JPH0645768B2 - Primer composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a primer composition, and more particularly to a primer composition in which, when a filler is blended, sedimentation and caking phenomenon due to a change with time thereof are prevented.

Problems to be Solved by the Prior Art Primers are used to improve adhesion to adherends such as adhesives and sealing materials. As such a primer, generally, a polyisocyanate compound, a silane coupling agent such as epoxyalkoxysilane or aminoalkoxysilane, or a mixture or reaction product of these polyisocyanate compound and a silane coupling agent is used as a main component, and this is suitable. Diluted with an organic solvent is usually used, but various fillers (carbon black, mica, talc, clay, etc.) are usually used to color the surface to be adhered or to improve weather resistance and workability. (Metal oxide, etc.) is blended. However, when such a filler is blended, the filler may precipitate or caking due to a change with time, which causes a decrease in adhesiveness or a situation in which the filler cannot be used. Especially in the recent application work using a robot, automation cannot be achieved due to sedimentation of the filler.

Therefore, the inventors of the present invention have made extensive studies to solve the problem in the case of blending this filler, and when a specific coupling agent and a fatty acid derivative are added, the initial action is to improve the adhesiveness due to their combined use. It was found that long-term prevention of the sedimentation of the filler can be achieved without impairing the effect,
The present invention has been completed.

Structures and effects of the invention That is, the present invention, in a primer composition containing a filler, a polyisocyanate compound or a silane coupling agent or a mixture or reaction product of a polyisocyanate compound and a silane coupling agent as a main component, 0.1 to 2 parts by weight of titanate-based coupling agent per 100 parts by weight of filler, and 0.1 to 2% by weight based on the total amount of the primer composition, diamines having 3 to 10 carbon atoms and carbon number. The present invention provides a primer composition characterized by adding a higher fatty acid nitrogen derivative consisting of 12 to 22 fatty acids.

Examples of the titanate coupling agent used in the present invention include:
The following (structural formula and general name) are listed, for example, commercially available from Ajinomoto Co., Inc. under the series name "KR".

Isopropyltriisostearoyl titanate Isopropyl tris (dioctyl pyrophosphate) titanate Isopropyl tri (N-aminoethyl-aminoethyl) titanate Tetraoctylbis (ditridecylphosphite) titanate Tetra (2,2-diallyloxymethyl-1-butyl)
Bis (ditridecyl) phosphite titanate Bis (dioctyl pyrophosphate) oxyacetate titanate Bis (dioctyl pyrophosphate) ethylene titanate Isopropyl trioctanoyl titanate Isopropyl dimethacryl isostearoyl titanate Isopropyltridodecylbenzenesulfonyl titanate Isopropyl Isostearoyl Diacrylic Titanate Isopropyl tri (dioctyl phosphate) titanate Isopropyl tricumyl phenyl titanate Tetra isopropyl bis (dioctyl phosphite)
Titanate These coupling agents have the function of modifying the surface of the filler and contribute to the short-term anti-settling effect. The amount used is 0.1 to 2 with respect to 100 parts by weight of filler (weight part, the same below).
Part, preferably 0.5 to 1 part. If it is less than 0.1 part, the desired surface modifying function cannot be achieved, and if it exceeds 2 parts, the storage stability of the primer tends to decrease.

The higher fatty acid nitrogen derivative used in the present invention has 3 to 10 carbon atoms.
An amide wax composed of diamines of 10 and fatty acids of 12 to 22 carbon atoms is referred to, and is usually a paste that is swollen in an appropriate organic solvent. For example, it is marketed by Kyoeisha Yushi Kagaku Kogyo Co., Ltd. under the series name "Tarlen".

When only the titanate coupling agent is added, a short-term (within 2 days) anti-settling effect can be obtained, but the effect gradually decreases with time and causes caking. Therefore, the higher fatty acid nitrogen derivative has a synergistic effect on the titanate coupling agent and can achieve a desired long-term anti-settling effect.
Further, it also serves as a redispersibility improving agent. When only the higher fatty acid nitrogen derivative is added, the viscosity increases and workability deteriorates as shown in Comparative Example 3 below. The amount used is 0.1 to 2 in the total amount of the primer composition.
Select so that it will be weight%. If it exceeds 2% by weight, the viscosity is excessively increased, which tends to hinder the coating operation. If necessary, a small amount of polyethylene oxide wax or the like may be added.

The primer composition according to the present invention is composed of a conventional primer composition containing the above-mentioned filler, to which a titanate coupling agent and a higher fatty acid nitrogen derivative are added at a predetermined ratio. For preparing the composition,
First, the filler is dispersed in an organic solvent (methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, ethyl ether, tetrahydrofuran, dioxane, toluene, xylene, methylene chloride, etc.), and a titanate coupling agent is added to and mixed with the filler. After modifying the surface of the polyisocyanate compound [Trimethylhexamethylene diisocyanate, Hexamethylene diisocyanate, Isophorone diisocyanate, Lysine diisocyanate methyl ester, Tolylene diisocyanate, Desmodule N, RF, R (Sumitomo Bayer Urethane Co., Ltd. Manufactured by Nippon Polyurethane Industry Co., Ltd.), silane coupling agent [-
Glycidoxypropyltrimethoxysilane, -Glycidoxypropylmethyldimethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-
Epoxyalkoxysilanes such as epoxycyclohexylethylmethyldimethoxysilane, aminomethyltriethoxysilane, N- (β-aminoethyl) aminomethyltrimethoxysilane, aminomethyldiethoxysilane, N- (β-aminoethyl) methyltributoxy Silane, -aminopropyltriethoxysilane, -aminopropylmethyldiethoxysilane, -aminoisobutyltrimethoxysilane, -mercaptopropyltrimethoxysilane, N-bis (β-hydroxyethyl)-
-Aminopropyltriethoxysilane, N- (β-aminoethyl) -aminopropyltrimethoxysilane, N- (β-aminoethyl) -aminopropylmethyldimethoxysilane, N- (β-aminoethyl)-
-Amino-β-methylpropyltrimethoxysilane and other aminoalkoxysilanes], or a mixture or reaction product of these polyisocyanate compounds and a silane coupling agent, and if necessary, a film-forming resin (polyester resin, chlorinated rubber) , Polyvinyl chloride resin,
Polyacrylate resin, silicone resin, ethylene vinyl acetate copolymer, etc.), dehydrating agent, plasticizer (butylbenzyl phthalate, dioctyl phthalate, dibutyl phthalate, paraffin chloride, etc.), etc. Finally, a higher fatty acid nitrogen derivative is added to the sand mill or It can be prepared by mixing with a ball mill. Viscosity of primer composition (20
C) may be usually set in the range of 10 to 100 cps.

Thus, by the combined use of the titanate-based coupling agent and the higher fatty acid nitrogen derivative, the sedimentation or caking phenomenon of the filler was not observed at all or for a week or more, and the redispersion became easy. It can be used without difficulty in coating work.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples.

Example 1 5% (by weight) (hereinafter referred to as w / w) of carbon black and 5% w / w of clay were dispersed in methyl ethyl ketone (MEK), and 1% of the total amount of carbon black and clay was dispersed. w / w Isopropyltriisostearoyl titanate ("KR TTS" manufactured by Ajinomoto Co., Inc.)
After pretreatment with a ball mill for 6 hours, 50% w / w of Desmodule RF (manufactured by Sumitomo Bayer Urethane Co.) in the total amount is added, and after 6 hours in a ball mill, 0.5% w / w of higher fatty acid nitrogen in the total amount is added. Derivatives (dihydroxy compound of 1,6-hexamethylenediamine 1 mol and stearic acid 2 mol, diamide compound, molecular formula = C ₄₂ H ₈₄ N
₂ O ₄ ) (Kyoeisha Yushi Kagaku Kogyo Co., Ltd. "Tarlen 870"
0 ") in 50% MEK solution, and ball mill for 1 hour to obtain the primer.

Comparative Example 1 (Blank) A primer is obtained in the same manner as in Example 1 except that both “KR TTS” and “Tarlen 8700” are omitted.

Comparative Examples 2 and 3 In Example 1, a primer is similarly obtained using only "KR TTS" or "Tarlen 8700".

Table 1 shows the coating workability (and viscosity) immediately after the preparation of the primer of each example, and the evaluation of the sedimentation property and its redispersibility over time.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-53-113835 (JP, A) JP-A-60-143820 (JP, A) JP-A-48-83122 (JP, A)

Claims (1)

[Claims] 1. A primer composition containing a polyisocyanate compound or a silane coupling agent, a mixture of a polyisocyanate compound and a silane coupling agent, or a reaction product as a main component, in which a filler is blended, and 100 parts by weight of the filler. 0.1 to 2 parts by weight of a titanate coupling agent, and 0.1 to 2% by weight based on the total amount of the primer composition, a diamine having 3 to 10 carbon atoms and a fatty acid having 12 to 22 carbon atoms. A primer composition, characterized in that a higher fatty acid nitrogen derivative consisting of the same is added.