JPH046220B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a resin composition containing polycarbonate as one component and having excellent wear resistance. [Prior Art] Polycarbonate has very good properties such as rigidity and flame retardancy, but it has a problem in friction and wear resistance. For this reason, it is rarely used as a structural material for parts subject to sliding, and nylon and polyacetal, which have good friction and wear resistance, have been used for these purposes. but,
Nylon has a high water absorption rate, and dimensional changes due to water absorption are also large. Therefore, changes such as warping and blistering are likely to occur, and the environmental conditions under which it can be used are limited.
Furthermore, polyacetal has a large molding shrinkage rate, which necessarily increases the variation in dimensions of molded products, and it also has problems such as being easily flammable. Although polyacetal and nylon have the above-mentioned problems, molded products that require friction and wear resistance are often made of nylon or polyacetal, insert molded nylon or polyacetal, or Friction and wear resistance is partially reinforced by inserting small parts. In addition, when friction and wear resistance is required on a simple surface, a sheet or film made of fluororesin or nylon resin is laminated to satisfy the purpose. However, although such combined use of resins can be applied to simple shapes, it is not applicable to resin molded products with complex shapes because the assembly work is difficult and the inserts are complicated. hard. In this way, the combined use of resins has limitations depending on the shape, and there are also many problems because it requires a lot of man-hours. As mentioned above, nylon has problems with dimensional changes due to water absorption, polyacetal has problems with dimensional accuracy and flammability, and the combined use of resins has problems such as shape problems and increased man-hours. [Problems to be Solved by the Invention] The purpose of the present invention is to obtain a resin molded product that does not have the above-mentioned disadvantages, has excellent mechanical properties, is flame retardant, and has excellent friction and wear resistance. The object of the present invention is to provide a composition of the invention. [Means for Solving the Problems] As a result of intensive studies to obtain such a resin composition, the present inventors have developed polycarbonate 100.
This objective was achieved by a resin composition containing 0.01 to 50 parts by weight of a polyamide copolymer composed of a polyamide block (a) and a polyester block (b). The polyamide copolymer having the polyester block does not have excellent frictional properties.
However, we have discovered that molded products obtained by molding a resin composition obtained by mixing such a polymer material with polycarbonate have significantly improved friction and wear characteristics, even though they are based on polycarbonate. It was. The polycarbonate used in the present invention can be obtained by any method known in the art, such as converting di-(mono-hydroxyphenyl)-substituted aliphatic hydrocarbons with phosgene. Examples include the phosgene method and the transesterification method in which the reaction is performed with a carbonic acid diester such as diphenyl carbonate. Polycarbonate can be used alone or in combination of two or more types. The polyamide copolymer used in the present invention has a proportion of the polyamide block (a) component in the total copolymer.
99-10, preferably 90-20, more preferably 80-20
30% by weight. If the ratio of (a) component is 99% or more, the effect of improving wear resistance is small, and if it is 10% or less, mechanical strength decreases. In the present invention, the polyamide block (a) is composed of a polyamide-forming compound and has 6 carbon atoms.
or more aminocarboxylic acids or lactams or m
It is made of nylon mn salt with +n≧12. Aminocarboxylic acid or lactam with 6 or more carbon atoms or nylon mn with m+n≧12
Examples of the salt (a) include aminocarboxylic acids such as ω-aminocaproic acid, ω-aminoenanthanoic acid, ω-aminocaprylic acid, ω-aminobergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. Acid or lactam such as caprolactam, laurolactam, nylon 6/6, 6/10,
6.12, 11.6, 11.10, 11.12, 12.6, 12.
Examples include nylon salts such as 10, 12, and 12. The polyester block (b) as used in the present invention refers to (1) a polyester synthesized from diacid and a diol, (2) a polyester synthesized from ε-caprolactone, ω-oxycaproic acid, or a C ₁ to C ₃ alkyl ester thereof. There is caprolactone polyester. Examples of polyesters synthesized from diacids and diols include phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, and diphenyl-4,4-dicarboxylic acid. , aromatic dicarboxylic acids such as diphenoxyethanedicarboxylic acid,
1,4-cyclohexanedicarboxylic acid, 1,2-
Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and dicyclohexyl-4,4'-dicarboxylic acid, and aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid, and dodecanedioic acid, and ethylene glycol, diethylene glycol, and tricarboxylic acid. Ethylene glycol, tetraethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, 1,5-pentanediol,
It is a polymer unit formed from diol components such as 1,6-hexanediol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Each of these ester-forming components can be used alone or in the form of a copolymer. Polycaprolactone polyester can be obtained, for example, as follows. That is, when ε-caprolactone is polymerized to form a polycaprolactone-based polyester, water or a compound having hydroxyl groups at both ends is used as a polymerization initiator. Examples of the polymerization initiator include resorcinol, pyrocatechol, hydroquinone, pyrogallol, phloroglucin, benzenetriol, bisphenol-A, bisphenol-F and their ethylene oxide adducts, dimethylolbenzene, cyclohexanedimethanol, tris(2-hydroxy Ethyl) isocyanurate, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 2-methyl-1,3-propylene glycol, neopentyl glycol, 1,5-pentanediol, glycerin, trimethylolpropane, 1,6-hexanediol, pentaerythritol, sorbitol, glucose, sucrose and terephthalic acid, isophthalic acid, adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, etc. Dicarboxylic acid components and ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, trimethylolpropane, glycerin, pentaerythritol ,
Polyester polyols with an average molecular weight of 200 to 6,000 formed from polyol components such as sorbitol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and block or random copolymers of ethylene oxide and propylene oxide with an average molecular weight of 200 to 6,000.
Examples include block or random copolymers of ethylene oxide and tetrahydrofuran. Polyamide block (a) and polyester block
The polyesteramide containing (b) may be produced (polycondensation reaction) by a conventional method. That is, while stirring in the presence of a catalyst for polycondensation reaction, 5 mm
Under a high vacuum of Hg or less, preferably 1 mmHg or less,
The reaction temperature is 220-28°C. Also, as a production method, there is a method of synthesizing a polyester block and then producing a polyester amide, but it is also possible to produce a polyester amide by simultaneously supplying a polyester monomer and a polyamide monomer to a polymerization can. Titanium-based catalysts give good results in the production of polyesteramides. Particularly preferred are tetraalkyl titanates such as tetrabutyl titanate and tetramethyl titanate, and metal salts of titanium oxalate such as potassium titanium oxalate. Other catalysts include tin compounds such as dibutyltin oxide and dibutyltin laurate, and lead compounds such as lead acetate. In the method for producing a polyesteramide comprising a polyamide block and a polyester block according to the present invention, both ends of the polyester component may be diol or diacid. When both ends are diols, dicarboxylic acids having 4 to 20 carbon atoms can be used. In the present invention, dicarboxylic acids having 4 to 20 carbon atoms include phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,
Aromatic dicarboxylic acids such as 4'-dicarboxylic acid and diphenoxyethane dicarboxylic acid, alicyclic dicarboxylic acids such as dicyclohexyl-4,4'-dicarboxylic acid, and succinic acid, oxalic acid, adipic acid, sebacic acid, and dodecanedioic acid. Examples include aliphatic dicarboxylic acids such as In particular, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, and dodecanedioic acid are preferably used. In addition, when the terminal is a diacid, a diamine is used. As the diamine, aromatic, alicyclic, and aliphatic diamines are used. Specifically, hexamethylene diamine is considered as the aliphatic diamine. In addition, in the present invention, the polyester component (b)
Polyalkylene polyols, such as polytetramethylene glycol and polypropylene glycol, which can be used as a soft component other than polyester, can be used as long as they can exhibit the characteristics of the present invention. In the present invention, 0.01 to 50 parts of a polyamide copolymer composed of a polyamide block and a polyester block is added to 100 parts by weight of polycarbonate.
Parts by weight, preferably 0.1 to 30, more preferably 0.5
Preferably, the amount is 15 parts by weight. When the amount of the polyamide copolymer blended is less than 0.01 part by weight per 100 parts by weight of polycarbonate, the effect of improving friction and wear properties is small. Further, if the amount is 50 parts by weight or more based on 100 parts by weight of polycarbonate, it is not preferable because mechanical strength will decrease. If necessary, a dispersant, a stabilizer, a pigment, and a filler or reinforcing agent such as talc or glass fiber may be added to the resin composition according to the present invention. [Effects of the Invention] The resin composition of the present invention is effective as a material for molded articles having sliding parts that require high tensile strength, impact strength, and dimensional stability as well as friction and wear resistance. Examples of molded products having sliding parts include bushings, switches, control levers, and enclosures for equipment having rotating receiving parts. Examples and comparative examples will be described below. Example The polycarbonate used in this experiment was "Ubilon S-" manufactured by Mitsubishi Gas Chemical Co., Ltd.
3000" was used, and the polyamide copolymer having a polyester block was used under the trade name "Diamid PAE E50A, E50D" manufactured by Daicel Chemical Industries, Ltd. E50A is 44.7% by weight of 12-aminododecanoic acid,
It is synthesized from 5.3% by weight of adipic acid and 50.0% by weight of polycaprolactone diol with an average molecular weight of 2000, and E50D is 12-aminododecanoic acid.
46.8% by weight, adipic acid 3.4% by weight, average molecular weight
It was synthesized from 49.8% by weight of 1,4-butylene glycol adipate polyester diol of 2000. Table 1 shows the positions of the individual components used as raw materials. Weigh the above raw materials in the proportions shown in Table 1, mix them, and make 40% of the mixture.
The mixture was kneaded and extruded using a mmφ extruder (L/D=26) and pelletized to obtain a resin composition. The resin composition pellets thus obtained were injection molded using an injection molding machine TS-100 manufactured by Nissei Plastics. The friction and wear test piece has an inner diameter of 20 mmφ, an outer diameter of 26 mmφ,
A cylindrical test piece for a Suzuki friction and wear tester with a height of 15 mm was molded. The molding conditions were a mold temperature of 50° C., an injection pressure of 65 kg/cm ² G, and a cycle of 60 seconds to mold the test piece. The same injection molding machine was used for measuring mechanical properties, with a mold temperature of 50° C., an injection pressure of 65 kg/cm ² G, and a cycle of 60 seconds. Friction and wear tests and mechanical strength tests were conducted using the test pieces formed in this manner. In the friction and wear test, a steel test piece of the same shape as this test piece was installed in the lower rotating part of the Suzuki type friction and wear tester, and a mixed resin molded test piece was installed in the upper stationary part, and a surface pressure of 1 kg /
cm ² and an average circumferential speed of 10 m/min under sliding conditions without lubrication. The specific wear amount (unit: mm ³ /Kg·Km) was calculated using the following formula. Specific wear amount (mm ³ /Kg・Km) = Wear weight (mg) / Density (mg
/mm ³ ) x Contact pressure (Kg/cm ² ) x Contact area (cm ² ) x Running distance (Km) Mechanical properties are measured using ASTM D638, ASTM
Based on the method of D790 and ASTM D256. Table 2 shows the results measured under the conditions described above. Comparative Example Similar to the example, polycarbonate was manufactured by Mitsubishi Gas Chemical Co., Ltd. under the trade name “Ubilon S-
3000" was used, and the compounding material was "Diamid L" manufactured by Daicel Chemical Industries, Ltd. as a polyamide.
−1500” was used. These materials were pelletized in the same manner as in the Examples at the blending ratios shown in Table 1. The molding conditions for the test piece and the measurement conditions were also the same as in the examples. The measurement results are shown in Table 2. The results in Table 2 show that abrasion properties can be improved by mixing polyesteramide elastomer containing polyamide blocks and polyester blocks with polycarbonate, but no improvement in abrasion properties can be obtained even when a polymer containing only polyamide blocks is added to polycarbonate. It turns out that there isn't.

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Claims (1)

[Claims] 1. A polycarbonate resin composition comprising 100 parts by weight of polycarbonate and 0.01 to 50 parts by weight of a polyamide copolymer composed of a polyamide block and a polyester block.