JPH0246631B2 - - 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 is a mixture of thermoplastic resin with silicone oil and silicone rubber, but it cannot sufficiently prevent the silicone oil from leaking out, and because it contains silicone rubber, the original properties of the thermoplastic resin are 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 -CF ₃ group or (-CF ₂ CF ₂ -) _k W (W represents a hydrogen atom or a fluorine atom, k is an integer from 1 to 4)]
An organopolysiloxane having ^one -OCOR group (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 blend 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, the present invention provides a -R ¹ -COOH group, -R ² -SH group, -R ³ - bonded to a silicon atom in one molecule.
OY group and -R ⁴ -X group [here, R ¹ , R ² , R ³
and R ⁴ is a divalent organic group, Y is a hydrogen atom or a monovalent hydrocarbon group, and X is a -CH ₂ Cl group or (-CF ₂ -)
_o A group (where A is a hydrogen atom or a fluorine atom,
n is a positive integer from 1 to 8). ] 4
The present invention relates to an organopolysiloxane lubricant whose main ingredient is an organopolysiloxane having at least one each of two types of functional groups arbitrarily selected from among various types of functional groups. The organopolysiloxane used as the lubricant of the present invention can have a linear, branched, or network molecular shape, but it is preferably a linear one, with a silicon atom combine, −
R ¹ -COOH group, -R ² -SH group, -R ³ -OY group (Y is a hydrogen atom or monovalent hydrocarbon group) and -R ⁴ -
X group (X is a CH ₂ Cl group or (-CF ₂ -) _o A group,
A is a hydrogen atom or a fluorine atom, and n is an integer of 1 to 8).
Therefore, -R ¹ -COOH group, -R ² -SH group, -R ¹
−COOH group and −R ³ −OY group, −R ¹ −COOH group and −
R ⁴ -X group, -R ² -SH group and -R ³ -OY group, -R ² -
SH group and -R ⁴ -X group, and -R ³ -OY group and -R ⁴
There are six combinations with the -X group. Here, R ¹ ,
Examples of the divalent organic group represented by R ² , R ³ and R ⁴ include alkylene groups such as methylene group, ethylene group, propylene group and butylene group, phenylene group, alkylene arylene group, (-CH ₂ CH ₂ O
−) _l ,

Examples include oxyalkylene groups and polyoxyalkylene groups represented by [Formula] (where l and m are integers of 1 to 50), and combinations of two or more of the exemplified organic groups. It shall include the divalent organic group. R ¹ , R ² bonded to silicon atoms in one molecule,
The two types of divalent organic groups selected from R ³ and R ⁴ may be the same or different. Among the divalent organic groups, ethylene, propylene and polyoxyalkylene groups are preferred. In the case of polyoxyalkylene groups, if the molecular chain becomes too long, the activity of the functional group bonded to the end of the group will weaken, and the bonding strength with synthetic resins, synthetic rubbers, or the various additives blended therewith will decrease. Alternatively, m is preferably in the range of 1 to 10. ^R3
Y in the -OY group is a hydrogen atom or a monovalent hydrocarbon group, and examples of the monovalent hydrocarbon group include a methyl group, ethyl group, propyl group, dodecyl group, cyclohexyl group, phenyl group, and β-phenylethyl group. Ru. Among these, hydrogen atoms are preferred. The positions of the two different types of functional groups bonded to the silicon atom of this organopolysiloxane are not particularly limited, and they may be present only at the ends of the molecular chain of the organopolysiloxane, or within the molecular chain. It may be present only at the end of the molecular chain or within the molecular chain. Other than this,
The organic group bonded to the silicon atom in one molecule is only a methyl group, or a methyl group and a phenyl group, and from the viewpoint of lubricity and mold release properties, it is preferable to use only a methyl group. The number of siloxane units (degree of polymerization) 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 be reduced, and if it is larger than this range, the viscosity will be too high. This is because handling becomes difficult. For lubricity or mold release properties and handling, the number of siloxane units is 20 or more.
A range of 400 is preferred. The ratio of the total number of two types 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 _. ＝CHCOOH, CH ₂ ＝CHCH ₂ SH, CH ₂
It can be easily obtained by addition-reacting two types of functional group-containing unsaturated compounds represented by =CHCH ₂ OH and CH ₂ =CHCF ₃ simultaneously or separately in the presence of a platinum-based 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 or 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 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-vinyl chloride-ethylene copolymer, isoprene rubber,
Examples include 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 or synthetic rubbers may be used in combination. Among these, particularly preferred are synthetic resins such as vinyl chloride resins, vinyl acetate resins, polyurethane resins, and epoxy 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 process silica,
Wet process silurica, 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, phosphates, metal soap, silicone oil, silane coupling agents, rosin, isocyanates, waxes, higher alcohols, organic tin fatty acid salts, plasticizers, stabilizers, flame retardants, ultraviolet absorbers, lubricants, antistatic agents, antioxidants, fungicides, foaming agents, colorants, Adhesive agents and the like can be added. The organopolysiloxane according to the present invention can be used in all applications of synthetic resins or synthetic rubbers suitable as lubricants or objects for imparting 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 can provide durable and excellent 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 an epoxy resin composition for molding, 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 Soda Co., Ltd.), polyethylene (Mitsui Mirason 24H manufactured by Polychemical 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 310 centistokes, Viscosity 300 centistokes, Viscosity 98 centistokes, Viscosity 350 centistokes, Viscosity 450 centistokes, Each organopolysiloxane with a viscosity of 180 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 both ends of the molecular chain endblocked with trimethylsilyl groups, methylphenylpolysiloxane with 500 centistokes endblocked with trimethylsilyl groups at both ends of the molecular chain, and polyurethane foam. 500 centistokes of dimethylpolysiloxane/polyoxyalkylene copolymer used as a foam stabilizer for
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 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 to be suitable for adding lubricity to the binder.

[Mold releasability]

In a mold having a cylindrical cavity with a cross-sectional area of 1 cm ² , 1.5 g of each composition was compression molded at 175°C for 2 minutes, and the extrusion force (Kg) from the mold immediately after molding was measured.
was measured with a push-pull gauge. This was repeated 10 times and the lowest and highest values were taken. [Mold dirt] Using a mold for 20 To-202 transistors,
Transfer molding was performed continuously at 175°C for 2 minutes 500 times, and stains on the mold after molding were visually observed. A case in which there was no clouding at all on the mirror surface of the mold was judged as "absent", and a case in which clouding occurred was judged as "presence". [Imprintability] Using a mold for 20 To-202 transistors,
Markem 7261 ink was stamped on the molded surface after transfer molding at 175℃ for 2 minutes, and 150℃ for 1 minute.
After curing the ink for a period of time, a cellophane tape was brought into close contact with the surface of the ink, and when the tape was rapidly peeled off, the transferability of the ink to the tape side was visually judged. Repeat this 10 times, and mark ○ if there is no transfer at all to the tape side in all 10 times, mark △ if there is at least one transfer to the tape side, or mark once or more if it is transferred to almost the entire surface of the tape. Some items were marked with an x. [Adhesion] Using a mold for 20 To-202 transistors,
The semiconductor was sealed by transfer molding at 175° C. for 2 minutes. Ten pieces of each molded product were immersed in Red-Check solution, boiled for 12 hours, taken out, and the extent to which the Red-Check solution penetrated into the interface between the molded product and the lead frame was observed using a microscope.
Mark ○ if no infiltration is observed in any of the 10 items, and mark △ if there are 5 or less infiltrates.
Those in which even a small amount of infiltration was observed in all 10 samples were marked with an x mark.

[Table] As is clear from Table 3, compared to comparative examples using conventional internal mold release agents such as carnauba wax, mold release properties are extremely superior, there is no mold staining, Since it has excellent marking properties and adhesion to semiconductor components, it is suitable for semiconductor encapsulants whose main material is epoxy resin. Example 4 100 parts of EP-43 (ethylene propylene terpolymer manufactured by Nippon Gosei Rubber Co., Ltd.) and 48 parts of Nipsil VN-3 (wet silica manufactured by Nippon Silica Kogyo Co., Ltd.) were thoroughly kneaded with two rolls, and then mixed with the following formula. 5 parts of organopolysiloxane with a viscosity of 300 centistokes and Antige RD (quinoline anti-aging agent manufactured by Kawaguchi Chemical Co., Ltd.) as an anti-aging agent.
0.5 parts of stearic acid, 1.0 parts of stearic acid, and 3.0 parts of dicumyl peroxide were added and mixed uniformly using two rolls, and this was mixed under the conditions of a temperature of 160℃ and a pressure of 200Kg/ ^cm2.
It was pressed for 20 minutes (primary vulcanization) to obtain a sheet with a thickness of 2 mm. Further, this was heat-treated (secondary vulcanization) at 150°C for 2 hours in a hot air circulation oven. The surface of this sheet was shiny. Polyester tape is applied to the surface of this rubber sheet.
31B (acrylic adhesive tape manufactured by Nitto Electric Industry Co., Ltd.)
After uniformly pasting the tape (width 5 cm) and peeling it off, the tape was easily peeled off by just pulling it lightly. Furthermore, even after heating the rubber sheet in a hot air circulation oven at 150°C for 168 hours, the rubber surface did not lose its luster. On the other hand, as a comparative example, organopolysiloxane G
A rubber sheet was prepared under the same conditions as above, except that the adhesive tape was not added, and the same test was conducted. As a result, the adhesive tape peeled off much more strongly than the above-mentioned rubber sheet. Furthermore, the rubber sheet had a glossy appearance before heating, but after heating at 150°C for 168 hours, it lost its luster. From this result, it is assumed that the present invention is useful for wiper blade rubber for automobiles, weather strip rubber, bladder rubber for tire molding, rubber for rolls, etc.

Claims (1)

[Claims] 1 -R ¹ - bonded to a silicon atom in one molecule
COOH group, -R ² -SH group, -R ³ -OY group and -
R ⁴ -X group [where R ¹ , R ² , R ³ and R ⁴ are divalent organic groups, Y is a hydrogen atom or a monovalent hydrocarbon group,
X is _-CH2Cl group or -( _CF2 ) _-oA group (here,
A is a hydrogen atom or a fluorine atom, n is a positive integer of 1 to 8). ] Two types of functional groups arbitrarily selected from among the four types of functional groups shown in
An organopolysiloxane lubricant containing at least one organopolysiloxane as a main ingredient. 2. The lubricant according to claim 1, wherein the other organic group bonded to the silicon atom of the organopolysiloxane is only a methyl group. 3. The lubricant according to claim 1, wherein the other organic groups bonded to the silicon atom of the organopolysiloxane are a methyl group and a phenyl group. 4. The lubricant according to claim 1, wherein the organopolysiloxane has 5 to 1000 siloxane units. 5. The lubricant according to claim 1, wherein the object to which lubricity is imparted is a synthetic resin or synthetic rubber. 6. The lubricant according to claim 5, wherein the synthetic resin is a vinyl chloride resin, a vinyl acetate resin, a polyurethane resin, or an epoxy resin, and the synthetic rubber is an ethylene-propylene-diene rubber. 7. For 100 parts by weight of synthetic resin or synthetic rubber,
The lubricant according to claim 5 or 6, wherein the organopolysiloxane is used in an amount of 0.05 to 20 parts by weight.