JPS63275674A - Coating material for facility excellent in prevention of fouling by soot - Google Patents

Abstract

PURPOSE:To provide a road facility coating material reduced in adhesion of soot and lowering of gloss and having excellent adherence, weather resistance and hardness, which comprises a particular room-temp. thermosetting resin compsn., a U.V. absorber and/or an antioxidant. CONSTITUTION:100pts.wt. mixture of a vinyl polymer contg. a basic nitrogen atom (a) [e.g., a diamonoethyl (meth)acrylate-maleic anhydride copolymer] with a compd. (b) having in its molecule 0.2-5 equivalent, per equivalent of the reactive group of component (a), of an epoxy group and a hydrolyzable silyl group is mixed with 1-1,000pts.wt. compd. having a silanol group (e.g., tetramethoxysilane) and/or a compd. having a hydrolyzable silyl group (c) exclusive of component (b) and 0.01-10wt.% hydrolysis-condensation catalyst (d) (e.g., NaOH), thereby obtaining a room-temp. thermosetting resin composn. (A). 100pts.wt. component (A) is mixed with 0.01-10pts.wt. U.V. absorber and/or antioxidant (B).

Description

Detailed Description of the Invention (Objective of the Invention) (Industrial Application Field) The present invention relates to guardrails, guard fences, pedestrian bridges, sound insulation walls, windbreak walls,
The present invention relates to road materials such as lighting poles, signal poles, sign poles, telephone poles, etc. that are used along with passageways, and particularly to road materials that have extremely excellent soot and smoke pollution removal properties.

(Prior Art) Hot-dip galvanized products, which are relatively inexpensive and have excellent corrosion resistance, have been used in large quantities as road materials, mainly guardrails. However, these road materials are exposed outdoors and exposed to large amounts of automobile exhaust gas containing nitrogen oxide gas, sulfur dioxide gas, etc., and salts sprayed to prevent road surface freezing, making them difficult to use for general exterior walls or roofing materials. It has been recognized that the dissolution of dumbbell is significantly faster than that of architectural materials, and its deterioration is significant.

In order to reduce the dissolution of zinc from hot-dip galvanized products, conventional chemical conversion treatments such as zinc phosphate treatment, primers using epoxy resins, and then oil-free alkyd resins, acrylic-urethane resins, etc. A coating treatment is applied, which suppresses zinc dissolution several times longer than without treatment, making it able to withstand relatively long-term exposure. However, when hot-dip galvanized products treated with these processing techniques are used for road applications, there is a significant rapid loss of surface gloss;
In addition, the current situation is that dirt from soot and smoke adheres quickly, and the adhered soot and smoke is difficult to remove by simple washing with water, resulting in a very rapid deterioration of the aesthetic appearance.

(Problems to be Solved by the Invention) However, in order to solve the various drawbacks or problems in the prior art as described above, the present inventors have developed a method for applying hot-dip galvanizing compared to resins used in conventional painting processes. We conducted extensive research into developing a resin that has excellent adhesion to products, as well as durability with excellent gloss and hardness. As a result, galvanized products coated with a resin composition of a vinyl polymer containing a basic nitrogen atom and a compound containing an epoxy group and a hydrolyzable silyl group (H) in one molecule were used as road materials. However, they discovered that it has excellent performance and completed the present invention.

The object of the present invention is to provide a road material that has extremely low gloss deterioration as a road material that is exposed to extremely harsh conditions, and also has minimal adhesion of dirt such as soot, and even if it does adhere, it can be removed by simple washing with water. The purpose of the present invention is to provide road materials that are easy to use and have excellent aesthetic appearance.

[Structure of the invention]

(Means for Solving the Problems) To summarize the present invention, the present invention provides road materials that have been subjected to hot-dip galvanization as a surface treatment, [I] basic nitrogen atoms (hereinafter referred to as basic nitrogen atoms) as an essential component. Abbreviated as nitrogen.

) containing a vinyl polymer (A>) and a compound having both an epoxy group and a hydrolyzable silyl group in one molecule (
B) and, if necessary, (C) a compound (C-1) having a silanol group, and/or the above compound (
Compounds containing hydrolyzable silyl groups except B) (C-
2), (D) Hydrolysis of the above-mentioned hydrolyzable silyl group -
To 100 parts of a room-temperature curable resin composition that also contains a condensation catalyst, add 0.0 of an ultraviolet absorber and/or an antioxidant.
The present invention relates to a road material having excellent contamination removal properties against soot and smoke, characterized by using a coating composition further coated with 1 to 10 parts of the present invention.

Hereinafter, the configuration of the present invention will be explained in detail.

Regarding the present invention, first, the above-mentioned basic nitrogen-containing vinyl polymer (A> refers to at least one, preferably at least two, basic nitrogen groups in one molecule, i.e., a -class amino group, a secondary amino group). and tertiary amino group J: refers to a vinyl polymer containing at least one amino group selected from the group consisting of: (co)polymerize a vinyl spinning wheel matrix (hereinafter also referred to as vinyl spinning wheel matrix (a to 1)) containing a carboxylic acid anhydride group (hereinafter abbreviated as an acid anhydride group). Containing vinyl polymer [hereinafter referred to as polymer (a-3)
)] and a compound having in one molecule both a group having at least one active hydrogen that can react with this acid anhydride group and a tertiary amino group [hereinafter referred to as compound (
a-4)] can be prepared by a known method such as the following.

Among them, the ribinyl polymer (A) was prepared by the method of
Typical amino group-containing vinyl monomers (a-1) used in the preparation include dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate.
meth)acrylate, dimethylaminopropyl(meth)
Acrylate or diethylamine propyl (meth)
Various dialkylaminoalkyl (meth)acrylates such as acrylate; N-dimethylaminoethyl (meth)acrylamide, N-diethylaminoethyl (meth)
Acrylamide, N-dimethylaminopropyl (meth)
Acrylamide or N-diethylaminopropyl (
N-dialkylaminoalkyl (meth)acrylamides such as meth)acrylamide; or t-butylaminoethyl (meth)acrylate, t-butylaminopropyl (meth)acrylate, aziridinylethyl (meth)acrylate, pyrrolidinyl Examples include ethyl (meth)acrylate and piperidinylethyl (meth)acrylate, but from the viewpoint of curability, dialkylaminoalkyl (meth)acrylates and N-
Particularly preferred are dialkylaminoalkyl (meth)acrylamides.

In addition, in the present invention, other vinyl monomers (a-1) copolymerizable with these amino group-containing vinyl monomers (a-1) are used.
a-2), typical examples of which are methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, 1so-propyl (meth)acrylate, and n-butyl (meth)acrylate. ) acrylate, 1so-butyl (meth)acrylate, ter
t-Butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate ,
Various types (such as 2-hydroxybutyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate)
meth)acrylic acid esters; unsaturated di-Ml dialkyl esters such as dimethyl maleate, di-engineered fumarate, dimethyl fumarate or dimethyl itaconate; (meth)acrylic acid, monobutyl maleate, monobutyl fumarate; Vinyl polymers containing carboxyl groups such as crotonic acid, maric acid, fumaric acid or itaconic acid; Vinyl monomers containing acid anhydride groups such as maleic anhydride or itaconic anhydride: (meth)acrylamide, N,N-dimethyl Vinyl monomers containing various carboxylic acid amide groups such as (meth)acrylamide, N-alkoxymethyl (meth)acrylamide, diacetone (meth)acrylamide or N-methylol (meth)acrylamide: p-styrenesulfonamide, N-methyl −
Various sulfonamide group-containing vinyl polymers such as p-styrene sulfonamide or N,N-dimethyl-p-styrene sulfonamide; cyano group-containing vinyl monomers such as (meth)acrylonitrile: (meth)
α such as hydroxyalkyl esters of acrylic acid,
Phosphoric ester bond-containing vinyl monomer which is a condensation product of β-ethylenically unsaturated saturated carboxylic acid droxyalkyl esters and phosphoric acid or phosphoric esters; p-styrenesulfonic acid or 2-acrylamido-2-methyl - Vinyl monomers containing sulfonic acid groups such as propane sulfonic acid: vinyl acetate, vinyl benzoate or various vinyl esters such as "Beoba" (vinyl ester manufactured by Shell, Netherlands); "Viscoat 8F, 8FM,
3F or 3FMJ (fluorine-containing product manufactured by Osaka Organic Chemical Co., Ltd.)
meth)acrylic monomers] or (per)fluoroalkyl group-containing vinyl polymers such as perfluorocyclohexyl (meth)acrylate, diperfluorocyclohexyl fumarate or N-1sopropyl perfluorooctanesulfonamidoethyl (meth)acrylate : Vinyl chloride, vinylidene chloride, vinyl buttonide,
Halogenated olefins such as vinylidene butyrate or chlorotrifluoroethylene: or sutyrene, α
- Aromatic vinyl monomers such as methylstyrene, p-tert-butylstyrene or vinyltoluene.

In order to prepare the vinyl polymer (A>) using the various monomers listed above, 0.5 to 100 weight of the amine group-containing vinyl monomer (a-1) is prepared. %, preferably 1 to 70% by weight, and 99.5 to O weight%, preferably 99 to 30% by weight may be copolymerized.

Further, as other vinyl monomers (a-2) copolymerizable with the amine group-containing vinyl monomer (a-1), carboxyl group-containing monomers or phosphoric acid ester bond-containing monomers as listed above may be used. By using the polymer in combination, a carboxyl group or a phosphoric acid ester bond can be introduced into the vinyl polymer (A), thereby further improving the curability of the composition of the present invention. , especially desirable.

To prepare the vinyl polymer (A) from the various monomers listed above, any conventionally known polymerization method can be applied, but the solution radical polymerization method is the simplest.

Typical solvents used in this process include various hydrocarbons such as toluene, xylene, cyclohexane, n-hexane, and octane; methanol, ethanol, 1so-propertool, n-butanol, 1so-butanol, and 5ec. - Various alcohols such as butanol and ethylene glycol monomethyl ether; various esters such as methyl acetate, ethyl acetate, vinegar f, -n-butyl, and amyl acetate; or various ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. These can be used alone or in combination.

Polymerization can be carried out by a conventional method using such solvents and various known and commonly used radical polymerization initiators such as azo or peroxide type. Chain transfer agents such as lauryl mercaptan, octyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, 3-mercaptopropionic acid or α-methylstyrene dimer can also be used as agents.

Next, the acid anhydride group-containing vinyl polymer (a-3) used in preparing the vinyl polymer (A) by the above method It can be prepared by radical copolymerization of monomers containing monomers and monomers copolymerizable with these monomers in a solvent other than alcohols among the solvents listed above. .

Here, such acid anhydride group-containing vinyl polymer (a
The copolymerizable monomers used in the preparation of -3) include the amino group-containing vinyl monomers (a-1) and Among other vinyl monomers that can be combined, any one other than monomer m1 containing a hydroxyl group can be used.

From the viewpoint of weather resistance and alkali resistance, the amount of the monomer containing an acid anhydride group as mentioned above should be 0.
A suitable range is 5 to 50% by weight, preferably 1 to 20% by weight, while the copolymerizable monomer is preferably used in a range of 99.5 to 50% by weight, preferably 99 to 80% by weight.
It is appropriate to fall within the following range.

In addition, in this case, when a carboxyl group-containing monomer or a phosphoric acid ester bond monomer as listed above is also used as a component of the copolymerizable monomer, acid The reaction time can be shortened when reacting with a compound (a-4) having both an active hydrogen that can react with an anhydride group (hereinafter abbreviated as an active hydrogen-containing group) and a tertiary amino group. is particularly desirable in that it can further improve the curability of the composition of the present invention.

Here, the term "compound (a-4)" refers to a compound having active hydrogen-containing groups such as a hydroxyl group, a -class or secondary amino group, or a thiol group. However, among these, the most preferred compounds include alcohols having a tertiary amino group and primary or secondary amines having a tertiary amino group.

Among these, typical amino alcohols include adducts of secondary amines and epoxy compounds, while typical secondary amines used here include dimethylamine, diethylamine, and dimethylamine. Propylamine, dibutylamine, edylenimine, morpholine,
There are also piperazine, piperidine or pyrrolidine, and there are also secondary amino group-containing amino alcohols obtained by addition of primary amines such as methylamine, ethylamine or butylamine with 7- or polyepoxy compounds; Typical epoxy compounds include ethylene oxide, propylene oxide, butylene oxide, dodecene oxide, styrene oxide, cyclohexene oxide, butyl glycidyl ether or phenyl glycidyl ether: or p-tert-butylbenzoic acid glycidyl ester or [ Monoepoxy compounds such as Cardura E-10J (glycidyl ester of branched fatty acids manufactured by Shell, Netherlands); or ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanesiol diglycidyl ether, bisphenol A; Polyglycidyl ethers of polyhydric alcohols (polyols) such as diglycidyl ether or triglycidyl ether of glycerin; polycarboxylic acids such as diglycidyl ester of phthalate, diglycidyl ester of isophthalic acid or diglycidyl ester of adipic acid ( Polyepoxy compounds such as various epoxy resins such as polyglycidyl esters (polycarboxylic acid) or diglycidyl ether type epoxy resins from bisphenol A or bisphenol F, novolac type epoxy resins, or hydantoin ring-containing epoxy resins, etc. Further examples include glycidyl ester ether of p-oxybenzoic acid and various vinyl (co)polymers having an epoxy group in the side chain.

By reacting such secondary amines with an epoxy compound, 1
Typical examples of the tertiary amino group-containing amino alcohols include dimethylaminoethanol, diethylaminoethanol, di-n-butylaminoethanol, di-1so-propylaminoethanol, di-n-butylaminoethanol, N- (2-hydroxyethyl)morpholine, N-(2-hydroxyethyl)pyrodine, N
-(2-hydroxyethyl)-aziridine, N, N-
Dimethyl-2-hydroxypropylamine, N.

N-diethyl-2-hydroxypropylamine, triethanolamine, or tripropaturamine, etc., but in addition to those listed above, the tertiary amino group-containing amino alcohols include ethanolamine or propatoolamine. Adducts of amino alcohols such as toolamine and (meth)acrylate monomers having a tertiary amine group such as dimethylaminoethyl (meth)acrylate or diethylaminoethyl (meth)acrylate, or the tertiary amino group A vinyl copolymer having both a tertiary amino group and a hydroxyl group in the side chain obtained by copolymerizing a containing (meth)acrylate monomer with a hydroxyl group-containing monomer such as β-hydroxyethyl (meth)acrylate. Consolidation can also be used.

Separately, typical examples of the above-mentioned primary or secondary amines containing a tertiary amine group include N,N-dimethyl-1,3
-propylene diamine or N.

N, such as N-diethyl-1,3-propylene diamine;
N-dialkyl-1,3 propylene diamines; N, N
N,N-dialkyl-1,4-tetramethylenediamines such as dimethyl-1,4-tetraethylenediamine or N,N-diethyl-1,4-tetramethylenediamine; N,N-dimethyl-1,6- N,N-dialkyl-1,6-hexamethylene diamines such as hexamethylene diamine or N,N-diethyl-1,6-hexamethylene diamine: N,N,N"-trimethyl-1
, 3-propylene diamine, N, N.

N,N,N-1 trialkylalkylene diamines such as N"-triethyl-1,3-propylene diamine or N,N,N-1 trimethyl-1,6-hexamethylene diamine; or N-methylpiperazine or N-
N-alkylpiperazines such as ethylpiperazine; or tertiary amino group-containing (meth)acrylate monomers as listed in 1 and ethylenediamine, propylenediamine, hexamethylenediamine, piperazine, methylamine, ethylamine, propylamine or ammonia There are additions such as.

From the viewpoint of curability, N,N-dialkylaminoethanol and N,N-dialkylalkylene diamine are particularly preferred as compounds (a-4>).

To obtain the basic nitrogen-containing vinyl polymer (A>, which is the base resin component in the composition of the present invention) from the polymer (a-3) and the compound (a-4> described above),
The number of active hydrogen-containing groups in compound (a-4) is 0.5 to 3 per equivalent of acid anhydride group in polymer (a'-3), respectively.
The two compounds may be mixed in a ratio such that they are approximately equivalent, and the reaction may be carried out in a temperature range from the lowest temperature to about 120'C.

In addition, the compound (a-4> and N,N-dimethyl-1,3
- When using a compound having both a tertiary amine group and a primary amino group such as propylene diamine, these (a
-3) and (a-4>), first, as shown in the reaction formula below, a polymer having a carboxyl group and an N-monosubstituted amide group is produced. Combined (I) is obtained.

(I) The polymer obtained here (I> can be used as it is in the present invention, but for uses such as stain resistance and alkali resistance of cured coatings, such polymers can be used as is). A polymer having an imide ring (II
) to convert the base resin component (A
It is preferable to use it as >.

Next, as the above-mentioned compound (B) having both an epoxy group and a hydrolyzable silyl group in one molecule, which are essential components in the room temperature curable resin composition of the present invention,
Typical examples include vinyl polymers having both of these types of reactive groups and silane coupling agents having epoxy groups.

Here, such hydrolyzable silyl groups include halosilyl groups, alkoxysilyl groups, acyloxysilyl groups, phenoxysilyl groups, iminooxysilyl groups, and alkenyloxysilyl groups represented by the general formula % ([[). Reactive groups that are easily hydrolyzed, such as:

Any known method can be applied to prepare the vinyl polymer (8) having the above-mentioned specific bireactive groups. -(meth)acryloyloxypropylmethyldimethoxysilane, γ-(meth)acryloyloxypropyl twine propenyloxysilane,
Hydrolyzable silyl groups such as γ-(meth)acryloyloxypropyltriiminooxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl(tris-β-methoxyethoxy)silane, vinyltriacetoxysilane or vinyltrichlorosilane and an epoxy group such as (B-methyl)glycidyl (meth)acrylate, allylglycidyl ether, di(β-methyl)glycidyl maleate or di(β-methyl)glycidyl fumarate. The vinyl monomers are mixed with a solution using, if necessary, various monomers such as those listed above as other vinyl monomers that can be copolymerized with the amine group-containing vinyl polymer. Radical copolymerization or ■γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane-mercap-ipropyltriisopropenyloxysilane or γ-mercaptopropyltriiminooxy A simple method includes solution radical (co)polymerization of a monomer mixture containing an epoxy group-containing vinyl monomer such as silane as an essential component.

Then, the compound (B) is obtained by the above-mentioned method (■).
Of course, the hydrolyzable silyl group-containing monomers mentioned above can also be used in preparation.

Representative examples of the epoxy group-containing silane coupling agents mentioned above include γ-glycidoxypropyltrimethoxysilane, T-glycidoxypropyltriethoxysilane, and γ-glycidoxypropylmethyljethoxysilane. , γ-glycidoxypropyltriisoprobenyloxysilane, γ-glycidoxypropyltriiminooxysilane, γ-isocyanatepropyltriisopropenyloxysilane or γ-isocyanatepropyltrimethoxysilane, etc., and adducts with glycidol:
Alternatively, adducts of γ-aminopropyltrimethoxysilane and jepoxy compounds may be mentioned, but γ-glycidoxypropyltrimethoxysilane or γ-glycidoxypropyltriisopropenyloxysilane is especially curable and economical. It is suitable from the following aspects.

Next, optional components in the room temperature curable resin composition of the present invention will be explained.

As one of the above-mentioned (C) component compounds which are optional components in the room temperature curable resin composition [I] of the present invention, there is a compound (C-1) containing a silanol group. ) Typical examples include low molecular weight silanols obtained by almost complete hydrolysis of halosilanes such as methyltrichlorosilane, phenyltrichlorosilane, ethyltrichlorosilane, dimethyldichlorosilane or diphenyldichlorosilane. Compounds: Polysiloxanes having silanol groups obtained by further dehydration condensation of these silanol compounds; Polysiloxanes having silanol groups obtained by hydrolyzing and condensing compounds such as the various alkoxysilanes and alkenyloxysilanes mentioned above Polysiloxanes; or silicone resins having a silanol group at the end; and silanol compounds having a cyclic siloxane structure, such as ``Toray Silicone 5H-6018J (product of Toshi Silicone ■)''.

On the other hand, the above-mentioned compound (C-2), a compound containing a hydrolyzable silyl group that does not contain an epoxy group, refers to a compound containing a hydrolyzable silyl group as shown in the above-mentioned general formula (I [I)]. It refers to low molecular weight compounds or resins that contain at least one epoxy group but do not contain any epoxy group.

Therefore, the compound (C-2) does not include the various compounds (B) listed above.

Representative examples of the compound (C-2) include tetramethoxysilane, trimethoxysilane, tetraethoxysilane, triethoxysilane, tetrapropoxysilane,
Tetrabutoxysilane, tetraoctoxysilane, tetrakis(2-methoxyethoxy)silane, tetrabenzyloxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyljethoxy Silane, diphenyljethoxysilane, γ-isocyanatepropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane,
Alkoxysilanes such as γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane silane or γ-(2-aminoethyl)aminopropyltrimethoxysilane: tetraisopropenyloxysilane, phenyltriisopropenyloxysilane, Alkenyloxysilanes such as γ-isocyanatepropyltriisopropenyloxysilane, γ-methacryloxypropyltriisopropenyloxysilane, γ-mercaptopropyltriisopropenyloxysilane or tetrabutenyloxysilane: tetraacetoxysilane, methyltriacetoxy Acyloxysilanes such as silane, gamma-mercaptopropyltriacetoxysilane, tetrapropionyloxysilane, phenyltripropylonyloxysilane or vinyltriacetoxysilane: tetrachlorosilane, phenyltricane, tetrabromosilane or benzyltribromosilane Halosilanes such as silane; tetrakis(dimethyliminooxy)silane, methyltris(dimethyliminooxy)silane, tetrakis(methyl-ethyliminooxy)silane, γ-methacryloxypropyltris(dimethyliminooxy)silane or γ-mercaptopropyl Iminooxysilanes such as tris(dimethyliminooxy)silane: Alkoxysilyl group-containing siloxane oligomers obtained by partially hydrolyzing and condensing alkoxysilanes such as those listed in 1; Partially hydrolyzing alkenyloxysilanes such as those listed in 1 Alkenyloxy group-containing siloxane oligomers obtained by condensation; various hydrolyzable ones such as γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane or T-methacryloxypropyltriacetoxysilane listed in item 1. Homopolymers of silyl group-containing vinyl monomers or copolymers with monomers copolymerizable with these monomers: listed γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriiso Hydrolyzable silyl group-containing mercaptans such as propenyloxysilane or γ-mercaptopropyltriacetoxysilane are used as chain transfer agents, and various listed hydrolyzable silyl group-containing vinyl monomers are used as necessary. Vinyl polymers containing hydrolyzable silyl groups at the terminals obtained by (co)polymerizing vinyl monomers containing polyhydric alcohols and hydroxyl group-containing acrylic resins. , various polyhydroxy compounds such as hydroxyl group-containing alkyd resins, water-11-containing polyester resins, or polyether polyols, and various hydrolyzable silyl group-containing compounds including alkoxysilanes such as those listed in JP-A-58- Resins obtained by reaction according to the method disclosed in Japanese Patent No. 188625; low molecular weight polyallyl compounds such as diallyl succinate, triallyl trimellitate or diallyl phthalate, unsaturated bond-containing vinyl polymers , adducts of various unsaturated bond compounds such as unsaturated bond-containing polyester resins or unsaturated bond-containing alkyd resins and hydrolyzable silyl group-containing hydrosilanes such as triethoxysilane or triethoxysilane; Adducts of various epoxy-containing compounds such as vinyl polymers or epoxy resins and various mekabutosilanes such as those listed;
Alternatively, various hydrolyzable silyl group-containing compounds having an isocyanate group, such as γ-isocyanatepropyl tritoxysilane and γ-isocyanatepropyltriisopropenyloxysilane, are reacted with various listed polyhydroxy compounds. 1q Urethane bond-containing resins: There are silicone resins containing hydrolyzable silyl groups at the molecular ends.

The room temperature curable resin composition [I] of the present invention has good curability without necessarily adding a curing catalyst, but if it is desired to further improve the curability, it is possible to add water as described above. There is nothing that precludes the addition of the catalyst (D) as a catalyst for hO water decomposition of decomposable silyl groups, and for condensation.

Typical examples of such catalysts (D) include basic compounds such as sodium hydroxide, lithium hydroxide, potassium hydroxide, or sodium methylate; tetraisopropyl titanate, tetrabutyl titanate, tin octylate, and lead octylate. , cobalt octylate, zinc octylate, calcium octylate, lead naphthenate, cobalt naphthenate, dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate or dibutyltin maleate; or p-toluenesulfonic acid. , trichloroacetic acid, phosphoric acid, monoalkyl phosphoric acid, dialkyl phosphoric acid, monoalkyl phosphorous acid, or dialkyl phosphorous acid.

In order to prepare the room-temperature curable resin composition [I] of the present invention from the components (A) to (D) listed above, the reactive groups present in the component (A), that is, the amino group and the carboxyl group and/or for a single leg such as a phosphate ester bond,
Both components (A> and (B)) are blended in such a proportion that the number of epoxy groups present in component (B) is approximately 0.2 to 5. , 1 to 1 of component C) for a total of 1 100 parts of both components of (B)
About 1,000 parts by weight, preferably 1 part by weight of 2 to 500 parts by weight, is also added, and if necessary, (D>component (A)) is mixed.

The total maximum of the three essential components (B) and (C) is 0. 01～
It is sufficient to add about 10% by weight.

In the present invention, 0.01 to 10 parts, preferably 0.2 to 10 parts of an ultraviolet absorber and/or antioxidant to 100 parts of the room temperature curable resin composition [I] thus obtained.
It is necessary to contain 8 parts.

Specific examples of the ultraviolet absorber and antioxidant used in the present invention are as follows.

Benzotriazoles such as Sumisorb 300 (Sumisorb ■), G-Soap 703 (Shiraishi Calcium ■), Tinuvin 328 (Ciba Geigy ■); cyaso
rb uv-207 (cyanamide [), lIc5
(benzophenone type such as Dcw Chemical (1); benzoate type such as Sumisorb 400 (Sumisorb Chemical ■): UniSClater-300 (
Daiichi Kasei ■), Uvinal N-35, (Oυtara
Chemical).

Cyanoacrylates such as Nievic JK-300 (Juzen Kagaku ■); Hindered amines such as Sanol 770 (Ciba Geigy@); G-Sorb 210.202.203
(Shiraishi Calcium [), Eastman Inhi
Salicylic acid esters such as bitor OPS (EaStman); Seesaw 7612NH (Shiraishi Calcium)
); chain initiation inhibitors such as organic nickel-based substances such as Sumilizer BHT (Japanese Chemical ■), BHT Swanox (Hindered phenol-based substances such as Marukubi Sekiyu @J>: Sumilizer BB) l (Sumira Chemical viJ), bisphenol A
Hindered bisphenol type such as (Honshu Kagaku ■): Hindered thiobisphenol type such as Sumilizer WX (Sumiman Kagaku ■): Alkylated hydroquinone type Nylganox 1010 (
Hindered polyphenol type such as Ciba Geigy); 5u
conox 4.9.12 or 18 (SIJmmer C
chemical), Amc.

Amine phenol antioxidants such as 531 (Amco); Antige OP (Kawaguchi Kagaku (41), Nau
Aromatic-aromatic amines such as gurd-445 (Uniroyal); Phenylalkylamines such as Antige 3C (Kawaguchi Kagaku ■) and Tsukuraiza 81ONA (Iriuchi Shinko Kagaku Kogyo ■): Tenamene 2.4 or 5 (E
astman Chemical), Eastoz
one 30, 31, 32. or 33 (Eastma
N,N''-dialkyl-p such as
- Phenylenediamine type: Dihydroquinoline type such as Sumilizer AW (Juju Kagaku (Tama), Tsukuraizer Acid or 224 (Iriuchi Shinko Kagaku Kogyo ■)): AranCX (Uniroyal).

Amine-based antioxidants such as Tsukuraizer C (Iriuchi fr Ko Kagaku Kogyo ■): Sumilizer TPP (Jinuchi Kagaku ■),
Phosphorous antioxidants such as Sumilizer TNP, Antige TNP, Tsukuraizer TNP, etc.: Sumilizer NBC
, Antige NBC, Tsukuraizer NBC, Sumilizer BZ, Tsukuraizer BZ, and other dialkyldithiocarbamic acid metal salts; Sumilizer Cho PL, or Tsukuraiza PS,
Thiodipropion oxide esters such as Seenox DL; Nopene-simidazole systems such as Sumilizer H8 and Tsukulyzer HBZ; Benzothiazole series such as Zerite (Du Pont): Xanthate metal salts such as Antigen NPX and Tsukulyzer ZBX, etc. It is not limited to these as long as it has an ultraviolet absorbing effect or an antioxidant effect.

The coating composition ([I] + [n]) used to coat the hot-dip galvanized steel sheet of the present invention may contain organic or inorganic pigments, flow regulators, and color separation preventive agents as required. various known and commonly used additives such as UV absorbers, UV absorbers or antioxidants; cellulose derivatives such as nitrocellulose or cellulose acetate butyrate; or chlorinated polyethylene, chlorinated polypropylene, petroleum resins or chlorinated rubber, etc. It is also possible to add various resins such as.

Room temperature curable resin composition thus obtained [I] 100
0, 0 between ultraviolet absorbers and/or antioxidants
The coating composition containing 1 to 10 parts is applied to hot-dip galvanized products. The coating method is not particularly limited, such as printing, spray coating, roll coating, and dipping.
The dry coating thickness is 10 to 100 on hot-dip galvanized steel sheet.
μm1 It is usually coated with a thickness of 20 to 80 μ7n. The coating composition of the present invention ([K]+IJI]) has excellent adhesion to hot-dip galvanized products, and therefore can be applied without a primer, but of course can be applied using a conventionally used primer. It is also possible to apply the coating composition of the present invention thereon.

Hot-dip galvanized products coated with the coating composition of the present invention can be dried for several days by a conventional method to improve adhesion.
A coating film with excellent weather resistance and hardness properties can be formed.

(Applications of the present invention) The hot-dip galvanized product thus obtained is generally used as road materials. Even when the road materials of the present invention are exposed outdoors and to a large amount of automatic exhaust gas containing nitrogen oxide gas, sulfur dioxide gas, etc. and salts, deterioration due to dissolution of zinc is suppressed, the loss of gloss is low, and the durability is low. It is noted that it has extremely excellent properties, such as the fact that it is difficult for soot and smoke to adhere to it, and even if it does, the soot and smoke can be easily removed by simple washing with water, and that the beauty of the Chomekuma inkstone is not damaged.

(Example) Next, the present invention will be explained in more detail with reference examples, examples, and comparative examples, but the present invention is not limited to these examples. Unless otherwise specified, all prices are based on weight.

Reference Example 1 [Preparation example of basic nitrogen-containing vinyl polymer (A)] 392 parts of toluene and 408 parts of 1so-butanol were placed in a reactor equipped with a stirring device, a thermometer, a reflux condenser tube, and a nitrogen introduction tube. and heated to 80'C in a nitrogen atmosphere to prepare 900 parts of methyl methacrylate, 100 parts of dimethylaminoethyl methacrylate, 5 parts of azobisisobutyronitrile (AIBN), and tert-butylperoxyoctoate. A mixture of 5 parts of (TBPO) and 200 parts of toluene was added dropwise over 3 hours.

After finishing dropping, keep at the same temperature for 2 hours, and then
A mixture consisting of 5 parts of BN, 448 parts of toluene and 37 parts of 1so-butanol was added dropwise over 1 hour. Next, the same temperature was maintained for 12 hours until the non-volatile content (NV) was 40.
% and a number average molecular weight of 12,000 was obtained. below,
This is abbreviated as polymer (A-1).

Reference Examples 2 to 5 (same as above) A solution of the tertiary amino group-containing vinyl polymer (A> Hereinafter, these will be sequentially referred to as polymers (A-2) to (A-5>).

(Margin below) Table 1 Reference Example 6 [Same as above] 300 parts of toluene and 400 parts of butyl acetate were charged into a reactor similar to Reference Example 1, and the mixture was heated to 110°C in a nitrogen atmosphere.
100 parts of styrene, 400 parts of methyl methacrylate, 300 parts of n-butyl methacrylate, 130 parts of n-butyl acrylate, 130 parts of acrylic, 40 parts of maleic anhydride, 10 parts of AIBN, and 5 parts of TBPO.
part, tert-buty) I, t-baroxybenzoate (
A mixture consisting of 5 parts of TBPB> and 300 parts of toluene was added dropwise over a period of 3 hours, and after the addition was completed, the mixture was kept at the same temperature for 1 hour.
The reaction was continued for 5 hours to obtain a solution of a vinyl polymer (a-3) having both an acid anhydride group and a carboxyl group, with a density of 50% and a weight of 10.000. Hereinafter, this will be abbreviated as polymer (a-3-1).

Next, the temperature of this polymer solution was lowered to 70°C, and then 40 parts of N,N-dimethylamine ethanol was added thereto, and then kept at the same temperature for 5 hours, and roughly 270 parts of n-butanol was added. A vinyl polymer having both a tertiary amino group and a carboxyl group (A
) was obtained. Hereinafter, this will be abbreviated as polymer (A-6>).

Reference Example 7 (same as above) A tertiary amine group and a carboxyl group were combined in the same manner as Reference Example 6, except that the same amount of itaconic anhydride was used instead of maleic anhydride, and the NV was 45%. A solution of a vinyl polymer (A>) was obtained. Hereinafter, this will be abbreviated as polymer (A-7).

Reference Example 8 (same as above) i, o of the (n-3-”l) solution obtained in Reference Example 6
The temperature of the oo portion was raised to 90'C in a nitrogen stream, and N was added to it.

20.8 of N-dimethyl-1,3-propylenediamine
of the solution was added and kept at the same temperature for 6 hours to cause a dehydration reaction. During this period, the acid value, which was 22.7 at the beginning of the reaction, decreased to 12.5 at the end of the reaction.

From this, it is known that about 90% of the amide bond once generated was converted into an imide ring.

Furthermore, according to IR spectrum analysis, the absorption of the amide bond disappeared, and instead the absorption of 1,700 due to the imide ring
-I Cm absorption was confirmed.

To the imide ring-containing polymer solution thus obtained, 135 parts of n-butanol was added to obtain a desired polymer (A>
A solution of was obtained. Hereinafter, this will be abbreviated as polymer (A-8>).

Reference Example 9 [Preparation example of compound (B) having both an epoxy group and a hydrolyzable silyl group in one molecule] In a reactor similar to Reference Example 1, 870 parts of toluene and 5
90 parts of CC-butanol was charged in a nitrogen stream.
℃ n'l? n-butyl methacrylate 3
10 parts of n-butyl acrylate, 500 parts of glycidyl methacrylate, 50 parts of γ-methacryloxypropyltrimethoxysilane, 50 parts of TBPO and 170 parts of toluene, and γ-mercaptopropyltrimethoxysilane. A mixture consisting of 40 parts of toluene and 160 parts of toluene was added dropwise over 6 hours, and the same temperature was maintained for 15 hours after the addition was completed until the NV was 40%.
A solution of a polymer (B) having both an epoxy group and a methoxysilyl group and having a molecular weight of 4.200 was obtained. Hereinafter, this will be abbreviated as polymer (B-1).

Reference Example 10 (same as above) Into a reactor similar to Reference Example 1, 1,100 parts of toluene and 300 parts of 5CC-butanol were charged, and the temperature was raised to 100°C in a nitrogen atmosphere to produce 100 parts of methyl methacrylate.
parts, 200 parts of n-butyl methacrylate, 100 parts of 1so-butyl acrylate, 400 parts of glycidyl methacrylate, 200 parts of γ-methacryloxypropyltrimethoxysilane, 50 parts of TBPO, 5 parts of di-BPB.
100 parts of N
A solution of a polymer (B) having both an epoxy group and a methoxysilyl group and having a V of 40% and a V of 4.500 was obtained. Hereinafter, this will be abbreviated as polymer (B-2).

Reference Example 11 (Preparation example of compound (C-2) containing no epoxy group and containing a hydrolyzable silyl group) In a reactor similar to Reference Example 1, 800 parts of toluene and n
- Charge 500 parts of butanol and raise the temperature to 110'C under a nitrogen gas atmosphere, then 200 parts of styrene, 300 parts of n-butyl methacrylate, 500 parts of γ-methacryloxypropyltrimethoxysilane, and 40 parts of TBPO. ,
A mixture consisting of 5 parts of TBP [3] and 200 parts of toluene was added dropwise over 8 hours, and the same temperature was maintained for 15 hours after the addition was completed, so that the NV was 40% and the horse was 5.
000 methoxysilyl group-containing vinyl polymer (C
-1 q of solution of 2) was taken.

Hereinafter, this will be abbreviated as compound (C-2-1).

Reference Example 12 (same as above) Except that the same amount of γ-methacryloxypropyltriisopropenyloxysilane was used instead of γ-methacryloxypropyltrimethoxysilane.
An isopropenyloxysilyl group-containing polymer (C-2) was obtained in the same manner as in Reference Example 11. Hereinafter, this will be referred to as the compound (C
-2-2).

Reference Example 13 (same as above) In a reactor similar to Reference Example 1, 134 parts (1 mol) of trimethylolpropane and 684 parts (1 mol) of ε-caprolactone were added.
6 mol) and 0.04 of tetrabutyl titanate, heated to 180'C in a nitrogen stream, and heated to 180'C at the same temperature.
The reaction was carried out for a period of time to obtain an adduct having a molar ratio of trimethylolpropane to ε-caprolactone of 6. Then 9
After cooling down to 0'C, 93 of tetraethyl silicate
6 parts (equivalent ratio of tetraethyl silicate to 1 part water = 1
．． 5) and 5.3 parts of tetrabutyl titanate were added and reacted at 110 to 120'C until distillation of ethanol stopped (3 hours) to obtain a tetraethoxysilane-modified resin. Hereinafter, this will be abbreviated as compound (C-2-3).

Reference Example 14 (same as above) In a reactor similar to Reference Example 1, 62% of ethylene glycol was added.
parts (1 mol), 2280 parts (20
mol) and 0.12 parts of tetrabutyl titanate, heated to 180°C in a nitrogen atmosphere, and heated to 180°C at the same temperature.
By reacting for a period of time, an adduct having a molar ratio of ethylene glycol to ε-caprolactone of 1:20 was obtained. Then 9
After cooling to 0″C, 118 parts of butyl acetate, γ-
Isocyanate propyltrimethoxysilane /110
and 0.14 parts of tin octylate were added and maintained at the same temperature for 10 hours to obtain a polyester resin having trimethoxysilyl groups at both ends and having an NV of 70%. below,
This is abbreviated as compound (C-2-4>).

Reference Example 15 (same as above) 157.4 parts of adipine 1, 300 parts of hexahydrophthalic anhydride, and 2 parts of trimethylolpropane were placed in a reactor equipped with a stirring device, a thermometer, a nitrogen inlet tube, and a reaction product water distillation tube.
03.8 parts, neopentyl glycol 23081S, and 200 parts of coconut oil fatty acid were charged, and the temperature was gradually raised to 230°C over 5 hours under a nitrogen stream, and maintained at the same temperature until the acid value reached 10. Dehydration condensation, water valence 11 125
1 q of alkyd resin. Next, the temperature was lowered to 90°C, and then 624 parts of butyl acetate, 456 parts of γ-isocyanatepropyltrimethoxysilane, and 0.5 parts of tin octylate were added.
07 parts was added and kept at the same temperature for 10 hours until the NV was 70%.
An alkyd resin having a trimethoxysilyl group was obtained. Hereinafter, this will be abbreviated as polymer (C-2-5).

<Examples 1 to 12. Comparative Examples 1 to 3> Toluene/xylene/n-butanol/celeryl acetate = 40/20/30/10 (weight ratio) The mixture was diluted to a spray viscosity with a mixed solvent, and spray-coated onto a hot-dip galvanized steel plate to a dry film thickness of about 50 μm, and then left to stand at room temperature for 7 days to harden. The obtained hot-dip galvanized steel sheet was used as a guardrail, and the weather resistance (gloss retention %) of the cured coating film and the S4% brush hardness of the coating film were evaluated.

In addition, as a comparative example, the performance of the coating treated with the coating composition shown in Table 2 was evaluated. The results are shown in Table 2.

The gloss retention rate (%) was measured using a gloss needle at 60%.
By measuring the partial reflectance.

That is, the gloss value of the coating film after exposure is divided by the gloss value before exposure,
This value is multiplied by 100, and the larger this value is, the better the weather resistance is.

(Left below) <Examples 13 to 17. Comparative Examples 4 to 7> Example 1 was prepared using a paint consisting of the resin composition shown in Table 3 (selected from the example compositions used in Examples 1 to 12) and a weathering stabilizer. ~ In the same manner as in 12, the dry coating thickness was approximately 5 on the hot-dip galvanized steel plate guardrail.
It was spray coated to give a coating of 0μ milk, and then allowed to stand for 7 days to harden.

The obtained guardrails were exposed outdoors for two years on city roads in the Miyazaki area to evaluate their weather resistance and decontamination performance.

As comparative examples, one that does not use a weathering stabilizer (Comparative Example 4), and a commercially available acrylic-urethane resin (Comparative Example 5)
, a commercially available oil-free alkyd-melamine resin (Comparative Example 6), and a commercially available isocyanate-cured fluororesin (Comparative Example 7) were used to perform similar performance evaluations using guardrails coated with the same.

The results are also shown in Table 3.

(Left below) (Effects of the invention) The [I] of the present invention essentially contains a vinyl polymer containing a chlorinated nitrogen atom and a compound having both an epoxy group and a hydrolyzable silyl group in one molecule. A hot-dip galvanized steel sheet coated with a room-temperature curable resin composition consisting of a cold-curing resin composition and a coating composition consisting of a weathering stabilizer [II] is coated with an interstitial nitrogen gas,
Since the dissolution of zinc due to the adhesion of large amounts of automobile exhaust gas including sulfur dioxide gas and salts for preventing freezing of passageways is effectively suppressed, deterioration is low and gloss loss is also low. It has the excellent property that it is difficult for soot and smoke to adhere to it, and even if it does, it can be easily removed.

Therefore, hot-dip galvanized steel sheets coated with 1% of the coating composition of the present invention can be used as road materials such as guardrails, guard fences, pedestrian bridges, sound insulation walls, windbreak walls, lighting poles, signal poles, sign poles, telephone poles, etc. It is extremely useful.

Claims (1)

[Scope of Claims] 1. Road materials subjected to hot-dip galvanization as surface treatment, [I] As essential components, (A) a vinyl polymer containing a basic nitrogen atom, and (B) Contains a compound that has both an epoxy group and a hydrolyzable silyl group in the molecule,
Furthermore, if necessary, (C) a compound (C-1) containing a silanol group, and/or a compound (C-2), (D) containing a hydrolyzable silyl group other than the above compound (B).
Room-temperature curable resin composition also comprising the above-mentioned catalyst for hydrolysis-condensation of hydrolyzable silyl groups...10
0 parts, [II] Ultraviolet absorber and/or antioxidant
A road material characterized by being coated with a coating composition having an excellent soot and smoke contamination removal property of 0.01 to 10 parts (solid content ratio). 2. The vinyl polymer (A) is dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, N-dialkylaminoalkylacrylamide,
and at least one vinyl monomer (a-1) selected from the group consisting of N-dialkylaminoalkylmethacrylamide, and another vinyl monomer (a-2) copolymerizable with these The road material according to claim 1, which is a polymer obtained by copolymerizing. 3. The vinyl polymer (A) contains a vinyl polymer (a-3) containing a carboxylic acid anhydride group, and each molecule contains active hydrogen that can react with at least one carboxylic acid anhydride group. The road material according to claim 1, which is a polymer containing a tertiary amino group, which is obtained by reacting a group having a tertiary amino group with a compound (a-4) having a tertiary amino group. 4. The vinyl polymer (A) has carboxyl groups and/or
The road material according to claim 1, which is a polymer also having a phosphate ester bond. 5. Claim 1, wherein the compound (B) having an epoxy group and a hydrolyzable silyl group is a vinyl polymer having an epoxy group and a hydrolyzable silyl group at the end of the main chain and/or in the side chain. Road materials listed in Section. 6. Claim 1, wherein the compound (B) having an epoxy group and a hydrolyzable silyl group is γ-glycidoxypropyltrialkoxysilane and/or γ-glycidoxypropyltriisopropenyloxysilane Road materials listed in . 7. Compound (C-2) containing a hydrolyzable silyl group, excluding compound (B), is a moiety of alkoxysilanes, partially hydrolyzed condensates of alkoxysilanes, alkenyloxysilanes, or alkenyloxysilanes Hydrolyzed condensate, alkoxysilane-modified resin obtained by reacting a compound containing at least two alkoxysilane groups in one molecule with a polyhydric alcohol, hydrolyzable silyl at the end of the main chain and/or side chain Claim 1, which is at least one compound selected from the group consisting of a vinyl polymer containing a group, an alkyd resin containing a hydrolyzable silyl group, and a polyester resin containing a hydrolyzable silyl group. Road materials listed in Section.