JPS5931543B2 - Modifier for synthetic resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a modifier for synthetic resins containing organopolysiloxane as a main ingredient, and particularly to improving molding workability when obtaining synthetic resin molded products, and improving molding properties of synthetic resin molded products. The purpose is to modify surface properties.

Conventionally, attempts have been made to reduce the coefficient of friction on the surface of synthetic resin molded products by imparting lubricity or mold releasability to the surface. For example, paraffin, carnauba wax,
Waxes such as polyethylene, metal soaps, oils and fats,
Alternatively, a method has been proposed in which a silicone oil such as dimethyl silicone oil or phenylmethyl silicone oil is applied to the surface of a molded article or added to a molding resin compound.

Among the above, dimethyl silicone oil in particular has excellent mold release performance and lubrication properties suitable for synthetic resins, and is also inert and has excellent thermal stability, so it is suitable for other types of oil. Although it is widely used, its lubricating performance may not be sufficient depending on the purpose of the molded product, or it may have poor compatibility with synthetic resins, so when added to synthetic resins, it may not meet the intended purpose. There were drawbacks, such as the effects not lasting.

As a result of intensive research to provide a synthetic resin modifier that does not have these drawbacks and exhibits better effects, the present inventors found that the general formula [wherein R1 is a number of carbon atoms of 7 to 21] a valent hydrocarbon group, R2 is a methyl group or phenyl group, R3 is a methyl group or a group represented by the formula -0C0RI, Y is -CF
3 group or a group represented by the formula -(- CF2CF2 inverted (W (in the formula, W represents a hydrogen atom or a fluorine atom, and k is an integer of 1 to 4), l is an integer of 0 to 250, m is 1-1
An integer of 00, n is an integer of 1 to 100, provided that 12<l+
Mfnku300, 12<Mfnku200, m+n>l/
5, and the phenyl group accounts for 10 mol% or less of the total organic groups bonded to silicon atoms. completed.

To explain this, the organopolysiloxane represented by the general formula (I) has the following general formula () (wherein, Z represents a hydrogen atom or a methyl group, and Y, l, m, and n have the same meanings as above. ); and a fatty acid represented by the general formula (R1 in the formula represents a monovalent hydrocarbon group having 7 to 21 carbon atoms). can be easily obtained by carrying out a dehydrogenation reaction in the presence of a catalyst such as a metal catalyst or a chloroplatinic acid catalyst.

In the organohydrodiene polysiloxane compound represented by the above formula (), 1, m, and n are each l20 to
250, m = 1 to 100, n = an integer in the range of 1 to 100, and 12<l+m+n 300) 12<
m+n<200,. Although it is necessary to satisfy the condition m+n>l/5, particularly preferably l+m+n<20
0. ．． It is preferable that m+n>l/4.

If these conditions are not met, the product obtained by reacting with field fatty acids will have poor compatibility with synthetic resins, and the purpose of improving the molding workability of synthetic resins and modifying the surface properties of synthetic resin molded products will not be possible. not achieved. (In the fatty acid represented by the formula, R1 in the formula must be a monovalent hydrocarbon group (including either saturated or unsaturated) having 7 to 21 carbon atoms.

The modifier for synthetic resins containing organopolysiloxane as a main ingredient of the present invention is used by adding it to the molding resin together with other appropriate additives, or by coating it on the surface of the synthetic resin molded product.

The amount added to this molding resin varies depending on the type of resin, the purpose of modification, the compatibility of the resin with the organopolysiloxane added, etc., but generally it is 100 parts by weight of the molding resin. 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight.

If it is less than 0.01 part by weight, the effect will be small;
Even if the amount is more than the weight part, not only can no further effect be expected, but in some cases bleeding, blooming,
This causes problems such as a decrease in the strength of the molded product.

In the case of a method of coating the surface of a synthetic resin molded product, the organopolysiloxane may be applied as is, but
Normally, it is often diluted with an appropriate organic solvent to facilitate the coating operation. Organic solvents used for this purpose include glycols such as methyl cellosolve, ethyl sorosolve, and carbitol; benzene, toluene,
Examples include aromatics such as xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and esters such as ethyl acetate and butyl acetate.

Note that these organic solvents are not limited to one type, and two or more types may be used in combination. The synthetic resins that can be modified are not limited, and effective results can be obtained with any of them, but particularly representative synthetic resins include polyethylene resins, polypropylene resins, and polychlorinated resins. Vinyl resin, polystyrene resin, ABS resin, AS resin, SB
Resin, vinyl chloride monovinyl acetate monopolymer resin, polymethyl methacrylate resin, saturated polyester polyamide resin, polyurethane resin, epoxy resin, phenol resin, amino resin, polycarbonate resin, polyfluorinated olefin resin, cellulose resin, silicone resin,
Examples include polybutadiene resin, alkyd resin, and melamine resin.

By reacting organohydrodiene polysiloxane and fatty acid according to the above method, the modifier of the present invention can be added to these resins, or by coating it on the surface of a molded product, it can be molded as a final product. The surface friction coefficient of the body is reduced, providing lubricity, making it less prone to scratches, and providing mold release properties.

Therefore, it is extremely significant that such improvements in properties can be brought about on the coating surface of a paint mainly composed of a synthetic resin, for example. Furthermore, by adding the modifier of the present invention to a molding resin, the effect of improving molding workability when manufacturing films and other various molded products is provided. Next, reference examples, working examples, and comparative examples will be given to explain in more detail.

However, in the following description, Me and Ph represent a methyl group and a phenyl group. Reference Example: In a reactor equipped with a stirrer, 423.89 oleic acid, 15009 mol of toluene, and 0.169 ml of a 5% isopropanol solution of chloroplatinic acid were charged, and while heating and refluxing, the organohydrodiene polysiloxane compound represented by the formula 10 was prepared.
32 g was added dropwise over 2 hours, and reflux was continued for a further 7 hours.

Next, when low boiling point substances were distilled off under reduced pressure, the viscosity was 69.
8 centistokes (25℃), specific gravity 1.106 (25
A yellow viscous substance 14129 was obtained with a refractive index of 1.4153 (25).

When this material was examined by infrared absorption spectrum analysis and NMR, it was confirmed that it was an organopolysiloxane represented by the following formula. Hereinafter, this will be referred to as S-1. Example 1 A reaction product of epoxy resin Epicoat 1004 (trade name, manufactured by Ciel Chemical Co., Ltd.) and linseed oil in a weight ratio of 1:1 was dissolved in toluene at a concentration of 50% by weight.

For 1 part by weight of this solution, acrylic resin Aron 1001 (
3 parts by weight of Toagosei Co., Ltd. (trade name) was mixed, and the mixture was adjusted with toluene so that the resin concentration was 40% by weight to prepare a paint. The various additives shown in Table 1 were added and mixed to the paint thus obtained in an amount of 0.2% by weight based on the resin content of the paint, and this was applied to 2 aluminum test panels (5 x 10c!n) each.
The sheet was flow-coated, air-dried for 1 hour, and then baked at 105° C. for 20 minutes.

The appearance of the coating surface of the test panel thus produced was examined and various tests (friction coefficient, sliding angle, coating damage) were conducted, and the results were as shown in Table 1.

However, experiment/F6 in the same table. 1 to 5 show comparative examples. Slip angle: coating surface of test panel (5 x 5 (
1-JMoV! ) were placed on top of each other, a load of 2509 was applied to this, and the slip angle was measured.

Paint film damage: The paint film surfaces of test panels (5 x 5 cm.) were placed on top of each other and a load of 250 g was applied to them. Silicone A: Damage to the paint film surface after forcibly sliding was evaluated on the following three levels. .

A: No damage or cloudiness.

B: Slightly hurt and cloudy.

C: Hurt and cloudy.

Silicone B: Example 2 For 100 parts by weight of the white enamel paint of the above composition,
0.2 parts by weight of the various additives shown in 2 were added and mixed, and this was coated on an aluminum test panel.

After being left at room temperature for 7 days, the appearance of the coated film surface was examined and a test was conducted in the same manner as in the previous example, and the results were as shown in Table 2. However, Experimental Waterfalls 10 to 15 are comparative examples. Silicone C: Example: A coating amount of 309% of the above-mentioned transparent paint was applied to printed plywood.
/ A, paint with a roll coater and heat at 60℃.
Heat curing was performed for 5 minutes.

The thus obtained coating surface was examined for peeling force (g/Cm) by adhesive tape, coating damage by adhesive tape, and coating damage in the same manner as in Example 1, and the results are shown in Table 3.
It was as shown in.

However, experiment. /F62l~24 are comparative examples.O Peeling force (9/?): Width 1.8CTfL on the coating surface
The pressure-sensitive cellophane adhesive tape was pressed under a load of 1 kg, and then the adhesive tape was peeled off using a peel tester (manufactured by Toyo Tester Co., Ltd.) to measure the peeling force.

Coating film breakage property: An adhesive tape was pressure-bonded in the same manner as in the above peeling force measurement, and after being left at room temperature for 7 days, the adhesive tape was suddenly peeled off and the state of the coating film surface was observed.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R^1 is a monovalent hydrocarbon group having 7 to 21 carbon atoms, R^2 is a methyl group or a phenyl group, R^3 is a methyl group or a group represented by the formula -OCOR^1, Y is -CF_
3 groups or formulas ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, W represents a hydrogen atom or a fluorine atom, and k is an integer from 1 to 4), l is an integer from 0 to 250, m is an integer from 1 to 100, n is an integer from 1 to 100, provided that 12
≦l+m+n≦300, 12≦m+n≦200) m+n
≧l/5, and phenyl groups account for 10 mol% or less of all organic groups bonded to silicon atoms.