TWI358465B - Etching agent compositions for copper-containing m - Google Patents

Description

1358465 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to an etching method for an etchant composition for a copper-containing material, and more particularly to a fine circuit for forming a shapeless material The etching method of the steel material of the pattern (circuit wire) is the same as that of the copper material. ^成成 [Prior Art] A printed circuit board (or film) on which a circuit lead is formed is used to assemble an electronic component or a semiconductor component or the like. Then, with the demand for miniaturization and high functionality of electronic devices in recent years, it has been desired to increase the density and shape of circuit leads for brush boards (or thin plates). ^ Methods for forming high-density circuit wires are known as methods of subtractive or semi-additive (semi_a (jditive) method, wet etching, etc. The micro-circuit wire is ideal for etching a low-residue residue-free film, the side of the circuit wire viewed from above is straight (linear), the cross section of the circuit wire is rectangular, and has a high etching coefficient (de-(four) factor) 'but actually Shapes due to residual film, poor linearity, side etching, (ΙΪ, eUt), and the width of the circuit lead (in the case where T is also referred to as the "top width") are too thin to cause an increase in the etching coefficient. Therefore, it is desirable to suppress such shape defects in wet etching. μ 4 Various improvements have been made in the formation of the above-mentioned circuit path-agent composition. For example, Patent Document f has been proposed by the technique. There is no way to remove the necessary component A gas, which is a method of engraving accelerator and steel containing: trivalent iron ion, hydrochloric acid, copper-containing material, and revealing - Epoxy Ethylene The active 11 group of the compound is added with an epoxy resin, and a compound using phosphoric acid to "cleaning effect or flatness of the steel surface is also disclosed." A steel or steel which is made thinner by the acid and aqueous solution name side and the upper part of the circuit wire. The moxibustion engraving composition 'the acid is selected from the group consisting of copper oxidant and salt acid salt. (4) Water-soluble (4) Eight substances containing a group consisting of poly-alcohol and a copolymer of polyamine and polyolefin ethylene glycol. Here, the oxidizing agent of copper reveals divalent copper ions and two 5 J7 ~ ^Mulberry iron 卞 卞 'The compound used to generate divalent copper ions reveals that gas ®), copper (II) bromide and copper arsenide (II) are used to generate trivalent cerium ion surface compounds to reveal gasification. Iron (III), iron (III) bromide, iron sulphide (III) iron (III), iron (III) nitrate and iron (III) acetate. In addition, poly-binders and diols reveal poly Ethylene glycol, polypropylene glycol, ethylene oxide, cyclo & alkane copolymer, copolymer of polyamine and polyolefin glycol reveals that ethylene-amine and di-extension Ethylenediamine, such as triamine, triamethylenetetramine, tetraethyleneamine, pentaethylenediamine, N-ethylethylenediamine, and polyethylene glycol, polypropylene glycol, cyclohexane, epoxy A copolymer of a propane copolymer. Further, Patent Document 3 discloses an aqueous solution containing an oxidizing metal ion, an acid selected from a mineral acid or an organic acid, and an aqueous solution containing an azole, and the like. The button engraving composition is cut, wherein the azole system has only a nitrogen atom as a hetero atom of the ring (10). The source of the oxidizing metal ion reveals a divalent copper ion or a ferric ion, and the acid system reveals phosphoric acid. Further, in order to carry out the uniform (4) surface shape, a nonionic surfactant such as a bulk polymer such as polyoxyethylene and polyoxyethylene is also disclosed. Japanese Unexamined Patent Application Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. The composition of the (four) agent disclosed in the first and second embodiments cannot perform a uniform patterning of the fine circuit pattern, and as a result, there is a problem that the circuit shape is defective (linearity is poor) or short circuit. Further, since the dispersibility of the age-like money disclosed in Patent Document 3 is low, the solution removal property with respect to the fine circuit pattern is poor, and there is a possibility that the circuit is peeled off due to a poor circuit shape (partial undercut). The problem caused by the generation of slag caused by the phosphoric acid and the salt of copper or iron causes a short circuit. SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for forming a smear-containing composition for a steel-containing material and a method for etching a copper-containing material without forming a shape. In order to solve the above problems, the inventors of the present invention have conducted a detailed review of the results of 1358465, and found that the composition of the composition of the scoring agent is closely related to the formation of the fine circuit, and is composed of a specific group of materials and using the etchant. When the object is etched, the problem can be solved, and the present invention is achieved. In the present invention, the present invention is a composition containing a substrate, and 1 is characterized in that it consists of an aqueous solution containing the following components:

(A) k from at least one cerium oxide component of a mussel copper ion and a divalent iron ion 0.1 to 1.5 mass%; (=) the arithmetic mean molecular weight is 1,500 to 3, and the epoxy dialkyl group = 15 to 50% by mass of epoxy ketone and epoxy acryl-based knife polyether diol 0 001 to 3 mass%; (C) 0.001 to 3 mass% of the polyol represented by the following formula (1); 1] '

(wherein, Ri represents an alkylene group having 2 to 6 carbon atoms, χ1 to χ3 is a functional group represented by the following formula (2), and Χ4 is a hydrogen atom or a ruthenium group represented by the following formula (2), and η represents The number) [Chemical Formula 2] ~^R2〇)?~{R3〇^pH (2) (wherein R and r3 do not extend ethyl or propyl, Ir 2 is stretch 7 for propyl, when When r2 is a propyl group, r3 is an exoethyl group, and the arithmetic mean molecular weight of p-epoxy B is 2GG~1G,000 and mass% · 2 at least one phosphoric acid component from phosphoric acid and phosphate ο.1~5 〇. 05 Two f:% at least one inorganic acid component of hydrogenated hydrogen and sulfuric acid. From the side of the invention, the method of the "steel-containing material" is characterized by V, · a productive yield of 110 Steel 2; 2:: Engraving gap (―(4)-)1~1〇") In the patterning, the above etchant composition is used. Micro-Xingming can provide an etching method capable of forming without shape. An etchant composition and a copper-containing material for a steel-containing material [Embodiment] · Agent % Ϊ Ϊ, a composition of a material for a steel material of the sun and the moon (hereinafter referred to as "money engraving"; The composition of the aqueous solution: (4) It is based on at least one oxidizing agent component of cerium and trivalent iron ions ((8), "), (Β) specific polymer polyglycol (hereinafter referred to as "knife"), (C) specific polyol (below It is called (c) into: ^::^^分分); the function of the machine-acid acid is / (4) the money will be oxidized by the sulphate to carry out the component of the side - the use of divalent copper ions, ferric iron Ion, or two 135*8465

a mixture of valence copper ions and ferric ions. These can usually be used as a supply source of copper or a copper (II) compound and/or an iron (III) compound. Examples of the copper (11) compound include vaporized divalent copper, copper dibromide, copper disulfate, hydrogen, divalent copper and divalent copper acetate, and iron (111) compounds are exemplified by ferric chloride and bromine. Ferric trioxide, trivalent iron iodide, ferric iron sulfate, ferric trivalent iron, and ferric acetate. These may be used singly or in combination of two or more. In the above, the use of one or the like is preferably copper, vaporized divalent copper, sulfuric acid from the viewpoint of stability of the composition of the cost m and (10) controllability of the speed. Second, and gasification of ferric iron, more preferably gasified iron. One side of the side (S) of the component (A) contains a bivalent shop and /, and the ferric ion is converted into aw f%, which is (%)_%. When the content of the component (A) is less than (the amount of u f is small, the secret is long, the filament is deteriorated, or the productivity is lowered.) The effect of the Nl_Cr seed phase (4) due to the _ surface

The residual film recording of f will be Wei H surface. When the content of (4) component is more than ^%, it is impossible to control _speed ^ engraving coefficient into 'right while (four) ferric ion and divalent steel controllable etchant composition When the redox of the substance is used, the copper concentration and the like can be automatically controlled, and the etchant % 驮 / □ degree can be automatically controlled, and in this case, the content of the valence neutron is changed by the _ sub. The mass% is preferably from 1 to 10% by mass. Prepare two 'for 〇.5~10 0.5% by mass, if there is less, then there will be no; = 9 Ί Ί another aspect 'When the content of divalent copper ions is 10 mass 夕 寸 ', there will be a paste composition The situation of slag. , ° penetration (through the silk fabric to improve the circuit pattern, and the propylene-based polymer poly-g diol. This high ^ is not particularly limited 'exemplified by, for example, ethylene glycol, propylene glycol and butyl:: * Ethylene oxide and alkylene oxide addenda of olefin ethyl alcohol are diol, polypropylene glycol and polybutylene glycol, etc., and ethylene oxide additions. Or use more than two kinds of combinations. The arithmetic average molecular weight of the molecular polyether diol is 1,500~3, when the arithmetic mean molecular weight is less than 1, the hour, the linearity of the shape = the shape will be reduced, and Obtaining the desired circuit pattern. On the one hand, when the arithmetic mean molecular weight is larger than 3,000, the etching will be slower or the etching efficiency will be lowered. 7-speed, the epoxide group in the polymer polyether diol When the content of the oxirane group is 15% by mass or less, the compatibility of the etchant composition may be lowered, and "&·^" may occur. When the content of the oxirane group is more than 5% by mass, the etching coefficient cannot be increased, and the period cannot be obtained. The circuit of the epoxy group and the epoxy propylene group may be distributed in a block shape or a shape. From the viewpoint of reducing the foaming property of the etchant composition, the '^ pieces are distributed in blocks. &"^ Among the polymer polyether diols, the compound represented by the formula (3) below can be used to obtain a better circuit shape, so that it is particularly preferable [Chemical Formula 3] In the above formula (3), 'R and R, a propyl group, when R is an ethyl group, R is a propyl group, when R is a propyl group, R is an ethyl group, and fb and C are such that the arithmetic mean molecular weight is 1,5 〇〇 3 And the content of the component (B) in the etchant composition is 〇〇〇1 to 3, and the mass% is preferably 0.05 to 2% by mass. When the content of the component (B) is less than the amount of _ = %, the sufficient yield can not be obtained. If the content of the component of the other component is more than 3 mass%, the viscosity of the etchant composition becomes high and the solution is high. The cooling performance is reduced by the linearity of the W-war. The lowering of the 3rd day makes the retention of the straight shape of the circuit shape to give a good circuit shape. The composition of the enclosing agent (C) is relative to The material does not have the wrong boring tool, and because of the affinity, it can also be added as the appropriate component of the (C) component, etc., and can form an effect by suppressing side etching, suppressing undercutting, and reducing And the effect of linearity, degree, etc. (4) Yan Cheng. (4) The upper part of the electric wire is wide to achieve the above effect, and the component (C) is the undercut 1358465 alcohol. One type of the polyol may be used singly or in combination of two or more. X1—M—(^-R1—: NV-X3 (1) L v I′; n In the above formula (1), R1 represents an alkylene group having a carbon number of 2 to 6, and X1 to X3 are lower. The functional group represented by the formula (2), X4 is a hydrogen atom or a functional group represented by the following formula (2), and η represents a number of 1 to 5. / 9 [Chemical Formula 5]

In the above formula (2), R2 and R3 represent an ethyl or propyl group, R3 is a propyl group when R2 is an ethyl group, and R3 is an ethyl group when R2 is a propyl group, and ρ and q are The polyol has an arithmetic mean molecular weight of 200 to 10,000 and an oxirane group content of 50% by mass or less. Examples of the alkylene group having 2 to 6 carbon atoms represented by R1 include, for example, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, etc., and the functional groups may be bonded at any position, or Branch status. The propyl group represented by R2 or R3 is -CYh-CY^KY1 and Y2 is hydrogen, the other is fluorenyl) or -CH2-CH2-CH2-. In the polyhydric alcohol represented by the above formula (1), the polyol having the functional group represented by the formula (2) wherein χ1 to χ4 is represented by the formula (2) has an excellent (four) shape defect prevention. The effect is better. Or the average molecular weight of the average number is _~1G, GG0, preferably $2:04. The arithmetic average molecular weight of the polyol is less than 2〇〇. On the other hand, when the multivariate average molecular weight is larger than 1G and _ is large, a sufficient etching rate cannot be obtained.

Further, the content of the oxirane group in the above polyol is 5 〇 mass / 〇 or less', preferably 15 to 5% by mass. When the content of the epoxy group is more than 50% by mass, the etching coefficient is lowered to obtain a desired circuit pattern. Further, when the content of the oxirane group is less than 15% by mass, there is a case where a sufficient use effect cannot be obtained.

The content of the component (C) in the insect-like composition is 〇 〜 1 to 3 mass%, and the car father is 0.05 to 2 mass%. When the content of the component (C) is less than 0.001% by mass, a sufficient use effect cannot be obtained. On the other hand, when the content of the component (C) is more than 3% by mass, the circuit shape is deteriorated due to penetration into the interface of the pupil y. / (D) component softens the photoresist by reacting with the resin of the photoresist component or the photoreceptor of the photoreceptor to inhibit the penetration of the above polyol into the interface between the copper and the photoresist. . Further, the component (D) also has an effect of promoting etching on the Ni-Cr seed layer on the inner surface of the copper. The component (D) is at least one selected from the group consisting of phosphoric acid and phosphate. Examples of the phosphate salt include sodium sulphate, potassium sulphate, acid sulphate, and squamous acid. Further, the phosphate may be an acidic salt (monohydrogen salt, dihydrogen salt) or a neutral salt of 13 1358465:. Phosphorus (4) is preferred if it has a shape in the county. The content of the component (9) in the composition of the composition is 〇1 to 5% by mass. When the content of the volume ^ component is less than the mass% of G1, sufficient effect cannot be obtained. On the other hand, the content of the component (9) is 5 mass. If there is a long time, the etchant composition between the wires and the wires will be retained, and the = method will be used to perform the butterfly of the uniform sentence, and the shape of the wire will be poor due to the re-precipitation of the copper. It is called (E) component #, has the function of removing the copper surface of the buckwheat surface after removing (4), or the function of stabilizing the oxidant, and improving the relative = steel (4) Wei of the flat domain, and it is a kind of The mash is selected from at least one of hydrogenated hydrogen and bowl acid. The content of the component (6) in the a-etching composition is 〇 0^ 〇 mass%. When the content of the second (8) component is less than the amount of (10) 5 f, the charge effect cannot be obtained. On the other hand, when the content of the (E) component is more than 1 〇 mass ^, the job becomes excessive and becomes uncontrollable. As a result, the shape of the circuit wire is poor. The etchant composition of the present invention can be added to any known component of the use in addition to the essential components (A) to (E) described above, without impairing the effects of the present invention. Examples of the optional component include a diol-based compound, a surfactant other than the components (B) and (C), and an inorganic acid, an organic acid, an amino acid compound, an azole compound, or a pyrimidine compound other than the component (E). Thiourea compounds, amine-like human 14-anthracene compounds 'organic integrator compounds, polyacrylonitrile female dogs, _ I, hydrogen peroxide, persulfate, inorganic salts, valence copper ions. When these optional components are used, the concentration is generally "in the range of 〇 001 % by mass, and the % by mass. - diol _ compounds are exemplified by, for example, ethylene glycol, ethylene glycol monoethyl, screaming, ethylene glycol monobutyl. (10), diethylenediyl-, diethylene glycol monoethyl shrine, diethylene glycol monobutyl (tetra), triethylene glycol monodecyl

Ether: diethyl alcohol monoethyl ether, triethylene glycol monobutyl bond, diglycol monoterpene test, propylene glycol, early glycol ethyl ether, propylene glycol monobutyl ether, dipropylene glycol monoterpene, dipropylene glycol Low molecular weight compound such as monoethyl hydrazine, dipropylene glycol monobutyl styrene, tripropylene glycol f methyl bond, tripropylene glycol monoethyl ether and 3-methyl-3-decyloxy-3-decyloxy tau A high molecular weight glycol ether compound such as polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether or polyethylene glycol monobutyl ether. The materials may be used alone or in combination of two or more.

The interface/tongue agent is exemplified by, for example, an anionic surfactant, a nonionic surfactant other than the components (B) and (C), a cationic surfactant, and an amphoteric surfactant. έ ^ anionic surfactants are exemplified by, for example, higher fatty acid salts, high and thiol ester salts, sulfurized olefin salts, higher alkyl sulfonates, α-enoates, sulfated fatty acid salts, sulfonated fatty acid salts, phosphoric acid Ester salt, sulfate salt of fatty acid ester, petroleum ester ester of back oil ester, sulfonium salt of fatty acid ester, methyl ester of sulfo fatty acid, polyoxyalkylene ether sulfate, salt, poly Oxyalkylene alkyl phenyl ether sulfate salt, polyoxyalkylene alkyl ether salt, sulfonated peptide, fatty acid alkyl decylamine or its cyclodecane addendum 15 sulfate salt, sulfosuccinic acid Esters, alkyl sulfonates, alkyl naphthenates, alkyl oxaidazolium sulfonates, polyoxyalkylene sulfosuccinates, salts of decyl fluorenyl ornithyl, N-fluorenyl A face acid or a salt thereof, a decyloxyethanesulfonate, an alkoxyethanesulfonate, a decyl-mercaptoic acid or a salt thereof, or a fluorenyl-fluorenyl-indole-ethyl tartaric acid or a salt thereof , Ν - 03⁄4 yl-mercapto-glycine or a salt thereof, decyl lactate, hydrazine-bristinate, and alkyl or alkenylamino carboxy-f-sulfate. Examples of the nonionic surfactant are, for example, polyoxyalkylene-based alkyl ether, polyoxyalkylene alkylene ether, polyoxyethylene polyoxypropylene alkyl ether (additional form of ethylene oxide and propylene oxide may be disordered) Any of the blocks, polyethylene glycol propylene oxide addenda, polypropylene glycol oxirane addenda, heterogeneous or bulky additions of ethylene oxide and propylene oxide with alkyl diamines, Glycerol fatty acid ester or its ethylene oxide addenda, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, alkyl polyglucoside, fatty acid monoethanolamine or its epoxy ethoxide addendum, fatty acid thiol Ethanolamine or its epoxy Ethylene add-on, fatty acid diethanolamine or its ethylene oxide addenda, sucrose fatty acid ester, alkyl (poly) glyceryl ether, polyglycerin fatty acid ester, polyethylene glycol fatty acid ester, fatty acid Methyl ester ethoxylate and N-long chain epoxy alkyl decylamine. The cationic surfactant is exemplified by, for example, an alkyl (alkenyl) tridecyl salt, a diheptyl (alkenyl) dimethyl ammonium salt, a pyrenyl (baked) quaternary ammonium salt, an ether group, and an ester group. Or an amine monoalkyl or dialkyl (alkenyl) quaternary ammonium salt, an alkyl (alkenyl) pyridinium salt, an alkyl (alkenyl) dimercaptobenzyl ammonium salt, an alkyl (alkenyl) Quinoline salt, dialkyl (alkenyl) morpholine salt, polyoxyethylene 1358465. * t · ^ graft (alkenyl) amine, alkyl (base) amine salt, polyamine fatty acid derivative, pentanol fatty acid Derivatives, gasified benzodiazepine ammonium and benzyl ammonium chloride, and the like. The amphoteric surfactants are exemplified by, for example, a carboxybetaine, a sultain beet test, an acid-based beet test, an acid amine amino acid, and an amido beet test interfacial activator. The above surfactants may be used singly or in combination of two or more. Examples of the inorganic acid include, for example, wall acid, poly-pot acid, and the like. These may be used alone or in combination of two or more. Examples of the organic acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, cholic acid, acrylic acid, crotonic acid 'isocrotonic acid, acid repair, malonic acid, succinic acid, glutaric acid, adipic acid, and pimelic acid. , maleic acid, fumaric acid, oxalic acid, malic acid, tartaric acid, citric acid, glycolic acid, lactic acid, sulfamic acid, nicotinic acid, ascorbic acid, hydroxypivalic acid, fructose, and chlorinated An acid sulfonic acid such as propionic acid; an acid sulfonic acid such as a phthalic acid, an ethyl sulphate, a sulphuric acid, a propane sulfonic acid, a benzene sulfonic acid or an benzene sulfonic acid. These can be used alone or in combination of two or more. Examples of the amino acid compound are, for example, glycine, alanine, valine, leucine, serine, albendine, tryptophan, glutamic acid, aspartic acid, lysine, glutamic acid. And an amino acid such as histidine or the like, and an alkali metal salt or an ammonium salt. It can be used in combination or in combination of two or more. Examples of the compound of the sitting type are, for example, alkyl imidazoles such as olfactory, 2-mercapto- σ-methane, 2-indenyl-4-methylimidazole, 2-phenylimidazole, 2-methylbenzimidazole, and the like; a benzo- σ sitting group of imidazole, 2-mercaptobenzimidazole, 2-11-phenylbenzopyrene, 2-phenylbenzopyrene, 2-thiol benzopyrene, etc.; , 2,3-two-degree sitting, 1,2,4-trimethyl, 5-phenyl-1,2,4-trimethyl, 5-amino-124-triazole, 1,2,3-benzo Triazole, 1-aminobenzotriazole, 4-aminobenzotriazole, 1-diaminomercaptobenzotriazole, 1-methyl-benzotriazole, methyl benzotriazole , 1-hydroxybenzotriazole, 5-methyl-1Η-stuppyrazole, 5-gas benzotriene, etc., three-degree sitting; 1Η-tetrasodium, 5-amino-1Η-tetrazine, 5methyl-1Η-tetrazole, 5-phenyl-1Η-tetrazole, 5-thiol-1Η-tetrasodium, 1-phenyl-5-thiol-1Η-tetrazole, 1·cyclohexyl- 5-thiol-1-pyrene-tetrazine, 5,5'-bis-1H-tetrazole, etc. tetrazolium; stupid thiazole, 2-thiol benzoxazole, 2-phenylthiazole, 2 - Aminobenzothiazole, 2-amino-6-benzoene sold out, 2-amino-6-methoxybenzoindole, 2-aminobenzoquinone. Wait for the thiazoles. These may be used alone or in combination of two or more. Examples of the pyrimidine compound include, for example, a diaminopyrimidine, a triamine-based pyrimidine, a tetraamine-based fine, and a money. The materials may be used alone or in combination of two or more. Examples of the thiourea compound include thiourea, ethyl thiourea, and thioglycol, and sulfur. It can be used in combination or in combination of two or more. Dibutylamine, triethylamine, triethanolamine, monoethanol isopropanolamine, and amine compounds are exemplified by, for example, diamylamine, amine, dipentylamine, monoethanolamine, diethanolamine isopropanolamine, and isopropylidene. Alcoholamine, triisopropanolamine, diethanol isopropanolamine are used. And such d, etc.: alone === mercapto-2-pyrrolidone

Examples of the pyrolysis compound include, for example, N N-ethylidene, quinolone, N-propylpyrrolidone, N-butyl-2-pyrrolidone, and various classes, Ν'"Hexyl-2 -° is slightly different, and Ν-heptyl-2-° is used in comparison to each ketone. When you are at the heart of the heart ^ These can be used alone or in combination of more than 2 types. B: The compound of the gum machine is exemplified by Shishikou E 2 145 acetic acid, di-extension - amine five cool

Acid, Wushen, Diethylenetetraamine hexaacetate, Tetraethylene, Ethylamine, Ammonium, Gua, hexamine, hexamine, triglycine, and the alkali metal salts and arms, can be used alone or in combination. Use above. The amine-producing compounds are exemplified by, for example, polyacrylamide and b. These may be used singly or in combination of two or more kinds, and for example, ammonium persulfate, sodium persulfate, and persulfuric acid may be used alone or in combination of two or more. No, salt, such as sodium carbonate, (10) _, silk recorded, sodium dihydrogen bromide, potassium bicarbonate, ammonium carbonate, sodium carbonate, potassium carbonate,

Friends = ammonium, sodium sulfate, potassium sulfate, sodium nitrate, potassium nitrate, ammonium nitrate, ammonium citrate, sodium chlorate and potassium chlorate. These may be used alone or in combination of two or more. Examples of the compound which supplies monovalent copper ions include copper chloride (1), brominated steel (iron), copper (I) sulfate, and copper hydroxide (1). Further, examples of the compound which supplies divalent iron ions include iron chloride (11), iron bromide (11), iron iodide (11), iron (II) sulfate, iron (II) nitrate, and iron (II) acetate. Wait. These may be used alone or in combination of two or more. Among the above-mentioned arbitrary components, the component which is particularly suitable for addition is ferrous iron 19 1358465 ion. Regarding the etching ability of the etchant composition, automatic control is performed at the original potential or specific gravity, acid concentration, copper concentration, etc. = ferrous iron ion, the bismuth iron ion in the composition contains ferrous ions To convert to ~5 %. When the content of divalent iron ions is less than the amount of 〇"f" = sufficient effect is obtained. The other side, a, 'j... method h. On the other hand, when the content of divalent iron ions is more than 5 K, the etching ability and the like are lowered. Mixing and mixing the device with the device is not particularly limited to the use of a well-known mixture of the preferred composition of the phase engraving agent to obtain a sufficient surface engraving than the L10, it will be impossible Face, when the specific gravity is lower than the 13Π coefficient. The other situation. .3 When the size is large, there will be a pattern of lowering the etching coefficient, but from the shape; the material can be formed in the form of copper, and the micro-rules are particularly suitable for the view of the silk and the side speed. Chemical. Moreover, 〇em, etching gap 1~10, copper containing 25em or less, worm, can also be applied to a thickness greater than 1〇wm • but the patterning gap of the steel-containing material is greater than 10 β m but less than 40 μm The etching of the copper-containing material can be carried out by using a known etchant composition, for example, a method of using silver steel. The copper alloy of the material to be etched, the copper alloy and the steel of the Mingjin alloy, and the copper 20 Further, the etching method is not particularly limited, and a dipping method, a spray method, or the like can be used, and the button etching condition can be appropriately adjusted by using an etchant composition or an etching method to be used. It is also possible to use a batch type, a flow type, an automatic control method using an oxidation-reduction potential or a specific gravity of an etchant, and an acid concentration, and the like. When the etchant composition of the present invention is used, the treatment temperature is preferably 30 to 5 ° C, the treatment pressure is 0 03 to 〇 2 MPa, and the treatment time is 20 to 300 seconds. Further, the etchant composition of the present invention is utilized. In the etching method performed, in order to return The solution is degraded by repeated etching, and the replenishing liquid is also added. In particular, in the above-mentioned automatic control type etching method, the replenishing liquid is preliminarily installed in the etching device, and when the solution is deteriorated, it is added to the surname composition. The replenishing liquid is, for example, the concentration of the component (A), the component (E), and the water component (A) and the component (E) is about 2 times the etchant composition. Further, in the replenishing solution, The component (B) to (D) or the optional component of the etchant composition of the present invention may be added as needed. Since the etchant composition of the present invention can form a fine pattern without a shape defect, in addition to the printed circuit board, It can be applied to a substrate for packaging requiring fine pitch, and a method for reducing the use of C〇F and TAB. [Examples] Hereinafter, the present invention will be described in detail by way of examples and comparative examples, but the present invention is not limited to scales. Comparative Example The polymer polyether 21 21358465 alcohol and polyol used in the following examples and comparative examples are shown in Tables 1 and 2. [Table 1] Polymer polyether diol type arithmetic average Molecular weight epoxy ethyl ketone (Mass%) a-1 polypropylene glycol ethylene oxide addenda 2,200 40 a-2 // 2,500 20 a-3 // 4,200 40 a-4 20 Polyethylene glycol 100

[Table 2] Polyol type arithmetic mean molecular weight oxiranyl group content (% by mass) b-1 Ethyl diamine propylene oxide and ethylene oxide bulk addition formula (1), R> Ethyl, n=l, R2=extended propyl, R3=extended ethyl, XV hydrogen 280 40 b-2 // 580 40 b-3 // 1,3〇〇40 b-4 ethylenediamine Propylene oxide addition formula (1), R1 = extended ethyl group, n = l, q = 0, R2 = extended propyl, X4 hydrazine 300 0 b-5 ethylenediamine propylene oxide group and epoxy a bulk addition of ethane in formula (1), an ethyl group, n = 1, R2 = a propyl group, R3 = an ethyl group, XV hydrogen 3,500 20 b-6 // 5,000 40 (Example 1) The polymer polyether diols and polyols shown in Tables 1 and 2, gas 22 1358465. Three irons (4.9 mass%), vaporized divalent copper (6.6 mass%), phosphoric acid, and hydrogen chloride are shown in Table 3. The composition was mixed to obtain etchant compositions No. 1 to 11. In Table 3, the content of ferric chloride is expressed in terms of trivalent iron ions, and the content of divalent copper chloride is expressed in terms of divalent copper ions. Also, the residual portion of the content is water. (Comparative Example 1) In the same manner as in Example 1, the components were mixed in the composition of Table 3 to obtain the button composition Nos. 12 to 19. [Table 3] 1 Etching composition (% by mass) Agent group Ferric iron divalent copper south molecular poly_ Polyol phosphoric acid hydrogen chloride ion ionic diol No. 1 1.7 3.1 a-1 (0.4) bl (1.2) 0.9 0.2 2 1.7 3.1 a-1(0.4) b-2(1.2) 0.9 0.2 3 1.7 ” 3.1 a-1(0.3) b-2(0.6) 0.9 0.2 4 1.7 ” 3.1 a-1(0.8) b-2(1.2 ) 0.9 0.2 5 1.7 3.1 a-1(0.4) b-3(1.2) 0.9 0.2 6 "1.7 3.1 a-1(0.3) b-3(0.6) 0.9 0.2 7 1.7 3.1 a-1(0.8) b-3 (1.2) 0.9 0.2 8 1.7 3.1 al(0.4) b-4(1.2) 0.9 0.2 9 1.7 3.1 al(0.4) b-5(1.2) Γθ.9 0.2 10 1.7 3.1 a-1(0.4) b-6( 1.2) 0.9 0.2 11 1.7 3.1 —a-2(0.4) b-2(1.2) 0.9 0.2 —12 1.7 3.1 — 0.9 0.2 13 1.7 3.1 al(0.4) - 0.9 0.2 14 1.7 3.1 - bl(1.2) 0.9 0.2 — 15 1.7 3.1 - b-2(1.2) 0.9 0.2 23 1358465 16 1.7 3.1 • b-3(1.2) 0.9 .0.2 17 1.7 3.1 - b-4(1.2) 0.9 0.2 18 1.7 3.1 a-3(0.4) b- 2(1.2) 0.9 0.2 19 1.7 3.1 a-4(0.4) b-2(1.2) 0.9 0.2 (Example 2) Coating light on a C〇F tape substrate (158 mm×l〇〇mm) having a steel thickness of 8 #m Resistance (PMER-P; manufactured by 臬京应化股份有限公司) and dried, using exposure The exposure (UFX-2458B; manufactured by USHIO Motor Co., Ltd.) was used for exposure, and development and rinsing were performed to form a photoresist pattern having a pitch of 20 am and a space of 6 m. Forming a c〇F tape base material having a photoresist pattern, using the above etchant composition at a treatment temperature of 45 Torr and a treatment pressure of 0.05 MPa, by the number of seconds at which a proper amount of Just etching can be achieved Spraying during (604 00 seconds) to carry out a thirst narration. _, the photoresist pattern (, acetone) was used to remove the photoresist pattern ', ', and copper was evaluated for the shape of the obtained copper circuit pattern. (1) Linearity Use KEYENCE Co., Ltd. to observe the shape of the copper power switch (4), and ^ line width U see rc 1 + ^ The offset of the deep view is less than 1/zm is 5"'1; ^ is not up to h7 heart Those who have not reached 2.4/zm are "3", 2.4& go up to "advance to the 5th stage of evaluation." (2) Upper wire width (top width) 24 The measurement was performed using a laser microscope image. (3) The quotation coefficient is calculated by the following formula. Where τ is the top width (μιη), (4) residual film

To the KEYENCE, the laser microscopic system of the 51st system is used to observe the residual of the side part. The remnant of the non-existing part is the official one. The remaining part of the surname is “!”, and the 5-stage 砰(5) scribe speed is performed on the tape substrate for 3G seconds of wet 彳 processing. The quality of the tape substrate before and after the J treatment (the copper to be eluted) was obtained, and was calculated by the following formula. Also, the unit is private m/min.

Also, the unit is Um. Etching speed = (weight of the web substrate before etching (▼ substrate weight (g) after phantom-etching) / (processing area (cm2) x S m3 〇〇 60/30 The above evaluation results are shown in Table 4. Comparative Example 2) _ In addition to the use of the money engraving composition N. - i 9 was carried out in the same manner as in Example 2, and the steel circuit pattern was obtained. The shape of the obtained copper circuit ® case was entered. The above evaluations (1) to (4). The evaluation results are shown in Table 4. 25 1358465 [Table 4] Button engraving composition go. 1

In 9

1.9 1.9 As shown in the results of Table 4, any one of the four (4) engraving compositions can obtain a good circuit shape. On the other hand, the etchant composition No. 12 which does not contain the polymer polyether diol and the polyol, the etchant composition N〇13 which does not contain the polyol, and the etchant composition which does not contain the molecular polyether diol N 〇 14 π π, none of the etchant compositions N 〇 19 containing no specific polymer polyether diol failed to obtain a good circuit shape. Further, since the amount of the etchant composition 26 is reduced, the linearity of the molecular weight is lowered and the residual film is increased. The ratio of the composition of the composition N0.2 to the composition of the No. 11 is better, and the more the content of the oxirane group, the better the top width or the _ coefficient can be obtained. According to the invention, according to the present invention, it is possible to provide a composition of a copper-containing material secret agent capable of non-products and the like [Simplified description of the drawing] None. [Main component symbol description] Innocent, 27

Claims (1)

: After the application without a line 4 Li Fantu Chinese text - Annex (3) Amended Claims in Chinese-Encl.fnn (Republic of China 100 August! Submitted on the next day) (Submitted on Aug. 10, 2011) VII, the scope of application for patents An etchant composition for a copper-containing material, which is characterized in that it is composed of an aqueous solution containing the following components: (A) at least one oxidizing agent component selected from the group consisting of divalent copper ions and ferric ions 0.1 to 15 (3) A polymer polyether diol having an oxyethylene group and an oxypropylene group having an arithmetic mean molecular weight of 1,500 to 3,000, 0,001 to 3% by mass, wherein the ring of the polymer polyether diol The content of the oxyethylene group is 15 to 50% by mass; (C) 0.001 to 3% by mass of the polyol represented by the formula (1); [Chemical Formula 1] (wherein R1 represents an alkylene group having 2 to 6 carbon atoms, X1 to X3 are a functional group represented by the following formula (2), X4 is a hydrogen atom or a functional group represented by the following formula (2), and η represents 1 ~5 number) [Chemical Formula 2] Η (2) (wherein R2 and R3 represent an extended ethyl group or a propyl group, when R2 is an extended ethyl group, R3 is a stretching propyl group, and when R2 is a stretching propyl group, the R3 is 28 1358465^ Replacing the page with ethyl, P and q are the arithmetic average molecular weight of the polyol. It is 200 to 1 〇, 0 〇〇 and the content of the oxirane group in the polyol is 50% by mass or less); The at least one phosphoric acid component selected from the group consisting of phosphoric acid and phosphate is 0.1 to 5 mass. /. And (E) at least one inorganic acid component selected from the group consisting of hydrogenated hydrogen and sulfuric acid. 0.05 to 10 mass 〇/〇. 2. The etchant composition for a copper-containing material according to the first aspect of the patent application, wherein the (B) polymer diol is the following formula (3): [Chemical Formula 3] H〇+〇访,〇»p Wherein R and R' represent an exoethyl or a propyl group; when an ethyl group is extended, R' is a propyl group, and when #R is a propyl group, r is a stretching group, and a, b and c represent The arithmetic mean molecular weight is such that the material (four) of the polymer second-in-class towel contains a number of '% by mass.川3. The composition of claim 1 or 2, wherein the above-mentioned (C) plurality of etchants for steel-containing materials are 200-1,500. 4. 5. The arithmetic mean molecular weight of the alcohol is as in the first or second item of the patent application scope.夕人# ^ Composition, in which the engraving agent is as claimed in the scope of the patent. The surface material is composed of two doses. 29 1358465 Factory, * κ ι° And R2 in the above formula (2) is a stretching propyl group. 6. A method for etching a copper-containing material, characterized in that in the patterning of a copper-containing material having a thickness of 1 to 10/zm and a silver-engraved gap of 1 to 10 #m, the first to fifth items of the patent application range are used. An etchant composition as described. 30