JPS5962635A - Crosslinked fluorine-containing thermoplastic rubber molded article - Google Patents

Abstract

PURPOSE:To obtain a crosslinked fluorine-containing thermoplastic rubber molded article having improved compression set, stress cracking resistance and high- temperature characteristics, by crosslinking a fluorine-containing thermoplastic rubber with irradiation. CONSTITUTION:A fluorine-containing thermoplastic rubber composed of preferably one or more elastomeric polymer chain segments and one or more non- elastomeric polymer chain segment, wherein at least one of the segment is fluorine-containing polymer chain segment and the weight ratio of the elastomeric polymer chain segment to the non-elastomeric polymer chain segment is preferably 40-95:5-90, is formed to a disired form, and crosslinked by irradiation with a radiation (e.g. electron ray, gamma ray etc.) at a dose of 1-20 Mrad at -20-+100 deg.C preferably in vacuum, to obtain the objective crosslinked fluorine-containing thermoplastic rubber molded article. EFFECT:There is no discoloration and the bleeding of rubber chemicals. The rubber has bactericidal activity.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a crosslinked fluorine-containing thermoplastic rubber molded article, and more specifically, the present invention relates to a crosslinked fluorine-containing thermoplastic rubber molded article, and more specifically, it is crosslinked by crosslinking to improve compression set and mechanical properties. [I] Concerning products made of plastic rubber.

The fluorine-containing heat-resistant rubber has heat resistance of 1 E, hardness and wear of 1, 1 chemical resistance, 11 (lsum A January, 1ωt?).
'l) 1 color, 1 glossy and lonely, tube, sheet,
Films, molded products (for example, molded into O ~ shilling seals (n), wires, exterior materials, group I:
The moon is used by the gods for temporary restoration.
Ru.

However, fluorine-containing plastics for disintegration are inferior in compression set and stress fracture resistance depending on the grade.

The inventors of the present invention have developed a 1ζ material that improves the shortcomings of fluorine-containing deweighted plastic rubber without impairing its other excellent properties.
[As a result of the research being 1'''F, radiation 1 The present inventors have discovered that the mechanical properties, especially the temperature characteristics, are improved and the present invention has been completed.

That is, the gist of the non-invention resides in a fluorine-containing thermoplastic rubber molded product cross-linked by a radial gland.

In the present invention, the fluorine-containing ρ Yamanashi injection column has a relatively low IML (7 words is near the constant angle) and has a rubber bullet of 1 life, and has plastic flow due to the 7IIJ diameter. Refers to the rubber shown.

The fluorine-containing plastic rubber preferably comprises at least one elanu 1-mer polymer segment and at least one elanu 1-mer polymer segment.
at least one of which is a fluorine-containing polymer frequent segment 1-. In particular, elanuttomeric polymers
It is preferable that the weight ratio of the segment to the non-elanuttomer 1 injection polymer segment is 40-95:5-90.

Particularly good as a fluorine-containing purple p god' enemy rubber - zt, z To give a specific example, 2 persimmon mutual 1 ζ consists of 3 types of polymer frequent segments]! ! a chain, an iodine atom present at one end of the chain and at least one iodine atom removed from an iodide compound present at the other end of the chain; 2 types of polymer segments) or 1 type each other or 24
(When the chain consists of 3 yuzu polymeric secumene I-), (1 novinylidene fluoride/hexafluoropropylene 17ζ is pentafluorophorophylene/tetrafluoroethylene (molar ratio 45-90:5-50: 0
~35) Polymer 2-U (24 perfluoro(C1-C
a Furkyl vinyl fluoride (molar ratio 15-7
5:o~85:.

~85) selected from polymers 1ζ, molecule j2130.
000-1,200,00 o Noelasto 7-1. aE
Since the polymer gradient segment appears, the remainder of the angle IJK self-polymer frequent segment is (31 vinylitene 7 Ruaphyte/tetraful A゛loenalene (
Molar ratio O ~ 100: o ~ 1oo) Polymer 2 (low ethylene/tetrafluoroethylene/hexafluoropropylene, 3.3.3-trifluoropropylene-1,2
~Trifluoromethyl-3,3,3-trifluoropropylene-1'17ζ is perfluoro(01-C3 alkyl vinyl ether) (mole ratio 40-60:60-40:
0-30) Molecular lid a, ooo selected from polymers
~400,000 non-elastomeric polymer steel segments, elastomeric polymer segment, non-elastomer 1 raw polymer fiber segment N ratio of 4
0-95: 5-60''T: Yes, fluorine-containing polymers include six plastics and three plastics.

Preferred fluorine-containing M5 type plastic rubber i' used in the present invention
li: Described in Japanese Unexamined Patent Publication No. 53-3495.

The open structure of the fluorine-containing Isamucho plastic rubber is expressed in 7 words: % formula %) , ... group is the polymer chain segment 1- (at least one of which is a fluorine-containing polymer brass segment), I is the iodine atom released from the iodide compound, and n is the bond of Q. Represents the number of hands 2. ] is basically a chain consisting of at least two polymer chain segments, and if it is an iodine atom bonded to both ends of the chain, at least one iodine atom is derived from the Q-recoiodide compound. It is an essential component of Obon disease. Therefore, at least two kinds of polymer segments described in rirJ are different from the polymer frequent segments 1-1 and 1- in contact with each other. ), and at least one of them is a fluorine-containing polymer base, with at least 14
a hard segment and at least one soft segment). Yoshiashi Shigu says that the Tani polymer fine segment has a molecular weight of 30. (J (10 or more? There are a lot of things, excluding the so-called telomer region.
When the iodide compound has a polymerizable double bond, the residue from which at least all iodine atoms have been removed from the self-I2Dite compound is added to the monomer constituting the polymer compound or the iodide compound. Yamayone may have some kind of substituted molecule. These fluorine-containing plastic rubbers contain 0.001 to 10% by weight of iodine atoms. 7ζ However, after thermal synthesis, iodine is removed by reaction or placed on other residues, which is also ionizing radiation.
It has sufficient commercial energy to penetrate the heat of the fluorine thermal coating. 1. The words are X-rays, gamma rays, 'senshi rays, single proton rays, alpha rays, alpha rays,
Beta radiation and the like are used alone or in combination. Among these, electron beams and force-mammary beams are preferred.

The radiation dose is 0.1 to 508 (rad, or 1 to z
□Pay with Mrad. If the irradiation amount is less than the lower limit, a sufficient crosslinking effect will not be obtained, and if it is more than the upper limit, the rubber will deteriorate.
Inviting Jakushichigameru.

Irradiation temperature f'; J, Isn't it fixed? -20 to 10
0°C, for example 10 to 50″C-'r: Effective.

The irradiation atmosphere also depends on the atmosphere, but in Makabe, Nitrogen, Nezumi,
In inert gases such as argon and helium, and even
It may also be carried out in the presence of nanatsuma.

Especially Makabe-GF? :, prefers a crab atmosphere.

The fluorine-containing thermoplastic rubber is molded and processed in a conventional manner, and then expelled using a conventional method.

After irradiation and cross-linking, when the awns are subjected to heat treatment in an egg tray, the mechanical 1'' three qualities are spread.

If radiation cross-linking is carried out inexplicably, the fluorine-containing end will easily lose the transparency of the tri-rubber, and no flesh color will be produced. It is very advantageous in the field of food industry, for example, because it does not contain cross-linked AIJ, etc., and there is no leaching from molded products. Furthermore, you can feel the effect of sterilization with Hosotsuki.

Next, Example 2 and Comparative Example will be shown to specifically explain the misunderstandings.

Examples From the heat 1-IJ plastic 1 Komi rubber shown in Table 1, 1' [7ζ
F-240 ring sample beef (melted at 230°C using an O-ring pressure molding stone and pressurized for 10 minutes,
From Naochinma Tsuki vc, ■, I7ζ is 1υM r a d
What did you delete? Then, the cross-linked sample piece was compressed by 25% for 24++1 with 7'1loO''C. 11
Natsu/ζ. The results are shown in Table 1."j-8 Table 1 Note 1) A: Vinylidene fluoride/hexafluoropropylene/tetrafluoroethylene (molar ratio 50:30
:20) Fluorine-containing thermal plastic 1 consisting of 85% by weight of polymer segments and 15% by weight of ethylene/tetrafluoroethylene/hexafluoropropylene (molar ratio 43:49:8) polymer segments 1 Raw rubber B: Rubber Al00m average section Triallylisocyanuride!
・Composition C distributed in the 4-risha club tray: Rubber A VCh- and the latter segment t polyvinylidene fluoride segment tojita fluorine-containing storage town'' ■ Kei San Rubber JJ: Vinylidene fluoride/hexafluoro Fluorine-containing thermoplastic rubber F, consisting of propylene (molar ratio 7B:22) polymer segment 85% by weight 2 and ethylene/tetrafluoroethylene/hexafluoropropylene (cell ratio 43:49:8J polymer segment 15% by weight): Rubber 1) 4 parts by weight of triallyl isocyanurate was blended with 100n weight part and 1ζ composition 'proboscis F: Rubber D had 2 segments and the latter segment I-'t polyvinylidene fluorite segment was made into a fluorine-containing thermoplastic rubber. Examples 7-8 and Comparative Examples 1-2 The fluorine-containing molded rubber shown in Table 1 was melted at 230"C.
! After 10 minutes of pressure, a sheet of 2# thick was immediately cooled with water under pressure and heated with gamma rays at room temperature.・1.This sheet sword) lE=+24°C according to JIsK6301Fc
T 4 +r dumbbell #J punch, each JJ! Always measure the physical properties. result? (shown in Table 2).

Table 2 Procedures 7 Yamasho (spontaneous) January 29, 1985 Commissioner of the Japan Patent Office Kazuo Wakamatsu 1, Indication of the case 1982 Patent Application No. 169152 2, Name of the invention Cross-linked fluorine-containing thermoplastic Rubber molded product 3, relationship with the case of the person making the amendment Patent applicant Shin-Hankyu Building (285, 285, 1-12-39 Umeda, Kita-ku, Osaka), Daikin Industries, Ltd. Voluntary action 6, Contents of amendment (1) Specification No. In the second line of page 3, the phrase ``Shiterumu'' is corrected to ``as rubber with 1.''

(2) Page 4, line 18 of the specification [1, 2J and rl,
Correct it to 2J.

that's all

Claims (1)

[Claims] ('') Radiation 4 = 1 gland 1: (Fluorine-containing thermoplastic resin cross-linked by fluorine-containing polyurethane 1). (2) Fluorine-containing polyurethane resin 1! :lE rubber contains at least one FSTMER 1 desirable polymer frequent segment 1゛2 and at least 1 mile of NEFUTOMER 1 fresh polymer ~ frequent segment 7J) and at least one of the following.
The molded article according to claim 1, wherein the molded article is a fluorine-containing plastic rubber which is a fluorine-containing polymer. (31 fluorine-containing ms -nJ plastic 1 discharged rubber is
A molded article according to Clause 2 of the scope of the Jrf patent, consisting of 40 to 95 polymer chain segments and 1 part of 5 to 60 non-mer polymer chain segments.