JPS5823838A - Nonadhesive rubber composition - Google Patents

Abstract

PURPOSE:A water-repellent and oil-repellent composition having improved nonadhesiveness, and improved mold release characteristics after molding and vulcanization, requiring no outer release agent, obtained by blending rubber with a specific fluorine-contained copolymer. CONSTITUTION:Rubber is blended with 0.1-20wt% based on rubber of a fluorine-contained polyester type copolymer having structural unit shown by the formulaIor II (Rf is 3-21C perfluoroalkyl; n is 0 or 1), structural unit shown by the formula III (R is a residue after removal of a group shown by the formula IV from a cyclic acid anhydride), and, if necessary, structural unit shown by the formula V (R1-R4 are each H, alkyl which may have a substituent group, or aryl which may have a substituent group) and/or structual unit shown by the formula VI. Preferably the amount of the component shown by the formulaIor the component shown by the formula II in the copolymer is 10- 60mol%, the amount of the component shown by the formula III is 40-50mol%, and the amounts of the component shown by the formula V and/or component shown by the formula VI are 0-40mol%.

Description

[Detailed description of the invention] Rubber molded product I! There are two known methods for imparting non-adhesive properties to surfaces. One is the method of forming a thick mold after vulcanization molding, and the other method is the method of forming a thick rubber after vulcanization molding.
This is a method of post-vulcanization molding using a K% anti-stick agent.

For the former, silicone-based, wax-based, etc. sII
Many agents have been developed and used in rolling machines to improve non-adhesive properties, but the non-adhesive properties themselves are by no means satisfactory, and they are not always effective in terms of durability and work efficiency. The method is warm. In addition, in the latter method, low-molecular polytetrafluoroethylene, dimethyl silica/oil, stearic acid, carbon fluoride, etc. have traditionally been used, but none of these compounds have a non-adhesive property.
f11 legs<f! The present invention focuses on the above points, and as a result of intensive research into the non-adhesive filler that should be incorporated into the composition of the vulcanizing agent, a certain fluorine-containing compound was found. The present invention was completed by discovering that the intended purpose could be achieved.

That is, the present invention provides a fluorine-containing polyester copolymer 1 having the following structural units: indicates an integer of l] indicates nine residues excluding ν and 0 0.] and according to must l! (o) 400B, l, 011 凰, + [kudashi s
1 to 4 are each a hydrogen atom, an alkyl group or an alkyl group having a substituent, and 9 is an aryl group or an aryl group having a substitution f#.] ν and /119 are (N(CH鵞)鳳) ) Ikuo = c-i.

[However, RI represents a hydrogen atom, 9 represents an alkyl group, an aryl group, and m represents an integer of 2t or 8. ] is contained in the rubber.

In the present invention, by blending the above-mentioned copolymer into a rubber composition, bleeding of the copolymer (seepage on the !I! surface) occurs on the surface of the rubber molded product after vulcanization molding. Leading to having a non-stick surface. l! In addition to the above objects, the present invention also provides the following effects. That is, (
1) Even in the process of rubber molding and vulcanization, the separation from the mold is improved and no external molding agent is required. (1) Water repellency based on perfluoroalkyl groups on the surface of the vulcanized molded product 9 It can impart oil repellency, improve resistance to water-based and oil-based stains, and suppress rubber deterioration. Furthermore, in order to prevent the adhesion that occurs between conventional rubber products when stacking them together, it is necessary to use a self-dispersion inhibitor such as talc powder. In the case of light coating, there is no need for anti-fouling agents such as carbon dioxide, and the workability is significantly improved.

The copolymer used in this book *@ is known to the Society, and if you look at it, you will find it in the article No. 58-11196911. tL listed in the issue? I'm coming.

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(9) formula: (Rf is a perfluoroalkyl group having carbons a8 to 21, n is O or 1
epoxide represented by the formula (B): 1 (representing an integer of or an alkyl group having a substituent, an aryl group having a substituent, or an aryl group having a substituent). It can be obtained by reacting [1i(/ether) represented by ) under heavy metal conditions.

Perfluoroalkyl-1,! - dipoquinethane (n=
case O) is described in German Patent Application No. 2160788. M9, 8-perfluoroalkyl-
L2-Epoxypropane (for n W 1) Du, 4I
1844-261! It is stated in the bulletin details of No. 86.
It can be produced by the reaction of p, 8-perfluoroalkyl-W-dobrobanol-1 and an alkali hydroxide. Here, the perfluoroalkyl group has 8 to 8 carbon atoms.
21, particularly preferably 6 to 16. Two raw materials with different numbers of carbon atoms in perfluoroalkyl groups are used.
Mixtures of more than one epoxide can also be used.

The cyclic acid anhydride (b), which is another raw material, is bonded to two adjacent O carbon atoms (which may be connected to each other by a single bond or a double bond) and has 98 silyl atoms in the carbo. It is a five-membered ring compound that is dehydrated from a group, and examples thereof include cono-phosphoric anhydride, maleic anhydride, phthalic anhydride, pyromellitic anhydride 11, L1! -Cyclohexanedicarboxylic anhydride, tetrahydrophthalic anhydride, 1.2
, 8.4-pa-bentanetetocarboxylic dianhydride,
l, 2-cyclobutanedicarboxylic anhydride, anhydride/Dick acid, 1. ! - naphthalene dicarboxylic acid 1m hydrate,
2.8 Naphthalene dicarboxylic acid anhydride and other substituted products thereof can be mentioned.

Terene oxide, propylene oxide, isoptylene t
Examples include epino-10-genhydrin such as oxide, butadiene oxide, styrene oxide, and shrimp chlorohydrin, and alkyl or aryl glycidyl ethers such as methyl glycidyl ether and phenyl glycidyl ether.

Another raw material - t' is a cyclic imino ether <c
-2> Examples include 2-oxazoline, 6゜6-shihi)'' a 4 EI L 8-oxazine, etc. These substituted conductors can be mentioned.9 In the copolymer according to the present invention 2, (the content of Jri is 10
~60 mol% is preferred. When the amount of paper is less than 4%, the non-adhesiveness is poor, and a large amount of addition to the rubber causes 2i1, which deteriorates the physical properties of the rubber. 60 mol%
If the amount is more than I, the affinity for rubber generally decreases, so it is not preferred. (b) Regarding 2 and (C), (b) is 40 to 60 mol% from the viewpoint of synthesis and compatibility.
, (C) is most preferably 0-40 mol%.

In the present invention, when (C) is used as a large polymer component, it is preferable because effects such as improved compatibility of the Rf group-containing polyester compound with rubbers can be expected.

The rubber to which the adhesive filler of the present invention is to be blended can be selected from a wide range, such as isoprene rubber,
Not only synthetic rubbers such as chloroprene rubber, epichlorohydrin rubber, fluororubber, silicone rubber, and urethane rubber, but also natural rubber can be used.

Various additives that have been commonly used in fiber-packing acid products can be added, such as vulcanizing agents, vulcanization accelerators, vulcanization aids, acid acceptors, and lubricants. , fillers, and other additives that are generally added to rubber.

Example 1 A paper rubber vulcanized molded product was produced using the following formulation and vulcanization conditions, and the non-adhesive property (tm) of the surface of the resulting nine molded products was determined.

Table 1 shows the contents of the fluorine-containing polyester copolymer used as a non-adhesive agent, and Table 2 shows the toe non-adhesive properties.

For comparison, Table 2 also shows the results of nine cases in which conventionally known additives were mixed.

[Blend composition]

Daiel G301 (7-piece rubber: Weight part: Gui Mein Kogyo Co., Ltd. II) ZG.

PerhexaLSI5 (Crosslinking agent: NOF #II)
L, S tie 2 (triallyl isocyanurate: cross-linking agent: manufactured by Nippon Kasei Co., Ltd.) 4.0 Carbon black ("Narmax") 20 Non-sticking agent
Predetermined amount (listed in Table 2) □ [Vulcanization equipment] Press vulcanization tSO℃ A sheet of 10wxllawxB is created by press vulcanization.

Part II! However, (1) and (1) in Table 1 above also indicate the following.

However, in 1), I113 is 65 mol%, m-4
is 28 mol%, 11!6 is 11 mol%, 臘=6 is 4 mol%, and Otori=7 is 24 mol%. Off, OF, ), OH, 0H10
F (011), and the physical properties were measured using the following method.

◎Water repellency 2 and oil repellency: The contact angle of water and n-hexadecane is measured using a contact angle measuring device (goniometer), and the water repellency and oil repellency are indicated by the contact angle 0. ◎Acrylic peeling crab A tape with acrylic $1 as adhesive was applied to the rubber plate am, and after basting it with a rubber roll (8 #/dG), the peeling method was tso' peeling, and the tensile speed was 111.
1! ! 00■/m, measure peel strength with tape width 801 〇◎ SMS of polyester resin: Polyester resin [Polyset F1g! 1mu FT-6=
After thoroughly mixing 100 parts by weight of Hitachi Chemical Co., Ltd. with 1 part by weight of methyl ethyl per as a hardening agent and 1 part by weight of the middle side,
Impregnate it with 8X@sO tape/Domatsu (Nitto Boseki Co., Ltd.) and press it onto the rubber plate surface with a hand wheel! After curing by leaving at 6°C for 24 hours, the peeling force at 9007% crease was measured using a tensile tester.

O rubber comrades O non-adhesiveness: Layer 3 rubber plates and jIP with a rubber roll (8#/dG)
The non-adhesiveness of the rubber plate was measured by pulling it off by hand after applying it.The light depends on the following criteria.

O: Not glued at all (even if you lift one, the other will not follow) (,): If you lift one, the other will follow, but it will collapse under its own weight.

Δ: Can be peeled off with little force.

×: Cannot be peeled off without extremely strong force.

Example 2 Fluorine-containing polyester polymer (experiment number) shown in Table 1
Table 8 shows the non-stick properties of the rubber surface after internal addition to chloroprene rubber and vulcanization. The molding conditions for chloroprene rubber are as follows.

〔Molding condition〕

l) Compounded product name Proportion (parts) Neoprene &-40100 Stearic acid (anti-blocking agent) 0.6 Magnesium oxide (vulcanizing agent) 2.0 Zinc oxide (vulcanizing agent) 6.0 Tsukura Rum (anti-aging agent) @) 10 Tsukuseller 2! (Vulcanization accelerator) 0.6 Carbon 5ay (filler > 80 Clay (filler) 40 Fluorine-containing polyester polymer O to 6 (experiment number) Press vulcanization at tSO℃XtO minutes A sheet F of 10s, 105 x 8c was prepared by kneading the mixture at the above ratio using a kneading roll and press vulcanization, and the non-adhesive properties of the rubber surface were examined using the same test method as in Embroidery Example 1.

Claims (1)

[Claims] ■ Fluorine-containing polyester Kyodo 2 having the following structural units:
Combination [However, Rfa carbon number is 3~! 1 is a perfluoroalkyl group, n is 019, and 1 is an integer. ] Residues excluding ν and 0 0 are shown. ] and as necessary (c) 400B, IL, 0chi84chi [however, %R
1 to B4 each represent a hydrogen atom, an alkyl group, an alkyl group having a substituent, an aryl group, or an aryl group having a substituent. ], [Friend, "@ is a hydrogen atom, -alkyl, ru group, or aryl 畢s m represents an integer of 2 or 3], -90
.
~20% by weight-addition of claim II characterized in that
Non-adhesive rubber molding as described in Section 1 of s.