JPH0641559B2 - Aqueous dispersion composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Field of Industrial Application) The present invention relates to an aqueous dispersion that can be added to a coating material to impart a lubricating effect to the coating film. The present invention relates to an aqueous dispersion containing a lubricant component that imparts excellent lubricity and does not cause the lubricant to desorb from the surface of the coating film or transfer to the contact product with the coating film and contaminate the contact product with the lubricant.

(Prior Art) Metal products such as iron and aluminum are often printed and painted for the purpose of appearance and prevention of metal corrosion. It is a general practice to add a lubricant to these metal coatings in order to ensure good transfer of the coated plate or product and to prevent scratches on the coating surface during transfer.
As these lubricants, natural waxes such as palm oil or carnauba wax, synthetic waxes, and silicone-based additives have been used.

However, in these conventional lubricants, the lubricant floating on the paint surface comes off due to contact with other substances and stains the non-contact surface, and the additive is extracted by contact with water, solvent, etc. to improve lubricity. There are problems such as aging, cratering, eye holes, etc. on the coated surface, and it has a high degree of lubricity, and there is little detachment from the coating surface or transfer to contact substances At the same time, there has been a demand for the development of a paint lubricant or paint that provides stable lubricity.

Printing, especially for paints on the outer surface of metal cans. The painted plate that has been painted is made into a can through the can making process, and then the contents are filled,
The above characteristics are extremely important for maintaining the performance of the metal can because various mechanical processes are performed after painting, such as sterilization, but the actual situation is that they are not at present satisfactory levels. .

(Problems to be Solved by the Invention) In order to solve the present situation, the present inventors have found that there is very little detachment from the coating film surface or transfer to a contact substance, and changes in lubricity due to environment or composition. We have conducted intensive research to develop a lubricant for paints that has excellent storage stability and does not adversely affect paintability.

[Structure of Invention]

(Means for Solving Problems) As a result, the present inventors have achieved the above object by reacting a wax having a functional group with a silicone resin having a functional group and mixing the product in a coating material. I have found what I can achieve.

That is, the present invention disperses a composition containing a modified silicone resin having at least one functional group selected from an epoxy group, a hydroxyl group and an amino group, and a reaction product of a polyolefin wax or a natural wax having a carboxyl group or a hydroxyl group. An aqueous dispersion composition obtained by dispersing in water in the presence of an auxiliary agent.

As the polyolefin wax having a carboxyl group or a hydroxyl group in the present invention, there is an acid-modified polyolefin wax obtained by copolymerizing or graft-polymerizing ethylene or propylene and a polymerizable carboxylic acid such as acrylic acid, methacrylic acid or maleic acid. , For example, high wax 11 manufactured by Mitsui Petrochemical Co., Ltd.
05A, 2203A, AC-540 manufactured by Allied Company, and the like. Further, as acid-modified polyethylene, AC629, AC680, AC330 manufactured by Allied Company, and high wax 4052E, 4202E manufactured by Mitsui Petrochemical Industry Co., Ltd.
There is. The acid value of these carboxyl group-containing polyolefin waxes is preferably in the range of 10 to 100 KOHmg / g. Further, as the hydroxyl group-containing polyolefin wax, polywax OH42 manufactured by Valeco
There are 5,550,700.

The natural wax having a carboxyl group or a hydroxyl group in the present invention includes a free fatty acid or a free alcohol in its component, for example, carnauba wax (free fatty acid content 3 to 4%; free alcohol content 10 to 12%, described in the same order below), candelilla wax (10-20%; 10-15%),
Plant wax such as wood wax (3.7-5.6%; 1.2-1.6%), animal wax such as beeswax (7-16%; 1-2 pa), lanolin wax (trace amount: 3-5%), montan Wax (acid value 115-175; saponification value 135-17)
Mineral waxes such as 5) can be mentioned. You may use what modified the natural wax and introduce | transduced the carboxyl group or the hydroxyl group.

The modified silicone resin used in the present invention contains a functional group that reacts with a carboxyl group or a hydroxyl group, and as the epoxy group-containing silicone resin, Shin-Etsu Chemical Co., Ltd. KF100T, KF101, KF102, X
-22-3667, X-22-163A, etc., and as a hydroxyl group-containing silicone resin, K manufactured by Shin-Etsu Chemical Co., Ltd.
Examples of F851, X-22-801, X-22-160A and amino group-containing silicone resin include KF393, KF857 and X-22-368 manufactured by Shin-Etsu Chemical Co., Ltd.
0, X-22-161A and the like. In particular, a modified silicone resin that is water-soluble or water-dispersible by modification with ethylene oxide or propylene oxide, which is effective in preventing the occurrence of coating defects such as cissing and eye holes on the coating surface when added to a coating material, is preferable. . Examples of such water-soluble or water-dispersible terminal hydroxyl group-containing silicone resins are KS-506 and KS-496 manufactured by Shin-Etsu Chemical Co., Ltd.
Can be mentioned.

First, the aqueous dispersion of the present invention comprises 5 to 90 parts by weight of a wax and 10 to 95 parts by weight of a modified silicone resin, preferably 3 parts by weight.
0 to 90 parts by weight are mixed so that the total is 100 parts by weight, heated to 150 to 230 ° C. to be melted, and then reacted in the presence or absence of an acid or alkali catalyst. If the amount of the wax used is less than 5 parts by weight, it will be close to that when used alone, which is not preferable. As the acid catalyst used in the reaction between the wax and the modified silicone resin,
Hydrochloric acid, phosphoric acid, p-toluenesulfonic acid, etc. are available, and alkali catalysts are sodium hydroxide, potassium hydroxide, organic amines, etc. The end point of the reaction varies depending on the functional group equivalent of the synthetic resin, the carboxyl group or hydroxyl group equivalent contained in the wax, and varies depending on the intended use, but the wax has a functional group concentration of 5 to 10
It is selected in the range of 0% reduction.

The composition containing the reaction product of the wax and the modified silicone resin is then dispersed in water. In order to make the composition containing the reaction product into an aqueous dispersion, the composition containing the reaction product is brought into a molten state and an emulsifier is added, and this is gradually added to warm water, or The phase may be converted by adding warm water to. As such an emulsifier, a nonionic or anionic emulsifier can be used alone or in combination. Preferable emulsifiers include, for example, stearic acid soap, laurate soap,
Basuf Emalfur 1178C, Necanil 910
Can be mentioned.

When the reaction product contains an acidic group such as a carboxyl group, a basic compound may be used as a dispersion aid and dispersed in water. Also in this case, it is preferable to use an emulsifier together. As the basic compound used for neutralization, alkali hydroxide, ammonia, alkanolamines such as methyldiethanolamine and triethanolamine, and dialkylalkanolamines such as dimethylethanolamine and diethyleneethanolamine can be used. The addition amount of the dispersion aid is preferably 1 to 40 parts by weight with respect to 100 parts by weight of the composition containing the reaction product.

Into the water in which the reaction product is dispersed, a water-compatible organic solvent such as alcohol or cellosolve or a compounding agent for improving the surface of the coating film may be added.

The dispersion thus obtained can be finely dispersed by a disperser such as a homomixer, a homogenizer, a ball mill, a sand mill and a citrator.

As the water-based paint to which the aqueous dispersion composition of the present invention is added, thermosetting paints such as acrylic paints, alkyd paints, polyester paints and epoxy paints are preferable.

The amount of the dispersion of the present invention added to a paint is usually 100
The solid content is in the range of 0.01 to 10 parts by weight based on parts by weight.

Examples will be described below. In the example, "part""%"
Indicates "part by weight" and "% by weight", respectively.

(Example) Example 1 Acid-modified polyethylene wax (Mitsui Petrochemical Industry Co., Ltd.)
Mitsui High Wax 2203A, acid value 30) 30 parts and epoxy resin modified with epoxy groups at both ends (X-22-163)
20 parts of A) was put into a four-necked flask and dissolved by heating. The reaction was carried out at a temperature of 140 ° C for 7 hours, and when the acid value of the resin mixture reached 15 KOHmg / g, the temperature was lowered to 100 ° C, 10 parts of triethanolamine was added,
The reaction product was neutralized with minute stirring. After adding 10 parts of stearic acid soap to the neutralized product, water 480 at 95 ° C was added.
Parts were gradually added over 30 minutes to obtain an aqueous dispersion having a solid content of 20%.

A part (solid content) of this aqueous dispersion was used as a water-soluble polyester resin (Almatex WP616 manufactured by Mitsui Toatsu Chemicals, Inc.).
9) 80 parts and 20 parts of melamine resin (CYMEL 350 manufactured by Mitsui Toatsu Kagaku Co., Ltd.) were mixed into an aqueous polyester coating composition as a component (solid content), and the dry film thickness was 6 on an aluminum plate.
A coating plate sample was prepared by coating so as to have a thickness of μ and heating and curing at 170 ° C. for 10 minutes.

The coated plate obtained above was subjected to the lubricant release property, but no release of the lubricant from the coating film surface was observed. The lubricant release property was observed by an optical microscope for the presence or absence of lubricant particles released from the coating film surface before and after wiping the coating film surface with gauze.

Next, when the dynamic friction coefficient of the coated plate sample was measured, it was 0.10.
Met. When the same sample was boiled for 30 minutes and measured, no change was observed in the dynamic friction coefficient. The dynamic friction coefficient was measured by placing a 5 cm × 5 cm stainless block (load of 500 g) on a coated plate sample and pulling this block at a speed of 15 m / min.

Example 2 An aqueous dispersion was obtained in the same manner as in Example 1 except that carnauba wax (acid value 3 KOHmg / g) was used in place of the acid-modified polyethylene wax.

A lubricant desorption test was conducted on a coated plate prepared using this aqueous dispersion in the same manner as in Example 1, but no desorption of the lubricant was observed.

The coefficient of kinetic friction of the coated plate was measured and found to be 0.
It was 1, and no change was observed after boil treatment.

Example 3 Instead of the acid-modified polyethylene wax in Example 1, oxidized polyethylene wax (Mitsui Petrochemical Industry Co., Ltd.)
Made, Mitsui High Wax 4052A, acid value 20KOHmg /
An aqueous dispersion was obtained in the same manner as in Example 1 except that g) was used.

A lubricant desorption test was conducted on a coated plate prepared using this aqueous dispersion in the same manner as in Example 1, but no desorption of the lubricant was observed.

The coefficient of kinetic friction of the coated plate was measured and found to be 0.
1, after boil treatment was 0.11.

Example 4 An aqueous dispersion was obtained in the same manner as in Example 1 except that montan wax (acid value 20 KOHmg / g) was used in place of the acid-modified polyethylene wax.

A lubricant desorption test was conducted on a coated plate prepared using this aqueous dispersion in the same manner as in Example 1, but no desorption of the lubricant was observed.

The coefficient of kinetic friction of the coated plate was measured and found to be 0.
09, after boil treatment was 0.10.

Example 5 A hydroxyl group-containing water-soluble silicone resin (SH3749 manufactured by Toray Silicone Co., Ltd.) was used instead of the epoxy-modified silicone resin, and an oxidized polyethylene wax (AC629 manufactured by Allied Chemical Co., an acid value of 16 KOHmg) was used instead of the acid-modified polyethylene wax. / G) was used in the same manner as in Example 1 to obtain an aqueous dispersion.

A lubricant desorption test was conducted on a coated plate prepared using this aqueous dispersion in the same manner as in Example 1, but no desorption of the lubricant was observed.

The coefficient of kinetic friction of the coated plate was measured and found to be 0.
After the boil treatment, it was 0.11.

Example 6 An aqueous dispersion was obtained in the same manner as in Example 5 except that the carnauba wax used in Example 2 was used instead of the oxidized polyethylene wax in Example 5.

A lubricant desorption test was conducted on a coated plate prepared using this aqueous dispersion in the same manner as in Example 1, but no desorption of the lubricant was observed.

The coefficient of kinetic friction of the coated plate was measured and found to be 0.
09, after boil treatment was 0.10.

Example 7 An aqueous dispersion was obtained in the same manner as in Example 1 except that a hydroxyl group-containing polyolefin resin (Polywax OH425 manufactured by Bareco Co., Ltd.) was used in place of the acid-modified polyethylene wax.

A lubricant desorption test was conducted on a coated plate prepared using this aqueous dispersion in the same manner as in Example 1, but no desorption of the lubricant was observed.

The coefficient of kinetic friction of the coated plate was measured and found to be 0.
It was 10, and no change was observed after boil treatment.

Example 8 An aqueous dispersion was prepared in the same manner as in Example 1 except that a silicone resin containing amine groups at both ends (X-22-161A manufactured by Shin-Etsu Chemical Co., Ltd.) was used in place of the epoxy-modified silicone resin. Got

A lubricant desorption test was conducted on a coated plate prepared using this aqueous dispersion in the same manner as in Example 1, but no desorption of the lubricant was observed.

The coefficient of kinetic friction of the coated plate was measured and found to be 0.
11, after boil treatment was 0.12.

Example 9 Instead of the epoxy-modified silicone resin in Example 1, a carboxyl group-containing silicone resin (X-22-370) was used.
1E), an aqueous dispersion was obtained in the same manner as in Example 1 except that lanolin wax (OH value 20) was used instead of the acid-modified polyethylene wax.

A lubricant desorption test was conducted on a coated plate prepared using this aqueous dispersion in the same manner as in Example 1, but no desorption of the lubricant was observed.

The coefficient of kinetic friction of the coated plate was measured and found to be 0.
After the boil treatment, it was 0.11.

Example 10 The aqueous dispersion prepared in Example 1 was treated with a water-soluble acrylic resin (manufactured by Mitsui Toatsu Chemicals, Inc., Almatex WA911).
80 parts and 20 parts of melamine resin (CYMEL 350 manufactured by Mitsui Toatsu Chemicals, Inc.) were mixed in an aqueous acrylic paint having a component (solid content), and a coated plate was prepared in the same manner as in Example 1 below.

A lubricant desorption test was conducted on this coated plate, but no lubricant desorption was observed.

The coefficient of kinetic friction of the coated plate was measured and found to be 0.
It was 10, and no change was observed after boil treatment.

Example 11 A coated plate was prepared in the same manner as in Example 9 except that the aqueous dispersion prepared in Example 9 was the aqueous dispersion prepared in Example 2.

A lubricant desorption test was conducted on this coated plate, but no lubricant desorption was observed.

The coefficient of kinetic friction of the coated plate was measured and found to be 0.
It was 10, and no change was observed after boil treatment.

Comparative Example 1 A coated plate was prepared in the same manner as in Example 1 except that the polyester-based coating used in Example 1 was mixed with the microcrystalline wax aqueous dispersion in the same amount as the lubricant solid content of Example 1.

When a lubricant desorption test was conducted on this coated plate, desorption of the lubricant from the coating film surface was observed.

Moreover, when the dynamic friction coefficient of the coated plate was measured,
The value of 0.10 was 0.15 after the boil treatment, and the coating film lubricity was greatly reduced.

Comparative Example 2 The same amount of the lubricant solid content of Example 1 as the aqueous dispersion of the carnauba wax used in Example 2 was blended with the polyester paint used in Example 1 and the same as in Example 1 below. Then a painted board was created.

When a lubricant release test was conducted on this coated plate, the release of the lubricant was found.

Moreover, when the dynamic friction coefficient of the coated plate was measured,
The value of 0.10 was 0.16 after the boil treatment, and the coating film lubricity was greatly reduced.

Comparative Example 3 The acrylic resin paint used in Example 9 was mixed with the montan wax used in Example 4 as an aqueous dispersion in the same amount as the lubricant solid content of Example 9, and the same as in Example 9 below. Then a painted board was created.

When a lubricant release test was conducted on this coated plate, the release of the lubricant was found.

Moreover, when the dynamic friction coefficient of the coated plate was measured,
What was 0.09 became 0.19 after boil treatment, and the lubricity of the coating film decreased significantly.

〔The invention's effect〕

INDUSTRIAL APPLICABILITY The aqueous dispersion composition of the present invention is useful as a compounding agent for paints, and even if the coating film obtained from this coating material is rubbed at room temperature or under heating, the lubricant particles do not fall off from the surface of the coating film. It also shows very good performance compared to conventional lubricants for paints. Such properties are extremely useful for industrial paints, especially for metal cans, crowns, and caps.

Claims (4)

[Claims] 1. A modified silicone resin having 10 to 95% by weight of at least one functional group selected from an epoxy group, a hydroxyl group and an amino group, and a polyolefin wax having a carboxyl group or a hydroxyl group or 5 to 90% by weight of a natural wax. An aqueous dispersion composition obtained by dispersing a composition containing the reaction product of 1. in water in the presence of a dispersion aid. 2. The aqueous dispersion composition according to claim 1, wherein the polyolefin wax is polyethylene oxide or an ethylene- (meth) acrylic acid copolymer. 3. The aqueous dispersion composition according to claim 1, wherein the natural wax is carnauba wax or montan wax. 4. The aqueous dispersion composition according to claim 1, wherein the modified silicone resin is water-soluble or water-dispersible.