JPH0212488B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing urethane-vinyl resins. More specifically, the present invention relates to a method for producing a urethane-vinyl resin having a hydrolyzable silyl group at its terminal or side chain. Curable resins containing a silyl group at the end are curable at room temperature and have excellent adhesion to glass, aluminum, etc., so they are used in paints and the like by taking advantage of the characteristics of the resin in the main chain. As such a resin, there is a vinyl resin having a silyl group at the terminal or side chain (Japanese Patent Application Laid-open No. 36395/1983). However, this vinyl resin has a problem in that the physical properties of the coating film are slightly lower than that of conventional vinyl resins. The inventor of the present invention has conducted intensive studies to improve this drawback, and as a result has arrived at the present invention. That is, the present invention provides a vinyl monomer that essentially contains a urethane prepolymer (A) whose terminal NCO group is capped with a vinyl compound having active hydrogen and a silane coupling agent having active hydrogen, and a vinyl group-containing silyl compound (V). (B) is a method for producing a urethane-vinyl resin. In the present invention, a urethane prepolymer whose terminal NCO group is capped with a vinyl compound having active hydrogen and a silane coupling agent having active hydrogen
(A) is a mixture of polyisocyanate, polyol and, if necessary, other active hydrogen-containing compounds.
A structure obtained by reacting an NCO-terminated urethane prepolymer (a), a vinyl compound containing active hydrogen (b), and a silane coupling agent containing active hydrogen (c) can be used. In the NCO-terminated urethane prepolymer (a),
Examples of polyisocyanates include aliphatic polyisocyanates and aromatic polyisocyanates. Aliphatic polyisocyanates are polyisocyanates in which all NCO groups are bonded to non-aromatic hydrocarbons, such as aliphatic polyisocyanates with a carbon number of 2 to 12 (excluding carbons in the NCO groups); Alicyclic polyisocyanates having 4 to 15 carbon atoms, araliphatic polyisocyanates having 8 to 12 carbon atoms, and modified products of these polyisocyanates ((carbodiimide group, uretdione group, uretoimine group, urea group, Biuret group and/or isocyanurate) Examples of such polyisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2, 4-trimethylhexane diisocyanate, lysine diisocyanate, 2,6-diisocyanate methyl caproate, bis(2-
isocyanate ethyl) fumarate, bis(2-
isocyanate ethyl) carbonate, 2-isocyanate ethyl-2,6-diisocyanate hexanoate; isophorone diisocyanate (IPDI) dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene dipolyisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-Isocyanate ethyl) 4-cyclohexene-1,2-dicarboxylate; xylylene diisocyanate, diethylbenzene diisocyanate; water modified product of HDI,
Examples include trimerized products of IPDI; and mixtures of two or more thereof. Aromatic polyisocyanates include tolylene diisocyanate (TDI), crude TDI, diphenylmethane diisocyanate (MDI), polyphenylmethane polyisocyanate (PAPI; crude MDI),
Naphthylene dipolyisocyanate and modified products of these polyisocyanates (containing carbon diimide groups, uretone dione groups, uretimine groups, urea groups, Biuret groups and/or isocyanate groups), such as carbodiimide-modified
MDI can be mentioned. Among these, preferred are aliphatic diisocyanates and alicyclic diisocyanates, and particularly preferred are hexamethylene diisocyanate and isophorone diisocyanate. Examples of polyols include high molecular polyols (polyether polyols, polyester polyols, polyether ester polyols) and low molecular polyols. Examples of polyether polyols include low molecular weight glycols (ethylene glycol, diesterene glycol, propylene glycol, 1,4-butadiol, 1,6-hexanediol, neopentyl glycol, hydrogenated bisphenol A, etc.), 3
Low molecular weight polyols (glycerin, trimethylolpropane, hexanetriol, pentaerythritol, sorbitol, seuucrose, etc.) or amines (alkanolamines such as ethanolamine, propanolamine; aliphatic polyamines such as ethylenediamine, aliphatic monoamines such as N-butylamine, etc.) adducts of alkylene oxides (alkylene oxides having 2 to 4 carbon atoms, such as ethylene oxide, propylene oxide, butylene oxide) and ring-opening polymers of alkylene oxides, specifically polyethylene glycol, polypropylene glycol, Contains polytetramethylene glycol. Polyester polyols include polycarboxylic acids (aliphatic saturated or unsaturated polycarboxylic acids such as adipic acid, azelaic acid, dodecanoic acid,
Maleic acid, fumaric acid, itaconic acid, double linoleic acid; aromatic fat polycarboxylic acids such as phthalic acid, isophthalic acid and low molecular weight polyols or polyether polyols containing terminal hydroxyl group-containing polyester polyols, polycaprolactone polyols such as initiators [glycol ( ethylene glycol, etc.), triol, etc.] and (substituted) caprolactone (ε-caprolactone, α-methyl-ε-caprolactone, ε-caprolactone,
-methyl-ε-caprolactone, etc.) in the presence of a catalyst (organometallic compound, metal chelate compound, aliphatic metal acylated product, etc.), such as polycaprolactone polyol. The polyester ether polyol includes a linear or branched polyester having an OH group in the molecular chain obtained by esterifying the polycarboxylic acid and the polyether polyol, or a mixture of this and the low molecular weight polyol, and a linear or branched polyester having an OH group at the end. Polyethers obtained by addition-reacting alkylene oxides (eg, ethylene oxide, propylene oxide, etc.) to polyesters having carboxyl groups and/or OH groups are mentioned. Among the polymer polyols, preferred are polypropylene glycol, polycaprolactone polyol and polytetramethylene glycol, and particularly preferred are polypropylene glycol and polycaprolactone polyol. As the low-molecular polyol, the same low-molecular polyols as mentioned in the section of polyether polyols can be used. Among the polyols, preferred are high-molecular polyols and, if necessary, combinations thereof with low-molecular polyols (the amount of low-molecular polyols is 0.001 to 30% by weight relative to high-molecular polyols). The average molecular weight of the polyol is usually 62 to 4000, preferably 200 to 2000
be. OH value is usually 20-1000, preferably 30-
It is 800. Other active hydrogen-containing compounds that may be used if necessary include the amines mentioned in the section regarding polyether polyols. When obtaining the NCO-terminated urethane prepolymer (a), the molar ratio of the NCO group of the polyisocyanate to the active hydrogen of the polyol and, if necessary, other active hydrogen-containing compounds is usually 1:0.1 to 1:0.9, preferably 1:0.3 to 1. :0.7. During the prepolymerization reaction, the reaction temperature is usually
The temperature is 40-140°C, preferably 50-120°C. The reaction can be carried out, if necessary, in the presence of an organic solvent inert to isocyanate groups. Examples of the organic solvent include aromatic fatty hydrocarbons (toluene, xylene, etc.), ketones (methyl ethyl ketone, methyl isobutyl ketone, etc.), and mixtures of two or more of these. If necessary, metal catalysts such as dibutyltin dilaurate, stannath-2-ethylhexoate, iron-acetylacetonate; amine catalysts such as triethylenediamine, N-methylmorpholine, etc. may be used as the decomposer, if necessary. The amount used is usually based on the resin solid content.
It is 0.005-0.2% by weight. As NCO-terminated urethane prepolymer (a), NCO from 1 mol of polypropylene glycol (MW-400) and 2 mol of isophorone diisocyanate is used.
Examples include NCO-terminated urethane prepolymers, such as NCO-terminated urethane prepolymers made from 1 mol of polycaprolactone (MW2000) and 2 mol of hexamelene diisocyanate. The average molecular weight of the NCO-terminated urethane prepolymer (a) is usually 200 to 40,000, preferably 500 to 20,000. The free NCO groups usually amount to 0.5 to 42% by weight, preferably 1 to 20% by weight, particularly preferably 2 to 8% by weight. Equivalent weight is usually 100-8400, preferably 210
-4200, particularly preferably 525-2100. Examples of the vinyl compound (b) having active hydrogen include vinyl compounds having active hydrogen such as a hydroxyl group, an amino group, and a mercapto group. The vinyl compound (b) having active hydrogen has the general formula [In the formula, X ₁ is -O-, -S- or

[Formula] (R ₁ H or an alkyl group) R is H or an alkyl group. A ₁ is a divalent organic group]. The divalent organic group of A ₁ is -AC-CO-, -A
-O- _CH2- ,

[Formula] -A-O- [where R' is H, -A-OH or an alkyl group, and A is an alkylene group or a residue of a polyol (low molecule or polymer)]. . Compounds represented by general formula (1) include hydroxyl group-containing vinyl compounds [polyols (alkylene glycols, glycerin, polyoxyalkylene polyols, etc.), unsaturated ethers or esters, such as hydroxylethyl (meth)acrylate, hydroxypropyl (meth)acrylate, Triethylene glycol (meth)acrylate, poly(oxyethylene, oxypropylene)
Glycol mono(meth)allyl ether, etc.; N
- hydroxyalkyl (meth)acrylamide such as N-methylol (meth)acrylamide;
Unsaturated alcohols such as allyl alcohol]; amino group-containing vinyl compounds [aminoalkyl vinyl ethers such as aminoethyl vinyl ether]; mercapto group-containing vinyl compounds [mercaptoalkyl (meth)acrylates such as mercaptopropyl (meth)acrylate]. Among these, hydroxyl group-containing vinyl compounds are preferred, and hydroxyethyl methacrylate and N-methylol methacrylamide are particularly preferred. The silane coupling agent (c) having active hydrogen includes an active hydrogen-containing group selected from the group consisting of hydroxyl group, amino group and mercapto group, and a hydrolyzable silyl group selected from the group consisting of alkoxysilyl group and halosilyl group. Examples include compounds that have Specifically, the general formula [In the formula, X ₂ is -O-, -S- or

[Formula] (where R ₄ is H or an alkyl group), R ₂ is an alkyl group, R ₃ is an alkoxy group or halogen, A ₂ is 2
It is a valent organic group. a is an integer from 0 to 2. ]
Examples of the compounds shown are: As a divalent organic group of A ₂ ,

【formula】

【formula】 or

[Formula], where p, q, r are integers of 0, 1,..., R ₅ ,
R ₆ is H, -(AO)H, A' is an alkylene group or

In [Formula], Z is an epoxy compound

It is a residue of [Formula]. R ₇ and R ₈ are amino compounds

It is a residue of [Formula]. Specifically, (c) is as follows. (1) Amino group-containing silane coupling agent Aminoalkyltrialkoxysilane (γ-
aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, aminomethyltriethoxysilane, etc.); N-(aminoalkyl)aminoalkyltrialkoxysilane [N
-(β-aminoethyl)aminomethyltrimethoxysilane, N-(β-aminoethyl)aminomethyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, etc.]; Aminoalkylalkyldi Alkoxysilane (aminomethylmethyldiethoxysilane, γ-aminopropylmethyldiethoxysilane, etc.); N-(aminoalkyl)aminoalkylalkyldialkoxysilane [N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane etc.; and partial hydrolysates of compounds containing an amino group-containing silane coupling agent and a hydrolyzable silyl group, such as the above-mentioned amino group-containing silane coupling agent and a compound containing a hydrolysable silyl group (ethyl silicate, (2) Silane coupling agents containing mercapto groups Mercaptoalkyl Alkoxysilane (γ-
mercaptopropyltriethoxysilane, etc.), etc. (3) Hydroxyl group-containing silane coupling agents (1) Amino group-containing silane coupling agents and compounds containing epoxy groups (ethylene oxide, butylene oxide, epichlorohydrin, epoxidized soybean oil, other shells) Epicoat Co., Ltd.
828, Epicote 1001, etc.); epoxy group-containing silane coupling agents [glycidoxyalkyltrialkoxysilanes (γ-glycidoxypropyltrimethoxysilane, etc.); glycidoxyalkylalkyldialkoxysilanes (γ- glycidoxypropylmethyldimethoxysilane, etc.), amines such as aliphatic aminos (ethylamino, diethylamine, triethylamine, ethylenediamine, hexanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc.), aromatic amines, etc. Aniline, diphenylamines), alicyclic amines (cyclopentylamine,
Cyclohexyamine, etc.); reaction products with alkanolamines (ethanolamines), etc. React NCO-terminated urethane prepolymer (a), active hydrogen-containing vinyl compound (b), and active hydrogen-containing silane coupling agent (c) In this case, the reaction order is to react (a) and (b), then react (c), (a)
and (c) are reacted first, and then (b) is reacted,
Examples include reacting (a), (b), and (c) simultaneously. During the reaction, the isocyanate group of (a) and (b) and (c)
The molar ratio of active hydrogen to active hydrogen is usually 1:0.5 to 1:1.5,
Preferably it is 1:0.8 to 1:1.2. Both when the molar ratio of the active hydrogens in (b) and (c) to the isocyanate groups in (a) is less than 0.5, and when it is greater than 1.5, the physical properties of the resulting resin after curing deteriorate. Regarding the amount of (c), (a) of silane coupling agent (c)
The molar ratio of isocyanate groups is usually from 0.25 to
1.5, preferably 0.8-1.2. Regarding the amount of (b), when reacting (b) with (c) at the same time or before (c), the molar ratio of vinyl compound (b) and silane coupling agent (c) is usually 1:1 to 1. 1:
100, preferably 1:2 to 1:50. When the molar ratio of (c) is less than 1, the curing speed is slow and the physical properties after curing are weak, and when it exceeds 100, no improvement in physical properties can be obtained even if more is added, and the chemical is wasted. Further, the molar ratio of active hydrogen in the vinyl compound (b) to the isocyanate group in (a) is usually 0.005 to 0.75, preferably 0.01 to 0.5. Furthermore, when (b) is reacted after (c), it may be added in a slightly excess amount than above. The reaction between (a), (b), and (c) can usually be carried out at 50 to 120°C. The reaction may be carried out in the presence or absence of an inert organic solvent that does not contain active hydrogen that reacts with isocyanate groups and does not contain vinyl groups. As this organic solvent, (a), (b) and (c)
Examples include the same ones as those described in the prepolymerization reaction. In addition, when carrying out the urethanization reaction, (a), (b) and (c) may be used as catalysts as necessary.
The same catalysts described in the urethanization reaction can be used. Contains isocyanate and active hydrogen remaining after reaction
(b) and (c) may be removed by topping or the like, or may be directly transferred to the next step. In addition to the urethane prepolymer (A) to be blocked, in addition to the one produced by the above method, the one produced by adding and reacting part or all of (b) and (c) during the production of the NCO-terminated urethane prepolymer (a). For example, part of the NCO group of polyisocyanate (b),
(c) and then reacted with a polyol (and other active hydrogen compounds if necessary), polyisocyanate and (b), (c) and polyol (and other active hydrogen compounds if necessary) reacted simultaneously. I can give you what you gave me. The average molecular weight of the blocked urethane prepolymer (A) used in the present invention is usually 300 to 45,000, preferably
600-25000. The equivalent amount of (A) [total of blocked vinyl groups and silyl groups] per molecule is usually
150-8600, preferably 260-4400, particularly preferably 600-2300. The obtained blocked urethane prepolymer (A) has the general formula [Wherein, Y is the NCO-terminated urethane prepolymer residue; Q is the residue of the silane coupling agent; X ₁ , X ₂
is -O-, -S-, -NH-,

[Formula] (R ₁ H or an alkyl group), m+n is an integer of 2 or more. ] can be shown. A urethane-vinyl resin is produced by copolymerizing this blocked urethane prepolymer (A) with a vinyl monomer (B) which essentially contains a vinyl group-containing silyl compound (V). The vinyl group-containing silyl compound (V) is also called a vinyl group-containing silane coupling agent, and specific examples thereof include the following. Vinylmethyldiethoxysilane, vinyltriethoxysilane, vinyldichlorosilane, vinyltriethoxysilane, vinyltris(β-ethoxysilane)silane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-acrylic Roxypropyltrimethoxysilane, γ-methacryloxypropylmethyldichlorosilane, γ-acryloxytricyclosilane. Specifically, the vinyl monomer (B) used together with the compound (V) includes the following in addition to the vinyl compound (b) having active hydrogen. [] Lipophilic monomer (i) Unsaturated carboxylic acid [(meth)acrylic acid,
esters of maleic acid, fumaric acid, itaconic acid, etc. (meth)acrylates of linear or branched natural or synthetic alcohols having 1 to 25 carbon atoms, such as methyl (meth)acrylate, (meth)acrylate
Ethyl acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate,
Methacrylic acid; the above carbon number of polycarboxylic acid (maleic acid, malic acid, itaconic acid, etc.) is 1
~25 diesters or half-esters with linear or branched natural or synthetic alcohols, etc. (ii) Aromatic fatty hydrocarbon vinyl monomers such as styrene, α-methylstyrene, chlorostyrene, vinyltoluene, etc. (iii) Vinyl ester or (meth)acrylic ester, vinyl acetate, vinyl propionate, divinyl phthalate, allyl acetate, diallyl phthalate, etc. (iv) Nitrile group-containing vinyl monomer (meth)acrylonitrile, etc. (v) Epoxy group-containing monomer Glycidyl alcohol carboxylic acid ester, for example, glycidyl (meth)acrylate. (vi) Halogen-containing vinyl monomers such as vinyl chloride, vinylidene chloride, chloroprene, etc. (viii) Aliphatic hydrocarbon vinyl monomers ethylene, propylene, butadiene, isoprene, etc. (ix) Vinyl ether monomers Vinyl methyl ether, etc. [] Hydrophilic monomers (i) Unsaturated mono- or polycarboxylic acids, their acid anhydrides or their salts (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid and their salts (alkali metal salts, ammonium salts) , amine salts, etc.), maleic anhydride, etc. (ii) Amido(meth)acrylamide, N-alkyl or N,N-dialkyl(meth)acrylamide, crotonic acid amide, itaconic acid diamide, N-ethylacrylamide, fumaric acid diamide, maleic acid of unsaturated mono- or polycarboxylic acids; diamide, N-butoxymethylacrylamide, N-butoxymethylmethacrylamide, etc.; vinyl lactam (N-
(vinylpyrrolidone, etc.) (iii) Tertiary nitrogen-containing monomer Amino group-containing esters of unsaturated mono- or polycarboxylic acids (e.g., dialkylaminoalkyl esters, morphoalkyl esters, etc.) [e.g., dimethylaminoethyl (meth)acrylate, diethylamino Ethyl (meth)acrylate, morpholinoethyl (meth)acrylate; multi-ring vinyl compounds [e.g. vinylpyridine (e.g. 2-vinylpyridine, 4-vinylpyridine, N-vinylpyridine), N-vinylimidazole] (iv) Sulfonic acid group-containing monomer: Aliphatic or aromatic monoethylenically unsaturated sulfonic acids such as vinyl sulfonic acid, styrene sulfonic acid, etc. Among these, preferred are unsaturated carboxylic acid esters, vinyl esters, tertiary nitrogen-containing monomers, and vinyl group-containing silane coupling agents. When a vinyl group-containing silane coupling agent is used, the terminal silyl group bonded to the urethane side and the side chain silyl group introduced to the vinyl polymer side can be crosslinked by hydrolysis during curing, which is extremely effective. Since a strong network structure is formed, the physical properties of the coating film are further improved. The weight ratio of the blocked polyurethane (A) and vinyl monomer (B) during copolymerization is usually 1:0.01 to 1:100,
Preferably it is 1:0.05 to 1:50. The percentage of (B) is
When it is less than 0.01, the physical properties of the resulting resin after curing cannot be expected to be improved and the physical properties become close to those of polyurethane, and when it exceeds 100, the physical properties after curing become similar to those of vinyl resin and it is difficult to improve the physical properties. Copolymerization can be produced by subjecting (A) and (B) to bulk or solution polymerization according to radical polymerization such as thermal polymerization, photopolymerization, or radiation polymerization. A preferred polymerization method is a radical polymerization method (solution polymerization method) using a radical initiator in an organic solvent. In the case of solution polymerization, the organic solvents used include aromatic hydrocarbons (toluene, xylene, ethylbenzene, etc.), aliphatic hydrocarbons (hexane, heptane, cyclohexane, etc.), aliphatic ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, Examples include dibutylketone, cyclohexane, etc.), aliphatic ethers (dioxane, tetrahydrofuran, etc.), halogenated hydrocarbons (carbon tetrachloride, ethylene dichloride, etc.), and mixtures of two or more of these. Preferred are toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone and ethylene dichloride, or a mixture of two or more thereof. The ratio of organic solvent (A) and (B) to the total weight can be selected arbitrarily, but is usually 0.2:1 to 20:
1, preferably 0.5:1 to 5:1. When carrying out a radical polymerization reaction, azo compounds (azobisisobutyronitrile, azobisisovaleronitrile, etc.), peroxides (benzoyl peroxide, di-t-butyl peroxide, etc.) are not used as radical initiators. cumene hydroperoxide, dicumyl peroxide, etc.), redox compounds (benzoyl peroxide,
N,N-dimethylaniline, etc.).
Preferred are azo compounds. The amount of catalyst added is usually the same as the solid content of (A) and (B).
0.001-20% by weight, preferably 0.1-10% by weight. The temperature of the radical polymerization reaction is usually 50 to 150°C, preferably 70 to 130°C. In addition, to adjust the molecular weight, n
A chain transfer agent such as -dodecylmercapto or t-dodecylmercaptan can be added. When carrying out solution polymerization, the resin produced by the dical polymerization reaction is obtained in an organic solvent in a solution state or in a precipitated state from a solution. This resin can be isolated by methods such as removal of the solvent by evaporation, filtration, washing, and drying, if necessary. The average molecular weight of the resulting urethane-vinyl resin is usually 1,000 to 80,000, preferably 2,000 to 40,000. When the silyl group urethane-vinyl resin in the present invention is exposed to the atmosphere, it forms a reticulated coarse weave and hardens at room temperature. Curing speed varies depending on ambient temperature, relative temperature, and type of hydrolyzable group. Specifically, the higher the temperature and humidity, the higher the curing rate, and the greater the number of hydrolyzable groups, or in the case of an alkoxy group, the lower the number of carbon atoms, the higher the curing rate. When curing the silyl group-containing urethane-vinyl resin in the present invention, a curing accelerator may be used if necessary. Examples of curing accelerators include titanates, amines, organotin compounds, acidic compounds, etc., such as alkyl titanates, metal salts of carboxylic acids such as tin octylate, dibutyltin dilaurylate, dibutyltin maleate, dibutylamine-2-hexoate, etc. and other curing catalysts described in JP-A-58-199361. The amount of curing accelerator added is usually 0.001 to the resin.
~20% by weight. Various fillers, pigments, etc. can be mixed into the urethane-vinyl resin of the present invention. Specifically, those described in JP-A-58-19361 can be used. The resin in the present invention can be applied to various inorganic and organic substances. Details of this are published in Japanese Patent Application Publication No. 58-
It is described in Publication No. 19361. Application methods include application methods such as brushing and spraying. The features of the urethane-vinyl resin obtained by the present invention are (1) It provides a tough coating film and has excellent coating film properties. (2) Cures at room temperature in the atmosphere. Curing is faster than conventional silyl group-containing urethane resins. (3) Good adhesion to inorganic materials such as glass and aluminum. (4) By changing the type and amount of urethane and vinyl compounds, it is possible to adjust the surface from highly flexible to highly hard. etc. The urethane-vinyl resin obtained by the present invention is useful as a paint, a sealant, an adhesive, a casting material, etc. The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto. Reference example 1 Isophorone diisocyanate in 60ml of xylene
0.2 mol and 0.05 g of dibutyltin dilaurate were mixed, and the temperature was raised to 80 to 90°C. 0.13 mol of polypropylene glycol (NW400) was dropped over 1 hour, and the mixture was reacted at the same temperature for 4 hours [prepolymer (a)]. Additionally 0.02 mol of 2-hydroxyethyl methacrylate and γ-aminopropyltrimethoxysilane
0.12 mol was added and reacted at the same temperature for 4 hours. (This xylene solution was used as it was in the subsequent vinyl polymerization reaction of Example 1.) After removing the solvent under reduced pressure, a blocked urethane prepolymer (A) with a molecular weight of about 1400 was obtained. Absorption at 1648 cm ^-1 was observed in the infrared absorption spectrum of this product. Also NCO
The content was 0. Reference Example 2 0.2 mol of hexamethylene diisocyanate and 0.1 g of dibutyltin dilaurylate were mixed with 60 ml of methyl isobutyl ketone, and the mixture was heated to 80 to 90°C.
Polycaprolactone polyol (MW2000)
0.1 mol was added in portions over 1 hour and reacted at the same temperature for 4 hours [prepolymer (a)]. Furthermore, 0.01 mol of 2-hydroxyvinyl ether and 0.18 mol of γ-mercaptopropyltrimethoxysilane were added.90
The reaction was carried out at ~100°C for 4 hours. After topping with methyl isobutyl ketone, a blocked urethane prepolymer (A) with a molecular weight of about 3000 was obtained. Absorption at 1648 cm ^-1 was observed in the infrared absorption spectrum of this product. Moreover, the NCO content was 0. Example 1 A xylene solution of the blocked urethane prepolymer (A) obtained in Reference Example 1 was heated to 100°C, and n-
A mixed solution of 0.3 mol of butyl methacrylate, 0.05 mol of γ-methacryloxypropyltrimethoxysilane and 0.5 g of azobisisobutyronitrile was added.
It was applied at 100-110°C for 30 minutes. After reacting at the same temperature for 3 hours, 0.1g of azobisisobutyronitrile
was added and reacted for 2 hours to obtain a urethane-vinyl resin. It was confirmed that the produced resin no longer had absorption at 1648 cm ^-1 in the infrared absorption spectrum. As a test, a coating film was made by adding 1wt% dibutyltin maleate to this resin, and it became tack-free and cured in about 20 minutes. Example 2 0.15 mol of styrene and methyl methacrylate
Vinyl polymerization was carried out in the same manner as in Example 1, using 0.15 mol in place of 0.3 mol of n-butyl methacrylate. 1648 of the infrared absorption spectrum for the product
It was confirmed that the absorption of cm ^-1 had disappeared, indicating that a urethane-vinyl resin was obtained. Example 3 The urethane prepolymer (A) obtained in Reference Example 2 was subjected to a vinyl polymerization reaction in the same manner as in Example 1 to obtain a urethane-vinyl resin. Comparative Example 1 A mixed solution of 0.3 mol of n-butyl methacrylate, 0.05 mol of γ-methacryloxypropyltrimethoxysilane and 0.5 g of azobisisobutyronitrile was dropped into 60 ml of xylene at 100 to 110°C for 30 minutes, and then The reaction was continued at the same temperature for 3 hours. Furthermore, when 0.1 g of azobisisobutylnitrile is reacted for 2 hours,
A vinyl resin having a hydrolyzable silyl group in the side chain was obtained. Test Example 1 2 parts of dibutyltin dilaurylate was added to 100 parts each of the resins of Examples 1 to 3, Comparative Example 1, and Reference Example 1, and the mixture was coated on an aluminum plate, and the film-forming ability and physical properties were measured. The results are shown in Table-1. The resulting coating was approximately 5-6 mils.

【table】

Claims (1)

[Scope of Claims] 1. A vinyl compound whose terminal NCO group essentially contains a urethane prepolymer (A) capped with a vinyl compound having an active hydrogen and a silane coupling agent having an active hydrogen, and a vinyl group-containing silyl compound (V) A method for producing a urethane-vinyl resin, which comprises copolymerizing a monomer (B). 2 The silane coupling agent has a hydroxyl group,
The method according to claim 1, which is a compound having an active hydrogen-containing group selected from the group consisting of an amino group and a mercapto group and a hydrolyzable silyl group selected from the group consisting of an alkoxysilyl group and a halosilyl group. 3 A vinyl compound with active hydrogen has the general formula [wherein, X ₁ is -O-, -S- or [Formula] (wherein R ₁ is H or an alkyl group), and R is H or an alkyl group. A ₁ is a divalent organic group] The manufacturing method according to claim 1 or 2, which is a compound represented by the following formula. 4. Claims in which (A) is a urethane prepolymer obtained by reacting an NCO-terminated urethane prepolymer (a), a vinyl compound having active hydrogen (b), and a silane coupling agent having active hydrogen (c) The manufacturing method according to any one of items 1 to 3.