CN111936558A - Polysiloxane compounds and compositions - Google Patents

Abstract

The problem to be solved by the present invention is to provide novel polysiloxane compounds and compositions comprising the same. By having a urea group and an X group [X group is one or more groups selected from -COOR, -SO ₃ R and -NR ₂ , R is a hydrogen atom, or can have an alkoxy group or a hydroxyl group In the range of 0.01 to 0.45, the ratio of the number of ureido groups to X groups in one molecule (urea group/X group) and a polysiloxane compound and a composition containing the compound can solve the above problems .

Description

Polysiloxane Compounds and Compositions

technical field

The present invention relates to polysiloxane compounds and compositions comprising the polysiloxane compounds.

Background technique

In recent years, various polysiloxane compounds have been used in various fields. For example, in Patent Document 1, a specific polysiloxane compound is used for the water-based metal surface treatment agent. The polysiloxane compound contains two or more of the formula -SiR ¹ R ² R ³ in one molecule (wherein R ¹ , R ² and R ³ independently represent an alkyl group, an alkoxy group or a hydroxyl group, and at least one Represents a functional group (a) represented by an alkoxy group) and one or more hydrophilic functional groups (b) selected from a hydroxyl group (which is different from a hydroxyl group that the functional group (a) can contain) hydroxyl), amino group, carboxyl group, phosphoric acid group, phosphonic acid group, sulfo group, polyoxyethylene chain and amide group, and the molecular weight of each functional group (b) is 100-10000.

prior art literature

Patent Literature

Patent Document 1: International Publication No. 2006/82946.

SUMMARY OF THE INVENTION

Invention to solve problem

An object of the present invention is to provide a novel polysiloxane compound and a composition containing the polysiloxane compound.

solution to the problem

The present invention is:

[1] A polysiloxane compound having a urea group and an X group [X group is one or more groups selected from -COOR, -SO ₃ R and -NR ₂ , R is hydrogen atom, or an alkyl group capable of having an alkoxy group or a hydroxyl group], and the ratio of the number of urea groups to X groups in one molecule (urea group/X group) is in the range of 0.01 to 0.45;

[2] The polysiloxane compound according to the above [1], wherein the polysiloxane compound has a weight average molecular weight of 1,000 to 1,000,000;

[3] A composition comprising the polysiloxane compound according to the above [1] or [2];

Wait.

Invention effect

According to the present invention, a novel polysiloxane compound and a composition containing the same can be provided.

Detailed ways

The polysiloxane compound and composition of the present invention will be described below.

<<Polysiloxane compound>>

The polysiloxane compound of this embodiment has a urea group (urea bond) and an X group [X group is one or more groups selected from -COOR, -SO ₃ R and -NR ₂ , and R is A hydrogen atom or an alkyl group capable of having an alkoxy group or a hydroxyl group], and the ratio of the number of urea groups to the number of X groups in one molecule (urea group/X group) is in the range of 0.01 to 0.45.

In addition, the above-mentioned polysiloxane compound has one or more Si groups to which a hydroxyl group or an alkoxy group is bonded. In addition, the above-mentioned polysiloxane compound may have an epoxy group, or may have a structure (-CH(OH)CH ₂ OH) in which the epoxy group is ring-opened by hydrolysis.

Here, the X group is, for example, a carboxyl group, an alkoxycarbonyl group, a sulfo group, an alkylsulfo group, an amino group, an N-alkylamino group, a N,N-dialkylamino group, an N-(alkoxyalkyl)amino group, N-(hydroxyalkyl)amino, N,N-bis(alkoxyalkyl)amino, N,N-bis(hydroxyalkyl)amino, etc. The polysiloxane compound may have one of these groups , and may have two or more types.

Examples of combinations of two or more types include a combination of a carboxyl group and an amino group, a combination of an alkoxycarbonyl group and an amino group, a combination of a sulfo group and an amino group, a combination of an alkylsulfo group and an amino group, a carboxyl group and an N-alkylamino group The combination of alkoxycarbonyl group and N-alkylamino group, the combination of sulfo group and N-alkylamino group, the combination of alkylsulfo group and N-alkylamino group, the combination of carboxyl group and N,N-dialkylamino group combination of alkoxycarbonyl group and N,N-dialkylamino group, combination of sulfo group and N,N-dialkylamino group, combination of alkylsulfo group and N,N-dialkylamino group, carboxyl group Combination with N-(alkoxyalkyl)amino, Combination of alkoxycarbonyl and N-(alkoxyalkyl)amino, Combination of sulfo and N-(alkoxyalkyl)amino, Alkyl Combination of sulfo group and N-(alkoxyalkyl)amino group, combination of carboxyl group and N-(hydroxyalkyl)amino group, combination of alkoxycarbonyl group and N-(hydroxyalkyl)amino group, sulfo group and N- Combination of (hydroxyalkyl)amino, combination of alkylsulfo and N-(hydroxyalkyl)amino, combination of carboxyl and N,N-bis(alkoxyalkyl)amino, alkoxycarbonyl and N, Combination of N-bis(alkoxyalkyl)amino, combination of sulfo and N,N-bis(alkoxyalkyl)amino, alkylsulfo and N,N-bis(alkoxyalkyl) Combination of amino group, combination of carboxyl group and N,N-bis(hydroxyalkyl)amino group, combination of alkoxycarbonyl group and N,N-bis(hydroxyalkyl)amino group, sulfo group and N,N-bis(hydroxyalkane) group) of amino groups, combinations of alkylsulfo groups and N,N-di(hydroxyalkyl)amino groups, etc., but not limited to these.

In this specification, alkyl groups, as well as alkoxy groups, alkoxycarbonyl groups, alkylsulfo groups, N-alkylamino groups, N,N-dialkylamino groups, N-(alkoxyalkyl)amino groups, N- Each alkyl moiety and each alkylene moiety in -(hydroxyalkyl)amino, N,N-bis(alkoxyalkyl)amino and N,N-bis(hydroxyalkyl)amino may be linear , can also be branched. Examples of the above-mentioned alkyl groups and alkyl moieties include alkyl groups having 1 to 20 carbon atoms, and methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl groups are preferred. , decyl, undecyl, dodecyl and other alkyl groups having 1 to 12 carbon atoms. In addition, as the above-mentioned alkylene moiety, for example, an alkylene chain having 1 to 20 carbon atoms can be mentioned, and a methylene chain, an ethylene chain, a propylene chain, a butylene chain, and a pentylene chain are preferable. , hexylene chain, heptylene chain, octylene chain, nonylidene chain, decylene chain, undecylidene chain, dodecylidene chain and other alkylene chains with 1 to 12 carbon atoms. Additionally, for N,N-dialkylamino, N,N-di(alkoxyalkyl)amino and N,N-di(hydroxyalkyl)amino, 2 alkyl moieties, 2 alkoxy The hydroxyalkyl moiety and the two hydroxyalkyl moieties may be the same or different.

Although the weight average molecular weight of a polysiloxane compound is not specifically limited, For example, it exists in the range of 1000-1000000, Preferably it exists in the range of 5000-500000, More preferably, it exists in the range of 10000-100000. The said weight average molecular weight is the value calculated|required as the molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC), for example.

<<Manufacturing method of polysiloxane compound>>

The polysiloxane compound can be produced, for example, by mixing the isocyanate compound (a1), the aminosilane compound (a2), and an aqueous medium in this order at a predetermined ratio, and reacting at a predetermined temperature (preferably 40 to 80°C), Thereby, a polysiloxane compound is produced. In production of the polysiloxane compound, in addition to the isocyanate compound (a1) and the aminosilane compound (a2), an amine compound (a3) may be further compounded. Moreover, the polysiloxane compound which has an N-alkylamino group or an N,N- dialkylamino group can also be manufactured by making the amino group of the polysiloxane compound obtained by manufacture react with an alkyl halide or an alkylene oxide as needed. In addition, examples of the alkyl moiety of the haloalkane are the same as above. As a halogen of a haloalkane, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned, for example. As an alkylene oxide, although ethylene oxide, propylene oxide, butylene oxide, etc. are mentioned, for example, it is not limited to these. In addition, the ratio of the number of ureido groups to X groups in the polysiloxane compound (ureido groups/X groups) can be obtained by calculating the peak of -NH- derived from ureido groups by ¹ H NMR analysis Intensity or peak intensity (I ₁ ) of -C=O- derived from urea group based on ¹³ C NMR analysis and peak intensity of X group based on ¹ H NMR analysis [in the case of two or more X groups, each The ratio (I ₁ /I ₂ ) of the sum of the peak intensities of the X groups] (I ₂ ) was obtained.

In order to promote the above reaction, for example, polycondensation catalysts such as dibutyltin diacetate, dibutyltin dilaurate, and lead naphthenate; known hydrolysis catalysts such as acidic catalysts; amine catalysts as polycondensation catalysts and hydrolysis catalysts, etc. can be used.

Isocyanate Compound (a1)

The isocyanate compound (a1) refers to a compound having one or more isocyanate groups. The isocyanate compound (a1) may have two or more isocyanate groups. In addition, the isocyanate compound (a1) may have a Si group to which a hydroxyl group or an alkoxy group is bonded. Examples of the isocyanate compound (a1) include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 1,4-diisocyanate butyl, 1,6-diisocyanate Hexyl isocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-cyclohexyldiisocyanate, 4,4'-diisocyanate dicyclohexylmethane, 2,4'-diisocyanate Isocyanate dicyclohexylmethane, isophorone diisocyanate, etc., but not limited to these. Moreover, these isocyanate compounds may use 1 type, and may use 2 or more types together.

Aminosilane compound (a2)

The aminosilane compound (a2) refers to a compound having one or more amino groups and a Si group to which a hydroxyl group or an alkoxy group is bonded. As the aminosilane compound (a2), for example, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyl Trimethoxysilane, 3-[2-(2-aminoethylaminoethylamino)propyl]trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, etc. , but not limited to these. Moreover, these aminosilane compounds may use 1 type, and may use 2 or more types together.

Amine compound (a3)

The amine compound (a3) is a compound having one or more amino groups, and is not particularly limited as long as it does not belong to the aminosilane compound (a2), and may have a COOR group and/or a SO ₃ R group. Examples of the amine compound (a3) include alkylamines such as methylamine and ethylamine; alkylenediamines such as ethylenediamine and hexamethylenediamine; aminomethanesulfonic acid and 4-aminobenzenesulfonic acid and other compounds with amino and sulfo groups; compounds with amino groups and SO ₃ R groups (R is an alkyl group) such as methyl-2-aminobenzene-1-sulfonic acid, methyl-4-aminobenzene-1-sulfonic acid, etc. ; Compounds with amino and carboxyl groups such as amino acids such as glycine and alanine; esters of compounds with amino and carboxyl groups (compounds with amino and alkoxycarbonyl groups); 1-methylguanidine, N-butylethylenediamine , N-methyl-1,3-propanediamine, N-ethyl-1,3-propanediamine and other compounds with amino and N-alkylamino groups; 4-dimethylaminoaniline, 4-amino- N,N-diethylaniline, 1,1-diethylguanidine, 2-(dibutylamine)ethylamine, N,N-dimethyl-1,3-propanediamine, N,N- Compounds with amino groups and N,N-dialkylamino groups such as diethyl-1,3-propanediamine; 4-[(2-methoxyethyl)amino]aniline and other compounds with amino groups and N-(alkoxy Alkyl)amino compounds; p-(p-hydroxymethylaminobenzyl)aniline, 3-nitro-4-(2-hydroxyethylamino)aniline, N-(2-hydroxyethyl)-1,3 - Propanediamine, N-(2-methoxyethyl)-1,3-propanediamine and other compounds with amino and N-(hydroxyalkyl) amino groups; 4-[bis(methoxymethyl) Amino]-6-phenyl-1,3,5-triazine-2-amine and other compounds with amino and N,N-bis(alkoxyalkyl)amino groups; N,N-bis(2-hydroxyethyl) base)-1,4-phenylenediamine, N,N-bis(2-hydroxyethyl)-1,3-propanediamine, N,N-bis(2-methoxyethyl)-1,3 - A compound having an amino group and a N,N-bis(hydroxyalkyl)amino group, such as propylenediamine, and the like. These compounds may be used alone or in combination of two or more.

A ureido group can be obtained by making the isocyanate group in the said isocyanate compound (a1) react with the amino group in an aminosilane compound (a2) or an amine compound (a3). The ratio of the number of ureido groups to the number of X groups in 1 molecule (urea group/X group) is not particularly limited as long as it is in the range of 0.01 to 0.45, but it is preferably in the range of 0.05 to 0.4, and more preferably within the range of 0.1 to 0.35. In addition, the polysiloxane compound containing the urea group and the X group in a ratio (urea group/X group) in the range of 0.01 to 0.45 can be adjusted appropriately by appropriately adjusting the isocyanate compound (a1), the aminosilane compound (a2), the amine compound ( a3) and other blending amounts to manufacture.

Moreover, the number of objects of the urea group in 1 molecule of polysiloxane compound may be 1 or more normally, and may be 2 or more, and may be 3 or more. In addition, it is usually 1000 or less, may be 100 or less, and may be 50 or less.

In the production of the above-mentioned polysiloxane compound, the isocyanate compound (a1) and the aminosilane compound (a2), or the isocyanate compound (a1), the aminosilane compound (a2), and the amine compound (a3) may be compounded Silicon-containing compound (a4). The silicon-containing compound (a4) refers to a compound containing Si other than the isocyanate compound (a1) and the aminosilane compound (a2), preferably a compound in which a hydroxyl group, an alkoxy group or a halogen group is bonded to Si. Examples of the silicon-containing compound (a4) include vinyltrichlorosilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinyltris(2-methoxyethoxysilane) group) silane, vinyltriethoxysilane, vinyltrimethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane , 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxyoctyltrimethoxysilane , 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercapto propyltrimethoxysilane, 3-chloropropyltrimethoxysilane, trimethoxysilane, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyl Trimethoxysilane, octyltrimethoxysilane, phenyltrimethoxysilane, dimethoxydimethylsilane, phenylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane Silane, N-methyl-3-(trimethoxysilyl)propylamine, N-ethyl-3-(trimethoxysilyl)propylamine, N,N-dimethyl-3 -(trimethoxysilyl)propylamine, N,N-diethyl-3-(trimethoxysilyl)propylamine, N-hydroxyethyl-3-(trimethoxysilyl) ) propylamine, N,N-dihydroxyethyl-3-(trimethoxysilyl)propylamine, N-methoxyethyl-3-(trimethoxysilyl)propylamine, N,N-dimethoxyethyl-3-(trimethoxysilyl)propylamine and the like, but not limited to these. These silicon-containing compounds may be used alone or in combination of two or more.

The aqueous medium is not particularly limited as long as it is a mixture of water or a water-miscible organic solvent. In addition, the mass % of water in the mixture may be 50 mass % or more, and more preferably 80 mass % or more, 90 mass % or more, 95 mass % or more, and 99 mass % or more in this order.

The water-miscible organic solvent is not particularly limited as long as it is an organic solvent mixed with water, and examples thereof include ketone-based solvents such as acetone and methyl ethyl ketone; N,N'-dimethylformamide, dimethylacetamide, and the like. Amide-based solvents; alcohol-based solvents such as methanol, ethanol, and isopropanol; ether-based solvents such as ethylene glycol monobutyl ether and ethylene glycol monohexyl ether; 1-methyl-2-pyrrolidone, 1-ethyl-2- Pyrrolidone-based solvents such as pyrrolidone, etc. One of these water-miscible organic solvents may be mixed with water, or two or more of them may be mixed with water.

<<Composition containing polysiloxane compound>>

The composition of this embodiment contains a polysiloxane compound and water and/or an organic solvent. The composition may consist solely of the polysiloxane compound and water and/or organic solvent, or may contain other ingredients. As other components, antiseptics, surfactants, etc. are mentioned.

Examples of the organic solvent include ketone-based solvents such as acetone and methyl ethyl ketone; amide-based solvents such as N,N'-dimethylformamide and dimethylacetamide; alcohol-based solvents such as methanol, ethanol, and isopropanol; Ether-based solvents such as glycol monobutyl ether and ethylene glycol monohexyl ether; pyrrolidone-based solvents such as 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, and the like. One of these organic solvents may be mixed with water, or two or more of them may be mixed with water.

As the antiseptic, a known antiseptic can be used.

The surfactant is not particularly limited as long as the wettability of the composition containing the polysiloxane compound can be improved, and surfactants such as cationic, anionic, amphoteric, and nonionic can be used. Specifically, cationic surfactants such as alkylamine salts and alkyltrimethylammonium halides; alkylsulfonates, polyoxyethylene alkylphenyl ether sulfates, dodecyl diphenyl Anionic surfactants such as sodium ether disulfonate and sodium lauryl sulfate; amphoteric surfactants such as alkyl aminopropionate and alkyl dimethyl betaine; polyoxyethylene alkyl phenyl ether, polyoxyethylene Nonionic surfactants such as alkylene fatty acid esters, fatty acid glycerides, sorbitan fatty acid esters, polyoxyethylene glycerin fatty acid esters, and polyoxyethylene propylene glycol fatty acid esters. These may be used individually by 1 type, and may be used in combination of 2 or more types.

The content of the polysiloxane compound in the composition is appropriately set according to the application, and is usually 0.01% by mass or more, may be 0.1% by mass or more, and usually 99% by mass or less, and may be 90% by mass or less. Moreover, content of other components in a composition can also be suitably set in the range which does not inhibit the effect of this invention. It is usually 0.01 mass % or more, and may be 0.1 mass % or more, and usually 10 mass % or less, and may be 5 mass % or less.

<<Manufacturing method of composition containing polysiloxane compound>>

The composition of this embodiment can be produced by mixing a polysiloxane compound and water and/or an organic solvent.

<<Use of polysiloxane compounds and compositions>>

The polysiloxane compound and composition of the present embodiment can be brought into contact with the surface or on the surface of a metal material or the like by a coating method, a dipping method, or the like, and then dried to form a coating having durability, corrosion resistance, and coating properties. Since it is a film with excellent appearance in packaging adhesion, it can be used as a film-forming agent or its component (additive). For example, it can be used as a film-forming agent for metal materials used in electronic parts, micro-device parts, cooking utensils, ships, building materials, etc. constituting industrial products such as automobiles, home appliances, office automation equipment, medical equipment, and medical instruments. or its components (additives). In addition to this, it is not limited to metal materials, and can be used as a film-forming agent or its components (additives) for substrates including plastics, rubbers, ceramics, glass, fibers, magnetic materials, and the like.

In addition, coating can be performed on the surface of the film formed by the polysiloxane compound of the present embodiment or the composition containing the same. The coating method is not particularly limited, and known methods can be applied, such as roller coating, spray coating, thermal spray coating, airless spray coating, electrostatic coating (eg electrostatic powder coating), roller coating, curtain coating Flow coating, brush coating, bar coating, flow dipping method, etc. In addition, the coating material on the surface of the coated substrate may be dried after coating. In addition, before coating, the surface of the base material which has the film formed with the polysiloxane compound of this embodiment or the composition containing it may or may not be washed with water. In addition, before coating, the surface of the base material after washing with water or without washing with water may or may not be dried.

Examples of the above-mentioned paints include oil-based paints, cellulose derivative paints, phenolic resin paints, alkyd resin paints, aminoalkyd resin paints, urea resin paints, unsaturated resin paints, vinyl resin paints, and acrylic resin paints. , epoxy resin paint, polyurethane resin paint, silicone resin paint, fluororesin paint, antirust paint, antifouling paint, powder paint, water-based paint, solvent paint and other well-known paints. In addition, the coating may be performed once using the same or different various paints, or may be performed twice or more. In addition, drying is a process of drying and curing the applied paint. Examples of the drying method include natural drying, vacuum drying, convection-type thermal drying (eg, natural convection-type thermal drying, forced convection-type thermal drying), radiation drying (eg, near-infrared drying, far-infrared drying), and ultraviolet curing. Drying, electron beam curing drying, steam curing, sintering drying and other drying methods. In addition, these drying methods may be implemented by 1 type, and may be implemented in combination of 2 or more types.

Known methods can be applied as coating methods such as spray coating using powder coating materials, electrostatic powder coating, and fluid dipping methods. Examples of the powder coating material include a polyester resin and a blocking isocyanate curing agent as a curing agent, a β-hydroxyalkylamide curing agent (for example, refer to Japanese Patent Laid-Open No. 2011-88083), or triglycidyl isocyanurate. Cyanurate powder coatings. The sintering is carried out within a specified temperature range for a certain period of time. Specifically, it is performed at 150-250 degreeC for 20 minutes.

Known methods can be applied as coating methods such as spray coating, electrostatic coating, and bar coating using the above-mentioned solvent paint. As a solvent coating material, the solvent coating material containing resins, such as melamine resin, acrylic resin, urethane resin, polyester resin, and organic solvents, such as a thinner, is mentioned, for example. The sintering is carried out within a specified temperature range for a certain period of time. Specifically, it was performed at 130°C for 20 minutes.

The coating film obtained by coating may be a single layer or a multilayer. In the case of multiple layers, the coating materials for forming various coating films, the coating method using the coating materials, the drying method of the coated substrate, and the like may be the same or different from each other.

In addition, the polysiloxane compound and composition of the present embodiment can be used not only as a film-forming agent or a component thereof, but also as a raw material for various products, pharmaceuticals, cosmetics, pharmaceuticals, rubber, wax, and the like.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

<<Production of polysiloxane compound (composition)>>

Based on the compositions shown in Tables 1 and 2, prescribed amounts of each compound and water were mixed. After making this mixture react at 60 degreeC for 5 hours, it cooled to 25 degreeC, and various polysiloxane compounds were manufactured. Performance evaluation was performed using the compositions of Examples 1 to 14 and Comparative Examples 1 to 8 containing various polysiloxane compounds and water. In addition, each symbol in Table 1 and Table 2 represents the following compounds. The unit of the numerical value in each raw material of Table 1 and Table 2 is a mass part.

<Isocyanate Compound (a1)>

(a1-1): 3-Isocyanatopropyltriethoxysilane

(a1-2): 1,4-butyl diisocyanate

(a1-3): 1,6-hexyl diisocyanate

(a1-4): isophorone diisocyanate

<Aminosilane compound (a2)>

(a2-1): N-2-(aminoethyl)-3-aminopropyltrimethoxysilane

(a2-2): 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane

(a2-3): 3-aminopropyltriethoxysilane

(a2-4): 3-aminopropyltrimethoxysilane

<Amine compound (a3)>

(a3-1): Ethylenediamine

(a3-2): 4-Aminobenzenesulfonic acid

<Silicon-containing compound (a4)>

(a4-1): Vinyltrichlorosilane

(a4-2): 3-glycidoxypropyltrimethoxysilane

(a4-3): Tetraethoxysilane

[Table 1]

Table 1: Production of polysiloxane compounds (compositions)

[Table 2]

Table 2: Production of polysiloxane compounds (compositions)

The weight average molecular weights of the polysiloxane compounds contained in the compositions of Examples 1 to 14 and Comparative Examples 1 to 8 were measured by gel permeation chromatography (GPC) under the following conditions using polystyrene as a standard sample. Convert. In addition, the peak intensity (I ₁ ) of -NH- derived from urea group of each polysiloxane compound by ¹ H NMR analysis and the peak intensity of X group by ¹ H NMR analysis [in the case of two or more X groups] were measured. In the case of , it is the sum of the peak intensities of various X groups] (I ₂ ), and the ratio of the number of ureido groups and X groups in each siloxane compound is calculated (urea groups/X groups=I ₁ /I _{2 )} . ). These results are shown in Table 1 and Table 2.

(GPC condition)

Column: Semi-micro column; manufactured by Tosoh Co., Ltd.; used by connecting two

Standard sample: PStQuick B; manufactured by Tosoh Co., Ltd.

Mobile phase: N,N-dimethylformamide (DMF)

Detector: RI, UV

<<Forming a coating film I using the composition>>

On the surface of a GI material [zinc adhesion amount of 60 g/m ² per side (double-sided coating); JIS G 3302: 2012] as a hot dip galvanized steel sheet, an alkaline degreasing agent [FINE CLEANER-E6406, Japan Pakar Degreasing was performed by spraying at 60° C. for 10 seconds, then by spraying with water for 10 seconds, washing with water, and drying.

The compositions of Examples 1 to 14 and Comparative Examples 1 to 8 were respectively coated on the surface of the GI material after washing with water and dried by a bar coating method, and dried at a maximum metal plate temperature (PMT) of 150° C. GI materials for seed coat membranes (No. 1 to 22). In addition, the film mass after drying was 1000 mg/m ² , respectively.

<<Performance evaluation>>

As the durability evaluation of the film, the following various performance evaluations were performed. In the evaluation, "S" and "A" satisfy practical performance.

<Acid resistance>

The GI materials having various coatings of Nos. 1 to 22 were immersed in a 1 mass % aqueous sulfuric acid solution for 1 minute, then washed with water and dried. Then, the presence or absence of peeling of the film and the discoloration (corrosion) of the surface of the GI material were visually observed, and the acid resistance was evaluated according to the following evaluation criteria. The results are shown in Table 3.

(Evaluation Criteria)

S: No peeling of the film was observed, and no discoloration on the surface of the GI material was observed

A: The peeling of the film is observed locally, and the discoloration on the surface of the GI material can be observed

B: The peeling of the film was observed on almost the entire surface, and significant discoloration was observed on the surface of the GI material

C: Most of the film is peeled off, and there is almost no residue

<Solvent resistance>

A load of 1 kg was applied to the gauze impregnated with ethanol, and the GI materials with various coatings of Nos. 1 to 22 were rubbed back and forth 20 times. Then, the presence or absence of peeling of the film and the discoloration of the surface of the GI material were visually observed, and the solvent resistance was evaluated according to the following evaluation criteria. The results are shown in Table 3.

(Evaluation Criteria)

S: No peeling of the film was observed, and no discoloration on the surface of the GI material was observed

A: The peeling of the film is observed locally, and the discoloration on the surface of the GI material can be observed

B: The peeling of the film was observed on almost the entire surface, and significant discoloration was observed on the surface of the GI material

[table 3]

Table 3: Evaluation Results

<<Forming a coating film II using the composition>>

On the surface of a cold-rolled steel sheet (thickness: 0.8 mm), an alkaline degreasing agent [FINE CLEANER-E6406, manufactured by Nippon Parker Seiki Co., Ltd., diluted with water to an aqueous solution of 20 g/L] was sprayed at 60°C for 10 seconds , thereby degreasing, and then spraying with water for 10 seconds, washing with water, and drying.

The compositions of Examples 1 to 9 and Comparative Examples 1 to 3 were appropriately diluted, and were respectively coated on the surface of the cold-rolled steel sheet after washing and drying by bar coating, and dried at a maximum metal sheet temperature (PMT) of 150°C. , to produce cold-rolled steel sheets with various coatings. In addition, the film mass after drying was 50 mg/m ² , respectively.

<<Production of solvent-coated cold-rolled steel sheet>>

An aminoalkyd resin paint [Amirac 1000, Kansai Paint Co., Ltd.] was applied to the film of the cold-rolled steel sheet with the film by bar coating, and dried at a maximum metal plate temperature (PMT) of 150°C to prepare a film with a film. Cold-rolled steel sheets (No. 23 to 34). In addition, the film thickness after drying was 30 micrometers.

<<Production of powder-coated cold-rolled steel sheet>>

An epoxy polyester powder coating (manufactured by Nippon Paint Co., Ltd.) was applied so that the thickness of the coating film after drying was 80 μm using a corona-charging electrostatic coating gun [GX-8000 hand gun manufactured by Parker Ionics Co., Ltd.]. Biryusia Ulticolor] is coated on the film of the above-mentioned cold-rolled steel sheet with film. Then, it sintered at 180 degreeC for 20 minutes, and produced the cold-rolled steel sheet (No.35-46) which has a coating film.

<<Performance evaluation>>

As the corrosion resistance evaluation of the film, the following various performance evaluations were performed. In the evaluation, "S" and "A" satisfy practical performance.

<<Corrosion resistance after solvent coating>>

According to JIS K 5600:2014, the cold-rolled steel sheets having various coating films of Nos. 23 to 34 were cut with cross cuts (x-shaped), and then immersed in a 5% NaCl aqueous solution at room temperature for 90 hours. Then, the adhesive tape is attached to the site where the cross cut is made, and then the adhesive tape is peeled off. The peeling width of the coating film was measured, and the corrosion resistance was evaluated based on the following evaluation criteria. The results are shown in Table 4.

(Evaluation Criteria)

S: peel width less than 0.1mm

A: The peeling width is 0.1 mm or more and less than 3.0 mm

B: The peeling width is 3.0 mm or more and less than 5.0 mm

C: The peeling width is 5.0 mm or more

[Table 4]

Table 4: Evaluation results of corrosion resistance after solvent coating

<<Corrosion resistance after powder coating>>

According to JIS K 5600:2014, the cold-rolled steel sheets having various coating films of Nos. 35 to 46 were cut with cross cuts (x-shaped), and then immersed in a 5% NaCl aqueous solution at room temperature for 90 hours. Then, the adhesive tape is attached to the site where the cross cut is made, and then the adhesive tape is peeled off. The peeling width of the coating film was measured, and the corrosion resistance was evaluated based on the following evaluation criteria. The results are shown in Table 5.

(Evaluation Criteria)

S: peel width less than 0.1mm

A: The peeling width is 0.1 mm or more and less than 3.0 mm

B: The peeling width is 3.0 mm or more and less than 5.0 mm

C: The peeling width is 5.0 mm or more

[table 5]

Table 5: Corrosion resistance evaluation results after powder coating

Claims (3)

1. A polysiloxane compound having a urea group and an X group, and the ratio of the number of the urea group and the X group in 1 molecule, that is, the urea group/X group, is in the range of 0.01 to 0.45, The X group is one or more groups selected from -COOR, -SO ₃ R and -NR ₂ , and R is a hydrogen atom or an alkyl group which can have an alkoxy group or a hydroxyl group. 2 . The polysiloxane compound according to claim 1 , wherein the polysiloxane compound has a weight average molecular weight of 1,000 to 1,000,000. 3 . 3. A composition comprising the polysiloxane compound of claim 1 or 2.