TW387000B - Thermosetting resin composition containing N-oxy compounds and producing process thereof - Google Patents

Description

A7 B7 V. Description of the invention (1. Field printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. The present invention relates to a hardening resin composition such as vinyl vinegar resin that can suppress coloring and is suitable for various uses. And a method for producing a hardenable resin composition. Love 1_Ming's background "Historic" Hardenable I synthetic resin (hereinafter, simply referred to as resin) It is known that if hardened, it will have excellent corrosion resistance, chemical resistance, and water resistance. Molded products with good mechanical properties, etc. Examples of the above resins include acetic acid resin, amino (meth) acrylic acid resin, unsaturated polyacetic acid resin, polyester (meth) acrylic resin, and acrylic resin slurry. Etc. The above-mentioned hardenability is the property of heating or irradiating light to harden the fat. "For example, the above-mentioned production of ethyl acetate resin-generally uses an esterification catalyst to react an epoxy compound with an unsaturated monobasic acid. However, Because these resins and their raw materials contain reactive groups such as ethyl groups, the resins are easily gelled during the production or storage due to the bonds between the reactive groups. In the past, it has been known that oxygen is effective in preventing the gelation of these resins into A. Therefore, during the manufacturing process, storage, or transportation, dry air can be circulated or the container can be opened at regular intervals, or the storage container can be lowered. The filling rate of the resin, work hard on these operations. However, such a part of the resin will be converted by the oxygen in the reaction and become a coloring compound. The obtained resin is obviously colored, for example, by Gardner color. The number shows 3 to 8. In addition, even if sufficient gas coexistence is often made, it is difficult to say that the gelation countermeasures of these resins are sufficient, and the possibility of causing gelation during transportation during the storage period of 1 month is extremely high. Wang Mech tree due to oxygenation (please read the precautions on the back first, then this page), νφ -4, the paper size applies the Chinese National Standard (CNS) A4 specification (21〇 > < 297mm) A7 V. Invention Therefore, in order to prevent condensation, various other methods have been studied. For example, in Japanese Patent Application Laid-Open No. 52-107090, it is disclosed that a thermosetting resin containing an active radical compound is stored and stabilized in the thermosetting resin. The thermosetting resin is a polymerizable unsaturated monomer in which the reaction product of epoxy resin and valeric acid and / or methacrylic acid < is dissolved in the polymerizable unsaturated monomer. Free radicals are very toxic, so you must pay attention to them. To prevent gelation and detect females, soils, and "quotes," he said, it is known that: adding a wall to the above resins, p-methoxyl , Third butyl catechin age, Shi Qin and other well-known inhibitors to improve storage stability. However, 'known polymerization inhibitors represented by any of the above, any one, polymerization: agent itself: coloring, 4, The obtained hardening is changed with time: tree moon H), the mouth is colored. That is, if the hardening resin composition is continuously exposed to outgassing, these polymerization inhibitors will be oxidized by dissolving in hardening oxygen 'It becomes a colored compound, and the curable resin group = colored. Furthermore, in order to further improve storage stability, if these polymerization inhibitors are used in combination or added in a large amount, the hardening resin composition tends to become longer, and the hardenability of the resin itself is impaired. These resins are easy to be colored 'Although they have excellent performance, they are also limited in use' In the fields of molding materials, materials, lining materials, coatings for FRP (fiber-reinforced plastic), the raw materials are used as The limited use of appearance. In other words, these resins are used in applications such as bath red, wash basins, and gel-coated surfaces where appearance is important, or applications requiring excellent light-hardening properties. -5 W-scale applications. Printed by the staff of the Central Standards Bureau of the Ministry of Economic Affairs Cooperatives A7 --------- ____ B7 V. Description of the invention (3) ~ The above becomes unsuitable ϋ, therefore, for example, the manufacture of a B which can suppress coloring and light color The method of alkenyl ester resin disclosed in U.S. Patent No. 3-34771 discloses the use of an esterification catalyst and the use of an epoxy compound and an unsaturated monobasic acid in the presence of triphenylsulfonium in an inactive atmosphere. And unsaturated polybasic acid reaction method. Also in Japanese Patent Publication No. 6-23 23 2, an esterification catalyst is used to disclose an epoxy compound and unsaturated monobasic acid and unsaturated in the presence of phosphorous acid and / or phosphorous acid di | Method of polyalkali acid reaction. However, when the above-mentioned method is used to produce an ethyl ester resin, or when the above-mentioned method is applied to the production of a urethane methyl) acryl resin or a polyester (/ meth) acrylate resin, In order to show obvious light color, a large number of additives such as triphenylphosphonium, phosphorous acid, and phosphorous acid diester must be introduced, and reacted in an inactive atmosphere or an oxygen-thin atmosphere. When manufacturing, it will cause raw materials and reactions. The problem of easy gelation. Intervention of the Invention · In order to avoid the above problems, Hachimoto et al. Determined to find out: Q 1 Ν-oxy groups and vinyl ester resins, urethane (meth) propane: ester resins, Unsaturated polyester resin, polyester (meth) acrylate tree: hardening resin composition of synthetic resins such as ancient acrylic «series resin slurry, two: excellent physical properties such as storage stability or hardening properties can be suppressed over time This color can be used for various purposes. The present invention is finally completed. = In view of the above problems, the purpose is to provide-a kind of hardenability t ° 2 it has excellent storage stability or hardenability and other physical properties, can be suppressed 1 I: interstitial coloring 'thus becomes a light color, and can be applied to various Use; (Please read the notes on the back before # 1 this page),-°

.--- I I -1- ί I-I scale is suitable -6 A4 size (210X297 male) 5. Description of the invention (4) and provide its manufacturing method. The curable resin composition of the present invention is a composition containing N-oxygen and synthetic resin, and the storage period under 60 days is more than 1 week, and the coloring degree obtained by the Hasen color number of the composition is 100. In the following, the difference in coloration between the composition before gelation during storage at 60 ° C and the Hasen color number of the composition before storage is less than or equal to 20, and 丨, 3, 3 _ When the weight part of tetramethylperoxybutyl-2-ethylhexylhexanoate is mixed with 100 parts by weight of the composition, the maximum heating temperature at 70 ° C when measuring the hardening characteristics is 100%. the above. In addition, such other hardened vegetable resin compositions of the present invention are printed with the formula ⑴ R1 R2 丨 Rc 〇 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (wherein, hydrogen atoms, _〇1 group, heart, R2, R3, and R4 each represent an alkyl group having a carbon number of i or more, and a rule 5 represents an alkyl group having a carbon number of 1 to 16 hydrogen atoms) and an N-oxyl group and a synthetic resin. In the curable resin composition, the synthetic resin is at least one selected from the group consisting of vinyl resin and aminomethyl ester as long as the synthetic resin has an unsaturation such as a double bond for polymerization reaction or crosslinking reaction. Acrylic resin grease, unsaturated polymer resin, poly (methyl) linden tree 7- This paper size is applicable to Chinese National Standard (CNS) Λ4 specification (210X297 Gong Λ7) 5. Description of the invention (5) Fat, propionic acid It is a resin in the group of resin slurry. In the curable resin composition, the ratio of 100 parts by weight of N-oxygen to synthetic resin is preferably 0.00001 to 1 part by weight. According to the present invention, it can provide -A hardening resin composition that not only preserves stability, but also has little coloring after storage, JL, and excellent hardenability. Therefore, this hardenable resin composition is suitable for use in, for example, male molding materials, injection molding materials, In the fields of lining materials, coatings, etc., it is especially suitable for applications that value appearance such as diluo cylinder, wash tank, gel coating, etc., and a wide range of uses such as applications where photocurable resins require excellent photocurability. The method for producing such a curable resin in the present invention is a reaction method in which the components forming the curable resin are reacted in the presence of N_M. In the above production method, 'the curable resin is preferably selected from the group consisting of ethylene fluorene resin and amine group. One of the resins in the group consisting of formic acid (fluorenyl) propionate resin and polyester (methacrylate resin). In the above manufacturing method, the amount of the base used is relative to the obtained curable resin. .OOOOi parts by weight to 丨 parts by weight. I know that it is the same type or heterogeneous "N-oxy group" added to the curable resin composition when the curable resin composition is manufactured. J 珠 口If the above method is used, the excellent physical properties such as corrosion resistance, chemical resistance, water resistance, heat resistance, and mechanical properties of the hardening resin are not impaired, and light-colored hardening resins can be effectively and sufficiently manufactured. '' Another aspect of the present invention A purpose, characteristics, and excellence, as described below -8-, I 1- I-1-—II. -------- Ϊ .----— install __ (please first Read the notes on the back side again # ^ This page)-Order the staff consumption of the Central Standards Bureau of the Ministry of Economic Affairs Printed on paper by the agency, suitable for financial purposes _Jiaxian (CNS) A4 specification (21QX297 public record_) Λ7 B? Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (6 can be fully understood. Also, the present invention The advantages are as follows. A more detailed description of one embodiment of the present invention is described below. In the present invention (the curable resin composition contains the aforementioned N_oxy group 4, and, for example, an ethyl acetate resin, Synthetic resins (hereinafter referred to as resins) such as urethane (meth) propionic acid ester, unsaturated polyester resins, polyester (meth) acrylate resins, and propionate-based resins, such as liquids, are known. This hardening resin: p-type is added to these resin towels, for example, oxy groups, or the components (raw materials) constituting the above resin are reacted in the presence of N-oxyl jaw, and the above formula is prepared. However, it can be easily obtained by further adding other resins or reactive monomers after molding. In d-curable resin composition, the storage period is preferably more than 1 week at 6 q; 、, * 'Usually these resin compositions can be stored in a dark place, but if the storage status in summer is considered It is possible to reach 40t :, so the number of staying days under 40 × is more than 2 months. At 40. (: The storage date of the next month or more is less than 6 months for the curing resin composition to be stored in a dark place at room temperature for at least 6 months. There is no obstacle when the curing resin composition becomes a product for circulation. The coloring degree obtained from the Hasson color number of the resin composition should preferably be 50 or less. Furthermore, if the coloring degree obtained from the Hasson color number of the composition is better. When the composition is visually inspected, the composition is not observed. The coloration is better, so the composition before gelation is preserved at 60 ° C, and the composition is kept. Σ The difference between the chromaticity of the person who is served by the limb number should be 20, which is a combination of hardening resin. Material at 70 c < Highest when measuring hardening characteristics

(Please read the notes on the back before filling in this education)

Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Λ7 ----B? V. Description of the invention (7) ~~ The temperature is 罝 100 t: above, and if it is above 5 °, it ensures the resin composition The hardened material may have higher mechanical properties or corrosion resistance, so it is more preferable. The N-oxyl group used in the present invention is not particularly limited, and specific examples thereof include 1-oxy-2,2,6,6-tetramethylhexahydropyridine, i_oxy-2,2,6,6 -Tetramethylhexahydropyridine-4-ol, 4-methoxy-2,2,6,6-tetramethylhexahydropyridine-1-oxy, 1-oxy-2,2,6,6-tetra Methyl hexahydro! 7-bital 4-methyl-acetic acid, 1-oxy-2,2,6,6-tetramethylhexahydropyridin-4-yl_2-ethylhexanoate, oxygen 2.2.6.6-Tetramethylhexahydropyridin-4-yl-stearate, oxygen _ 2.2.6.6- Tetramethylhexanidine hydrogen 11 ratio _4_yl. _4_ tert-butylbenzoate, bis (1-oxo-2,2,6,6-tetramethylhexahydropyridine_4-yl) succinate, bis〇_oxy_2,2,6,6-tetramethylhexahydropyridine_4 _Yl) adipate, bis (oxo_ 2.2.6.6- tetramethylhexahydropyridine_4-yl) sebacate, bis (1_oxo_ 2.2.6.6- tetramethylhexacloose P ratio Disease_4-yl) n-butylmalonate 'bis (〖_ oxy_2,2,6,6-tetramethylhexahydropyridine_4_yl) phthalate, bis (1_oxy_ 2.2 .6.6- Tetramethylhexahydropyridine_4_yl) isophthalate, bis (1_oxy_ 2.2.6.6- Tetramethylhexahydropyridine_4_yl) paraphthalate, bis (1_oxy _ 2.2.6.6- tetramethylhexahydropyridine _4_ ) Hexahydroparaphthalate, ^ _bis (1-oxo-2,2,6,6-tetramethylhexahydropyridine_4-yl) hexamethylenediamine, ^ _〇_oxy_2, 2,6,6_tetramethylhexahydropyridine_4-yl) hexylamine, 2.2.6.6 -tetramethylhexahydropyridine_4-yl) dodecylsuccinimide, 2.4.6-tris -[N_butyl · N_ (1_oxy_2,2,6,6_tetramethylhexapyridine_4_yl)]-S- —acridine, ^ oxy— ^ tetramethylhexahydropyridine 4-ketone and the like are not particularly limited. You can use only one of these N-oxygens, or -10- f paper size is applicable to Chinese national ST ^ s) Λ4 specification (210χτ ^^ ~~ ---- (Please read the precautions on the back before writing bridge_write (This page)-, 1T 3 Λ7 B7 V. Description of the invention Mix two or more types appropriately. In the present invention, the N-oxyl group which is more suitable for use can be exemplified by 4-hydroxy. Ά6_ Tetramethylhexapyridine] -oxygen , 4-methoxy-2,2,6,6_tetramethyl ~ late bite -1 · oxygen. These are toxic to you and excellent in operability, and a small amount of Timing has excellent storage stability. Also the present invention The above-mentioned resin to be used is not particularly limited, but at least one ^ k is derived from a vinyl ester resin, a urethane (meth) acrylate, an unsaturated polyurethane resin, and a poly (meth) acrylate resin. The vinyl ester resin is the most preferable resin in the acrylic resin slurry. The vinyl ester resin is not particularly limited, and for example, an epoxy compound and an unsaturated monobasic acid may be used by using a catalyst. The response can be obtained. The staff consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs printed the above ethyl acetate resin raw materials. The epoxy compound may be a compound having at least one epoxy group in the molecule, and is not particularly limited, but specific examples include bisphenols such as bisphenol A, bisphenols, and propylene oxide The epi-bis-glycidyl ether type epoxy resin obtained by the firing condensation reaction; the condensation reaction of phenols such as phenol, methylphenol, bisphenol, and formalin, namely the condensation reaction of novolac and epihalohydrin The obtained phenolic glycidyl ether epoxy resin; the glycidyl ether epoxy resin obtained by the condensation reaction of tetrahydrophthalic acid, hexahydrophthalic acid, benzoic acid and fluorene | Glycidyl ether type epoxy resin obtained by condensation reaction of bis or _ alcohols and epihalohydrin; amine glycidyl group obtained by condensation reaction of hydantoin or cyanuric acid and epoxy_propane Ether type epoxy resin, etc. And, -11-This paper size is applicable to Chinese National Standard (CMS) A4 specification (210X297 mm) Λ7 B7 V. Instruction (^ You can use this kind of epoxy resin and multi-acid test And / or biphasic compounds, compounds having an epoxy group in the molecule. These epoxy And only one kind can be used, and two or more kinds can also be appropriately mixed. 13 The unsaturated of the above-mentioned vinyl vinegar resin raw materials-test &gt; Don't limit, but specifically, for example, acrylic acid, nail, and bounty Hexabismuth and crotonic acid can also use semi-advances such as maleic acid, decomposing aconitic acid, and the like: 'These compounds can also be used in combination with fumaric acid, decomposing aconitic dibasic acid, Or a saturated monovalent carboxylic acid such as acetic acid, propionic acid, lauric acid, palmitic acid, or a saturated polyvalent carboxylic acid such as phthalic acid or its acid, or a compound whose terminal group is a carboxyl group, that is, a saturated or unsaturated alkyd acid, etc. . These unsaturated monobasic acids may be used alone, or two or more kinds may be appropriately mixed. Specific examples of the above-mentioned catalysts include tertiary amines such as dimethylbenzylamine and dibutylamine; Tertiary ammonium salts such as trimethylbenzyl ammonium chloride; inorganic salts such as chlorinated noodles and chromium chloride; flavorazole compounds such as 2-ethyl-4-methylimidazole; tetramethylphosphonium chloride, Dimethylphenylpropylphosphonium chloride, triethylphenyl chloride, benzyltriethylphenylphosphonium chloride, diphenyl Scale salts of methyl ethyl methylphosphonium chloride, benzyl methyl 5-methyl chloride, tetraphenylphosphonium bromide, etc .; secondary amines; tetrabutylurea; triphenylphosphine; tricresyl Phosphine; triphenylphosphonium and the like are not particularly limited, but a quaternary ammonium salt, an inorganic salt, a 5-salt salt, and triphenylphosphine are used; triphenylphosphonium, because a resin with a lesser degree of coloration can be obtained. suitable. These esterification catalysts may be used alone, or two or more kinds may be appropriately mixed. In addition, the urethane (meth) acrylate resin is not particularly limited. For example, after reacting polyisocyanate with a polyhydroxy compound or a polyvalent alcohol, the paper size is subject to the Chinese National Standard (CNS ) A4 specification (210X297g t) an · —m · I af Please read the notes on the back before writing this page), -0 The Central Standards Bureau of the Ministry of Economic Affairs, the Consumer Cooperative, Printing the Central Prototype Bureau of the Ministry of Economic Affairs, employee consumption Cooperatives Infanches Λ7 B7 V. Description of the invention (10)-Obtained by reacting a (meth) acrylic compound containing a hydroxyl group and an allyl ether compound containing a hydroxyl group as required. The polyisocyanate may be further reacted after the (meth) propionic acid compound containing a hydroxyl group is reacted with a polyhydroxy compound or a polyvalent alcohol. Specific examples of the polyisocyanate used in the above-mentioned urethane (meth) acrylate resin raw materials include toluene-2,4-diisocyanate and its isomers, diphenylmethane diisocyanate, hexamethylene Methyl diisocyanate, isophorone diisocyanate, xylyl diisocyanate, hydrogenated xylyl diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, hydrazone ^ (trade name; Sumitomo Bayer Co., Ltd.]] Kou Taka-Bu Doku (trade name 'made by Polyurethane Co., Ltd.), Yuki Choi, -Bu D 1 02 (Trade name, manufactured by Takeda Pharmaceutical Co., Ltd.), 彳 Y Cai'-Bu 143 L (Trade name; manufactured by Mitsubishi Chemical Corporation), etc., and the like is not particularly limited, but 'uses xylylene diisocyanate represented by aliphatic diisocyanates or hydrogenated xylyl represented by alicyclic diisocyanates Diisocyanate, dicyclohexylmethane diisocyanate, etc. are more suitable because resins with a lower degree of coloration can be obtained. These polyisocyanates may be used singly or in combination of two or more kinds. Specific examples of the polyvalent alcohols used in the aforementioned urethane (meth) acrylate resin raw materials include ethylene glycol, diethylene glycol, triethylene glycol, polyglycol, and propylene glycol. Propylene glycol 'Polypropylene glycol, 2-methyl_i, 3-propanediol, 1,3-butanediol, adduct of bisphenol a with propylene oxide or ethylene oxide, 1, 2, 3, 4-tetra Butyl, glycerol, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexanediol, ι, 3-cyclohexanediol, L4-cyclohexanediol, p-xylene Alcohol, dicyclohexyl_4,4, _diol, 2,6_decahydrofluorene-2-13- Towels and household materials_ (CNsTa Sight (210X297)) &quot; ~ Y-—11 n In «—- .-1 al · i I 1:! I 1 rL (please read the precautions on the back first and then on this page). Order 5. Invention Description (11) Kinds of alcohols, etc., but there are no special restrictions. Mix two or more types as appropriate. For example, using the urethane (meth) acrylic acid resin resin base compound, for example, polyacetate polyol, polyglyceride, for example, glycerol, ethylene oxide, etc. Adduct concrete, glycerol-tetrahydrocran Adducts, glycerol-ethylene oxide, trimethylolpropane-ethylene oxide adducts A: oxypropene ::? Propane adduct 'tri-methyl even produced — + 尨 methylpropane milk幺 methylpropane-tetrahydrofuran adduct, trihydroxyl, oxypropyl hydrazone adduct, quaternary quaternary tetrol, quaternary quaternary adduct, pentaerythroxyethylene propylene oxide adduct, dipentaerythritol-cyclo Lactane k adduct, dipentaerythritol. Propylene oxide adduct, dipentaerythritol: tetrahydrofuran adduct, dipentaerythritol · epoxyepoxide-epoxyepoxide adduct, but it is not particularly limited. These polybasic compounds can be used only-types, and 3F can be used as a mixture of two or more types. After printing by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Benzene, the above urethane (meth) acrylate resin raw materials The (meth) acrylic compound containing a hydroxyl group is not particularly limited, but it is preferably a (meth) acrylic acid ester having a hydroxyl group, and specifically, for example, 2-hydroxyethyl (meth) acrylic acid Ester, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, polyethylene glycol (Meth) acrylate, polypropylene glycol mono (meth) propionate, tris (hydroxyethyl) isocyanate di (meth) acrylate, pentaerythritol di (meth) propionate, etc. For the (meth) acrylic fe compounds containing Xiang group, only one kind can be used, or two or more kinds can be appropriately mixed and used. 14- This paper size is applicable to China National Standard (CNS) A4 specification (2 丨 OX297) v. Description of the invention (12 B? Onium urethane (meth) acrylic acid <allyl ether compound containing hydroxyl group needs to be used: allyl chain, diethylene glycol monoethene: top: : Example: "..., Polyethylene glycol monoglycyl ether, ： B, _ _ ·, 12-Butyl-Study Glycylidene-Alcohol allyl U Butyl-allyl ether , -Butanediol, and I. —Alcohol allyl ether, Alcohol propyl iiH monomethyl propylene, propyl ether, glycerol diallyl ether, pentaerythritol tri'propane -No particular olefin. These materials include noodles, noodles, etc., but they can be used in combination with two or more types. The silk compound may be used only-there is no particular limitation on the vinegar resin. For example, it can be obtained by a diacid-type condensation reaction. ^ Examples of the second acid used in the above unsaturated polyacetate resin raw materials include maleic acid, helmet maleic acid-copper cup, Ruan sacrifice acid, ba ..., fumaric acid, decomposing aconite , η „,. — Red test, phthalic acid, phthalic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, anhydride, di- &amp; Anong agricultural phthalic anhydride, hexahydrop-Europeic acid, Erchengzhan # π ^ ^ /, lice X is too old, printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs:, glutaric acid, adipic acid, sebacic acid, i 10-Second Junhong, 2,6-Benzodicarboxylic Acid, 2,7 Changji Acid, 2, acid, 2,3-Fandicarboxylic Acid, 4,4, _Biphenyl Dicarboxylic Acid · ;-&Quot; ffi dagger, from 2 and the dialkyl of this temple, the saturated dibasic acid of f, etc., but is not limited to these. With-species, you can also mix more than two types. This temple diacid test Only the polyvalent alcohols used for the above unsaturated polyether resin raw materials can be made, and the aforementioned polyvalent alcohols can be exemplified physically, but it is not limited to these. These polyvalent alcohols can be only -15- this paper Standards apply to China National Standard (CNS) Λ4 specifications (21 0X297 public dust) Λ7 Β7 V. Description of the invention (13 species can be used in combination with more than two species. If necessary, a soil pentadiene-based compound can be implanted into the resin skeleton. (Please read the note on the back first) Reprinted Matter 1) The polyester (meth) acrylate resin is not particularly limited. For example, it can be obtained by reacting an unsaturated or saturated polyester terminal with a (meth) propionic acid compound. The polyester raw material may be The same compounds as those exemplified as the raw material of the unsaturated polyester resin are used. Examples of the (meth) acrylic compound used as the raw material of the polyester (meth) acrylate resin include unsaturated glycidyl compounds and (methyl) ) Unsaturated monobasic acids such as acrylic acid and their glycidyl esters are not particularly limited. These (meth) acrylic compounds may be used singly or in an appropriate mixture of more than one kind. There is no particular limitation on the feminine resin slurry. For example, a (meth) acrylic acid ester and a monomer component (raw material mixture) containing an ethylene compound may be partially polymerized. Or, a polymer obtained by polymerizing the monomer component is obtained by adding a monomer such as (meth) propylene bromide, osmanthyl ester, or ethylene cotton compound. The acrylic resin slurry may also use a thermoplastic resin, However, thermosetting resins are preferred. The above-mentioned (meth) propanoate is printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Concrete. Specific examples include methyl (meth) acrylate and ethyl (meth) acrylate. Ester, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) ) Glycidyl acrylate and the like, but are not limited thereto. These (meth) acrylates may be used alone, or two or more of them may be appropriately mixed and used. The above ethylene bromide compounds can be specifically exemplified by styrene ·, α _ phenyl phenyl ethyl-16.-This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm J 1-^ V. Description of the invention (14 Λ7 B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Etc. This temple ethyl compound can be used only one kind, or two or more kinds can be mixed and used 疋. Γ 甲 2 等. The formation of trees ^ namely the above ethanoyl @ purpose resin, amino formic acid, enoic acid The blending conditions of each raw material in the production of resins such as brewed, unsaturated polyacetate resin, polyacetic acid (methyl) acetic acid and acrylic acid, etc., are specifically limited according to the respective desired physical properties of the resin ... The reactive monomer used in the curable resin component may be appropriately selected in accordance with the purpose or application, and is not particularly limited. Specifically, for example, styrene, diethylalcohol, chlorophenylethyl, (a (Base) Women's Bacteria-Said,-Alloprofen, Ethyl Acetate Etc. These reactive monomers may be used singly, or two or more kinds may be mixed and used. Or, a monofunctional monomer may be used orally, and a monofunctional monomer and a polyfunctional monomer may be mixed to make Chuanxiong. Other reactive monomers can also be used as a solvent for resin synthesis, and can also be used as a solvent for high viscosity resins to adjust the viscosity. = N_Oxygen addition method is not particularly limited. Can be used: Resin & amp After completion, for example, before adding reactive monomers or other resins or after mixing them, the method of adding them, or the method of polymerizing them in advance on the basis of the tree ^ and other methods. Ι · γ 扣 pN_ θ : In a 'case', the amount of the above-mentioned N · oxyl group is relative to 100 phr of the resin. It should be added in the range of ⑼ ^ parts by weight, and more preferably in the range of 0.001 to 0.05 parts by weight. The above Ν _ Prepare the amount of U base added. Read the precautions for δ first, and then load it to make the oxygen heavy. -17- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). 5. Description of the invention () Less than 0 · 0001 parts by weight, not available The effect of improving the storage stability or coloring resistance obtained by adding N-oxygen is not good. In addition, if the amount of oxygen added exceeds! Parts by weight, the resin hardenability will be impaired. In addition, such a curable resin composition in the present invention may further contain a polymerization inhibitor, a hardening agent or a hardening accelerator other than an N-oxy group, a shake modifier, a shake modifier, and Solvents, filling swords, UV absorbers, 1 branch, thickeners, viscosity reducers, low shrinkage agents, defoamers, oxidation inhibitors, various additives such as can, aggregate, difficult, and reinforcing agents are used as auxiliary Materials. Moreover, the amount of these additives is not particularly limited. In the present invention, the use of the above-mentioned N-oxyl group can greatly improve the storage stability of the curable resin composition. In addition, the curable resin composition contains the above-mentioned N-oxyl group. For example, the amount of oxygen used during production can be reduced, and gelation can be prevented even when oxygen is not used. Therefore, according to the present invention, in order to prevent gelation during manufacture, storage, or transportation, the trouble of circulating dry air or opening the container at regular intervals can be eliminated, and workability can be improved. The manufacturing method for printing the hardening resin of the present invention by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs is to make the components forming the hardening resin, that is, the raw materials of the hardening resin react in the presence of oxygen groups to A method for preparing the curable resin. The production method of the present invention is applicable to the production of a general curable resin and is not particularly limited. Among them, the manufacturing method of the present invention is particularly suitable for a curable resin selected from the group consisting of a vinyl ester resin, a urethane (meth) acrylate resin, and a polyester (meth) acrylate resin. Production method. -18- This paper size applies Chinese national standard (CNS> A4 specification (210X297mm> B7) V. Description of the invention (16) The amount of N · oxyl groups in the reaction system, even if the amount is not particularly limited 'but With respect to 100 parts by weight of the curable resin, it is preferably in the range of 100,000 parts by weight to 丄 parts by weight, more preferably in the range of 0.001 parts by weight to 0 005 parts by weight. If the N-oxy group is mentioned above. The amount used is less than 0.0000 parts by weight, the gelation suppressing effect at the time of manufacture cannot be obtained, and there is a possibility that manufacturing problems caused by gelation are not good. In addition, if the N-oxygen type is If the amount used exceeds 1 part by weight, gelation does not occur during production, and even if a resin can be obtained, the hardening property of the obtained resin may be impaired, so it is not good. A method for coexisting the above-mentioned N-oxygens in a reaction system, There is no particular limitation, for example, 'feed the raw material that becomes the hardening resin into the reaction device, while searching and stirring-heating to the pre-sufficient temperature, that is, the method of supplying N_oxys after the reaction temperature, or Supply of N_oxygen in raw material of hardening resin Various methods, such as the method of starting the reaction. Printed in the present invention by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, the conditions for formulating the raw materials of the hardening resin, etc., are particularly limited by the Codex, as long as the predetermined hardening resin The physical properties and the like are adequately set as appropriate. Also, the reaction temperature when performing each reaction is not particularly limited, as long as it is appropriately set so that each reaction can be effectively performed. For example, an epoxy compound and an unsaturated monobasic acid are used. The reaction temperature when reacting with an esterification catalyst in the presence of N-oxygens is not particularly limited, but it should be set within 60t ~ i50cm. (The reaction time is also not particularly limited, according to the raw materials. The type, combination, amount, reaction temperature, etc. may be appropriately set such that the reaction is completed, p may be further increased, and the reaction pressure is not particularly limited, and any of normal pressure (atmospheric pressure), reduced pressure, and pressurization may be used. At the time, if necessary, it can also be used in accordance with N _ oxygen type -19- national standard rain M specifications (-——_ printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Invention Description (17) Different polymerization regulators (polymerization inhibitors) or solvents. Reactive monomers. Specific examples of the aforementioned polymerization regulators include hydroquinone, methylhydroquinone, methoxyhydroquinone, third butylhydroquinone, and quinone. , Catechol, copper naphthenate, copper powder, etc., but there is no particular limitation. Also, the amount used is not particularly limited. Among the above-mentioned additions of the polymerization inhibitor, the amount of the polymerization inhibitor added to the resin 10 0 The weight part is 0.005 part by weight or less, and it is more preferable to use it in combination with 0.00001 part by weight to 1 part by weight of the N-oxy group, because the coloration of the resin composition with time changes is small. Each of the above reactions can be performed in a solvent-free state. It is also possible to use a solvent. The above-mentioned solvent is not particularly limited, and the amount of -I used is also not particularly limited. The reactive monomer may be appropriately selected depending on the purpose of use, application, and the like, and is not particularly limited, but is specifically limited. Examples can be mentioned: phenethylhydrazone, divinylbenzene, chlorostyrene, (meth) acrylic acid vinegar, di-propyl acetoacetate, vinyl acetate and the like. These reactive monomers may be used alone, or two or more of them may be appropriately mixed and used. Monofunctional monomers may be used alone, or a mixture of monofunctional monomers and polyfunctional monomers may be used. These reactive monomers can also be used as a solvent in the synthesis of a curable resin, and can also be used as a solvent for a highly viscous curable resin to adjust the viscosity. Description of Embodiments The present invention will be described more specifically with reference to the following Examples and Comparative Examples, but the present invention is not limited thereto. The coloration, hardening characteristics, and storage days of each curable resin composition were measured by the methods described below. In addition, "part" described in each of the following Examples and Comparative Examples means "part by weight", and "%" means "% by weight". -20- (Please read the precautions on the back nk page first) Binding. The size of the paper is applicable to the Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 5. Description of the invention () A7 B7 Central Ministry of Economy and Trade消费 Printed by the staff of the quasi-station bureau. (A) Can be stored. Put 600 ml of vinyl resin composition into a 650 ml screw-open glass bottle with a volume of 'remaining space in the bottle. Stand the glass bottles separately. In the strange temperature bath of 60 τ and 40 C. Then, "For every 60 kt, after 1 yr, for 4 OC, after about 10 hrs.," Investigate the gelation of the vinyl ester resin composition, and check whether it is gelled. Invert the glass bottle. Invert the glass. When the bottle is in the bottle, air bubbles appear in the glass bottle and move from the bottom of the glass bottle to the top. When the milk bubble completely moves from the bottom to the top of the glass bottle, it is judged as "no gelation", and the bubble is in the glass bottle. When it stopped halfway, it was judged as "gelation." From the day when the screw-mouth glass bottle was placed in the thermostat to the day before the day when the resin composition was initially judged as "gelation", the process passed. The number is the number of days that the resin composition can be stored. (B) Coloring degree The coloring degree of each curable resin composition is evaluated by Hasson's number. The Harbin number is based on ^! ^ Κ 69 〇1。 First, 2_49 g of potassium chloride (special grade) and 2.00 g of cobalt vaporized (special grade) were dissolved in 200 ml of hydrochloric acid (special grade), and diluted to 2000 w with distilled water as a standard. Stock solution. Secondly, dissolve at the ratio specified in JIS K 6901. This standard stock solution is all used as Hasson's color number standard solution. ° $, this Hasen's color number standard solution and hardening resin composition are respectively injected = Wang colorless and transparent, 23 mm inner diameter flat bottom glass tube with a common plug, from From the bottom to a height of 100 mm, standing side by side on a white plate. Then, the flat bottom of the resin composition was placed ^ «3, λ Λ 卞 圾 ^ S, and the Hasson color number standard solution was placed Ping-21-c Please read the notes on the back ^: 4 nests on this page)-Packing--5 k Paper G degree suitable (CNS) A4 size (2 ^^ 97 mm)

Bottom broken glass tube to diffuse daylight compared to flat bottom glass. At this time, it has the Hardest color number of the concentrated resin composition of the Zhao Yue composition, which is the closest to the tested hardness = the ratio of the naked eye, and the Hasen color number standard solution is selected. As the above-mentioned rigidity, the resins that can be stored in the aforementioned 4th and 6th generations are stored as "resin before storage" as the "resin before storage". It is estimated that the "resin before storage" is investigated separately by each temperature method: The degree of coloration can be described, and the number of measurements that can be saved at the above temperatures is tolerated "green gelatinization" • of the gas line in the glass bottle :: the resin is identified as "gel Former resin ... Formerly: == Upper: Ministry investigated the coloration of "resin before gelation". (C) Hardening characteristics Each of the hardening characteristics of each resin composition is measured according to coffee (谙 Read the precautions on the back first each page of this page} • 装 _

'1T Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs The hardening characteristics are measured by the following method. First, 100 parts of the resin composition was fired, and "Ya-Toyoji, 2 parts (manufactured by Nippon Oil & Fats Co., Ltd.), 2 7 WO 1Z_" as a hardener were mixed to obtain a mixture. Furthermore, eight- "Feng Er Lei W0" refers to 丨 丨 Ί q 丁 其 9 r 1 ρ 甘 乂 込 1,3,3-Tetramethylperoxy, ㈣. _ 1 Diethyloctyl phthalate 50% dilute: Then, the above mixture was placed in a 18-mm diameter tube for deep inspection] (mm This test tube was kept at a temperature of 7 °. In the temperature bath, the temperature of the foot and child mixture is measured from the reaction temperature from 55ΐ to ΐ by the heat of the reaction. During the day, this time is used as the gelation time. It becomes --- P I ----- -22 It is a paper-based standard, it finances CNS) A4 ^ m (210X297 ^ Γ Printed by the staff consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 ---_____ B7 V. Invention Description f3 ) Simultaneous temperature is taken as the maximum heating temperature, and the time from the temperature of the mixture from 5 5 to the maximum heating temperature is taken as the minimum hardening time. [Example 1] A 5 liter four-necked flask equipped with a stirrer, a reflux cooling tube, a gas introduction tube, and a thermometer was fed with a bisphenol epoxy resin (manufactured by Toto Kasei Co., Ltd. under the trade name "YD_901" "; Hereinafter referred to as" ¥ 1) _ 901 ") 2500 g, epoxy equivalent 1S5 bisphenol epoxy resin (manufactured by Toto Kasei Corporation, trade name" YD_127 "; hereinafter referred to as" YD_i27 "58 g 750 g of unsaturated-alkali acid, methacrylic acid preparation, 2,2-methylene-bis (4-methyl-third butyl phenol), 0600 g, and esterification catalyst (tetrabenzene Phosphorus bromide Π.50 g, and then stirred. "Into the above four-necked flask, pass dry air at 30 ml / min, and react at 115 C for 7 hours, and then add phenylethyl chloride as a reactive monomer. 100 g of body 2 was obtained to obtain a vinyl ester resin (hereinafter referred to as vinyl ester resin (υ). The acid value of the vinyl ester resin (1) measured by a predetermined method was 5.0 mg KOH / g. In addition, 0.600 g of the above-mentioned 2,2_styrene_bis (4-methyl-6-tert-butylphenol) was equivalent to 0.001 part of the vinyl ester resin. Then, the phase To 100 parts of the above-mentioned ethynyl ester resin (1), 2 parts of 4-hydroxy_2,2,6,6_tetramethylhexahydropyridyloxy, which is n-oxyl group, was added to obtain ^ ethyl Ester resin composition. The vinyl ester resin composition obtained can be stored for a number of days, curing characteristics, and the degree of coloration of the vinyl ester resin composition before storage and before gelation were measured by the aforementioned method. The main manufacturing conditions and test results of the above-mentioned vinyl ester resin composition show that -23- this paper size is suitable for g210X297 ^ ----- J ----- pack----- (please first Read the notes on the back? Write this page)

, 1T I line 0 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 ___ B7 21 I — — —......... V. Description of the invention () ^ -― See Table 1 (a) and Table 1 (b). [Example 2] In Example 1, except for changing the mixing ratio of 4-hydroxy-2,2,6,6-tetramethylhexahydrohowl to 100 parts of vinyl ester resin (1) to 0. Except for 0.02 parts to 0.01 parts, the remainder was reacted and operated in the same manner as in Example 1 to obtain a vinyl ester resin composition. The days of storage, hardening characteristics, and coloring degree of the ethimidate resin composition before storage and before gelation of the obtained ethylene ester resin composition were measured by the methods described above. In summary, the main manufacturing conditions and test results of the alkenyl resin composition are shown in Tables 1 (a) and 1 (b). [Example 3] In Example 1, except that 4-methoxy-2,2,6,6_tetramethylhexahydropyridine_ 丨 -oxygen 0.002 parts was substituted for 4-hydroxy- Except for 2,2,6,6-tetramethylhexahydropyridine-1. Oxygen, the rest were the same as the reaction and operation of Example 1 to obtain an ethylene ester resin composition. The obtained vinyl ester resin composition can be stored for a number of days, curing characteristics, and the coloration of the vinyl fluorene tree 1 composition before storage and before gelation were measured by the methods described above. The main manufacturing conditions and test results of the above-mentioned vinyl ester resin composition are summarized, and are shown in Table 1 (a) and Table i (b). Table 1 (a) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Addition amount in HTMPO reaction — — ___. 0.04-0.001 __- — -24- (Please read the notes on the back to write this page)

Size of this paper _ (CNs jMiFr210X297 ^ iT Printed by A7 B7 ~ ^ 22 of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention () (parts) Addition amount after reaction 0.02 0.01 One — _ _ — ΜΤΜΡΟ Addition amount in reaction — — — One 0.04 _. _ _ _ (Parts) Addition amount after reaction — — 0.002 One • — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — to add 0.04 _. -0.02 _ _ _ TMP (Servings) — One One — — 0.005 _ _ _ Pyriminium (Servings) — One — _ _ 005 N ·% # · Ethyl Acetylamine G Score) — — — One — — — — 0.2 HTMPO in the above table means 4-Jing-2,2,6,6-tetramethylhexahydroeodo-1 -oxygen. MTMPO in the above table represents 4-methoxy-2,2,6,6-tetramethylhexahydropyridine-1_oxy. MBMBP in the above table represents 2,2-methylene-bis (4-methyl-6-tertiarybutyl). The TMP in the above table represents 2,2,6,6-tetramethylhexahydropyridine. Table 1 (b) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Gelation time 2.4 4.2 2.7 2.4 2.7 2.8 2.2 4.6 5.5 Minimum hardening time (minutes ) 3.5 5.9 3.9 3.5 3.9 4.1 3.3 6.3 7.3 Highest patching temperature fc) 195 198 198 195 198 198 199 188 188 60 ° C Days (days) 10 16 10 7 7 15 1 6 6 Before Harson 20 50 20 10 10 20 10 &gt; 1000 70 -25- This paper size is applicable to Chinese National Standard (CNS) M specification (2 Ιχχ297). A7 A7 Consumer cooperation of the China Standards Bureau of the Ministry of Economic Affairs. Printed by the agency. B7 V. Invention Description ( Color number before gelation 20 50 20 10 10 70 10 &gt; 1000 &gt; 1000 Number of days that can be stored (days) 85 130 90 60 63 100 10 45 48 40 ... Before Harson 20 50 20 10 10 20 10 &gt; 1000 70 Color number before gelation 20 50 20 10 10 20 10 &gt; 1000 &gt; 1000 [Example 4] In the same four-necked flask as Example 1, feed r YD _ 9〇J ″ 2500 g '"YD-127" 580 g, 750 g of methacrylic acid, and 11.50 g of tetraphenylphosphorobromide, while feeding 4_hydroxy_2,2,6,6_tetramethyl Hexahydropyridyloxy was added to the final obtained vinyl ester resin in an amount of 0.004 parts, and stirred sufficiently. Next, dry nitrogen was passed through the four-necked flask at 30 ml / min, and After reacting at 115 ° C for 7 hours, 2100 g of a styrene monomer was added to obtain a vinyl ester resin composition. The acid value of the ethyl acetate resin composition measured by a predetermined method was 50. mg KOH / g. The storage life of the obtained 4-vinyl ester resin composition, the hardening characteristics, and the coloring degree of persons in the ethyl acetofluoride group before storage and before gelation were measured by the methods described above. The above Acetylated Cool Tree: The main manufacturing conditions of the composition and the results of each test are shown in Table 1 (and 1 (b). Clothing [Example 5] In Example 4, renmethoxy 2 was used , 2,6,6_tetramethylhexachlorob oxygen substituted 4-by-2,2,6,6-tetramethylhexazine small oxygen in: 100 parts of the vinyl vinegar resin finally obtained is 0.004 parts Except for the reaction and operation in Example 4, the ethynyl ester resin composition was obtained. . ； Performance applies to Chinese National Standards (CNS) (Please read the precautions on the back before writing this page) -install

'1T -26 A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 24 ~~~~~~ -------- 5. Description of the invention () The acidity of the vinyl ester resin composition measured by a predetermined method The valence is 50 mg ΚΟΗ / g. The storage number, hardening characteristics, and coloration of the vinyl ester resin composition before storage and before gelation were measured by the method described above. Table 1 (a) and Table 1 (b) summarize the main manufacturing conditions and test results of the above-mentioned androstyl vinegar resin composition. [Example 6] · In the same four-necked flask as in Example 1, 2500 g of "γ D _ 90 1", 580 g of "YD-127", 750 g of methacrylic acid, and tetraphenylphosphorobromide were fed. 1 1.50 g, while simultaneously feeding 4_hydroxy_2,2,6,6_tetramethylhexahydropyridine_j_oxy 'with respect to 100 parts of the vinyl ester resin composition finally obtained. 〇〇1 份 'and stir it. Next, "the above four-necked flask was aerated with dry air at 30 ml / min" and reacted at 115 t for 7 hours. Then, 0.02 parts of 2,2-methylene-bis (4-methyl-6-third-butylphenol) was added to 200 parts of the ethynyl ester resin obtained, and 2 was added simultaneously. 5,000 parts of 2,6,6-tetramethylhexahydropyridine, and 2100 g of a styrene monomer was further added to obtain a vinyl ester resin composition. The acid value of the vinyl ester resin composition measured by a predetermined method was 50 mg KOH / g. It is known that the storage time of the ethyl feminine vinegar resin composition, the hardening characteristic γ, and the coloration of the vinyl ester resin composition before storage and before gelation were measured by the following method. The main manufacturing conditions and test results of the above-mentioned vinyl ester resin composition are summarized in Tables i (a) and i (b). [Comparative Example 1] -27-^ The paper size is applicable to China ___ _________________, LNS) Α4 size (210X297 mm) —s --------- install — ', .y. (Please read first (Notes on the back again ^^ write this page)

, 1T Λ7 B? Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (25 Using the same method as in Example 1, the obtained shaks are transferred to J &lt; vinyl ester resin (I) = insurance. The number of days, hardening characteristics, and the coloring degree of the B: group before storage and before gelation were measured by the methods described above. In summary, the main manufacturing conditions of the ethyl ethoxylate resin (I) are as follows: , Force. Λ ± Yi 1 畑 仟 The results of each test are shown in Table 1 (a) and Table 1 (b). [Comparative Example 2] The same method as that used in the implementation of m was used with respect to the obtained B. One hundred parts of the natural hydrangea month is added (1), and fentanyl is added as a conventional polymerization inhibitor, so as to know that the ethyl acetyl resin composition is better than that used. The shelf life of the resin 2 composition, the hardening characteristics, and the coloration of the vinyl lysin composition before storage and before curing are measured by the aforementioned method. The main manufacturing conditions and test results are shown in Tables i (a) and yb). [Comparative Example 3] Using the same method as in Example 1, with respect to 100 parts of the obtained vinyl ester resin E! (I), N_morpholinylacetamidoacetic acid was added as a conventional polymerization inhibitor. 0.2 parts of amine 'to obtain an ethyl androstyl ester resin composition for comparison. The storability days, hardening characteristics, and coloration of the obtained vinyl ester resin composition before storage and before gelation were measured by the method described above. The main manufacturing conditions and test results of the above-mentioned vinyl ester resin composition are summarized and shown in Tables 1 (a) and 1 (b). [Example 7] In the same four-necked flask as in Example 1, 1500 g of hexamethylene diisocyanate, which is polyisocyanate, 1400 g of styrene monomer, and -28 as a catalyst were fed. Zhongguanjia County (CNS) Eight-four specifications (· 297 public epidemic (please read the precautions on the back before filling this page) Order 0 Λ7 ΒΊ V. Description of the invention (26) ~-Dibutyltin dilaurate 2_4 g, And 4-1 and 9-0 each of 2,2,6,6-tetramethylhexahydropyridine-: 240 mg of 1-oxygen and stirred. 4- and -9. &Lt; into 2,6,6 -Tetramethylhexahydropyridine- 丨 -oxygen 240 mg is 0.05 part of the predetermined yield obtained finally in Example 7. Next, the above-mentioned four-necked flask was passed into dry air at a temperature of 30 mm, and the temperature was raised. After reaching 60 ° C, 59 g of dipropylene glycol as a polyvalent alcohol was added, and the reaction solution was kept at 60-70 ° C for 3 hours. Then, a hydroxyl group-containing (meth) acrylic compound, which is a hydroxyl group, was further added. 1270 g of propyl methacrylate, heated to 100 ° C. and reacted for 5 hours to obtain urethane (meth) acrylate resin [hereinafter referred to as urethane ( Base) acrylate resin (I)] Further, 4-kis-2,2,6,6-tetramethyl is added to 100 parts of the urethane (meth) acrylate resin (work) described above. Hexahydrogen is used to obtain 1-2 parts of 1-2 groups to obtain a urethane (meth) acrylate resin composition. The obtained urethane (meth) acrylate resin composition may be The storage curing characteristics and the coloring degree of the urethane (meth) acrylic acid resin composition before storage and before gelation were measured by the aforementioned methods. The above-mentioned urethane (methyl) was summarized. The main manufacturing conditions and test results of the acrylate resin composition are shown in Table 2. Table 2 Example 7 Addition amount (parts) in the HTMPO reaction 0.005 Addition amount (parts) after the reaction 0.02 -29- Paper size applies to China g | Home Standards (CNS) Correction (21Qx 297 Gongchu) Please read the precautions before reading _ ^ _ a copy of the Consumer Cooperative Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Λ7 Η7 V. Description of the invention (27 Gelation time ( Points) 5.0 minimum hardening time (minutes) 6.8 maximum heating temperature ( ° C) 200 Preservable days (days) 16 60 ° C 20 days before Hussen gelation 20 days before gelation 138 40 ° C 20 days before Hussen preservation-gelation i 20 (Please read the notes on the back before writing this page)

HTMPO in the above table means 4-hydroxy-2,2,6,6-tetramethylhexahydropyridine-1-oxyl. [Example 8] A 3 liter four-necked flask equipped with a stirrer, a reflux cooling tube, a gas introduction tube, and a thermometer was fed with ethylene glycol, which was a polyvalent alcohol, 3 10 g, diethylene glycol 3 00 g, And, 32 g of dipropylene glycol, 700 g of diacid anhydride which is g of dibasic acid, and 520 g of maleic anhydride are stirred and mixed. Next, 'the above-mentioned four-necked flask was purged with nitrogen at 30 ml / min, and reacted at 210 ° C for 7 hours', and 1110 g of a styrene monomer was added to obtain an unsaturated polyester resin [hereinafter referred to as an unsaturated polyester resin (1)]. The acid value of the aforementioned unsaturated polyacetate resin (I) measured according to a predetermined method was 43 mg KOH / g. Then, 0.005 parts of 4-hydroxy-amidine, 6,6-tetramethylhexahydropyridine-1-oxyl was added to 100 parts of the unsaturated polyester resin (1) to obtain an unsaturated polyester resin combination. Thing. The obtained unsaturated polyester resin composition can be stored at 30-sheet paper size applicable to Chinese National Standards (CNS). It is required to set the specifications printed by the staff of the Central Bureau of Standards of the Ministry of Economic Affairs and the cooperatives. The Δ7 B? Number, the hardening characteristics, and the coloring degree of the unsaturated polysaccharine composition before storage and before gelation were measured by the methods described above. Table 3 summarizes the main manufacturing conditions and test results of the polyester resin composition described above. Printed by the Central Standards Bureau, Ministry of Economic Affairs, Consumer Cooperatives Table 3 Example 8 Example 9 Example 10 Comparative Example 4 — ^ Comparative Example 5 HTMPO (parts) 0.005 0.02 MTMPO (parts) — »0.02 — Congestion. Well (parts) __... 0.005 φ third butyl catechol (parts) one------- 0.005 gelation time (min) 4.8 9.7 9.7 1.2 ------ 1.3 minimum hardening Time (minutes) 10.6 15.3 14.8 6.3 6.6 Maximum temperature of fictional heat fc) 172 172 172 170 168 60 ° C Number of days that can be stored (days) 40 80 70 40 40 Hasson color number before storage 20 50 50 30 200 before gelation 20 50 50 &gt; 1000 &gt; 1000 40 ° C can be stored for several days (days) 200 350 320 200 210 Hasson color number before storage 20 50 50 30 200 before gelation 20 50 50 &gt; 1000 ------ -&gt; 1000 HTMPO in the above table represents 4-hydroxy-2,2,6,6-tetramethylhexahydropyridyloxy. MTMPO in the above table indicates 4-methoxy-2,2,6,6-tetramethylhexahydro-31- This paper is again applicable to the Chinese National Standard (East Milk) Six 4 Specification (210 '/ 297 Public #_) (Please read the notes on the back first—sf page) '| ding Λ7 ______ B7 〇Q' '~ · -------- V. Description of the invention () 唉 -1-oxygen . [Example 9] In Example 8, except that the mixing ratio of 4 __ _ 2,2,6,6-tetramethylhexahydropyridine- 丨 _ oxygen to unsaturated polyacetal resin (I) was changed from 005 parts were changed to other than 0.02 parts, and the same reaction and operation as in Example IX were performed to obtain an unsaturated polyester resin composition. The storage life of the obtained unsaturated polyester resin composition, the curing characteristics, and the coloration of the unsaturated polyester resin composition before storage and before gelation were measured by the methods described above. Table 3 summarizes the main manufacturing conditions and test results of the unsaturated polyester resin composition. [Example 10] In Example 8, except that 4-methoxy-2,2,6,6_tetramethylhexahydropyridine-1 -oxo was replaced by 0.02 parts of 4-hydroxy-2,2,6 Except for 6-tetramethylhexahydropyridine, the rest were the same as the reaction and operation of Example 1 to obtain an unsaturated polymer resin composition. The storability number, hardening characteristics, and coloration of the unsaturated polyester resin composition obtained before the storage and gelation were measured by the methods described above. Table 3 summarizes the main production conditions and test results' of the unsaturated polyester resin composition. [Comparative Example 4] Using the same method as in Example 8, with respect to the obtained unsaturated polyester tree (I) 100 parts' added 添加 嗔 p well 0.05 parts to obtain a comparison Used for unsaturated polyester resin composition. The obtained unsaturated polyester resin combination for comparison -32- Zhongguanjia Standard (CNS) A4 Regulation i (21GX) 97 for this paper; i ^ 7 Five 'Invention Description (30 A7 B? Employees of the Central Bureau of Standards, Ministry of Economic Affairs Consumption cooperatives print sundial, hardening properties, and storage before storage and gelation :: The coloration of the resin composition is measured by the method described above. The main manufacturing conditions of unsaturated polyg resin composition are summarized. The results with each test agency 'are shown in Table 3. σ [Comparative Example 5] For the unsaturated polyacetate resin obtained in the same manner as in Example 8, "2" = 4_Third Ding, which is a conventional polymerization inhibitor. Base catechin. 005 Unsaturated polyester resin composition for comparison of knives. Comparison of the obtained unsaturated polyester resin composition for storage, curing characteristics, and pre-storage and gelation The coloring degree γ of the unsaturated polyester resin composition before the conversion is fully described by the method described above. The manufacturing conditions and test results of the king of the unsaturated polyester resin composition are summarized in Table 3. [Example 1 1] In the same four-necked flask as in Example 1 1650 g of propylene glycol, which is a polyvalent alcohol, 1800 g of isophthalic acid, which is a dibasic acid, and 1,720 g of maleic anhydride, were fed and stirred. Next, the above-mentioned four-necked flask was fed with dry air at 30 ml / mm. After reacting at 200 C for 8 hours, the sharpness and polyester were obtained. The acid value of the unsaturated polyester measured by a predetermined method was 60. Secondly, compared with the unsaturation in the four-necked flask. 100 parts of polyester, 4-hydroxy-2,2,6,6_tetramethylhexahydropyridine_ ^ 3 part and 60.0 g of glycidyl methacrylate (meth) acrylic compound Dry air was passed through the four-necked flask at 30 ml / min, and reacted at 40.0 ° C for 3 hours to obtain a poly (acetic acid) acrylic acid ester resin composition. Shelf Life of Poly (Meth) acrylate Resin Composition-33 Paper Rule Money and Family Standard (CNS) A4 Specification (2 丨 (Please read the precautions on the back before filling in a broken page)

'1T .II I- I- Ϊ. Λ7 Λ7 31 V. Description of the invention (number, hardening characteristics, and coloration of poly (vinyl) acrylate resin composition before storage and gelation) The method was determined. The main manufacturing conditions and test results of the polyester (meth) acrylate resin composition are summarized in Table 4. [Example 1 2] In the same four-necked flask as in Example 1 1,650 g of propylene glycol, 1800 g of phthalic acid, and 1,720 g of maleic anhydride were fed and stirred. Next, dry air was passed into the four-necked flask at 30 ml / min, and 200. After 8 hours of reaction, 'unsaturated polyester was obtained.' The acid value of the unsaturated polyester determined by a predetermined method was 60 mg KOH / g.-Secondly, 'as compared to the unsaturated polyester in the four-necked flask described above. Parts, 2,2-amidinolidene-bis (4-methyl-6-third-butyl-pan) 〇〇〇〇〇ιι part, and, glycidyl methacrylate 65 0 g, to a four-necked flask with Dry air was introduced at 300 ml / min and reacted at 140 ° C for 3 hours. A 'synthetic polyester (meth) acrylate oligomer' was mixed with the Polyester (meth) acrylate resin was obtained from 60 parts of oligomer and 40 parts of styrene. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. Then, it was i00 parts of the polyester (meth) acrylate resin. Then, 4- (2-, 2,6,6-tetramethylhexahydropyridine-1-oxo02) was added to obtain a polyester (meth) acrylic resin composition. The obtained poly (g) The storage time of the methyl) propionate resin composition, the curing characteristics, and the coloration of the polyester (meth) acrylate resin composition before storage and before gelation were measured by the methods described above. The main manufacturing conditions and test results of the above polyester (meth) acrylate resin composition are shown in Table 4. -34- This paper size applies to China National Standard (CNS) A4 (210X 297) V. Description of the invention. (32) Table 4 Example 11 Example 12 Comparative Example 6 Comparative Example 7 Addition amount (parts) in HTMPO reaction 0.03 — Addition amount (parts) after reaction 0.02 — — MBMBP (parts) — 0.01 0.01 monomorphine (parts) mono-0.05 monohydroquinone (Parts) — — --- 0.01 4-tert-butylcatechol (parts) — — — 0.02 Gelation time (minutes) 5.0 4.3 8.5 10.1 Minimum hardening time (minutes) 6.8 · 5.9 10.7 15.3 Maximum 4 heat Temperature (° C) 180 180 172 155 Number of days that can be stored (say) 30 20 8 10 60 ° C 20 days before storage 20 &gt; 1000 600 Number of days before gelation 20 20 &gt; 1000 &gt; 1000 days (Say) 150 80 32 40 40 ° C Hasson 20 20 before storage &gt; 1000 600 Color number before gelation 20 20 &gt; 1000 &gt; 1000 (Please read the precautions on the back before filling in &quot; this page)

Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs of the 1T. The HTMPO in the above table represents 4-hydroxy-2,2,6,6-tetramethylhexahydropyridine-1-oxy. MB MBP in the above table represents 2,2-methylene-bis (4-methyl-6-third butyl brewer '). [Comparative Example 6] In Example 12, except that 0.05 parts of fenthionine was used instead of 4-hydroxy-35-35- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 male t> 387000 Λ7 ^ · '~~ ---------- Β7 ^ _ V. Description of the invention (33) &quot;' 2,6,6 -Tetramethylhexahydrogen ρ than bite _1_ oxygen, the other uses are the same as the implementation The method of Example 12 was used to obtain a comparative polyester (meth) acrylate resin composition. The obtained comparative polyester (meth) acrylate resin composition had a shelf life, curing characteristics, and storage The coloration of the polyester (meth) acrylate resin composition before and before gelation was measured by the method described above. The main manufacturing conditions and tests of the poly (meth) acrylate resin composition are summarized. The results are shown in Table 4. [Comparative Example 7] In T Example 12 except that 100 parts of hydroquinone was used instead of 2,2-methylene-bis (4-methyl-6-tert-butyl) Phenol), and 4-tert-butylcatechol was used in place of 4-¾-2,2,6,6-tetramethylhexahydropyridine- ^ oxy, the rest were the same as in Example 12 to obtain Comparative use (Meth) acrylate resin composition. The comparative polyester (meth) acrylate resin composition obtained has a storage number, a hardening characteristic, and a polyester (meth) acrylic acid before storage and before gelation. The coloration of the ester resin composition is measured by the aforementioned method. The main manufacturing conditions and test results of the polyester (meth) propionic acid resin composition are summarized in Table 4. Employees of the Central Bureau of Standards, Ministry of Economic Affairs It is clear from the results printed in the above-mentioned cooperative tables that the resin composition obtained in this example is superior to the resin composition obtained in the comparative example in comparison with the resin composition obtained in the comparative example, and has excellent storage stability and hardening characteristics. Inhibition of burning over time. [Comparative Example 8] In the same flask as in Example 1, 2500 g of the aforementioned "q JY uy〇l", 580 g of the aforementioned YD-127 ", 48 g of methacrylic acid, Tetrabenzyl-36-i paper size is applicable to China National Standards (Specifications (210 &gt; &lt; ^ 97 公 楚> ---------_ p- ^ 187000) 5. Description of the invention (34) ~ ^ ~ ~ Bromine 8.90 g and 4-A as a known polymerization inhibitor Based on the same method as in Example 1, a comparative vinyl ester resin was obtained. The acid value of the comparative vinyl ester resin measured by a predetermined method was 50 KOH / g, Hasson's color. The number is 120. [Comparative Example 9] In Example 4, 'except the use of hydroquinone, which is a known polymerization inhibitor, 20 g was substituted for 4-¾- 2,2,6,6-tetramethylhexahydro p Except for the base, the rest was the same as in Example 4 to obtain a vinyl ester resin for comparison. The acid value of the comparative vinyl ester resin measured by a predetermined method was 50 mg κη / g 'Hasson color number was 800. — [Comparative Example 10] In Example 4, except for using 4-methoxyphenol 丨 i 80 g to replace 4_ji_ 6-tetramethylhexahydropyridin-1-yl, and the circulating gas was replaced with nitrogen Except air, the rest was the same as the reaction and operation of Example 4. After the reaction started, it gelled in 2 hours. [Comparative Example 1] In Example 7, except that 4-methoxydi-2,2,6,6-tetramethylhexahydropyridine-1 -yl was replaced with 4-methoxyphenol uo g, the rest were the same as The printing method of the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs of Example 7 'obtained a urethane (meth) acrylate resin for comparison. The obtained comparative urethane (meth) acrylate resin had a Hasson color number of 200. [Comparative Example 1 2] In Example 7, 'except for the use of 4-methoxyphenol 100, which is called Substituted 4-from 2,2,6,6 -tetramethylhexahydro p-ratio-1-yl', the rest Same as in Example 7 I__ · 37_ This paper ^ Chinese National Standard (CMS) __ M specification (210 × 297 g t) —— printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 387000 V. Description of the invention (35) After reaction and operation 'After adding 1270 g of hydroxypropylmethylpropionate, the temperature was raised to 100 C and the reaction was carried out for 10 minutes, followed by gelation. _ [Comparative Example 1] In ΛShe Example 1 except that 1.20 g of hydroquinone was used in place of 4-hydroxy-2,2,6,6-tetramethylhexahydropyridine-1. In the method of Example 1, a comparative intention polyester (meth) acrylate resin was obtained. The obtained polyester (meth) acrylate resin for comparison had a Hasson color number of 500. [Comparative Example 1 4] In Example 11, except that 100 mg of hydroquinone was used in place of 4-hydroxy-2,2,6,6-= methylhexahydropyridyl, the same reaction as in Example &quot; was performed. After the addition of methylglycidyl glycidol, dry thoron gas was passed in at 30 ml / min, and the reaction was performed at 14 ° C for 15 minutes before gelation.。 上 从 贝 施 例 1 It is clear from the results described in ~ 12 and Comparative Examples 1 ~ 14 that the manufacturing method of the resin composition of this example does not require gelation in the production, and is generally used as a method of manufacturing a curable resin composition that suppresses coloration. Description of the invention of Zen Lake &lt; In the project, the specific implementation form or embodiment is basically a disclosure of the technical content of the present invention, and should not be limited to such &lt; specific examples and explained in a narrow sense. In the spirit of the present invention and the following Within the scope of the patent application, various changes can be made and implemented. ___ _ 38 _ National Standards (CNS) Α microgrid (210X 297) on the scale of wealth (Please read the notes on the back before filling (I page)

Claims (1)

No. 86119507 Patent Application Decree Application Patent Park Amendment (June 88) 8 888 ABCD Dou &quot; June: Filling in \ H '· ·. 813-' Patent Application Range 387,000 Kinds of N-Oxygen Basic hardening resin composition containing X2 ^] Ri ^ n ^ RsR2 | Ri 〇C 1) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (where 乂 丨, χ2, and X3 represent hydrogen atoms, respectively) _〇R5 group; h, R3, and R4 respectively represent an alkyl group having a carbon number of i to 8; I represents a hydrogen atom or an alkyl group having a carbon number of 1 to 16); Synthetic resin is at least one selected from the group consisting of ethylene-based brewing resin, urethane (meth) acrylate resin, unsaturated polyester resin, polyester (meth) acrylate resin, and acrylic resin slurry. The ratio of the above N-oxygens to the above-mentioned synthetic resins is 0.00001 parts by weight to 1 part by weight ^ The N_oxy group-containing hardening resin combination according to item 丨 of the application scope Material 'wherein the curable resin composition, Q, can be stored at 60 ° C The number of days is more than one week, and the composition has a coloring degree obtained by Hasson's color number of 100 or less. The composition before gelation during storage at 60 ° C has a coloration degree of 100 or less obtained by Hasson's color number. The difference between the coloration of the composition before gelation during storage at 60 ° C. and the composition before storage under Hasson's color number is less than or equal to 20 ′. 1,1,3,3-Tetramethyl Butyl peroxy-2-ethylhexylhexanoate 1 weight (Please read the precautions on the reverse side before filling out this page) Order-Rev. 86119507 Patent Application Decree Application for Patent Garden Amendment (June 88) 8 888 ABCD Dou &quot; June: Filling in \ H '··. 813 一' The scope of application for patents is 387,000 kinds of N-oxygen-containing hardening resin compositions containing Yitong X2 ^] Ri ^ n ^ RsR2 | Ri 〇C 1) Employee Consumer Cooperative of Central Standards Bureau, Ministry of Economic Affairs Printed (where, 、 丨, χ2, and X3 represent a hydrogen atom and a _〇R5 group, respectively; h, R3, and R4 represent an alkyl group having a carbon number of i to 8; I represents a hydrogen atom or a carbon number of 1 to 16; N · oxy group and synthetic resin shown by alkyl group; the above synthetic resin is at least one selected from the group consisting of ethylenic resin, urethane (meth) acrylate resin, unsaturated polyester resin, polyester (Meth) Acrylic resin in the group consisting of acrylic resin and acrylic resin slurry; the ratio of the above-mentioned N-oxygen to the above-mentioned synthetic resin is 0.00001 parts by weight to 1 part by weight ^ according to the application N-oxygen-containing curable resin composition in the scope of the patent item ′ The curable resin composition has a shelf life of Q at 60 ° C for more than one week, a coloring degree of the composition based on the Hasson color number of 100 or less, and gelation during storage at 60 c. The previous composition has a coloring degree of less than 100 obtained by Hasson's color number, the composition before gelation during storage at 60 ° C., and the coloring degree obtained by Hasson's color number of the composition before storage. The difference is less than 2 ′. 1,1,3,3-tetramethylperoxybutyl-2-ethylhexylhexanoate is 1 weight (Please read the precautions on the reverse side before filling out this page) Order-387 ❹ 00: VI. Patent Application Scope When the printed parts of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs are mixed with 100 parts by weight of the composition, When measuring the following hardening characteristics, the maximum heating temperature is 100 to 300. 3. —A method for producing an N-oxyl-containing hardening resin composition, which is selected from the group consisting of vinyl ester resins and amine groups. The resins in the group of formate (meth) propionate resins, resins, unsaturated polyester resins, polyester (meth) acrylate resins, and acrylic resin slurries are characterized by forming a curable resin. The component is reacted in the presence of 0.000 (n parts by weight to 1 part by weight of N · oxy groups) with respect to 100 parts by weight of the obtained curable resin. 4. N-oxygen content according to item 3 of the scope of patent application A method for producing a base curable resin composition, wherein the obtained curable resin has a shelf life of more than 1 week at 60 ° C, and a coloring degree of the composition with a Hasson color number of 100 or less, Before gelation during storage at 60 ° C The difference between the coloring degree of the composition obtained by the Hasson color number is 100 or less, and the composition before the gelation during storage at 60 c, and the coloring degree obtained by the composition before the preservation using the Hasson color number. When it is less than or equal to 20, 1,1,3,3-tetramethylperoxybutyl-2-ethylhexylhexanoate is mixed with 1 part by weight of the composition at a temperature of 700 c. When measuring the hardening characteristics, the maximum heating temperature is 100 ～ 3 〇t> c or more. (Please read the precautions on the back before filling in this page) •----Is— I -I · • I —1—- ---------- t ^ i. P. 21〇x 归 楚)