JPS63248877A - Lubricant composition for coating - Google Patents

Abstract

PURPOSE:To provide the titled composition of little elimination of the lubricant from the coating film surface or of little migration of said lubricant into the contacted matter, thus having no adverse effects on coatability, as well as affording coating film with good lubricity, comprising a reaction product from a modified silicone resin and polyolefin wax, etc. CONSTITUTION:The objective composition outstanding in terms of lubricity change caused by the environment and in storage stability, capable of imparting coating film with good lubricating effect, can be obtained by heating to melt a mixture of (A) 5-95wt.% of a modified silicon resin having at least one kind of functional group selected from epoxy, hydroxyl and amino groups (pref. having functional groups at the both ends) and (B) 5-95wt.% of polyolefin wax having carboxyl or hydroxyl group [e.g., polyethylene oxide, ethylene-(meth) acrylic acid copolymer] plus natural wax (e.g. carnauba wax, montan wax).

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Field of Application) The present invention relates to a lubricant composition that can be incorporated into a paint and impart a lubricating effect to the paint film.

The present invention relates to a lubricant composition that provides excellent lubricity to a coating film and prevents the lubricant from desorbing from the surface of the coating film or transferring to objects that come in contact with the coating film and contaminating the objects with the lubricant.

(Prior Art) Fully flexible products such as iron and aluminum are often printed and painted for the purpose of aesthetics and prevention of metal corrosion. A lubricant is generally added to these raw materials for metals in order to facilitate the transfer of painted plates or products and to prevent scratches on the coating surface during transfer. These lubricants have been made of natural waxes such as palm oil or carnauba wax, synthetic waxes, or silicone additives.

However, these conventional lubricants have problems such as: (1) the lubricant floating on the paint surface comes off when it comes into contact with other substances and contaminates the contacted surface, and (2) additives are extracted by contact with water, solvents, etc., causing lubrication. Gender changes over time. ■Ceiling, eye holes, etc. may occur on the painted surface.

It has the following problems: it has a high degree of lubricity and is less likely to detach from the coating surface or transfer to objects it comes in contact with.

There has been a demand for the development of paint lubricants or paints that provide stable lubricity over time.

In particular, in the case of external paint for metal cans, the printed and painted painted plates are made into cans through a can-making process, and then filled with the contents.
Since metal cans go through various mechanical processes such as sterilization treatment after painting, the above characteristics are extremely important to maintain the performance of metal cans, but the reality is that they are currently not at a satisfactory level. .

(Problems to be Solved by the Invention) In order to solve the current situation, the present inventors have found that detachment from the coating surface or migration to the object to be contacted is extremely small.

Also, for paints that have excellent lubricity changes due to the environment and storage stability of the composition, and do not have a negative effect on paintability.
We have been conducting intensive research with the aim of developing ln agents.

(Structure of the Invention) (Means for Solving the Problems) As a result, the present inventors reacted Fuchs having a functional group with a silicone resin having a functional group.

It has been found that the above object can be achieved by incorporating the product into a paint.

That is, 1. The present invention is characterized by containing a reaction product of a modified silicone resin having at least one functional group selected from epoxy groups, hydroxyl groups and amino groups, and polyolefin wax or natural wax having carboxyl groups or hydroxyl groups. This is a lubricant composition for paint.

An example of the polyolefin wax having a carboxyl group or hydroxyl group in the present invention is acid-modified polyethylene obtained by oxidizing polyethylene. These are Allied's AC629°AC680, AC3
30, Hiwax 405 manufactured by Mitsui Petrochemical Industries, Ltd.
2E and 4202E are commercially available.

Also, ethylene or propylene and acrylic acid.

Polymerizable unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, or their acid anhydrides are grafted onto copolymerized methacrylic acid or synthetic waxes mainly composed of polyethylene or polypropylene. Modified polyolefin inwanx obtained by polymerization may also be used, and these include Hiwax 1105A, 2203A, AC340 manufactured by Allied Co., Ltd.
It is available as .

It is desirable that these carboxyl group-containing polyolefin waxes have an acid value in the range of 10 to 100 KOH+mg/H.

Further, the hydroxyl group-containing polyolefin wax is available as Polywax 0H425, 550, 700 manufactured by Valeco.

The natural wax having a carboxyl group or hydroxyl group in the present invention is one that contains free fatty acid or free alcohol in its components.

For example, carnauba wax (3-4% free fatty acid content)
; Free alcohol content 10-12%, hereinafter in the same order. ), candelilla wax (10-20%; 10
~15%), wood wax (3.7~5.6%; 1.2~1.
6%), etc., beeswax (7-16%; 1-
2ba), animal waxes such as lanolin wax (minor amount; 3-5%), montan wax (acid value 115-175;
Examples include mineral waxes having a saponification value of 135 to 175). Natural waxes modified with polymerizable carboxylic acids and the like to introduce carboxyl groups may also be used.

The modified silicone resin used in the present invention is dimethylpolysiloxane or diphenylpolysiloxane.

It has an organopolysiloxane skeleton such as dimethyldiphenylpolysiloxane, and further contains a functional group that reacts with a carboxyl group or a hydroxyl group. These modified silicone resins include epoxy group-containing silicone resins such as KF100T and KFI manufactured by Shin-Etsu Chemical Co., Ltd.
OI, KF102. X-22-3667, X-22-1
63A, etc., and hydroxyl group-containing silicone resins include KF851, X-22-801, and X-2 manufactured by Shin-Etsu Chemical Co., Ltd.
2-160A.

As an amine group-containing silicone resin, Shin-Etsu Chemical Co., Ltd.
Manufactured by KF393. KF857. X-22-3680, X-
22-161A etc. These reactive silicone resins are broadly divided into types with side chains containing functional groups and types with functional groups at both ends. Types with groups are preferable. The reason for this cannot be analyzed at present, but 5i
It is thought that there is a difference in the ease with which hydrolysis of the -0-Si bond occurs. Examples of such silicone resins that are reactive at both ends include X-22-160A and X-22 from the above-mentioned examples.
-161A is mentioned.

The coating lubricant composition of the present invention has modified silicone resin 5
A mixture containing ~95% by weight, preferably 10-70% by weight, and 5-95% by weight, preferably 30-90% by weight of wax is heated to 150-230°C to melt, and then an acid or alkali catalyst is added. React in the presence or absence of The reaction may be carried out by dissolving the raw materials in an organic solvent.

The acid catalysts used at this time include hydrochloric acid, phosphoric acid, p-
There are toluenesulfonic acid, etc., and as an alkaline catalyst,
Examples include sodium hydroxide, potassium hydroxide, and organic amines. When the amount of wax used is less than 5% by weight, it becomes close to the case where modified silicone is used alone, and when the amount of wax used is less than 5% by weight,
If the amount is higher, it will be closer to when wax is used alone,
This is not preferable because the lubricant tends to transfer from the coating surface. The end point of the reaction varies depending on the functional group equivalent of the modified silicone resin and the acid value of the modified polyolefin, and also depends on the intended use, but when the initial acid value is 5 to 100,
% reduction is selected.

The dispersion thus obtained is a homomixer.

Fine dispersion can be carried out using a dispersing machine such as a homogenizer, ball mill, sand mill, attritor, etc.

As the paint in which the lubricant composition of the present invention is blended, thermosetting paints such as acrylic paints, alkyd paints, polyester paints, and epoxy paints are preferred.

The amount of the dispersion of the present invention added to the paint is usually 1/100
The solid content is in the range of 0.01 to 10 parts by weight.

Examples will be described below. In examples, "part""%"
indicate "parts by weight" and "% by weight", respectively.

(Example) Example 1 [Preparation of lubricant dispersion] 30 parts of acid-modified polyethylene wax (Mitsui Hiwax 2203A manufactured by Mitsui Petrochemical Industries, acid value 30) and a silicone resin modified with epoxy groups at both ends (Shin-Etsu Chemical Co., Ltd.) Manufactured by X-22
10 parts of -163A) and 60 parts of xylene were placed in a four-piece flask and melted by heating.

When the reaction was carried out at a temperature of 140 DEG C. for 7 hours, the acid value of the resin mixture, which was initially 22.5 KOH/g, became 11.2 KOH/g. A suspension having a solid content of 15% was obtained by dropping the reaction product solution at 140° C. into 166.7 parts of xylene at room temperature. The resulting suspension was redispersed using a sand mill, and then dispersed using a tube gauge to a maximum of 15 μm.

[Preparation of paint]

50 parts of oil-free alkyd resin (Almatex P-646 manufactured by Mitsui Toatsu Chemicals: solid content 60%) and melamine resin (Imel 350 manufactured by Mitsui Toatsu Chemicals ■: solids content 60%)
33.3 parts, 1.7 parts of the above lubricant dispersion.

15 parts of butyl cellosolve were mixed to prepare an oil-free alkyd/amino baking paint (solid content: 50%).

[Evaluation of lubricity]

Using a roll coater, coat a tin plate (thickness 0.24 +n
) to a uniform dry film thickness of 6 μm.

Baking was performed at 170° C. for 10 minutes with gas open.

Using an optical microscope, we observed the surface of the baked paint film before and after wiping it with gauze.
It was observed that the wax particles adhered to the coating surface and were not removed even by wiping.

Also, the painted board is 20C! 2 x 5G sections
0 sheets are stacked, and a load of 20 kg is applied on top of that, and 50
After being left at ℃ for 5 hours, a white paint was applied to the back side and the transfer to the back side was observed by looking at the repellency of the white paint, but no repellency was observed.

Furthermore, regarding the slipperiness of the surface, 5C1 x 5
Place the stainless steel block (load 500g) from 1, and
The coefficient of dynamic friction was calculated from the tensile load by pulling at a speed of m/min and found to be 0.09.

Comparative Example 1 [Preparation of lubricant] High density polyethylene wax (Mitsui Hiwax 100
P) was heated and dissolved in xylene, and then added dropwise to xylene, and then redispersed using a sand mill and dispersed using a tube gauge to a maximum particle size of 15 μm. The solid content of the obtained dispersion was 15
%Met.

[Preparation of paint]

50 parts of oil-free alkyd resin of Example 1 and 33.3 parts of amino resin, 1.2 parts of the above polyethylene wax dispersion
A baking paint (solid content: 50%) was prepared by mixing 14.8 parts of butyl cellosolve with 0.62 parts of a silicone additive (Paintad M manufactured by Dow Corning; solid content: 10%).

[Lubricant evaluation]

When the state of the coating film surface was observed in the same manner as in Example 1,
It was observed that before the wiping process, polyethylene wax was scattered in spherical shapes on the surface, but after the wiping process, there were no wax particles and all of them were wiped off with the gauze.

In addition, when we investigated the transferability to the back side in the same manner as in Example 1, we found that the white paint applied to the back side showed a repelling phenomenon on the entire surface.
The effect of lubricant transfer to the back surface was observed.

Further, the dynamic friction coefficient was 0.09, which was the same as in Example 1.

Comparative Example 2 A similar dispersion was obtained in the preparation of the lubricant dispersion in Example 1 by heating and melting without performing any reaction, and a paint was prepared and the lubricity was evaluated in the same manner as in Example 1. .

The state of the coating film surface and the coefficient of dynamic friction were the same as in Example 1, but in the test for transfer to the back surface, a repelling phenomenon was observed on the entire surface of the white paint, and the results were inferior to those in Example 1.

Example 2 Acid-modified polyethylene wax (Mitsui Hiwax 405
2E: acid value 20) was used in place of the acid-modified polyethylene wax used in Example 1.

The reaction was carried out in the same manner as in Example 1. The initial acid value of the resin mixture was 15KOH/g, but after the reaction it was 7°6KO
It became H■/g. The preparation and redispersion of the suspension were carried out in the same manner as in Example 1.

Using the obtained dispersion, a paint was prepared in the same manner as in Example 1 and evaluated. The evaluation results were the same as in Example 1.

Example 3 Two dispersions were obtained in the same manner as in Example 1, except that silicone resin X-22-16OA modified with hydroxyl groups at both terminals was used in place of the modified silicone resin used in Example 1. Note that the second reaction was a hydrophilic condensation reaction, and the reaction proceeded while separating the water distilled out during the second reaction.

Using the obtained dispersion, a paint was prepared in the same manner as in Example 1 and evaluated. The evaluation results were the same as in Example 1.

Example 4 Both terminal amino group-modified silicone resin X-22-161A
The procedure was carried out in the same manner as in Example 1, except that the modified silicone resin used in Example 1 was replaced with .

A dispersion was obtained.

Using the obtained dispersion, a paint was prepared in the same manner as in Example 1 and evaluated. The evaluation results were the same as in Example 1.

Example 5 A dispersion was obtained in the same manner as in Example 1, except that the amount used was changed from 16 parts of acid-modified polyethylene wax to 24 parts of silicone resin modified with epoxy groups at both ends.

Using the obtained dispersion, a paint was prepared in the same manner as in Example 1 and evaluated. Detachability from paint film.

The transferability is the same as in Example 1, and the dynamic friction coefficient is 0.08.
Met.

Example 6 A dispersion was obtained in the same manner as in Example 1, except that the amount used was changed to 32 parts of acid-modified polyethylene wax and 8 parts of silicone resin modified with epoxy groups at both ends.

Using the obtained dispersion, a paint was prepared and evaluated in the same manner as in the example. Detachability from paint film.

The transferability is the same as in Example 1, and the dynamic friction coefficient is 0.12.
Met.

Example 7 In place of the modified silicone resin used in Example 1, a modified silicone resin (molecular weight 3000), which is a 5/1 (molar ratio) copolymer of diphenylsiloxane/dimethylsiloxane and has alcoholic hydroxyl groups at both ends, was used. The reaction was carried out in the same manner as in Example 1 except for the following. The acid value of the resin mixture was initially 22.5 KOH/g, but after the reaction it was 9.8.
KOH■/g. The suspension was prepared and redispersed in the same manner as in Example 1.

Using the obtained dispersion, a paint was prepared in the same manner as in Example 1 and evaluated. Detachability from paint film.

The transferability is the same as in Example 1, and the dynamic friction coefficient is 0.12.
Met.

Example 8 A dispersion was obtained in the same manner as in Example 1 except that a hydroxyl group-containing polyolefin wax (Polywax 0H425, manufactured by Bareco) was used in place of the acid-modified polyethylene wax.

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

Using the obtained dispersion, a paint was prepared in the same manner as in Example 1 and evaluated. Detachability from paint film.

The transferability is the same as in Example 1, and the dynamic friction coefficient is 0.13.
Met.

Example 9 A dispersion was obtained in the same manner as in Example 1 except that carnauba wax was used instead of acid-modified polyethylene wax.

Using the obtained dispersion, a paint was prepared in the same manner as in Example 1 and evaluated. Detachability from paint film.

The transferability is the same as in Example 1, and the coefficient of dynamic friction is 0.09.
Met.

Example 10 A dispersion was obtained in the same manner as in Example 1 except that montan wax was used instead of acid-modified polyethylene wax.

Using the obtained dispersion, a paint was prepared in the same manner as in Example 1 and evaluated. Detachability from paint film.

The transferability is the same as in Example 1, and the dynamic friction coefficient is 0.10.
Met.

Example 11 In Example 1, carboxyl group-containing silicone resin (X-22-370
1E) A dispersion was obtained in the same manner as in Example 1, except that lanolin wax (OHH2O2) was used instead of acid-modified polyethylene wax.

Using the obtained dispersion, a paint was prepared in the same manner as in Example 1 and evaluated. Detachability from paint film.

The transferability is almost the same as in Example 1, and the coefficient of dynamic friction is 0.
It was 13.

〔Effect of the invention〕

Even when a coating film obtained from a coating composition containing the coating lubricant composition of the present invention is rubbed at room temperature or in a heated, subdued state, the lubricant particles do not fall off the coating surface, and are less likely to be transferred upon contact. It shows extremely better performance than conventional paint lubricants. Such performance is extremely useful for industrial coatings, especially for coating the exterior of metal cans, crowns, and can knobs.

Claims (1)

[Claims] 1. A modified silicone resin having at least one functional group selected from epoxy groups, hydroxyl groups, and amino groups;
A lubricant composition for paints, characterized by containing a polyolefin wax having a carboxyl group or a hydroxyl group, or a reaction product of a natural wax. 2. The lubricant composition for paint according to claim 1, wherein the polyolefin wax is polyethylene oxide or ethylene-(meth)acrylic acid copolymer. 3. The lubricant composition for paint according to claim 1, wherein the natural wax is carnauba wax or montan wax. 4. The lubricant composition for paint according to claim 1, wherein the modified silicone resin having functional groups is a modified silicone resin having functional groups at both ends.