TW200406433A - Water-dilutable/dispersible radiation curable compositions - Google Patents

Abstract

The invention provides in one form a water-dilutable and/or dispersible radiation curable composition that is developable in aqueous alkaline solution and which comprises the reaction product of a (meth)acrylated polymeric binder containing acid group with a primary, or more preferably, a secondary amine containing compound of Formula I, where R1 and R2 independently represent H or optionally substituted hydrocarbo, such as alkyl, aryl, cycloalkyl, arylalkyl, hydroxy alkyl, hydroxy aryl, hydroxy cycloalkyl and hydroxy cycloaryl. R1 and R2 may also contain, within them, the organo linkages such as (poly)amido, (poly)ester, (poly)urethane, (poly)urea, (poly)ether, and (poly)carbonate. A further requirement is that R1 and R2 must not both represent H at the same time.

Description

i i200406433

(Ii) Description of the invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a radiation-hardening composition that can be diluted (and / or dispersed) in water and can be used as a liquid photoresist composition to manufacture articles such as printed circuit boards. The radiation-curable composition is mobile without being subjected to a liquid alkaline water-hardening treatment. In printed circuit boards, the image of a circuit element is defined by the area of the hardened composition that remains after removing the alkaline solution from the unhardened area. Prior art_ A typical printed circuit board is coated with a radiation-curable coating to The substrate is prepared on the copper surface. A negative film of a desired circuit image is then applied to a hardenable coating film, and the coating film is exposed to an ultraviolet light source. After the coating is hardened, the printed circuit board is rinsed in an alkaline solution to remove areas of the coating that are not exposed to the UV light source. The plate is then etched to remove uncoated areas ' Other imaging techniques can also be used. In addition to forming printed circuit boards, these techniques can also be used to form other surfaces such as printed circuit boards. The radiation-hardening composition in this field is called a photoresist composition. Xin has taught in U.S. Patent No. 3,95 3,309 that a photoimaging composition can be used as a photoresist in forming a printed circuit board. The photoimageable composition is radiation-hardenable because it contains a photopolymerizable material, and can be developed in an alkaline solution by an acidic functional binder. The presence of an acid group such as a carboxylic acid is required in the photopolymerizable material so that the photoresist composition is developed in an alkaline solution. If desired, the photocurable composition can be removed by soaking the acid group in a second bath that is more alkaline than the imaging bath solution. However, if the above is desired then this requirement is one to one 6-

X X200406433 has the disadvantage that it still produces a hardening coating film, but the subsequent treatment solution is experimental. The photopolymerizable part is easily degraded in higher alkaline solutions (such as ammonia-based etching solution or metal plating solution). In this case, such a photoresist will be easily peeled and removed. U.S. Patent No. 4,9 4 3,5 1 6 teaches that a photosensitive thermosetting composition system includes a photosensitive polymer based on an acid-functional epoxy (meth) propionic acid ester and a finely powdered epoxy compound. , Can be used for liquid light imaging welding mask. The composition described in this patent is superior in chemical resistance and heat resistance but lacks fast-drying properties. Before contact copying, it is necessary to dry for a long time to obtain a non-sticky surface and image the circuit pattern on the photoresist coating film. It is often unsatisfactory to use an oven to speed up the tack-free time. Prolonged exposure in the oven makes the photoresist susceptible to dust particles, and then micro-defects can occur during subsequent photoimaging steps. French Patent No. 2,253,7 72 teaches a photopolymerizable composition for lithographic imaging plates or photoresists, which contains an addition copolymer of maleic anhydride and an ethylene or styrene monomer. This copolymer is then esterified with an ethylenically unsaturated alcohol or a partially esterified polyol with itself and an unsaturated fatty acid. Unsaturated alcohols or polyols may contain alkoxy groups. The presence of water or alkali-sensitive groups such as alkoxy (ethoxy or methoxy) can improve the basic visibility of the unpolymerized areas of the photoresist, but it will also decrease in subsequent acidic or alkaline etching solutions. Hardening photoresist is resistant to acid and alkali. In addition, the incomplete ring-opening anhydride (reaction 60 to 80%) will also reduce the basic development of photoresist. U.S. Patent No. 5,296,334 teaches the use of a polymeric composition as a solder mask. The composition includes a binder polymer made from-7-

V V200406433 Esterification product of styrene maleic anhydride copolymer containing less than 15% free anhydride, and at least 50% useful anhydride group esterified with hydroxyalkyl (meth) acrylate, and at least 0.1% useful anhydride The group is esterified with a monohydric alcohol. It also contains polyfunctional (meth) acrylate monomers and polyfunctional epoxides. The use of high concentrations of (meth) acrylate monomers (such as TMPTA, TPGDA or DPHA) will increase the UV reactivity of the photoresist. However, the thickness of the photoresist composition is usually increased. U.S. Patent No. 4,370,403 teaches a polymeric composition based on (a) the reaction product of a styrene maleic anhydride copolymer with 2-hydroxyethyl acrylate, and (b) other ethylenically unsaturated compounds. And (c) a photoinitiator. φ U.S. Patent No. 4,7 2 2,9 4 7 describes a radiation curable polymer based on a styrene / maleic anhydride copolymer with a hydroxyalkyl acrylate and another alcohol (such as an aryl alkyl Monohydric alcohol). The presence of acrylate-unsaturated alcohols reduces the UV reactivity of the coating film and the UV cross-linking of the product. In addition, the chemical resistance of photoresist will be reduced in the subsequent alkaline or acid treatment. US Patent No. 4,72 3,857 describes that the photoimageable composition contains a styrene / maleic anhydride copolymer with methanol and isopropyl The alcohol is partially esterified. As a result, the polymer φ itself is acidic, but does not contain acrylate unsaturation, which makes it photopolymerize under ultraviolet radiation. It is expected that the photoresist composition has a short non-tacky time and can be dissolved in an alkaline solution in a relatively short time. All the above examples are based on solvents, and the use of such materials is commonly used in today's industry. Due to the limitation of the light source, the volatile organic content (VOC) is released to the environment. However, it is necessary to reduce the use of solvents or completely exclude the liquid photoresist composition. Mon 8-200406433

WO 98/457755 (Advanced Coatings International) describes aqueous dispersions of aliphatic urethane acrylate oligomers for use in the manufacture of photoresists. The composition needs to be added based on, for example, ammonia, morpholine and. Potassium hydroxide makes the polymer binder water-soluble by neutralizing acid groups.

U.S. Patent Nos. 5,69 1,006 and 5,501,942 and European Patent No. 493317 (Ciba) teach commercially available solid acids that are neutralized with ammonia or amines before dispersing in water Acrylic copolymers such as Carboset 5 2 5, XL37 and 531. Because of the high Tg binder, it is necessary to dissolve the resin before neutralization. H U.S. Patent No. 5,741,621 and European Patent No. 747769 / A2 (Du Pont) describe a method for preparing an aqueous photoimageable liquid emulsion using a photoimageable film. A polymer of methyl methacrylate / ethyl acrylate / styrene / methacrylic acid prepared by an emulsification polymerization reaction based on the use of a perphosphoric acid heuristic is more stable in polymer emulsion reaction. It is generally believed that the discharged sulfate is conducted to the surface of the emulsified particles to stabilize the product emulsion by increasing the potential of the emulsified particles. U.S. Patent No. 5,045,43 5 describes an aqueous medium and an aqueous development coating H composition. The examples describe the use of commercially available latex copolymer compositions, such as using Neocryl CL-340, Acrysol 1-2074, and Neocry 1 BT_175 as basic polymers, and neutralizing the reaction with ammonia. After drying at 70 ° C for 10 minutes, a non-sticky film was obtained. U.S. Patent No. 5,364,737 describes the use of an associative thickener based on a polyether polyurethane (such as Henkel's DSX-15 14) to stabilize the emulsion, which allows for less amine or ammonia neutralization reactions, And can increase the photoresistance of -9-200406433, · κ academic resistance. The method for preparing water-based photoresist consists of two parts, one is a hydrophobic phase containing (meth) acrylate monomer, heuristic agent, antioxidant and dye, and the other is acidic acrylic copolymer (Neocry 1) in water. CL- 3 40), mothproofing agent (By k 303), neutralizer (DM AMP-90, and AMP-95) and associative thickener (DSX-1 5 1 4). The hydrophobic and aqueous phases are blended to form a hydrophobic phase in the aqueous emulsion. Use surface tension modifiers (such as F 1 no r ad FC-170C) and coalescing agents (such as propyl methoxyacrylate) up to 5%. The final composition has 20 to 40% solids, and 3 to 20% (meth) acrylate monomers in osmium, and most of them are ethoxylated (such as TMP (EO) TA). φ U.S. Patent No. 5,38 7,494 describes the use of polydimethoxypentanoxane (PDMS) in an aqueous medium composition, such as Dom Coming's Q4-3667, which is terminally terminated. It claims that PDMS can increase the non-tackiness of the surface after drying. U.S. Patent No. 5,3,93,643 describes the use of an amino acrylate, such as dimethylamino ethyl acrylate, in the neutralization reaction system. Tertiary amino acrylates such as N, N-diethylaminoethyl acrylate, N, N-dimethylaminoethyl (meth) acrylate, and N, N -dimethyl Aminopropylpropyl (meth) acrylate. It claims that the amine acrylate should remove the developing residues, and the etching obstacle is caused by the high solubility of the unhardened photoresist in the alkaline solution. It provides faster drying time and exposure time, and fewer pinholes, and the hardened part of the photoresist can be quickly removed at the end. U.S. Patent No. 5,9 42, 371 describes neutralizing an acrylate oligomer-containing acid with ammonia, an amine, or an organic base to prepare an oligomer that is soluble or dispersible in water. A preferred oligomer is an epoxy acrylate which is further acidified by an anhydride -1 0-200406433

. The oligomer may contain up to 15% by weight of solvent. Prior to the neutralization reaction, the acid hydrazone of the C00H-containing oligomer must be at least 25 mg KOH / gm, preferably more than 60 mg KOH / gm. The composition was tested as a solder mask application and reported good results. All of the above examples describe the addition of an amine-containing composition to neutralize the acidic functionality of the main polymeric binder. The disadvantage of this approach is that these amines are generally low molecular weight and volatile. This results in release to the environment during the drying of the oven, produces an unpleasant odour, and without proper ventilation systems can harm anyone working nearby. Another potential problem is that the rheology (such as viscosity) and other properties of the composition are changed by the addition of the aforementioned amines. Although the problem of volatility can be avoided by using a cross-linked amino acrylate as described in U.S. Patent No. 5,3 9 3,6 4 3, the addition of the amino acrylate may affect the composition after hardening. Desire characteristics. In addition, since the composition rheology is changed due to the addition of amine acrylate, it may be necessary to add other compositions to restore the proper characteristics of the composition for application. SUMMARY OF THE INVENTION The present invention provides a water-thinning / dispersible hardening composition Substances, which can be developed in a liquid alkaline solution, and include reaction products of (meth) acrylated polymer binders containing a primary, or preferably more, secondary amine composition of formula I, I is as follows:. 'Λ HNs R2

Formula I _ 1 1-200406433 wherein R1 and r2 are hydrogen or optionally substituted hydrocarbon groups, such as alkyl, aryl, cycloalkyl, arylalkyl, hydroxyalkyl, hydroxyaryl, and hydroxycycloalkyl And cyclic aryl groups, R1 and R2 may also include (poly) amidoamine, (poly) ester, (poly) urethane, (poly) urea, (poly) ether, and (poly) carbonate Organic bonding. Another requirement is that Ri and R2 must not both be hydrogen at the same time. A radiation-curable composition obtained by reacting a composition of formula I with an unsaturated carboxylic acid functional copolymer prepared by (meth) acrylic polymerization of formula I A. Formula I A is as follows:

Where X is Η or CH3 and CH3 is preferred, and L and R2 are substituted hydrocarbons, hydrocarbyl ethers, poly (hydrocarbyl ether), hydrocarbyl ether, poly (hydrocarbyl ether), and poly (hydrocarbyl ether hydrocarbyl ester), respectively, as required It is preferably substituted alkyl, aryl, cycloalkyl, or arylalkyl as necessary, and the molecular weight of the copolymer is preferably 10,000 to 100,000, and the acid value is preferably 50 to 30. 1112 {((^ / 2 and unsaturated functionality is 1 to 100, m and η are 1 or more. It is preferred that the reaction of an amine-containing compound of formula I and an unsaturated carboxylic acid-functional copolymer of formula I A It is partially carried out and provides a reaction product containing a carboxyl group, a (meth) acrylate functionality and an amine functionality. The acid-containing (meth) acrylated polymer binder can be used as a composition 1 2-200406433 (A) a copolymer, which is a partially esterified product of a styrene maleic anhydride copolymer and at least two hydroxyl-containing compounds having a compound of formula II,

Where φ P is 0 or 1, and η is an integer from 1 to 7,

Ra, Rb, and Re are hydrogen or methyl, respectively, preferably Ra is methyl or hydrogen and Rb and Re are both hydrogen (that is, Formula I is represented as (methacrylate)); W is a substituted organic as needed The divalent linking moiety is preferably selected from the group consisting of one or more optionally substituted hydrocarbyl, hydrocarbyl ether, poly (hydrocarbyl ether), hydrocarbyl ester, poly (hydrocarbyl ester), and poly (hydrocarbyl ether hydrocarbyl ester) The base is more preferably a base selected from the group consisting of alkenes, alkylene ethers, polyethers, polyesters, alkylene esters, and polyether polyesters, and X is (n + 丨), Which is a group selected from the group consisting of one or more optionally substituted hydrocarbyl, hydrocarbyl ether, poly (hydrocarbyl ether) 'hydrocarbyl esters, poly (hydrocarbyl ester), and poly (hydrocarbyl ether hydrocarbyl ester), more It is preferably a group selected from the group consisting of alkenes, alkylene ethers, polyethers, polyesters, alkylene esters, and polyether polyesters, and Y is an oxy group (-0-), an imino group NH _), or Hydrocarbyl-substituted imino-13-200406433 · l (-NIV, where R is a hydroxyl group, preferably an alkyl group); (b) one or more of the following formulas optionally Product of partially esterified styrene maleic anhydride copolymer of hydroxy compound:

HO \ AR "N, R3 and / or R2- (NHC = 0) m— R4—0H (ie, any substituent may be attached to any N or C atom of the N-substituted carbamoyl moiety)) Therefore, R2 and R3 are respectively Η or optionally substituted hydrocarbon groups, preferably substituted alkyl, aryl, cycloaryl, or arylalkyl groups. EU is a direct bond in each formula ( That is, in the formula, Η is connected to a nitrogen group or a carbonyl group) or an organic linking portion is substituted as needed, preferably a divalent, preferably a substituted hydrocarbon group, and more preferably a substituted fluorenyl group, An aryl, cyclic, or aryl group, and ㈤ is greater than 1. Or (acid-containing (meth) acrylate polymer adhesives can also be H containing the following composition: (a) doped Copolymer, which is a product of partial esterification of styrene maleic anhydride and formula melon composition;

Style melon one 14 one 200406433

In the formula, r is 0 or 1, and s is an integer of 1 to 7. When Υ is an oxygen group, Ra ', Rb, and R. '' Are hydrogen or methyl, respectively, and it is preferred that Ra 'is methyl or hydrogen and' and R are. Are all hydrogen (that is, the formula n is represented by (methacrylate)); X 'is (n + 1) the organic linking moiety which is optionally substituted, which is selected from one or more substituted if necessary. The group consisting of a hydrocarbon group and a hydrocarbon ether, a group consisting of a poly (alkyl ether), a hydrocarbon ester, a poly (alkyl ester), and a poly (alkyl ether ether), more preferably selected from an olefin and an alkylene ether , Polyether, polyester, alkylene ester and polyether polyester, W 'is an organic linking moiety which is substituted if necessary, which is selected from one or more substituted if necessary. Hydrocarbyl, hydrocarbyl ether, poly (hydrocarbyl ether), hydrocarbyl ester, poly (hydrocarbyl ester) and poly (hydrocarbyl ether hydrocarbyl ester) group, which is more preferably selected from the group consisting of olefin, alkylene ether, polyether, poly The group 'Y of the group consisting of esters, alkylene esters, and polyether polyesters is an oxy group (-〇-), an imine group (-NH-), or an imine group (-NR,-, (Wherein R'i is a radical, preferably a radical); (b) optionally, one or more of the following formulas are partially esterified styrene maleic anhydride copolymer Product of things: with HO, FV4-N,

Ra

And / or R2- (NHC = 0) t — R4 — 0H 200406433 (ie, any substituent may be attached to any ~ N or C atom of the N_substituted carbamoyl moiety); therefore R 2 and R '3 is fluorene or optionally substituted hydrocarbyl, preferably substituted hydrocarbyl, aryl, cycloaryl, or arylalkyl, respectively. In the formulas, each is a direct bond (ie, formula Wherein 〇Η is connected to a nitrogen group or a carbamoyl group) or an organic linking portion is substituted as necessary. The bivalent 'is preferably a substituted hydrocarbon group as needed, and more preferably a substituted alkyl group or a substituted group as needed. Aryl, cycloalkylene, or arylalkylene, and t is 1 or more. Or 'unsaturated residual acid, which includes acrylic polymers derived from: (I) carboxylic acids containing acrylic polymers and unsaturated epoxides, or (Π) acrylic polymers containing and Epoxides of carboxylic acids, or methacrylic acid or (meth) acrylates. An example of a commercially available acrylic polymer-containing unsaturated carboxylic acid is the Cyc lomer-P ACA series of Daicel Chemical of Japan. The preferred molecular weight of the adhesive is from 1,000 to 100,000, the preferred acid is from 50 to 2000, and the preferred functionality is between 5 and 50. Detailed description of the present invention The copolymer of the present invention is the addition of a primary or secondary amine from Michael (Michae 1's) to the (meth) acrylic acid-based (meth) acrylate adhesive (meth) Acrylate-based. The example products obtained by the present invention are described in the following chemical reaction, which is a half-ester between styrene maleic anhydride copolymer and monomethylethylethanolamine, a 16-200406433

In the formula, η and m are 1 or more, X = H or CH3, (in this case, it is less preferred to use a hydroxylated amine, unlike ipd256.93, because there is no further reaction after the Michael addition reaction). Examples of acidic (meth) acrylate polymerizable adhesives include commercially available acrylic resins, such as Cyclomeir-P ACA2 50 (copolymer of methyl methacrylate / methacrylic acid, , 4-epoxycyclohexyl methacrylate functionalization, manufactured by Daicel Chemical, Japan. Another example of an acidic (meth) acrylate polymerizable adhesive is an esterified copolymer, which It is preferred that at least 50 mole% of the free anhydride groups in the styrene maleic anhydride copolymer be esterified with hydroxyalkyl (meth) acrylic acid 'and less than 50 mole% of the free anhydride groups and the The esterification reaction of a caprolactone or alkoxy group via a (meth) acrylate. In order to ensure that almost all anhydrides are ring-opened, the reaction is preferably carried out with an excess of hydroxyl groups. The reaction is usually carried out in an organic solvent. Typical solvents used for liquid photoresist systems are propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, butyl ether glycol acetate, and butylcarbitol acetate. The solvents are generally Add to glass container and slowly Heat to 6 (rc. At this temperature, the addition of phenylethyl-17-200406433 enemaleic anhydride copolymer is accompanied by a polymerization inhibitor to prevent (meth) acrylate unsaturated thermal polymerization. The typical inhibitor used is Hydroquinone and its derivatives triphenyl antimony and trinonyl phosphite. Then add the hydroxy (meth) acrylate monomer to the copolymer solution in the container. Increase the temperature to 90 ° C ~ 100 ° C And it lasts until all the anhydride groups of the ring are ring-opened. When the acid of the reaction product is equal to the half of the ester, the reaction is complete. The copolymer can be prepared by two different methods. The first method In order to react styrene maleic anhydride copolymer with two kinds of hydroxy (meth) acrylates and blend these two different copolymers, the mixture includes styrene maleic anhydride and 2 different hydroxy groups ( The method of partially esterifying the product of meth) acrylate is to react the benzecan male liver copolymer with two different methacrylates at the same time. The typical structure of the copolymer of the present invention is as follows As shown:

Where 'R is a divalent alkyl ester, a divalent alkyl ester moiety, and / or 200406433 OR,

CNH R20 ——— 〇R4——N (R3) —r2〇 (that is, the ether divalent substituent can be connected to N of either N or C and & N 'substitutes for the amino formamyl moiety) Zhong and R;} are respectively substituted as necessary @ 其, preferably substituted as needed, aryl, cyclic, or aryl radical R 4 is a direct bond in each formula Or a bivalent substituted organic linking moiety as needed, preferably a substituted hydrocarbyl group, more preferably a substituted alkylene, arylene, cycloalkylene, and arylalkylene, e , F, g, and / or h are preferably 1 or more, more preferably an integer of 1 to 7 (including endpoints); and _k and 1 are integers of 0 or 1 to 7 (including endpoints) ), M is 1 or more, preferably 1; more preferably, when 1 is 0, R is as follows: ~ 0 ~

II —〇R4—CNH—R2-1 9- 200406433 or 0¾ ~ N (R3) —r2 where R3 is a hydrocarbon group other than fluorene or optionally substituted, preferably substituted courtyard or aromatic Group, ring aryl group, or aryl group group, R4 in each formula is a direct bond or an organic compound which is substituted if necessary. It is preferably a substituted hydrocarbon group if necessary. The head of the subject is a substituted alkylene, arylene, cycloalkylene, or arylalkylene, if necessary. More preferably, right 1 is 1 to 7, and R is a divalent alkyl ester or a divalent alkyl ether portion. Commercially available resins, such as E i f

Atochem's SMA and Leuna Harze Cmbl ·! Leumal resin, the preferred molecular weight of the copolymer of maleic anhydride copolymers are 丨 00 and 30,000, and the molybdenum of maleic anhydride Ear ratios are in the range of (丨: 丨) to (3: 丨), respectively. An example of a suitable esterification of a hydroxyalkyl (meth) acrylate with a styrene maleic anhydride copolymer is 2-hydroxyethyl acrylic acid. Esters, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, hydroxypropyl methacrylate, 1 methylol methacrylamide and N-hydroxymethacrylamide. Suitable hydroxy monosystems containing more than one (meth) acrylate group are ditrimethylolpropane triacrylate, isopentaerythritol triacrylate, and diisopentaerythritol pentaacrylate. The (meth) acrylic acid ester monomer having a functionality of 1 or more is preferably a photoresist composition having a very high photosensitivity. -20-200406433 Examples of hydroxy (meth) acrylate-containing caprolactone are commercially available products Tone M-100 and M-200 manufactured by Union Carbide Corporation. Examples of the alkoxy-containing hydroxy (meth) acrylate are polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monopropionate, polypropylene glycol monomethacrylate, and Mixtures of ethylene and propylene glycol (such as polybutanediol). The above examples are available from Bisomer PEM63p and PPMM6 3E. The maleic anhydride ring of all copolymers need not necessarily react with the (meth) acrylic acid monomer. For example, smaller amounts of amine- or hydroxyl-containing moieties can be used to form non- (meth) acrylate amine or ester side chains, respectively. Side chains may affect the total solubility of the copolymer composition. An example of a possible non (meth) acrylate side chain is methylol polyethylene glycol. Another example is a melamine of the formula HONR2R3 and a pinanol of the formula H0R4 (NHC0) mR2, where R2 and / or R3 may be alkyl, aryl, cycloalkyl, arylalkyl and m is Greater than 1. The reaction of (meth) acrylated polymer binders with amines is usually carried out in the presence of a polymer inhibitor to avoid the thermal polymerization of (meth) acrylated unsaturated almonds. Typical inhibitors used are hydroquinone and its derived triphenyl antimony, and trinonylphenyl phosphite. Due to the exotherm and the temperature rises, the amine is added dropwise to the polymer binder. During the addition, the temperature remained approximately below 50 ° C. After the exotherm was over, the reaction was maintained at 45 ° C for 2 hours before the reaction was terminated. The amount of the amine-based compound reacted with the (meth) acrylated polymer binder is 0.1 to 0.9 amine equivalent based on the double bond equivalent of each (meth) acrylate functionality. The terms "optional substituents" and "optionally substituted" as used herein (unless there is another list of substituents) means ~ or more of the following groups (or substituted with the following groups): carboxyl , Sulfo, formamyl, hydroxy, amine, imine, nitrogen, hydrogenthio, cyano, nitrogen, methyl, methoxy, and / or combinations thereof. If necessary, the basic system includes all the chemically possible components in the same (more than two) identical parts of the above-mentioned groups (for example, amino and sulfo are linked together as sulfamoyl). Preferred optional substituents include a carboxyl group, a sulfo group, a hydroxyl group, an amine group, a hydrogenthio group, a cyano group, a methyl group, and / or a methoxy group. The same nouns used "organic substituent" and "organic group" (referred to as organic [of]) are any univalent or multivalent part (connected to one or more other parts as necessary), including One or more carbon atoms and optionally one or more other heteroatoms. Organic groups can include organic hetero groups (known as organic elemental groups) that include monovalent valences containing organic carbon, but are free atomic valences compared to other carbons (eg, organic sulfur groups). The organic group may optionally or additionally include an organic group containing any organic substituent, which has a free atomic value in the carbon atom regardless of the functional type. The organic group may also include a hydrogen atom formed by removing a hydrogen atom from a heterocyclic compound (in the case of a carbon atom, it is a cyclic compound containing at least 2 different elements as cyclic constituent atoms). Heterocyclyl of a monovalent group. The non-carbon atom in the organic group is preferably selected from the group consisting of hydrogen, halogen, phosphorus, nitrogen, oxygen, and / or sulfur, and more preferably a group consisting of hydrogen, nitrogen, oxygen, and / or sulfur. The term "hydrocarbyl" used is a subset of organic groups and is expressed as any-22- 200406433

A monovalent or polyvalent moiety (connected to one or more other moieties as needed), which consists of one or more hydrogen atoms and one or more carbon atoms. The hydroxyl group may include one or more of the following groups. The hydrocarbyl system includes a monovalent group formed by removing a hydrogen atom from a hydroxyl group. The amidine system includes a divalent radical formed by removing two hydrogen atoms from a hydrocarbon, in which a free atomic valence is not connected to a double bond. Hydrocarbylidene includes a divalent group (represented by R2C) formed by removing two hydrogen atoms from the same carbon atom of a hydrocarbon, in which a free atomic valence is connected to a double bond. The hydrocarbon fluorenyl group includes a trivalent group (represented by RC) formed by removing three hydrogen atoms from the same carbon atom of a hydrocarbon, in which a free atomic valence is connected to a reference bond. Hydrocarbyls may include any saturated, unsaturated double and / or para-bonds (eg, alkenyl and / or alkynyl, respectively) and / or aromatic groups (eg, aryl) and those that may be substituted by other functional groups . More preferably, the organic group includes one or more of the following carbon-containing moieties: alkyl, alkoxy, alkanol, carboxyl, carbonyl, formamyl, and / or combinations thereof, as necessary in combination with the following heteroatom-containing moieties It is an oxy group, a thio group, an arylene group, an amine group, an amine group, an amido group, and / or a nitrogen group and / or a combination thereof. Organic groups include all chemically possible combinations of the same part plural (preferably 2) of the above carbon atom and / or heteroatom-containing portions (for example, an alkoxy group and a hydrocarbyl group in direct contact with each other are represented as alkoxyhydrocarbyl groups). The term "alkyl" or its equivalent (e.g., a 1 k) used can be easily and appropriately substituted with any of the above-mentioned hydrocarbyl groups unless there are other bases that are pointed out clearly. Unless otherwise stated or otherwise pointed out (for example: the alkylene moiety may include a divalent radical attached to 2 other moieties), any substituents, radicals or moieties mentioned are monovalent. Contains radicals represented by a chain of three atoms, all of which -23- 200406433

Or part of it is linear, branched and / or cyclic (including spiral and / or fused rings). The total number of exact atoms can be detailed as an exact substituent such as a c i _ x organic group, which is an organic group having 1 to X atomic numbers. In any formula described herein, if more than one substituent does not indicate that it is connected to any particular atom in this section, the substituent may replace any hydrogen atom connected to other atoms and / or in this section it may be located At any useful position (chemically appropriate) and / or with a free atomic valence (which can be indicated by an arrowed formula). Certain parts of the chemical terminology used herein are in parentheses, and unless indicated otherwise (for example: IUPAC brackets), the bracketed parts are appropriate. For example, the term "(meth) acrylate" means both methacrylate and acrylate. Some organic groups such as listed hydrocarbon groups, alkyl groups, etc. do not specify the number of carbon atoms, and they preferably contain 1 to 36 carbon atoms, and more preferably 1 to 8 carbon atoms. Particularly preferred are carbon atoms including 1 to 10. Unless the context clearly indicates otherwise, plural forms used herein can be construed to include the singular form and vice versa. For example, the terms "group (group)" and "0 Lu Chengji" refer to a single group or several groups and a single functional group or several functional groups, respectively. The term "effective" (for example) can be considered to apply to these ingredients, if used in the correct place, it can provide materials, compounds, compositions, monomers, oligomers, polymeric precursors, and / or added or combined to any Characteristics required for more than one polymer used and / or application. The term "appropriate" means a functional group consistent with the production of an effective product. The substituents of the repeating unit may be used to improve the compatibility of materials with polymers and / or resins, which can be organized and then inserted to form effective materials. Therefore, the size and length of the substituents may be selected so that the resin makes full use of the intense entanglement or insertion or it may or may not contain other chemically reactive entities and / or crosslink the resin. Including some or all of the identified parts, species, groups, repeating units, compounds, oligomers, polymers, metals, mixtures, compositions and / or formulations described in this invention may be more than one stereoisomer (such as Mirror image isomers, non-image isomers, geometric isomers, tautomers and / or structures), salts, zwitterions, complexes (such as chelates, crystal cage compounds, crowns) Compounds, cryptate ligands, inclusion compounds, intercalation compounds, phase compounds, ligand compounds, non-stoichiometric compounds, organometallic complexes; r-adducts, solvates and / or hydrates), Isotropic systems in substituted form, polymer configuration [such as homo-, copolymers, random, grafted or block copolymers, linear or branched copolymers (eg, star and / or side chain copolymers) 'high scores Dendrimers and / or dendritic macromolecules (as described in WO 93/17060), cross-linked and / or network polymers, polymers obtainable from di- and / or trivalent repeat units, dendrimers Polymers with different stereoregularities (Zhao For example: polymers in the same row, opposite row, or hetero row)], polymorphs (eg, staged, crystalline, amorphous, phase, and / or solid solution) may be combinations and / or mixtures thereof. The invention of this case includes all such useful types. The certain features of the present invention are described in detail in each of the examples in the text, and can also be combined in a single example. Conversely, different features of the present invention are briefly described in a single instance herein, and may be in separate or appropriate subcombinations. -25- 200406433 The term "including (including)" is used to indicate the non-missing listed below, and may include or not include any other additional appropriate nouns, which details such as one or more further features, compositions Substances, ingredients and / or substituents. In some examples, the acid containing the (meth) acrylated copolymer binder may be a composition, which comprises: U) a copolymer, which is a styrene maleic anhydride copolymer and at least two compounds containing formula η The product of esterification of the hydroxyl portion of compound a, formula Π a is as follows:

Formula Π a • II Π HO—x-4-γ \! Where P is 0 or 1 (that is, when P is 0, then Y is directly connected to the carbonyl group), and η is an integer from 1 to 7,

Ra, Rb and R. Respectively hydrogen or methyl, preferably Ra is methyl or hydrogen and Rb and Re are both hydrogen (ie, formula I is represented by (meth) acrylate); X and W are each selected from one or more Substituted hydrocarbyl, hydrocarbyl ether, poly (hydrocarbyl ether), hydrocarbyl ester, poly (hydrocarbyl ester) and poly (hydrocarbyl ether hydrocarbyl ester), more preferably selected from olefin, alkylene ether, polyether, poly The organic linking group of the group consisting of the ester, the alkylene ester and the polyether polyester is optionally substituted with a divalent group, and Y is an oxy group (· 0-), an imino group (-NH-), or a hydrocarbon group. Imino (-NI-, L is a hydrocarbon group, preferably an alkyl group). -26-200406433 Further aspects of the invention are described in the scope of patent applications. Description of preferred embodiments-The present invention is described by the following preferred examples without being limited thereto. Example 1 This example illustrates the preparation of a copolymer composition according to the present invention. 195 g of styrene maleic anhydride copolymer, SM A3 000 (having a molecular weight of 10,000, a molar ratio of styrene to maleic anhydride of 3: 1, and a trade name commercially available from Elf At ochem 3 ^ 183) and 180 grams of propylene glycol methyl ether acetate were added to a stirred 1 liter three-neck glass container and heated to 85-90 ° C to dissolve the copolymer. Then 27.27 grams of hydroquinone and 0.27 grams of triphenyl antimony inhibitor were added to the solution, and 75.9 grams of hydroxyethyl methacrylate and 0.54 grams of 4 were slowly added over a period of 1 hour. -A mixture of ethylmorpholines into a reaction vessel. The reaction mixture is heated to 90 ° C for 8 to 24 hours until the total acid content is equal to the theoretical acid content, or until the total acid content stops decreasing. The reaction mixture was stabilized with 0.2 g of trinonyl phosphite inhibitor. The total acid content of the copolymer ester was 1 17 mg KOH / gm and its nonvolatile content was 60%. This copolymer half-ester is called A. Example 2 This example illustrates the preparation of a copolymer composition according to the present invention. 166 grams of copolymer A and 20 grams of monomethylethanolamine (MMEA) were added to a 400 ml beaker, and the mixture was stirred for 30 minutes. An exothermic temperature increase was observed. One formed soft material can be physically separated from the solvent. This amine hydrate system is designated as copolymer B. -27- 200406433 Add a 99.9 g quantity of copolymer A to a 500 ml container and continue stirring at room temperature, and then slowly add 3.9 g of diethylamine (DEA) over 20 minutes. An increase in exothermic temperature was observed and controlled below 50 ° C. When the exothermic reaction was completed, the reaction temperature was maintained at 45 ° C for 2 hours, and the obtained amine-modified copolymer was represented as copolymer c. 500 grams of commercially available acrylic copolymer Cyclomer · * P ACA2 50 (copolymer of methyl methacrylate / methacrylic acid, Malonate was functionalized, and the product of Daicel Chemical in Japan) was added to a 1000 ml glass container, and then continuously stirred at room temperature. 38 grams of diethylamine (DEA) was slowly added dropwise over 20 minutes. The exothermic temperature rise is maintained at not more than 50 ° C. When the exothermic reaction has ended, the product is matured at 45 ° C for 2 hours. The amine-modified copolymer is represented by D. Example 3 This example illustrates the water dilution of copolymers B, C, and D according to the invention of this application. 20 grams of copolymer B was added to a 50 ml beaker. With continuous vigorous stirring, 6 grams of deionized water was added. The resulting homogeneous mixture is designated as Mixture E. 20 grams of copolymer C was added to a 50 ml beaker. A homogeneous mixture obtained by adding 5 g of deionized water under continuous vigorous stirring is designated as Mix F. 20 grams of copolymer D was added to a 50 ml beaker. The homogeneous mixture obtained by adding 13 grams of deionized water under continuous vigorous stirring is shown as Mixture-28-200406433 Compound G. This example evaluates the non-stickiness and alkaline solubility of mixtures E, F and G diluted with water. The non-tackiness and alkaline solubility of each copolymer were evaluated in the 1% Na2C03 solution by the following methods. Non-tacky time The copolymer was coated onto a clean copper plate using a # 1 6 copper wire pull rod to produce a wet film with a thickness of about 20-30 microns, and the coated plate was placed in an 80 ° C oven. The confirmation of the thickness of the plate was started immediately after 5 minutes after the plate was removed from the oven. If no finger marks remain on the film surface, the copolymer film is considered non-sticky. The alkali solution is dissolved in 1% Na2C03 3 (TC copolymer solubility is measured using a spray device with an alkaline solution. The amount of copolymer remaining on the board was confirmed during 30 seconds of spraying with the alkaline solution. No stickiness The results of the basic solubility are shown in the following table. In the present invention, the results of the copolymer A are included to show the improvement of the obtained φ: The time when the copolymer does not stick (hot viscosity) is completely dissolved Time at l% Na2C03 A 5 minutes, 100 ° C > 1 minute E 5 minutes 1 minute F 5 minutes 1 minute G 5 minutes 1 minute

From the above examples, compared with the mixtures E, F, and G, it can be seen that copolymers B-29-200406433, C, and D are conducive to imparting water dilution (as shown in Example 3), and copolymer A and the resin obtained commercially Cyclomer-P ACA250 itself is not water-dilutable. Another advantage is that as shown by the mixtures E and F in the examples, it can improve the non-tackiness and alkaline solubility of the copolymer A. Schematic description: None

-30-

Claims (1)

200406433 The scope of patent application: 1 · A radiation-hardenable composition, which is dilutable and / or dispersible in an aqueous solution, and includes a reaction product of a (meth) acrylated polymer binder, which Polymeric binders include acid groups containing a primary or secondary amine-containing composition of formula I. The amine groups of the amine-containing compound are (meth) acrylated with vinyl groups via Michael's addition molding reaction. Compound reaction, the formula I is shown as follows: wherein R1 and R2 are hydrogen or a substituted hydrocarbon group, if necessary, preferably a substituted group, an aryl group, a cyclic group, an aryl group, and an economic group. Group, hydroxyaryl group, hydroxycycloalkyl group, and hydroxycycloaryl group, and if Ri and R2 must not be hydrogen at the same time, Ri and 1 may optionally include an organic linking moiety, which is selected from (poly) amidamine, ( Groups consisting of poly) esters, (poly) urethanes, (poly) ureas, (poly) ethers, and (poly) carbonates. .2 If the radiation-hardenable composition of item 1 of the patent application scope, wherein the composition is obtained by reacting a primary or secondary amine-containing compound of formula I with an unsaturated quaternary acid functional copolymer of formula IA, the formula IA is as follows Shown ... -3 1-200406433 In the formula, X is 3 or CH3, and L and R2 are substituted hydrocarbons and hydrocarbyl ethers as needed; poly (hydrocarbyl ether), hydrocarbyl ether, poly (hydrocarbyl ether) and poly (hydrocarbyl ether hydrocarbyl ester), preferably as A substituted alkyl, aryl, cycloalkyl, or arylalkyl group is required. The molecular weight of the copolymer is preferably 1,000 to 100, 000, and the acid value is preferably 50 to 300 mgKOH / g and unsaturated. The functionality is 1 to 100, and m and η are 1 or more. 3. The radiation-hardenable composition according to item 2 of the scope of the patent application, wherein the reaction of the primary or secondary amine-containing compound of formula I with the unsaturated carboxylic acid functional copolymer of formula I A is a partial reaction, and is obtained A reaction product comprising a carboxyl group, a (meth) acrylate functionality, and an amine functionality. 4. The radiation-hardenable composition according to any one of the foregoing claims, wherein the (meth) acrylic polymer binder containing an acid group comprises a styrene-maleic anhydride copolymer and at least one formula Π The copolymer of a partially esterified product of a hydroxy-containing compound is represented by the following formula: -32-200406433 HO-X In formula II, P is 0 or 1, n is an integer from 1 to 7, Ra, Rb, and hydrogen, and methyl 'are each preferably Ra is methyl or hydrogen, and ^ and R. Both are hydrogen, and W is an organic linking moiety which is substituted if necessary, which is selected from one or more optionally substituted hydrocarbyl, hydrocarbyl ether, poly (hydrocarbyl ether), hydrocarbyl ester, poly (hydrocarbyl), and Poly (hydrocarbyl ether hydrocarbon ester) group; more preferably a group selected from the group consisting of M, alkylene ether, polyether, polyester, alkylene ester and polyether polyester, γ is an oxy group (-〇_), imine (-ΝΗ-) or a hydrocarbyl-substituted imine (, & is a hydroxyl group, preferably an alkyl group), X is (η + 1), and a substituted organic The linking part is selected from one or more groups consisting of optionally substituted hydrocarbon groups, hydrocarbon ethers, poly (alkyl ethers), alkyl esters, poly (alkyl esters), and poly (alkyl ester ethers), More groups selected from the group consisting of alkenes, alkylene ethers, polyethers, polyesters, alkylene esters, and polyether polyesters, wherein Υ is an oxy group (-0-), and an imine group (-ΝΗ-) Or a hydrocarbyl-substituted imino group (-NRr, I is a hydroxyl group, preferably an alkyl group), more preferably Y is 0, P is 0, X is a hydrocarbon group, Ra is a methyl group, and Rb and V are both hydrogen. 5. The radiation-curable composition according to item 4 of the patent application, wherein the (meth) acrylic polymer binder having an acid group includes a styrene maleic anhydride copolymer and one or more of the following formulas containing Partial esterification of hydroxy compounds yields 33-200406433, where the alkyl groups substituted by r2 and β are straight, preferably alkyl, and arylene, respectively. 6 · As in the previous application, the copolymers with acid groups are different, and the hydroxyl-containing H0, A R-nn Ra and / or R2— (NHC = 〇) —R4—0h 3 are H or substituted if necessary. The hydrocarbyl group is preferably a warp, square, cycloaryl, or arylfluorenyl group. In each formula, a bond or a divalent organic linking moiety is substituted as necessary. If a substituted hydrocarbyl group is used, it is more preferably Substituted, cycloalkylene, or arylalkylene, and m is 1 to any of the radiation curable compositions in the patent range, the (meth) acrylated polymer binder system includes a The copolymer is a partially esterified product of a styrene maleic anhydride copolymer and at least 2 truncated compounds. The formula is as follows In the formula, r is 0 hydrogen or methyl, which is monovalent as needed. More if necessary Formula Π or 1, s is an integer from 1 to 7, Ra ', Rb, and R. 'Respectively, it is preferable that Ra is methyl or hydrogen and Rb' and RC 'are both R, and W' is a substituted organic linking moiety, which is selected from mono- or substituted hydrocarbyl, hydrocarbyl ether, and poly (hydrocarbyl Ether), hydrocarbyl 34-200406433 Esters, poly (hydrocarbyl esters), and poly (hydrocarbyl ether hydrocarbyl esters) are more preferably selected from the group consisting of alkenes, alkylene ethers, polyethers, polyesters, alkylene esters, and polyether polyesters. Group base, X 'is (s + l) valence optionally substituted organic linking moiety, which is selected from one or more optionally substituted hydrocarbyl, hydrocarbyl ether, poly (hydrocarbyl ether), hydrocarbyl ester, poly (Alkyl ester) and poly (Alkyl ether alkyl ester); more preferably a group selected from the group consisting of olefin, alkylene ether, polyether, polyester, alkylene ester and polyether polyester , Y 'is an oxy group (-0-), an imino group (-NH-) or a hydrocarbyl-substituted imino group (-NR,-, R, is a hydroxyl group, preferably an alkyl group), more preferably Y 'Is 0, p is 0, X' is a hydrocarbon group, Ra 'is methyl or hydrogen, and Rb' and Re 'are both hydrogen. 7 · The radiation-hardenable composition according to item 6 of the patent application, wherein the (meth) acrylic polymer binder having an acid group further includes a styrene maleic anhydride copolymer and one or more of the following formula Partial esterification products of hydroxy-containing compounds, HOR.2 RVN, and / or R2- (NHC = 〇) t-R4-—OH where R'2 and R'3 are H or a substituted hydrocarbon group if necessary Is preferably a substituted alkyl, square, cycloaryl, or arylalkyl group, and R is a direct bond or a divalent organic linking moiety that is substituted as necessary in each formula, preferably as A substituted hydrocarbyl group is required, more preferably a substituted alkylene, arylene, cycloalkylene, or arylalkylene, and t is i -35- 200406433 or more. 8. The radiation-hardenable composition according to any one of the foregoing patent claims, wherein at least 50 mole% of the free anhydride groups in the styrene maleic anhydride copolymer are carried out with the alkyl (meth) acrylate. Esterification. 9 · The radiation-hardenable composition according to item 8 of the scope of the patent application, in which less than 50 mole% of the free anhydride group is reacted with a hydroxy (meth) acrylate having caprolactone or an alkoxy group, or Reaction of a compound containing a hydroxyl group of the formula: ΗΟ, Λ RVN, R_3 · and / or 1? 2- (NHC = 0) t— R4 — OH where R'2 and R'3 are Η or substituted if necessary Hydrocarbyl, preferably substituted alkyl, aryl, cycloaryl, or arylalkyl, r, 4 in each formula is a direct bond or a divalent organic linking moiety that is substituted as necessary, preferably In order to substitute a hydrocarbyl group as needed, it is more preferable to substitute an alkylene group, an arylene group, a cycloalkylene group, or an arylalkylene group as necessary, and t is 1 or more. 10. The radiation-curable composition according to item 8 of the scope of patent application, wherein substantially all of the free anhydride groups are esterified. 1 1. A method for preparing a radiation-hardenable composition, comprising the step of partially esterifying styrene maleic anhydride: a. Selecting one selected from propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, butane The group consisting of ether glycol acetate and butyl carbitol acetate is heated to 60 ° C, -36- 200406433 b. · Styrene maleic anhydride copolymer and a compound selected from hydroquinone and its derivatives such as Polymerization inhibitors of groups consisting of triphenyl antimony and trinonylphosphite are added simultaneously to prevent (meth) acrylate unsaturated thermal polymerization reactions. C. Separate styrene maleic anhydride copolymers. React with 2 different types of hydroxy (meth) acrylates, and d. Blend the 2 different copolymers formed in step (a), wherein the resulting mixture comprises styrene maleic anhydride and 2 Product of partial esterification of different hydroxy (meth) acrylates. i 2. The method for preparing a radiation-curable composition according to item 11 of the scope of patent application, wherein the preparation of a styrene maleic anhydride copolymer is a process in which the styrene maleic anhydride copolymer is simultaneously with two different hydroxyl (methyl) groups. Acrylate reaction. 1 3-A method for preparing a water-dilutable / dispersible radiation-curable composition, which comprises the following steps: a. Mixing a styrene maleic anhydride copolymer with propylene glycol methyl ether acetate and heating the mixture, b. Hydrogen awakening and dibenzyl chain inhibitors are added to the solution obtained in step (a), c. Slowly add hydroxyethyl methacrylate and 4-ethylmorpholine, and d. Maintain the reaction mixture in step (c) The temperature is carried out at 90 ° C for 8 to 24 hours until the total acid tritium is equal to the theoretical partial acid tritium, or until the total acid tritium stops decreasing, e. Post-stabilization step by adding a trinonylphenyl phosphite inhibitor Mixture, f · adding monomethylethanolamine (MMEA) or diethylamine (DEA) to the mixture of step (e) 200406433 Λ, g · maintaining the reaction mixture after excessive exotherm to obtain an amine-modified copolymer The temperature is 45 t for 24 hours, h. The composition of step (f) is diluted / dispersed in water, and i. The solid material in the solvent of step (f) is separated as appropriate. 1 4 · If the radiation-curable composition of item 6. or 7 of the scope of patent application, the partially esterified styrene maleic anhydride copolymer is defined as follows: -Where R is a monovalent alkyl ester, a divalent alkyl ester moiety, or 100R4-N (R3)-r2o-r2-__OR u UR4 ~, CNH R2 and h are A substituted hydrocarbyl group is required, preferably a substituted alkyl, aryl, cycloaryl, or arylalkyl group. R4 in each formula is a straight M㉟ divalent, optionally substituted organic linking㈣, Hydrocarbyl groups to be substituted as preferred, more preferably substituted alkylenes-38-200406433, arylene, cycloalkylene, or arylalkylene, e, f, g and / or h is preferably 丨 or above, more preferably an integer of 1 to 4 (including endpoints), k and 1 are integers of 0 or 1 to 7, including endpoints, and m is 1 or more, more Better to be 1. 15 · The method for preparing a radiation-hardenable composition according to item 14 of the scope of the patent application, wherein when I is 0, Pii R is: 100R4-n (r3)-r2 II FL- 〇R4—- CNH where R2 and R3 are η or optionally substituted hydrocarbon groups, preferably substituted alkyl, aryl, cycloaryl, or arylalkyl groups. R4 is different in each formula. It is a direct bond or a divalent organic linking moiety which is optionally substituted, preferably a substituted hydrocarbon group, more preferably a substituted alkylene, arylene, cycloalkylene, or arylalkylene, if necessary. More preferably, when 1 is 1 to 7, R is a divalent alkyl ester or a divalent alkyl ether moiety. 16 · A method for preparing a radiation-hardenable composition as described in item 14 of the scope of patent application ′, wherein 1 is a pyrene of 1 to 7 and R is a divalent alkyl ester or a divalent alkyl ether portion. 1 7 · A method for preparing a radiation-curable composition, comprising the following steps: a) methyl methacrylate / methacrylic acid functionalized with 3,4-epoxycyclohexyl methacrylate The copolymer is slowly mixed with diethylamine (DEA), and then the temperature of the reaction mixture is maintained below 50 ° -39-200406433 b) After the excessive exotherm to obtain the amine-modified copolymer, the reaction temperature is maintained at 45 ° C is carried out for 2 hours, c) the product of step (b) is diluted or dispersed in water, and d) the material in the solvent of step (b) is optionally separated. 1 ··· Copolymer, which is prepared according to any one of the methods in the scope of application for patents Nos. 1, 1, 2, 1, 3, 15, 5, 16 and 17. 19 · An article obtained or obtainable in accordance with the method of any one of claims 1, 1, 3, 15 and 17 of the scope of patent application. 20. An article obtained or obtained by using a product such as any one of claims 1 to 10 or 13 in the scope of a patent application. 2 1. Articles in the scope of patent application No. 19 or 20 are used for the manufacture of printed circuit boards or printing plates. -4 0-200406433 (1) Designated representative map: (1) The designated representative map in this case is: (). (2) Brief description of the representative symbols of the components in this representative map: 捌 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: -5-