JPS6244786B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel modifier for synthetic resins with improved 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 release properties to the surface.For example, waxes such as paraffin, carnauba wax, polyethylene wax, and metal soaps A method has been proposed in which silicone oils such as oils and fats or silicone oils such as dimethyl silicone oil and phenylmethyl silicone oil are applied to the surface of the molded article or added to the molding resin compound. Among the above, dimethyl silicone oil in particular has excellent mold release performance, has lubricating properties suitable for synthetic resins, and is inert and has excellent thermal stability, so it is widely used. However, the lubricating performance may not be sufficient depending on the intended use of the molded product, or the desired effect may not last when added to synthetic resins due to poor compatibility with synthetic resins. There were flaws. The present inventors first developed a general formula for the purpose of eliminating the above-mentioned drawbacks in modifiers for synthetic resins. [In the formula, R' is a monovalent hydrocarbon group having 7 to 21 carbon atoms,
R'' is a methyl group or a phenyl group, R is a methyl group or a group represented by the formula -OCOR', and Y' is -CF ₃
A group or a group represented by the formula - (CF ₂ CF ₂ 〓〓〓W (in the formula, W represents a hydrogen atom or a fluorine atom, and k' is an integer from 1 to 4), l' is a group from 0 to 250. Integer, m' is an integer from 1 to 100, n' is an integer from 1 to 100, provided that l'+
m′+n′≦300, m′+n′≧l′/5, and the phenyl group is 10 out of all the organic groups bonded to the silicon atom.
We have proposed a modifier for synthetic resins containing as a main ingredient an organopolysiloxane represented by the following formula (see JP-A-56-41256). However, the inventors of the present invention continued their intensive research and found that although the above-mentioned modifiers do indeed exhibit excellent lubricating performance, they were not sufficiently compatible with synthetic resins, so they were added to transparent resins in particular. When blended, there is a problem that turbidity occurs, and therefore it is difficult to use it for synthetic resins to obtain molded products that require transparency. Since the organopolysiloxane that is said to have hydrolyzable carboxysilyl groups, there is a problem that the performance deteriorates over time in a high temperature and high humidity atmosphere, especially in surface treatment systems. I found out that
Although there are shortcomings in the prior art, in order to solve these problems, further research has been carried out and the present invention has been completed. That is, the present invention provides the general formula [In the formula, R ¹ is a monovalent hydrocarbon group having 7 to 21 carbon atoms, R ² is a methyl group or the formula -CH (C ₆ H ₅ ) CH ₂ CH ₂ OCOR ¹ ......(ii) (wherein R ¹ has the same meaning as above), Y is -C _k F _2k+1 ......(iii) (where k is an integer from 1 to 8) perfluorohydrocarbon group represented by ), l is an integer of 0 to 250, m
is an integer from 0 to 100, n is an integer from 1 to 100, where l
+m+n≦300, m+n≧l/10] The present invention aims to provide a modifier for synthetic resins containing an organopolysiloxane as a main ingredient. The modifier for synthetic resins according to the present invention will be explained in detail below. The organopolysiloxane used as the main ingredient in the present invention is represented by the above-mentioned general formula (i), in which R ¹ represents a monovalent hydrocarbon group having 7 to 21 carbon atoms; For example, n−C ₇ H ₁₅ −, n
−C ₉ H ₁₉ −,

[Formula] C ₁₁ H ₂₃ −, C ₁₃ H ₂₇ −, C ₁₇ H ₃₅ −, C ₁₇ H ₃₃ −, C ₁₇ H ₃₁ −,
C ₂₁ H ₄₃ -, etc., and R ² represents a methyl group or a 1-phenyl-3-acyloxypropyl group represented by the above formula (ii), and this formula (ii)
As R ¹ therein, the same groups as mentioned above can be mentioned. In addition, sufficient lubricity cannot be obtained from the above-mentioned siloxane in which R ¹ has 6 or less carbon atoms,
On the other hand, if the number is 23 or more, the performance will not improve commensurately with the increase in the number of carbon atoms, and the melting point will increase, making it easier to cause blooming (a state where the surface of the molded product looks like powder). Become. Furthermore, Y is a perfluorohydrocarbon group represented by the above-mentioned formula (iii), and k in this formula is an integer of 1 to 8. l, m and n in the general formula (i) are each l=
Indicates an integer in the range of 0 to 250, m = 0 to 100, n = 1 to 100, and the relationship between l, m, and n is l
It is necessary to satisfy the conditions of +m+n≦300 and m+n≧l/10, particularly preferably l+m
It is desirable that +n≦200 and m+n≧l/8. Those containing organopolysiloxane as a main ingredient that do not satisfy these conditions have poor compatibility with synthetic resins, and cannot achieve the objectives of improving the moldability of synthetic resins and modifying the surface properties of synthetic resin molded products. The above general formula (i) used as the main ingredient in the present invention
For example, the organopolysiloxane represented by the general formula (In the formula, Z is a hydrogen atom or a methyl group,
Y, l, m and n have the same meanings as above) and the general formula C ₆ H ₅ CH=CHCH ₂ OCOR ¹ ......(v) (wherein R ¹ has the same meaning as above) It can be easily obtained by reacting an ester represented by (which has the same meaning as ) in the presence of a platinum-based catalyst or the like. 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. Around,
The amount is in the range of 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, while if it is more than 20 parts by weight, not only will no further effect be expected, but in some cases it may cause problems such as bleeding, blooming, and a decrease in the strength of the molded product. It begins to occur. In the case of applying the organopolysiloxane to the surface of a synthetic resin molded product, the organopolysiloxane may be applied as is, but it is usually necessary to dilute it with an appropriate organic solvent to make the application process easier. often,
Organic solvents used for this purpose include glycols such as methyl cellosolve, ethyl cellosolve and carbitol, aromatics such as benzene, toluene and xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate,
Examples include esters such as butyl acetate, chlorinated hydrocarbons such as trichloroethylene and tetrachloroethane, and fluorinated hydrocarbons such as trifluorotrichloroethane. 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 resin, polypropylene resin, and polyvinyl chloride resin. , polystyrene resin, ABS resin,
AS resin, SB resin, vinyl chloride-vinyl acetate copolymer resin and partially saponified products thereof, polymethyl methacrylate resin, saturated polyester resin, polyamide resin, polyurethane resin, epoxy resin,
Examples include phenolic resins, amino resins, polycarbonate resins, cellulose resins, silicone resins, and alkyd resins. Adding the modifier of the present invention to these resins or
Alternatively, by applying it to the surface of the molded product, the final product of the molded product has the effect of reducing its surface friction coefficient, giving it lubricity, making it less likely to get scratches, and giving it mold releasability. . 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: Cinna Milka plate in a reactor with a stirrer
288g, toluene 600g and 0.15g of a 5% isopropanol solution of chloroplatinic acid were heated to 110°C and while stirring, the formula 247 g of the organohydrodiene polysiloxane represented by was gradually added dropwise over a period of 1 hour, and after the addition was completed, reflux was continued for an additional 8 hours. At this point, the residual Si--H bonds in the reaction product were quantified and the reaction rate was found to be 94.3%. Next, low boiling point substances were distilled off under reduced pressure.
Viscosity 1472cS (25℃), specific gravity 1.034 (25℃), refractive index
520.6 g of a pale yellow viscous substance with a temperature of 1.4639 (25° C.) was obtained. This substance has the formula from IR and NMR It was confirmed that the main component was a polysiloxane represented by (hereinafter referred to as S-1). S-2 to S-8 were synthesized by reacting organohydrodiene polysiloxane and fatty acid cinnamyl ester according to the above method. The melting point, specific gravity, viscosity and refractive index of the polysiloxanes S-2 to S-8 obtained above were examined and the results are shown in Table 1 below.

[Table] Example 1 A reaction product of epoxy resin Epicote 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. This solution 1
Three parts by weight of acrylic resin Aron 1001 (trade name, manufactured by Toagosei Co., Ltd.) was mixed with each part by weight, and the mixture was adjusted with toluene so that the resin concentration was 40% by weight to obtain a paint. The various additives shown in Table 2 were added and mixed to the paint thus obtained in an amount of 0.1% by weight based on the resin content of the paint, and this was applied to an aluminum test panel (5 x 10 cm).
Flow-coat each two sheets and air dry for 1 hour at 105℃.
Bake 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 2. Slip angle: The coated surfaces of test panels (5 x 5 cm) were placed one on top of the other, a load of 250 g was applied, and the slip angle was measured. Paint film damage: The paint film surfaces of the test panels (5 x 5 cm) were stacked on top of each other, a load of 250g was applied to them, and the damage to the paint film surface after forcibly sliding was measured as follows:
Evaluated in stages. A: No damage or cloudiness. B: Slightly hurt and cloudy. C: Hurt and cloudy.

[Table] Example 2 Betsukosol ER-3400 (alkyd resin, manufactured by Nippon Reichhold) 38 parts by weight Super Betsukamine G-821 (butylated melamine resin, manufactured by Nippon Reichhold) 20 〃 Titanium oxide 30 〃 Xylene 12 〃 0.3 parts by weight of the various additives shown in Table 3 were added and mixed to 100 parts by weight of the white enamel paint of the above composition, and this was applied to an aluminum test panel. After being left at room temperature for 7 days, the appearance of the coated film surface was examined and the coefficient of dynamic friction and sliding angle were measured, and the results were as shown in Table 3. Dynamic friction coefficient: using HEIDON-14 type measuring machine,
Measurements were made under the conditions of a load of 100 g, a speed of 50 mm/min, and a temperature of 25°C.

[Table] Example 3 Acrylic resin A-801 (acrylic resin, manufactured by Nippon Reichhold Co., Ltd.) 100 parts by weight Burnock D-750 (urethane resin, manufactured by Nippon Reichhold Co., Ltd.) 15 parts by weight xylene 4 Additives (Table - 4) 1.5 The transparent paint with the above formulation was applied onto printed plywood using a roll coater at a coating amount of 30 g/m ² and cured by heating at 60° C. for 15 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 4. It was hot. Peeling force (g/cm): After pressing a pressure-sensitive cellophane adhesive tape with a width of 1.8 cm on the coating surface with a load of 1 kg, the peeling force is determined by peeling off the adhesive tape using a peel tester (manufactured by Toyo Tester Co., Ltd.). was measured. 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.

[Table] Example 4 Using a small kneader, 100 parts by weight of polystyrene with an average degree of polymerization of 1700 and 1 part by weight of the additives shown in Table 5 below were melt-kneaded at a temperature of 200°C for 10 minutes. Compression molding was performed at a temperature of 200°C and a pressure of 100 kg/cm ² to produce a sheet with a thickness of 2 mm. When this sheet was examined for appearance, friction and abrasion properties, fluidity and bending strength, the results shown in Table 5 below were obtained. Appearance: The transparency of the sheet was visually observed and evaluated on the following three scales. A: Transparent B: Semi-transparent C: White opaque Friction and abrasion properties: Using a tester made by Toyo Baldwin Co. ^, Ltd., steel (CS- 45), the amount of wear after 10 minutes of friction was measured. Fluidity: 200℃ using Koka type flow tester,
The outflow rate was measured under the conditions of a load of 40 kg and a nozzle size of 1 mmφ x 10 mm. Bending strength: 80cm long and 10cm wide from the formed sheet
Cut out a test piece with a distance between fulcrums of 32 mm and a loading speed of
Measurement was performed at 1.5 mm/min.

【table】

Claims (1)

[Claims] 1. General formula [In the formula, R ¹ is a monovalent hydrocarbon group with 7 to 21 carbon atoms, R ² is a methyl group or the formula -CH (C ₆ H ₅ ) CH ₂ CH ₂ OCOR ¹ (herein, R ¹ is the same as above) 1-phenyl-3-acyloxypropyl group represented by -C _k F _2k+1 (where k is an integer from 1 to 8), l is an integer from 0 to 250, m
is an integer from 0 to 100, n is an integer from 1 to 100, where l
+m+n≦300, m+n≧l/10] A modifier for synthetic resins comprising an organopolysiloxane as a main ingredient.