX50, AEROSIL NAX50, AEROSIL RX200, AEROSIL RX300, AEROSIL R504, AEROSIL DT4, the レ オ ロ シ ー Le MT-10 of (strain) ト Network ヤ マ system, MT-10C, DM-10, DM-10C, DM-20S, DM-30, DM-30S, KS-20S, KS-20SC, HM-20L, HM-30S, PM-20L etc.
Can use the various dispersion mixed methods such as three-roll grinder, two roller mills, sand mill, masher, bowl mill, kneader, propeller(type)stirrer (agitator mixer), ultrasonic stirrer, strand grinding machine to carry out the dispersion of silica filler.During dispersion, in order to make the good dispersion of filler, can add suitable dispersing aid.The effect of aggegation again after can helping to disperse because dispersing aid has, preventing from disperseing simultaneously, the homogeneous that can be maintained forms, the light-cured type composition of excellent in stability.
Printing resist of the present invention is the material that is applicable to following method with activity energy-line solidifying type resin composition: by mode of printing, in object shape (pattern), will print in advance resist with after resin combination is coated with on substrate, and make the formation method of curing corrosion-resisting pattern by illumination.By using above-mentioned substance, can High-efficient Production through mode of printing, form the printing resist layer laminate of object corrosion-resisting pattern.
Substrate used during pattern of the present invention forms, can be used the conductive poly condensation materials such as PEDOT, polypyrrole, polyaniline; The metal oxides such as ITO, ZTO, indium oxide, tin oxide, zinc paste; The inorganic material such as silicon or glass; The metal materials such as aluminium, stainless steel, copper; Outside the resin materials such as pet resin, vibrin, polyimide resin, epoxy resin, polyvinyl resin, acrylic resin, ethylene-vinyl acetate copolymer resin, polyvinyl acetate resin, polyvinyl alcohol resin, Corvic, polyvinylidene chloride resin, polystyrene resin, plexiglass, nylon resin, polycarbonate resin, norbornene resin, tri acetyl cellulose resin, also has paper etc.The tack of resin combination for printing resist, through processing such as oxidation processes, acid treatment, plasma treatment, discharge process, can be improved in the surface of above-mentioned substrate.Because printing resist is usually located at the surface of substrate with resin combination, so the thickness of substrate can be set arbitrarily.In addition,, between printing resist is with resin combination and substrate, also the resin bed irrelevant with light reaction etc. can be set.Among above-mentioned, preferred glass, metallic silicon, pet resin.In addition,, while being substrate, film or thin slice due to substrate, easy coating and printing resist resin combination, therefore be preferred.
Printing process as using in the present invention, is not particularly limited, and can enumerate for example letterpress reverse hectographic printing, serigraphy, intaglio printing, intaglio offset, letterset.
Exposure to active energy ray is not particularly limited, according to printing suitable decision such as the classes of compounds of using in activity energy-line solidifying type resin composition, thickness for resist, in ultraviolet situation, for example, the accumulative total light quantity of take is 50～10000mJ/cm 2left and right is irradiated.In addition,, in the situation that being coated with and filling with thick film, preferably, by adding light trigger or photosensitizer in said composition as previously mentioned, photo-curable is improved.
As the active energy ray that solidifies use, can enumerate HEIR line and ultraviolet ray.As HEIR line, for example, can use the industrial use most convenient accelerating by accelerators such as croft (Cockcroft) type accelerator, van de graaf accelerator, linear accelerator, betatron (betatron), cyclotrons (cyclotron), simultaneously most economical electron beam, also can use from radiation other radioactive ray out such as radioactive isotope and nuclear reactors: gamma-rays, X ray, alpha ray, neutron beam, proton beam etc.As ultraviolet light source, can enumerate such as ultraviolet fluorescent lamp, low pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, xenon lamp, carbon arc lamp, sunlamp etc.Irradiation time to active energy ray is not particularly limited, and can adopt known condition.In the situation that printing resist contains solvent with activity energy-line solidifying type resin composition, according to the volatilization method of the suitable decision solvents such as the kind of solvent, amount, thickness, can be in 40～150 ℃ of left and right of heating, preferably 60～100 ℃, under normal pressure or the condition that reduces pressure lower about 5 seconds～2 hours, carry out.
In addition,, in the situation that being heating and curing, the kind, solvent species, solidfied material thickness that can consider used composition (B), composition (C) etc. determines solidification temperature and heat time aptly.Conventionally, preferably with under 20～150 ℃ of left and right, the condition about 1 minute～24 hours.In addition,, after having solidified, further by 100 ℃～300 ℃ left and right, preferably at more than 120 ℃, lower than 250 ℃, heat further promotion curing reaction when residual solvent is removed completely about 1 minute～6 hours.Therefore, the cured film obtaining can be passed through the effect of silicon dioxide Composite, obtains the feature of chemical resistance excellence.Can be active energy line curing, being heating and curing is cured separately respectively, also can be used in combination.In the situation that being used in combination, it is sequentially not particularly limited, conventionally ultraviolet ray is irradiated to the solidfied material obtaining and heat by further, can make the physical property of solidfied material better.Heating method can determine aptly, optional 40～300 ℃ of left and right, are preferably and are heated to 100～250 ℃, the condition about 1 minute～6 hours.
During above-mentioned pattern forms, in the situation that the printing resist after illumination etc. is solidified is removed and is developed with the cured portion of activity energy-line solidifying type resin composition or uncured portion dissolving, the solvent of using as developer solution, can enumerate for example 1-METHYLPYRROLIDONE, methyl alcohol, ethanol, toluene, cyclohexane, isophorone, cellosolve acetate, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, dimethylbenzene, ethylbenzene, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, isoamyl acetate, ethyl lactate, methyl ethyl ketone, acetone, cyclohexanone, N, dinethylformamide, acetonitrile, alkaline aqueous solution etc.Above-mentioned substance can be used alone or is used in combination.Further, in above-mentioned solvent, can add the alkaline matters or surfactant-based such as trimethylamine, triethylamine.
As above-mentioned alkaline aqueous solution, can use the aqueous solution of the inorganic salts such as NaOH, potassium hydroxide, sodium carbonate, sal tartari; The aqueous solution of the organic salts such as hydroxyl tetramethyl-ammonium, hydroxyl tetraethyl ammonium.Above-mentioned substance can be used alone or is used in combination.
It is transparent that the corrosion-resisting pattern obtaining as mentioned above makes formed layered product, and the cure shrinkage before and after pattern forms is 0.1～5% left and right.
The formed layered product useful etch of above-mentioned corrosion-resisting pattern liquid carries out the printed circuit board (PCB) that etching obtains patterning.Above-mentioned printed circuit board (PCB) can directly be used, and also after peelable corrosion-resisting pattern, uses.
As above-mentioned etching solution, have no particular limits, can enumerate for example aqueous solution of iron chloride, cupric chloride, persulfate, hydrogen peroxide/sulfuric acid.
Means as peeling off corrosion-resisting pattern, are not particularly limited, and can use the corresponding method of solvent that for example above-mentioned developer solution is used.Wherein, the alkaline aqueous solution such as sodium hydrate aqueous solution, hydroxyl tetramethyl-ammonium aqueous solution particularly preferably.
Embodiment
Below by enumerating embodiment and comparative example is specifically described the present invention.In addition,, in each embodiment, in the situation that not specifying, " part " and " % " is weight standard.
The manufacture of Production Example 1(condensation product (A-1))
In thering is the reaction unit of stirrer, condenser, water trap, thermometer, nitrogen inlet, add 3-sulfydryl propyl trimethoxy silicane (SHIN-ETSU HANTOTAI's chemical industry (strain) system: 17.0 parts, trade name " KBM-803 ") 3400 parts, ion exchange water 936 parts ([molal quantity of institute's water in hydrolysis reaction]/[molal quantity of contained alkoxy in composition (a1)] (mol ratio)=1.0), 95% formic acid, under room temperature, hydrolysis reaction is 30 minutes.In reaction, due to heat release, temperature rises to the highest 35 ℃.After reaction, add 5670 parts of toluene, heating.While being warming up to 71 ℃, start methyl alcohol and part toluene that dephlegmate solution produces.Through 2 hours, be warming up to 75 ℃, carry out condensation reaction, dephlegmate.Further, react after 1 hour at 75 ℃, under 70 ℃, 20kPa, residual part toluene, methyl alcohol, water, formic acid are removed in decompression distillation.The concentration of condensation product (A-1) is 99.0%.In addition, the sulfydryl concentration of condensation product (A-1) is 7.41mmol/g.
The manufacture of Production Example 2(condensation product (A-2))
With the same reaction unit of Production Example 1 in, add 2500 parts of 3-sulfydryl propyl trimethoxy silicanes, methyltrimethoxy silane (SHIN-ETSU HANTOTAI's chemical industry (strain) system: trade name " KBM-11 ") 347 parts ([molal quantity of contained sulfydryl in composition (a1)]/[total mole number of composition (a1) and composition (a2)]=0.83, [total mole number of the alkoxy containing separately in composition (a1) and composition (a2)]/[total mole number of composition (a1) and composition (a2)]=3), 824 parts of ion exchange waters ([molal quantity of water used in hydrolysis reaction]/[in composition (a1) and composition (a2) separately the total mole number of contained alkoxy] (mol ratio)=1.0), 14 parts, 95% formic acid, under room temperature, hydrolysis reaction is 30 minutes.In reaction, due to heat release, temperature rises to the highest 32 ℃.After reaction, add 3000 parts of toluene, heating.While being warming up to 71 ℃, start methyl alcohol and part toluene that dephlegmate solution produces.Through 1 hour, be warming up to 75 ℃, carry out condensation reaction, dephlegmate.Further, react after 1 hour at 75 ℃, under 70 ℃, 20kPa, residual part toluene, methyl alcohol, water, formic acid are removed in decompression distillation.Further, under 70 ℃, 0.7kPa, toluene is removed in decompression distillation, obtains 1820 parts of condensation products (A-2).The concentration of condensation product (A-2) is 98.7%.In addition, the sulfydryl concentration of condensation product (A-2) is 7.00mmol/g.
The manufacture of activity energy-line solidifying type resin composition for embodiment 1(printing resist)
28.8 parts of the condensation products obtaining with respect to Production Example 1 (A-1), mix acryloxy ethyl hexahydrophthalic acid as composition (B) (GongSakae society oil chemical industry (strain) system: the concentration 3.6mmol/g of trade name " ラ イ ト ア Network リ レ ー ト (Light Acrylate) HOA-HH ", carbon-carbon double bond, carboxylic acid valency 281.96, hereinafter referred to as HOA-HH.) 120.4 parts ([molal quantity of the carbon-carbon double bond containing in composition (B)]/[molal quantity of the sulfydryl containing in composition (A)] (mol ratio)=2.00), hydroxy-cyclohexyl benzophenone (チ バ ジ ャ パ Application (strain): trade name " イ Le ガ キ ュ ア 184 " as light-cured catalyst, hereinafter referred to as Irg184) 0.75 part, as solvent ethylene glycol dimethyl ether (the Japanese emulsification drug (strain): trade name " DMG " that Irg184 is dissolved, hereinafter referred to as DMG) 1.5 parts, obtain the printing resist activity energy-line solidifying type resin composition of carboxyl equivalent 354.67g/mol.
The manufacture of activity energy-line solidifying type resin composition for embodiment 2(printing resist)
43.0 parts of the condensation products obtaining with respect to Production Example 2 (A-2), mixing, as HOA-HH158 part ([molal quantity of the carbon-carbon double bond containing in composition (B)]/[molal quantity of the sulfydryl containing in composition (A)] (mol ratio)=2.00) of composition (B), as Irg1841.0 part of light-cured catalyst, as solvent DMG2.0 part that Irg184 is dissolved, obtains the printing resist activity energy-line solidifying type resin composition of carboxyl equivalent 364.57g/mol.
The manufacture of activity energy-line solidifying type resin composition for embodiment 3(printing resist)
34.2 parts of the condensation products obtaining with respect to Production Example 2 (A-2), mixing is as HOA-HH100 part of composition (B), as the cyanacrylate of composition (C) (hereinafter referred to as TAIC, Japan changes into (strain) system: trade name " TAIC ", the concentration 12.0mmol/g of carbon-carbon double bond) 12.5 parts (([molal quantity of the carbon-carbon double bond containing in composition (B)]+[molal quantity of the carbon-carbon double bond containing in composition (C)])/[molal quantity of the sulfydryl containing in composition (A)] (mol ratio)=2.01), Irg1840.75 part as light-cured catalyst, as solvent DMG1.5 part that Irg184 is dissolved, obtain the printing resist activity energy-line solidifying type resin composition of carboxyl equivalent 421.39g/mol.
The manufacture of activity energy-line solidifying type resin composition for embodiment 4(printing resist)
37.2 parts of the condensation products obtaining with respect to Production Example 2 (A-2), mixing is as HOA-HH96.5 part of composition (B), TAIC12.1 part (([molal quantity of the carbon-carbon double bond containing in composition (B)]+[molal quantity of the carbon-carbon double bond containing in composition (C)])/[molal quantity of the sulfydryl containing in composition (A)] (mol ratio)=2.01) as composition (C), Irg1840.75 part as light-cured catalyst, as solvent DMG1.5 part that Irg184 is dissolved, with decollator, disperse the silica filler of using as adjustment viscosity (hereinafter referred to as DM-20S, ト Network ヤ マ (strain) system: trade name " レ オ ロ シ ー Le DM-20S ") 3.5 parts, obtain the printing resist activity energy-line solidifying type resin composition of carboxyl equivalent 431.26g/mol.
The manufacture of activity energy-line solidifying type resin composition for embodiment 5(printing resist)
19.2 parts of the condensation products obtaining with respect to Production Example 2 (A-2), mixing as the methacrylic acid of composition (B) (hereinafter referred to as MAA, Mitsubishi's レ イ ヨ Application (strain) system: trade name " メ タ Network リ Le acid (methacrylic acid) ", the concentration 11.6mmol/g of carbon-carbon double bond) 17.1 parts, TAIC4.2 part (([molal quantity of the carbon-carbon double bond containing in composition (B)]+[molal quantity of the carbon-carbon double bond containing in composition (C)])/[molal quantity of the sulfydryl containing in composition (A)] (mol ratio)=2.00) as composition (C), Irg1840.20 part as light-cured catalyst, as solvent DMG0.4 part that Irg184 is dissolved, 1.4 parts of the silica fillers of using as adjustment viscosity with decollator dispersion, obtain the printing resist activity energy-line solidifying type resin composition of carboxyl equivalent 214.27g/mol.
The manufacture of activity energy-line solidifying type resin composition for embodiment 6(printing resist)
15.6 parts of the condensation products obtaining with respect to Production Example 2 (A-2), mixing is as MAA18.2 part and HOA-HH8.6 part of composition (B), TAIC5.0 part (([molal quantity of the carbon-carbon double bond containing in composition (B)]+[molal quantity of the carbon-carbon double bond containing in composition (C)])/[molal quantity of the sulfydryl containing in composition (A)] (mol ratio)=3.00) as composition (C), Irg1840.21 part as light-cured catalyst, as solvent DMG0.42 part that Irg184 is dissolved, 1.7 parts of the silica fillers of using as adjustment viscosity with decollator dispersion, obtain the printing resist activity energy-line solidifying type resin composition of carboxyl equivalent 205.18g/mol.
The manufacture of activity energy-line solidifying type resin composition for embodiment 7(printing resist)
15.6 parts of the condensation products obtaining with respect to Production Example 2 (A-2), mixing is as MAA18.2 part and HOA-HH8.6 part of composition (B), TAIC5.0 part (([molal quantity of the carbon-carbon double bond containing in composition (B)]+[molal quantity of the carbon-carbon double bond containing in composition (C)])/[molal quantity of the sulfydryl containing in composition (A)] (mol ratio)=3.00) as composition (C), as composition, (F) ビ ー system セ ッ ト 255D(is hereinafter referred to as BS255D, waste river chemistry (strain) system: trade name “ ビ ー system セ ッ ト 255D ") 26.0 parts, Irg1840.21 part as light-cured catalyst, as solvent DMG0.42 part that Irg184 is dissolved, 2.6 parts of the silica fillers of using as adjustment viscosity with decollator dispersion, obtain the printing resist activity energy-line solidifying type resin composition of carboxyl equivalent 314.76g/mol.
The manufacture of activity energy-line solidifying type resin composition for comparative example 1(printing resist)
With respect to composition (B) HOA-HH100 part, mix the Irg1841.0 part as light-cured catalyst, solvent DMG2.0 part that conduct is dissolved Irg184, obtain the printing resist activity energy-line solidifying type resin composition of carboxyl equivalent 290.42g/mol.
The manufacture of activity energy-line solidifying type resin composition for comparative example 2(printing resist)
44.0 parts of the condensation products obtaining with respect to Production Example 1 (A-1), do not use composition (B), mixing, as TAIC23.7 part ([molal quantity of the carbon-carbon double bond containing in composition (C)]/[molal quantity of the sulfydryl containing in composition (A)] (mol ratio)=1.00) of composition (C), as Irg1841.0 part of light-cured catalyst, as solvent DMG2.0 part that Irg184 is dissolved, obtains the printing resist activity energy-line solidifying type resin composition of carboxyl equivalent 0g/mol.
The manufacture of activity energy-line solidifying type resin composition for comparative example 3(printing resist)
With respect to the pentaerythrite four as mercaptan composition (3-sulfydryl butyric acid) ester (clear and Electricity work (strain) system: trade name " カ レ Application ズ MT PE1 " that replaces composition (A), hereinafter referred to as PE1) 38.7 parts, mixing is as composition (B) HOA-HH160 part ([molal quantity of the carbon-carbon double bond containing in composition (B)]/[molal quantity of the sulfydryl containing in composition (A)] (mol ratio)=2.00), Irg1841.0 part as light-cured catalyst, as solvent DMG2.0 part that Irg184 is dissolved, obtain the printing resist activity energy-line solidifying type resin composition of carboxyl equivalent 355.31g/mol.
Above embodiment 1～7, the printing resist of comparative example 1～3 use the composition of activity energy-line solidifying type resin composition as shown in table 1.
Table 1
Figure BDA00003444254900221
Mark in table 1 is as follows:
HOA-HH: acryloxy ethyl hexahydrophthalic acid (GongSakae society oil chemical industry (strain), trade name " ラ イ ト ア Network リ レ ー ト HOA-HH ")
PE1: pentaerythrite four (3-sulfydryl butyric acid) ester (clear and Electricity work (strain) trade name " カ レ Application ズ MT PE1 ")
TAIC: (Japan changes into (strain) system to cyanacrylate: trade name " TAIC ")
Irg184: hydroxy-cyclohexyl benzophenone (チ バ ジ ャ パ Application (strain): trade name " イ Le ガ キ ュ ア 184 ")
DMG: glycol dimethyl ether (Japanese emulsification drug (strain): trade name " DMG ")
MAA: methacrylic acid (Mitsubishi's レ イ ヨ Application (strain) system)
The waste river chemistry of BS255D: ビ ー system セ ッ ト 255D((strain) system: trade name “ ビ ー system セ ッ ト 255D ")
(formation of pattern)
The printing resist that embodiment 1～7, comparative example 1～3 are obtained is coated Copper Foil or aluminium foil with activity energy-line solidifying type resin composition with thickness 10 μ m, use ultraviolet lamp (ウ シ オ Electricity Machine (strain) system: trade name " UV-152 "), with the detecting device of 254nm, take accumulated light as 500mJ/cm 2by ultraviolet ray, irradiate and obtain resist layer.
The resist layer that the printing resist being obtained by embodiment 1～7, comparative example 1～3 is obtained with activity energy-line solidifying type resin composition is to the tack of aluminium foil, alkali-soluble, etch resistance, as shown in table 2 to the check result of the transfer printing of substrate by silicon rubber blanket.
Copper shown in table 2, aluminium tack are square for resist layer is made to 10mm * 10mm, paste adhesive tape (ニ チ バ Application (strain) CT-24 processed), from top tension evaluation, peel off situation.Evaluation criterion is as follows:
1: do not peel off completely.
2: almost do not peel off, but material slightly damages.
3: occur peeling off.
Alkali-soluble shown in table 2 by soaking resist layer and evaluate for 1 minute in 1.0% sodium hydrate aqueous solution.Etch resistance is passed through resist layer at 40%FeCl 3in aqueous solution, soak and evaluate for 1 minute.Evaluation criterion is as follows:
1: resist layer dissolves completely.
2: a part for resist layer is not dissolved.
3: resist layer does not dissolve completely.
Transfer printing shown in table 2 is evaluated by the varnish printed state from silicon rubber blanket to copper substrate.Evaluation criterion is as follows:
1: varnish is transferred to substrate completely.
2: varnish is transferred to substrate substantially.
3: varnish is transferred to substrate, but on silicon rubber blanket still residual half left and right.
4: varnish is left on silicon rubber blanket substantially.
Table 2
? Copper tack Aluminium tack Alkali-soluble Etch resistance Transfer printing
Embodiment 1 2 2 1 3 3
Embodiment 2 2 2 1 3 3
Embodiment 3 1 1 1 3 3
Embodiment 4 1 1 1 3 2
Embodiment 5 1 1 1 3 2
Embodiment 6 1 1 1 3 2
Embodiment 7 1 1 1 3 1
Comparative example 1 2 3 1 2 4
Comparative example 2 1 3 3 3 4
Comparative example 3 3 2 1 3 4
[0121]the corrosion-resisting pattern that embodiment 8(printing forms)
The printing resist obtaining in embodiment 4 is carried out to intaglio printing with activity energy-line solidifying type resin composition by silicon rubber blanket (candy strips of line width 200 μ m, line interval 300 μ m) on copper facing Kapton, with the detecting device of 254nm, take accumulated light as 500mJ/cm 2by ultraviolet ray, irradiate, obtain having the layered product of striped corrosion-resisting pattern.Above-mentioned layered product by 40% ferric chloride aqueous solutions etch copper, is peeled off corrosion-resisting pattern with 2% sodium hydrate aqueous solution, obtains being formed with the Kapton of candy strip of the copper of line width 200 μ m, line interval 300 μ m.
The corrosion-resisting pattern that embodiment 9(printing forms)
Similarly to Example 8, the printing resist obtaining in embodiment 5 is carried out to intaglio printing with activity energy-line solidifying type resin composition by silicon rubber blanket (candy strips of line width 200 μ m, line interval 300 μ m) on copper facing Kapton, with the detecting device of 254nm, take accumulated light as 500mJ/cm 2by ultraviolet ray, irradiate, obtain having the layered product of striped corrosion-resisting pattern.Above-mentioned layered product by 40% ferric chloride aqueous solutions etch copper, is peeled off corrosion-resisting pattern with 2% sodium hydrate aqueous solution, obtains being formed with the Kapton of candy strip of the copper of line width 200 μ m, line interval 300 μ m.
The corrosion-resisting pattern that embodiment 10(printing forms)
Similarly to Example 8, the printing resist obtaining in embodiment 6 is carried out to intaglio printing with activity energy-line solidifying type resin composition by silicon rubber blanket (candy strips of line width 200 μ m, line interval 300 μ m) on copper facing Kapton, with the detecting device of 254nm, take accumulated light as 500mJ/cm 2by ultraviolet ray, irradiate, obtain having the layered product of striped corrosion-resisting pattern.Above-mentioned layered product by 40% ferric chloride aqueous solutions etch copper, is peeled off corrosion-resisting pattern with 2% sodium hydrate aqueous solution, obtains being formed with the Kapton of candy strip of the copper of line width 200 μ m, line interval 300 μ m.
The corrosion-resisting pattern that embodiment 11(printing forms)
Similarly to Example 8, the printing resist obtaining in embodiment 7 is carried out to intaglio printing with activity energy-line solidifying type resin composition by silicon rubber blanket (candy strips of line width 200 μ m, line interval 300 μ m) on copper facing Kapton, with the detecting device of 254nm, take accumulated light as 500mJ/cm 2by ultraviolet ray, irradiate, obtain having the layered product of striped corrosion-resisting pattern.Above-mentioned layered product by 40% ferric chloride aqueous solutions etch copper, is peeled off corrosion-resisting pattern with 2% sodium hydrate aqueous solution, obtains being formed with the Kapton of candy strip of the copper of line width 200 μ m, line interval 300 μ m.
By embodiment 8～11, obtain solidifying rear conductor adhesion, etch-resistance, alkali-soluble excellence, by printing, have the substrate of corrosion-resisting pattern, further by etching, against corrosion peeling off, can on substrate, form circuit pattern.From the above mentioned, printing resist of the present invention with activity energy-line solidifying type resin composition applicable to the resist layer as using in printed circuit board (PCB), lead frame, LCD industry.

Claims (7)

1. a printing resist activity energy-line solidifying type resin composition, is characterized in that, described resin combination contains condensation product (A) and compound (B), and described condensation product (A) is general formula (1) R 1si (OR 2) 3the shown alkoxy silane that contains sulfydryl (a1) hydrolysis is (except R 2the situation that is all hydrogen atom is outer), condensation obtains, in described general formula (1), R 1expression has the alkyl of the carbon number 1～4 of at least one sulfydryl, R 2the alkyl that represents hydrogen atom or carbon number 1～4, described compound (B) has at least one carboxyl and at least one carbon-carbon double bond in molecule.
2. printing resist activity energy-line solidifying type resin composition as claimed in claim 1, wherein, described condensation product (A) contains as metal alkoxide its constituent, that do not have sulfydryl (a2).
3. printing resist activity energy-line solidifying type resin composition as claimed in claim 1 or 2, wherein, as constituent, contains the compound (C) that does not have carboxyl but have at least two carbon-carbon double bonds.
4. the printing resist activity energy-line solidifying type resin composition as described in any one in claim 1～3, wherein, as constituent, contain polymkeric substance (F) weight-average molecular weight 1000～50000, that become by the monomer polymerization that contains ethylenically unsaturated group.
5. a formation method for corrosion-resisting pattern, is characterized in that, the printing resist described in any one in claim 1～4 is printed on substrate with activity energy-line solidifying type resin composition, and described composition is solidified to form.
6. print a resist layer laminate, described printing resist layer laminate obtains by the formation method of the corrosion-resisting pattern described in claim 5.
7. a printed circuit board (PCB), described printed circuit board (PCB) is by after the printing resist layer laminate etching described in claim 6, further peels off printing resist and obtains.
CN201310272330.1A 2012-06-29 2013-07-01 Print resist activity energy-line solidifying type resin composition and its corrosion-resisting pattern Expired - Fee Related CN103713470B (en)

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