JPS606748A - Swimming and diving implements made of silicone rubber and part thereof - Google Patents

Abstract

PURPOSE:To provide the titled implements which have improved resistance to sea water, weather and aging by chlorine disinfectant and is prepd. from a silicone rubber having specified rubber hardness, 100% modulus and tear strength. CONSTITUTION:Swimming and diving implements and parts thereof are prepd. from a silicone rubber having a rubber hardness (JIS) of 10-80, 100% modulus of 1-80kg/cm<2> and tear strength of 5kg/cm or above. Examples of the silicone rubbers are those prepd. from, e.g., a silicone rubber compsn. comprising 100pts. wt. diorganopolysiloxane of the formula (wherein R<1> is methyl, phenyl, trifluoropropyl, vinyl with the proviso that at least 50mol% thereof is methyl; a is 1.98- 2.02), 1-200pts.wt. silica filler having a specific surface area of 100m<2>/g or above and an org. peroxide catalyst. Products having greatly improved resistance to weather and water at sea as well as aging by chlorine disinfectant in a swimming pool, can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to swimming and diving equipment made of silicone rubber and parts thereof.

In particular, the object is to provide swimming/diving equipment and parts thereof that have improved anti-aging resistance to disinfectant chlorine in swimming ghouls, or have significantly improved weather resistance and seawater resistance in the ocean.

In recent years, public or private swimming pools have been constructed in various places, and 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, the swimming equipment currently in use, such as swimming cags, made of natural rubber or synthetic rubber made from petroleum and other raw materials, fades in a short period of time, becomes brittle with age, and loses its elasticity. There was a problem. Moreover, when they get wet with water, the rubber surfaces stick together, making it difficult to put on and take off.

Regarding equipment used for diving and sea bathing, which have recently become more and more popular due to the leisure boom, and their rubber parts, conventional products have poor weather resistance and seawater resistance. The problem is that the rubber ages and loses its elasticity (i.e., it loses its function to an extreme extent.) Also, these tools are becoming more colorful as more and more fashionable items are valued. However, with conventional materials, there are limits to coloring, and it was not possible to obtain the desired color, nor was it possible to obtain a transparent material. Second, silicone rubber's excellent water repellency eliminates unnecessary water resistance, making swimming and diving more comfortable, while also improving the ease with which it conforms to the skin and wearability (sensibility). ).

In addition, the masks worn during diving were made of non-transparent synthetic rubber, resulting in extremely narrow visibility underwater, causing 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 bags, 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 training, power Rubber, training paddle.

Diving mask (including strap), snorkel,
Fins, regulator mouthpieces, other diving accessories, rubber parts, and rubber rugs and balls for poolside and coastal areas.

There are various types of balloons and the like, but as mentioned above, there are problems with their durability due to the effects of disinfectant chlorine, seawater, ultraviolet rays, etc.

The present invention has solved these conventional problems. The purpose is to provide swimming/diving equipment and its parts with excellent durability, which is characterized by being made of silicone rubber and has a special rubber hardness (JIB) of 10.
~80 (preferably 15-60), 100% modulus 80t/- (preferably 5-60Kf/1ffl),
Tear strength 5 to 910n or more (preferably 10Kf/α
This is based on the confirmation that products made from silicone rubber having the above physical properties are significantly superior.

To explain this, first, the silicone rubber used in the present invention is required to have the physical properties described above. This is because the target object is swimming/diving equipment and its parts, so if the rubber is too hard or too soft, it will not feel good when used, and it will not tear easily. This is because it is required to be as high as possible.

Therefore, the raw material silicone rubber composition (compound) that provides silicone rubber with such physical properties includes -1'-thyl group, phenyl group, and trifluorogmipyl group.

It represents vinyl groups, of which at least 50 mole percent are methyl groups. 100 parts by weight of diorganopolysiloxane (a is a number from 1.98 to 2.02).

(2) Glue filler 1 to 2 with a specific surface area of 100 &/g or more
00 parts by weight.

(3) Organic peroxide catalyst An organic peroxide catalyst-curable silicone rubber composition comprising: (3) an organic peroxide catalyst is preferably used.

All of the diorganopolysiloxanes as component (1) have the unit formula (R810) (where R is derived from a polycia chitin skeleton represented by a methyl group, a trifluorogummy pyl group, a phenyl group, or a vinyl group). These include, for example, ogtamethyltetracyclosiloxane, hexamethyltrisiglosiloxane, tetraalkyl-travinylciglosoxane, ogtaphenyltetracyclosiloxane, hexaphenyltrisiglosiloxane-tetramethyltetra It can be obtained by polymerizing a mixture of cyclic simiquitin such as phenylsiglosiloxane to a desired degree of polymerization in the presence of an alkali or acid catalyst.The terminal end of the molecule is a hydroxyl group, a vinyl group, or a methyl group. , a phenyl group, or any other organic group - there is no particular restriction on this, but if each of these components contains a large amount of phenyl group in its molecule, the resulting silicone rubber will have poor elasticity, etc. It becomes inferior in quality.

Note that the diorganopolysiloxane as component (1) is not limited to one type, and two or more types of C2 or more may be used in combination.

On the other hand, the adhesive filler as the component (2) may be a conventionally known silicone rubber (for example, fine silica powder such as Hiko-Mudoshiriyoku or silica aerogel). If this particle size is large, it will reduce the mechanical strength of silicone rubber.
This means, for example, that the measured value by the cumulative absorption method is at least to
off//,! It must be applied in a fine powder having a specific surface area of i'.

Bidobe).

(3) Component organic peroxide catalysts include benzoyl peroxide-tert-butyl peroxide, digmylopenediyl peroxide, digmyl peroxide, and tert-butyl peroxide.
Butyl perbenzoate is exemplified, and these are used in an amount of about 0.1 to 5% by weight of diorganopolysiloxane (diorganopolysiloxane).

In the present invention, a platinum compound-based catalyst-curing silicone rubber composition acid comprising tX and (al to dl) components is also preferably used.

2 Indicates a methyl group, phenyl group, trifluoroglobyl group, or vinyl group, of which at least 50 moles are methyl groups, b is a number of 1.98 = 2.02), and in one molecule 100 parts by weight of a diorganopolysiloxane having at least two vinyl groups.

(b) One molecule has three or more water R atoms bonded to a silicon atom, and the number of hydrogen atoms bonded to this silicon atom is 0.3 to 4 per vinyl group of the fat component. Corresponding amount of organohydrodiene polysiloxane, icl specific surface area 100 m'/9 or more glue filler 0
~200 parts by weight.

(d) Platinum-based compound catalyst.

The above diorganopolysiloxane (at) is
It can be synthesized by employing conventionally known methods such as a method of hydrolysis or a method of equilibrating disiloxane and cyclic siloquitin, which serve as terminal groups, in the presence of an alkali catalyst.

The diorganopolysiloxane used as the fal component is not limited to one type, and two or more types may be used in combination.

JJd (The organohydrodiene polysiloxane of the BL component is not particularly limited in its molecular structure as long as it satisfies the above conditions, and it may be non-linear) - branched, cyclic or network-like. also a single i
It may be either a homopolymer consisting of 10 xane units or a block or random copolymer consisting of two or more types of i10 chitin units.

There is also no limit to the degree of polymerization, and it includes high degrees of polymerization with a few to several tens of silicon atoms, but depending on the capacity of one synthesis, it can range from a few to a hundred. It is considered suitable.

The platinum compound catalyst as component (d) above includes monochloroplatinic acid, chloroplatinic acid, olefin, and alcohol.

Examples include complexes with aldehydes and the like, and these are used in a pt amount of approximately 0.1 to 100 ppm.

The above composition requires 1: RSiO units and 30.5 8102 units, or R,Sin,, units -R2SiO
Consisting of unit and 5iO2j 1st position -R3S i Oo
,, unit or R"SiO unit and the molar ratio of R"SiO unit and 30.62SiO unit is 0.5 to 1.5, and ≧ contains an aliphatic unsaturated group in the molecule Organopolysilochitin (R3 represents a monovalent organic group) can also be added. On the other hand, it is also possible to add a nisilanol group-containing polyaxane of composition C, whereby a silicone rubber sponge is obtained.

For colored deposits, desired pigments and dyes may be added.
EK-3Green-SEK -121Yellow-
8EK-122B1ue % Violet SEK -
119Red, and the second one is F5RK of M from Juyo Shiki Co., Ltd.
(red) is exemplified. The amount of these additions is approximately 0.1 to 5 times the total amount of the composition! within the scope of the department.

The silicone rubber composition used in the present invention is:

It is obtained by kneading the above-mentioned components using a mixer such as a roll, a kneader, or a Banbury mixer. (= There is no limit.

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

Various swimming/diving equipment and parts thereof related to the mini-mini of the present invention can be manufactured easily by known molding methods (2) from the above-mentioned silicone rubber composition.
This product has excellent aging resistance to disinfectant chlorine in swimming ghouls, 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 Dimethylpolysiloxane 10 with a sitting degree of polymerization of about s, ooo
0 parts, 90 moles of dimethylsiloxane units, 10 moles of methylvinylsiloxane units, and 7 parts of methylvinylborisyloxane with an average M content of about 8,000, and 95 moles of dimethylsiloxane units.

) 2 parts of a methylvinylpolysiloxane having a degree of polymerization of about 100 and consisting of 5 moles of rubinylsiloxane units.

Ratio - Table i 40 parts of silica aerosil with a value of 300 m'/g and 1 dimethylbo'I/a xane with terminal hydroxyl groups having a viscosity of about 20 cS (25°C)
5 parts were roll-kneaded and the mixture was then heat treated at 1.50° C. for 1 hour to remove volatile siloxane components and water. Next, this roll-kneaded product F was uniformly mixed with 05 parts of benzoyl peroxide as a dicondensation catalyst to obtain a thermosetting silicone rubber composition.

Using this composition, a temperature of 120°C and a molding pressure of 30~/
Compression molding was carried out for 10 minutes under the conditions of d, and then demolded at 200
Diving masks were manufactured by heat treatment at a temperature of 0.degree. C. for 4 hours. In addition, strugs for underwater goggles were manufactured under the same conditions.

The diving mask and strap thus obtained have excellent transparency, and are actually easier to use than the conventional product C: they are easy to swim in and are weather resistant.

It had excellent seawater resistance.

In order to investigate the physical properties of the above silicone rubber, a sheet with a thickness of disaccharide was prepared under the same conditions and a physical property test was conducted, and the results were as follows.

Rubber hardness (JIS) 50 Elongation rate (%) 70°100% modulus (Kr/i) 40 Tear strength (Kf/cm) 35 Tensile strength (Kf/d) 82 Impact modulus (modulus) 41 Example 2 Dimethylsiloxane 90 parts of diorganopolysiloquitin, consisting of 99.85 moles of units and 0.15 moles of methylvinylsiloquitin units, with a degree of polymerization of about s, o o o, and whose molecular chain terminal is a vinyldimethylsilyl group, dimethyl vc
*Diorganopolysiloxane 10 consisting of 97 moles of f-units and 3 moles of qb-methylvinylsiloxane units, with a degree of polymerization of approximately 5.000, and whose molecular chain ends are trimethylsilyl groups.
40 parts of specific surface area 200i/, 9.

5in(OH) SiO□ unit S for 2 moles of O unit
0.73 parts of methyl hyde σ diembolysia xane containing 1 mol of 20J, '5EX-12 manufactured by Dainichiseika Chemical Co., Ltd.
1 part of 2B1ue' and 14.5 ppm of chloroplatinic acid
were uniformly mixed according to a conventional method to obtain a thermosetting silicone rubber composition.

Using this composition, the temperature was 170°C and the molding pressure was 309°C.
A rubber member for a snorkel was manufactured by compression molding for 10 minutes under the conditions of /cPl and then heat treating at a temperature of 200° C. for 4 hours. This product, like the previous one, was of excellent quality.

In order to examine the physical properties of the silicone rubber, a sheet with a thickness of 2 wI was prepared under the same conditions and a physical property test was conducted, and the results were as follows.

Rubber hardness (JIS) 50 Elongation (CH) 520 100 Thymodulus (CKylad) 50 Tear strength (Kf/cm) 45 Tensile strength (Kf/cd) 96 Example 3 Dimethylsiloxitin units 96.85 moles, diphenylsiloxane 4113 moles %, mail = /L/
degree of polymerization approximately 7.0, consisting of 0.15 mole g loxane units
The molecular chain terminal of 00 was vinyldimethylsilyl group The same treatment as in Example 1 was performed to obtain a rubber compacted product. 0.5 part of tertiary butyl digmyl peroxide was uniformly mixed into this mixture to obtain a thermosetting silicone rubber composition.

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

The swimming cag obtained in this way was used for a long period of time in a swimming ghoul 52 which was disinfected with chlorine, and it had excellent durability.

In order to investigate the physical properties of the silicone rubber, a sheet with a thickness of 2 sheets was prepared under the same conditions and a physical property test was conducted, and the results were as shown below.

Rubber hardness (JIS) 20 Elongation (%) 6oO ioo% Modulus (Kt/ctI) 10 Tensile strength CKy/crI) er.

Tear strength Kp/crn) 20

Claims (1)

[Claims] 1. Comb hardness (JIS) 10-80.1001 Modulus 80 Kq/in-Tear strength 5 V4/cI
Swimming/diving equipment and its parts 2 characterized by being made of silicone rubber having physical properties of n or more, the silicone rubber marked #J has the following formula: diorganopolysilochitin represented by a phenyl group, phenyl 1-) IJ fluoro a glopyl group - vinyl group, of which at least 50 moles are methyl groups, a is a number from 1.98 to 2.02) ioom Dobe, (2) Silica filler 1 to 1 with a specific surface area of 100 m''/g or more
2001it part. (3) Organic peroxide catalyst. 3. Swimming/diving equipment and parts thereof according to claim 1, wherein the silicone rubber is a cured product of a silicone rubber composition. (at General formula R810 (R in the formula is methi b 4-1
), phenyl group, trifluoroglovir group. A diorganopolysiloxane having at least 2 vinyl groups in one molecule, including at least 50 moles of 1-functional methyl groups and 1.98 to 2,020 methyl groups, and having at least 2 vinyl groups in one molecule. Dobe. (b) One molecule has three or more hydrogen atoms bonded to silicon atoms, and the number of hydrogen atoms bonded to silicon atoms corresponds to 0.3 to 4 per vinyl group of the tal component. Children's Organohide I Niadiene Polysiloxane. (0) 0 to 200 parts by weight of a silica filler having a specific surface area of 100 rl/E1 or more. Swimming/diving equipment and parts thereof according to claim 1, which are a cured product of a silicone rubber composition consisting of (a) a platinum-based compound catalyst;