JP2003128942A - Room temperature-curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a moisture curing room temperature-curable composition in which degree of cure is identifiable with decoloration or discoloration of the composition simultaneously with the curing caused by the moisture. SOLUTION: This composition comprising (A) an organic compound having at least one silicon which has a hydroxyl group or a hydrolysable group, in the molecule, (B) a moisture-curing catalyst, (C) a compound manifesting alkalinity, (D) a derivative of benzotriazole, (E) a component dissolving the derivative of benzotriazole, manifests the decoloration simultaneously with the moisture curing.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a room temperature curable composition which is cured by moisture, and a curable composition in which the color of the composition is decolored simultaneously with crosslinking by moisture.

[0002]

2. Description of the Related Art Conventionally, silicone compositions and the like have been known as compositions that react with moisture in the atmosphere to crosslink and cure. The silicone composition is a composition composed of a compound containing silicon having a hydrolyzable group such as alkoxysilane in its molecule and a moisture curing catalyst such as a tin compound, and is crosslinked by moisture in the air to cure into an elastic body. In addition to the silicone composition, it contains silicon having a hydrolyzable group in the molecule, and the main chain is composed of an alkylene oxide polymer, a polyurethane resin, a polyacrylate polymer, a saturated carbon organic polymer such as polyisobutylene, etc. Moisture-curing compositions containing a compound as a curable component are commercially available. These are widely used industrially as adhesives, pressure-sensitive adhesives, paints, coating agents, sealing agents because of their excellent workability, economy, weather resistance, adhesion, and electrical characteristics.

[0003]

The above-mentioned silicon-containing organic compound having a hydrolyzable group is provided as a one-part composition and a two-part mixed composition, but the one-part composition does not require mixing. It has the advantage that it can be used easily. These one-pack compositions are stored in a closed container, and when discharged from the container during use, they react with moisture in the air and harden. However, the cross-linking reaction does not occur rapidly, and it is not possible to externally judge how much curing has progressed. When the degree of curing is checked by touching the finger, the appearance of the cured product becomes dirty. In addition, when the curable composition is used as an adhesive, it cannot be confirmed that the original adhesive force cannot be obtained if the adherend is moved to see if it has been cured. Therefore, a method for confirming the degree of curing of the curable composition has been desired.

The present invention can meet the demands, and the degree of curing can be visually confirmed without impairing the moisture curability and without adversely affecting the cured product. That is, the present invention provides a room temperature curable composition that is decolored or discolored by moisture curing.

[0005]

The composition of the present invention comprises (A)
An organic compound having at least one silicon having a hydroxyl group or a hydrolyzable group in the molecule, (B) a moisture curing catalyst, (C) a compound exhibiting alkalinity, (D) a benzotriazole derivative, and (E) a benzotriazole derivative. It is a room temperature curable composition composed of soluble components, which is decolorized simultaneously with moisture curing.

The present invention will be described in detail below. The organic compound (A) that is crosslinked by moisture used in the present invention is one in which the component (A) undergoes a crosslinking reaction due to moisture in the air, moisture contained in the filler, etc., and as a result, the molecules are polymerized and cured. .

The main chain of the component (A) includes organopolysiloxane, alkylene oxide polymer, polyether, ether / ester block copolymer, polyurethane resin, polyacrylic ester polymer, polybutadiene, polyisoprene, styrene- Butadiene copolymer,
Examples thereof include acrylonitrile-butadiene copolymer, ethylene-propylene copolymer, ethylene-acrylic acid ester copolymer, saturated carbon organic polymers such as polychloroprene and polyisobutylene.

Silicon having a hydroxyl group or a hydrolyzable group is a functional group which causes a polycondensation reaction by moisture, and specifically, a halogenated silyl group, an alkoxysilyl group, an alkenyloxysilyl group, an acyloxysilyl group, an aminosilyl group. , An aminooxysilyl group, an oxime silyl group, an amidosilyl group, and the like. One to three hydrolyzable groups can be bonded to one silicon. Among these, an alkoxysilyl group, an oxime silyl group, an alkenyloxysilyl group and the like are preferable because they are particularly easy to handle. These may be present at the terminal or the side chain in the molecule of the component (A), but are preferably present at both terminals.

There are no particular restrictions on the number average molecular weight of the component (A) used in the present invention. A high molecular weight is desirable when used as an adhesive / sealant, and a low molecular weight when used as a paint or coating agent. The thing of is desirable. Such an organic polymer can be produced by a known method, but a commercially available one may be used. For example,
Modified silicone composition MS of Kanegafuchi Chemical Industry Co., Ltd.
Polymers, saturated carbon organic polymers such as EPION polymer manufactured by Kanegafuchi Chemical Industry Co., Ltd. may be mentioned.

It is preferable to add the component (B) as a component for promoting the moisture curability of the component (A). As the moisture curing catalyst of the component (B), RT such as metal carboxylate is used.
Examples include moisture cure catalysts used in V silicones.
For example, dibutyltin bistriethoxysilicate, dibutyltin dimethoxide, dibutyltin diacetate, dibutyltin dilaurate, butyltin tri-2-
Ethylhexoate, lead-2-ethyloctoate, iron-2-ethylhexoate, cobalt-2-ethylhexoate, manganese-2-ethylhexoate, zinc-
Metal salts of organic acid carboxylic acids such as 2-ethylhexoate, stannous caprylate, tin naphthenate, tin oleate, tin butyrate, tin naphthenate, zinc naphthenate, cobalt naphthenate and zinc stearate; Alkoxy aluminum compounds; quaternary ammonium salts such as benzyltriethylammonium acetate; lower fatty acid salts of alkali metals such as potassium acetate, sodium acetate and lithium oxalate; dialkylhydroxylamine such as dimethylhydroxyamine and diethylhydroxyamine. . Among these, chelate compounds such as dibutyltin dimethoxide and dibutyltin bisacetylacetonate are more preferable because they have high activity as a room temperature curing catalyst and accelerate the curing rate of the curable composition. These curing catalysts may be used alone or in combination of two or more kinds.

The amount of these moisture curing catalysts used is (A)
0.01 to 10 parts by weight, particularly 0.
1 to 5 parts by weight is preferable. The amount of the moisture curing catalyst blended is 0.
If the amount is less than 01 parts by weight, the curing speed of the obtained resin composition will be slow, while if it is more than 10 parts by weight, the physical properties of the obtained cured product will be deteriorated, and it will be economically disadvantageous. Absent.

The component (C) exhibiting alkalinity is an inorganic alkaline substance such as a metal hydroxide or a metal oxide, or an organic alkaline substance such as an amine compound. In the presence of these compounds exhibiting alkalinity, the (D) benzotriazole derivative described later develops yellow color.

As the metal hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, zinc hydroxide, barium hydroxide, titanium hydroxide, cobalt hydroxide, iron hydroxide, water Copper oxide etc. can be mentioned. Examples of the metal oxide include calcium oxide. Among these metal hydroxides, magnesium hydroxide, aluminum hydroxide, and water are most easily available from the viewpoint of easy availability and relatively low cost, and storage stability of the room temperature curable composition after compounding. It is calcium oxide.

Examples of the organic alkaline substance include amine compounds. As the amine compound, any of mono-, di-, and polyamines can be used. Examples thereof include ethylamine, propylamine, butylamine, laurylamine and the like. As the polyamine, ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, trimethylhexamethylenediamine, N
-Aminoethylpiperazine, 1,2-diaminopropane, iminobispropylamine, methyliminobispropylamine, 1,5-diamino-2-methylpentane,
Metaxylenediamine, polyamidoamine, isophoronediamine, 1,3-bisaminomethylcyclohexane,
1-cyclohexylamino-3-aminopropane, 3-
Examples include norbornanediamines such as aminomethyl-3,3,5-trimethyl-cyclohexylamine and norbornanediaminomethyl. Examples of other alkaline organic compounds include tetrabutylammonium,
1,4 bis (3-aminopropyl) pyridine etc. are mentioned.

Further, aminosilane or the like can be used. These aminosilanes are silane compounds having two or three alkoxy groups in one molecule and further having an amino group. Specifically, (β-aminoethyl) -β-aminoethyltrialkoxysilane, (β-aminoethyl) -γ
-Aminopropyltrialkoxysilane, (γ-aminopropyl) -β-aminoethyltrialkoxysilane,
(Γ-aminopropyl) -β-aminopropyltrialkoxysilane, aminopropyltrialkoxysilane,
Silane compounds of secondary amines such as aminopropylmethyldialkoxysilane, N-methylaminopropyltrimethoxysilane, N-benzylaminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, (β
-Aminoethyl) -γ-aminopropyltrialkoxysilane, (γ-aminopropyl) -β-aminoethyltrialkoxysilane, (γ-aminopropyl) -γ-aminopropyltrialkoxysilane, aminopropyltrialkoxysilane, amino A silane compound of a primary amine such as propylmethyldialkoxysilane, or obtained by a Michael addition reaction with an acrylate monomer 2
Examples thereof include primary aminosilane compounds. The alkoxy group is a hydrolyzable group, and examples thereof include a methoxy group, an ethoxy group, a propoxy group and a propenoxy group. One or more of these aminosilane compounds are preferably used.

Of these organic alkaline compounds, aminosilane is more preferable because it has the effects of a curing accelerator and an adhesion promoter. The amount of these alkaline compounds used is 0.01 to 1 with respect to 100 parts by weight of the component (A).
5 parts by weight, particularly 0.1 to 10 parts by weight are preferred.

The component (D) used in the present invention is a benzotriazole derivative. It is known that this component is originally added as an ultraviolet absorber, and plastic, rubber,
It was widely used to impart weather resistance and light resistance to paints, adhesives, and sealants. In the present invention, the benzotriazole derivative has the function of the original ultraviolet absorber,
A yellow substance is produced by the interaction between the alkaline substance (C) and the component (E) described later. Although the detailed reaction mechanism is not clear, the produced yellow substance is decolorized when exposed to compounds such as alcohol, acetic acid, oxime, and acetone. That is, an organic compound containing silicon having a hydrolyzable group causes a crosslinking reaction due to moisture in the air, and a gas such as alcohol, acetic acid, oxime, or acetone is released. It is expected that these gases will cause the originally yellow formulation to bleach and become colorless. As the moisture crosslinking reaction progresses, the color changes from yellow to colorless, and the uncured portion is yellow, so it can be visually confirmed how far the curing reaction has proceeded.

Specific examples of these benzotriazole derivatives are 2- (2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-).
5'-methylphenyl) -5-carboxylic acid butyl ester benzotriazole, 2- (2'-hydroxy-5 '
-Methylphenyl) -5,6-dichlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) -5-ethylsulfonebenzotriazole, 2-
(2'-hydroxy-5'-t-butylphenyl) -5
-Chlorobenzotriazole, 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2
-(2'-hydroxy-5'-aminophenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-
Dimethylphenyl) benzotriazole, 2- (2'-
Hydroxy-3 ', 5'-dimethylphenyl) -5-methoxybenzotriazole, 2- (2'-methyl-4'
-Hydroxyphenyl) benzotriazole, 2-
(2'-stearyloxy-3 ', 5'-dimethylphenyl) -5-methylbenzotriazole, 2- (2'-
Hydroxy-5-carboxylic acid phenyl) benzotriazole ethyl ester, 2- (2'-hydroxy-3 ',
5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-methyl-
5'-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-t-butyl-
5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-methoxyphenyl) benzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-cyclohexylphenyl) benzotriazole, 2-
(2'-hydroxy-4 ', 5'-dimethylphenyl)
-5-carboxylic acid benzotriazole, 2- (2'-hydroxy-5-methylphenyl) -5-carboxylic acid butyl ester benzotriazole, 2- (2'-hydroxy-4 ', 5'-dichlorophenyl) benzo Triazole, 2- (2'-hydroxy-3 ', 5'-dimethylphenyl) -5-ethylsulfobenzotriazole, 2-
(2'-Hydroxy-4'-octoxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-methoxyphenyl) -5-methylbenzotriazole, 2-
(2'-hydroxy-5'-methylphenyl) -5-carboxylic acid ester benzotriazole, 2- (2'-acetoxy-methylphenyl) benzotriazole and the like can be mentioned.

These derivatives are Ciba Specialty
It is sold under the trade name TINUVIN of Chemical Co., Ltd. Specifically, TINUVIN 213,
TINUVIN P, TINUVIN 234, TINU
VIN320, TINUVIN326, TINUVIN
327, TINUVIN328, TINUVIN32
9, TINUVIN 571 or the like can be used.

The amount of the above-mentioned benzotriazole derivative is 0.01 to 20 parts by weight, particularly 0.1 to 10 parts by weight, based on 100 parts of the component (A). When the amount is less than 0.1 part by weight, the degree of color change during moisture curing is small and difficult to understand. On the other hand, if the amount is more than 10 parts by weight, a large amount of solvent is required to dissolve the benzotriazole, and the physical properties of the obtained composition deteriorate, which is not preferable.

The component (E) used in the present invention is a component which dissolves the benzotriazole derivative, and dissolves the benzotriazole derivative such as an organic solvent, a plasticizer, a monomer and an oligomer, and dissolves or is compatible with the component (A). It is a thing. Furthermore, compounds that do not adversely affect the storage stability of the room temperature curable composition of the present invention and the physical properties after curing are preferable. Examples of the organic solvent in which the benzotriazole derivative is dissolved include aromatic solvents such as toluene and xylene, chlorinated aromatic solvents, chlorinated hydrocarbons, hydrocarbons, ketones, ethers and esters. A plasticizer can also be used as a component that dissolves benzotriazole. For example, phthalic acid esters such as dioctyl phthalate, dibutyl phthalate, butylbenzyl phthalate and the like; aliphatic dibasic acid esters such as dioctyl adipate, isodecyl succinate, dibutyl sebacate and the like; diethylene glycol dibenzoate, pentaerythritol ester Glycol esters such as butyl oleate, methyl acetylricinoleate and the like; phosphate esters such as tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate and the like;
Epoxy plasticizers such as epoxidized soybean oil and benzyl epoxystearate; polyester plasticizers such as polyesters of dibasic acids and dihydric alcohols; polyethers such as polypropylene glycol and its derivatives; poly-α -Polystyrenes such as methylstyrene and polystyrene; plasticizers such as polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, and chlorinated paraffins can be used alone or in the form of a mixture of two or more kinds.

The amount of these components (E) to be used may be such an amount as to dissolve the benzotriazole derivative. The required addition amount varies depending on the used amounts of the component (E) and the component (D) used, but 10 to 200 parts can be added to 100 parts of the component (A). As described above, a mixture of the components (C) to (E) is combined with the component (A) to develop a yellow color, which is decolored simultaneously with moisture curing. Heated stirring is generally used as the dissolution step.

The component (F) used in the present invention is an inorganic filler. The role of the inorganic filler is generally to reinforce the organic polymer. Heavy calcium carbonate, colloidal light calcium carbonate, talc, fumed silica, pyrogenic silica, precipitated silica, pulverized silica, as an inorganic filler often used industrially.
Examples thereof include fused silica, quartz powder, diatomaceous earth, precipitated calcium carbonate, ground calcium carbonate, magnesium carbonate, magnesium hydroxide, zinc carbonate, alumina, aluminum hydroxide, wax clay, kaolin clay and calcined clay. Any of these inorganic fillers can be used in the present invention, but colloidal calcium carbonate is more effective.

In the present invention, the component (F) has the effect of making it easier to visually confirm a color change from yellow to decoloring or discoloring by making the color of the composition cloudy, in addition to reinforcing the composition. When the component (F) is not added, the color of the composition is yellow and transparent, and the color changes to colorless and transparent due to the effect, but it is difficult to confirm visually, but since the component (F) is added, the yellow color changes to white. You can see it clearly. The amount of the component (F) added is about 0 to 300 parts per 100 parts of the component (A).

Further, in addition to the components (A) to (F) described above, dyes or pigments can be added. That is, by utilizing the principle of three primary colors, not only a yellow composition before curing but also a composition of any color can be prepared. The three primary colors are colors that cannot be mixed with other colors, such as red, blue, and yellow. A secondary color is created by mixing two of the three primary colors. For example, a mixture of blue and yellow becomes green, a mixture of yellow and red becomes orange, and a mixture of blue and red becomes purple. Since the curable composition of the present invention is yellow, the composition before curing becomes green by adding a blue dye or pigment, but the yellow disappears due to moisture curing,
Only the blue color remains. That is, by adding a blue dye or pigment, a room temperature curable composition that changes color from green to blue can be prepared. Similarly, a room temperature curable composition that turns from orange to red can be made by adding a red dye or pigment to an originally yellow composition. By adding two or more kinds of dyes according to the same principle, it is possible to make a composition which changes a desired color from a desired color. Further, the color density can be changed by the addition amount of the dye.

In addition to the above essential components (A) to (F), if necessary, a fibrous filler, an oil resistance improver, a heat resistance improver, a cold resistance improver, a thixotropic agent, a dehydrating agent,
Add rust inhibitor, adhesion improver, oil adhesion improver, solvent, plasticizer, antioxidant, UV absorber, light stabilizer, flame retardant, surfactant, antistatic agent, etc. Good. These are added in an appropriate amount according to the required physical properties.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be specifically described with reference to Examples, but the scope of the present invention is not limited to these Examples. In the following description of the examples, all parts are parts by weight.

Example 1 As a component (A), MA440 manufactured by Kanegafuchi Chemical Industry Co., Ltd. was used. MA440 is composed of a (meth) acrylic acid alkyl ester monomer unit having an alkyl group having 1 to 8 carbon atoms and a (meth) acrylic acid alkyl ester monomer unit having an alkyl group having 10 to 30 or more carbon atoms. It is a mixture of an oxyalkylene polymer which is a copolymer and has a dimethoxysilyl group at the molecular end. 100 copies of MA
In 440, 3 parts of aminosilane (A-1110 of Nippon Unicar Co., Ltd.) which is the (C) component, 2 parts of tin catalyst (U-303 of Nitto Kasei Co., Ltd.) which is the (B) component, and (F) component Certain colloidal calcium carbonate (SP-T: Takehara Industry Co., Ltd.)
70 parts and a benzotriazole derivative (TINUVIN327) as the component (D), which had been dissolved in the phosphoric acid triester (TOP) as the component (E) in advance, were mixed in an anhydrous state and degassed under vacuum to prepare the mixture.

Examples 2 to 21 and Comparative Examples 1 to 7 Similarly, various compositions were blended as shown in Tables 1 and 2. However, the abbreviations in the table are as follows. MA440: Acrylic polymer having a dimethoxysilyl group at the terminal (Kanebuchi Chemical Industry) SAT200: Polypropylene oxide having a dimethoxysilyl group at the terminal (Kanebuchi Chemical Industry) EPION EP505S: Polyisobutylene having a dimethoxysilyl group at the terminal Polymer (Kanebuchi Chemical Industry) -U-303: Dibutyltin bistriethoxysilicate (Nitto Kasei) -U-220: Dibutyltin bisacetylacetonate (Nitto Kasei) -U-373: Mixture of dibutyltin oxide and phthalic acid diester (Nitto Kasei) Chemical formation) -SCAT-27: dibutyltin dimethoxide (Osaka Organic Synthesis) -TPT: tetrapropoxytitanium-A-1110: aminopropyltrimethoxysilane (Nippon Unicar) -TBA: tetrabutylammonium-BAP: , 4-bis (3-aminopropyl) pyridine · TINUVIN327: 2,4- di -tert- butyl-6- (5-chloro-benzotriazol-2-yl)
Phenol (Ciba Specialty Chemicals) -TINUVIN P: 2- (2H-benzotriazol-2-yl-p-cresol (Ciba Specialty Chemicals) -TINUVIN 320: 2-benzotriazole-2
-Yl-4,6-di-tert-butylphenol (Ciba Specialty Chemicals) -TINUVIN 329: 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol ( Ciba Specialty Chemicals) ・ TOP: phosphoric acid triester ・ DOP: phthalic acid diester ・ P-3000: polypropylene oxide (Asahi Denka Co., Ltd.) ・ Neolite SP-T: colloidal calcium carbonate (Takehara) ・ Softon 1800: heavy calcium carbonate (Takehara Industry)

The initial color of each formulation and the color upon room temperature moisture cure were visually observed. The results are shown in Tables 1 and 2.

[0031]

[Table 1]

[Table 2]

[0032]

INDUSTRIAL APPLICABILITY The present invention relates to a room temperature curable composition which is cured by moisture, and a curable composition in which the color of the composition is decolored simultaneously with crosslinking by moisture. Therefore, it is possible to see from the outside how much hardening has progressed,
Since it is not necessary to confirm the degree of curing with a finger or to confirm whether or not it has been cured by moving the adherend, the appearance of the cured product does not become dirty and the adhesive strength does not decrease.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J002 AC031 AC061 AC071 AC081                       AC091 AC111 BB071 BB081                       BB151 BB181 BB201 BG021                       CH051 CK021 CP061 DE057                       DE067 DE079 DE087 DE097                       DE107 DE117 DE137 DE149                       DE239 DE249 DJ019 DJ039                       DJ049 EG026 EG046 EN006                       EN008 EN028 EN038 EN106                       EU048 EU178 EX078 EZ046                       EZ056 FD019 FD156 GH00                       GH01 GJ01 GJ02

Claims (3)

[Claims] 1. An organic compound having at least one (A) silicon having a hydroxyl group or a hydrolyzable group in the molecule,
A room temperature curable composition that discolors simultaneously with moisture curing, which comprises (B) a moisture curing catalyst, (C) a compound exhibiting alkalinity, (D) a benzotriazole derivative, and (E) a component that dissolves the benzotriazole derivative. object. 2. The main chain of the component (A) is an organopolysiloxane, an alkylene oxide polymer, a polyether,
Ether / ester block copolymer, polyurethane resin, polyacrylic acid ester polymer, polybutadiene,
Room temperature curing according to claim 1, which is polyisoprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene copolymer, ethylene-acrylic acid ester copolymer, polychloroprene, polyisobutylene. Sex composition. 3. The room temperature curable composition according to claim 1, further comprising (F) an inorganic filler.