JPH02150404A - Curing accelerating catalyst - Google Patents

Abstract

PURPOSE:To obtain the title catalyst used for coating and molding material by bringing a specific tetrapod like zinc oxide whisker into contact with a solution, etc., of a specific curing accelerator such as an organotin compound and drying the treated whisker. CONSTITUTION:The aimed catalyst obtained by bringing (A) a tetrapod like zinc oxide whisker consisting of a nucleus part and needle crystal part extending in tetra-axial direction different from the nucleus part and being 0.7-14mum in diameter of base of the above-mentioned needle crystal part and 3-200mum in length from the base of the above-mentioned needle crystal part to the tip into contact with (B) a solution or slurry of curing accelerator selected from a group of an organotin compound (e.g. dibutyltinoxide or dibutyl tin laurate), peroxide (e.g. benzoyl peroxide), organic amine (e.g. triethylamine), organic acid (e.g. dinonylnaphthalenedisulfonic acid), ammonium salt and metal chelate compound and drying the treated whisker.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a curing accelerating catalyst, and more particularly to a curing accelerating catalyst used in paints or molding materials containing zinc oxide as an extender and a curing accelerator.

Conventional paints and molding materials use various resins as their main ingredients, and are hardened by drying at room temperature or baking. Furthermore, these often contain zinc oxide as a wood pigment, white pigment, etc., and various catalysts are added to further promote curing. For example, in the case of urethane resins, organotin compounds as block dissociation promoters for blocked isocyanates, various peroxidation catalysts for unsaturated polyester resins, various acid f-type or polymerization dryers, fatty acid modification synthesis, etc. Various metal soaps such as 1 fats and fats, organic amines such as tertiary amines and bases such as ammonium salts are used for epoxy resins, and acids such as organic acids and metal chelate compounds for amine resins.

The purpose of adding such a so-called curing accelerator is to eliminate as much as possible the non-uniformity of hardness, such as the top drying of the coating film and the red hardness inside.

However, when adding and mixing extender pigments and accelerators to the coating M or molding material, it is still difficult to achieve uniform distribution even after sufficient stirring, and this results in problems such as the daily concentration of the catalyst and the non-uniformity of curing inside the film layer. Problems such as the delay in stiffness due to

Problems to be Solved by the Invention Therefore, zinc oxide is allowed as an extender pigment, and in paints or molding materials to which a curing accelerator is added, hardening of the inside of the coating film or the inside of the molded body can be achieved uniformly and in a short time. There has been a demand for a catalyst that can be used in various ways, and it is an object of the present invention to meet this problem.

Means for Solving the Problems According to the present invention, the above object of the invention is comprised of a core and an acicular crystal part extending from the core in four different axial directions, and the diameter of the base of the acicular crystal part is , 0.7-14
[mu]m and the length from the base to the tip of the needle-like crystal part is 3 to 200 [mu]m. This is achieved by using a hardening promoter obtained by contacting with a solution or slurry of a hardening promoter selected from the group consisting of salts and metal chelate compounds and drying.

The present inventors previously proposed that high-purity acid-monomerzinc whiskers are composed of a core and needle-like crystal parts extending from the core in four different axial directions, and the diameter of the base of the needle-like crystal part is 0.7 mm. ~14μm
and the length from the base to the tip of the needle-like crystal part is 3
We succeeded in producing tetrabot-like zinc oxide whiskers with a diameter of ~200 μm on an industrial scale using a new manufacturing method that we developed independently.
No. 63-41329 and No. 63-41330.

The present invention is one of the inventions related to the use of a novel acid C arsenic zinc oxide whisker according to the same production method, but the zinc oxide whisker has a special tetrapot-like shape and has an extremely low bulk density. Zinc acid itself is hardly soluble in water,
In view of the fact that it is extremely stable against heat, and is also used as a catalyst for dehydrogenation and hydrogenation reactions, and is often used as a white pigment or extender pigment in coating films 1, etc., the above-mentioned tetrapod-like oxidized As a result of research into the use of zinc whiskers as a catalyst component, we discovered that they are extremely useful as carriers for specific hardening agents added to paints or molding materials, and completed the present invention. I ended up doing it.

That is, the first group of curing accelerator compounds supported on the tetrapot-shaped at-zinc whiskers in the present invention are organotin-f-sulfur compounds used as deblocking agents for block isocyanates as raw materials for polyurethane. Specific examples of such compounds include dibutyltin oxide, dibutyltin laurate, dibutyltin maleate, dimethyltin oxide, and the like.

The second group of compounds includes various peracids used as radical generating sources in unsaturated polyester resins, such as benzoyl peroxide, lauroyl peroxide, acetyl peroxide, t-butyl hydroperoxide, and cumene hydroperoxide. , MEK peroxide, dicumyl peroxide, etc.

The third group of f-hybrid compounds is cobalt, manganese, barium, which is used as a decomposition accelerator called dryer.
Carboxylate salts of metals such as cerium, lead, zinc, calcium, titanium, zirconium, iron, copper, tin, and molybdenum;
These include tertiary amines such as -(2-hydroxyethyl)tetrahydroquinoline, quaternary ammonium salts, acids such as para-toluenesulfonic acid, and dinonylnaphthalenedisulfonic acid.

In addition to these, any curing accelerator other than amphoteric acids or acids or bases in which zinc oxide forms a complex salt can be suitably used for the purpose of the present invention.

These curing accelerators are usually dissolved or dispersed in water or an organic solvent, and the above-mentioned zinc oxide whiskers are brought into contact with the curing accelerator and dried to obtain a zinc oxide whisker-supported catalyst.

As a method for preventing the hardening accelerator from coming into contact with the tin oxide whiskers, in addition to immersing them in the above solution or dispersion, methods such as bringing the whiskers into contact with the solution or dispersion in a fluidized state in an atomized state have been adopted. good.

The hardening accelerator catalyst of the present invention allows the addition of zinc oxide as an extender pigment or a white pigment, and the supported catalyst is added to a paint or molding material as a curing accelerator. It is used in place of drugs or as a partial substitute for them.

By using the hardening accelerator catalyst of the present invention, the curing accelerator can be uniformly distributed in the paint or molding material, mainly based on the uniform dispersibility of the tetrapot acid (zinc whisker carrier), and Uniform hardening of the material can be achieved.

Furthermore, since the zinc oxide whiskers themselves can be used as extender pigments and white pigments, they do not cause any inconvenient problems due to being mixed in as unnecessary foreign substances like catalyst carriers in ponds. Tetrapotate acid [zinc whiskers have a special shape and a small bulk density, which makes them extremely advantageous as a catalyst support for the above-mentioned hardening promoter. Furthermore, since it is extremely stable against heat, it does not melt at normal paint baking temperatures, molding temperatures, or curing temperatures, and can fully exhibit its filler function.

The present invention will be explained below with reference to Examples.

(Example) 20 parts of tetra-shaped whiskers were mixed in a toluene solution of 20 parts of 25% lead naphthenate dissolved in 200 parts of toluene in a beaker for 15 minutes, and after 10 minutes, the toluene was removed under reduced pressure and dried. Obtain catalyst body (1).

120.5 parts of the catalyst fl was added to 210 parts of an oxidative polymerization type anti-corrosion anti-rust paint (trade name: Cyanamid Hergon Undercoat Red Rust (manufactured by Nippon Paint)).

(Comparative example) 210 parts of the above anti-rust paint and 2.0 parts of 25% naphthenic acid button
part was added.

The above paint was applied to a matte steel plate and glass plate of 150 order x 7011IIll x 0.8 strokes with a dry film thickness of 100μ, and
The state of the coating film was evaluated after being left at 0°C for 4 hours and 64 hours.

Surface drying: A finger is pressed onto the surface of the coating film, and judgment is made based on the adhesion of the paint to the fingerprint and the finger. Fingerprints and adhesion to fingers A finger was pressed against the film on a curable glass plate, and the shift and tear of the coating film was determined based on JIS-5400.○: There was no shift of the coating film.

Claims (1)

[Claims] Consisting of a core and a needle-like crystal part extending from the core in four different axial directions, the diameter of the base of the needle-like crystal part is 0.7 to 14
μm and the length from the base to the tip of the needle-like crystal part is 3 to 200 μm. A curing accelerating catalyst obtained by contacting with a solution or slurry of a curing accelerator selected from the group consisting of compounds and drying.