JPS59232110A - Production of urethane-vinyl resin - Google Patents

Abstract

PURPOSE:To produce the titled resin curable at room temperature in air, having good adhesion to glass, etc., and useful as a sealant, adhedive, casting material or the like, by copolymerizing a specified urethane prepolymer with a vinyl monomer. CONSTITUTION:The titled resin is produced by copolymerizing a vinyl monomer with a urethane prepolymer having terminal NCO groups blocked with an active hydrogen-containing vinyl compound and an active hydrogen-containing silane coupling agent, prepared by reacting an NCO-terminated urethane prepolymer (a) with an active hydrogen-containing vinyl compound (b) and an active hydrogen-containing silane coupling agent. The titled resin thus produced can be cured rapidly at room temperature in air, provides tough paint films of excellent properties and shows good adhesion to inorganic materials such as glass. It is possible to produce a composition capable of forming films of various properties including ones rich in flexibility and ones of a high surface hardness by varying the kinds and amount of the urethane and the vinyl compound.

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 resin, there is a vinyl resin having a silyl group at the terminal or side chain (Japanese Patent Application Laid-open No. 86895/1989).

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 present inventor has conducted intensive studies to improve this drawback, and as a result has arrived at the present invention. That is, the present invention is characterized in that the urethane prepolymer (8) whose terminal NCO group is capped with a vinyl compound having active hydrogen and a silane coupling agent having active hydrogen is copolymerized with vinyl monomer [F]). This is a method for producing urethane-vinyl resin.

In the present invention, the urethane prepolymer (g) whose terminal NGO group is capped with a vinyl compound having active hydrogen and a silane coupling agent having active hydrogen is a polyisocyanate, a polyol, and if necessary, another active hydrogen-containing compound. NGO-terminated urethane prepolymer (a), vinyl compound containing active hydrogen (b) and silane coupling agent containing active hydrogen (c)
) can be used.

In the NGO-terminated urethane prepolymer (a), examples of the polyisocyanate include aliphatic polyisocyanates and aromatic polyisocyanates. Aliphatic polyisocyanates are polyisocyanates in which all NGO groups are bonded to non-aromatic hydrocarbons, such as aliphatic polyisocyanates having 2 to 12 carbon atoms (excluding carbons in NCO groups); 4 to 15 ring-type polyisocyanates, araliphatic polyisocyanates having 8 to 12 carbon atoms, and modified products of these polyisocyanates (carposiimide groups, uretdione groups, uretdione groups, urea groups, biuret groups, and/or Modified products containing isocyanurate groups, etc.) can be used.

Such polyisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-)limethylhexane diisocyanate, and lysine diisocyanate. 2,6-diycyanatomethyl caproate, bis(2-isocyanateethyl) fumarate, bis[2-isocyanateethyl)carbonate, 2-isocyanateethyl-2,
6-diucyanate hexanoate; isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate) (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis(2-isocyanate) ethyl) 4-cyclohexene-1,2-dicarboxylate; xylylene diisocyanate, diethylbenzene diisocyanate; HDI water modified physical product PDI
and mixtures of two or more thereof.

Aromatic polyisocyanates include tolylene diisocyanate (CTDI), crude [TDl, diphenylmethane diisocyanate) (MDI), polyphenylmethane diisocyanate (PAPI; crude MDI), naphthylene diisocyanate, and these polyisocyanates. Modified products (containing a carposiimide group, a uretdione group, a urea imide group, a urea group, a biuret group and/or an isocyanurate group) include, for example, carposiimide-modified MDI.

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 glycols (ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neoheny7-tyl glycol, hydrogenated bisphenol A, etc.), and low-molecular polyols with 8 or more functional groups. (glycerin, trimethylolpropane, hexanetriol, pentaerythritol, sorbitol, sucrose, etc.) or amines (alkanolamines such as ethanolamine, propatoolamine; aliphatic positive amines such as ethylenediamine, aliphatic monoamines such as n-butylamine). Examples include adducts of oxides (alkylene oxides having 2 to 4 carbon atoms, such as ethylene oxide, propylene oxide, butylene oxide) and ring-opening polymers of alkylene oxides, and specifically include polyethylene glycol, polypropylene glycol, and 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, trimerized linoleic acid; aromatic polycarboxylic acids such as phthalic acid). , polyester polyols containing terminal hydroxyl groups of isophthalic acid and low-molecular-weight polyols or polyether polyols, polycaprolactone polyols For example, initiators [glycol (ethylene glycol,
YoktxJ:),)1. O) L/j, x E
) months, -38, and (substituted) caprolactone (ε-
caprolactone, α-methyl-ε-caprolactone, ε
-methyl-ε-caprolactone, etc.) in the presence of a catalyst (organometallic compound, metal chelate compound, fatty acid 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. Examples include polyethers obtained by subjecting polyesters having carboxyl groups and/or OH groups to an addition reaction with alkylene oxides (eg, ethylene oxide, propylene oxide, etc.).

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 polyol is 0.001 to 30% by weight versus high-molecular polyol). The average molecular weight of polyol is usually 62~
4000, preferably 200 to 200o. The OH value is usually 20 to 100, preferably 30 to 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 NGO-terminated urethane prepolymer (a), the molar ratio of the NGO groups of the polyisocyanate to the active hydrogen of the polyol and, if necessary, other active hydrogen-containing compounds is usually 1:0.1 to 1:09, preferably 1:0. 1-1:
It is 0.7.

During the prepolymerization reaction, the reaction temperature is usually 40 to 140℃.
℃, preferably 50 to 120℃.

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 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. can also be used. The amount is usually 0.005 to 02% by weight based on the resin solids content.

NGO-terminated urethane prepolymer (a) is an NGO-terminated urethane prepolymer from 1 mol of polypropylene glycol CMW-400) and 2 mol of isophorone diisocyanate, polycaprolactone (MW2000).
1 mole of hexamethylene diisocyanate and 2 moles of hexamethylene 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 NGO groups are usually 05 to 42% by weight, preferably &=5 to 20% by weight, particularly preferably 2 to 8% by weight.
Ru.

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 % (1) [wherein X1 is partially -, -S- or -N- (However, R1 is H or 1 or an alkyl group. ) R is H or an alkyl group. A1 is a divalent organic group].

The divalent organic group of A1 is -AO-CO-, -A-
0-CH2-1-A-N-CO-1-A-0-C However, R
' is H, -A-R' 0H or an alkyl group, A is an alkylene group, or a residue of an untreated polyol (low-molecular or high-molecular weight)]
etc. Examples of the compound represented by general formula (1) include hydroxyl group-containing vinyl compounds [unsaturated ethers or esters of polyols (alkylene glycols, glycerin, polyoxyalkylene polyols, etc.), such as hydroxyethyl [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 (methacrylates such as mercaptopropyl (meth)acrylate) and the like.

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, general formula (2) % formula % (2) [wherein, X2 is -0-1-8- or -N- (however, R4
is H4 or an alkyl group), R2 is an alkyl group, R3 is an alkylene group or a halogen, and A2 is a divalent organic group. a is an integer from 0 to 2. ] Examples include compounds represented by:

The divalent organic group of A2 is 5R6 or partially -A'-, where p, q, r are 0, 1. ... integer, R5゜R6 is H, -(Ao)H, A' is an alkylene group or -
In C-C-, Z is the residue 1 of the epoxy compound (Z-<7)

It is 0. R7 and R8 are amino compounds (::;NH,)
is the residue of

Specific examples of (c) include the following.

(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-aminopropyltrimethoxysilane, etc.]; Aminoalkylalkyldialkoxysilane (aminomethylmethyljethoxysilane, γ-amino propylmethyljethoxysilane, etc.); N
-(aminoalkyl)aminoalkylalkyldialkoxysilane [N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, etc.]; and a compound containing an amino group-containing silane coupling agent and a hydrolyzable silyl group Partial hydrolysates of, for example, the above-mentioned amino group-containing silane coupling agents and compounds containing hydrolyzable silyl groups (ethyl silicate, methyltrimethoxysilane,
(2) Silane coupling agent containing a mercapto group Mercaptoalkylalkoxysilane (γ- Mercaptopropyltrimethoxysilane, etc.) etc. (3) Hydroxyl group-containing silane coupling agent (1) An amino group-containing silane coupling agent and a compound containing an epoxy group (ethylene oxide, butylene oxide, epichlorohydrin, epoxidized soybean oil, other shells) Epicoat 828 manufactured by c stock)
, Epicote 1001, etc.); epoxy group-containing silane coupling agent [glycidoxyalkyltrialkoxysilane (γ-glycidoxypropyltrimethoxysilane, etc.); glycidoxyalkylalkyldialkoxysilane [γ-glycidoxypropyltrimethoxysilane, etc.]; sidoxypropylmethyldimethoxysilane, etc.) and amines such as aliphatic amines (ethylamine, diethylamine, triethylamine, ethylenediamine, hexanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentaE)
NCO-terminated urethane prepolymers (a ), active hydrogen stand (1g) When reacting the vinyl compound (b) and the active hydrogen-containing silane coupling agent (c), the reaction order is to react (a) and (b), then (c). react, (
Examples of the order include reacting a) and (c) first and then reacting (b), or reacting (a), (b), and (c) simultaneously.

During the reaction, the isocyanate group of a) and (b) and (
The molar ratio of C) to active hydrogen is usually 1:0.5-1
: 1.5, preferably 1:08 to 1:1.2. (b) and (for the isocyanate group of (a)
Also when the molar ratio of active hydrogen in c) is less than 0.05, 1.5
If it is larger, the physical properties of the resulting resin after curing will also deteriorate.

Regarding the amount of (C), the silane coupling agent (c) (
The molar ratio of a) to isocyanate groups is usually 0.25
-1.5, preferably 0.8-1.2.

Regarding the amount of (b), ■ (b) can be used simultaneously with (c) or (
When reacting before c), the molar ratio of vinyl compound (b) and silane coupling agent (c) is usually 1:1 to 1.
: 100.

The ratio is 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 (
I6) It is weak, and if it exceeds 100, no improvement in physical properties can be obtained even if more is added, and the drug is wasted.

Further, the molar ratio of the active hydrogen of the vinyl compound (b) to the isocyanate group of (a) is usually o, oo5 to 0.75, preferably 0.01 to 0.5. Also, (b) is (C)
If the reaction is carried out after the reaction, it may be added in a slightly excess amount than above.

The reaction between (a), (b), and (c) is usually performed at 50 to 120°C.
It can be done with 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. Examples of this organic solvent include those described above in the prepolymerization reactions (a), (b), and (c). In addition, when performing the urethanization reaction, the same catalysts as those described in the urethanization reactions (a), (b), and (c) may be used as catalysts (containing hydrogen) as necessary.
(b) and (c) may be removed by topping or the like, or may be transferred to the next step as is).

In addition to the urethane prepolymer (a) to be blocked, in addition to the one produced by the above method, it is produced by adding and reacting part or all of (b) and (c) during the production of the NCO-terminated urethane prepolymer (a). For example, some NGO groups of polyisocyanate may be reacted with (b) and (c), and then a polyol (and other active hydrogen compounds as necessary) may be reacted, and polyisocyanate and (b) may be reacted.
), (c) and a polyol (and other active hydrogen compounds if necessary) are reacted simultaneously.

Blocked urethane prepolymer used in the present invention The obtained blocked urethane prepolymer (A) has the general formula [wherein, Y is an NGO-terminated urethane prepolymer residue;
is the residue of the silane coupling agent; Xl, X2 bar 0-l
-5-1-NH-1-N- (R, is H or an alkyl group)'+ m+n is an integer of 2 or more. ] can be shown.

This blocked urethane prepolymer (A) and vinyl monomer (I3) are copolymerized to produce a urethane-vinyl resin.

Specific examples of the vinyl monomer Q3) include the following in addition to the vinyl compound (b) having active hydrogen.

[I] Lipophilic monomer (1) Ester of unsaturated carboxylic acid (methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc.) Straight chain or branched natural or synthetic alcohol having 1 to 25 carbon atoms ( meth)acrylates such as methyl (meth)acrylate, ethyl [meth)acrylate, butyl [meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl methacrylate; polycarboxylic acids (maleic acid, fumaric acid) acid, itaconic acid, etc.) with the above linear or branched natural or synthetic alcohol having 1 to 25 carbon atoms.

(II) Aromatic hydrocarbon vinyl monomer styrene, α-
Methylstyrene, chlorostyrene, vinyltoluene, etc.

(HD vinyl ester or (meth)allyl ester vinyl acetate, vinyl propionate, divinyl phthalate, allyl acetate, diallyl phthalate, etc.)

6V) Nitrile group-containing vinyl monomer (meth)acrylonitrile etc.

(V: vinyl group-containing silyl compound (vinyl group-containing silane coupling agent) vinylmethyldimethoxysilane, vinyltrimethoxysilane, vinyldichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, γ
- Methacryloxy (daprovirtrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldichlorosilane, γ-acryloxytrichlorosilane, etc.).

(Carboxylic acid ester of VD epoxy group-containing monomer glycidyl alcohol, such as glycidyl (meth)acrylate.

&t) Halogen-containing vinyl monomer Vinyl chloride, vinylidene chloride, chloroprene, etc.

(v+::) aliphatic hydrocarbon vinyl monomer ethylene,
Propylene, butadiene, isoprene, etc.

(Kin vinyl ether monomer vinyl methyl ether etc.

(l [] Hydrophilic monomer (1) 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.

(11) Amides of unsaturated mono- or polycarboxylic acids (meth)acrylamide, N-alkyl or N,N-dialkyl [meth)acrylamide, crotonic acid amide, itaconic acid shea EF, N-ethylacrylamide, fumaric acid diamide, maleic acid Acid diamide, N-butoxymethylacrylamide, N-butoxymethylmethacrylamide, etc.; vinyl lactam (N-vinylpyrrolidone, etc.); O++) a-class nitrogen-containing monomeric unsaturated mono- or polycarboxylic acid containing amino groups (e.g. aminoalkyl nitrates, morpholinoalkyl esters, etc.) [e.g. dimethylaminoethyl [meth]acrylate, diethylaminoethyl (meth)acrylate, morpholinoethyl [meth)acrylate; heterocyclic vinyl compounds [e.g. vinylpyridine 6 examples, 2- vinylpyridine, 4-vinylpyridine, N-vinylpyridine),
N-vinylimidazole] (iψSulfonic acid group-containing monomeric aliphatic or aromatic monoethylenically unsaturated sulfonic acid 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, making it extremely strong. Since a network structure is formed, the physical properties of the coating film are further improved.

During copolymerization, the weight ratio of the blocked polyurethane (a) and the vinyl monomer (a) is usually 1:0.01 to 1:100.
．． Preferably it is 1:, 0.05 to 1:50. 03)
If the ratio of
If it exceeds 0, the physical properties after curing will be similar to those of vinyl resin, making it difficult to improve the physical properties.

Copolymerization can be produced by subjecting (a) and CB) 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 are aromatic hydrocarbons (toluene, xylene, ethylbenzene, etc.), aliphatic hydrocarbons [hexane, heptane,
cyclohexane, etc.), aliphatic ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, dibutyl ketone, cyclohexanone, etc.), aliphatic ethers (dioxane, tetrahydrofuran, etc.), halogenated hydrocarbons (carbon tetrachloride, ethylene dichloride, etc.), and these A mixture of two or more types can be mentioned. Preferred are toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, and ethylene dichloride, or a mixture of two or more of these. Usually 0.2: 1~2o:
1 Preferably 0.5:1 to 5:1 〇 When carrying out a radical polymerization reaction, the radical initiator used is an azo compound (such as azobisisobutyronitrile or azobisisovaleronitrile). oxides (benzoyl peroxide, di-t-butyl panioxide, cumene hydroperoxide, dicumyl peroxide, etc.)
N], N-dimethylaniline, etc.). Preferred are azo compounds.

The amount of catalyst added is usually 0 based on the solid content of (5) and
．． 001-20% by weight, preferably 0.1-10% by weight
It is.

The temperature of the radical polymerization reaction is usually 50 to 150°C, preferably 70 to 180°C.

Further, in order to adjust the molecular weight, a chain transfer agent such as n-dodecylmercaptan or t-dodecylmercaptan can be added as necessary.

In the case of solution polymerization, the resin produced by the radical polymerization reaction is obtained in an organic solvent in a solution state or in a precipitated state from the solvent. If necessary, the resin can be isolated by methods such as removal of the solvent by evaporation, filtration, washing, and drying.

The average molecular weight of the resulting urethane-vinyl resin is usually 1.
．． OOO~80,000, preferably 2,000~40
,000.

The silyl group-containing urethane-vinyl resin in the present invention forms a network structure and hardens at room temperature when exposed to the atmosphere. 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 more hydrolyzable groups there are, the higher the curing rate of an alkoxy group with fewer carbon atoms.

The metal salt of silyl group-containing urethane-vinyl□ (2/I) in the present invention is usually 0,001 to 20% by weight based on the fat of dibutylamine-2-hexoate.

Various fillers, pigments, etc. can be mixed into the urethane-vinyl resin of the present invention. Specifically, Japanese Patent Publication No. 5
Those described in Japanese Patent No. 8-19861 can be used.

The resin in the present invention can be applied to various inorganic and organic substances. The details are described in Japanese Patent Application Laid-Open No. 19361/1983.

Application methods include brushing, spraying, and the like.

The features of the urethane-vinyl resin obtained by the present invention are (1) Provides a tough coating film with 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)
) be.

(4) By changing the type and amount of urethane and vinyl compounds, it is possible to adjust the properties from high flexibility to high surface hardness.

etc.

The urethane-vinyl resin obtained by the present invention can be used as a paint,
It is useful as a sealant, adhesive, 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 0.2 isophorone diisocyanate in 60 ml of xylene
mo6 and dibutyltin dilaure) 0.05F were mixed and the temperature was raised to 80 to 90°C. Polypropylene glycol (MW400) 0.18 mo 11 was added dropwise over 1 hour and reacted at the same temperature for 4 hours [prepolymer (a
)]. Furthermore, 2-hydroxyethyl methacrylate 0.0
2mo6 and 0.12mog of γ-aminopropyltrimethoxysilane were added and reacted at the same temperature for 4 hours. (This xylene solution was used as it was in the subsequent vinyl polymerization reaction in Example 1.) When the solvent was removed under reduced pressure, a blocked urethane prepolymer (a) having a molecular weight of about 1400 was obtained. The infrared absorption spectrum of this substance has 1648
cm” absorption was observed and the NGO content was O.

Reference Example 2 0.2 mo6 of hexamethylene diisocyanate and 0.1 f of dibutyltin dilaurate were mixed with 60 mff of methyl isobutyl ketone, and the mixture was heated to 80 to 90°C.

Polycaprolactone polyol (MW2000) 0
．． 1 moe (1!) was added in portions over 1 hour and reacted at the same temperature for 4 hours [prepolymer (ω)]. Furthermore, 0.01 moe of 2-hydroxy vinyl ether and 0.18 moe of γ-mercaptopropyltrimethoxysilane were added to give a mixture of 90 to
The reaction was carried out at 100°C for 4 hours. After topping with methyl isobutyl ketone, a capped urethane prepolymer (8) with a molecular weight of approximately 8,000 was obtained. In the infrared absorption spectrum of this product, absorption at 1648 cm 2 was observed. Also, the NGO content was O.

Example 1 Blocked urethane prepolymer obtained in Reference Example 1 (
The xylene solution of 5) was heated to 100°C, and a mixed solution of 0.8ml of n-butyl methacrylate, 0.05mo6 of Lγ-methacryloxypropyltrimethoxysilane, and 0.59% of azobisisobutyronitrile was heated to 100-110°C.
It was added dropwise over 30 minutes. After reacting at the same temperature for 3 hours, 0.14 g of azobisisobutyronitrile was added and reacted for 2 hours to obtain a urethane-vinyl resin. It was confirmed that the produced resin had no absorption at 1648 cm-' in the infrared absorption spectrum. As a test, a coating film was prepared by adding and mixing 1 wt 0% dibutyltin maleate to this resin, and it became tack-free and cured in about 20 minutes.

Example 2 0.15 moe of styrene and 0 methyl methacrylate
．． 15mo (? n-butyl methacrylate 0.8mo
Vinyl polymerization was carried out in the same manner as in Example 1 by using 1 instead of 6. 164 of the infrared absorption spectrum for the product
It was confirmed that the absorption of 8 cm''-' was gone, and it was found that uretayu/-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 After dropping a mixed solution of n-butyl methacrylate 0.8 moLγ-methacryloxypropyl trime 1-xysilane 0.05 moff and azobisisobutyronitrile 0.5 g into 60 ml of xylene at 100 to 110°C over 30 minutes. , and reacted at the same temperature for 3 hours. Further, 01 g of azobisisobutyronitrile was added and reacted for 2 hours to obtain a vinyl resin having a hydrolyzable silyl group in the side chain.

Test Example 1 10 each of the resins of Examples 1 to 3, Comparative Example 1, and Reference Example 1
2 parts of dibutyltin dilaurate was added to 0 parts and applied to an aluminum plate, and the film forming ability and physical properties were measured. The results are shown in Momme. The resulting coating was about 5-6 mils.

(31) C32)

Claims (1)

[Claims] 1. Copolymerizing a urethane prepolymer (8) whose terminal NGO group is capped with a vinyl compound having an active hydrogen and a silane coupling agent having an active hydrogen and a vinyl monomer (2). Characteristic method for producing urethane-vinyl resin. 2. The silane coupling agent has a hydroxyl group. A process for producing the remark in 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. Vinyl compounds with active hydrogen have the general formula % formula % (1
) [In the formula, Xl is (i)-, -S- or -N-C, but R
I1 is H or an alkyl group), R is H or an alkyl group. A1 is a divalent organic group. 4. (a) is NCO-terminated urethane prepolymer (a),
A urethane prepolymer obtained by reacting a vinyl compound (b) having active hydrogen and a silane coupling agent (c) having active hydrogen.
The manufacturing method described in any of paragraph 8.