JPS61225244A - Room temperature curing resin composition - Google Patents

Abstract

PURPOSE:To provide the titled resin compsn. which gives cured articles having excellent weather resistance and hardness, containing a basic nitrogen-contg. vinyl polymer, a compd. contg. both epoxy and hydrolyzable silyl groups, a silanol group-contg. compd., etc. CONSTITUTION:The titled room temperature curing resin compsn. contains a basic nitrogen-contg. vinyl polymer (A) (e.g. diethylaminoethyl acrylate/ethyl acrylate copolymer), a compd. (B) contg. both epoxy and hydrolyzable silyl groups (e.g. gamma-glycidoxypropyltrialkoxy silane), a silanol group-contg. compds. (e.g. hydrolyzate of methyltrichlorosilane) and/or a hydrolyzable silyl group- contg. compd. (e.g. trimethoxysilane) (C) other than component B, and optionally a catalyst (D) for hydrolysis-condensation of the hydrolyzable silyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel and useful room-temperature curable resin composition, and more particularly, the present invention relates to a novel and useful room-temperature curable resin composition, and more specifically, a resin composition comprising a specific vinyl polymer containing a basic nitrogen atom, an epoxy group, and a hydrolyzable silyl group. The essential components are a specific compound having a silyl group, a silanol group-containing compound and/or a hydrolyzable silyl group-containing compound other than the above-mentioned compounds, and if necessary, a specific hydrolysis-condensation catalyst. It also relates to a resin composition which is particularly useful as a paint, an adhesive or a sealant, and which provides a cured product with particularly excellent weather resistance and hardness.

[Conventional technology]

Conventionally, compositions have been known in which a vinyl polymer containing a basic nitrogen atom is used as a base resin component and an IJ-4X compound is blended as a curing agent, and such compositions can be easily cured at room temperature. It has been said that it cures to give a cured product with excellent weather resistance (Japanese Patent Laid-Open No. 52-7633).
8 and Japanese Unexamined Patent Publication No. 59-56423).

[Problem that the invention seeks to solve]

Under these circumstances, in recent years, there has been a desire to develop maintenance-free outdoor paints or sealants that have a high degree of weather resistance. However, there was a problem in that the gloss and strength decreased significantly after being exposed outdoors for about two years, and the weather resistance was therefore insufficient.

[Means for solving problems]

However, in order to eliminate and solve the numerous drawbacks or problems in the prior art as described above, the present inventors added a curing agent to a vinyl polymer having a basic nitrogen atom.
Compounds having both a 4-hydroxy group and a hydrolyzable silyl group in one molecule, and compounds containing a hydrolyzable silyl group as an essential group without a 4-oxy group and/or
The present invention has been completed by discovering that by blending with a compound containing a silanol group, it is possible to obtain a composition that provides a cured product with significantly improved weather resistance and excellent hardness. reached.

That is, the present invention comprises, as essential components, a vinyl polymer (A) containing a basic nitrogen atom (hereinafter abbreviated as basic nitrogen), and an epoxy group and a hydrolyzable silyl group in one molecule. The compound (B) that is also present, and the compound (B)
) Compounds containing hydrolyzable silyl groups (C-
2) and/or a compound containing a silanol group (C
-1) as an essential component, and further contains a catalyst (B) for hydrolysis-condensation of the hydrolyzable silyl group, if necessary, and has particularly excellent weather resistance and hardness. The present invention provides a room temperature curable resin composition that provides a cured product.

First, the above-mentioned basic nitrogen-containing vinyl polymer (A) is defined as having at least one, preferably at least two, basic nitrogens in one molecule, that is, a -class amino group, a secondary amino group, and This refers to a vinyl polymer containing at least one type of 7-mino group selected from the group consisting of a tertiary amino group. Containing vinyl monomer [hereinafter also referred to as vinyl monomer (a-1)]. ] is (co)polymerized, or (1) A vinyl polymer containing a carboxylic acid anhydride group (hereinafter abbreviated as acid anhydride group) [hereinafter also referred to as polymer (a-3). ]
and a compound having in one molecule at least a group having an active hydrogen capable of reacting with the acid anhydride group and a tertiary amino group [hereinafter, this will be abbreviated as compound (a-4). ] It can be prepared by a known method such as reacting with.

Among them, a typical example of the amino group-containing vinyl monomer C&-1) used in preparing the divinyl polymer (4) by the method (2) above is dimethylaminoethyl (meth). Acrylate, diethylaminoethyl (
meth)acrylate, dimethylaminopropyl(meth)
Acrylates or diethylaminotscubir (meth)
Various dialkylaminoalkyl (meth)acrylates such as N-dimethylaminoethyl (meth)acrylamide, N'-diethylaminoethyl (meth)acrylamide, N-dimethylaminopropyl (meth)acrylamide or N-diethylaminotcubyl (meth)acrylate; ) N-dialkylaminoalkyl (meth)acrylamides such as acrylamide: or t-butylaminoethyl (meth)acrylate, t-butylaminoglobil (meth)acrylate, aziridinylethyl (
Examples include meth)acrylate, pyrrolidinylethyl (meth)acrylate, and piperidinylethyl (meth)acrylate; Alkyl (meth)acrylamides are particularly preferred.

In addition, these amino group-containing vinyl monomers (a-1)
Typical examples of other vinyl monomers (a-2) copolymerizable with are methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and 0-propyl. (meth)acrylate, n-butyl (meth)acrylate, 1mo-butyl (meth)acrylate, t@rt-butyl (meth)acrylate,
2-ethylhexyl (meth)acrylate, lauryl (
meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-human mixibutyl (meth)acrylate
Acrylate or various (meth)acrylic acid esters such as 4-human mixibutyl (meth)acrylate;
Dialkyl esters of unsaturated dibasic acids such as dimethyl maleate, dimethyl fumarate, dibutyl fumarate or dimethyl itaconate; (meth)acrylic acid, motsputyl maleate, motsputyl fumarate, crotonic acid, maleic acid, fumaric acid Carboxyl group-containing vinyl monomers such as acid or itaconic acid; acid anhydride group-containing vinyl monomers such as maleic anhydride or itaconic anhydride;
(meth)acrylamide, N, N-dimethyl (meth)acrylamide, N-alkoxymethyl (meth)acrylamide, diacetone (meth)acrylamide or N
- Vinyl monomers containing various cardanamide groups and acid anhydride groups such as methylol(meth)acrylamide, sulfonamides, N-methyl-p-styrenesulfonamides, or N,N-dimethyl-p-styrenesulfonamides. Various sulfonamide group-containing vinyl monomers: cyano group-containing vinyl monomers such as (meth)acrylonitrile; hydroxyalkyl esters of (meth)acrylic acid such as those listed above; Phosphoric acid ester bond-containing vinyl monomers that are condensation products of hydroxyalkyl esters of carcinic acid and phosphoric acid or phosphoric acid esters; sulfones such as p-styrenesulfonic acid or 2-acrylamido-2-methyl-propanesulfonic acid Vinyl monomers containing acid groups; various vinyl esters such as vinyl acetate, vinyl benzoate or "Beopa" (vinyl ester manufactured by Shell, Netherlands); "Viscoat sF, 8FM, 3F or 3FMJ (manufactured by Osaka Organic Chemical Co. Fluorine-containing (meth)acrylic monomer M:l manufactured by
a/mother-fluorocyclohexyl (meth)acrylate, di-gloss-fluorocyclohexyl fumarate 4L
< is (/4-
) Fluoroalkyl group-containing vinyl monomers; halodanated olefins such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, or a-rotrifluoroethylene; or styrene, α-methylstyrene,
Examples of p-tart-butylstyrene 4L include aromatic vinyl monomers such as vinyltoluene.

In order to prepare the vinyl polymer Q using the various monomers listed above, 0.5 to 100% by weight of the amino group-containing vinyl monomer (a-1), Preferably 1 to 70% by weight and 99% of the other vinyl monomer (a-2) copolymerizable with the amino group-containing vinyl monomer.
5 to 0% by weight, preferably 99 to 30% by weight, may be copolymerized.

In addition, as other vinyl monomers (a-2) copolymerizable with the amino group-containing vinyl monomer (a-1), wheat carboxyl group-containing monomers or phosphoric acid ester bonds as mentioned above may be used. By using the containing monomer in combination, a carboxyl group or a phosphoric ester bond can be introduced into the vinyl polymer (A), thereby further improving the curability of the composition of the present invention. This is especially desirable since it can also be used to

To prepare the vinyl polymer (4) from the various monomers listed above, any conventionally known polymerization method can be applied, but solution radical polymerization is the simplest method.

Typical solvents used in this process are +7) K
tli) Various hydrocarbons such as toluene, xylene, cyclohexane, n-hexane, octane; methanol,
Ethanol, quantity go de a panol, n-butanol, 1
Various alcohols such as so-butanol, II@e-butanol, ethylene glycol monomethyl ether;
Various ester systems such as methyl acetate, ethyl acetate, n-butyl acetate, amyl acetate; or various keto/systems such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc., either alone or in combination. Can be used.

Polymerization may be carried out in a conventional manner using such solvents and various known and commonly used radical polymerization initiators such as azo-based or peroxide-based radical polymerization initiators. Chain transfer agents such as lauryl mercagutan, octyl mercaptan, dodecyl 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 divinyl polymer (2) by the above-mentioned method (1) is a vinyl polymer (a-3) containing an acid anhydride group such as maleic anhydride or itaconic anhydride. It can be prepared by radical copolymerization of the monomers contained and a monomer copolymerizable with these monomers in a solvent other than alcohols among the solvents listed above. can.

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 possible vinyl monomers, any one other than the monomer containing a hydroxyl group can be used. and 0.0 from the point of view of alkali resistance.
The appropriate amount is 5 to 50% by weight, preferably 1 to 20% by weight, while the amount of copolymerizable monomer used is 99.5 to 50% by weight, preferably 99 to 80% by weight. % is appropriate.

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

Here, the compound (a-4) refers to a compound having various groups such as a hydroxyl group, a -class or secondary amide group, or a thiol group as an active hydrogen-containing group present in the compound. 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, the most typical amino alcohols include secondary amines and alcohols. Typical secondary amines used here include dimethylamine, diethylamine, dipropylamine, dibutylamine, ethyleneimine, morpholine,
These include piperazine, piperidine or pyrrolidine, as well as primary amines such as methylamine, ethylamine or butylamine and mono- or pyrrolidine. There are secondary amino group-containing amino alcohols obtained by addition with chemical compounds, and on the other hand, typical examples of chemical compounds include ethylene oxide, propylene oxide, butylene oxide, dodecene oxide, Styrene oxide, cyclohexene oxide, butyl glycidyl ether or phenyl glycidyl ether; or mononyxy compounds such as p-tert-butylbenzoic acid glycidyl ester or "Carpoola E-10" (glycidyl ester of branched fatty acids manufactured by Shell, Netherlands) ; or polyhydric alcohols (/liols) such as ethylene glycol diglycidyl ether, neobentyl glycol diglycidyl ether, 1,6-hexanesiol diglycidyl ether, diglycidyl ether of bisphenol A or triglycidyl ether of glycerin; Glycidyl ethers;
Polyglycidyl esters of polyvalent carganic acids (Ilicarmenic acid) such as diglycidyl esters of phthalic acid, diglycidyl esters of isophthalic acid or diglycidyl esters of adipic acid; or diglycidyl ethers from bisphenols or bisphenol F. There are 4-reengineered epoxy compounds such as various epoxy resins such as epoxy resins, lac type epoxy resins, and pidantoin ring-containing epoxy resins, and even glycidyl ester ethers of p-oxybenzoic acid or There are various vinyl-based (co)polymers having epoxy groups.

Typical examples of the tertiary amino group-containing amino alcohols obtained by reacting such secondary amines with the compound I are dimethylaminoethanol, diethylaminoethanol, di-n-butylaminoethanol, and di-n-butylaminoethanol.
1go-propylaminoethanol, di-n-butylaminoethanol, N-(2-hydroyaethyl)morpholin, N-(2-hydroyaethyl)pyrrolidine, N
-(2-Hydroyaethyl)-aziridine, N,N-dimethyl-2-hydroxypropylamine, N,N-diethyl-2-hydroxypropylamine, triethanolamine or tripropaturamine, and the like. In addition to those listed above, tertiary amino group-containing amino alcohols include amino alcohols such as ethanolamine or pro/gnolamine, and dimethylaminoethyl (meth)acrylate or diethylaminoethyl (meth)acrylate. adducts with (meth)acrylate monomers having a tertiary amino group, such as tertiary amino group-containing (meth)acrylate monomers, or hydroxyl group-containing monomers such as β-hydroxyethyl (meth)acrylate; A vinyl copolymer having both a tertiary amine group and a hydroxyl group in the side chain obtained by copolymerization with a vinyl chloride or the like can also be used.

Separately, typical examples of the above-mentioned primary or secondary amines containing a tertiary amino group include N,N-dimethyl-1,3
-propylene diamine or N,N-diethyl-1
N,N-dialkyl- such as ,3-propylenediamine
1,3-propylene diamines; N,N-dimethyl-1
,4-tetramethylenediamine or N,N-dialkyl-1,4-tetramethylenediamines such as N,N-diethyl-1,4-tetramethylenediamine: N,
N,N-dialkyl-1,6-hexamethylenediamines such as N-dimethyl-1,6-hexamethylenediamine or N,N-diethyl-1,6-hexamethylenediamine: N,N,N' -trimethyl-1,3-propylenediamine, N,N,N'-triethyl-1,3-propylenediamine or N,N,N'-)diethyl-
N, N, N' such as 1,6-hexamethylene diamine
-trialkylalkylene diamines; or N- such as N-methylpiperazine or N-ethylpiperazine
Alkylpiperazines; or adducts of tertiary amino group-containing (meth)acrylate monomers and ethylenediamine, propylenediamine, hexamethylenediamine, piperazine, methylamine, ethylamine, propylamine or ammonia, etc. be.

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

Then, in order to obtain the basic nitrogen-containing vinyl polymer (A) which is the paste resin component in the composition of the present invention from the polymer (a-3) as described above and the compound (a-4),
Both compounds are mixed at a ratio such that the active hydrogen-containing group in compound (a-4) is about 0.5 to 3 equivalents per 1 equivalent of acid anhydride group in polymer (a-3). , the reaction may be carried out in a temperature range from room temperature to about 120°C.

Further, as compound (a-4), N,N-dimethyl-1,
When using a compound having both a tertiary amino group and a primary amino group such as 3-propylene diamine, these (
Due to the addition reaction between both compounds a-3) and (a-4), first, a carmexyl group and an N-monosubstituted amide group are combined as shown in the reaction formula below. [I] The polymer [■] obtained here can also be used in the present invention even in its form, but the requirements such as stain resistance and alkali resistance of the cured coating film are met. For such uses, the polymer is then held at a temperature of about 70 to 150°C to undergo dehydration and ring closure, thereby producing an imide ring-containing polymer [I
The paste resin component () of the composition of the present invention is converted into [).
It is preferable to use it as 4).

Next, as the compound (B) having both an epoxy group and a hydrolyzable silyl group in one molecule,
Vinyl polymers having both of these types of reactive groups and
A typical example is a silane coupling agent having an xyl group.

Here, the hydrolyzable silyl group refers to a halosilyl group, an alkoxysilyl group, a phenoxysilyl group, an iminooxysilyl group, an alkenyloxysilyl group, etc. represented by the general formula %[[]. It refers to reactive groups that are easily hydrolyzed, such as.

Any known method can be applied to prepare the vinyl polymer (B) having the above-mentioned specific bireactive groups; -(meth)acryloyloxyglopylmethyl ditoxysilane, r-(meth)acryloyloxyzolopyltriisoglopenyloxysilane, r-(meth)acryloyloxypropyltriiminooxysilane, vinyltrimethoxysilane, vinyltriethoxine Vinyl monomers having a hydrolyzable silyl group, such as vinyl (tris-β-methoxyethoxy)silane, vinyltriacetoxysilane or tahabinyltrichlorosilane, and (β-methyl)glycidyl (meth)
Vinyl monomers having an epoxy group such as acrylate, allyl glycidyl ether, di(β-methyl)glycidyl fumarate or di(β-methyl)glycidyl fumarate, and if necessary, an amine group-containing Solution radical copolymerization may be carried out using various other vinyl monomers as mentioned above as other vinyl monomers that can be copolymerized with the vinyl monomer, or ■γ-mercaptopropyltrimethoxysilane, γ-mercapto In the presence of a chain transfer agent such as glopyltriethoxysilane, γ-mercadetoglobilmethyldimethoxysilane, γ-mercaptogropyltriisoprobenyloxysilane or γ-mercazotoderovyltriiminooxysilane, the above-mentioned Shita-like work I
A simple method includes solution radical (co)polymerization of a monomer mixture containing vinyl monomers containing a xyl group as an essential component.

Then, the compound (B) is obtained by the above-mentioned method (1).
Of course, in order to perform the v4 cleavage, the hydrolyzable silyl group-containing monomers mentioned above can also be used in combination.

Next, typical examples of the above-mentioned epoxy group-containing silane coupling agents include γ-glycidoxysiloxytrimethoxysilane, r-glycidoxysolobyltriethoxysilane, and r-glycidoxyzolopylmethyljethoxy. Silane, r-glycidoxyzolopyltriinzorobenyloxysilane, γ-glycidoxyzolopyltriiminooxysilane, γ-incyanatepropyltriimpro(nyloxysilane or γ-incyanatezolopyltrimethoxysilane) etc. and adducts with glycidol:
Alternatively, examples include adducts of r-amitube a-pyrutrimethoxysilane and diethyloxy compounds, particularly r-glycidoxyprobyltrimethoxysilane or r-glycidoxyzorobyltriimpro(nyloxysilane). is preferable in terms of curability and economical efficiency.

Further, as one of the component (C) compounds described above, there is a compound (C-1) containing a silanol group, and typical examples of such compound (C-1) include: methyltrichlorosilane, phenyl Low molecular weight silanol compounds such as those obtained by almost complete hydrolysis of halosilanes such as trichlorosilane, ethyltriclosilane, zomethylduchlorosilane or diphenylnochlorosilane;
Monosiloxanes having silanol groups obtained by further button dehydration condensation of these silanol compounds: Siloxanes having silanol groups obtained by hydrolyzing and condensing the aforementioned various alkoyasisilanes and alkynyloxysilanes. Polysiloxanes having a silanol group; a certain h is a silicone resin having a silanol group at the end; furthermore, a silicone resin having a cyclic siloxane structure as typified by "Toray Silicone SH-6018J [product of Toshi Silicone Co., Ltd.]" These include silanol compounds.

On the other hand, the above-mentioned compound (C-2), which contains a hydrolyzable silyl group and does not contain an epoxy group, is a compound containing one molecule of a hydrolyzable silyl group as shown in the above general formula [button]. It refers to low molecular weight compounds or resins that contain at least one epoxy group but do not contain any epoxy groups. Therefore, the compound (C-2) Ic does not correspond to the various compounds (B) listed above.

Typical examples of the compound (C-2) include tetramethoxysilane, trimethoxysilane, tetraethoxysilane, triethoxysilane, tetraacetoxysilane, tetrabutoxysilane, tetraoctoxysilane, tetrakis(2-methoxysilane), ethoxy)silane, tetrabenzyloxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane,
dimethyljethoxysilane, zophenyldiethoxysilane, r-incyanateglopyltrimethoxysilane,
Vinyltrimethoxysilane/, vinyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercadetoglobiltrimethoxysilane, γ-aminopropyltrimethoxysilane or γ-(2-aminoethyl)
Alkoxysilanes such as aminopropyltrimethoxysilane; tetrainpropenyloxysilane.

Phenyltriinzorobenyloxysilane, γ-incyanate delopyltriinde abenyloxysilane, r
- Alkenyloxysilanes such as methacryloxyderobyltriingroinyloxysilane, γ-mercadetodelopyltriinderobenyloxysilane or tetrabutenyloxysilane: tetraacetoxysilane, methyltriacetoxysilane, γ-mercaptopropyl Acrylic compounds such as triacetoxysilane, tetrapropionyloxysilane, phenyltripropylonyloxysilane or vinyltriacetoxysilane;
Tetrachlorosilane/, phenyltrichlorosilane, tetrabromosilane or penciltribromosilane, etc. Category 57: Tetrakis(nomethylinooxy)silane/, Methyltris(dimethylibanooxy)silane, Tetrakis(methyl-ethyliminooxy) Silane.

r-methacryloxypropyltris (dimethylsilane) silane or r-mercaptoglopyltris (
Iminooxysilanes such as dimethylibanooxysilane; alkoxysilyl group-containing siloxane oligomers obtained by partially hydrolyzing and condensing alkoxysilanes such as those listed in 1; partial hydrolysis of alkenyloxysilanes such as silane Alkenyloxy group-containing siloxane oligomers obtained by condensation; γ-metacycloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetyloxysilane/Maku is r-methacryloxynoropyltriacetoxysilane. Homopolymers of various hydrolyzable silyl group-containing vinyl monomers such as, or copolymers of these monomers and copolymerizable monomers; 1
r-mercazotoderopyltrimethoxysilane, γ-
A mercaptan containing a hydrolyzable silyl group such as mercaptopropyltriingropenyloxysilane or r-mercaptopropyltriacetoxysilane is used as a chain transfer agent, and if necessary, various hydrolyzable silyl groups such as those listed in 1. Vinyl polymers containing a hydrolyzable silyl group at the end obtained by (co)polymerizing a vinyl monomer containing a silyl group-containing vinyl monomer; polyhydric alcohols, hydroxyl group-containing acrylic resins , various polyhydroxy compounds such as hydroxyl group-containing alkyd resins, hydroxyl group-containing ester resins, or polyether-liols, and alkoxysilanes such as those listed above.

hydrolyzable silyl group-containing compound, according to JP-A-58-16
Resins obtained by the reaction according to the method disclosed in Japanese Patent No. 8625; low molecular weight tetraallyl compounds such as diallyl succinate, triallyl trimellitate or diallyl phthalate, unsaturated bond-containing vinyl polymers, Adducts of various unsaturated compounds such as unsaturated bond-containing polyester resins or unsaturated bond-containing alkyd resins and hydrolyzable silyl group-containing hydrosilanes such as trimethoxysilane or triethoxysilane; epoxy group-containing vinyl polymers Adducts of various mercaptosilanes such as mercaptosilanes listed in 1 with various compounds containing I-oxy groups such as combined epoxy resins; or γ-incyanate dea-pyltrimethoxysilane and γ-incyanate propylene) urethane bond-containing resins obtained by reacting various hydrolyzable silyl group-containing compounds having an incyanate group, such as z+impropenyloxysilane, with various I-lyroxy compounds listed in 1; There are silicone resins containing a hydrolyzable silyl group at the end of the molecule.

Although the composition of the present invention has good curability even without the addition of a curing catalyst, if it is desired to further improve this curability, it is necessary to use a composition for hydrolysis of hydrolyzable silyl groups as described above, and for condensation. There is no hindrance to adding the catalyst (DJ) as a catalyst for use.

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

In order to obtain the composition of the present invention from the components (4) to (D) listed above, it is necessary to combine the reactive groups present in the components (4), the diamino group and the carboxyl and/or phosphate ester bond. The amount of I present in component (B) relative to the equivalent amount
While blending both of these components (4) and
, 1 to 1,000 parts by weight, preferably about 2 to 500 parts by weight of component (C) are also added to 100 parts by weight of the total amount of both components (B), and if necessary, 10) component t. -(4), (B) and (C) may be added in an amount of about 0.01 to 10% by weight of the total amount of the three essential components.

The composition of the present invention further contains various known and commonly used additives such as organic or inorganic pigments, fluidity regulators, color separation inhibitors, ultraviolet absorbers, and antioxidants. ; cellulose s conductors such as nitrocellulose or cellulose acetate guccilate; some b is chlorinated? Various resins such as polyethylene, chlorinated polypropylene, petroleum resins or comb chloride can also be added.

Further, the composition of the present invention can be used as a solvent-free composition or as a solvent-based composition in which a solvent is added.

The room-temperature curable resin composition of the present invention thus obtained is applied to various base materials in a conventional manner, and then dried in a conventional manner for several days to form a cured product with excellent durability, weather resistance, and hardness. I will die with what I give. .

[Applications of the present invention]

The room-temperature curable resin composition of the present invention thus obtained can be widely used as a paint for automobile repair, woodworking, architecture, building materials, plastics, or various glass products, as well as as a sealant or adhesive. can be used.

〔Example〕

Next, the present invention will be explained in more detail with reference to Reference Examples, Examples, and Comparative Examples. In the following, parts and parts are all based on weight unless otherwise specified.

Reference Example 1 [Preparation Example of Basic Nitrogen-Containing Vinyl Polymer (A)] In a reactor equipped with a stirring device, a thermometer, a reflux condenser, and a nitrogen introduction tube, 392 parts of toluene and 1 so-! Charge 408 parts of tanol, raise the temperature to 80'cK in a nitrogen atmosphere, and add 900 parts of methyl methacrylate, 100 parts of dimethylaminoethyl methacrylate, 5 parts of azobiswintimitrile (AIBN), and tert-butylperoxy. A mixture of 5 parts of octoate (TBPO) and 200 parts of toluene was added dropwise over 3 hours.

After dropping, maintain the same temperature for 2 hours, then add AI again.
A mixture of 5 parts of BN, 448 parts of toluene and 37 parts of 1IIO-butanol was added dropwise over the course of 1 hour. Then, it was kept at the same temperature for 12 hours until the nonvolatile content (NY) was 40
1 and a number average molecular weight (Mn) of 12,000, a solution of a tertiary amino group-containing vinyl polymer (A) was obtained. Hereinafter, this will be abbreviated as polymer rA-1).

Reference Examples 2 to 5 (same as above) A solution of the containing vinyl polymer (A) was obtained. Hereinafter, these will be abbreviated as polymers (A-2) to (A-5) in order.

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 at 110°C in a nitrogen atmosphere.
100 parts of styrene, 400 parts of mether methacrylate, 300 parts of n-butyl methacrylate,
130 parts of n-butyl acrylate, 30 parts of acrylic acid
parts, 40 parts of maleic anhydride, 10 parts of AIBN, TB
A mixture consisting of 5 parts of PO, 5 parts of tart-butylperoxybenzoate (TBPB) and 300 parts of toluene was added dropwise over 3 hours, and after the addition was completed, the reaction was continued by maintaining the same temperature for 15 hours. A solution of a vinyl polymer (a-3) having both an acid anhydride group and a carboxyl group and having W of 50% and Mn of io and ooo was obtained. 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 KN,N-dimethylaminoethanol was added thereto.Then, the temperature was maintained for 5 hours, and then 270 parts of n-butanol were added. A vinyl polymer having both a tertiary amino group and a xyl group (45% NY
) was obtained. Hereinafter, this will be abbreviated as polymer (A-6).

Reference Example 7 (same as above) A tertiary amino group and a carboxyl group with an NV of 45% were prepared in the same manner as Reference Example 6, except that the same amount of itaconic anhydride was used instead of maleic anhydride. A solution of vinyl polymer (4) was obtained. Hereinafter, this will be abbreviated as polymer (A-7).

Reference Example 8 (same as above) 1.000 parts of the solution (a-3-1) obtained in Reference Example 6 was heated to 90°C in a nitrogen stream, and this was mixed with ICN, N-dimethyl-1,3-pre 20.8 parts of pyrene diamine 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, once 8E
It is known that about 90% of the formed amide bond 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 disappeared.
cm-' absorption was confirmed.

To the thus obtained imide mt-containing polymer solution, 135 parts of n-butanol was added to make NY 45%.
Thus, a solution of the desired polymer having a donor color of 1 or less 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 300 parts of 5ee-butanol were added. 310 parts of n-butyl methacrylate, 100 parts of n-butyl acrylate, 500 parts of glycidyl methacrylate, and γ-metacyclooxyglobyltrimethoxysilane were charged. 50 copies, TBPO's 50
and 170 parts of toluene and γ
- A mixture consisting of 40 parts of mercagtoderopyltrimethoxysilane and 160 parts of toluene was added dropwise over a period of 6 hours, and after the dropwise addition was completed, the same temperature of VCl was maintained for 5 hours.
A solution of a polymer (B) having both an epoxy group and a methoxysilyl group with an Mn of 0% and an Mn 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 5eC-butanol were charged, and the temperature was raised to 100°C in a nitrogen atmosphere.
0 parts, 200 parts of n-butyl methacrylate, 100 parts of 1■-butyl acrylate, 400 parts of glycidyl methacrylate, 200 parts of r-methacryloxypropyltrimethoxysilane, 50 parts of TBPO, 5 parts of TBPH.
A mixture of 100 parts of toluene and 100 parts of toluene was added dropwise over 8 hours and maintained at the same temperature for 15 hours to form an epoxy group and a methoxy A solution of a polymer (B) having all silyl groups 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] Using the same reactor as in Reference Example 1, 800 parts of toluene and 500 parts of n-butanol. 200 parts of styrene, 300 parts of n-butyl methacrylate, 500 parts of γ-metacyclooxyglobyltrimethoxysilane, and 40 parts of TBPO.
A mixture of 5 parts of TBPH and 200 parts of toluene was added dropwise over a total of 8 hours, and the same temperature was maintained for 15 hours after the addition was completed, resulting in a concentration of 40% and a Mn content of s,
oo.

Methoxysilyl group-containing vinyl polymer (C-2)
A solution of was obtained. Hereinafter, this will be abbreviated as compound (C-2-1).

Reference Example 12 (same as above) Except that the same amount of r-methacryloxyglopyltriisoderopenyloxysilane was used instead of γ-metacycloxypropyltrimethoxysilane.
An isozolobenyloxysilyl group-containing polymer (C-2) was obtained in the same manner as in Reference Example 11. Below, all these compounds (C
-2-2).

Reference Example 13 (same as above) Reactor K similar to Reference Example 1, 134 parts (1 mol) of trimethylolpropane, 684 parts (1 mol) of ε-caprolactone
B mole) and 0.04t- of tetrabutyl titanate
The temperature was raised to 180℃ in a nitrogen stream, and the temperature was increased to 60℃ at the same temperature.
By reacting for a period of time, an adduct of trimethylolpropane:ε-caprolactone with a molar specific strength of 6 was obtained. Then 90
'CK After cooling down, 936 of tetraethyl silicate
parts (equivalent ratio of tetraethyl silicate to hydroxyl group = 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
mole) and 0.12 parts of tetrabutyl titanate, heated to 180°C in a nitrogen atmosphere, reacted at the same temperature for 6 hours, and ethylene glycol:6-ka! An adduct with a molar ratio of rolactone of 1=20 was obtained. Then 90
After the temperature was lowered to ℃, 118 parts of butyl acetate, 410 parts of r-incyanatoglopytrimethoxysilane, and 0.14 parts of tin octylate were added and kept at the same temperature for 10 hours until a total of 70 parts was removed. A polyester resin having trimethoxysilyl groups at both ends was obtained. Hereinafter, this will be abbreviated as compound (C-2-4).

Reference Example 15 (same as above) 157.4 parts of adipic acid, 300 parts of hexahydrophthalanhydride rIk, and 4 parts of trimetherol furono were placed in a reactor equipped with a stirring device, a thermometer, a nitrogen inlet tube, and a reaction product water distillation tube.
7203.8 parts of neopentyl glycol, 230 parts of neopentyl glycol, and 200 parts of coconut oil fatty acid were charged, and the temperature was gradually raised to LC230°C over 5 hours under a nitrogen stream, and the temperature was maintained until the acid value reached 10. Dehydrated and condensed, hydroxyl value 12
An alkyd resin of No. 5 was obtained. After the temperature was lowered to 90°C, 624 parts of butyl acetate, 456 parts of r-incyanate globil trimethoxysilane and 0.0 parts of tin octylate were added.
7 parts were added thereto and maintained at the same temperature for 10 hours to obtain an alkyd resin having a trimethoxysilyl group with V2O. Hereinafter, this will be abbreviated as polymer (C-2-5).

Reference Example 16 [Compound containing silanol group (C-1)
p! Example] 534 parts of methyltriethoxysilane, 162 parts of water, and 0.5 part of 0.1N hydrochloric acid were placed in a reactor equipped with a stirrer, a thermometer, and a reflux condenser, and the mixture was heated to 80% while stirring well.
The mixture was heated under reflux for 4 hours. Next, the ethanol was distilled off to obtain a solution of Nv50qIb, which was further heated under reflux for 20 hours. The residual ethanol and water were distilled off under reduced pressure from the solution thus obtained to obtain a hydrolyzed condensate of methyltriethoxysilane in the form of a white powder. Hereinafter, this will be abbreviated as polymer (C-1-1).

Examples 1-1O and Comparative Examples 1-8 The blending ratio (expressed in parts) as shown in Table 2.

), a white paint vp+s with a PwC of 40 cm was diluted to a spray viscosity K with a mixed solvent of toluene/xylene/n-butanol/cellosolve acetate) = 40/20/30/10 (weight ratio), and phosphoric acid A zinc-treated steel plate was spray coated to a dry film thickness of about 50 μm, and then dried at room temperature for 7 days to obtain each cured film.

The coating films obtained in this manner were exposed outdoors for two years in Miyazaki Prefecture, and their weather resistance and hardness were evaluated.

The results are summarized in the same table.

〔Effect of the invention〕

As is clear from the results in Table 2, the cured aS obtained from the room temperature curable resin composition of the present invention is known to have excellent weather resistance and hardness.

Agent Patent Attorney Katsutoshi Takahashi Procedural Amendment 7 May 1985 Commissioner of the Patent Office Manabu Shiga 2 Name of the invention Room temperature curable resin composition 3 Relationship with the person making the amendment Patent applicant 3-35-58 Sakashita, Itabashi-ku, Tokyo 174 (2
88) Dainippon Ink & Chemicals Co., Ltd. Representative: Shigeru Kuni Mura 4, Agent Address: 3-7-20 Nihonbashi, Chuo-ku, Tokyo 103 Dainippon Ink & Chemicals Co., Ltd. Phone: Tokyo ((B) 272-4511 ( Representative).

(8876) Patent attorney Katsutoshi Takahashi 5, date of amendment order 6, "Detailed description of the invention" column of the specification to be amended -1, /:
-,' 7. Contents of the amendment (1) The statement on page 7, lines 5 and 6 of the specification is corrected as follows.

r polymer (a-3)] and active water j that can react with at least one acid anhydride group in each molecule (2) The description on page 12, line 13 of the specification ``Tool'' is corrected to ``Lso-Property Tool j''.

(3) The statement on page 13, lines 6-7 of the specification is corrected as follows.

"Uryl mercaptan, octyl mercaptan, 2-mercaptoethanol, j (4) The statement on page 25, lines 6-7 of the specification is corrected as follows.

Typical r-ring agents include T-glycidoxypropyl trimethoxysilane, T-glycid J (5)
The statement "tetraisopropyl titanate" on page 31, line 20 of the specification is replaced by rtetraisopropyl titanatej
Correct.

that's all

Claims (1)

[Scope of Claims] 1. As essential components, (A) a vinyl polymer containing a basic nitrogen atom, and (B) a compound having both an epoxy group and a hydrolyzable silyl group in one molecule; (C) contains a compound (C-1) containing a silanol group and/or a compound (C-2) containing a hydrolyzable silyl group other than the above compound (B), and further contains (D
) A room temperature curable resin composition which also contains the above-mentioned catalyst for hydrolysis-condensation of a hydrolyzable silyl group. 2. The vinyl polymer (A) described above is at least one vinyl monomer selected from the group consisting of dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, N-dialkylaminoalkylacrylamide, and N-dialkylaminoalkylmethacrylamide. Claim 1, characterized in that it is a polymer obtained by copolymerizing the monomer (a-1) and another vinyl monomer (a-2) copolymerizable with these. The composition described in item 1. 3. The vinyl polymer (A) described above has an activity of reacting with the vinyl polymer (a-3) containing a carboxylic acid anhydride group and at least one carboxylic acid anhydride group in each molecule. Claim 1, which is a polymer containing a tertiary amino group obtained by reacting a compound (a-4) having both a hydrogen-containing group and a tertiary amino group. Composition as described. 4. The composition according to claim 1, wherein the vinyl polymer (A) is a polymer having a carboxyl group and/or a phosphoric acid ester bond. 5. The compound (B) having an epoxy group and a hydrolyzable silyl group described above 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. The composition according to claim 1. 6. The compound (B) having an epoxy group and a hydrolyzable silyl group is γ-glycidoxypropyltrialkoxysilane and/or γ-glycidoxypropyltriisopropenyloxysilane, A composition according to claim 1. 7. The compound (C-2) containing a hydrolyzable silyl group other than the above-mentioned compound (B) is an alkoxysilane,
A partially hydrolyzed condensate of alkoxysilanes, alkenyloxysilanes, a partially hydrolyzed condensate of alkenyloxysilanes, a compound containing at least two alkoxysilyl groups in one molecule, and a polyhydric alcohol are reacted. an alkoxysilane-modified resin obtained by The composition according to claim 1, which is at least one compound selected from the group consisting of polyester resins.