TW200307696A - Radiation curable compositions - Google Patents

Abstract

The invention provides in one form a water-dilutable and/or dispersible radiation curable composition that is soluble in aqueous alkaline solution and which comprises the reaction product of a hydroxy functionalised amino (meth)acrylate with anhydride containing compounds. The hydroxy functionalised amino (meth)acrylate is prepared from the Michael addition of a primary, or more preferably, a secondary amine to a multifunctional (meth)acrylated monomer. The amine compound shall be as described in Formula I, where R1 and R2 independently represent H or optionally substituted hydrocarbo, such as but not limited to, 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, but not limited to, (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

200307696 发明 Description of the invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a radiation-curable composition that can be diluted (and / or dispersed) in water, and can be used as a liquid photoresist composition or additive to make, for example, printed circuits. Board items. The radiation-curable composition is mobile unless it has been subjected to 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 孀 A typical printed circuit board is prepared by applying a radiation-curable coating film to a copper surface of a substrate. 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. Lu 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 can be hardened by radiation 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, this requirement is one-to-one. 6-200307696 Disadvantage, it still produces a hardening coating film but the subsequent treatment solution is alkaline. At this time, the photopolymerized part is easily degraded in a higher alkaline solution (such as an ammonia-based etching solution or a metal plating solution). In this case, such a photoresist will be easily peeled and wiped off. U.S. Patent No. 4,943, 516 teaches that photosensitive thermosetting compositions include acid-functionalized epoxy (meth) acrylate-based photosensitive polymers and finely powdered epoxy compounds that can be used for liquid photoimaging. Welding mask. The composition described in this patent is superior in chemical resistance and heat resistance but lacks fast-drying properties. It takes a long time to dry before contact copying to obtain a non-sticky surface and image the circuit pattern onto 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. 2,25 3,772 teaches a photopolymerizable composition for a lithographic imaging plate or a photoresist, 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 alkalinity 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 ~ 80%) will reduce the basic development of photoresist at the same time. U.S. Patent No. 5,296,333 teaches the use of a polymeric composition as a solder mask. The composition includes a binder polymer, which is an esterified product of styrene maleic anhydride copolymer containing less than 15% free anhydride, and at least 50% useful anhydride groups and hydroxyl groups. Alkyl (meth) acrylates are esterified, and at least 0.1% of useful anhydride groups are esterified with monohydric alcohols. It also contains polyfunctional (meth) acrylate monomers and polyfunctional epoxides. The use of high concentrations of (meth) acrylic acid ester monomers (such as TMPTA, TPGDA or DPHA) will increase the UV and reactivity of the photoresist. However, the thickness of the photoresist composition is generally increased. U.S. Patent No. 4,370,403 teaches a polymeric composition based on the reaction product of (a) a styrene maleic anhydride copolymer with 2-hydroxyethyl acrylate, and (b) other ethylenically unsaturated compounds. And (c) a photoinitiator. U.S. Patent No. 4,722,947 describes a radiation-curable polymer based on the reaction of a styrene / maleic anhydride copolymer with a hydroxyalkyl acrylate and another alcohol, such as an arylalkyl monohydric alcohol. The presence of acrylate-unsaturated alcohols reduces the UV reactivity of the coating film and the UV cross-linking of the product. It also causes a reduction in the chemical resistance of the photoresist in subsequent alkaline or acid treatments. U.S. Patent No. 4,723,857 describes that the photoimageable composition contains a styrene / maleic anhydride copolymer and is partially esterified with methanol and isopropanol. As a result, the polymer itself is acidic, but does not contain acrylate unsaturation, which causes it to 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. Limitations on light sources can cause emissions of volatile organic content (VOC) to the environment. However, it is necessary to reduce the use of solvents-8-200307696 or completely exclude the liquid photoresist composition. WO 98/457755 (Advanced Coatings International) describes aqueous dispersions of aliphatic urethane acrylate oligomers for use in making photoresists. The composition needs to be added based on, for example, ammonia, morpholine, and the like. Potassium hydroxide · Makes the polymer binder water-soluble by neutralizing acid groups. U.S. Patent Nos. 5,691,006 and 5,501,942 and European Patent No. 49 3317 (Ciba) teach commercially available solid acids containing acrylic acids neutralized with ammonia or amines before dispersing in water Copolymers such as Carbose t 5 2 5, XL37 and 531. Because of the high Tg binder, the solvent still needs to dissolve the resin before neutralization. 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 healer 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 a water-based imaging coating composition. The examples describe the use of commercially available latex copolymer compositions, such as using Neocryl CL-340, Acrysol 1-2074, and Neocryl BT-175 as basic polymers, and neutralizing the reaction with ammonia. A non-sticky film was obtained after drying at 70 ° C for 10 minutes. U.S. Patent No. 5,3 64,7 3 7 describes the use of an associative thickener based on a polyether polyurethane (such as Henkel's DSX-1514) to stabilize the emulsion 200307696, which allows less amines Or ammonia neutralization reaction, and can increase the chemical resistance of photoresist. The method for preparing water-based photoresist consists of two parts, one is a hydrophobic phase containing (meth) acrylate monomer, heuristic, antioxidant and dye, and the other is acidic acrylic copolymer (Neocry 1) in water. # CL- 3 40), antifoaming agent (By k 3 03), 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 uo r ad FC- 170C) and coalescing agents (such as propyl methacrylate) up to 5%. The final composition is 20 to 40% solids, and 3 to 20% (meth) acrylate monomers of osmium, and most of them are ethoxylated (such as TMP (EO) TA). U.S. Patent No. 5,387,494 describes the use of polydimethoxysilane (PDMS), such as Dow Coming's Q4- 3667 hydroxyl terminated PDMS, in aqueous compositions. 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 Aminoaminopropyl (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. 5,942,37 describes the neutralization of an acid containing an acrylate oligomer with ammonia, an amine or an organic base to prepare an oligomer that is soluble or dispersible in water-10-200307696. A preferred oligomer is an epoxy acrylate which is further acidified with an anhydride. 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, and preferably higher than 60 mg KOH / gm. The composition was tested as a solder mask application and reported good results. t All the examples above 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 are volatile. This results in release to the environment during the drying period of the oven, produces an unpleasant odour and may harm anyone working nearby if a proper ventilation system is not available. Another potential problem is that rheology (such as viscosity) and other properties of the composition are altered by the addition of the aforementioned amines. Although the problem of volatility can be avoided by using a crosslinked amino acrylate as described in U.S. Patent No. 5,3 9 3,643, the addition of the amino acrylate may affect the composition as desired after hardening. characteristic. 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 properties of the composition for application. German Patent No. 1 965 363 1 A (BASF Coatings AG) describes Preparing a radiation-crosslinkable polymer (meth) acrylate, wherein the (meth) acrylate copolymer having a reactive side group is a base with a copolymer containing (1) a reactive side group, and (2) A compound that forms a radical group under photo-like radiation reacts. However, this document does not disclose that amines with NH functionality can undergo Michael addition reactions. German Patent No. 878926A (BF Goodr i ch) claims a polymer 200307696, which is mainly a polymer containing most amine units and reacts with the following: 1. At least 20 mole% amine [乂 州 (11) 1] X and Y are hydrogen or a hydrocarbon of 1 to 20 carbons, and / or 2. at least 20 mole% alcohol [X-0Η], X is a hydrocarbon of 1 to 20 carbons, where the alcohol may include Tertiary amine group. So the products include amine (amine-anhydride) and ester (alcohol-anhydride) linkages. No mention is made of amine acrylates or 0H functionalized acrylates. There are no amine compounds of Michael addition reaction in acrylate compounds. European Patent No. 0365020A (Kanegafuchi Kagaky Kogyo) describes the Michael addition \ reaction of an amine, such as dodecylamine, with a urethane acrylate. The "pre-copolymer" is then copolymerized with other monomers (such as methyl methacrylate, methacrylic acid) to obtain the final acrylic product. There is no Michael addition reaction of amine alcohol addition to polyfunctional (meth) acrylates. European Patent No. 07 3 1 1 2 1 A2 describes the carbamates obtained by: (a) If necessary, a poly (ether, ester, epoxy) · (meth) acrylate containing a hydroxyl group is reacted with a primary or secondary compound containing at least one hydroxyl group to form 0.5 to 60 mole% of the amine compound The (meth) acrylate group of the Michael adduct, (b) reacting the hydroxyl group of the first stage product with an isocyanate. Among them, there is no Michael addition reaction of amine alcohol to polyfunctional acrylate monomer after reaction with an anhydride group. SUMMARY OF THE INVENTION-12-200307696 The present invention provides a water-thinning / dispersible hardening composition that is soluble in a liquid alkaline solution and includes a hydroxyl-functionalized amine (meth) acrylate and an anhydride-containing compound Reaction product. Hydroxyl-functional amine compounds are prepared from the Michael addition reaction of primary, or more preferably secondary amine addition to polyfunctional (meth) * acrylated monomers. Amine-based compounds, as shown in formula I:

HN 、 R2

Formula I wherein L and R2 are hydrogen or optionally substituted hydrocarbon groups, such as alkyl, aryl, cycloalkyl, arylalkyl, hydroxyalkyl, hydroxyaryl, hydroxycycloalkyl, and hydroxycyclic aryl , But not limited by it. Ri and R2 may also include organic linkages of (poly) amidamine, (poly) ester, (poly) urethane, (poly) urea, (poly) ether, and (poly) carbonate, but are not subject to their organic linkages limit. Another requirement is that h and R2 must not both be hydrogen at the same time. Polyfunctional (meth) acrylate monomers can be obtained from the following materials, such as trimethylolpropane triacrylate, isopentaerythritol tetraacrylate, tripropylene glycol diacrylate, and diisopentaerythritol pentaacrylate Make up. The monofunctional poly (meth) acrylate system is shown in Formula Π:

Y

Rc 〇

Formula II 1 1-200307696 where P is 0 or 1, η is an integer from 1 to 10,

Ra, Rb, and Re are hydrogen or methyl, respectively, preferably Ra is methyl or hydrogen and Rb and Re are both hydrogen; Y is oxygen (-0-), imino (-NH-), or Hydrocarbyl-substituted imine group (-NR! •, where R! Is a hydroxyl group, preferably an alkyl group); W is a divalent substituted organic linking moiety as required, preferably selected from one or more as required Substituted hydrocarbyl, hydrocarbyl ether, poly (hydrocarbyl ether), hydrocarbyl ester, poly (hydrocarbyl ester) and poly (hydrocarbyl ether hydrocarbyl ester) group, more preferably selected from olefin, alkylene ether, polyether , Polyesters, alkylene esters and polyether polyesters, X is an organic linking moiety of which the valence is optionally substituted, which is preferably selected from one or more substituted hydrocarbon radicals or hydrocarbon radicals as required Ether, poly (hydrocarbyl ether), hydrocarbyl ester, poly (hydrocarbyl ester) and poly (hydrocarbyl ether hydrocarbyl ester) group, more preferably selected from olefins, alkylene ethers, polyethers, polyesters, and alkylenes The group of the group consisting of a base ester and a polyether polyester, preferably Υ is an oxy group, and ^ is a methyl or hydrogen group and Rb and Re are both hydrogen (that is, Formula II is represented by mono (meth) acrylate . It is desirable that the combination of the amino compound of formula I and the (meth) acrylated monomer of formula I must include at least one hydroxyl functionality. The anhydride group-containing compound is represented by Formula I I I: 200307696

Formula III wherein P is 0 or more, preferably 0; η is 1 or more; ^ is 1 when ρ is ο; m is 1 or more, preferably 1 to 40; Z is substituted as necessary Organic linking moiety, which is selected from one or more optionally substituted hydrocarbyl, hydrocarbyl ether, poly (hydrocarbyl ether), hydrocarbyl ester, poly (hydrocarbyl ester) and poly (hydrocarbyl ether hydrocarbyl ester), olefin, and alkylene Ethers, polyethers, polyesters, alkylene esters and polyether polyesters, oxy (-0-) or hydrocarbyl-substituted imine groups (-NR ^, where & is a hydroxyl group, preferably an alkyl group ), But not limited by it. R is an optionally substituted organic linking moiety, which is selected from one or more optionally substituted hydrocarbyl, hydrocarbyl ether, poly (hydrocarbyl ether), hydrocarbyl ester, poly (hydrocarbyl ester), and poly (hydrocarbyl ether hydrocarbyl) Esters), olefins, alkylene ethers, polyethers, polyesters, alkylene esters and polyether polyesters, oxy (-0-) or hydrocarbyl-substituted imine groups (-NL-, where L is A hydroxyl group, preferably an alkyl group, is not limited thereto. Each of the above anhydride groups forms a ring, the smallest and more preferably a 5-membered ring having 2 to 15-200307696 atoms on R. When IΏ is 1 or 2, R is preferably a group selected from the group consisting of optionally substituted alkyl, aryl, alkenyl, alkynyl, and alkalkyl groups. Therefore, each anhydride group part forms a ring, the smallest And more preferably a 5-membered ring having 2 atoms on R. When m is 2 or more, R is an optionally substituted organic linking moiety, which is selected from one or more optionally substituted hydrocarbyl, hydrocarbyl ether, poly (hydrocarbyl ether), hydrocarbyl ester, poly (hydrocarbyl ester) ) And poly (hydrocarbyl ether hydrocarbon ester), olefin, alkylene ether, polyether, polyester, alkylene ester and polyether polyester, so each anhydride group part forms a ring, the smallest and more It is preferably a 5-membered ring having 2 atoms on R, more preferably R is an ethylene linkage and Z, wherein Z is preferably a polyarene having an anhydride group and styrene as a copolymer, and styrene-Malay Examples of wild copolymers are shown in Formula IIIA:

Formula IIIA, a styrene-maleic anhydride copolymer wherein η and m are 1 or more. More particularly, the base is preferably any cyclic (di) carboxylic acid anhydride, such as maleic anhydride, succinic anhydride, orthophthalic anhydride. Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, bis (phenol) -A two Anhydride and benzophenonetetracarboxylic dianhydride are not limited thereto. The high molecular weight, anhydride-containing copolymer is preferably a styrene-maleic anhydride copolymer (SMA), and styrene-maleic anhydride in various proportions. 200307696 As required: t also can also use other hydroxyl-containing compounds with hydroxyl-containing amine (meth) acrylates. The hydroxyl-containing compound may be: (a) any optionally substituted monohydric alcohol or a school-substituted polyhydric alcohol such as methanol, ethanol, (poly) ethylene glycol, methoxypropanol, and trimethoxypropion alcohol. (b) a compound represented by formula IV, H0 x ~ f ~ Wp- γ-c-C = c / II V Jn o

Formula IV where 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 ... and Re are hydrogen (that is, when Y is oxygen, formula IV is (meth) acrylate); Y Is an oxy group (-0-), an imino group (-NH-) or a hydrocarbyl group-substituted imino group (-NR ", where & is a hydroxyl group, preferably an alkyl group); W is a divalent as required The substituted organic linking portion is preferably composed of one or more optionally substituted hydrocarbyl, hydrocarbyl ether, poly (hydrocarbyl ether), hydrocarbyl ester, poly (hydrocarbyl ester), and poly (hydrocarbyl ether hydrocarbyl ester). The group group is more preferably a group selected from the group consisting of alkenes, alkylene ethers, polyethers, polyesters, alkylene esters, and polyether polyesters, and X is a (n + 1) valence-substituted organic compound as required. The linking part is selected from one or more of hydrocarbyl, hydrocarbyl ether, poly (hydrocarbyl ether), which are substituted as necessary, from -17 series-200307696. The group constituting the group is more preferably a group selected from the group consisting of alkenes, alkylene ethers, polyethers, polyesters, alkylene esters, and polyether polyesters. (C) A hydroxyl group containing the following formula Was: ΗΟ, Λ r4-n, R3 factory Ο 1

II HO—R4 — · CNH——R2 — J m (that is, any substituent can be attached to any N or C atom of the N —substituted aminoformyl moiety); therefore, R 2 and R 3 are Η or The substituted hydrocarbon group, if necessary, is preferably a substituted alkyl group, an aryl group, a cycloaryl group, or an arylalkyl group. In each formula, R4 is a direct bond (that is, 0Η in the formula is connected to a nitrogen group or a carbonyl group) or a bivalent substituted organic linking portion as required, preferably a substituted hydrocarbon group as necessary, and more preferably Substituted alkylene, arylene, cycloalkylene, or arylalkylene, as needed, and m is 1 or more. The polyfunctional (meth) acrylate monomer of Formula II preferably corresponds to the following formula: P is 0;

Optionally, another step of the present invention includes an insertion reaction of a nitrogen-containing compound having an unsaturated end group or a pendant group of a (meth) acrylic acid ester, the nitrogen-containing compound is derived from the compounds of formulas I, VII, and 1Π via Reaction of carboxyl group, C00H-18- 200307696 and epoxy-containing compound with (meth) acrylate unsaturated. Epoxy-containing compounds with (meth) acrylate unsaturated systems are shown in Formula V and Formula VI: 〇 〇

〇 into Y ^ CH2 R6

Wherein V6 is -CH2-, -0-alkyl, etc., and R6 is fluorene or CH3, and

Embodiments The amine-containing amine compound of the present invention is prepared by adding a primary or secondary amine to a (meth) acrylate-based polyfunctional monomer via Michael addition. The reaction of the monomer having an amine alcohol is usually carried out in the presence of a polymerization inhibitor to avoid the (meth) acrylate unsaturated thermal polymerization reaction. The typical inhibitors used in Qin are hydroquinone and its derivatives, triphenyl antimony, and trinonylphenyl phosphite, and the inhibitors are usually added before the reaction starts. The amine is added dropwise to the monomer (and vice versa), causing the exothermic temperature to rise. During the addition, the temperature should be kept below 50 ° C. After the end of the exothermic reaction, the reaction was performed at 45 ° C for about 2 hours before termination. Examples of the amine alcohol include -19-200307696 monomethylethanolamine, monoethylethanolamine, diethanolamine, ethanolamine, butanolamine, and amine polyethylene glycol monomethyl ether, without being limited thereto. Examples of the polyfunctional monomer include, but are not limited to, trimethylolpropane triacrylate, isopentaerythritol tetraacrylate, tripropylene glycol diacrylate, and diisopentaerythritol hexaacrylate. Optionally, a similar reaction can occur between the alkylamine and the hydroxyl-containing (meth) acrylate. Examples of the alkylamine include, but are not limited to, diethylamine, dibutylamine, dipropylamine, and ethylenediamine. Examples of the hydroxyl-containing (meth) acrylate include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, diisoprene The reaction adducts of alcohol hydroxypentaacrylate, trimethylolpropane diacrylate, and hydroxyethyl (meth) acrylate with lactones (such as caprolactone and butyrolactone), but not limited thereto . Another option is to perform a similar reaction between an amino alcohol and a hydroxyl-containing (meth) acrylate. The reaction of a hydroxyl-containing amine acrylate with an anhydride is usually carried out in the absence of an organic solvent, which is a low-molecular weight mono- or dianhydride, and is usually carried out in the presence of a solvent of a high-molecular weight polymeric anhydride. Typical solvents used are propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, butyl ether glycol acetate, and butcarbitol acetate. In the absence of solvent synthesis, hydroxyl-containing amino acrylates are generally added to the reaction vessel with any polymerization inhibitors to prevent exothermic polymerization of unsaturated (meth) acrylates. Typical inhibitors used are hydroquinone and its derivatives, triphenyl antimony, and trinonylphenyl phosphite. At this stage, also-2 0-200307696, if necessary, a hydroxyl-containing compound as outlined in formula i v is added. The temperature of the mixture is maintained at 70 ~ 80 ° C. Anhydride can be added to the mixture while maintaining the reaction temperature in the range of 100 ~ 110 ° C. When the partial and total acid hydrazones are similar or when the total acid hydrazone maintains a constant for more than a period of time, it is confirmed as a complete reaction. < In the case of high molecular weight polymeric anhydrides, the solvent and the preferred formula IV containing a hydroxylation compound are generally added to a glass container first. Polymerization inhibitors were also added to prevent exothermic polymerization of unsaturated (meth) acrylates. Typical inhibitors are hydroquinone and its derivatives, triphenyl antimony, and trinonyl phosphite. The mixture is heated to 60 ° C at which the polymeric anhydride can be added slowly. Then add the hydroxyl-containing amine (meth) acrylate to the solvent in the container. Optionally, other non (meth) acrylated hydroxyl-containing compounds may be added at this stage. Maintain the temperature at 100 ~ 11 ° C and continue until almost all of the anhydride groups are ring-opened. When the acid hydrazone of the reaction product is almost equal to the acid hydrazone of the half ester, it can be confirmed that the reaction is complete. Anhydrides include styrene-maleic anhydride copolymers. Commercially available resins of styrene-maleic anhydride copolymers, such as SMA from E 1 f Atochem, and Leumal resins from Leuna Harze GmbH, preferably styrene-maleic anhydride copolymers. The molecular weight of the resin is 1 000 and 1 100,000, and the molar ratio of styrene to maleic anhydride is in the range of about (1: 1) to (3: 1), respectively. Suitable hydroxyalkyl (meth) acrylates Examples of partial esterification with styrene maleic anhydride copolymers are 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, hydroxypropyl methacrylate, N- Methyl methacrylamide and N-methyl methacrylamide. Examples of hydroxy monomers containing more than one (meth) -21-200307696 acrylate group are ditrimethylolpropane triacrylate, Isopentaerythritol triacrylate and diisopentaerythritol pentaacrylate. The photoresist composition having a very high photosensitivity is desirable, and it is preferably a (meth) acrylate monomer having a functionality of 1 or more. '' An example of caprolactone containing a hydroxy (meth) acrylate is a combination Carbide, commercially available products manufactured by Union Carbide Corporation, Tone M-100 and M- 200. Examples of alkoxy-containing hydroxy (meth) acrylates are polyethylene glycol monoacrylate, Polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, and a mixture of ethylene and propylene glycol (such as polyalkylene glycol monomethacrylate). The above examples can be obtained from Bisomer PEM63P and PPMM63E. The maleic anhydride ring of all copolymers does not necessarily need to react with (meth) acrylate monomers. For example, smaller amounts of amine- or hydroxyl-containing moieties can be used to form non (meth) acrylates, respectively. Amine or ester side chains. Side chains may affect the total solubility of the copolymer composition, especially in dilute alkaline solutions. An example of a possible non (meth) acrylate side chain is methylol polyethylene Another example is an alkanolamine of the formula HONR2R3 and an amine alcohol of the formula H0R4 (NHC0) mR2, where R2 and / or R3 may be alkyl, aryl, cycloalkyl, arylalkyl and m is greater than 1. Examples of epoxy-containing compounds with (meth) acrylate unsaturated are glycidyl acrylate, glycidyl methacrylate, glycidyl methyl methacrylate, 4-hydroxybutyl acrylic acid Ester glycidyl ether, 3,4-epoxy-cyclohexyl methyl acrylate, and 3,4-epoxy cyclohexyl methacrylic acid 22-200307696 methyl ester are not limited thereto. The terms "optionally substituted" and / or "optionally substituted" as used herein (unless there is an additional list of substituents) means one or more of the following (or substituted with) : A carboxyl group, a sulfo group, a methylamino group, a hydroxyl group, an amine group, an imino group, a nitrogen group, a hydrogen thio group, a cyano group, a nitro group, a methyl group, a methoxy group, and / or a combination thereof. If necessary, the base system includes all the chemically possible compositions in the same (or possibly 2) plural part of the above-mentioned base (for example, if the amine group and the sulfo group are directly connected to each other). Preferred optional substituents include: carboxyl, sulfo, hydroxyl, amine, hydrogenthio, cyano, methyl, and / or methoxy. The same terms “organic substituent” and “organic group” (referred to as organic [of]) are used to indicate any monovalent or polyvalent moiety (connected to one or more other parts as necessary), which includes a Or more carbon atoms and optionally one or more other heteroatoms. The organic group may include an organic hetero group (a known organic element group), which includes a carbon-containing monovalent group, but is a free atomic group compared to other carbons (for example, an organic sulfur group). The organic group may alternatively or additionally include an organic group containing any organic substituent, which has a free atomic valence in a 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). A monovalent group of a heterocyclic 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 -23-200307696 monovalent or polyvalent moiety (connected to one or more other parts 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. Hydrocarbyl radicals include β divalent radicals formed by removing two hydrogen atoms from a hydrocarbon, where free atomic valences are not linked to double bonds. Hydrocarbylidene system · Includes a divalent group (represented by R2C =) formed by removing two hydrogen atoms from the same carbon atom of a hydrocarbon, where the free atomic valence is connected to a double bond. The hydrocarbon fluorenyl group includes a trivalent group (represented by RC ^) formed by removing 3 hydrogen atoms from the same carbon atom of a hydrocarbon, in which a free atomic valence is connected to a reference bond. The hydrocarbyl group may include any saturated, unsaturated double bond and / or reference bond (for example, alkenyl and / or alkynyl, respectively) and / or aromatic group (for example, aryl) and those which 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 · An oxy group, a thio group, a fluorenylene group, a fluorenyl group, an amine group, an amine group, and / or a nitrogen group and / or a combination thereof. The organic group system includes all chemically possible combinations of the same part plural (preferably 2) of the above-mentioned carbon atom and / or heteroatom-containing portion (for example, if the alkoxy group and the hydrocarbon group are in direct contact with each other, it is represented as an alkoxyalkyl group) . 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 connected to 2 other moieties), any mentioned -24-200307696 oxo, radical or part is a unit price kind. A radical represented by a chain of three or more atoms, all or part of which is linear, branched, and / or cyclic (including helical and / or fused rings). The exact number of atoms can be described in detail as an exact substituent such as a Crx organic group, which is an organic group representing a number of atoms with 1 to χ atoms. In any formula described herein, if more than one substituent is not indicated in this section to be connected to any particular atom, the substituent may replace any hydrogen atom connected to other atoms and / or in this section It can be in any useful position (chemically appropriate) and / or have 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 (eg, 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 18 carbon atoms. Particularly preferred is a carbon atom comprising 1 to 10 (inclusive). Unless the context clearly indicates otherwise, plural forms used herein can be construed to include the singular and vice versa. The term "effective" (for example, reference to treatment, use, product, material, compound, monomer, oligomer, polymer precursor, and / or polymer of the present invention) means that when referring to the above materials, if used correctly Where materials, compounds, compositions, monomers, oligomers, polymer precursors, and / or polymers required for addition or incorporation into any of the uses and / or applications described herein characteristic. The term "appropriate" means a functional group that is consistent with the manufacture of an effective product-25-200307696. The substituent of the repeating unit may be selected to improve the compatibility of the polymer and / or resin material, which may be organized and then inserted to form an effective material. Therefore, the size and length of the substituents can be selected to make the resin fully-utilize intense entanglement or insertion or it may or may not contain other chemical reactions. 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 the present 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, cage compounds, crown compounds, Cryptands, inclusion compounds, intercalation compounds, phase compounds, ligand compounds, non-stoichiometric compounds, organometallic complexes, 7Γ-adducts, solvates, and / or hydrates), isotropic Department of substituted form, polymer configuration [such as homo-, copolymer, random, graft or block copolymer, linear or branched copolymer (such as star and / or side chain copolymer), high branched copolymer And / or dendritic macromolecules (of the type 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 (eg : Polymers in the same row, opposite row, or hetero row)], polymorphs (eg, staged, crystalline, amorphous, phase, and / or solid solution) may be a combination and / or a mixture 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 herein, and may be combined in a single example. Conversely, the different features of the present invention are described briefly in a single instance of this text, and in separate or appropriate subcombinations. The term "including (including)" is used as a non-missing list, and may include or not include any other additional appropriate nouns, which are detailed-such as one or more further features, compositions, ingredients And / or substituents. · Another aspect of the invention is described in the scope of patent application. In some specific embodiments, the multifunctional (meth) acrylated mono system is shown in Formula 11a:

X——Y——W——c— ~ c L Jp | 〇 Formula Ila where P is 0 or 1 (that is, when p is 0, γ is directly connected to the carbonyl group), and η is 1 to 10 Integer

Ra, Rb, and Re are hydrogen or methyl, respectively, preferably Ra is methyl or hydrogen and 1 ^ and Re are both hydrogen (that is, formula I is represented as (meth) acrylate); X and W are respectively Divalent optionally substituted organic linking moiety, which is selected from one or more optionally substituted hydrocarbyl, hydrocarbyl ether, poly (hydrocarbyl ether) 'hydrocarbyl ester, poly (hydrocarbyl ester), and poly (hydrocarbyl ether hydrocarbyl) A group of a group consisting of an ester) is more preferably a group selected from the group consisting of an ene, an alkylene ether, a polyether, a polyester, an alkylene ester, and a polyether polyester, and -27-200307696 Y is an oxy group ( -0 ·), an imino group (-NH-), or an imino group substituted with a hydrocarbon group (-NR!-, L is a hydrocarbon group, preferably an alkyl group). The meridian-containing compound may be a compound other than the formula I V a:

〇

η Formula IVa where P is 0 or 1 (that is, when ρ is 0, γ is directly connected to the carbonyl group), 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 1 ^ and Re are both hydrogen (that is, formula I is represented as (meth) acrylate); X and W are respectively Divalent optionally substituted organic linking moiety, which is selected from one or more optionally substituted hydrocarbyl, hydrocarbyl ether, poly (hydrocarbyl ether), hydrocarbyl ester, poly (hydrocarbyl ester), and poly (hydrocarbyl ether hydrocarbyl) A group consisting of an ester), more preferably a group selected from the group consisting of an olefin, an alkylene ether, a polyether, a polyester, an alkylene ester, and a polyether polyester, and Y is an oxy group (-0-) , An imino group (-NH-) or a hydrocarbyl group-substituted imino group (-NIV, Ri is a hydrocarbon group, preferably an alkyl group). Description of the preferred embodiments Description of the preferred embodiments-The present invention is described by, but not limited to, the following preferred embodiments. Example 1 200307696 This example is based on the invention of the present invention to illustrate the preparation of a hydroxylamine-containing acrylate for use in a composition. 750 grams of trimethylolpropane triacrylate (TMPTA) was added to the flask, and then 11.4 grams of trinonyl phosphite (TNPP) and 1.9 grams of triphenylantimony were added. 187.5 g of monomethylethanolamine (MMEA) was added to the mixture over 40 minutes *, and the reaction temperature during the exothermic period was maintained below 50 ° C. When the exothermic reaction was completed, the temperature was maintained at 45 ° C for 2 hours to produce a yellow liquid product. This single system is represented as monomer A, and the reaction is as described in Formula VI A below.

VIA 200307696

Formula VIB (Example 2) 600 g of TMPTA, 9.0 g of TNPP, and 1.8 g of TPS were added to the flask, and then 300 g of MMEA was added to the mixture over 40 minutes. The reaction temperature during the exothermic period was maintained below 5 ° C. When the exothermic reaction was completed, the temperature was maintained at 45 ° C for 2 hours to produce a yellow liquid product. This single system was designated as monomer B. 500 g TMPTA, 9.7 grams of TNPP, and 1.9 grams of TPS were added to the flask, and then 412 grams of MMEA was added to the mixture over 40 minutes. The reaction temperature during the exotherm was maintained at 50 ° C Below C. After the exothermic reaction is completed, the temperature is maintained at 45 ° C for 2 hours to produce a yellow liquid product. This single system is represented as monomer C. This example is based on the present invention to illustrate the low molecular weight amino acid (methyl ) Preparation of acrylic esters. Add 80 grams of monomer A to the flask, and then add 1.1 grams of 4--30-200307696 ethyl morpholine, 0.3 grams of TPS, and 0.3 grams Hydroquinone (HQ). Heat the mixture to 75t Celsius before adding 150 grams of phthalic anhydride (PA) over 20 minutes. An exothermic temperature increase is observed. The reaction is matured until all the anhydride is used up The total acid content is 1 12 mgKOH / g, and the product is expressed as a single D, the reaction is as described in Formula VIB. 300 grams of monomer B was added to the flask, and then 1.0 grams of 4-ethylmorpholine, 0.25 grams of TPS, and 0.25 grams of hydrogen were added. Quinone (HQ). Heat the mixture to 65t Celsius before adding 197 grams of PA more than 20 minutes. An exothermic temperature increase is observed. The reaction is matured until all of the anhydride

Run out. The total acid hydrazone was 163 mgKOH / g, and the product was expressed as monomer E. 300 grams of monomer B was added to the flask, and then 1.0 g of 4-ethylmorpholine, 0.25 g of TPS, and 0.25 were added. Grams of hydroquinone (HQ). Heating the mixture to 87 ° C before adding 203 grams of tetrahydroxyphthalic anhydride (THPA) over 20 minutes, an exothermic temperature increase was observed. This reaction is performed until all the anhydride is used up. The total acid hydrazone was 156 mgKOH / g, and the product was expressed as monomer F. Example 3 This example illustrates the preparation of a mixture of high molecular weight amino anhydrides. 263 grams of monomer A was added to the flask, and then 0.8 grams of 4-ethylmorpholine, 0.2 grams of TPS, and 0.2 grams of HQ were added. The mixture was heated to 99t Celsius before 73 grams of PA was added over 10 minutes to produce an exothermic reaction. The mixture was aged for 50 minutes and then 43 g of a styrene-maleic anhydride copolymer (SMA1 000, MW5 5 00, 1: 1 styrene: maleic anhydride) was added 200307696. A yellow dispersion was obtained after one hour. The final acid hydrazone was 102 mgKOH / g, and the product was expressed as monomer G.

Example 4 This example describes the preparation of amino acid (meth) acrylates based on pyromellitic dianhydride (PMDA). 132 grams of hydroxyethyl methacrylate, 170 grams of PMDA, 0.25 grams of TPS, and 0.25 grams of HQ were added to the flask, and then heated to 67 ° C. 1.0 g of tetraethylmorpholine was added to the mixture at this temperature to cause an exothermic reaction. The reaction was carried out for 3 hours and then 123 g of monomer B was added over 45 minutes. Add 70 grams of acid (meth) acrylate SRD 1042 (commercially available product, UCB chemistry) to reduce viscosity. After 30 minutes, an additional 0.25 grams of TPS and HQ were added. The reaction was matured for 4 hours, and the final acid hydrazone was 209 mgKOH / g, and the product was expressed as product hydrazone. 45 g of hydroxyethyl methacrylate, 150 g of PMDA, 79 g of PI ac cel FA2D (caprolactone-hydroxyethyl acrylate adduct, Japan Daicel Chemical Product), 0.04 g of TPS, and 0.04 Grams of HQ were added to the flask and then heated to 71 ° C. At this temperature, 0.71 g of -32-200307696 tetraethylmorpholine was added to the mixture to produce an exothermic reaction. The reaction was performed for 2 hours, and then 120 g of monomer C was added at 110 ° C for more than 65 minutes. A mixture of 50 g of TMP (E0) TA and 100 g of acid (meth) acrylate SRD1 042 was added to reduce viscosity. Then, 3 g of TNPP was added to the < mixture, and the reaction was matured for 2.5 hours, and finally the acid was 191 mgKOH / g-, and the product was expressed as product J. Example 5 This example describes a method for preparing a high Tg and a high molecular weight amino acid methacrylate based on a styrene-maleic anhydride copolymer and a hydroxyl-containing amino acrylate. 50.2 grams of hydroxyethyl methacrylate (HEMA), 217 grams of propylene glycol methyl ether acetate, 0.27 grams of triphenyl antimony, and 0.27 grams of hydroquinone were added to a 1 liter glass container, and The mixture was heated to n0 ° C. Then, 75.0 g of a styrene-maleic anhydride copolymer (SM A1000) was slowly added over 30 minutes. And another 40 grams of propylene glycol methyl ether acetate was added. Then, 102 g of a styrene-maleic anhydride copolymer (SMA2000, MW 7500, 2: 1 styrene: maleic anhydride) was slowly added over 30 minutes, and the mixture was matured until a clear liquid was obtained. After adding 96.6 grams of hydroxyl-containing amino acrylate A to the mixture over 20 minutes, a highly viscous material was obtained immediately. Dilute the material with 56 grams of water to obtain a yellow sticky liquid. This product is designated as copolymer K. Example 6 This example evaluates the water solubility of resins D, E, F, G, H, J and κ. The evaluation was performed by adding a certain amount of deionized water to each resin sample, -33- 200307696, and then observing whether a homogeneous mixture was obtained or whether the water phase and the organic phase were separated. Resin Η and J have very high viscosity and are heated in a microwave oven or a conventional oven to shorten the dissolution time. The results are shown in Table 1. Table 1. Evaluation results of water solubility Resin addition amount Deionized water phase separation appearance D 15 5 No clear liquid E 10 5 No clear liquid F 30 15 No clear liquid G 12 4 No clear liquid Η 40 20 No 淸The clear liquid J 40 10 has no clear liquid. The results show that the resins D, E, F, G, H and H of the specific examples are: [water solubility can be imparted, and no separation of the water phase and the organic phase was observed. Example 7 This example evaluates the ability of amino (meth) acrylates to add water dilubility / dispersibility characteristics to general water-incompatible resins. The amino acid acrylates are first diluted in water, then the diluted resin is added to the water-insoluble resin and the mixture is dispersed. Confirm the appearance of the mixture for any signs of phase separation. If the mixture can absorb an additional amount of water, a larger amount of water can be added. The non-tacky properties were evaluated by coating the resin mixture onto a copper plate and heating the plate at 80 ° C for 10 minutes or more in an oven. The film was evaluated as non-tacky if no finger marks remained on the film surface. -34- 200307696 The basic solubility of the copolymer (at 30 ° C in a 1% Na2C03 solution) is measured using a spray unit containing an alkaline solution. The amount of the copolymer remaining on the plate was confirmed after spraying at a 30-second interval in a short period containing an alkaline solution. The results of all evaluations are summarized in Table 2. Table 2. Results of water solubility, non-tackiness, and basic visualization Composition I Π IV V VI Additive resin (% water) D (25) D (25) F (33) G (25) H ( 33) Η (33) Usage, g 5 3 5 5 5 5 ACA210P1, g 15 0 15 15 15 0 SRD10431, g 0 12 0 0 0 0 SRD10741, g 0 0 0 0 0 17 Add water, g 0 0 1.5 1 1 1 Appearance: liquid liquid, liquid, liquid, liquid, liquid, liquid, liquid, liquid, phase separation -fnr ^ \\\ no yfrrr no ^ rrr Μ no tacky yes yes yes yes is alkaline The degree is, < 1 is, < 1 is, < 1 is, < 1 is, < 1 is > 5 minutes, minutes, minutes, minutes, minutes and minutes-35-1 ACA210P is epoxy epoxy cyclohexyl acrylic acid Ester acrylate methyl methacrylate / acrylic resin, Japan Dai ce Bu UCB products. * SRD1 043 is an acid-functionalized, rubber modified epoxy baseline phenolic resin in 30% methoxypropyl acetate, a product of UCB Chemicals. * SRD1 074 is a styrene-malenomethacrylate half ester in 40% methoxypropyl acetate, a product of UCB Chemicals. It can be found that amino acrylates D, E, F, G, H, and J can provide 200307696 water dilubility / dispersibility to resins ACA210P, SRD1043, and SRD1074 that were originally water-insoluble resins, while maintaining this type Desired properties of the resin, such as non-tackiness and alkaline visualization before hardening. Example 8. This example evaluates the water-thinnability, non-tacky properties of the copolymer κ, and the visual inspection degree ° _ I Π Π copolymer K 20 g 20 g 24 g deionized water 0 g 1 g 2.5 g Phase separation No Arrr No tackiness < 10 minutes < 10 minutes < 10 minutes Basic solubility 30 seconds 30 seconds 30 seconds A specific example of finding copolymer K can insert water into the resin, where the resin remains Non-tacky, usually associated with SMA- (meth) acrylate half-esters. Alkaline solubility is also well commented. Example 9 This example describes the treatment of a low molecular weight product which is finally capped with a compound of formula V. Add 600 grams of trimethylolpropane triacrylate (TMPTA) to the flask, and then add 9 grams of trinonylphosphite (swelling and K8 grams of triphenyl antimony (TPS). 300 grams of Monomethylethanolamine (MMEA) was added to the mixture over 40 minutes. During the exothermic reaction, the reaction temperature was maintained below 50 ° C. After the exothermic reaction was completed, the temperature was maintained at 45 ° C for 2 hours to produce a yellow liquid The oligomer is expressed as oligomer L. -36- 200307696 300 g of oligomer L, 1.02 g of 4-ethylmorpholine, 0.25 g of triphenylantimony, and 0.25 g of hydrogen Quinone was added to the flask. The mixture was heated to 90 ° C and 202.87 grams of tetrahydroxyphthalic anhydride was added to the mixture in the flask at a temperature exceeding 20 minutes. The reaction · temperature system was maintained at about Celsius during the exothermic reaction. 90 ° C. After the end of the exothermic reaction, the temperature was maintained at -90 ° C for 2 hours. The final acid series of the final product was 156 mgKOH / gm. This oligomer was designated as oligomer M. 291.5 g of oligo Polymer M, 0.75 g of 8% solution chromium octoate, and 0.4 g of hydrogen Add to the flask. Heat the mixture to 100 ° C and add 207.65 grams of 4-hydroxybutyl acrylate glycidyl ether to the mixture in the flask while maintaining the temperature at 100 ° C for more than 1.5 hours. During the exothermic reaction, the temperature of the mixture in the flask was maintained at about 1000 ° C. for 10 to 15 hours. The residue acid of the final product was 6.6 mg KOH / gm ′ and the residue epoxy The base content is 4.7%. The final product is expressed as oligomer N. Example 10 This example describes the use of copolymer N in an alkali developable photoresist formula ° I Π ACA210P 55 g 55 g 55 g pigment paste 15 Grams 1.5 grams 1.5 grams modified flow agent, fluidity additives 1 grams 1 grams 1 gram propylene glycol methyl ether acetate 30 grams 30 grams 30 grams of light starter blend (4.5 ρ Irgacure 907, 0.5 p iso Propyl 9-oxomonothiopiran) 6.25 g 6.25 g 6.25 g copolymer N 0 g 9.3 g 0 g Ebecryl 81 0 g 0 g 0 g 200307696 Ring-P ACA250 is commercially available from Daicel Chemical Unsaturated propionic acid polymer. The pigment paste is based on 60 parts by weight of phthalocyanine blue pigment. Material, plus honing with a three-roller mill to 40 parts by weight of diisopentaerythritol hexaacrylate having a particle size of 5 to 10 microns. Ebecryl 81 is an amine acrylate commercially available from UCB Chemical. Formula I, Π, and ΙΠ are tested for their alkaline visualization and sensitivity. Each formulation is coated on a pre-cleaned copper plate using a wire ingot coater to produce a wet film of about 25-30 microns. The coated plate was placed in an oven at 80 ° C for 2 to 5 minutes to rapidly dry the solvent, and a non-sticky coated plate was manufactured. The coated plate was exposed to an iron-doped metal halogen lamp with a power of 3 kW, via a glass plate, and via a 21-steps Stouffer tablet. The UV intensity on the coated surface was about 10 mW / cm2. The exposure time is 5 to 60 seconds. The coating of the unhardened portion was developed using a 1% potassium carbonate solution at 35 ° C for 1 minute, and it left an image of the 21-stage Stofo ingot on the coating plate. The number of stages remaining on the plate is valuable, so the highest number of stages remaining is indicated as the highest sensitivity of the formulation. The following table shows the last stages of different formulations remaining on the board, and the board was exposed to different exposure times. -3 8-200307696 Exposure time (seconds) I Π Π 5 5 7 7 10 7 9 8 15 8 11 9 20 9 12 11 30 10 12 12 40 12 13 13 50 14 13 15 60 14 14 15 The formulation of oligomer N can improve the sensitivity of photoresist under low exposure conditions. Schematic description

Claims (1)

200307696 Patent application scope: 1 · A radiation-hardenable composition, which is dilutable and / or dispersible in an aqueous solution, and includes a hydroxyl-functional amine (meth) acrylate and an anhydride-containing compound Reaction product in which a hydroxyl-functional amine (meth) acrylic acid ester is a primary, or more preferably a secondary amine, added by Michael (s :) _ to a polyfunctional (meth) acrylate Monomers in which the amine formula I is as follows: In the formula, R: and R2 are hydrogen or optionally substituted hydrocarbon group, preferably substituted alkyl, aryl, cycloalkyl, arylalkyl, hydroxyalkyl, hydroxyaryl, or hydroxy ring, if necessary. Alkyl and hydroxy ring aryl, and I and R2 may optionally be selected from (poly) amidamine, (poly) ester, (poly) urethane, (poly) urea, (poly) ether, and (poly) ) The organic linking part of the base group of the carbonate group is subject to the limitation that R1 and r2 must not be hydrogen at the same time. 2. The radiation-hardenable composition according to item 1 of the patent application scope, wherein the multifunctional (meth) acrylated single system is as shown in Formula II: 〇 Formula II where P is 0 or 1, η is an integer from 1 to 10, ", envy and R. Respectively hydrogen or methyl, preferably {^ is methyl or hydrogen and ... and ^ are both hydrogen, a 40-200307696 w is a divalent organic linking moiety which is optionally substituted, which is preferably selected from one or More optionally substituted bases of the group consisting of hydrocarbyl, hydrocarbyl ether, poly (hydrocarbyl ether), hydrocarbyl ester, poly (hydrocarbyl ester) and poly (hydrocarbyl ether hydrocarbyl ester), more preferably selected from alkenes and alkylenes Ethers, polyethers, polyesters, alkylene esters, and groups of polyether polyesters, where Y is an oxy (-0-), imine (-NH-), or hydrocarbyl-substituted imine (-NR!-, Where M is a hydroxyl group, preferably an alkyl group), and X is an organic linking moiety of which the valence is optionally substituted, which is selected from one or more optionally substituted hydrocarbon groups, hydrocarbon groups Ether, poly (hydrocarbyl ether), hydrocarbyl ester, poly (hydrocarbyl ester) and poly (hydrocarbyl ether hydrocarbyl ester) group, more preferably selected from olefin, alkylene ether, polyether, polyester, and alkylene The group consisting of a base ester and a polyether polyester is subject to the limitation that the composition of the amine compound of the formula I and the (meth) acrylate monomer of the formula Π must be Must contain at least one hydroxyl functionality, and the anhydride-containing compound in it should be as shown in formula: In the formula, P is 0 or more, preferably 0, and η is 1 or more. When ρ−4,200,307,696 is 0, η is 1, and m is 1 or more, preferably 1 to 40. Z and R are each optionally substituted organic linking moieties, which are preferably selected from one or more optionally substituted hydrocarbyl, hydrocarbyl ether, poly (hydrocarbyl ether), hydrocarbyl ester 'poly (hydrocarbyl ester), and poly (Hydrocarbyl ether hydrocarbyl ester), olefin, alkylene ether, polyether, polyester, alkylene ester and polyether polyester, oxy (_ 0 _), or imide group (-Nl- In the formula, R: is a radical, preferably a radical), and the limitation is that each anhydride moiety forms a ring, and the smallest and more preferable is a 5-membered ring having 2 atoms on R. 3. The radiation-hardenable composition according to item 2 of the patent application range, wherein m is 1 or 2, and R is selected from the group consisting of optionally substituted alkyl, aryl, alkylene, acetal, and cycloalkyl The foundation of the ethnic group. 4. The radiation-curable composition according to item 2 of the patent application range, wherein R is an ethylene bond bonded to Z, and Z is preferably a polyarylene. 5. The radiation-curable composition according to item 4 of the application, wherein the polyarylene is a polystyrene of an anhydride group and a styrene copolymer. 6. The radiation-curable composition according to item 5 of the patent application, wherein the anhydride is any cyclic (di) carboxylic acid anhydride. 7 · The radiation-hardenable composition according to item 1 of the patent application scope, wherein the hydroxy-containing compound is used together with a hydroxy-functional amine (meth) acrylate, and the hydroxy-containing compound includes: a) any substituted as necessary Monohydric alcohols or substituted polyhydric alcohols as required, or b) Compounds of formula IV: 200307696 HO X — [— Wp-YC—C = C 1 butyl p 丨 丨 V Jn ο Formula IV-where P is 0 Or 1, η is an integer of 1 to 7, Ra, Rb and Re are hydrogen or methyl, respectively, preferably Ra is methyl or hydrogen and Rb and R. Both are hydrogen, and W is an organic linking moiety which is substituted as necessary, preferably selected from one or more optionally substituted hydrocarbyl, hydrocarbyl ether, poly (hydrocarbyl ether), hydrocarbyl ester, poly (hydrocarbyl ester) ) And poly (hydrocarbyl ether hydrocarbon ester), olefin, alkylene f-ether, polyether, polyester, alkylene ester and polyether polyester. The group 'X is (n + 1). The substituted organic linking moiety is preferably selected from one or more substituted hydrocarbyl, hydrocarbyl ether, poly (hydrocarbyl ether) 'hydrocarbyl esters, poly (hydrocarbyl ester) and poly (hydrocarbyl ether hydrocarbyl ester), Groups of groups consisting of alkenes, alkylene ethers, polyethers, polyesters, alkylene esters, and polyether polyesters, Y is oxy (-0-), imino (-NH-), or substituted with a hydrocarbon group The imino group (-# NL- 'I is a hydroxyl group, preferably an alkyl group) or a hydroxyl-containing compound has the following formula: Η0, Λ' r4-n, and / or -43- 200307696 〇 HO——R4— — II CNH——R2 where R 2 and R 3 are η or optionally substituted hydrocarbon groups, preferably substituted. Substituted courtyard, aryl, cycloaryl, or aryl groups Alkyl, 1-4 is a direct bond or a divalent organic linking moiety which is substituted as necessary in each formula, preferably a substituted hydrocarbyl, alkylene, arylene, cycloalkylene, Or arylalkylene, and m is 1 or more. φ 8 · The radiation-hardenable composition according to item 1 and 2 of the scope of patent application, in which the nitrogen-containing compound is derived from the reactive compound of formula I, Π, and Π with a free carboxylic acid group, C00H, and further with Formula V and IV reaction of epoxy compounds with (meth) acrylate unsaturated compounds' Formulas V and IV are as follows: In the formula, R6 may be -CH2-, -0 alkyl, etc., and is Η or CH3, and 〇 Formula VI-44-200307696 wherein R7 may be -CH2-, -0-alkyl, etc., and R8 is fluorene or CH3. 9 · A method for preparing a radiation-curable composition, which is dilutable and / or soluble in an aqueous solution, which comprises the following steps: a. Selecting a polyfunctional monosystem from trimethylolpropane triacrylate '(TMPTA), isopentaerythritol tetraacrylate, tripropylene glycol diacrylate · (TPGDA) and diisopentaerythritol hexaacrylate, and at least one polymerization inhibitor is selected from hydroquinone and / Or its derivatives, triphenyl antimony, and trinonyl phosphite groups, and the inhibitor is added before the reaction begins, b. Slowly add a primary or secondary amine, which is A group selected from the group consisting of monomethylethanolamine, monoethylethanolamine, diethanolamine, ethanolamine, butanolamine, and amine polyethylene glycol monomethyl ether, c. Maintaining the reaction temperature during step (b) as 5 (below TC, and at the end of the exothermic reaction in step (b), the reaction is maintained at 45 ° C for about 2 hours, d. Dilute or disperse the product obtained in step (c) in water, and e. The solid material is separated from the solvent in step (d). 0 · A method for preparing a radiation-hardenable composition, which is dilutable and / or soluble in an aqueous solution, which comprises the following steps: a. A hydroxyl-containing (meth) acrylate is selected from hydroxyethyl acrylic acid Ester, hydroxyethyl methacrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, diisopentaerythritol hydroxypentaacrylate, and trimethylolpropane diacrylate Groups of groups, and hydroxyalkyl (meth) acrylates and lactones, and adducts with alkylene oxides as needed, and at least one polymerization inhibitor are selected from hydroquinones and / or derivatives thereof, 200307696 Triphenyl antimony and trinonyl phosphite are mixed together. The inhibitor is added before the reaction starts. B. Slowly add an alkylamine, which is selected from the group consisting of diethylamine, dibutylamine, dibutylamine Groups of groups consisting of propylamine and ethylenediamine, c. Maintain the reaction temperature below 50 ° C during step (b), and at the end of the exothermic reaction in step (b), the reaction system is maintained at 45 ° C for about 2 Hours, d. Dilute the product from step (c) Disperse in water, and e · Separate the solid material from the solvent in step (d) if necessary. 1 1. The method for preparing radiation-hardenable composition as described in item 9 and 10 of the patent application, wherein the steps are Insertion reaction of nitrogen-containing compounds including (meth) acrylate unsaturated end groups or side groups, the nitrogen-containing compounds are derived from compounds of formulae I, Π and m via free carboxyl, COOH and epoxy-containing compounds respectively Reaction of (meth) acrylate unsaturated: 〇 Wherein R6 may be -CH2-, -0-alkyl, etc., and R6 is R or CH3, and Formula VI -46- 200307696 wherein R7 may be -CH2-, -0-alkyl, etc., and R8 is fluorene or CH3. 1 2. A method for preparing a radiation-curable composition, which is dilutable and / or soluble in an aqueous solution, including the following steps: a. Selecting a hydroxy-containing (meth) acrylate system from a hydroxyethyl group Acrylate, hydroxy 'ethyl methacrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (' meth) acrylate, diisopentaerythritol hydroxypentaacrylate, trimethylolpropane diacrylate The group of the ester group, and the reaction adduct of hydroxyalkyl (meth) acrylate with lactone, and optionally with alkylene oxide, and at least one polymerization inhibitor are selected from hydroquinone and / or its derivative Groups of triphenyl antimony, trinonylphosphite, and the inhibitor are added before the reaction begins, b. Slowly adding an amino alcohol, c. Maintaining the reaction temperature during step (b) Below 50 ° C, and at the end of the exothermic reaction in step (b), the reaction is maintained at 45 ° C for about 2 hours, d. Dilute or disperse the product obtained in step (c) in water, and e. It is necessary to separate the solid material from the solvent in step (d). 1 3-A method for preparing a radiation-curable composition, which is dilutable and / or soluble in an aqueous solution, which includes the following steps: i. Hydroxyl amine acrylate compound, added to at least one group selected from the group consisting of trimethyl methacrylate triacrylate, isopentaerythritol tetraacrylate, tripropylene glycol diacrylate, and diisopentaerythritol hexaacrylate Group polymerization inhibitors, wherein at least one group selected from the group consisting of hydroquinone and / or its derivative, triphenylantimony, and tri-nonylphenyl phosphate is added before the reaction starts. Polymerization inhibitor 9 ii. Raise the temperature of the reaction mixture to 70 ° C ~ 80 ° C, iii. Add the anhydride composed of mono or dianhydride to the mixture obtained in step (b), iv, Maintaining the reaction temperature between 100 ° C and 110 ° C, v. Diluting or dispersing the product obtained in step (d) in water, and vi. Separating solid materials from the solution in step (d) if necessary. 1 4. A method for preparing a radiation-hardenable composition, which is dilutable and / or β-soluble in an aqueous solution, which comprises the following steps: a. Dissolving in the formula IV as defined in formula IV A hydroxyl-containing amino acrylate compound of a solvent, which is a group selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, butyl ether glycol acetate, and butcarbitol acetate, and is added To the polymerization inhibitor, and the temperature is raised to 100 ° C, b. Slowly add the polymeric anhydride to the mixture of step (i), and optionally add a hydroxyl-containing amine (meth) acrylate and / Or other non- (meth) acrylic acid esterified hydroxylated compounds into the mixture while maintaining a temperature of 100 ° C to 110 ° C, 嚎 c. Dilute or disperse the product obtained from step (b) in water , And § d. If necessary, separate solid materials from the solution in step (d). 15. The radiation-hardenable composition according to claims 1 to 8 of the application, wherein the composition is added to a water-insoluble C00H functional polymer. 16. The radiation-hardenable composition according to item 15 of the scope of the patent application, wherein the non-aqueous 4 8-200307696 soluble functional polymer is selected from methyl methacrylate, epoxy epoxy cyclohexyl acrylate Modified methacrylate resin, acid-functionalized and rubber modified epoxy baseline phenolic resin in 30% acetoxy-methoxypropyl ester, styrene-horse in 40% methoxypropyl acetate The semi-ester of methacrylic acid anhydride is the base of the group. 17 · The method for preparing a radiation-hardenable composition according to claims 9 to 4 in the scope of patent application, wherein the separated solid material is added to a water-insoluble COOH functional polymer. 18 · Method for preparing radiation-curable composition according to item 15 of the scope of patent application ', wherein the water-insoluble functional polymer is selected from methyl methacrylate, acrylic acid cyclohexyl acrylate Acrylate resin, acid-functionalized and rubber modified epoxy baseline phenolic resin in 30% methoxypropyl acetate, styrene-maleic anhydride in 40% methoxypropyl acetate The base of a group of acrylate half-esters. 49 一 200307696 (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 drawing: 捌 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: