JPH0212490B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a coating composition that is flexible and strong and has excellent adhesion, heat resistance, and hydrolysis resistance. In recent years, radiation-curable resins have been attracting attention as materials using curing systems using radiation such as electron beams and ultraviolet rays in response to the progress of environmental pollution, increases in energy costs, and restrictions on energy use. As such photosensitive compositions, resin compositions having a backbone of polyester resin, polyurethane resin, epoxy resin, etc. and having double bonds that can be polymerized by radiation are often used, but they generally do not contain volatile organic solvents. It is very desirable from the point of view of environmental conservation, as it contains no or only a small amount of paint. It has been put to practical use in a wide range of fields, including printing inks, adhesives, flexible circuit overlays and other coating materials, solder resists for printed circuit boards, etching resists, plating resists, and inks for printed circuits. However, the above-mentioned conventional photosensitive compositions have drawbacks in either curability, toughness of the obtained coating, or adhesion to various adherends, and improvements have been desired. The purpose of the present invention is to provide a coating composition that provides flexibility and toughness to the resulting cured product by modifying the unsaturated polyurethane resin itself, and that also has significantly improved adhesion to various adherends. Our goal is to provide the following. The present invention provides at least organic polyisocyanate,
A polyol, an ethylenically unsaturated compound having active hydrogen, and a quaternizing agent, which have two or more terminal groups having a polymerizable double bond, and which contain a quaternary ammonium base of 0.05 meq/ The present invention relates to a coating composition characterized in that it contains an unsaturated polyurethane resin having a polyurethane resin of at least 100 g, and optionally a crosslinking agent, a coloring agent, and the like. The coating composition of the present invention has excellent curability,
The resulting coating has excellent toughness and adhesion. In particular, the presence of quaternary ammonium bases provides excellent adhesion to metals, and the presence of quaternary ammonium bases is thought to improve the reactivity of ethylenic double bonds.As a result, even thick coating layers can be coated uniformly and Strong curing is now possible. The unsaturated polyurethane resin of the present invention includes, for example, an organic polyisocyanate (A), a polyol (B), an ethylenically unsaturated compound (U) having active hydrogen, two or more active hydrogens and at least one tertiary amino acid. A compound having a group (C) and, if necessary, a chain extender (D)
It can be obtained by treating polyurethane obtained using a quaternizing agent (E) with a quaternizing agent (E). As another method, an organic polyisocyanate (A), a polyol (B), an ethylenically unsaturated compound (U) having active hydrogen, a molecular weight having two or more active hydrogens and at least one tertiary amino group, Chain extender below 500
It can also be obtained by treating polyurethane obtained using (F) and, if necessary, a conventional chain extender (D), with a quaternizing agent (E). In addition, in the above, the compound (C) or the chain extender (F) can also be treated with the quaternizing agent (E) in advance. Organic polyisocyanate (A) used in the present invention
Examples of the diisocyanate include diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), tolidine diisocyanate (TODI), xylylene diisocyanate (XDI), naphthylene diisocyanate (NDI), and isophorone diisocyanate ( IPDI),
Examples include diisocyanates such as hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), and lysine diisocyanate (LDI), and polyisocyanates such as triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate (PAPI), and carbodiimide-modified MDI. can be used alone or in combination of two or more. As the polyol (B), various polyester polyols, polyether polyols, and other polyols can be used. Examples of polyester polyols include aliphatic dicarboxylic acids having 4 to 20 carbon atoms such as adipic acid, suberic acid, sebacic acid, and brassylic acid, terephthalic acid, and isophthalic acid as acid components, and ethylene glycol, propylene glycol, neopentyl glycol, Polyester polyols whose polyol components include aliphatic diols having 1 to 6 carbon atoms such as hexamethylene glycol, ether glycols such as diethylene glycol and dipropylene glycol, spiroglycols, and N-alkyl dialkanolamines such as N-methyldiethanolamine; Polycaprolactone polyol etc. can be used,
Specific examples include polyethylene adipate polyol, polybutylene adipate polyol,
Adipate polyols such as polyethylene propylene adipate polyol, terephthalic acid polyols (e.g. Toyobo Co., Ltd., product name Vylon RUX,
Vylon RV-200L), polycaprolactone polyol (e.g., Daicel Chemical, trade name Plaxel)
212, Praxel 220), etc. Specific examples of polyether polyols include polyoxyethylene polyol, polyoxypropylene polyol, polyoxytetramethylene polyol, and the like. In addition, other polyols include polycarbonate polyol (e.g., West Germany, Bayer AG, trade name Desmofene 2020E), polybutadiene polyol (e.g., Nippon Soda, trade name G-1000, G-
2000, G-3000, Idemitsu Petrochemical, product name Poly bd
R-45HT), polypentadiene polyol, castor oil polyol, and the like. These polyols can be used alone or in combination of two or more. In the present invention, various types of ethylenically unsaturated compounds (U) having active hydrogen can be used, but representative examples include ethylene glycol,
Propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, diethylene glycol, dipropylene glycol, polyethylene glycol, mono(meth)acrylate of dihydric alcohol such as polypropylene glycol, trimethylolethane , mono- and di(meth)acrylates of trihydric alcohols such as trimethylolpropane and glycerin, and di- and tri(meth)acrylates of tetrahydric or higher alcohols such as pentaerythritol. More than one species can be used as well. Examples of the compound (C) having two or more active hydrogens and at least one tertiary amino group include N-
Methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, bis-hydroxyethylpiperazine, N-phenyldiethanolamine, N,N-dimethylamino-
Examples include polyesters containing N-alkyl dialkanolamines such as 2,2-bishydroxymethylethylamine and N-methyldiethanolamine as polyol components. In the synthesis of the unsaturated polyurethane resin of the present invention, it is optional to use a chain extender (D) in addition to the above-mentioned components, and such chain extenders include, for example, 2- to 6-functional chain extenders with a molecular weight of 500 or less. Examples include polyols having a molecular weight of 500 or less and diamines having a primary or secondary terminal amino group. Suitable chain extenders include (a) ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, hexanediol,
Polyols such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, xylylene glycol (b) hydrazine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 1,
Diamines such as 4-cyclohexanediamine (c) Alkanolamines such as ethanolamine, diethanolamine, and triethanolamine (d) Hydroquinone, pyrogallol, 4,4'-isopropylidene diphenol, aniline, and the above polyols and diamines , polyols with a molecular weight of 500 or less obtained by adding propylene oxide and/or ethylene oxide to alkanolamines in any order. Examples of the quaternizing agent (E) include dialkyl sulfates such as dimethyl sulfate and diethyl sulfate, halogenated hydrocarbons such as methyl chloride, methyl iodide, ethyl bromide, and benzyl chloride, acetic acid, propionic acid, and monochloroacetic acid. Various compounds such as organic acids and various other inorganic acids can be used. Also, a chain extender having a molecular weight of 500 or less and having two or more active hydrogen atoms and at least one tertiary amino group.
As (F), the same compounds as those listed for compound (C) can be used. The unsaturated polyurethane resin of the present invention is synthesized by various methods using the above-mentioned components. For example, a method in which urethane is synthesized from an organic polyisocyanate (A), a polyol (B), an ethylenically unsaturated compound (U), and a compound (C), and then a quaternizing agent (E) is added and reacted; (A) A method of synthesizing a terminal NCO prepolymer from (B) and (U), reacting it with a chain extender (F), and then reacting (E),
A method of synthesizing a prepolymer of NCO, adding (U) to synthesize urethane, and reacting this with (E), or a method of synthesizing a prepolymer of terminal NCO from (A), (B), and (U). On the other hand, examples include a method in which (F) and (E) are reacted in advance and then both are reacted. In the present invention, the ratio of each component can be appropriately determined from a wide range depending on the desired polyurethane, but it is usually within a range where the chemical equivalent ratio of NCO groups to active hydrogen groups is about 0.9 to 1.4, preferably about 0.95 to 1.2. It is best to react, and the reaction is usually about 30 to 130
℃, preferably about 40 to 120℃. Further, the treatment with the quaternizing agent of the present invention is usually about 40 to
Preferably, the temperature is 100°C. In the present invention, it is necessary for the concentration of the quaternary ammonium base to be 0.05 meq/g or more in order to cure the coating film quickly and uniformly, and also to improve the adhesion to various adherends including metals. It is also necessary for sufficiency. In the present invention, the unsaturated polyurethane resin can be synthesized without a solvent, in the presence of an organic solvent, or in the presence of an ethylenically unsaturated compound used as a crosslinking agent described later. Examples of organic solvents include ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and methyl propionate, ethers such as dioxane and cellosolve acetate, and dimethylformamide and dimethyl sulfoxide. In the present invention, an ethylenically unsaturated compound can be used as a crosslinking agent if necessary when curing the unsaturated polyurethane resin. Various known compounds can be used as ethylenically unsaturated compounds, but typical examples include styrene,
Vinyltoluene, chlorostyrene, t-butylstyrene, α-methylstyrene, divinylbenzene, acrylic acid, methacrylic acid, methyl, ethyl, isopropyl, n-butyl, t-butyl, α-ethylhexyl, n -Nonyl, n-decyl, lauryl, stearyl esters, etc., n-butoxyethyl, cyclohexyl, phenoxyethyl, tetrahydrofurfuryl, glycidyl, allyl, benzyl, tribromophenyl of acrylic acid or methacrylic acid,
2,3-dichloropropyl, 3-chloro-2-hydroxypropyl, N,N-dimethylaminoethyl, N,N-diethylaminoethyl, Nt-butylaminoethyl ester, etc., ethylene glycol mono(meth)acrylate, propylene Glycol mono(meth)acrylate, diethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate with molecular weight (hereinafter referred to as MW) 200-1000, MW200-
1000 polyethylene glycol monomethyl ether mono(meth)acrylate, MW200~1000 polypropylene glycol mono(meth)acrylate, MW200~1000 polypropylene glycol monomethyl ether mono(meth)acrylate, MW200~1000 polyethylene glycol monoethyl ether mono(meth)acrylate ) acrylate,
MW200-1000 polypropylene glycol monoethyl ether mono(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,3
- propanediol di(meth)acrylate,
1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, glycerin di(meth)acrylate, glycerin tri(meth)acrylate,
trimethylolethane di(meth)acrylate,
Trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide,
Examples include ethylene bisacrylamide, diallyl phthalate, triallyl isocyanurate, dibutyl fumarate, and vinyl acetate. However, if present during the urethanization reaction, ethylenically unsaturated compounds having active hydrogen should be excluded from the above. Among the above crosslinking agents, particularly preferred compounds have the general formula (In the formula, A represents an alkylene group or haloalkylene group having 2 to 4 carbon atoms), and specific examples include ethylene glycol, propylene glycol,
Monomethacrylates such as 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 3-chloro-
Examples include 2-hydroxypropyl methacrylate. In the present invention, the ratio of the unsaturated polyurethane resin to the ethylenically unsaturated compound is preferably 20:80 to 95:5, and 50:5 by weight.
50 to 80:20 is more preferred. For the purpose of stably storing the composition of the present invention, a known thermal polymerization inhibitor can be added. It is desirable that these thermal polymerization inhibitors prevent only the thermal polymerization reaction (dark reaction) without inhibiting the photocuring reaction, so the amount added should be based on the total amount of the unsaturated polyurethane resin and crosslinking agent. 0.01 to 2.5% by weight, preferably 0.005 to 1% by weight
It is desirable that it be within the range of . Furthermore, in the present invention,
If necessary, commonly used additives such as colorants, dispersants, lubricants, abrasives, and antistatic agents can be added. The composition of the present invention can be obtained by mixing the above-mentioned components by various known methods, and for example, a mixer, roll mill, ball mill, sand mill, high-speed impeller, etc. can be used. The composition of the present invention can be cured by a known method. For example, when curing with an electron beam, the accelerating voltage is 100 to 1000 KeV, preferably 150 to 1000 KeV.
A cured product can be obtained by irradiating in an inert gas atmosphere using a 300 KeV electron beam irradiation device such that the total absorbed dose is 0.5 to 20 Mrad, preferably 2 to 15 Mrad. In addition, in the present invention, other curing means, such as methods using thermal energy such as infrared rays, high frequency waves, or microwaves, i.e., methods of curing by heating, methods of curing using ultraviolet rays obtained from mercury lamps, xenon lamps, etc., or
A method of curing by irradiating with other radiation such as rays or gamma rays can also be used. In the present invention, when using high-energy ionizing radiation such as electron beams, X-rays, and γ-rays, which have the effect of being absorbed by substances and emitting secondary electrons, it is not necessary to add a polymerization initiator. is also good, but
When curing by heating or ultraviolet rays, it is preferable to add a thermal polymerization initiator or a photopolymerization initiator. As described above, the composition of the present invention is characterized by containing an unsaturated polyurethane resin containing a hydrophilic quaternary ammonium base in its molecular chain,
It has excellent curability, and the resulting coating is tough, has excellent adhesion to metals, and can be applied thickly. A detailed explanation will be given below with reference to synthesis examples and examples. Note that "parts" or "%" simply means parts by weight or percent by weight. Synthesis example 1 Place TDI (138.5g) in a reactor equipped with a stirring device and
Warmed to °C, Byron RV200L (molecular weight 2030)
A mixed solution of 807.2 g of dibutyltin dilaurate (HEA), 0.2 g of dibutyltin dilaurate, and 261.0 g of methyl ethyl ketone (MEK) was gradually added dropwise and reacted for about 3 and a half hours with stirring. The mixed solution was added dropwise in the same manner and the reaction was continued for about 3 hours.
Gradually add 34.0 g of phenyldiethanolamine. After reacting for about 2 hours, the temperature of the liquid was lowered to 60℃, and 16.9 g of dimethyl sulfate was added little by little.
The reaction was carried out for a minute to obtain an unsaturated polyurethane resin solution () having a solid content of 80% and a quaternary ammonium base concentration of 0.10 meq/g in the solid content. Synthesis Example 2 Put MDI (212.0 g) into a reactor equipped with a stirring device and approx.
Heated to 80℃, polyoxytetramethylene glycol (molecular weight 1000) 112.3g, Byron RUX (molecular weight 1920) 327.3g, dibutyltin dilaurate
A mixed solution of 0.15g of MEK and 196.2g of MEK was added dropwise and reacted for about 4 hours with stirring, followed by 62.5g of HEA and 196.2g of MEK.
After adding a mixed solution of 1.55 g of hydroquinone dropwise and reacting for another 3 hours, a solution of 95 wt% of N-methyldiethanolamine treated with dimethyl sulfuric acid was added.
69.0g was gradually added and reacted for about 2 hours to reduce the solid content.
80%, an unsaturated polyurethane resin () with a concentration of quaternary ammonium base in the solid content of 0.35 meq/g was obtained. Synthesis Example 3 Put MDI (247.0g) into a reactor equipped with a stirrer and add approx.
Warm to 80℃ and add Plaxel 210 (molecular weight 980) 277.3
g, Byron RV-200L (molecular weight 1840) 184.2g,
Dibutyltin dilaurate 0.18g, dioxane
357.5g of the mixed solution was added dropwise and reacted for about 3.5 hours, then a mixed solution of 68.7g of HEA and 1.69g of hydroquinone was added dropwise and reacted for about 2.5 hours, and then 5.7g of ethylene glycol and N-methyl 24.0 g of diethanolamine was gradually added dropwise, and the mixture was allowed to react for about 1.5 hours. After cooling to 60℃, 25.4g of dimethyl sulfate was added little by little and reacted for about 30 minutes until the solid content was 70.
%, the concentration of quaternary ammonium base in the solid content is
A 0.24 meq/g unsaturated polyurethane resin solution () was obtained. Synthesis Example 4 An unsaturated polyurethane resin solution () was obtained in the same manner as in Synthesis Example 1 except that dimethyl sulfate was removed. Synthesis Example 5 An unsaturated polyurethane resin solution () was obtained in the same manner as in Synthesis Example 2 except that N-methyldiethanolamine was used without being treated with dimethyl sulfuric acid. Synthesis Example 6 An unsaturated polyurethane resin solution () was prepared at the same time as in Synthesis Example 3 except that ethylene glycol was used instead of N-methyldiethanolamine.
I got it. Examples 1 to 5 and Comparative Examples 1 to 5 The unsaturated polyurethane resin solutions obtained in the above synthesis examples were mixed with the compositions shown in Tables 1 and 2, and kneaded in a ball mill for 40 hours. A coating composition was obtained. Regarding the preparation of the coating film, the above composition was applied to a 50μ thick steel plate with a degreased surface using an applicator so that the dry thickness was 30μ, and dried for 5 minutes in an open air at 80℃. After letting
Using a curtain beam type electron beam irradiation device, with an acceleration voltage of 150 KeV and a beam current of 7.4 mA,
The coating film was cured by irradiation at an irradiation dose of 10 Mrad. The physical properties of the resulting coating film were measured in accordance with JIS K5400. In addition, in the table, PU is unsaturated polyurethane resin solution (parts are based on solid content), HEMA is hydroxyethyl methacrylate, HPMA is hydroxypropyl methacrylate, EMA is ethyl methacrylate, HDA is 1,6-hexanediol diacrylate, TMP-tA indicates trimethylolpropane triacrylate, and THF-A indicates tetrahydrofurfuryl acrylate. The Dupont impact uses a load of 500g and is measured in cm.

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Claims (1)

[Claims] 1. A compound having two or more terminal groups having a polymerizable double bond, obtained by reacting at least an organic polyisocyanate, a polyol, an ethylenically unsaturated compound having active hydrogen, and a quaternizing agent. and the fourth
an unsaturated polyurethane resin having a grade ammonium base of 0.05 meq/g or more, and if necessary a crosslinking agent,
A coating composition characterized by containing a colorant and the like. 2. The composition according to claim 1, wherein part or all of the polyol component of the unsaturated polyurethane resin is a compound having two or more active hydrogens and at least one tertiary amino group. 3. According to claim 1, the unsaturated polyurethane resin is obtained using a chain extender having a molecular weight of 500 or less and having two or more active hydrogens and at least one tertiary amino group. Composition of. 4. The composition according to claim 3, wherein the chain extender is treated with a quaternizing agent in advance. 5 The crosslinking agent has the following general formula The composition according to claim 1, which is an ethylenically unsaturated compound represented by the formula (wherein A represents an alkylene group or a haloalkylene group having 2 to 4 carbon atoms). 6. The composition according to claim 1, which is curable by radiation.