JPS62558A - Coating composition - Google Patents

Abstract

PURPOSE:To obtain a coating compsn. which exhibits an effect due to fluorine on the surface of a coating film by the addition of a small quantity thereof and has good resistance to washing, by blending a specified polymer composed of a fluorovinyl monomer unit, a silyl group-contg. monomer unit and other vinyl monomer unit. CONSTITUTION:A coating compsn. contains a hydrolyzable silyl group-contg. fluoropolymer selected from among vinyl polymers (i) composed of a fluorovinyl monomer unit (a) and other vinyl monomer unit (h) and containing a hydrolyzable silyl group (c) of the formula at one or both terminals and polymers (ii) composed of a fluorovinyl monomer unit (a'), a silyl group-contg. monomer unit (h') and other vinyl monomer unit (c'). In the formula, R1 is a bivalent org. group; R2 is H, a 1-4C alkyl; R3 is a 1-4C alkyl; a is 1-3.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a fluorine-containing vinyl coating composition.

[Prior art] There are fluorine-containing paints that exhibit excellent properties such as weather resistance, water and oil repellency, and copolymers of alkyl vinyl ether and fluoroolefin are particularly well known as solvent-based and curable paints. (Japanese Unexamined Patent Publication No. 55-25411). However, this product is expensive due to its high fluoroolefin content, and its uses are limited. In order to counter this, there are paints that add fluorine-containing additives to paints that try to produce the properties of fluorine at a low cost, and the main component is a fluorine-containing graft block polymer (oligomer).
is used (Japanese Unexamined Patent Publication No. 184656/1983).

This is an attempt to impart fluorine properties to the coating film interface by adding approximately 1% to the main resin.

During drying of the coating film, the fluorine-containing graft block polymer (oligomer) migrates to the surface and concentrates, improving the weather resistance of the surface.
a.Improves properties such as water repellency, oil resistance, and chemical resistance. However, the method for synthesizing graft block polymers (oligomers) is complicated and troublesome. It is not satisfactory due to problems such as insufficient wash resistance.

[Problems to be Solved by the Invention] As a result of studies to easily obtain fluorine that exhibits the effect of fluorine on the coating surface by adding a small amount and has good wash resistance, the present invention has been arrived at.

[Means for Solving the Problems] The present invention provides: (1) a polymer composed of a fluorine-containing vinyl monomer unit (a) and another vinyl monomer unit (b); At the end, the general formula (wherein R1 is a divalent organic group, and R2 is hydrogen or an alkyl group having 1 to 4 carbon atoms).

R3 is an alkyl group having 1 to 4 carbon atoms.

a is an integer from 1 to 3. ), and (11) a fluorine-containing vinyl monomer unit (a'), a monomeric unit containing a silyl group (b''), and others. Coating composition characterized by containing a hydrolyzable silyl group-containing fluoropolymer (first invention); and a coating characterized by containing the hydrolyzable silyl group-containing fluorine-containing polymer [AI] and a silyl group-containing polymer [8] having one or more silyl groups in one molecule at the terminal or side chain. A composition (second invention).

The monomer serving as the fluorine-containing vinyl monomer unit (a) of the polymer (1) in the present invention is as follows.

C7F 15CH20CO-CH=CH2.

C8F 17302 N (Pr) CHz CH20C
O-CH=CH2.

Ca F 17soz N(Me) CH2C820G
OC(He)=CH2゜CH2=CH-C0O-CH
zCH2.

C7F 15CON(Et) CH2CH20CO-C
(I(e)=CH2.

CF3 (CF2) 9 CH2CH20GO-C1
1=Ctlz.

CaF 17(CH2) 110CO-C(He)=
CH2.

C8F 17302 N(CH2CH20CO-CH=
CH2) 2-CF302N(Me,)(CHz
) 100CO-CH2CH=CH2.

C8F 17SO2N(Et) CH2CH20CO-
CH=CH-COOEt.

C6F 13SO2N(Me) CH2CH20COC
H=CH2-c F3 (CF2) 2 C820C
OC()le)=CHz.

CF3 (CF2) 4 CH2CH20CO-C(
)le)=CH2.

HCF2 (CF2) 7 CH20CO-C(t(
e) Perfluoroalkyl group-containing (meth)acrylic acid esters such as =CHz; e.g. C7F 15CH20C
H=CH2.

Vinyl or allyl ethers with perfluoroalkyl groups as above, such as C7F15CH20-CH2CH=CH2: e.g. C8F17(CH2)1l-OCO-CH=CH-
COOHe.

C3lf 17(CH2) 1l-OCO-CH=CH
Maleic acid mono- or diesters having perfluoroalkyl groups as in the case of the above (meth)acrylic acid esters such as -COOCH2C7F ts; e.g. C3j17so2 N!ICHz CH2SOz CH
Vinyl sulfonic acids having the above-mentioned perfluoroalkyl groups such as =CH2; fluoroolefin monomers such as chlorotrifluoroethylene and tetrafluoroethylene. Above and below, He, Et.

Pr represents a methyl, ethyl, or propyl group, respectively.

Among these, preferred are (meth)acrylic acid esters containing a perfluoroalkyl group having 3 to 21 carbon atoms.

Other monomers that can become the vinyl monomer unit (b) include:

(a) Acrylic acid, methacrylic acid, and their derivatives:
Acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid and their salts, methyl acrylate, °methyl methacrylate, ln-butyl methacrylate, dimethylaminoethyl methacrylate, acrylic amide, methacrylic amide, etc. Preferably methyl methacrylate, n-butyl methacrylate and acrylonitrile.

(b) Aromatic vinyl monomers: styrene, °α-methylstyrene, etc.

(/9 Olefinic hydrocarbon monomers: ethylene, propylene, butadiene, isobutylene, isoprene, 1.
4-pentagene, etc.

) Vinyl ester monomer: Vinyl acetate, etc.

(e) Vinyl halide monomers: vinyl chloride, vinylidene chloride, etc.

N-vinyl ether monomer: vinyl methyl ether, etc.

can be given.

Among these, preferred are (meth)acrylic acid derivatives and aromatic vinyl monomers, and particularly preferred are methyl methacrylate, Mn-butyl methacrylate, and styrene.

The composition ratio of (a) and (b) is usually 120 to 1:10 by weight, preferably 1:0.
．． 5-1:5. When the composition is 1=10 or more, the effect of fluorine in the polymer is hardly expressed.

The hydrolyzable silyl group (C) of general formula (1) has the general formula:
(In the formula, R1 is a divalent organic group, and R2 is hydrogen or an alkyl group having 1 to 4 carbon atoms.

R3 is an alkyl group having 1 to 4 carbon atoms.

a is an integer from 1 to 3. ) It is a residue of the silyl mercaptan (d) excluding H, and is produced by the reaction of this silyl mercaptan with the copolymer of (a) and (b).

An example of the silyl mercaptan of general formula (2) is:

R3CH2Cl1z CH25i (OHe) 3.

R3CH2CH2CH25i (OEt) 3.

83 CH2CH2CH20CONH-CH2CH2C
Examples include H25i(OEj) 3.

Preferred is R3CH2CH2CH25i(0)1e)
3.

+13 CH2CH2CH25i (OEt) 3.

The content of (C) in polymer (1) is (a) + (b)
), usually 1 to 20%, preferably 2 to 1%
It is 0% by weight.

The production of polymer (1) involves polymerization of (a) and (b) and (d)
It can be produced by 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. For soak polymerization.

The organic solvents used include aromatic hydrocarbons (toluene, xylene, ethylbenzene, etc.) and aliphatic hydrocarbons (
Hexane, heptane, siloxane-bound viscous aliphatic esters (ethyl acetate, n-butyl acetate, 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 mixtures of two or more of these. Preferred are toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, n-butyl acetate and ethylene dichloride alone or in mixtures of two or more thereof. The ratio of the organic solvent to the total weight of the monomers [(a), (b) and (d)] can be selected arbitrarily, but is usually 0.2:1 to 20:1, preferably 0.5:1 to 5:1. 1
It is.

When carrying out a radical polymerization reaction, the radical initiators used include azo compounds (azobisisobutyronitrile, azobisisovaleronitrile, etc.), peroxides (benzoyl peroxide, di-1-butyl peroxide, cumene, etc.). hydroperoxide, dicumyl peroxide, etc.).

Redox compounds (benzoyl peroxide.

N,N-dimethylaniline, etc.).

Preferred are azo compounds.

The amount of catalyst added was determined by the amount of monomer [(a), (b) and (d
)] is usually o, ooi to 20%, preferably 0.1 to 10%.

The temperature of the radical polymerization reaction is usually 50 to 150"C, preferably 70 to 130"C.

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.

In radical polymerization, (d) acts as a chain transfer agent to stop the polymerization reaction, and at the same time is introduced as (C) at one end to produce polymer (1). . At this time, a fluorine-containing vinyl polymer containing no (C) is also produced, which is not the vinyl polymer (i) of the present invention, but may be contained in the polymer (1).

The molecular weight of the polymer (1) is 500 to 10,000. Preferably it is 800-5,000.

Since the vinyl polymer (i) has a silyl group at least at one end, when exposed to the atmosphere, it forms siloxane bonds and hardens at room temperature. Curing speed is at atmospheric temperature.

Varies depending on relative humidity 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 alkoxy groups, the lower the number of carbon atoms, the higher the curing rate.

Those having only one silyl group at one end have a slower curing rate than ordinary vinyl polymers having two or more silyl groups in the molecule.

Examples of the fluorine-containing vinyl monomer unit (ao) of the polymer (11) in the present invention include those mentioned in (a).

Silyl group-containing monomer unit (bo
) is a general formula (wherein R'l is a divalent organic group or a direct bond).

R'2 is hydrogen or an alkyl group having 1 to 4 carbon atoms, R'3 is an alkyl group having 1 to 4 carbon atoms, and b is an integer of 1 to 3. ) is a vinyl monomer unit having a hydrolyzable silyl group.

Examples of polymerizable monomers containing a silyl group represented by the general formula (1°) include vinylsilanes such as vinylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris(β-methoxyethoxy).
Silanes and (meth)acryloxyalkylsilanes such as γ-methacryloxypropyltrimethoxysilane,
γ-methacryloxypropylmethyldimethoxysilane.

γ-acryloxypropyltrimethoxysilane.

e ■ CH2=C-COOCH2Ctfz 0CONH(CH
2) 3Si(OMe)3.

etc.

Other vinyl spinning wheel solid units (Co) of polymer (ii)
Examples include the same as (b).

In polymer (11), (a'), (b') and (
The amount of Co) is.

Based on the weight of polymer (11), (a') is usually 1
0-90%.

Preferably 20-70%, (b') usually 1/90%
, preferably 5 to 50%, (C') usually O to 89%
, preferably 10 to 50%. If (ao) is less than 10%, the effect of fluorine in the polymer will hardly be exhibited.

If it exceeds 90%, the compatibility with the resin to be compatible becomes poor.

If (bo) is less than 1%, the durability of the fluorine effect will be poor. When it exceeds 90%, the effect of fluorine is no longer expressed. 8
If it exceeds 9%, the effect and durability of fluorine will be poor.

The weight ratio of (ao) and [(b') + (c')] is usually 1
: 0.1 to 1:10, preferably 1:0.5
~1:5. [(b') + (C')] is 0.1
If it is less than 10, the curability of the polymer will be too low, and if it exceeds 10, the effect of fluorine in the polymer will hardly be expressed.

The weight ratio of (bo) and (Co) is usually 1: O to 1:
100°, preferably 1:0.5 to 1:50. (C
``) exceeds 100, the curability of the polymer is poor.

A polymer consisting of (a'), (b') and (Co) can be produced by (1) a method of polymerizing (a"), (b') and (Co), or (2) instead of (b'). After polymerization using its precursor.

Method of introducing hydrolyzable silyl group It can be manufactured by

In methods (1) and (2), polymerization is carried out to form one polymer (1
) can be carried out using the same method and one condition. In some cases, the molecular weight can be increased by using a chain transfer agent such as n-dodecylmercaptan, t-dodecylmercaptan, or γ-mercaptopropyltrimethoxysilane.

Further, as a method for introducing the silyl group represented by the general formula (1) during the preparation of the polymer, the following two methods I and II can be mentioned.

1.1 is a method in which hydrosilane and a vinyl polymer having a double bond are reacted in the presence of a group II transition metal catalyst.

For the production of vinyl polymers, the monomers used are (i
There are no particular limitations other than the monomer containing a hydroxyl group in i) and (c'), and (ao) and (Co
) may be the same. In order to introduce a double bond at the center of the vinyl polymer, for example, compounds having at least two polymerizable double bonds such as allyl lylate, allyl methacrylate,
Copolymerize diallyl phthalate, etc.

The blending ratio of each polymerizable monomer in this method may be arbitrary, but is preferably the same as in the case of polymerizing using the initial monomer containing a silyl group. That is, allyl acrylate or allyl methacrylate may be used instead of (bo).

The hydrosilane has the general formula (wherein R'2, R'3, b are the general formula (1°
). ] Examples include the compounds shown below.

Specifically, alkoxysilanes (methyldimethoxysilane, trimethoxysilane, triethoxysilane, etc.), acyloxysilanes (methyldiacetoxysilane, triacetoxysilane, etc.), methyldiaminoxysilane, triaminoxysilane.

Examples include various silanes such as methyldiaminosilane, bis(dimethylketoximate)methylsilane, and methyldiisopropenooxysilane.

The amount of hydrosilane may be any amount relative to the carbon-carbon double bond contained in the vinyl polymer, but is preferably 0.5
~1.5 times the mole.

■Platinum and rhodium are catalysts for group transition metals.

Complex compounds of Group I transition metals such as cobalt, palladium, and nickel can be used.

The hydrosilylation reaction temperature is usually 50 to 150'C, and the reaction time is usually 1 to 10 hours.

(2) The second method is to copolymerize a hydroxyl group-containing monomer with another monomer and then react the copolymer with isocyanate silane.

The copolymerizable monomer in the vinyl polymer containing a hydroxyl group may be the same as the water M group-containing monomer and other copolymerizable monomers in (Co) in (if).

In this case, the blending ratio of the monomers may be arbitrary, but preferably,
The hydroxyl group-containing monomer to be reacted with isocyanate silane has the same weight ratio as (bo). The excess hydroxyl group-containing monomer may be included in (Co).

Specific examples of the isocyanate silane include γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropylmethyljethoxysilane, γ-isocyanatepropyltrimethoxysilane, and γ-isocyanatepropylmethyldimethoxysilane.

The reaction between the hydroxyl groups in the vinyl polymer and isocyanate silane is the same as a normal urethanization reaction.

The temperature is usually 50 to 150°C and the reaction time is usually about 1 to 15 hours. Catalyst for urethanization reaction if necessary.

For example, it is also possible to accelerate the reaction by adding an organic tin compound, amine, or the like.

The molecular weight of the fluorine-containing silyl group-containing polymer (ii) is not particularly limited, but a lower molecular weight is preferable in view of compatibility with the resin (1), etc., and usually 800 to 30,000. Preferably it is 100-10,000.

When the fluorine-containing silyl group-containing polymer (ti) is exposed to the atmosphere, it forms a network structure and hardens at room temperature.

In the present invention (second invention), a silyl group-containing polymer [B] having one or more silyl groups in one molecule at the terminal or side chain is used in combination with the hydrolyzable silyl group-containing fluorine-containing polymer [A]. ] Examples include silyl group-containing vinyl polymers and silyl group-containing polyurethanes.

Examples of the silyl group-containing vinyl polymer include polymers composed of silyl group-containing monomer units and other vinyl monomer units.

The silyl group-containing monomer unit and other vinyl monomer units are (bo) in the case of polymer (11), respectively.
and (Co) can be used.

The content of the silyl group-containing monomer in the silyl group-containing vinyl polymer is usually 4 to 70%, preferably 7 to 30%, based on the weight of the polymer.

The polymerization method can also be carried out in the same manner as in polymer (11) except that (ao) is omitted.

The molecular weight is preferably lower depending on the storage stability, appearance, etc. of the composition, and is usually i, ooo to 30,000. Preferably it is 3.000 to 20.000.

Examples of the silyl group-containing polyurethane include polyurethanes formed from a polyol, a polyisocyanate, an active hydrogen-containing silane coupling agent, and/or an isocyanate group-containing silane coupling agent (isocyanate silane).

Polyols used in the above polyurethane production include high molecular polyols [polyether polyols such as polyethylene glycol; polypropylene glycol and polytetramethylene glycol; polyester polyols such as polycaprolactone polyol; polyetherester polyol; preferred are polypropylene glycol, polytetramethylene glycol and polycaprolactone polyol, particularly preferred are polypropylene glycol and polycaprolactone polyol] Examples include molecular polyols [low molecular glycols and trifunctional or higher functional low molecular polyols].

Among the polyols, preferred are high-molecular polyols and their combination with low-molecular polyols (the amount of low-molecular polyol is from 0,001 to 30% by weight relative to high-molecular polyol).

The average molecular weight of polyol is usually 62 to 4000. Preferably it is 200-2000. Ol-1 value is usually 20~
1000°, preferably 30-800°.

As the polyisocyanate, aliphatic polyisocyanates having 2 to 12 carbon atoms (excluding the carbon in the NGO group) are used. Alicyclic polyisocyanate having 4 to 15 carbon atoms.

Aroaliphatic polyisocyanate having 8 to 12 carbon atoms.

Aromatic polyisocyanates having 6 to 20 carbon atoms and modified products of these polyisocyanates (carposiimide group,
Modified products containing uretdione groups, uretoimine groups, urea groups, biuret groups, and/or isocyanurate groups, etc.) can be used. Examples of such polyisocyanates include ethylene diisocyanate and tetramethylene diisocyanate.

Hexamethylene diisocyanate, (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexane diisocyanate, lysine diisocyanate.

2.6-Diucyanate methyl caproate, bis(
2-Isocyanate ethyl) fumaray 1~. Bis(2-
isocyanate ethyl) carbonate, 2-isocyanate ethyl-2,6-diitsocyanate hexanoate: isophorone diisocyanate (IPDI>, dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI) , bis(2-
ethyl isocyanate) 4-cyclohexene-1,2-
Dicarboxylate: xylylene diisocyanate, diethylbenzenediisocyanate-1~: water-modified product of HDI, trimerized product of IPDI, etc.; tolylene diisocyanate (TDI), crude TD1. Examples include diphenylmethane diisocyanate (MD I ), polyphenylmethane polyisocyanate 1- (PAPT: crude MD I ), modified MDI (carposiimide modified etc.), naphthylene diisocyanate: and mixtures of two or more of these. Among these, preferred from the viewpoint of weather resistance are aliphatic diisocyanates and alicyclic diisocyanates 1-1, and particularly preferred are hexylylene diisocyanate and isophorone diisocyanate. TDI is preferred for applications where weather resistance is not an issue.

As the active hydrogen-containing silane coupling agent, a compound having an active hydrogen-containing group selected from the group consisting of hydroxyl group, amine group and mercapto group and a hydrolyzable silyl group carried from the group consisting of alkoxysilyl group and herosilyl group is used. can give.

Specific examples include the following compounds.

(1) Amino group-containing silane coupling agent Niaminoalkyltrialkoxysilane (T-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, aminomethyltriethoxysilane, etc.); N-(aminoalkyl)aminoalkyltrimethoxysilane Alkoxysilane [N
-(β-7minoethyl)aminomethyltrimethoxysilane.

N-(β-aminoethyl)aminemethyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, etc.) Niaminoalkyl, alkyldialkoxysilane (aminomethylmethyljethoxysilane, γ- N-(aminoalkyl)aminoalkylalkyldialkoxysilane [N-(β-aminoethyl>-r-aminopropylmethyldimethoxysilane, etc.]); and amino-containing silane coupling agents and a partial hydrolyzate of a compound containing a hydrolyzable silyl group, such as the above amino group-containing silane coupling agent and a compound containing a hydrolyzable silyl group (ethyl silicate, methyltrimethoxysilane, methyltriethoxysilane, etc.) Reactants obtained by partially hydrolyzing by adding water and, if necessary, an acidic or alkaline catalyst.

(2) Silane coupling agent containing a mercapto group: mercaptoalkylalkoxysilane (γ-mercaptopropyltrimethoxysilane, etc.), etc.

(3) Hydroxyl group-containing silane coupling agent: (1
) amino group-containing silane coupling agents and compounds containing epoxy groups (ethylene oxide, butylene oxide, epichlorohydrin, evaporated soybean oil, and other shells)
Epicoat 828. Epoxy group-containing silane coupling agent [glycidoxyalkyltrialkoxysilane (γ-glycidoxypropyltrimethoxysilane, etc.); glycidoxyalkylalkyldialkoxysilane (γ- glycidoxypropylmethyldimethoxysilane) and amines such as aliphatic amines (ethylamine, etc.).

diethylamine, triethylamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine), aromatic amines (aniline, diphenylamine)
, alicyclic amines (cyclopentylamine, cyclohexylamine, etc.); reaction products with alkanolamines (ethanolamines), etc.

The isocyanate silane is not particularly limited as long as it has an NCO group and a silyl group. Isocyanate alkyl alkoxysilanes such as T-isocyanate propyltriethoxysilane.

γ-isocyanate propylmethyljethoxysilane,
γ-Isocyanatepropyltrimethoxysilane, γ-
Examples include isocyanate propylmethyl dimethoxysilane.

There are the following two methods for forming the silyl group-containing polyurethane. (1) is a method in which an NGO-terminated urethane prepolymer made from a polyol and a polyisocyanate is reacted with a silane coupling agent having an active hydrogen that reacts with NCO, and (2) is a method in which an NGO-terminated urethane prepolymer made from a polyol and a polyisocyanate is reacted with a silane coupling agent having an active hydrogen that reacts with NCO. This is a method of reacting a prepolymer with an isocyanate silane that reacts with OH.

When obtaining an NGO-terminated urethane prepolymer from a polyol and a polyisocyanate in the method (1), the equivalent ratio of the NCO group of the polyisocyanate to the active hydrogen-containing group of the polyol and, if necessary, the active hydrogen-containing compound is usually 1: 0.9-1:0.1 preferably 1:0.7
~1:0.3. The number of terminal NCO groups per molecule of the NCO-terminated urethane prepolymer is usually 2 to 6, preferably 2 to 4, particularly preferably 2 to 3 on average.

The average molecular weight of the NGO-terminated urethane prepolymer is usually 200 to 40,000. Preferably 500-20.00
It is 0.

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. The equivalent weight is usually 100 to 8,400, preferably 21
0-4.200. Particularly preferably 525 to 2,100
It is.

The molar ratio of the silane coupling agent having active hydrogen to the isocyanate groups of the NGO-terminated urethane prepolymer is usually 0.25 to 1.5. Preferably 0.8-1.
It is 2. If the silane coupling agent is less than 0.25, the curing speed is slow and the physical properties of curing are weak.
If it exceeds this amount, no improvement in physical properties can be obtained even if more is added, and the chemical is wasted.

In the case of (2), the molar ratio of polyol and polyisocyanate is usually 1:0.9 to 1:0.1. Preferably 1
:0.7 to 1:0.3. The terminal of the OH-terminated urethane prepolymer usually has an average of 2 to 6, preferably 2 to 4, particularly preferably 2 to 3 OH per molecule. The average molecular weight of the OH-terminated urethane prepolymer is usually 200 to 40,000. Preferably 500-20.00
It is 0.

The amount of isocyanate silane is usually 0.25 to 1.5 in molar ratio to OH of the OH-terminated urethane prepolymer. Preferably it is 0.8 to 1.2. When the molar ratio is less than 0.25, the curing speed is slow and the physical properties of the curing flame are weak, and when it exceeds 1.5, no improvement in physical properties can be obtained even if more is added, and the chemical is wasted.

In addition to methods (1) and (2>) above, (3) a method in which a polyol, a polyisocyanate, and an active hydrogen-containing silane coupling agent or an isocyanate silane are simultaneously reacted, (4) a method in which a polyol and an isocyanate silane are reacted, and then Method of reacting polyisocyanate, (
5) Method of reacting a polyisocyanate with an active hydrogen-containing silane coupling agent and then reacting with a polyol (
Polyurethane can also be formed by a method that combines two or more of 1) to (5).

In the polyurethane forming reaction (urethanization of a polyol and polyisocyanate, and reaction of these or a prepolymer with a silane coupling agent), the reaction temperature is usually 0 to 150°C, preferably 25 to 90°C. The reaction can be carried out, if necessary, in the presence of an organic solvent inert to incyanate groups. Examples of the organic solvent include aromatic hydrocarbons (toluene, xylene, etc.), ketones (methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (ethyl acetate, fin-butyl acetate, etc.), and mixtures of two or more of these. Further, if necessary, a catalyst such as a metal catalyst 1 (dibutyltin dilaurate, stannath-2-ethylhexoate) may be used.

iron-acetylacetonate) and amine catalysts (such as iron-acetylacetonate) and amine catalysts (such as iron-acetylacetonate)
(triethylenediamine, N-methylmorpholine, etc.) can also be used, and the amount used is usually 0.005 to 0.2% by weight based on the polyurethane (or its agent). At the end of the reaction, the isocyanate group was determined by infrared analysis (~2
, 250 cm-1~), it can be checked when it becomes undetectable.

The average molecular weight of the silyl group-containing polyurethane obtained in this way is usually 300 to 45,000. Preferably 600
~25,000. When this silyl group-containing polyurethane is exposed to the atmosphere, it forms a network structure and hardens at room temperature.

In the present invention, the hydrolyzable silyl group-containing polymer [A]
Although it may be used alone to form a coating, it is usually used by adding it to other coating resins. Other resins include various resins currently used as paints and coatings, such as lacquer paints, acrylic lacquer paints, thermosetting acrylic paints, alkyd paints, melamine paints, epoxy paints, silicone paints, and silyl group-containing paints. Examples include those used in paints, etc. Particularly preferred are those used in silyl group-containing paints [polymer [B1]]. Polymer [A] is added to these resins in an amount of 0.01 to 5
If 0% by weight, preferably 0.1 to 10% by weight is blended,
During coating film formation, this vinyl polymer migrates to the surface and exhibits the interfacial properties of fluorine on the surface.

In the coating composition of the present invention (second invention).

The mixing ratio of [A] and [31 is usually 1:1 by weight.
000~1:1. Preferably 1:500 to 1:5. Particularly preferably, the ratio is 1:100 to 1:10. [B] is 1
If it exceeds ,000, the effect of fluorine will no longer be expressed, and if it is less than 1, the effect of fluorine will not be improved any further and the price will only increase, so it is a waste.

The coating composition of the present invention may contain curing catalysts, stabilizers, solvents, fillers, pigments, additives (ultraviolet absorbers, heat resistance improvers, leveling agents, anti-sagging agents, etc.) if necessary. be. Specifically, those described in JP-A-58-19361 can be used.

Curing catalysts include those conventionally used as silanol condensation catalysts, such as dicarboxylic acid type tin compounds (such as tin dioctylate, dibutyltin dilaurate, and dibutyltin maleate), sulfide type, and mercaptide type sulfur-containing organic compounds. Tin compounds (dibutyltin sulfide, dibutyltin dioctyl mercaptide, etc.), acidic phosphate esters (
monomethyl acid phosphate, dimethyl acid phosphate, diethyl acid phosphate, monobutyl phosphate, etc.), carboxylic acids and their acid anhydrides (adipic acid, maleic acid, citric acid, etc.).

succinic acid, phthalate, trimellitic acid, etc.), aminosilanes (T-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, etc.), amines and their salts (triethylamine).

dibutylamine-2-hexoate, etc.), organic titanate compounds (isopropyltriisostearoyl titanate, inpropyltri(dioctylpyrophosphate) titanate, tetraisoprovir di(lauryl phosphite) titanate.

etc.) Other examples include curing catalysts described in JP-A-58-19361. The amount of curing catalyst added is usually 0.001 to 20% by weight based on the total silyl group-containing polymer.

Stabilizers include hydrolyzable esters, alcohols, etc. Hydrolyzable esters include trialkyl orthoformates (trimethyl orthoformate, triethyl orthoformate, etc.), silanes (methyltrimethoxysilane, tetramethoxysilane, vinyltriethoxysilane, etc.). silane, T-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-ureidopropyltriethoxysilane, silicates, etc.).

The alcohol preferably has 1 to 10 carbon atoms, such as methanol, ethanol, isopropanol, isobutyl alcohol, octyl alcohol, cellosolve, and the like. The amount of stabilizer is preferably from 1 to 30% by weight, based on the total silyl group-containing polymer.

The solvent may be the same as the solvent used in synthesizing the silyl group-containing polymer and is inert to the silyl group-containing polymer. Furthermore, it is also possible to dilute with a solvent. The amount of solvent is usually 0 to 600% by weight based on the silyl group-containing polymer.

Fillers and pigments include extender pigments (calcium carbonate, kaolin, tartar, aluminum silicate).

Aerosil, etc.), inorganic pigments (titanium oxide, iron oxide, yellow lead, cadmium oxide, carbon black.

aluminum phosphorus flakes), organic pigments (azo type, azo lake type,
phthalocyanine-based, quinacridone-based, isoindolinone-based organic pigments, etc.).

It is also possible to mix commonly used ultraviolet absorbers, heat resistance improvers, leveling agents, anti-sagging agents, and the like.

The amount of pigment is usually 0 to 200% based on the silyl group-containing polymer.
% by weight, and the amount of additives such as ultraviolet absorbers is usually 0 to 10% by weight.

The coating composition of the present invention can be used to coat a variety of inorganic and organic materials. For details of the object to be used and the method of use, those described in JP-A-58-19361 may be used.

[Examples] The present invention will be briefly described below with reference to Examples, but the present invention is not limited thereto. Parts and percentages in the examples are by weight.

Production Example 1 100 parts of toluene was added to a Kolben, heated to ioo'c, and 35 parts of methyl methacrylate was added.

CH2=C(He)COOCtlz (CF2) 6
A mixed solution of 355 parts of CF, 3 parts of Y-mercaptopropyltrimethoxysilane 7-bisisobutyronitrile, and 5 parts of toluene was added dropwise over 2 hours, and then reacted at the same temperature for 2 hours. Furthermore, 1 part of azobisisobutyronitrile was added and the mixture was reacted at the same temperature for 2 hours to obtain a polymer A1. In the IR (infrared absorption spectrum) of polymer A1, there was no absorption of 1B48Cm-' due to carbon-carbon double bonds. G.P.
The molecular weight was measured at C and found to be approximately 1300.

Production Example 2 100 parts of toluene was added to Kolben and heated to 100°C, followed by 30 parts of methacrylic lln-butyl and 20 parts of styrene.

CH2=C(He)COOCHz-(CF2)
A mixed solution of 50 parts of 8CF2H and 2 parts of Y-mercaptopropyltriethoxysilanezobisisobutyronitrile was added dropwise over 2 hours, and then reacted at the same temperature for 2 hours.

Further, 1 part of azobisisobutyronitrile was added and the mixture was reacted at the same temperature for 2 hours to obtain Polymer A2.

The IR of polymer A2 has 164 due to carbon-carbon double bond.
There was no absorption at 8 cm-1. When the molecular weight was measured by GPC, it was found to be about 3,000.

Production example 3 n-butyl acrylate instead of methyl methacrylate,
C112 = C(He) COOCHz (CF 2 )
6 CH2 = CH-COOCH2 instead of CF3
(CF2)6CF3 Polymer A3 was obtained in the same manner as in Production Example 1 using Y-mercaptopropylmethyldimethoxysilane instead of Y-mercaptopropyltrimethoxysilane. When the molecular weight is measured by GPC, it is approximately 1.7
It was 00.

Production example 4: Put 100 parts of toluene into Kolben and raise the temperature to 100°C.
90 parts of methyl methacrylate.

CH2=C()Ie)COOCH2(CF2) 6
375 parts of CF, 37 parts of Y-methacryloxypropyltrimethoxysilane.

20 parts of azobisisobutyronitrile and 10 parts of toluene
0 parts of the mixed solution was added dropwise over 3 hours, and then 3 parts of the mixed solution was added at the same temperature.
It was allowed to react for 0 minutes. Furthermore, 1 part of azobisisobutyronitrile was added three times at 30 minute intervals. Then, the mixture was further reacted at the same temperature for 1 hour to obtain polymer A4.

The IR of polymer A4 has 164 due to carbon-carbon double bond.
There was no absorption of 8cffl'. The molecular weight measured by GPC was approximately 2.600.

Production Example 5 100 parts of toluene was placed in a Kolben, heated to 100°C, and 80 parts of styrene was added.

CH2=C(He)COOCH2(CF2) B C
F2 70 parts of H 35 parts of j''-methacryloxypropyltrimethoxysilane.

20 parts of azobisisobutyronitrile and 10 parts of toluene
0 parts of the mixed solution was added dropwise over 3 hours, and then at the same temperature for 30 minutes.
It was allowed to react for a minute. Further, 1 part of azobisisobutyronitrile is added three times at 30 minute intervals. Then, the reaction was further carried out at the same temperature for 1 hour to obtain heavy substance A5. There was no absorption of 164 BCm'' due to carbon-carbon double bonds in the IR of Polymer A5. When the molecular weight was measured by GPC, it was approximately 2,300.

Production Example 6 100 parts of toluene was added to a Kolben, heated to 100'C, and 90 parts of butyl acrylate was added.

CH2=C()ie) COOCHz (CF2) 6
350 parts of CF, 40 parts of T-methacryloxypropyltrimethoxysilane.

A mixed solution of 20 parts of 2-hydroxyethyl methacrylate, 2 parts of azobisisobutyronitrile, and 100 parts of 1 to 100% was added dropwise over 3 hours, and then reacted at the same temperature for 30 minutes. Furthermore, 1 part of azobisisobutyronitrile was added three times at 30 minute intervals. The reaction mixture was further reacted at the same temperature for 1 hour to obtain a dipolymer 6. In the IR of 6 to the polymer, there was no absorption of 1648α-1 due to carbon-carbon double bonds. G.P.
The molecular weight was measured at C and was approximately 2.500.

Production Example 7 100 parts of toluene was placed in Kolben and heated to 100'C, followed by 50 parts of butyl methacrylate, 10 parts of styrene, 5 parts of 2-hydroxyethyl methacrylate, 20 parts of methyl methacrylate, and 3.5 parts of glycidyl methacrylate.

A mixed solution of 10 parts of γ-methacryloxypropyltrimethoxysilane, 0.5 parts of toticanethiol, and 2 parts of azobisisobutyronitrile was added dropwise over 3 hours, and then reacted at the same temperature for 30 minutes. Further, 0.2 parts of azobisisobutyronitrile was added three times at 30 minute intervals, and the reaction was continued for an additional hour at the same temperature to obtain Polymer B1. I of polymer B1
There was no absorption of 1648 Cm-1 in R due to carbon-carbon double bonds. When molecular weight is measured by GCP, it is approximately 5,60
It was 0.

Production Example 8 Put 100 parts of toluene into Kolben and raise the temperature to 100°C.
60 parts of butyl methacrylate, 10 parts of styrene, 15 parts of methyl methacrylate, 5 parts of acrylamide, T-methac I
10 parts of J roxypropyltrimethoxysilane, 0.5 parts of dodecanethiol and 2 parts of azobisisobutyronitrile
part of the mixed solution was added dropwise over 3 hours.

Thereafter, the mixture was reacted at the same temperature for 30 minutes. Further, 0.2 part of azobisisobutyronitrile was added three times at 30 minute intervals.

Then, 1 q of polymer B2 was added to the reactor at the same temperature for an additional hour. There was no absorption of 1648 Cm-1 due to carbon-carbon double bonds in the IR of the obtained polymer B2. The molecular weight measured by GPC was approximately 5,500.

Production Example 9 100 parts of toluene, 49 parts of polypropylene glycol (molecular weight: 400), 36 parts of isophorone diisocyanate, and 0.11 parts of dibutyltin dilaurate were placed in Kolben, and the temperature was raised to 75°C. After reacting for 7 hours.

14.6 parts of Y-aminopropyltrimethoxysilane was added and reacted for 1 hour to obtain Polymer B3. The infrared absorption spectrum of Polymer B3 is from NGO.

There was no absorption of 2.250 parts m-1. The molecular weight is about 2,
It was 400.

Polymers A1 to A6 and B1 to obtained in Production Examples 1 to 9
B3. A coating composition of the present invention was prepared using commercially available paint C1 (solvent type acrylic resin) and commercially available paint C2 (two-component type acrylic urethane resin).

Also, for comparison, polymer A1-86 was not included.

Alternatively, a coating composition was prepared using commercially available additive D (fluorine-containing graft block polymer) in place of A1 to A6.

Their formulations are shown in Table 1.

These compositions are applied onto a polished mild steel plate that has been cleaned with toluene (for water repellency, oil repellency, and wash resistance), or onto which a commercially available white acrylic urethane paint is applied (for gloss, weather resistance, and test purposes). ) It was spray coated to a thickness of 50 μm and left at room temperature for 5 days [Heated at 60° C. for 30 minutes. after that,
The following items were measured. The results are shown in Table 2.

Light gloss: 60’C specular reflectance Water repellency: Contact angle with water.

Oil repellency: contact angle to n-decane.

Washing resistance: Commercially available powder detergent 1g/, 1! 40 in an aqueous solution of
'CX Contact angle with water after 4 hours immersion.

Weather resistance: Sunshine Ether-O-Meter i, 00
Contact angle with water after 0 hours.

Table 1 Table 1 (Continued) (Note) *1: Methyltrimethoxysilane *2 Nidibutyltin dilaurate Table 2 Table 2 (Continued) [Effects of the Invention] The present invention has the following advantages: (1) Synthesis from conventional fluorine-containing graft block polymers The method is very simple.

In the conventional synthesis of fluorine-containing graft block polymers, two or more reaction steps are required for the synthesis of the macro-septamer, and since there is an additional step of polymerizing the graft block polymer, three or more steps are required. The vinyl polymer of the present invention requires only one polymerization step, so the synthesis method is very simple.

(2) The interfacial properties of fluorine can be expressed at low cost.

By adding a small amount of fluorine to conventional acrylic, melamine, urethane, and silicone resins, the interfacial properties of fluorine are expressed, so the properties of conventional resins can be improved. Since the content is very low (even if the amount of Polymer A used is about 1 to 5% by weight), the interfacial properties of fluorine can be expressed at a low cost. The interfacial properties of fluorine include water and oil repellency, weather resistance, chemical resistance, and stain resistance.

(3) Good wash resistance. Since it has a moisture-curable silyl group, it reacts on the surface to form a durable coating. In particular, when polymer A and polymer B are used in combination (second invention), the silyl groups of both react and bond firmly, resulting in increased durability. It has particularly good wash resistance compared to conventional fluorine-containing graft block polymers. A coating composition having the following characteristics is formed. Since it exhibits the above effects, the composition to be subjected to M of the present invention can be used as a paint, a coating material, or a sealing material.

Useful for casting materials, etc.

Claims (1)

[Scope of Claims] 1. (i) A polymer composed of a fluorine-containing vinyl monomer unit (a) and another vinyl monomer unit (b), at least one end of which has the general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) (In the formula, R_1 is a divalent organic group, R_2 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R_3 is a divalent organic group having 1 to 4 carbon atoms. a vinyl polymer having a hydrolyzable silyl group (c), and (ii) a fluorine-containing vinyl monomer unit (a') , a hydrolyzable silyl group-containing fluoropolymer selected from the group consisting of a polymer composed of a silyl group-containing monomer unit (b') and another vinyl monomer unit (c'). A coating composition comprising: 2. The composition according to claim 1, wherein (a) is a vinyl monomer unit containing a perfluoroalkyl group having 3 to 21 carbon atoms. 3. The composition according to claim 1 or 2, wherein the weight ratio of (a) and (b) is 1:0 to 1:10. 4. The content of (c) is 1 to 1 of the total weight of (a) and (b)
A composition according to claim 1, 2 or 3, wherein the composition is 20%. 5, (b) is a (meth)acrylic acid ester monomer unit,
Claims 1 to 4 selected from the group consisting of aromatic hydrocarbon vinyl monomer units and vinyl ester monomer units
A composition according to any of paragraphs. 6. Claim 1, wherein (a') is a vinyl monomer unit containing a perfluoroalkyl group having 3 to 21 carbon atoms.
The composition according to any one of items 1 to 5. 7. (b') is a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R'_1 is a divalent organic group or a direct bond,
R'_2 is hydrogen or an alkyl group having 1 to 4 carbon atoms, R'_3 is an alkyl group having 1 to 4 carbon atoms, and b is an integer of 1 to 3. ) The composition according to any one of claims 1 to 6, which is a vinyl monomer unit having a hydrolyzable silyl group. 8, (a') is 10 based on the weight of the polymer in (ii)
~90%, (b') 1-90%, (c) 0-89%
The composition according to any one of claims 1 to 7. 9, (i) A polymer composed of a fluorine-containing vinyl monomer unit (a) and another vinyl monomer unit (b), at least one end of which has the general formula ▲ mathematical formula, chemical formula, table etc.▼(1) (In the formula, R_1 is a divalent organic group, R_2 is hydrogen or an alkyl group having 1 to 4 carbon atoms, R_3 is an alkyl group having 1 to 4 carbon atoms, a is an integer of 1 to 3.) A vinyl polymer having a hydrolyzable silyl group (c) represented by (c), and (ii) a fluorine-containing vinyl monomer unit (a') containing a silyl group Hydrolyzable silyl group-containing fluorine-containing polymer [A] selected from the group consisting of polymers composed of monomer units (b') and other vinyl monomer units (c')
and a silyl group-containing polymer [B] having one or more silyl groups per molecule at the terminal or side chain. 10. [B] is a silyl group-containing vinyl resin whose main chain is substantially composed of a vinyl polymer and which has at least one silicon group in one molecule bonded to a hydrolyzable group at the terminal or side chain. A composition according to claim 10. 11. The weight ratio of [A] and [B] is 1:1000 to 1:1
The composition according to claim 9 or 10.