JPS5911374A - Coating composition - Google Patents

Abstract

PURPOSE:To provide a coating compsn. with improved surface physical properties such as resistance to mar, chemicals, and humidity, and antistatic properties by applying to surfaces of metals, ceramics, synthetic resins, etc., by incorporating a particular silicon atom-contg. aromatic compd. CONSTITUTION:A coating compd. which contains aromatic compds. having two or more silicon atoms, wherein one or more silicon atoms combine with one to three hydrolyzable atoms and/or atomic groups (e.g., halogen, alkoxy, alkoxyalkoxy, acyloxy) and the total no. of said atoms and/or atomic groups is 3 or more [e,g., 1,4-bis(trichlorosilyl)benzene, bis(4-trichlorosilylphenyl)dimethylsilane], and/or their hydrolyzates. By applying to surfaces of metals, ceramics or synthetic resins and curing, it is possible to improve surface physical properties such as resistance to mar, chemicals, solvents, rust, and humidity, and antistatic properties.

Description

[Detailed Description of the Invention] The present invention provides scratch resistance, chemical resistance, and
The present invention relates to a resin composition for paint used for the purpose of improving various surface properties such as solvent resistance, rust prevention, moisture resistance, and charging characteristics.

Although plastics have excellent properties such as light weight, transparency, and impact resistance, their scratch resistance is poor, and therefore, they are currently used in window glass, lenses, transparent protective materials, and airplanes. In order to further expand the scope of use of plastics, which are used in large quantities in canopy containers, etc., coating to improve scratch resistance is essential.

Paints used to improve the scratch resistance of plastics are divided into several types, including acrylic, urethane, melamine, and silicone paints.

Regarding silicone-based paint resin compositions, a large number of patents have been filed, published, and announced, and some of them have been put into practical use.

The silicon compound used in these silicone paint resin compositions is R'n5i(OR2)4-1 (n
= 0 to 3), organoalkoxysilane, RnSi, C14-n (n = 0 to 3), and organochlorosilane having the at- structure, and in the above formula, R1 and R are double bonds or epoxy Most of them are silane coupling agents containing a group, a mercapto group, an amino group, etc.

These silicon compounds are often used after hydrolysis-polycondensation. Furthermore, these silicon compounds are often used after being modified with organic compounds, and fine silica powder and the like are often used as fillers and reinforcing agents.

Examples of such silicone-based paint resin compositions include US Patent No. 33g! No. 7.2, a composition containing a linear polyorganosiloxane and a fluorine-containing polymer; JP-A No. 3II-11371, a composition containing an organotrialfuxidisilane; Composition containing methyltrimethoxysilane and colloidal silica, No. O11,2, Composition containing glyci-1doxypropyltrialkoxysilane and epoxy compound, No. 13336, Japanese Patent Publication No. Sho 33-/29 Composition containing ω~ruaminoalkylsilane epoxyalkylalkoxysilane of No. 1, JP-A-5II-ZA11100 composition containing epoxyalkylalfukidisilane, a vinyl monomer containing an epoxy group, and a vinyl group-containing alkoxysilane , and numerous other patents.

In these compositions, the silicon component often undergoes hydrolysis-polycondensation to form polysiloxane, but before hydrolysis, all of the silicon component is R1nSi (OR
2) 4-1 (In the formula, R1 is an organic atomic group, R2 is 7)
b Kill group, n=0~. ? ) or Rn5iCA'4-n
(In the formula, R is an organic atomic group, n=o to 3). The reason why these compounds are used as starting materials is that the siloxane bond formed by the polycondensation of silanol is strong, and that the organic atomic group bonded to the silicon atom via a carbon-silicon bond is strong. The main feature is that flexibility can be imparted by changing the chain length. However, if this organic atomic group becomes long enough to provide sufficient flexibility, it becomes a factor that reduces scratch resistance. Therefore, it was considered to introduce some kind of reactive group into this organic atomic group to cause crosslinking. This is the reason why silane coupling agents are used in many silicone resin compositions. In the silane coupling agent, the organic functional group at the end of the organic atomic group is a vinyl group.

There are methacryloyl groups, epoxy groups, amino groups, etc.
These polymers further introduce crosslinking into polysiloxanes that have been previously polycondensed by addition polymerization or ring-opening polymerization. This increases the crosslinking density of the organic atomic groups, which had been made longer to provide flexibility and lowered the crosslinking density, thereby preventing a decrease in scratch resistance. However, the weather resistance (J) of coating films produced by this method is generally not very good.

In order to improve the weather resistance of a cured coating, it is necessary that the resulting coating be as inert as possible. Therefore, linear polyorganosiloxane can be said to be an effective material in terms of weather resistance, but at present, ordinary linear polyorganosiloxane has too large a molecular weight and cannot provide a high crosslinking density.

As a result of various studies based on the above facts, the present inventors have found that a coating film using the following paint resin composition has various performances such as scratch resistance, chemical resistance, and weather resistance. It has been found that it has good performance in the following conditions. That is, the present invention is a coating composition containing seven or more aromatic compounds having two or more silicon atoms and/or a hydrolyzate thereof, wherein one of the silicon atoms is Each of the parts or the whole has 1 to 3 hydrolyzable atoms and/or atomic groups bonded thereto, and the total number of such atoms and/or atomic groups in the aromatic compound molecule is at least 3.

The hydrolyzable atoms and/or (6) atomic groups referred to herein are, for example, C1j+ pr, I
Halogen atoms such as -00H3+-0G2H51-
Alkoxy group such as 003H7, -00HgOC2H
5,-00gH40C2H5°-0OH20C3H7 and other alkoxyalkoxy groups.

-0COOH3, -0(EOO2H5, -00003H
As with acyloxy groups such as No. 7, it can be done by simply adding water, or by adding water with an appropriate amount of acid or base catalyst added and stirring while heating under normal reflux conditions → 5i
-X (←) bond is hydrolyzed → SiOH and HX (←
) is an atom and/or atomic group that produces

In addition, when each of the silicon atoms is connected to each other by a path that minimizes the number of atoms included in that path, the atoms adjacent to the silicon atom in that path are the next to that atom. When the incoming atom is carbon, carbon is preferred. In other words, if we describe the atoms up to the β position of the silicon atom in the path, it is preferable to have a 5i-C-00 bond.1If the next atom is not carbon, then 5i-c- o, 5i-c-si, si-
It is preferable to have an o-si-natono bond.

Examples of such aromatic compounds include l, goobis(trichlorosilyl)benzene, /, II-bis(
Trimethoxysilyl (trimethoxysilyl)benzene + /. 3,! ;
-) IJ su(triacetoxysilyl)benzene,
/-triacetoxysilyl-3,j-bis(methyldichlorosilyl)benzene, /,lI-bis(methyldichlorosilyl)benzene, /-1-dichlorosilyl-l-methyldichlorosilylbenzene, two-trichlorosilyl-11- dimethylchlorosilylbenzene, /
-trimethoxysilyl-methyldimethoxysilylbenzene, /-trimethoxysilyl-l-dimethylacetoxysilylbenzene, /-trimethoxysilyl-3,S
-Bis(dimethylacetoxysilyl)benzene + Si
, Si'-bis(q-trimethoxysilylphenyl)tetramethoxydisiloxane.

Sj-, Si/- His (gutrimethoxysilylphenyl)tetraacetoxydisiloxane, bis(+
-trimethoxysilylphenyl)dimethoxysilane.

Bis(lI-monotrichlorosilylphenyl)dimethylsilane, /, goobis(trichlorosilylmethyl)benzene, /-trichlorosilylmethyl-goomethyldichlorosilylmethylbenzene, /, 4'-bis(trimethoxysilylmethyl)benzene, / ,lI-His(,2/
-trichlorosilylethyl)benzene.

/, goobis(,21-trimethoxysilylethyl)benzene, /,t/. -bis(,i!/-)lyacetoxysilylethyl)benzene, /-(,27-)limethoxysilylethyl)-gu(2tl-methyldichlorosilylethyl)benzene, /,'iZ-bis(trichlorosilyl)naphthalene , /, goobis(triacetoxysilyl)naphthalene, /, l-bis(trimethoxysilyl)naphthalene, /-trimethoxysilyl-l-dimethylchlorosilylnaphthalene, h-bis(trichlorosilyl)naphthalene, /, j-bis (trimethoxysilyl)naphthalene, /-trimethoxysilyl(9) lyluj-dimethylchlorosilylnaphthalene, hexa(
Examples include trimethoxysilylmethyl) melamine.

Methods for producing these compounds include a method in which an organic alkali metal compound is reacted with a silicon halide or a silicon alkoxysilide, a method in which a Grignard reagent is reacted with a silicon halide or a silicon alkoxylate, or a method in which a Grignard reagent is reacted with a silicon halide or a silicon alkoxylate. A method of adding H--Si← to a bond using a platinum catalyst or the like is well known, and a direct method of reacting a halide with metal silicon in the presence of a copper catalyst or the like is also an effective production method.

These compounds may be used by mixing 7 or more of them and then hydrolyzing them, or by hydrolyzing each of them individually, or by hydrolyzing some of them and then mixing them. Although it may be used without being hydrolyzed at all, it is preferable to use it after hydrolysis.

The coating composition of the present invention preferably contains the above-mentioned aromatic compound and/or its hydrolyzate in an amount of 5% [1% or more, (10)] more preferably 30% by weight or more, still more preferably 50% by weight.

Compounds that can be added to the above aromatic compounds include:
Silicon compounds such as those conventionally used in this type of composition,
Tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane; methyltrimethoxysilane, ethyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, methyltriethoxysilane, ethyl Triethoxysilane, isopropyltriethoxysilane, butyltriethoxysilane,
Alkyl trials such as methyltriisopropoxysilane, ethyltriisopropoxysilane, isobrobyltriisobroboxysilane, butyltriisopropoxysilane, methyltributoxysilane, ethyltributoxysilane, isopropyltributoxysilane, butyltriptoxysilane Fukidisilane; dimethyldimethoxysilane, diethyldimethoxysilane, diisopropyldimethoxysilane, dibutyldimethoxysilane.

Dimethyljethoxysilane, diethyljethoxysilane, diisopropyljethoxysilane, dibutyljethoxysilane, dimethyldiisopropoxysilane, diethyldiisobroboxysilane, diisobrobildiisobutoxysilane, dibutylisopropoxysilane, diethyljethoxysilane, Diethyldibutoxysilane, diisopropyldibutoxysilane, dibutyldibutoxysilane and similar alkyldialkoxysilanes; trimethylmethoxysilane, triethylmethoxysilane, triisopropylmethoxysilane, tributylmethoxysilane, trimethylethoxysilane, triethylethoxysilane, triisopropylethoxysilane , tributyl ethoxysilane, trimethylisopropoxysilane, triethylisopropoxysilane, triisopropylisopropoxysilane, tributylisopropoxysilane, trimethylbutoxysilane, triethylbutoxysilane.

Mention may be made of trialkylalkoxysilanes such as triisopropylbutoxysilane, tributylbutoxysilane, and the like.

In addition, up to 50% by weight in the coating composition of the present invention.
up to, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane,
r-methacryloxypropyltrimethoxysilane, β-
(3,11-epoxycyclohexyl)ethyltrimethoxysilane, r-glycidoxypropyltrimethoxysilane, r-aminopropyltriethoxysilane, N-β
-(aminoethyl)-r-aminopropyltrimethoxysilane, N-bis(β-hydroxyethyl)-r-aminopropyltriethoxysilane, r-chloropropyltrimethoxysilane, r-mercapropyltrimethoxysilane, N A silane coupling agent such as -β-(aminoethyl)-r-ami/propylmethyldimethoxysilane may be used in combination. In addition to the silicon compounds listed above, ordinary organic polymer compounds such as ethylene, propylene, butene, vinyl chloride, and vinyl chloride (1
3) Nylidene, tetrafluoroethylene, vinylidene fluoride,
Polymers and copolymers such as styrene, stilbene, alkyl acrylates and methacrylates, vinyl alcohol, vinyl acetate, butadiene, methacrylic acid, and acrylic acid; polyethers such as polyethylene glycol and polypropylene glycol; polycarbonates, etc., in the coating composition of the present invention. It can be added up to 30% by weight.

If necessary, add a curing catalyst to the coating composition.
, OS to IO, preferably 0.1 to 5% by weight. i.e. perchloric acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, sulfonic acid, para-toluenesulfonic acid, boron trifluoride and its complex with an electron donor; 5nC74+
Zn (313, Fee/31 AA!OA!3sSb
Lewis acids and their complexes such as C15, TiCl4; Organometallic salts such as sodium acetate, zinc 7thenate, cobalt 7thenate, zinc octylate, tin octylate; Hou7
Metal borofluoride salts such as zinc fluoride and tin borofluoride; boric acid organic esters such as ethyl borate and methyl borate (/40); sodium hydroxide.

Alkali such as potassium hydroxide; titanate esters such as tetrabutoxytitanium and tetraisopropoxytitanium; chromium acetylacetonate.

Metal acetylacetonates such as titanyl acetylacetonate, aluminum acetylacetonate, cobalt acetylacetonate-1, nickel acetylacetonate; n-butylamine, di-n-butylamine, tri-n-butylamine, guanidine, biguanide, imidazole etc. can be added to this composition as an amine catalyst.

Examples of solvents that may be included in the resin composition include alcohols, ketones, esters, and ethers.

Examples include cellosolves, halides, carboxylic acids, aromatic compounds, aliphatic hydrocarbons, and seven or more of these can be used as a mixed solvent. Especially methanol, ethanol, propatool,
Lower alcohols such as Impropatol, butanol; Methyl cellosolve.

Cellosolves such as ethyl cellosolve and butyl cellosolve; lower alkyl carboxylic acids such as formic acid, acetic acid, and propionic acid; aromatic compounds such as triene and xylene; aliphatic compounds such as n-hexane and n-heptane; and ethyl acetate and butyl acetate. It is preferable to use esters such as these alone or as a mixed solvent.

Furthermore, in order to obtain a smooth coating film, if necessary, a fluorine-based surfactant such as FC-113/(trade name) manufactured by 3M or Y- manufactured by Nippon Unicar may be used as a flow control agent.
A silicone surfactant such as 700≦(trade name) can be added.

The amount of these flow control agents added is sufficient in a small amount, and may be about 0.0/~j% by weight, more preferably about 0.03~3% by weight, based on the entire resin composition.

In addition, stabilizers and deterioration inhibitors such as antioxidants and ultraviolet absorbers; coloring agents such as pigments and dyes; alumina sol, gypsum,
Kaolin, carbon blank, graphite, mica,
Silica gel, silica sol.

It can contain reinforcing agents and fillers such as titanium oxide, talc, glass flakes, glass fibers, and carbon fibers.

After coating the composition of the present invention by a commonly used coating method such as a dipping method, a spraying method, a roller coating method, or a 70-coating method,
By baking and curing at a temperature below the deformation temperature of the base material, a coating film with good wear resistance, hot water resistance, fj adhesion and weather resistance can be obtained.

The preferred thickness of this coating is 7 to 30 microns, more preferably 3 to 15 microns. If it is less than 7 microns, the wear resistance will not be sufficient, and if it is more than 30 microns, cracks will easily occur.

The composition of the present invention can be applied to a wide range of substrates such as plastic substrates such as polycarbonate, polymethyl methacrylate, polystyrene and polyvinyl chloride; metal materials such as aluminum and steel; ceramics; and wood. (17) If adhesion is particularly a problem, a coating film with sufficiently effective adhesion can be obtained by primer treatment.

The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited by these Examples.

Note that "part 1%" in the examples indicates 1% by weight.

Example/ 21 g of metal magnesium was placed in a well-dried reactor, and then 12 dag of Balajibromobenzene was added dropwise/left for day and night. This was added dropwise to 27 g of methyl silica (1I), left to stand day and night, and then purified by distillation. 0. ．． 2
The IH-NMR signals of the fractions in the go-, rsoC range at mm Hg were divided into two major groups: upfield and downfield. Their intensity ratio was 3:/.

7.2N HC was added to the roo part of the bis(P-trimethoxysilylphenyl)dimethoxysilane synthesized in this way.
After stirring and discarding the aqueous layer (7 g), 210 parts of methyl ethyl ketone, 520 parts of benzyl alcohol, 5 parts of ammonium perchlorate as a curing catalyst and the surfactant FC-'13/(3M Co., Ltd.) were added. After adding 2 parts of the product (trade name), apply it to a poly(diethylene glycol bis(allyl carbonate)) plate and heat it at 730°C.
It was heated for 7 hours. A transparent coating with a thickness of g microns of high hardness was obtained.

Example - Balajibromobenzene Og diluted 1 times with diethyl ether was added dropwise to 3 g of magnesium metal, left to stand day and night, and this was added dropwise to 230 g of methyl silicate.
The aqueous solution was heated to about 10"C and refluxed for 2 hours. Diethyl ether was removed from the reaction mixture by evaporation.
It was purified by distillation under reduced pressure. 0.23-0.30 mmHg
The LH-NMR signals of the fraction in the range of 7/~7j°C were divided into two groups, high-field and low-field, and their intensity ratio was W:2. /,4(-bis(1-limethoxysilyl)benzene2) synthesized in this way
Add 560 parts of methanol silica sol to 0 parts of
Add 130 parts of kJ of HGl and stir.

After 7 hours, 700 parts of benzyl alcohol, 3 parts of ammonium perchlorate as a curing catalyst, and 7 parts of an interfacial oil-forming agent FC-y3i (trade name, 3M Co., Ltd.) were added. )) It was applied to a plate and heated at 730°C for 7 hours. A transparent coating with a thickness of g microns of high hardness was obtained.

Claims (1)

[Claims] ], an aromatic compound having one or more silicon atoms;
At least 7 atoms and/or atomic groups capable of hydrolysis are bonded to each of the silicon atoms, and the total number of the atoms and/or atomic groups capable of hydrolysis is A coating composition comprising one or more aromatic compounds selected from at least 3 aromatic compounds and/or a hydrolyzate thereof. 2. The coating composition according to claim 1, wherein the hydrolyzable atom and/or atomic group is a hahalogen atom, an alkoxy group, an alkoxyalkoxy group, or an acyloxy group. 3. When the aromatic compound connects each of the silicon atoms with each other in a path that minimizes the number of atoms included in the path, silicon-carbon-carbon bonds, silicon - A coating composition according to claims having a carbon-oxygen bond, a silicon-carbon-silicon bond, or a silicon-oxygen-silicon bond.