JPS58198564A - Silicone rubber swimming and diving implement and component thereof - Google Patents

Abstract

PURPOSE:To provide the titled swimming and diving implement (and components thereof) excellent in resistance to salt water, aging owing to the presence of disinfectant chlorine, and the like, by molding and curing a silicon rubber compsn. with particular characteristics in a given shape. CONSTITUTION:A silicone rubber compsn. having the following physical properties: hardness (JIS) 20-80; 100% modulus 20-50kg/cm<2>; tear strength 15kg/cm or above, is molded. Said comspn. is formed by kneading 100pts.wt. linear diorganopolysiloxane (degree of polymn. 3,000 or more) of the formula[wherein R is methyl, phenyl, trifluoropropyl, vinyl (the content of methyl is 50mol% or more); a is 2-2.001], 20-200pts.wt. silica filler (e.g., fumed silica), specific surface area 100m<2>/g or above and an org. peroxide catalyst (e.g., about 0.1-5wt% benzyl peroxide relative to diorganopolysiloxane) by a roll, a Banbury mixer, and the like.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to swimming/diving equipment made of silicone rubber and parts thereof, and particularly to improving aging resistance against disinfectant chlorine in swimming pools.
Another object of the present invention is to provide swimming/diving equipment and parts thereof that have significantly improved weather resistance and seawater resistance at sea.

In recent years, public or private swimming pools are popping up all over the place.
The number of users is rapidly increasing. However,
In order to manage the hygiene of the increasing number of swimmers, swimming pools are usually disinfected with very strong chlorine. For this reason, swimming equipment such as swimming caps made of natural rubber or synthetic rubber made from petroleum or other mineral materials that are currently in use tend to fade in a short period of time, become brittle due to aging, and lose their elasticity. There was a problem. Also, when they get wet, the rubber surfaces stick together, making it difficult to put on and take off.

Regarding the equipment and rubber parts used in diving and sea bathing, which have recently become increasingly popular due to the leisure boom, conventional products have poor weather resistance and seawater resistance, so the rubber deteriorates in a short period of time. However, there is a problem in that the function is drastically lost due to loss of elasticity. These tools have recently come to be valued for their fascination, and more colorful items have been sought after, but with conventional materials, there is a limit to the coloring that can be achieved and it is not possible to obtain the desired color. There was no, and I couldn't get anything transparent. Material 11 that has no problem with this problem at all
1v. Furthermore, silicone rubber's excellent water-repelling properties eliminate unnecessary water resistance, making swimming and diving more comfortable, and at the same time improving the fit and feel of the product.

In addition, the masks worn while diving were made of non-transparent synthetic rubber, resulting in extremely limited visibility underwater, which caused a sense of psychological anxiety among divers. In order to eliminate this sense of anxiety, the present invention uses highly transparent silicone rubber to widen the field of vision and ensure safety by allowing even a small amount of light to pass through.

In addition to swimming caps, rubber products and rubber parts currently used in swimming pools and the sea include rubber parts for goggles (sponges, straps), ear plugs, nose plugs, bands, belts, stroke rubber for practice, power Rubbers, training paddles, diving masks (including straps), snorkels, fins, regulator mouthpieces, and other diving accessories - rubber parts, Sarah's various rubber mats, balls, balloons, etc. for poolside and beach use. However, as mentioned above, the durability of any of these varies due to the effects of disinfectant chlorine, seawater, ultraviolet rays, etc.

The present invention aims to solve such conventional problems and provide swimming/diving equipment and parts thereof having excellent durability.This invention is characterized by being made of silicone rubber, and has a particularly high hardness (JIB >20 to 80.
100% Mofuyurasu 20-50 Instant/-1 Tear Strength 15
This is based on the fact that products made from silicone rubber having physical properties of (2) or higher are significantly superior.

To explain this, the silicone rubber used in the present invention must have the physical properties described above.This is because the object II is swimming/diving equipment and its parts. If the hardness is too hard or too soft, the feeling of use will be inferior, and in the case of swimming caps, etc., if the 100% hardness value is too low or too high, it will not feel good. is suffering from illness. Furthermore, the tear strength is required to be as high as possible so that it does not tear easily.

Therefore, a silicone rubber composition (compound) having such physical properties as a silicone rubber has the following formula: +1) General formula R&SiO, -,1 (R1
-j methyl)-, phenyl, trifluoropropyl, vinyl group, of which at least 50 mol% is a methyl group, a is a number from 2 to 2001). (2) 20 to 20011 parts of a glue filler with a specific surface area of 100 d/f or more, (3) an organic peroxide catalyst, Catalyst curing silicone rubber 11A
1 composition is preferably used.

All of the diorganopolysiloxanes mentioned above (11 components) consist of a polysiloxane skeleton represented by the unit formula (R, 5iO)n (where R is a methyl group, a trifluoropropyl group, a phenyl group, or a vinyl group). For example, octamethyltetrancrosiloxane,
Hexamethyltrilecrosiloxane, tetraalkyltetravinylcyclosiloxane, offtaf1nyltetraν
7 Siloxane, hexaphenyl tricyclosiloxane, tetramethyltetraphenyl ν chloro ν loxannat cyclic siloxane are mixed and fermented in the presence of an alkali or #catalyst σ) to form the desired polymerization reaction. The terminal of the molecular chain may be a hydroxyl group, a vinyl group, a methyl group, a phenyl group, etc., and there is no particular restriction on this. Ingredients containing too many phenyl groups in
In this case, the obtained silicone rubber becomes inferior in properties such as elasticity.

Note that the diorganopolysiloxane as the component (1) is not limited to 1#, and 2# or more may be used in combination.

On the other hand, the silica filler as component (2) may be a known filler conventionally used in silicone rubber, and examples thereof include fine silica powder such as hume silica and silica aerogel. It must be a fine powder that exhibits the mechanical area of silicone rubber. The amount of silica filler 1 to be blended is 20 to 200 parts by weight based on the 11 components mentioned above.

(3) Component organic peroxide catalysts include benzoyl peroxide, tertiary butyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, and tertiary butyl peroxide.
Examples include butyl perbenzoate, which is approximately 0.1 to diorganopolysiloxane! 51t
%used.

Also included in the present invention are systems (a) to (n) described below.

A platinum compound vehicle-curable silicone rubber composition is also preferably used.

(a) represented by the general formula (R in the formula represents a methyl group, phenyl group, trifluoropropyl group, or vinyl group, of which at least 50 mol% is a methyl group; n is a number of 400 or more); υ100 parts by weight of organopolysiloxane, (b) 3a hydrogen atoms bonded to silicon atoms in one molecule
Based on the above, the salivary organohydrodiene polysilochitin has 03 to 4 hydrogen atoms bonded to silicon atoms per vinyl group of component 1j (a), and (c) specific surface area 100 rr. 0 to 200 parts by weight of silica filling side on /1fPJ, ((1) (R')S810°, unit, (R'
1, 810 units and S10. Unit (R in these formulas
' represents a vinyl group and a saturated-valent hydrocarbon group) organopolysilochitin θ ~ 50 parts by weight, (e) a platinum-based compound catalyst, and (a) the above-mentioned glue organopolysilochitin is a corresponding silane compound. Conventionally known methods, such as (co)hydrolyzing one or more of the following, or equilibrating and reacting di-v-chitin and cyclic silochitin, which serve as terminal groups, in the presence of an alkali catalyst. It can be adopted and synthesized.

Note that the diorganopolysilochitin used as component (a) is not limited to one type, and two or more types may be used in combination at the same time.

The organohydrodiene polysiloxane as the component (b) is not particularly limited in its molecular structure as long as it satisfies the conditions described above.
It may be either cyclic or network-like, and may be either a homopolymer consisting of a single siloxane unit or a block or random copolymer consisting of two or more types of siloxane units.

There is also no limit to polymerization, and it includes highly polymerized products with a few to several tens of silica particles, but from the four day period of synthesis, it is possible to produce a few to a hundred silica particles. preferred.

The organopolysilochitin of the above component (6) is a known one described, for example, in Japanese Patent Publication No. 45-9476.
contains a silicon-bonded vinyl group, (R'), 81
0. , unit pair S10. A unit ratio of 0.5:1 to 1:l is preferred.

The platinum-based compound catalyst of component (e) above includes chloroplatinic acid,
Examples include complexes of chloroplatinic acid and olefins, alcohols, aldehydes, etc., which have a pt content of approximately 0.1 to 100 pt.
used.

It is also possible to add a polysiloxane containing a relanol group to the above composition, whereby an i/Il cone rubber sponge can be obtained.

In addition, when coloring is applied, desired pigments and dyes may be added.
EK-3Green, 8gK-121Yel
low, BEK-122Blue, Violet) sgK-119Red % Kieolo
rv, and FISRK (red) manufactured by Juyo Shiki Co., Ltd. are exemplified. The amount of these additives to be added is approximately 0.1 to 5% by weight based on the total amount of the composition.

The silicone rubber composition used in the present invention is obtained by mixing the above-mentioned components using a mixer such as a roll, kneader, bumper mixer, etc., and there is no particular restriction on the order of blending.

The silicone rubber composition used in the present invention includes:
Known additives to improve storage stability and reduce heat shrinkage during crushing, as well as other known additives or foaming agents to improve the physical properties of silicone rubber, as necessary. It is also possible.

Various swimming/diving equipment and parts thereof related to the present invention can be made from the above-mentioned silicone rubber compositions.
It can be easily produced by a known molding method, and has excellent aging resistance to disinfectant chlorine in swimming pools, weather resistance in the sea, seawater resistance, etc.

Next, an example will be given. However, in the following description, all parts simply refer to parts by weight.

Example 1 100 parts of dimethylpolysiloxane with a degree of polymerization of 10,000, 90 mol% of dimethylsiloxane units, and 10 mol% of methylvinylsiloxane units.
Methyl bierbo 9LI lochifufu moiety, 95 mol% of dimethylsiloquitin units, 5 mol% of dimethylsiloquitin units, 2 parts of methyl and nylpolysiloquitin with a degree of polymerization of 100, and a specific surface area of 300 rd/P. 40 parts of silica airgel and 4 parts of diphenylsilanediol were roll-kneaded, and then the kneaded product was mixed with 150 parts of silica airgel.
A heat treatment was performed at ℃ for 1 hour to remove volatile simixane components and moisture. Next, 0.5% of benzoyl peroxide as a curing catalyst and 1 part of "SgK-121YelIOW" manufactured by Dainichiseika Kagyo Co., Ltd. were mixed uniformly into this roll mixed material to form a thermosetting silicone rubber composition. I got it.

Using this composition, a temperature of 120°C and a molding pressure of 3011
A bright yellow swimming cap was produced by compression molding for 10 minutes under the condition of 7 txl, then demolding and heat treatment at a temperature of 200° C. for 4 hours. A strap for underwater goggles was also manufactured under the same conditions. The cap and strap thus obtained were used for a long period of time in a chlorinated swimming pool and were extremely durable.

In order to investigate the physical properties of the V9 cone rubber, a 2-thick sheet was prepared under the same conditions and a physical property test was conducted, and the results were as follows.

Hardness (JIS) 30 elongation (%)
700 100%, Modulus (Q/j) 40 Tear strength? /am) 3 Is tensile strength CEP/1
xl) 82 rebound modulus (%)
4m Example 2 Dimethylsilochitin units 99.8! Polymerization degree s consisting of S mol% and methylvinyl vty chitin units 015 mol%, 90 parts of diorganopolysiloxitin in which the molecular chain terminal of ooo is a vinyldimethylsilyl group, 97 mol% dimethylsiloxitin units, methylvinyl siloquitin 10 parts of diorganobossilochitin, which has a degree of polymerization of 5,000 and is composed of 3 mol% of chitin units, and whose molecular chain terminal is a trimethylsilyl group;
40 parts of fume silica with a specific surface area of 200w1/7, 81
)T(OH,), O,, 810.0 for 2 moles of units. 0.73 parts of methylhydrodienepolysilochitin containing 1 mole of units, "5EK-12" manufactured by Dainichiseika Chemical Co., Ltd.
2B1ue” 1 part, and 14.5p of chloroplatinic acid
pm was uniformly mixed according to a conventional method to obtain a thermosetting silicone rubber composition.

Using this composition, temperature 170"C1 molding pressure 30I
A rubber member for a snorkel was produced by compression molding under P/cd conditions for 10 minutes, then demolding and heat-treating at a temperature of 200° C. for 4 hours. This product, like the previous one, was of excellent quality.

In order to investigate the physical properties of the above silicone rubber, a 2-thickness plate was prepared under the same conditions and a physical property test was conducted, and the results were as shown in the pot.

Hardness (JIB) 30 Elongation (%) 520 100 Mofuyuras (?/cj) 50 Tear strength I
P/(211) 45 Tensile strength ('P/(1
1/) 96 Example 3 A molecule of approximately 7,000 molecules consisting of 9685 mol% of dimethylsilox+7 chitin units, 3 mol% of diphenylsilokinane in the middle, and 015 mol% in the middle of methylvinylsilokinane. Diorganopolysiloxane as a group 11. ) (1 part, Hijumenbeak 200rr//,
40 parts of hume silica of No. 9 and 0.5 part of tertiary butyl cumyl peroxide were uniformly mixed to obtain a thermosetting silicone rubber composition.

Using this composition, a diving mask and swimming goggles were made under the conditions of 170°C x 8 minutes and after-cure at 200°C x 4 hours.

The feature of this Mli product is that it obtains highly transparent silicone rubber, and naturally the diving masks and swimming goggles that were manufactured were also highly transparent. These products had a wider field of vision and were easier to swim in than conventional products.

Patent originator: Shin-Etsu Chemical Co., Ltd. -4!50

Claims (1)

[Claims] 1. Swimming and diving characterized by being made of silicone rubber having physical properties of hardness (JI8) 20-80, 100% modulus 20-509/ej, and tear strength 15Q/as+ or more. Tools and their parts! , the silicone rubber has the following general formula: (11)
7" Indicates a phenyl group, a phenyl group, a trifluoropropyl group, or a vinyl group, of which at least 50 mol% is a methyl group. & is a number from 2 to 2.001) Diorganopolylerochitin 100 polymeric part having a degree of polymerization of 3.000 or more and having a linear structure, (2) Filled with glue having a specific surface area of 100tn''/j' or more 20 to 200 M parts of swimming/diving equipment and its parts 3, which is a cured product of a silicone rubber composition comprising: (3) an organic peroxide catalyst; and (3) an organic peroxide catalyst. The rubber has the general formula (&) (R in the formula represents a methyl group, phenyl group, trifluoropropyl group, or vinyl group, of which at least 50 mol% is a methyl group, n is a number of 400 or more) 1 oya 1 part of diorganopolysilochitin, (b) having 3 or more hydrogen atoms bonded to a silicon atom in one molecule, and bonding to this silicon atom per vinyl group of the component (1). (o) kk, surface area toom''/p or more v9 force filling MO ~ 200 parts by weight, (d) (R') , 810. , unit, (R'),
810 units and 810. Curing of a silicone rubber composition comprising 0 to 50 parts by weight of an organopolysilochitin unit (R' in these formulas represents a vinyl group and a saturated-valent hydrocarbon group), (e) a platinum-based compound melting medium, and Swimming/diving equipment and parts thereof according to claim 1, which are products