JPH0443940B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an organopolysiloxane lubricant, and particularly to an organopolysiloxane lubricant useful for imparting durable and excellent lubricity or mold release properties to synthetic resins or synthetic rubbers. It is. Conventionally, synthetic resins or synthetic rubbers have been used in a wide range of applications such as molded products, cast products, laminates, films, fibers, foams, adhesives, and paints. Since it requires lubricity or mold release properties, attempts have been made to improve its properties by adding additives such as silicone oil, wax, higher alcohols, and metal soaps. In particular, the addition of silicone oil significantly improves lubricity and mold release properties, but it lacks compatibility with the resin, so the silicone oil separates from the resin and oozes out, causing various problems. ing. In order to improve this, for example,
Publication No. 121344 mixes silicone oil and silicone rubber with a thermoplastic resin, but it cannot sufficiently prevent oozing of the silicone oil, and because the silicone rubber is mixed, the original properties of the thermoplastic resin are lost. The downside is that it changes. Furthermore, Japanese Patent Publication No. 52-6751 discloses a compound containing an organopolysiloxane having an -OCOR' group (R' is a substituted or unsubstituted monovalent hydrocarbon group) directly bonded to a silicon atom in a vinyl chloride resin. However, since the -OCOR' group is directly bonded to the silicon atom, it is easily hydrolyzed and gels due to moisture in the air, which significantly impairs the lubricity and appearance of the resin. Also, JP-A-56-41256
In the publication, as a modifier for synthetic resins, -CH ₂ CH ₂ Y group, [Y
is _-CF3 group or ( _-CF2CF2 ) _-kW ( _W represents a hydrogen atom or a fluorine atom, k is an integer from 1 to 4)]
An organopolysiloxane having -OCOR ¹ (R ¹ is a monovalent hydrocarbon group having 7 to 21 carbon atoms) is disclosed, but as mentioned above, ^one -OCOR group is directly bonded to a silicon atom. Therefore, it has the disadvantage that its properties change over time due to moisture absorption and decomposition. As a result of intensive research into organopolysiloxane lubricants, particularly lubricants for synthetic resins or synthetic rubbers that do not have the above-mentioned drawbacks, the present inventors have found that synthetic resins or synthetic rubbers or additives blended therewith. By blending an organopolysiloxane that has a specific functional group that is easy to bond with and provides compatibility, the organopolysiloxane does not ooze out and provides durable, excellent lubricity and mold release properties. We have discovered that it is possible, and have arrived at the present invention. That is, in the present invention, the total number of siloxane units in one molecule is 5 to 1000, and the siloxane unit is an epoxy group, a carboxyl group, a hydroxyl group, or an alkoxy group that is bonded to a silicon atom via an alkylene group as a functional group. The ratio of the number of functional groups to the total number is
This invention relates to an organopolysiloxane lubricant whose main ingredient is an organopolysiloxane having a ratio of 100:2 to 100:50. The organopolysiloxane used as the lubricant of the present invention may have a linear, branched or network molecular shape, but preferably a linear organopolysiloxane. Epoxy group, carboxyl group, bonded to silicon atom via alkylene group,
At least one hydroxyl group or alkoxy group may be present in one molecule, and its position is not particularly limited, and it may be present at the end of the molecular chain, within the molecular chain, or both. Here, the epoxy group is

[Formula] In addition to the group

Contains an epoxycyclohexyl group such as [Formula]. Examples of alkylene groups that act as bridges between these functional groups and silicon atoms include ethylene, propylene, and butylene groups. Organic groups bonded to silicon atoms other than this alkylene group include monovalent hydrocarbon groups,
Examples thereof include methyl group, ethyl group, propyl group, octyl group, pentadecyl group, cyclohexyl group, phenyl group, and β-phenylethyl group. A methyl group is preferred from the viewpoint of lubricity and mold release properties. However, from the standpoint of compatibility, it is preferable that synthetic resins such as polyethylene and polypropylene have an alkyl group having 5 to 30 carbon atoms in addition to the methyl group, while polystyrene and the like preferably have an alkyl group other than a methyl group. preferably has a phenyl group or a β-phenylethyl group. The total number of siloxane units (degree of polymerization) in one molecule of the organopolysiloxane used is in the range of 5 to 1000. If it is smaller than this range, the lubricity or mold release properties will decrease, and if it is larger than this range, the viscosity will decrease. This is because the temperature is too high and it becomes difficult to handle. In view of lubricity, mold release properties, and handling, the total number of siloxane units in one molecule is preferably in the range of 20 to 500. The ratio of the number of functional groups to the total number of siloxane units contained in one molecule is preferably in the range of 100:2 to 100:50. When using a particularly preferable synthetic resin or synthetic rubber as a target for imparting lubricity or mold release properties, the amount used depends on the type of synthetic resin or synthetic rubber, the type of organopolysiloxane and the density of its functional groups, The amount of organopolysiloxane is usually 0.05 to 20 parts by weight, preferably 0.5 parts by weight, per 100 parts by weight of synthetic resin or synthetic rubber, although it is not limited as it varies depending on the purpose of lubricity or mold release.
Used in the range of ~10 parts by weight. If it is less than 0.05 part by weight, the effect of lubricity or mold release is small;
This is because if the amount exceeds 20 parts by weight, it is not only economically disadvantageous, but also affects the inherent properties of the synthetic resin or synthetic rubber. The organopolysiloxane of the present invention can be used in the form of liquid, solution, emulsion, or paste, and may be added to or blended into the object to impart lubricity or mold release properties, or may be applied or impregnated. . In short, any method that can impart lubricity or mold releasability to the object can be used. An example of a method for producing the organopolysiloxane of the present invention is the addition reaction described in Japanese Patent Publication No. 33-9969 _. It can be easily obtained by carrying out an addition reaction of a functional group-containing unsaturated compound represented by =CHCOOH, CH ₂ =CHCH ₂ OH, etc. in the presence of a platinum catalyst. Suitable objects that impart lubricity or mold release properties are conventionally known synthetic resins or synthetic rubbers. Naturally, synthetic resins include thermoplastic resins and thermosetting resins. These synthetic resins and synthetic rubbers include polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyamide, polyester, polyurethane, polyacrylonitrile, polyvinylidene chloride, polystyrene,
Polycarbonate, polyvinyl fluoride, polyacrylic ester, polymethacrylic ester, polyvinyl alcohol, polyvinyl acetal, polyvinyl formal, epoxy resin, silicone resin, alkyd resin, melamine resin, cellulose resin, phenolic resin, vinyl chloride-vinylidene chloride co. Polymer, vinyl chloride-methyl acrylate copolymer, vinyl chloride-methyl methacrylate copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-styrene copolymer, vinyl chloride-ethylene copolymer, styrene-acrylonitrile Copolymer, methacrylic ester-acrylic ester copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, vinyl acetate-vinyl chloride copolymer, vinyl acetate-ethylene copolymer, vinyl acetate - Acrylic acid copolymer, vinyl acetate-acrylonitrile copolymer, vinyl acetate-acrylic acid ester copolymer, vinyl acetate-maleic acid copolymer, vinyl acetate-styrene copolymer, vinyl acetate-polyvinyl alcohol copolymer , vinyl acetate-vinyl chloride-polyvinyl alcohol copolymer, vinyl acetate-
Examples include vinyl chloride-ethylene copolymer, isoprene rubber, chloroprene rubber, fluorine rubber, polyurethane rubber, polyether rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, butyl rubber, acrylic rubber, and acrylonitrile-butadiene rubber. Note that synthetic rubber does not normally include natural rubber, but since its molecular structure is similar to isoprene rubber, the synthetic rubber referred to in the present invention includes natural rubber. Two or more of the exemplified synthetic resins and synthetic rubbers may be used in combination. Among these, particularly preferred are synthetic resins such as vinyl chloride resins, vinyl acetate resins, and polyurethane resins, and ethylene-propylene-diene rubbers as synthetic rubbers. The term "system" as used herein is meant to include all copolymers or mixtures containing it. The form of synthetic resin or synthetic rubber is liquid, solution,
It can be used in any form: emulsion, paste, latex, powder, or solid. For example, molded products, cast products, laminates, films, fibers,
It can take the form of adhesive, foam, paint, etc. depending on the application. The organopolysiloxane of the present invention and either one or both of the synthetic resin and the synthetic rubber,
When used as a solution, an organic solvent may be used, and when used as an emulsion, a surfactant can be used. In addition, various conventionally known additives can be added to one or both of them. For example, dry method silica,
Wet process silica, magnesium silicate, aluminum silicate, calcium carbonate, clay, mica, talc, titanium oxide, aluminum oxide, magnesium oxide, red iron oxide, magnetic iron oxide, various metal powders, carbon black, asbestos, glass fiber, glass bulbs , phthalates, phosphoric esters, metallic soaps, silicone oils, silane coupling agents, rosins, isocyanates, waxes, higher alcohols, organic tin fatty acid salts, plasticizers, stabilizers, flame retardants, ultraviolet absorbers, lubricants , an antistatic agent, an antioxidant, an antifungal agent, a foaming agent, a coloring agent, an adhesion promoter, and the like can be blended. The organopolysiloxane according to the present invention can be used for all purposes of synthetic resins or synthetic rubbers suitable for imparting lubricity or mold release properties. Examples include molded products, cast products, laminates, films, fibers, foams, adhesives, paints, etc. This organopolysiloxane can be blended with the functional groups of organopolysiloxane and the synthetic resin, synthetic rubber, or by adding, blending, coating, impregnating, or dipping into the synthetic resin or synthetic rubber. Because it has a strong affinity with additives, it does not ooze out and can provide excellent, durable lubricity and mold release properties. For example, when blended into a molded product, it has the effect of an internal lubricant or an internal mold release agent, and when applied to the surface of a molded product, or when molded by applying it to the inner surface of a molding die, it has the effect of acting as an internal lubricant or internal mold release agent. It is possible to impart lubricity or mold releasability to. Similarly, when made into a resin plate or film, it has non-blocking properties, and when added to a paint or applied to the surface of the film, a cured film with excellent lubricity, water repellency, and gloss can be obtained. Although the uses of the organopolysiloxane lubricant of the present invention are not limited, some particularly useful examples include magnetic tapes, magnetic toners, magnetic cards, magnetic disks, audio disks, etc. Synthetic resin or synthetic rubber is used as a binder or By adding it to the base material, it can impart excellent and durable lubricity. In addition, by adding it to polyurethane resin used as a material for automobile bumpers, it has an excellent effect as an internal mold release agent or internal lubricant during injection molding.
By adding it to various synthetic resin compositions and molding it, it exhibits excellent mold releasability without mold staining during molding. In addition, automotive muzzle guards, packing, gaskets, etc. that require lubricity or mold release properties,
It is useful as a film for food packaging, a film for agricultural vinyl houses, medical equipment, synthetic resin bearings, and a lubricant for textiles. The organopolysiloxane lubricant of the present invention can be used as a lubricant for machines and equipment in the form of an oil or compound, in addition to imparting lubricity or mold release properties to synthetic resins or synthetic rubbers. Next, examples will be shown. In the examples, parts and % mean parts by weight and % by weight, and the viscosity is 25°C.
This is the measured value at . Example 1 Polyvinyl chloride (Mitsubishi Monsanto P-
455), vinyl chloride-vinyl acetate copolymer (Denkabinyl MM-90 manufactured by Denki Kagaku Co., Ltd., vinyl acetate content 10%), ethylene-vinyl acetate copolymer (Ultracene 680 manufactured by Toyo Sotaku Co., Ltd.), polyethylene (Mitsui Polymer Co., Ltd.) Mirason 24H (manufactured by Chemical Co., Ltd.), polypropylene (Noblen H501, manufactured by Sumitomo Chemical Co., Ltd.), polymethyl methacrylate (Sumipetx LG, manufactured by Sumitomo Chemical Co., Ltd.),
For 100 parts of each resin of polyamide (6 nylon for fiber manufactured by Toray Industries) and polyester (polyethylene terephthalate for textile manufactured by Toray Industries), the following formula, Viscosity 270 centistokes, Viscosity 210 centistokes, Viscosity 230 centistokes, Each organopolysiloxane with a viscosity of 100 centistokes is
A film with a thickness of 1.5 mm was prepared by adding 1.5 parts. For each film, the seepage of organopolysiloxane onto the film surface was observed with the naked eye before heating and after being placed in a hot air circulation oven at 70°C for 5 days, and evaluated on a four-level scale as follows. ◎ There should be no seepage on the film surface. ○ Almost no seepage onto the film surface. △ Slight seepage onto the film surface. × Significant seepage onto the film surface. As a comparative example, an experiment similar to the above was conducted using a 300 centistoke dimethylpolysiloxane with trimethylsilyl groups endblocked at both ends of the molecular chain. These results are shown in Table 1. The film to which the organopolysiloxane of the present invention was added did not seep out onto the film surface and was extremely superior to the film to which dimethylpolysiloxane was added as a comparative example. It was observed that the organopolysiloxane of the present invention tends to have excellent affinity and compatibility with vinyl chloride resins and vinyl acetate resins. These results indicate that vinyl chloride resins and vinyl acetate resins are used in fields that require lubricity or mold release properties, especially magnetic recording media such as magnetic tapes and disks, agricultural vinyl house films, and medical equipment. It is expected to be effective for this purpose.

[Releasability]

Grade 1: Very easy to peel. Grade 2: Peeling is somewhat heavy. Grade 3: Peeling is very heavy or difficult. [Paintability] Grade 1: Magic ink does not fade and the ink is applied evenly. Grade 2: There is some fading of the magic ink. Grade 3: Magic ink becomes dotted and not uniform. The results are shown in Table 2. As a comparative example, instead of the organopolysiloxane of the present invention, 500 centistoke dimethylpolysiloxane with trimethylsilyl groups endblocked at both ends of the molecular chain, and two methylphenylpolysiloxanes each with 500 centistoke endblocked with trimethylsilyl groups at both ends of the molecular chain. The releasability and paintability of the product molded under the same conditions as above except that 100% was added was examined. The results are shown in Table 2. All products using the organopolysiloxane of the present invention had good releasability, that is, internal mold releasability, and also had good paintability because there was no oozing to the surface even when heated. This result is useful as an internal mold release agent when manufacturing automobile bumpers, which are polyurethane resin molded products, and also as a mold release agent when coating fabric with polyurethane resin and performing embossing. It is shown that. Furthermore, when a polyurethane resin is used as a binder for a magnetic tape, it is presumed that it is also suitable to add it to the binder to impart lubricity.

【table】

Claims (1)

[Scope of Claims] 1. The total number of siloxane units in one molecule is from 5 to 1,000, and the epoxy group, carboxyl group, hydroxyl group, or alkoxy group is bonded to the silicon atom via an alkylene group as a functional group. The ratio of the number of functional groups to the total number of units is 100:2 to 100:50
An organopolysiloxane lubricant whose main ingredient is an organopolysiloxane having the following range. 2. The lubricant according to claim 1, wherein the other organic group bonded to the silicon atom of the organopolysiloxane is a monovalent hydrocarbon group. 3. The lubricant according to claim 2, wherein the monovalent hydrocarbon group of the other organic group bonded to the silicon atom of the organopolysiloxane is a methyl group. 4. The lubricant according to claim 1, wherein the object to which lubricity is imparted is a synthetic resin or synthetic rubber. 5. The lubricant according to claim 4, wherein the synthetic resin is a vinyl chloride resin, a vinyl acetate resin, or a polyurethane resin, and the synthetic rubber is an ethylene-propylene-diene rubber. 6. The lubricant according to claim 5, wherein the synthetic resins vinyl chloride resin, vinyl acetate resin, and polyurethane resin are used as a magnetic paint for magnetic recording media. 7. For 100 parts by weight of synthetic resin or synthetic rubber,
The lubricant according to claim 4, 5 or 6, wherein the organopolysiloxane is used in an amount of 0.05 to 20 parts by weight.