CN111936558A - Polysiloxane compounds and compositions - Google Patents
Polysiloxane compounds and compositions Download PDFInfo
- Publication number
- CN111936558A CN111936558A CN201980024369.7A CN201980024369A CN111936558A CN 111936558 A CN111936558 A CN 111936558A CN 201980024369 A CN201980024369 A CN 201980024369A CN 111936558 A CN111936558 A CN 111936558A
- Authority
- CN
- China
- Prior art keywords
- group
- compound
- coating
- groups
- amino group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/54—Nitrogen-containing linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Silicon Polymers (AREA)
Abstract
The problem to be solved by the present invention is to provide a novel polysiloxane compound and a composition comprising the same. By having urea groups and X groups [ X groups being selected from-COOR, -SO3R and-NR2Wherein R is a hydrogen atom or an alkyl group which may have an alkoxy group or a hydroxyl group]And 1 the number ratio of urea groups to X groups in the molecule (urea groups/X groups) is in the range of 0.01 to 0.45, and a silicone compound and a composition containing the same can solve the above problems.
Description
Technical Field
The present invention relates to a polysiloxane compound and a composition comprising the same.
Background
In recent years, various silicone compounds have been used in various fields. For example, in patent document 1, a specific polysiloxane compound is used in an aqueous metal surface treatment agent. The polysiloxane compound contains more than 2-SiR in 1 molecule1R2R3(in the formula, R1、R2And R3Independently represents an alkyl group, an alkoxy group or a hydroxyl group, at least 1 represents an alkoxy group), and 1 or more hydrophilic functional groups (b) selected from at least 1 of a hydroxyl group (a hydroxyl group different from the hydroxyl group that can be contained in the functional group (a), an amino group, a carboxyl group, a phosphate group, a phosphonate group, a sulfo group, a polyoxyethylene chain and an amide group, and having a molecular weight of 100 to 10000 per 1 functional group (b).
Documents of the prior art
Patent document
Patent document 1: international publication No. 2006/82946.
Disclosure of Invention
Problems to be solved by the invention
The object of the present invention is to provide a novel silicone compound and a composition comprising the same.
Means for solving the problems
The invention is as follows:
[1]polysiloxane compound having urea group and X group [ X group is selected from-COOR, -SO3R and-NR2Wherein R is a hydrogen atom or an alkyl group which may have an alkoxy group or a hydroxyl group]1 the number ratio of ureido groups to X groups in a molecule (ureido/X group) is in the range of 0.01 to 0.45;
[2] the polysiloxane compound according to [1], wherein the polysiloxane compound has a weight-average molecular weight of 1000 to 1000000;
[3] a composition comprising the polysiloxane compound according to [1] or [2 ];
and the like.
Effects of the invention
According to the present invention, a novel polysiloxane compound and a composition comprising the same can be provided.
Detailed Description
The silicone compound and the composition of the present invention are explained below.
< polysiloxane Compound > <
The polysiloxane compound of the present embodiment has a urea group (urea bond) and an X group [ X group is selected from-COOR, -SO3R and-NR2Wherein R is a hydrogen atom or an alkyl group which may have an alkoxy group or a hydroxyl group]The ratio of the number of urea groups to the number of X groups in 1 molecule (urea groups/X groups) is in the range of 0.01 to 0.45.
The polysiloxane compound has 1 or more Si groups to which a hydroxyl group or an alkoxy group is bonded. The polysiloxane compound may have an epoxy group, or may have a structure in which the epoxy group is opened by hydrolysis (-CH (OH) CH2OH)。
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, an N, N-dialkylamino group, an N- (alkoxyalkyl) amino group, an N- (hydroxyalkyl) amino group, an N, N-di (alkoxyalkyl) amino group, an N, N-di (hydroxyalkyl) amino group, or the like, and the polysiloxane compound may have 1 kind of these groups, or may have 2 or more kinds.
Examples of the combination of 2 or more 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 combination of a carboxyl group and an N-alkylamino group, a combination of an alkoxycarbonyl group and an N-alkylamino group, a combination of a sulfo group and an N-alkylamino group, a combination of an alkylsulfo group and an N-alkylamino group, a combination of a carboxyl group and an N, N-dialkylamino group, a combination of an alkoxycarbonyl group and an N, N-dialkylamino group, a combination of a sulfo group and an N, N-dialkylamino group, a combination of an alkylsulfo group and an N, N-dialkylamino group, a combination of a carboxyl group and an N- (alkoxyalkyl) amino group, a combination of an alkoxycarbonyl group and an N- (alkoxyalkyl) amino group, a combination of a sulfo group and an N- (alkoxyalkyl) amino group, a combination of, A combination of a carboxyl group and an N- (hydroxyalkyl) amino group, a combination of an alkoxycarbonyl group and an N- (hydroxyalkyl) amino group, a combination of a sulfo group and an N- (hydroxyalkyl) amino group, a combination of an alkylsulfo group and an N- (hydroxyalkyl) amino group, a combination of a carboxyl group and an N, N-di (alkoxyalkyl) amino group, a combination of an alkoxycarbonyl group and an N, N-di (alkoxyalkyl) amino group, a combination of a sulfo group and an N, N-di (alkoxyalkyl) amino group, a combination of a carboxyl group and an N, N-di (hydroxyalkyl) amino group, a combination of an alkoxycarbonyl group and an N, N-di (hydroxyalkyl) amino group, a combination of a sulfo group and an N, N-di (hydroxyalkyl) amino group, a combination of an alkylsulfo group and an N, N-di (hydroxyalkyl) amino group, or the like, but is not limited thereto.
In the present specification, each alkyl moiety and each alkylene moiety in an alkyl group, and an alkoxy group, an alkoxycarbonyl group, an alkylsulfo group, an N-alkylamino group, an N, N-dialkylamino group, an N- (alkoxyalkyl) amino group, an N- (hydroxyalkyl) amino group, an N, N-di (alkoxyalkyl) amino group, and an N, N-di (hydroxyalkyl) amino group may be linear or branched. Examples of the alkyl group and the alkyl moiety include alkyl groups having 1 to 20 carbon atoms, and alkyl groups having 1 to 12 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like are preferable. Examples of the alkylene moiety include alkylene chains having 1 to 20 carbon atoms, and alkylene chains having 1 to 12 carbon atoms such as a methylene chain, an ethylene chain, a propylene chain, a butylene chain, a pentylene chain, a hexylene chain, a heptylene chain, an octylene chain, a nonylene chain, a decylene chain, an undecylene chain, and a dodecylene chain are preferable. In addition, the 2 alkyl moieties, the 2 alkoxyalkyl moieties and the 2 hydroxyalkyl moieties may be the same or different for the N, N-dialkylamino, N-di (alkoxyalkyl) amino and N, N-di (hydroxyalkyl) amino groups.
The weight average molecular weight of the polysiloxane compound is not particularly limited, and is, for example, in the range of 1000 to 1000000, preferably 5000 to 500000, and more preferably 10000 to 100000. The weight average molecular weight is a value determined as a molecular weight in terms of polystyrene, measured by Gel Permeation Chromatography (GPC), for example.
< method for producing polysiloxane Compound >)
The polysiloxane compound can be produced, for example, by: the polysiloxane compound is produced by mixing an isocyanate compound (a1), an aminosilane compound (a2) and an aqueous medium in this order at a predetermined ratio, and reacting the mixture at a predetermined temperature (preferably 40 to 80 ℃). In the production of the polysiloxane compound, an amine compound (a3) may be further blended in addition to the isocyanate compound (a1) and the aminosilane compound (a 2). Further, if necessary, the amino group of the polysiloxane compound obtained by the production may be reacted with an alkyl halide or an alkylene oxide to produce a polysiloxane compound having an N-alkylamino group or an N, N-dialkylamino group. Examples of the alkyl moiety of the alkyl halide are the same as those described above. Examples of the halogen of the alkyl halide include a fluorine atom, a chlorine atom, a bromine atom and the like. Examples of the alkylene oxide include, but are not limited to, ethylene oxide, propylene oxide, and butylene oxide. The ratio of the number of urea groups to the number of X groups (urea groups/X groups) in the polysiloxane compound can be determined as follows: is calculated based on1H NMR analysis of the intensity of the-NH-peak from the urea group or on the basis of13Peak intensity of-C ═ O-from ureido group analyzed by C NMR (I)1) And is based on1The peak intensity of X group in H NMR analysis [ in the case where the number of X groups is 2 or more, the sum of the peak intensities of the various X groups](I2) Ratio of (I)1/I2) Thus, it is obtained.
In order to accelerate the above reaction, for example, a polycondensation catalyst such as dibutyltin diacetate, dibutyltin dilaurate or lead naphthenate; known hydrolysis catalysts such as acid catalysts; amine catalysts as polycondensation catalysts and hydrolysis catalysts.
Isocyanate Compound (a1)
The isocyanate compound (a1) is a compound having 1 or more isocyanate groups. The isocyanate compound (a1) may have 2 or more isocyanate groups. Further, 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, but are not limited to, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 1, 4-diisocyanatobutyl, 1, 6-diisocyanatohexyl, 1, 3-bis (isocyanatomethyl) cyclohexane, 1, 4-cyclohexyldiisocyanate, 4 '-diisocyanatodicyclohexylmethane, 2, 4' -diisocyanatodicyclohexylmethane, isophorone diisocyanate, and the like. These isocyanate compounds may be used in 1 kind, or 2 or more kinds may be used in combination.
Aminosilane Compound (a2)
The aminosilane compound (a2) is a compound having 1 or more amino groups and a Si group to which a hydroxyl group or an alkoxy group is bonded. Examples of the aminosilane compound (a2) include, but are not limited to, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3- [2- (2-aminoethylaminoethylamino) propyl ] trimethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane. Further, these aminosilane compounds may be used in 1 kind, or 2 or more kinds may be used in combination.
Amine compound (a3)
The amine compound (a3) is a compound having 1 or more amino groups, is not particularly limited as long as it is not an aminosilane compound (a2), and may further have a COOR group and/or SO3And R is a radical. Examples of the amine compound (a3) include: alkylamines such as methylamine and ethylamine; alkylene diamines such as ethylenediamine and hexamethylenediamine; compounds having an amino group and a sulfo group such as aminomethane sulfonic acid and 4-aminobenzene sulfonic acid; methyl-2-aminobenzene-1-sulfonic acid, methyl-4-aminobenzene-1-sulfonic acid etc. having amino group and SO3Compounds of the R group (R is alkyl); amino acid compounds having an amino group and a carboxyl group such as glycine and alanine; an esterified product of a compound having an amino group and a carboxyl group (a compound having an amino group and an alkoxycarbonyl group); compounds having an amino group and an N-alkylamino group such as 1-methylguanidine, N-butylethylenediamine, N-methyl-1, 3-propanediamine, and N-ethyl-1, 3-propanediamine; compounds having an amino group and an N, N-dialkylamino group such as 4-dimethylaminoaniline, 4-amino-N, N-diethylaniline, 1-diethylguanidine, 2- (dibutylamine) ethylamine, N-dimethyl-1, 3-propanediamine, and N, N-diethyl-1, 3-propanediamine; 4- [ (2-methoxyethyl) amino group]Compounds having an amino group and an N- (alkoxyalkyl) amino group such as aniline; compounds having an amino group and an N- (hydroxyalkyl) amino group such as p- (p-hydroxymethylaminobenzyl) aniline, 3-nitro-4- (2-hydroxyethylamino) aniline, N- (2-hydroxyethyl) -1, 3-propanediamine, and N- (2-methoxyethyl) -1, 3-propanediamine; 4- [ bis (methoxymethyl) amino group]Compounds having an amino group and an N, N-di (alkoxyalkyl) amino group such as 6-phenyl-1, 3, 5-triazin-2-amine; and compounds having an amino group and an N, N-di (hydroxyalkyl) amino group such as N, N-bis (2-hydroxyethyl) -1, 4-phenylenediamine, N-bis (2-hydroxyethyl) -1, 3-propanediamine, and N, N-bis (2-methoxyethyl) -1, 3-propanediamine. These compounds may be used in 1 kind, or 2 or more kinds may be used in combination.
The urea group can be obtained by reacting the isocyanate group in the isocyanate compound (a1) with the amino group in the aminosilane compound (a2) or the amine compound (a 3). The ratio of the number of urea groups to the number of X groups in 1 molecule (urea groups/X groups) is not particularly limited, but is preferably in the range of 0.01 to 0.45, more preferably 0.05 to 0.4, and still more preferably 0.1 to 0.35. The polysiloxane compound containing an ureido group and an X group in a ratio (ureido/X group) within a range of 0.01 to 0.45 can be produced by appropriately adjusting the blending amounts of the isocyanate compound (a1), the aminosilane compound (a2), the amine compound (a3), and the like.
The number of urea groups in the 1-molecule polysiloxane compound is usually 1 or more, and may be 2 or more, and may be 3 or more. The content is usually 1000 or less, may be 100 or less, and may be 50 or less.
In the production of the polysiloxane compound, the silicon-containing compound (a4) may be blended with the isocyanate compound (a1) and the aminosilane compound (a2), or the isocyanate compound (a1), the aminosilane compound (a2), and the amine compound (a 3). The silicon-containing compound (a4) is a compound containing Si, which is not the isocyanate compound (a1) and the aminosilane compound (a2), and is 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-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane, 3,3, 3-trifluoropropyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyloctyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinylmethyldiethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, 3, 3-trifluoropropyltrimethoxysilane, 3- (3, 4-epoxycyclohexyl), Trimethoxysilane, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, octyltrimethoxysilane, phenyltrimethoxysilane, dimethoxydimethylsilane, phenylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methyl-3- (trimethoxysilyl) propylamine, N-ethyl-3- (trimethoxysilyl) propylamine, N-dimethyl-3- (trimethoxysilyl) propylamine, N-diethyl-3- (trimethoxysilyl) propylamine, N-hydroxyethyl-3- (trimethoxysilyl) propylamine, N-dihydroxyethyl-3- (trimethoxysilyl) propylamine, N-hydroxyethoxy-3- (trimethoxysilyl) propylamine, N-dimethyltrimethoxysilane, N-dimethyl, N-methoxyethyl-3- (trimethoxysilyl) propylamine, N-dimethoxyethyl-3- (trimethoxysilyl) propylamine and the like, but are not limited thereto. These silicon-containing compounds may be used in 1 kind, or 2 or more kinds may be used in combination.
The aqueous medium is not particularly limited as long as it is water or a mixture of water and a water-miscible organic solvent. The mass% of water in the mixture may be 50 mass% or more, and is 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 miscible with water, and examples thereof include ketone solvents such as acetone and methyl ethyl ketone; amide solvents such as N, N' -dimethylformamide and dimethylacetamide; alcohol solvents such as methanol, ethanol, and isopropanol; ether solvents such as ethylene glycol monobutyl ether and ethylene glycol monohexyl ether; pyrrolidone-based solvents such as 1-methyl-2-pyrrolidone and 1-ethyl-2-pyrrolidone. These water-miscible organic solvents may be obtained by mixing 1 kind of organic solvent with water, or by mixing 2 or more kinds of organic solvents with water.
< composition containing polysiloxane Compound >)
The composition of the present embodiment includes a silicone compound and water and/or an organic solvent. The composition may consist of the silicone compound alone and water and/or an organic solvent, or may contain other ingredients. Examples of the other components include preservatives, surfactants, and the like.
Examples of the organic solvent include ketone solvents such as acetone and methyl ethyl ketone; amide solvents such as N, N' -dimethylformamide and dimethylacetamide; alcohol solvents such as methanol, ethanol, and isopropanol; ether solvents such as ethylene glycol monobutyl ether and ethylene glycol monohexyl ether; pyrrolidone-based solvents such as 1-methyl-2-pyrrolidone and 1-ethyl-2-pyrrolidone. These organic solvents may be mixed with water in 1 kind, or may be mixed with water in 2 or more kinds.
As the preservative, a known preservative can be used.
The surfactant is not particularly limited as long as it can improve the wettability of the composition containing the silicone compound, and cationic, anionic, amphoteric, nonionic, and the like surfactants can be used. Specifically, there may be mentioned: cationic surfactants such as alkylamine salts and alkyltrimethylammonium halides; anionic surfactants such as alkylsulfonate, polyoxyethylene alkylphenyl ether sulfate, sodium dodecyl diphenyl ether disulfonate, and sodium dodecyl sulfate; amphoteric surfactants such as alkyl aminopropionates and alkyl dimethyl betaines; nonionic surfactants such as polyoxyethylene alkylphenyl ethers, polyoxyalkylene fatty acid esters, fatty acid glycerides, sorbitol fatty acid esters, polyoxyethylene glycerin fatty acids, and polyoxyethylene propylene glycol fatty acid esters. These can be used alone in 1 kind, also can be combined with more than 2 kinds.
The content of the silicone compound in the composition is appropriately set according to the use, and is usually 0.01% by mass or more, and may be 0.1% by mass or more, and is usually 99% by mass or less, and may be 90% by mass or less. The content of other components in the composition may be appropriately set within a range not to impair the effects of the present invention. Usually, it is 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.
< method for producing composition containing Silicone Compound >)
The composition of the present embodiment can be produced by mixing the silicone compound and water and/or an organic solvent.
< use of Silicone Compound and composition >)
The polysiloxane compound and the composition of the present embodiment can be brought into contact with the surface or the surface of a metal material or the like by a coating method, an immersion method, or the like, and then dried to form a coating film having durability, corrosion resistance, and coating adhesion and having excellent appearance, and therefore can be used as a coating film forming agent or a component (additive) thereof. For example, the composition is useful as a coating film forming agent for metal materials and the like used for electronic parts, microdevice parts, cooking utensils, ships, building materials and the like constituting industrial products such as automobiles, home appliances, office automation equipment, medical instruments and the like, or a component (additive) thereof. In addition, the coating agent is not limited to a metal material, and may be used as a coating film forming agent for a substrate including plastic, rubber, ceramic, glass, fiber, magnetic material, or the like, or a component (additive) thereof.
Further, the coating may be applied to the surface of the film formed from the polysiloxane compound or the composition containing the polysiloxane compound of the present embodiment. The method of coating is not particularly limited, and known methods such as roll coating, spray coating, thermal spray coating, airless spray coating, electrostatic coating (e.g., electrostatic powder coating), roll coating, curtain flow coating, brush coating, bar coating, and fluid immersion method can be applied. In addition, the coating on the surface of the coated substrate may be dried after coating. Before coating, the surface of the substrate having the coating film formed from the polysiloxane compound or the composition containing the same according to the present embodiment may be washed with water or may not be washed with water. The surface of the substrate may be dried after or without washing with water before coating, or may not be dried.
Examples of the coating material include: known paints such as oil-based paints, cellulose derivative paints, phenol resin paints, alkyd resin paints, amino alkyd resin paints, urea resin paints, unsaturated resin paints, vinyl resin paints, acrylic resin paints, epoxy resin paints, urethane resin paints, silicone resin paints, fluororesin paints, rust preventive paints, antifouling paints, powder paints, water-based paints, and solvent paints. The coating may be performed 1 time or 2 or more times using the same or different coating materials. The drying is a process of drying and curing the coated paint. Examples of the drying method include drying methods such as natural drying, drying under reduced pressure, convection-type heat drying (e.g., natural convection-type heat drying and forced convection-type heat drying), radiation-type drying (e.g., near infrared ray drying and far infrared ray drying), ultraviolet ray curing drying, electron beam curing drying, steam curing, and baking drying. These drying methods may be carried out in 1 kind, or 2 or more kinds may be carried out in combination.
As a coating method such as spray coating, electrostatic powder coating, or fluidized immersion method using a powder coating material, a known method can be applied. Examples of the powder coating material include powder coating materials containing a polyester resin and a blocked isocyanate curing agent, a β -hydroxyalkylamide curing agent (see, for example, japanese patent application laid-open publication No. 2011-88083), or triglycidyl isocyanurate as a curing agent. The sintering is carried out for a certain time within a predetermined temperature range. Specifically, the reaction is carried out at 150-250 ℃ for 20 minutes.
As a coating method such as spray coating, electrostatic coating, bar coating, etc. using the above solvent coating, a known method can be applied. Examples of the solvent coating include a solvent coating containing a resin such as a melamine resin, an acrylic resin, a polyurethane resin, or a polyester resin, and an organic solvent such as a diluent. The sintering is carried out for a certain time within a predetermined temperature range. Specifically, it was carried out at 130 ℃ for 20 minutes.
The coating film obtained by coating may be a single layer or a multilayer. In the case of a multilayer, the coating materials used for forming various coating films, the coating method using the coating materials, the method of drying the coated substrate, and the like may be the same or different.
The polysiloxane compound and the composition of the present embodiment can be used not only as a coating film-forming agent or a component thereof but also as a raw material for various products, pharmaceuticals, cosmetics, medicines, rubbers, waxes, and the like.
Examples
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
< production of Silicone Compound (composition) >
Based on the compositions shown in tables 1 and 2, prescribed amounts of each compound and water were mixed. After allowing the mixture to react at 60 ℃ for 5 hours, it was cooled to 25 ℃ to produce various silicone compounds. The compositions of examples 1 to 14 and comparative examples 1 to 8, which contain various silicone compounds and water, were used for performance evaluation. In addition, each symbol in table 1 and table 2 represents the following compound. The unit of numerical value in each raw material in table 1 and table 2 is part by mass.
< isocyanate Compound (a1) >
(a 1-1): 3-isocyanatopropyltriethoxysilane
(a 1-2): 1, 4-Diisocyanatobutyl ester
(a 1-3): 1, 6-diisocyanatohexyl ester
(a 1-4): isophorone diisocyanate
< aminosilane Compound (a2) >
(a 2-1): n-2- (aminoethyl) -3-aminopropyltrimethoxysilane
(a 2-2): 3- [2- (2-aminoethylamino) ethylamino ] propyltrimethoxysilane
(a 2-3): 3-aminopropyltriethoxysilane
(a 2-4): 3-aminopropyltrimethoxysilane
< amine Compound (a3) >
(a 3-1): ethylene diamine
(a 3-2): 4-Aminobenzenesulfonic acid
< silicon-containing Compound (a4) >
(a 4-1): vinyl trichlorosilane
(a 4-2): 3-glycidoxypropyltrimethoxysilane
(a 4-3): tetraethoxysilane
[ Table 1]
Table 1: production of Silicone Compound (composition)
[ Table 2]
Table 2: production of Silicone Compound (composition)
The weight average molecular weight of the polysiloxane compound contained in the compositions of examples 1 to 14 and comparative examples 1 to 8 was measured by Gel Permeation Chromatography (GPC) under the following conditions, and was converted using polystyrene as a standard sample. In addition, the respective determination is based on1H NMR analysis of the peak intensity of-NH-derived from urea group of each polysiloxane Compound (I)1) And based on1The peak intensity of X group in H NMR analysis [ in the case where the number of X groups is 2 or more, the sum of the peak intensities of the various X groups](I2) The ratio of the number of urea groups to the number of X groups in each siloxane compound (urea group/X group ═ I) was calculated1/I2). These results are shown in tables 1 and 2.
(GPC conditions)
Column: a semi-microcolumn; tosoh (manufactured by Tosoh Corp.); is connected with 2 pieces of use
Standard sample: PStQuick B; tosoh (strain)
The mobile phase: n, N-Dimethylformamide (DMF)
The detector: RI, UV
< Forming coating film Using composition I >)
GI Material as a hot-dip galvanized steel sheet [ zinc adhesion amount 60g/m per surface ]2(double-sided plating); JIS G3302: 2012]On the surface of (1), an alkaline degreasing agent [ FINE CLEANER-E6406, manufactured by JAPONICA Rice-Lindl., RICE MILL, was diluted with water to an aqueous solution of 20g/L]Degreasing was performed by spraying at 60 ℃ for 10 seconds, and then washing and drying were performed by spraying with water for 10 seconds.
The compositions of examples 1 to 14 and comparative examples 1 to 8 were applied to the surface of the washed and dried GI material by a bar coating method, and dried at a maximum metal plate temperature (PMT) of 150 ℃. The mass of the dried coating was 1000mg/m2。
< evaluation of Performance >)
As the durability evaluation of the coating film, various performance evaluations were performed as follows. In the evaluation, "S" and "a" satisfy practical performance.
< acid resistance >
GI materials having various coatings of Nos. 1 to 22 were immersed in a1 mass% sulfuric acid aqueous solution for 1 minute, and then washed with water and dried. Then, the presence or absence of peeling of the coating and 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: neither peeling of the coating nor discoloration of the surface of the GI material was observed
A: peeling of the coating was observed locally, and discoloration of the surface of the GI material was observed
B: peeling of the coating was observed almost over the entire surface, and significant discoloration was observed on the surface of the GI material
C: most of the coating was peeled off and almost no residue remained
< solvent resistance >
A1 kg load was applied to the gauze impregnated with ethanol, and the GI materials having various films of Nos. 1 to 22 were rubbed in a reciprocating manner 20 times. Then, the presence or absence of peeling of the coating and 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: neither peeling of the coating nor discoloration of the surface of the GI material was observed
A: peeling of the coating was observed locally, and discoloration of the surface of the GI material was observed
B: peeling of the coating was observed almost over the entire surface, and significant discoloration was observed on the surface of the GI material
[ Table 3]
Table 3: evaluation results
< formation of coating film Using composition II >)
On the surface of a cold-rolled steel sheet (thickness: 0.8mm), an alkaline degreasing agent [ FINE CLEANER-E6406, an aqueous solution prepared by JAPONICA Rice-scale essence, Ltd., diluted with water to 20g/L ] was sprayed at 60 ℃ for 10 seconds to degrease, and then sprayed with water for 10 seconds to wash with water and dry.
The compositions of examples 1 to 9 and comparative examples 1 to 3 were diluted as appropriate, and applied to the surfaces of the cold-rolled steel sheets washed with water and dried by a bar coating methodThe steel sheets were dried at a maximum sheet metal temperature (PMT) of 150 ℃ to produce cold-rolled steel sheets having various coatings. The mass of the dried coating was 50mg/m2。
< production of solvent-coated Cold-rolled Steel sheet >)
An amino alkyd resin coating [ Amirac 1000, Kansai Paint (ltd) ] was applied on the coating film of the cold-rolled steel sheet having the coating film by a bar coating method, and dried at a maximum sheet metal temperature (PMT) of 150 ℃ to produce a cold-rolled steel sheet having a coating film (nos. 23 to 34). The film thickness after drying was 30 μm.
< production of powder-coated Cold-rolled Steel sheet >)
An epoxy polyester powder coating (made by Nippon Paint, Biryusia Ulticolor) was applied onto the coating film of the cold-rolled steel sheet having the coating film by using a corona charging type electrostatic coating gun (GX-8000 Manual gun made by Parker Ionics Co., Ltd.) so that the thickness of the dried coating film became 80 μm. Then, the steel sheet was sintered at 180 ℃ for 20 minutes to produce cold rolled steel sheets (Nos. 35 to 46) having a coating film.
< evaluation of Performance >)
As the corrosion resistance evaluation of the coating, the following various performance evaluations were performed. In the evaluation, "S" and "a" satisfy practical performance.
< Corrosion resistance after solvent coating >
According to JIS K5600: 2014, cross cuts (X-shaped cuts) were made in cold-rolled steel sheets No.23 to 34 having various coating films, and then the sheets were immersed in a 5% NaCl aqueous solution at room temperature for 90 hours. Then, an adhesive tape is attached to the portion cut into the cross-shaped notch, 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: peeling width less than 0.1mm
A: the peeling width is more than 0.1mm and less than 3.0mm
B: the peeling width is more than 3.0mm and less than 5.0mm
C: the peeling width is more than 5.0mm
[ Table 4]
Table 4: evaluation results of Corrosion resistance after solvent coating
< Corrosion resistance after powder coating >
According to JIS K5600: 2014, cross cuts (cut in a X-shape) were made in cold-rolled steel sheets having various coatings of No.35 to 46, and then the sheets were immersed in a 5% NaCl aqueous solution at room temperature for 90 hours. Then, an adhesive tape is attached to the portion cut into the cross-shaped notch, 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: peeling width less than 0.1mm
A: the peeling width is more than 0.1mm and less than 3.0mm
B: the peeling width is more than 3.0mm and less than 5.0mm
C: the peeling width is more than 5.0mm
[ Table 5]
Table 5: evaluation results of Corrosion resistance after powder coating
Claims (3)
1. A polysiloxane compound having urea groups and X groups, wherein the ratio of the number of urea groups to the number of X groups in 1 molecule, i.e., urea groups/X groups, is in the range of 0.01 to 0.45,
the X radical is selected from-COOR, -SO3R and-NR2Wherein R is a hydrogen atom or an alkyl group which may have an alkoxy group or a hydroxyl group.
2. The polysiloxane compound of claim 1, wherein the polysiloxane compound has a weight average molecular weight of 1000 to 1000000.
3. A composition comprising the polysiloxane compound of claim 1 or 2.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018-087611 | 2018-04-12 | ||
| JP2018087611 | 2018-04-12 | ||
| PCT/JP2019/015593 WO2019198746A1 (en) | 2018-04-12 | 2019-04-10 | Polysiloxane compound and composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111936558A true CN111936558A (en) | 2020-11-13 |
| CN111936558B CN111936558B (en) | 2022-03-18 |
Family
ID=68163202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201980024369.7A Active CN111936558B (en) | 2018-04-12 | 2019-04-10 | Polysiloxane compounds and compositions |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6932249B2 (en) |
| CN (1) | CN111936558B (en) |
| WO (1) | WO2019198746A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2023106679A (en) | 2022-01-21 | 2023-08-02 | 日本パーカライジング株式会社 | Surface treatment agent, material to be treated having film and method for producing the same |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4322310A (en) * | 1980-06-12 | 1982-03-30 | Uop Inc. | Chiral supports for resolution of racemates |
| US5908948A (en) * | 1997-03-11 | 1999-06-01 | Bayer Corporation | Compounds containing urea and alkoxysilane groups |
| EP2093252A1 (en) * | 2003-08-01 | 2009-08-26 | Cemedine Co., Ltd. | Curing composition and method for producing curing composition |
| CN101528871A (en) * | 2006-10-16 | 2009-09-09 | 旭化成化学株式会社 | Fluorine coating composition |
| US20090317541A1 (en) * | 2008-06-24 | 2009-12-24 | Hoya Corporation | Functional silane compound, coating solution, and method for manufacturing plastic lens |
| CN101993522A (en) * | 2009-08-19 | 2011-03-30 | 赢创高施米特有限公司 | Novel urethane-containing silylated prepolymers and process for preparation thereof |
| CN102329336A (en) * | 2010-06-02 | 2012-01-25 | 信越化学工业株式会社 | Ureido silane compound and room temperature curable organopolysiloxane composition |
| US20130137792A1 (en) * | 2011-11-29 | 2013-05-30 | Shin-Etsu Chemical Co., Ltd. | Method for preparing an organopolysiloxane compound and curing composition using the compound |
| CN103459470A (en) * | 2011-03-31 | 2013-12-18 | 道康宁公司 | Optically clear composition |
| WO2014151485A1 (en) * | 2013-03-15 | 2014-09-25 | Dow Corning Corporation | Urea-siloxane compositions and methods of making the same |
| JP2016050276A (en) * | 2014-09-01 | 2016-04-11 | スリーボンドファインケミカル株式会社 | Surface treatment agent for coated steel panel |
-
2019
- 2019-04-10 WO PCT/JP2019/015593 patent/WO2019198746A1/en active Application Filing
- 2019-04-10 JP JP2020513423A patent/JP6932249B2/en active Active
- 2019-04-10 CN CN201980024369.7A patent/CN111936558B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4322310A (en) * | 1980-06-12 | 1982-03-30 | Uop Inc. | Chiral supports for resolution of racemates |
| US5908948A (en) * | 1997-03-11 | 1999-06-01 | Bayer Corporation | Compounds containing urea and alkoxysilane groups |
| EP2093252A1 (en) * | 2003-08-01 | 2009-08-26 | Cemedine Co., Ltd. | Curing composition and method for producing curing composition |
| CN101528871A (en) * | 2006-10-16 | 2009-09-09 | 旭化成化学株式会社 | Fluorine coating composition |
| US20090317541A1 (en) * | 2008-06-24 | 2009-12-24 | Hoya Corporation | Functional silane compound, coating solution, and method for manufacturing plastic lens |
| CN101993522A (en) * | 2009-08-19 | 2011-03-30 | 赢创高施米特有限公司 | Novel urethane-containing silylated prepolymers and process for preparation thereof |
| CN102329336A (en) * | 2010-06-02 | 2012-01-25 | 信越化学工业株式会社 | Ureido silane compound and room temperature curable organopolysiloxane composition |
| CN103459470A (en) * | 2011-03-31 | 2013-12-18 | 道康宁公司 | Optically clear composition |
| US20130137792A1 (en) * | 2011-11-29 | 2013-05-30 | Shin-Etsu Chemical Co., Ltd. | Method for preparing an organopolysiloxane compound and curing composition using the compound |
| WO2014151485A1 (en) * | 2013-03-15 | 2014-09-25 | Dow Corning Corporation | Urea-siloxane compositions and methods of making the same |
| JP2016050276A (en) * | 2014-09-01 | 2016-04-11 | スリーボンドファインケミカル株式会社 | Surface treatment agent for coated steel panel |
Non-Patent Citations (1)
| Title |
|---|
| 杨芳等: "硅烷封端聚氨酯的制备及其应用研究进展", 《有机硅材料》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019198746A1 (en) | 2019-10-17 |
| CN111936558B (en) | 2022-03-18 |
| JPWO2019198746A1 (en) | 2021-02-18 |
| JP6932249B2 (en) | 2021-09-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2382277B1 (en) | Silane coating compositions containing silicon-based polyether copolymers, methods for coating metal surfaces and articles made therefrom | |
| CN100418994C (en) | Silane-crosslinkable coating formulations | |
| CN101297008A (en) | Compositions containing a silanol functional polymer and related hydrophilic coating films | |
| JP5814929B2 (en) | Anti-stain coating composition with excellent durability | |
| WO1996034063A1 (en) | Coating composition, process for preparing the composition, and process for preparing dispersion of inorganic oxide sol | |
| AU2007225424B2 (en) | Water dispersible silanes as corrosion-protection coatings and paint primers for metal pretreatment | |
| WO2012078469A1 (en) | Coating compositions containing silane-terminated polysiloxanes | |
| WO2017188330A1 (en) | Composition | |
| CN107936814A (en) | The net taste woodcare paint of high hardness polyurethane that a kind of POSS is modified | |
| KR101152564B1 (en) | Surface-treating agent, metallic material treated with the same, and novel compound and process for producing the same | |
| CN111936558B (en) | Polysiloxane compounds and compositions | |
| WO2012036183A1 (en) | Contamination resistant coating composition having excellent durability | |
| JP7101066B2 (en) | Chromium-free metal surface treatment agents, metal surface treatment methods, and metal substrates | |
| KR20200140841A (en) | Mixed composition | |
| JPH08337754A (en) | Aqueous coating composition and outdoor article | |
| JP4533476B2 (en) | Fluorine resin-containing cationic electrodeposition coating and production method | |
| JP5308636B2 (en) | Coated metal substrate, active energy ray-curable coating composition, and method for producing coated metal substrate | |
| JP2023106679A (en) | Surface treatment agent, material to be treated having film and method for producing the same | |
| JP7428539B2 (en) | Materials with surface treatment agents and surface treatment films | |
| JP2013006898A (en) | Heat ray highly reflective paint composition, kit for preparing heat ray highly reflective paint composition, heat ray highly reflective coated article, and production method of heat ray highly reflective coated article | |
| JP2018090663A (en) | Surface conditioner for coating agent | |
| JP2008221128A (en) | Method for improving cissing resistance of coating film | |
| JP7379043B2 (en) | Two-component urethane paint composition | |
| JPH10298290A (en) | Hydrophilic polymer and coating composition containing the same | |
| JP2014231587A (en) | Rust preventive coating film and aqueous rust preventive coating material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |