JPS6038452A - Vinylidene fluoride resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which gives moldings having excellent mechanical properties, surface smoothness and gloss, by adding a potassium titanate fiber to a vinylidene fluoride resin. CONSTITUTION:5-40wt% potassium titanate fiber having an average fiber diameter of 0.1-2mum, an average fiber length of 5-100mum and an aspect ratio of 10-200 and of formula I or II (wherein n is 2-8) is added to a vinylidene flouride resin having a vinylidene fluoride content of 90mol% or above and an intrinsic viscosity of 0.5-2.0. EFFECT:A compsn. suitable for use in molding parts having complicated shapes and very small, thin-wall parts having excellent tensile strength, flexural strength and flexural modulus, high dimensional accuracy and exhibiting low orientation during molding, can be obtd. USE:Gear, bearing, miniature gear, roller, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a vinylidene fluoride yarn AK composition to which other excellent properties are newly imparted by adding potassium fibers without impairing the properties originally possessed by the resin.

Vinylidene fluoride resin JI'ii such as polyvinylidene fluoride (hereinafter referred to as PvDF) has chemical resistance, weather resistance, oil resistance, radiation resistance, etc., as well as other fluorine 4J resins such as polytetrafluoroethylene and t'tJm. In addition, it has the best mechanical properties such as tensile strength and creep resistance among fluororesins, so it is used as an industrial material such as pipes, gaskets, punctures, and paints. has been done.

However, in terms of moldability, although it is very easy compared to polytetrafluoroethylene etc., it has a high molding shrinkage rate when compared to general thermoplastic resins, and its heat resistance is not necessarily sufficient. Currently, the field of use of aluminum is limited because its mechanical strength is still not at a satisfactory level for use as a structural material in the fJ4.

73) Various studies have been made to solve this problem, and by adding carbon fiber or graphite fiber with a fiber length of 0.1 to 5 mm within a range of 30% (weight %, the same applies hereinafter). It has been found that improved heat resistance, improved molding shrinkage rate, and enhanced mechanical properties can be observed only in this case.

However, the effect of improving mechanical properties by adding carbon fiber or graphite fiber is not sufficient, and the tensile strength and bending strength are at most 1.5 times that of the unfilled case.
The bending elastic modulus, which is a feature of the effect of adding carbon fiber or graphite fiber, is only 2.5 times higher. More carbon fiber or black @F'JI'J! < K, 10 is a relatively long fibrous material with an average fiber diameter of 7 to 12 μm and an average fiber length of 10,077 m or more, so it is oriented during molding and does not cause anisotropy in the molding shrinkage rate. It also causes anisotropy in terms of strength, and in products with complex shapes, there are parts that are hardly strengthened, resulting in a major problem in that the product cannot be changed to the desired product. In view of the above-mentioned circumstances, the inventors of the present invention have conducted intensive studies and found that the size of the fiber is 1.
We have discovered that all of the above problems can be solved by using potassium titanate fibers that are even smaller by an order of magnitude, and have arrived at the present invention. The present invention relates to a colloidated bicolidene-based fat composition characterized by adding %.

Vinylidene fluoride resins that can be used in the present invention include not only vinylidene fluoride homopolymers obtained by producing vinylidene fluoride monomers by suspension polymerization, emulsion polymerization, solution polymerization, or any other method, but also It also refers to a vinylidene fluoride copolymer containing 90 mol% or more of a vinylidene fluoride component that has essentially the same properties as such a homopolymer. Examples of monomers that can be copolymerized with the vinylidene fluoride monomer in the copolymer include tetrafluoroethylene, hexafluoropropylene:z, trifluoroethylene monochloride, and vinyl fluoride.

The degree of polymerization of vinylidene fluoride resin is approximately 0.5 to 2.0% expressed as intrinsic viscosity ηinh. olna cancer <o, 8-1.5
It is preferable that the ηi described here
Blood has the formula: (wherein C is the concentration CD of the dimethylformamide solution of the polymer, 49/dl), η is f? The viscosity of the polymer dimethylformamide solution and .eta.0 represent the viscosity of dimethylformamide alone, and are the values measured at 60.degree. C.).

++iJ If the η1 oil is less than 0.5, the mechanical properties of the vinylidene fluoride resin will deteriorate, while if it exceeds 2.0, the melt viscosity will become too high, causing problems in moldability. Undesirable.

The potassium titanate fiber that can be used in the present invention means a single crystal fiber represented by the general formula: % formula % (where n represents an integer of 2 to 8), and specifically, for example, 4 Single dipotassium titanium fiber, potassium hexatitanate fiber, potassium octitanate fiber, etc., or a combination thereof, with an average fiber diameter of 0.1 to 2 μm, an average fiber length of 5 to 100 μm, and an average fiber length/average Fiber diameter (aspect ratio) is 10~
200 is preferably used.

In this specification, the number of titanium monojaw potassium fibers was investigated, and at least 10 or more fibers KHH per field of view.
The aspect ratio is the average value of the values measured for such fibers, and the aspect ratio refers to the value obtained by dividing the average yarn length of such fibers by the average fiber diameter.

・Average fiber diameter of f-potassium tannate fiber, average fiber length 4
-3 and the aspect ratio is outside the above range, for example, the average fiber diameter is greater than 1 μm and the average fiber length is 5 μm.
smaller than μm, i.e. the aspect ratio is 5 and 10
If it is smaller than this, the reinforcing effect will be reduced, which is not preferable. Furthermore, ultrafine fibers with an average fiber diameter of 0.1 μm or less or fibers with a fiber length longer than 1007 m are difficult to produce industrially and are of little practical use.

The appropriate amount of potassium titanate fiber is 5 to 40%. If it is less than 5%, the reinforcing effect will be poor;
If it exceeds 0%, the effect of improving physical properties will not be significant considering the amount filled, and the melt viscosity will become too high, causing problems in moldability, both of which are unfavorable.

The potassium titanate fibers used in the present invention have been surface-treated with a silane coupling agent, a titanate thread coupling agent, an epoxy resin, an epoxy urethane resin, etc. in order to improve the adhesion with the vinylidene fluoride resin. is preferably used. 7) A method in which a silane coupling agent or the like is added when producing a resin composition (pellet) by extruding a mixture of vinylidene chloride thread resin and unsurface-treated potassium titanate fibers 7 can also be used. There is a tendency for the effect of improving physical properties to be even greater than when Jil's potassium titanate fibers are used as they are.

Various methods can be applied to the production of the resin composition of the present invention, such as (1) a method in which potassium titanate b<M'i is blended from the beginning of polymerizing vinylidene fluoride monomer, and (2) polymerization. or a method in which potassium titanate fibers are blended during polymer extraction; (3) potassium titanate fibers are added to the resin using an extruder or the like at the stage of pelletizing vinylidene fluoride resin after polymerization or extraction and drying; Methods such as kneading and extruding, followed by water cooling and cutting to form pellets are applicable, and method (3) is particularly the most practical.

In addition, % OaS BINZn, Mg may be added to the resin composition of the present invention within a range that does not interfere with the improvement effect of the present invention.
Heat stabilizers such as hydroxides and carbonates, crystallinity improvers such as terephthalic acid, kaolin, talc, and silica earth (
Depending on the purpose, additives such as a crystal nucleating agent) and a crosslinking agent such as tributyl pargyl cyanurate may be added as appropriate.
1) The resin composition of the present invention has a fiber size approximately 1/10 to 1/100 of that of conventionally known carbon fiber reinforced products.
Despite using potassium titanate fiber, which is Miku's AFL fiber material, as a reinforcing material, the mechanical property improvement effect is greater than that of the carbon-reinforced product, which is a unique feature not found in other plastic materials. In addition, the orientation during molding, which is a feature of microfiber filling (
Small anisotropy of molding shrinkage rate), greatly improved dimensional accuracy, molding force (pJ ability) for parts with close-contact shapes or very small and thin parts, and conventional carbon fiber reinforcement Its practical value is extremely great, as it has better surface smoothness and gloss compared to TT products, and has excellent external value (excellent value). Precision parts such as small gears, sliding parts that require surface precision such as rolls), and applications such as conventionally used lining sheets and powder coating for linings. ■It is a dragon and can be expected to improve the above physical properties.

EXAMPLES The present invention will be described below in detail based on Examples, but the present invention is not limited to these Examples.

Examples 1 to 5 and Comparative Example 1 PVDF powder (trade name, KIT' polymer + 1000s
Kureha Chemical Industry 9 (manufactured by lie, ηinh = 1.00
) is treated with epoxy silane and has an average fiber diameter of 0.6 μm.
1 Potassium titanate fibers with an average fiber length of 15 μm (trade name: TEISMO-D102, manufactured by Daikyu Kagaku Yakuhin (F (Ten))) were added in the range of 5 to 40% as shown in Table 1, and comparisons. 4 using something that was not added.
Melt and knead at a temperature of 230°C in a 5mm single-screw extruder7.
Thereafter, it was cooled down and made into pellets.

Then, using the obtained pellets, the injection temperature was 220°C.
1 gold 41. Sll'l ff,! 1'1・111 at 90°C and injection pressure 800 kg/am
After carrying out the IS5 test and creating two pieces of the following test pieces, the test pieces were used to produce the following 11-! 1
The first J Pi was 14 years old. Summary of the results
Shown in the table.

(1) Tensile Wv strength: J Engineering S K 71161 test piece (4mm thickness), distance between jacks 100mm, test speed 1
0mm/min (2) Bending strength and bending elasticity 1. Rate: J Engineering S K 7
203 (length 185+nm, width 10mm, height 4mm)
, pressure between fulcrums M6omm.

Test speed: 5 mm/min (3) Molding shrinkage rate and surface smoothness: The molding shrinkage rate was determined by a micrometer and the surface smoothness was determined by the naked eye for 6 side gate flat plates each having a length of 60 mm, a width of 50 mm, and a height of 3 mm. .

From Table 1, the filling effect of potassium titanate fibers is clearly visible at 5 to 40%, and at 40% it is difficult to significantly improve the physical properties even if the content exceeds that range. Comparative Examples 2 to 5: Average fiber diameter of 12.59 m instead of potassium titanate fiber
1 Carbon fibers with an average fiber length of 3 mm (trade name: Tare Chikara Chop A-103, manufactured by Ou Kagaku Kogyo ■) were used, and the carbon fibers were added in the range of 5 to 60% as shown in Table 2. Resin compositions and test pieces were prepared in the same manner as in Examples 1 to 5, and various physical properties were measured. The results are shown in Table 2.

Comparing the measurement results in Tables 1 and 2, it can be seen that the resin composition of the present invention has a greater effect on improving physical properties than the carbon fiber filled product, which has traditionally been considered to have a large effect on improving physical properties, and has a lower molding shrinkage rate. It can be seen that the anisotropy of
Useful effects such as ease of mold design and small internal distortion of the molded product are obtained.

Procedural amendment (voluntary) September 7, 1988 1.1r Indication 1982 Patent Application No. 147246/Relationship with JFf'l Patent applicant 4 agents 540 Address Kyo+A 3, Higashi-ku, Osaka -J-Ll 6 (No. 1 Kitayo Building Name (6522) Patent Attorney Sota Asahina Telephone (06) !1.13-8922 (Main) 5 Subjects of Amendment (1) Specifications of the "Detailed Description of the Invention" Contents of the '5W6 amendment (1) "Kotsuka" on page 4, line 12 of the specification is corrected to "fluoride".

(2) "Polymerization or removal" on page 8, line 19 is amended to "polymerization, removal".

that's all

Claims (1)

[Scope of Claims] 1. A vinylidene fluoride resin composition comprising 5 to 40% by weight of potassium titanate fibers added to a vinylidene fluoride resin. 27 Vinylidene fluoride thread ladle fat contains 90 mol% or more of vinylidene fluoride component, and has an intrinsic viscosity η1n]1 of 0.5 to
The vinylidene heptafluoride resin composition according to claim 1, which is a vinylidene fluoride homopolymer or copolymer of 2.0. 6 The average fiber diameter of potassium titanate fibers is 0.1 to 2μ
The vinylidene heptafluoride resin composition according to claim 1, wherein the m1 average fiber length is 5 to 100 μm and the average mechanical fiber diameter/average fiber diameter (aspect ratio) is 10 to 200.