JPH046202B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for producing a new urethane (meth)acrylate prepolymer, and more specifically, a novel urethane (meth)acrylate prepolymer that has excellent viscosity characteristics and cured physical properties and is useful for various uses. This invention relates to a method for producing polymers. [Conventional technology] Urethane (meth)acrylate prepolymer,
So-called urethane (meth)acrylate is an important component in the production of thermosetting resins or photocuring resins, and is used in paints, adhesives, inks, hard coats,
It is used in a wide range of applications such as resists. Urethane (meth)acrylate prepolymers are generally produced by reacting polyols, polyisocyanates, and hydroxyalkyl ((meth)acrylates. Until now, urethane (meth)acrylate prepolymers have been produced by reacting polyols, polyisocyanates, and hydroxyalkyl ((meth)acrylates). , a vast variety of urethane (meth)acrylate prepolymers have been synthesized. However, hitherto known prepolymers are mostly very viscous or solid and require large amounts of reactive diluents. It was necessary to use these prepolymers with the addition of There is a need for the development of a urethane (meth)acrylate prepolymer that has a fast curing speed and has excellent cured physical properties such as hardness and adhesion of the cured product. [Problems to be solved by the invention] The present inventors As a result of various studies in view of the above circumstances, we have arrived at the present invention.The present invention therefore relates to a method for producing a novel urethane (meth)acrylate prepolymer having a specific structure that can be used for various purposes. Means and operation for solving the problems] That is, the present invention has the general formula [] (However, in the formula, R ¹ is a hydrogen atom or a methyl group, and each may be the same or different, and Z is a divalent organic group having 2 to 20 carbon atoms, and each may be the same. may also be different,
p is an integer from 1 to 100. ) Hydroxyl group-containing (meth)acrylate oligomer (A) represented by the general formula Y-(NCO) _1+n+o
(However, in the formula, Y is a residue of an organic compound containing a (l+m+n)-valent isocyanate group, and
is an integer from 1 to 6. ) and, if necessary, a hydroxyl group-containing organic compound (C) other than the hydroxyl group-containing (meth)acrylate oligomer (A) represented by the above general formula (). Featured general formula〔〕 [However, in the formula, R ¹ is a hydrogen atom or a methyl group, which may be the same or different, and Z is a divalent organic group having 2 to 20 carbon atoms, even if they are the same. It may also be different, p
is an integer from 1 to 100, ^R2 is a residue of a hydroxyl group-containing organic compound (excluding the hydroxyl group-containing (meth)acrylate oligomer represented by the above general formula []), and l is 1 to 6. m is an integer of 0 or 1 to 5,
n is 0 or an integer of 1 to 5, l+m+n is an integer of 1 to 6, and Y is a (l+m+n)-valent isocyanate group-containing organic compound residue. ] A method for producing a urethane (meth)acrylate prepolymer represented by: It is related to. More briefly, the present invention relates to a urethane (meth)acrylate prepolymer obtained by reacting an isocyanate group-containing compound with a hydroxyl group- and unsaturated group-containing compound,
A novel urethane (meth)acrylate characterized by using a specific hydroxyl group-containing (meth)acrylate oligomer (A) represented by the above general formula [] as a compound containing a hydroxyl group and an unsaturated group. This invention relates to a method for producing a prepolymer. Hydroxyl group-containing (meth)acrylate oligomer represented by the general formula [] used in the present invention
(A) is the general formula [] (However, in the formula, R ¹ is a hydrogen atom or a methyl group,
Z is a divalent organic group having 2 to 20 carbon atoms. ) is obtained by addition polymerizing a hydroxyl group-containing (meth)acrylate to oligomerize it. Specific examples of hydroxyl group-containing (meth)acrylates represented by the general formula [] include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxyhexyl acrylate, and hydroxyhexyl acrylate. Examples include methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, dipropylene glycol monoacrylate, dipropylene glycol monomethacrylate, hydroxycyclohexyl acrylate, hydroxycyclohexyl methacrylate, and the like. These may be used alone or as a mixture.
In order to oligomerize hydroxyl group-containing (meth)acrylates by addition polymerizing them, for example,
As described in No. 59-256558, hydroxyl group-containing (meth)acrylates are treated with protonic acids such as sulfuric acid and para-toluenesulfonic acid; Lewis acids such as boron trifluoride and tin tetrachloride; oxysulfates such as titanium oxysulfate; It may be maintained at a temperature of 10 to 150° C. in the presence of a catalyst such as a heteropolyacid such as tungstophosphoric acid, tungstosilicic acid, molybdophosphoric acid, or molybdosilicic acid. A hydroxyl group-containing (meth)acrylate oligomer (A) represented by the above general formula [], an isocyanate group-containing organic compound (B) represented by the above general formula, and if necessary a hydroxyl group-containing (meth)acrylate oligomer (A)
The urethane (meth)acrylate prepolymer of the present invention can be obtained by reacting a hydroxyl group-containing organic compound (C) other than the acrylate oligomer (A). Examples of the isocyanate group-containing organic compound (B) used in the present invention include monoisocyanates (B1), polyisocyanates (B2), and terminal isocyanate group-containing prepolymers (B3) listed below, These compounds can be used alone or in mixtures.
Furthermore, these isocyanate group-containing organic compounds (B)
Among them, compounds containing two or more isocyanate groups in one molecule are collectively referred to as polyisocyanate group-containing organic compounds (B4). Examples of monoisocyanates (B1) include methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, hexyl isocyanate, chloroethyl isocyanate, isocyanatoethyl methacrylate, octadecyl isocyanate, phenyl isocyanate, toxyphenyl isocyanate, chlorophenyl isocyanate, Examples of polyisocyanates (B2) such as benzyl isocyanate, naphthyl isocyanate, and dichlorophenyl isocyanate include ethylene diisocyanate, trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,10-decamethylene diisocyanate, octadecamethylene diisocyanate, lysine diisocyanate, o-, m-
or p-phenylene diisocyanate, 4-
Isopropyl-1,3-phenylene diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate, xylylene diisocyanate, m- or p-tetramethylxylylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 2,4-diisocyanate diphenyl ether, 3,3'-dimethyl -4,
4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, triphenylmethane triisocyanate, tris-(p-isocyanatophenyl) thiophosphite, polymethylene polyphenylisocyanate (novolac type) polyisocyanate), 1,4
-cyclohexylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, diphenylsulfone diisocyanate,
Isocyanate polymers such as 1,6-hexamethylene diisocyanate dimer and 2,4-tolylene diisocyanate dimer, and crude products of tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate containing terminal isocyanate groups. As the prepolymers (B3), the above-mentioned polyisocyanates (B2), the polyols (C1) listed below, the polyether polyols (C2),
Hydroxyl group-containing compounds such as polyester polyols (C3), ester diols (C4), polyolefin polyols (C5), and polycarbonate polyols (C6) at a ratio of isocyanate group number/hydroxyl group number greater than 1.0. Prepolymers containing isocyanate groups at the terminals obtained by the reaction can be mentioned. Examples of polyols (C1) used in the synthesis of prepolymers containing terminal isocyanate groups (B3) include ethylene glycol, propylene glycol, trimethylene glycol, 1,2-,
1,3- or 1,4-butanediol, 1,
5-pentanediol, hexanediol, neopentyl glycol, dibromneopentyl glycol, trimethylpentanediol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, cyclohexanediol, cyclohexanedimethanol, glycerin, diglycerin, sorbitol ,
Trishydroxyethyl isocyanurate, bisphenol A, 2,2'-di(4-hydroxypropoxyphenyl)propane, hydrogenated bisphenol A, triethanolamine, N,N,N',
Examples of polyether polyols (C2) such as N'-tetrakis(β-hydroxyethyl)ethylenediamine include polyester polyols (C3) such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, and dipropylene glycol.
Examples include the above polyols (C1) and/or polyether polyols (C2) and polyhydric carboxylic acids (e.g. phthalic anhydride, maleic anhydride, succinic anhydride, dodecynylsuccinic anhydride, citraconic anhydride, trimellitic acid, pyromellitic anhydride, methylcyclohexenetricarboxylic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, hymic anhydride, tetrachlorophthalic anhydride, hexic anhydride, orthophthalic acid, isophthalic acid, terephthalic acid, maleic acid, A polyester polyol, such as bis( Examples include 2-hydroxyethyl) terephthalate. Examples of ester diols (C4) include 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate (hydroxypivalylhydroxypivalate), 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate (hydroxypivalylhydroxypivalate), Polyolefin polyols (C5 Examples of polycarbonate polyols (C6) include reaction products of 1,6-hexanediol and ethylene carbonate. Furthermore, ethylene oxide, propylene oxide, Obtained by ring-opening addition reaction of cyclic compounds such as butylene oxide, styrene oxide, higher fatty acid monoepoxide, epichlorohydrin, allyl glycidyl ether, butyl glycidyl ether, glycidol, phenyl glycidyl ether, tetrahydrofuran, ε-caprolactone, etc. Hydroxyl group-containing compounds such as ethylene oxide addition to trimethylolpropane, ε-caprolactone addition to neopentyl glycol, butyl glycidyl ether to terminal hydroxyl group-containing polyester polyols prepared from butylene glycol, azelaic acid and isophthalic acid. Addition reaction product, ε-caprolactone addition reaction product to hydroxypivalyl hydroxypivalate, propylene oxide addition reaction product to polybutadiene diol, ethylene oxide addition reaction product to 1,6-hexanediol and ethylene carbonate (1:1) reaction product. The prepolymers containing terminal isocyanate groups (B3) can also be obtained by reacting the polyisocyanates (B2) with the polyisocyanates (B2). The ring-opening addition reaction of cyclic compounds can be carried out by known methods, and it is generally desirable to carry out in the presence of a catalyst. Examples of such catalysts include Lewis acids,
Organic titanium compounds, organic tin compounds, etc. can be used. The hydroxyl group-containing organic compound (C) used if necessary in the present invention is an organic compound containing at least one hydroxyl group capable of reacting with an isocyanate group other than the above-mentioned hydroxyl group-containing (meth)acrylate oligomer (A). If so, it can be used without any restrictions. Examples of the hydroxyl group-containing organic compound (C) include the aforementioned polyols (C1), polyether polyols (C2), and polyester polyols (C3) used to obtain terminal isocyanate group-containing prepolymers (B3). ),
Ester diols (C4), polyolefin polyols (C5) and polycarbonate polyols (C6) are their cyclic compound addition reaction products (these are collectively referred to as polyol compounds (C1)).
~6). ); aliphatic monohydric alcohols such as methanol, ethanol, propanol, butanol; (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; (poly)alkylene glycols such as ethylene glycol monoacetyl ester Examples include monoalkyl esters. In addition, unsaturated acid partial esters of polyol compounds (C1 to 6) such as 1,4-butanediol mono(meth)acrylate, 1,6-hexanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, Trimethylolpropane mono(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerin mono(meth)acrylate, di Glycerin tri(meth)
Acrylate, hydrogenated bisphenol A mono(meth)acrylate, di(meth)acrylate of trimethylolpropane with 6 moles of ethylene oxide, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, diethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate,
Dipropylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc.; cyclic compounds to hydroxyalkyl(meth)acrylates (aliphatic glycidyl ethers such as butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, etc.) Aromatic glycidyl ether, epichlorohydrin, ε-caprolactone, tetrahydrofuran, etc.) adducts, such as ε-caprolactone-added hydroxyalkyl (meth)acrylate, ε-caprolactone-added 2 mol hydroxyethyl (meth)acrylate, etc.; having an epoxy group Addition reaction between a compound and a compound having an ethylenically unsaturated group For example, addition of monoepoxides such as butyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, epichlorohydrin, glycidyl (meth)acrylate and (meth)acrylic acid Reactants and addition reaction products of polyepoxides such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and N,N-diglycidylaniline with (meth)acrylic acid. It goes without saying that compounds containing a hydroxyl group and an ethylenically unsaturated group in the molecule, such as the following, can also be used as the hydroxyl group-containing organic compound (C). The hydroxyl group-containing organic compound (C) can be used singly or as a mixture from among those listed above. A known manufacturing method can be used for manufacturing the urethane (meth)acrylate prepolymer of the present invention. That is, a hydroxyl group-containing (meth)acrylate oligomer represented by the general formula []
(A) and an isocyanate group-containing organic compound (B), or a hydroxyl group-containing (meth)acrylate oligomer (A) represented by the general formula [], a hydroxyl group-containing organic compound (C), and a polyisocyanate group-containing organic compound It can be produced by reaction with compound (B4). The ratio of these raw materials may be charged depending on the urethane (meth)acrylate prepolymer to be obtained, but usually the ratio of the number of isocyanate groups to the number of hydroxyl groups may be in the range of 1.0±0.1. However, it is also possible to use a large excess of the hydroxyl group-containing organic compound (C), and in that case, the hydroxyl group-containing organic compound ( ^C ) may be The group-containing organic compound residue contains a hydroxyl group. Furthermore, as the isocyanate group-containing organic compound (B), compounds having other functional groups such as hydroxyl groups in addition to isocyanate groups may be freely used, and in that case, Y in the general formula [] The isocyanate group-containing organic compound residue may contain other functional groups. There is no particular restriction on the order in which the raw materials are added, but when using the above polyol compounds (C1 to 6) as the hydroxyl group-containing organic compound (C), add the polyol compounds (C1 to 6) and the polyisocyanate group-containing organic compound in advance. It is convenient to react with the organic compound (B4). An embodiment of the production method of the present invention includes, for example, (a) a method of reacting a hydroxyl group-containing (meth)acrylate oligomer (A) represented by the general formula [] with an isocyanate group-containing organic compound (B); (b) After reacting the hydroxyl group-containing (meth)acrylate oligomer (A) represented by the general formula [] with the polyisocyanate group-containing organic compound (B4) in a proportion such that isocyanate groups remain, A method of reacting a group-containing organic compound (C). (c) After reacting the hydroxyl group-containing organic compound (C) and the polyisocyanate group-containing organic compound (B4) in such a ratio that the isocyanate group remains, the hydroxyl group-containing compound represented by the general formula [] A method of reacting (meth)acrylate oligomer (A). (d) A method in which a mixture of a hydroxyl group-containing (meth)acrylate oligomer (A) represented by the general formula [] and a hydroxyl group-containing organic compound (C) is reacted with a polyisocyanate group-containing organic compound (B4). (e) After reacting the hydroxyl group-containing organic compound (C) and the polyisocyanate group-containing organic compound (B4) in such a ratio that the isocyanate group remains, the hydroxyl group-containing compound (C) represented by the general formula [] A method in which a meth)acrylate oligomer (A) is reacted in such a proportion that isocyanate groups remain, and then a hydroxyl group-containing organic compound (C) is reacted. (F) After reacting the hydroxyl group-containing organic compound (C) and the polyisocyanate group-containing organic compound (B4) in such a ratio that the isocyanate group remains, the hydroxyl group-containing compound (C) represented by the general formula [] A method of reacting a mixture of a meth)acrylate oligomer (A) and a hydroxyl group-containing organic compound (C). (g) After reacting the hydroxyl group-containing (meth)acrylate oligomer (A) represented by the general formula [] with the polyisocyanate group-containing organic compound (B4) in such a proportion that the isocyanate group remains, A method in which a group-containing organic compound (C) is reacted in such a proportion that isocyanate groups remain, and then a hydroxyl group-containing (meth)acrylate oligomer (A) represented by the general formula [] is reacted. (h) After reacting the hydroxyl group-containing (meth)acrylate oligomer (A) represented by the general formula [] with the polyisocyanate group-containing organic compound (B4) in a proportion such that the isocyanate group remains, the polyisocyanate A method in which a group-containing organic compound (B4) is blended and then a hydroxyl group-containing organic compound (C) is reacted. (li) After reacting the hydroxyl group-containing (meth)acrylate oligomer (A) represented by the general formula [] with the polyisocyanate group-containing organic compound (B4) in such a proportion that the isocyanate group remains, the polyisocyanate The group-containing organic compound (B4) is blended, and then the general formula []
Examples include a method of reacting a mixture of a hydroxyl group-containing (meth)acrylate oligomer (A) represented by hydroxyl group-containing organic compound (C), but the present invention is not limited to these embodiments. . The reaction in the present invention is carried out at 10-150°C, especially at 30-100°C.
Preferably, the temperature is within the range of .degree. If the reaction temperature is high, the polymerization reaction of the vinyl groups in the raw materials and the reaction product tends to occur. If the reaction temperature is too low, the reaction rate will be low. Furthermore, in order to avoid polymerization of vinyl groups in the raw materials and reaction products, it is preferable to carry out the reaction in the presence of a polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, methylhydroquinone, t-butylhydroquinone, di-t-butylhydroquinone, t-butylcatechol, phenothiazine, N,N'-di-2-naphthyl-p
-phenylenediamine, 4,6-dinitro-o-
Cresol, N-nitrosodiphenylamine, α
-Naphthol, copper salts, etc. The amount used is usually 0.005 to 1% by weight based on the raw material.
Furthermore, in the reaction of the present invention, in order to promote the urethanization reaction between an isocyanate group and a hydroxyl group, the reaction is carried out in the presence of a known catalyst, such as an organotin compound such as dibutyltin dilaurate or dioctyltin dilaurate, or a tertiary amine. can be implemented. Note that the reaction may be carried out in a suitable solvent if necessary. The solvent is not particularly limited, but for example, styrene,
Vinyl acetate, methyl (meth)acrylate, ethylene glycol di(meth)acrylate, 1,6
Hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate,
Trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, methoxyethyl(meth)acrylate,
Reactive solvents such as phenoxyethyl (meth)acrylate and tetrahydrofurfuryl (meth)acrylate; aromatic hydrocarbons such as benzene, toluene, and xylene; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; methyl acetate Organic solvents such as esters such as , ethyl acetate, propyl acetate, and butyl acetate; ethers such as isopropyl ether, dioxane, and tetrahydrofuran; and halogenated hydrocarbons such as methylene chloride, chloroform, trichloroethylene, and ethylene dichloride can be used. . The novel urethane (meth)acrylate prepolymer thus synthesized can be used in paints, adhesives, inks, hard coats, resists, and the like. Furthermore, the urethane (meth)acrylate prepolymer synthesized by the production method of the present invention can be used with ethylenically unsaturated compounds, various polymers (for example, unsaturated polyester, epoxy, polyamide, acrylic, polyvinyl alcohol, etc.). ), organic solvents, fillers, tackifiers, stabilizers, plasticizers, leveling agents, dyes, pigments, etc., in combination with urethane (meth)acrylate prepolymers represented by the general formula [] and ethylenically unsaturated. It can also be used as a composition containing the compound as a main component. Examples of ethylenically unsaturated compounds include styrene,
α-methylstyrene, acrylonitrile, (meth)
Acrylamide, diacetone acrylamide, N
- Methyl (meth)acrylamide, N-methylol (meth)acrylamide, N-vinylpyrrolidone, diallyl phthalate, allyl glycidyl ether, (meth)acrylic acid, alkyl (meth)acrylates such as methyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, methoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, dibromopropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, ethylene glycol di(meth)acrylate , diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate , 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate,
Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)
Acrylate, dipentaerythritol hexa(meth)acrylate, trishydroxyethyl isocyanurate tri(meth)acrylate, ethylene oxide addition bisphenol A di(meth)acrylate
Acrylate, hydrogenated bisphenol A di(meth)acrylate, polyester (meth)acrylate obtained by the reaction of (meth)acrylic acid, glycols, and polybasic acid, obtained by the reaction of (meth)acrylic acid with an epoxy compound. epoxy (meth)acrylate obtained by the reaction of an isocyanate group-containing compound with a hydroxyalkyl (meth)acrylate,
Dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate,
Examples include silicone (meth)acrylate, amide (meth)acrylate, phosphoric acid (meth)acrylate, and the like. These can be used alone or as a mixture. The timing of blending the ethylenically unsaturated compound is not particularly limited, and in the case of an ethylenically unsaturated compound that does not react with isocyanate groups, it may be blended before the urethanization reaction. The amount of the ethylenically unsaturated compound is not particularly limited, but
The amount is not more than 99% by weight, preferably not more than 90% by weight, based on the total amount of the composition of the invention. Urethane (meth) synthesized by the production method of the present invention
Compositions based on acrylate prepolymers and ethylenically unsaturated compounds can be applied or molded by means known to those skilled in the art, and can be cured by means such as heat, radiation, and the like. In the case of thermal curing, common radical polymerization initiators such as benzoyl peroxide, methyl ethyl ketone peroxide, lauroyl peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, di-t-amyl are used. Peroxide, dicumyl peroxide, t-butyl perbenzoate, azobisisobutyronitrile, etc. can be used,
If necessary, radical polymerization accelerators such as organic metal salts such as cobalt octenoate, cobalt naphthenate, iron octenoate, manganese octenoate, and vanadium octenoate, organic amines such as N,N-dimethylaniline, etc. are used in combination. be able to. Radiation curing can be performed using electron beams, ultraviolet rays, etc. In the case of ultraviolet curing, ordinary photopolymerization initiators,
If necessary, add a photopolymerization initiator and sensitizer to 0.1 to 10
It is incorporated into the composition at a concentration of parts by weight. Examples of photopolymerization initiators include benzoin alkyl ethers such as benzoin, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenones such as benzophenone, Michler's ketone, and methyl-o-benzoyl benzoate;
Acetophenone, trichloroacetophenone,
Acetophenones such as 2,2-diethoxyacetophenone, pt-butyltrichloroacetophenone, 2,2-dimethoxy-2-phenylacetophenone, p-dimethylaminoacetophenone; xanthone, thioxanthone , 2-chlorothioxanthone, 2-isopropylthioxanthone; benzyl, 2-ethylanthraquinone, methyl-benzoylformate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy -4'-isopropyl-2-methylpropiophenone, 1-
Examples include hydroxycyclohexyl phenyl ketone, tetramethylthiuram monosulfide, and allyldiazonium salt. Examples of the sensitizer include amine compounds, sulfur compounds, and phosphorus compounds. These may be used alone or in combination. Furthermore, ultraviolet curing and thermosetting, or electron beam curing and thermosetting can also be used together. [Effects of the Invention] The urethane (meth)acrylate prepolymer having a novel structure synthesized by the production method of the present invention can be polymerized to form a (co)polymer containing a urethane bond, or an ethylenically unsaturated compound. By curing the composition, it can be used for a wide range of applications such as paints, adhesives, inks, ultraviolet or electron beam curable resins, hard coats, resists, protective groups for printed wiring boards, sealants, binders, and insulating varnishes. It is possible. Next, the present invention will be explained by examples, but the present invention is not limited to these examples.
Note that parts in the examples are parts by weight. Reference Example 1 A reaction vessel equipped with a thermometer and a stirrer was charged with 232 parts of 2-hydroxyethyl acrylate, 0.07 parts of hydroquinone monomethyl ether as a polymerization inhibitor, and 2.3 parts of 12-tungstophosphoric acid as a catalyst, and then maintained at 80°C for 7.5 hours. did. After the reaction is complete, add 12 parts of powdered magnesium silicate as an adsorbent and heat at 40°C.
After stirring for 30 minutes, the reaction product was purified by pressure filtration to produce a colorless transparent liquid reaction product (hereinafter referred to as hydroxyl group-containing acrylate oligomer (1)).
228 parts (yield 98.3%) were obtained. IR, NMR, GPC
From the analysis results, it was found that the reaction product was a hydroxyl group-containing acrylate oligomer with an average molecular weight of 401 and the following structure. Reference Example 2 After charging 260 parts of 2-hydroxypropyl acrylate, 0.08 parts of hydroquinone monomethyl ether as a polymerization inhibitor, and 2.6 parts of 12-tungstosilicic acid as a catalyst into the same reaction vessel as in Reference Example 1,
It was kept at 100℃ for 5 hours. After the reaction is complete, 13 parts of powdered basic magnesium aluminum hydroxy carbonate hydrate, which is an adsorbent, is added, stirred at 60°C for 30 minutes, and purified by pressure filtration to form a colorless transparent liquid. product (hereinafter referred to as
It is called hydroxyl group-containing acrylate oligomer (2). ) 251 parts (yield 96.5%) were obtained. The reaction product was a hydroxyl group-containing acrylate oligomer with an average molecular weight of 510 and the following structure. Reference Example 3 Into the same reaction vessel as in Reference Example 1, 232 parts of 2-hydroxyethyl acrylate, 0.07 parts of hydroquinone monomethyl ether as a polymerization inhibitor, and 4.6 parts of tungstosilicic acid as a catalyst were charged, and the mixture was heated to 80°C.
It was held for 10 hours. After the reaction, 12 parts of powdered magnesium silicate as an adsorbent was added and stirred at 40°C for 30 minutes, followed by purification by pressure filtration to produce a colorless transparent liquid reaction product (hereinafter referred to as hydroxyl group-containing acrylate oligomer). (3)) 227 parts (yield
97.8%). The reaction product was a hydroxyl group-containing acrylate oligomer with an average molecular weight of 1098 and the following structure. Reference Example 4 Into a reaction vessel similar to Reference Example 1, 260 parts of 2-hydroxyethyl methacrylate, 0.13 parts of hydroquinone monomethyl ether as a polymerization inhibitor, and 2.6 parts of tungstophosphoric acid as a catalyst were charged.
It was kept at ℃ for 4 hours. After the reaction was complete, 260 parts of water was added, stirred at room temperature, allowed to stand, and the aqueous layer (upper layer) was removed.The resulting residual liquid was kept at 80°C for 30 minutes under a reduced pressure of 3 mmHg to remove water and residual liquid. As a result of removing a portion of the raw material, 102 parts (yield: 39.2%) of a colorless transparent liquid reaction product (hereinafter referred to as hydroxyl group-containing methacrylate oligomer (4)) was obtained. The reaction product was a hydroxyl group-containing methacrylate oligomer with an average molecular weight of 297 and the following structure. Example 1 In a reaction vessel equipped with a thermometer, dropping funnel, reflux tube, and stirrer, 201 parts (0.5 equivalents) of the hydroxyl group-containing acrylate oligomer (1) obtained in Reference Example 1 and 0.025 parts of hydroquinone monomethyl ether as a polymerization inhibitor were added. , 0.13 parts of dibutyltin dilaurate was added as a urethanization reaction catalyst, and then 53 parts (0.5 equivalents) of trimethylhexamethylene diisocyanate (manufactured by Hyulus) was added dropwise over 1 hour while stirring so that the temperature did not rise above 60°C. . By keeping it at 60-65℃ for an additional 4 hours,
254 parts of a reaction product (hereinafter referred to as urethane acrylate prepolymer (1)) was obtained. The reaction product was found to be a urethane acrylate prepolymer having the following structure from the free isocyanate group content (0.1% or less) and infrared absorption spectrum of the reaction product. (However, C ₉ H ₁₈ indicates the residue of trimethylhexamethylene diisocyanate.) The infrared absorption spectrum of the reaction product was
As shown in the figure. Example 2 The hydroxyl group-containing acrylate oligomer (1) obtained in Reference Example 1 was placed in the same reaction vessel as in Example 1.
After adding 201 parts (0.5 equivalent), 0.029 part of hydroquinone monomethyl ether as a polymerization inhibitor, and 0.14 part of dibutyltin dilaurate as a urethanization reaction catalyst, 87 parts (1 equivalent) of 2,4-tolylene diisocyanate was added with stirring. The mixture was added dropwise over 2 hours while being cooled so as not to exceed 60°C. By maintaining the temperature at 60 to 65°C for an additional 4 hours, the reaction product (hereinafter referred to as urethane acrylate prepolymer (2)
It is called. ) Obtained 288 copies. From the free isocyanate group content (7.2%) and infrared absorption spectrum of the reaction product, it was found that the reaction product was a urethane acrylate prepolymer having the following structure. However, C ₇ H ₆ represents a residue of 2,4-tolylene diisocyanate. ) In addition, the infrared absorption spectrum of the reaction product was
As shown in the figure. Example 3 After charging 288 parts of the urethane acrylate prepolymer (2) obtained in Example 2 into the same reaction vessel as in Example 1, 58 parts (0.5 equivalents) of 2-hydroxyethyl acrylate was added under stirring at a temperature of The mixture was added dropwise over 2 hours while being cooled so as not to exceed 60°C. By maintaining the temperature at 60 to 65°C for an additional 4 hours, the reaction product (hereinafter referred to as urethane acrylate prepolymer)
It is called (3). ) 346 copies sold. The reaction product was found to be a urethane acrylate prepolymer having the following structure from the free isocyanate group content (0.1% or less) and infrared absorption spectrum of the reaction product. (However, C ₇ H ₆ indicates the residue of 2,4-tolylene diisocyanate.) The infrared absorption spectrum of the reaction product was
As shown in the figure. Example 4 Into the same reaction vessel as in Example 1, 122 parts (0.9 equivalents) of polymethylene polyphenyl isocyanate (Millionate MR-100, manufactured by Nippon Polyurethane Industries, Ltd.) was charged, and while stirring, the reaction mixture obtained in Reference Example 1 was added. A mixture consisting of 120 parts (0.3 equivalents) of hydroxyl group-containing acrylate oligomer (1), 0.14 parts of hydroquinone monomethyl ether as a polymerization inhibitor, and 0.14 parts of dibutyltin dilaurate as a urethanization reaction catalyst was added dropwise at 65°C over 1 hour. 60
Hold at ~65°C for 1 hour. Next, 35 parts (0.3 equivalents) of 2-hydroxyethyl acrylate was added dropwise at 65°C for 1 hour, and the temperature was further maintained at 60 to 65°C for 2 hours to form a reaction product (hereinafter referred to as urethane acrylate prepolymer (4)). ) Obtained 277 copies. The free isocyanate group content of the reaction product is
It was 4.5%. The infrared absorption spectrum of the reaction product is shown in FIG. Examples 5 to 11 According to the same procedure as in Example 1, a reaction was carried out using the raw materials shown in Table 1, and urethane (meth)
Acrylate prepolymers (5) to (11) were obtained. In addition,
The infrared absorption spectrum of the urethane methacrylate prepolymer (9) obtained in Example 9 is shown in FIG. Examples 12-22 0.01 part of hydroquinone monomethyl ether and benzyl methyl ketal (Ciba Geigy) were added to 100 parts of the mixture of the urethane (meth)acrylate prepolymers obtained in Examples 1 to 11 and the ethylenically unsaturated compounds shown in Table 2. Manufactured by Irugaki Your
651) to prepare photocurable compositions (12) to (22). This composition was applied to a thickness of 15 μm on a steel plate panel, and irradiated with an 80 W/cm high-pressure mercury lamp from a distance of 10 cm while moving the panel at a conveyor speed of 6 m/min. Only 20) required three irradiations to obtain a cured coating, but all of the others yielded tack-free cured coatings with just one irradiation. The performance of the obtained cured coating film is shown in Table 2. Example 23 When 3 parts of methyl ethyl ketone peroxide and 1 part of cobalt naphthenate were added to 100 parts of the urethane acrylate prepolymer (1) obtained in Example 1 and left to stand, it gradually hardened and reached pencil hardness after 24 hours. A tough 5H cured resin was obtained. Comparative Example 1 In a reaction vessel similar to Example 1, 116 parts (1 equivalent) of 2-hydroxyethyl acrylate and 0.029 parts of hydroquinone monomethyl ether as a polymerization inhibitor were added.
After adding 0.14 parts of dibutyltin dilaurate as a urethanization catalyst, 87 parts (1 equivalent) of 2,4-tolylene diisocyanate was added under stirring at a temperature of 60°C.
The mixture was added dropwise over 2 hours while being cooled so as not to exceed .degree. By maintaining the temperature at 60 to 65°C for further 8 hours, 203 parts of a reaction product (hereinafter referred to as comparative urethane acrylate prepolymer (1)) was obtained. The free isocyanate group content of the reaction product was less than 0.1%. The viscosities (25°C, B-type viscometer) of the urethane acrylate prepolymer (3) obtained in Example 3 and Comparative Example 1 and the comparative urethane acrylate prepolymer (1) are shown below. Meth)acrylate prepolymers have low viscosity;
It was found that it has excellent viscosity characteristics.

【table】

【table】

【table】

【table】 [Brief explanation of drawings]

FIG. 1 is an infrared absorption spectrum diagram of the urethane acrylate prepolymer (1) obtained in Example 1,
Figure 2 is an infrared absorption spectrum diagram of the urethane acrylate prepolymer (2) obtained in Example 2, and Figure 3 is an infrared absorption spectrum diagram of the urethane acrylate prepolymer (3) obtained in Example 3. Yes, 4th
The figure is an infrared absorption spectrum diagram of the urethane acrylate prepolymer (4) obtained in Example 4, and FIG. 5 is an infrared absorption spectrum diagram of the urethane methacrylate prepolymer (9) obtained in Example 9.

Claims (1)

[Claims] 1. General formula [] (However, in the formula, R ¹ is a hydrogen atom or a methyl group, and each may be the same or different, and Z is a divalent organic group having 2 to 20 carbon atoms, and each may be the same. may also be different,
p is an integer from 1 to 100. ) Hydroxyl group-containing (meth)acrylate oligomer (A) represented by the general formula Y-(NCO) _1+n+o
(However, in the formula, Y is a residue of an organic compound containing a (l+m+n)-valent isocyanate group, and
is an integer from 1 to 6. ) and, if necessary, a hydroxyl group-containing organic compound (C) other than the hydroxyl group-containing (meth)acrylate oligomer (A) represented by the above general formula (). Featured general formula [] [However, in the formula, R ¹ is a hydrogen atom or a methyl group, which may be the same or different, and Z is a divalent organic group having 2 to 20 carbon atoms, even if they are the same. It may also be different, p
is an integer from 1 to 100, R ² is a residue of a hydroxyl group-containing organic compound (excluding the hydroxyl group-containing (meth)acrylate oligomer represented by the general formula []), and l is 1 to 6. m is an integer of 0 or 1 to 5,
n is 0 or an integer of 1 to 5, l+m+n is an integer of 1 to 6, and Y is a (l+m+n)-valent isocyanate group-containing organic compound residue. ] A method for producing a urethane (meth)acrylate prepolymer represented by: