JPH07292504A - Cup for swimming suit - Google Patents

Abstract

PURPOSE:To obtain a cup for swimming suit, excellent in heat, whether, chemical, deformation and discoloration resistances and by coating the skeleton lattice surface of a plastic foam base material having an open-cell foam structure with a silicone rubber (foam) and forming the resultant composite material into a bust cup shape. CONSTITUTION:The skeleton lattice 2 surface of a plastic foam base material 1 having an open-cell foam structure is coated with a silicone rubber or a silicone rubber foam 3 and the resultant plastic foam/silicone rubber composite material 4 is formed into a bust cup shape. As the silicone rubber for coating the plastic foam base material, an addition reaction curing type composition obtained by curing a curable liquid silicone rubber composition is preferably used. As the curable liquid silicone rubber composition, a composition essentially composed of a diorganosiloxane, an organohydrogenpolysiloxane, a platinum- based catalyst and an antimicrobial agent is preferably used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bathing cup used to protect a bust when wearing a swimsuit, form an aesthetic shape, and enhance fashionability.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
As a cup for wearing water used to protect the bust when wearing a swimsuit, various materials, shapes and structures are commercially available. For example, ethylene-vinyl acetate copolymer (E
There is a thermoplastic plastic film such as VA) coated with cloth, but it has no heat resistance,
There is a problem that the shape is deformed by drying with a dryer or washing with warm water. There is also a plastic foam such as polyethylene foam coated with cloth, but this also has no heat resistance and has the same drawbacks as EVA. Further, although there is a polyurethane foam covered with a cloth, it has a defect that it is yellowed by ultraviolet rays, and when it is subjected to external pressure, it causes a settling, which makes shaping difficult.
In addition, there is also a non-woven fabric covered with a cloth, but this has a drawback that the shape is severely deformed by washing.

The present invention has been made in view of the above circumstances, and is excellent in heat resistance, weather resistance, durability, chemical resistance, and a water-wearing cup that does not easily lose its shape or discolor, and is particularly excellent in antibacterial property. It is intended to provide a watering cup.

[0004]

In order to achieve the above-mentioned object, the present invention provides a plastic foam / silicone rubber in which a skeleton lattice surface of a plastic foam substrate having an open cell structure is coated with silicone rubber or silicone rubber foam. A cup for wearing made by molding a composite, or a plastic foam / silicone rubber composite with a woven cloth, a non-woven cloth, a plastic film, or a synthetic rubber sheet laminated on either or both of the front and back surfaces thereof to form a bust cup shape. I will provide a. In this case, it is preferable to use the above-mentioned composite material, especially one in which an antibacterial agent such as antibacterial ceramics is mixed in the silicone rubber or the silicone rubber foam. In addition, a plastic foam / silicone rubber composite, or a laminate of a woven fabric, a non-woven fabric, a plastic film, or a synthetic rubber on one or both of the front and back surfaces has a flexural repulsion property according to JIS-L-1096, and is a C method ( Loop hardness in loop compression method) is 200
A material having a loop repulsion rate of 30% or more at 50% compression and up to 3000 gf is more suitable because it is particularly excellent in fit, resilience and bust shaping.

The swimming cup of the present invention, which is formed from the above composite, has the following effects. 1. The water-immersive cup made of the above composite has excellent heat resistance and does not deform due to thermal deformation when it is dried in a swimsuit dryer with hot air, so that the cup does not lose its shape. 2. Since the above composite has excellent weather resistance, particularly UV resistance, even if it is exposed to direct sunlight for a long time in a sea bath, a tanning salon, etc., it will not yellow or settle, and the performance as a swimsuit cup will deteriorate. There is no. 3. The composite has excellent chemical resistance against chlorine and sun oil for disinfecting the pool, and does not deteriorate the performance as a swimsuit cup. 4. As a swimsuit cup, it has excellent bust shaping and softness. 5. As a swimsuit cup, it has excellent elasticity and shock absorption, and has a high ability to protect the bust. 6. Since the composite has a lower water absorption rate than the plastic foam alone, it is quick-drying, and it dries quickly even if it gets wet in a sea bath or swimming, and it dries quickly even when it is washed. 7. Excellent antibacterial and deodorant performance due to the combination of antibacterial agents. 8. The cup has high bending resilience, does not lose its shape when worn, and has excellent resilience even when deformed by external force.

The present invention will be described in more detail below. As shown in FIG. 1, in the cup for wearing of the present invention, the surface of the skeleton lattice 2 of the plastic foam substrate 1 having an open-cell structure is silicone rubber or silicone rubber foam. It is mainly composed of a plastic foam / silicone rubber composite 4 coated with 3. In this case, the silicone rubber or the silicone rubber foam 3 may cover the skeleton lattice 2 so as to leave the structure of the open cells (three-dimensional internal open spaces) of the plastic foam substrate 1 or completely fill the open cells. It is also possible to coat the entire surface of the plastic foam substrate 1 to form a thin layer consisting of silicone rubber or silicone rubber foam, but in order to prevent the cup from becoming too hard, leave open cells. It is preferable to coat silicone rubber or silicone rubber foam 3 on the. In addition, the wearing cup 5 is shown in FIG.
As shown in FIG. 3, it may be formed into a bust cup shape using only the composite 4, and as shown in FIG.
One of the front and back surfaces of this composite 4, preferably both, laminated with a woven fabric, a non-woven fabric, a plastic film or a rubber sheet 6 may be formed into a bust cup shape (FIG. An example in which both surfaces are covered with a woven cloth, a nonwoven cloth, a plastic film or a rubber sheet 5 is shown).

In this case, the plastic foam having an open cell structure preferably has a relatively uniform foaming structure and flexibility, and specifically, the number of cells is 10.
0 to 100,000 pieces / cm ³ , specific gravity of 0.01 to 0.
It is preferably about 5. Examples of the material include polyethylene, polypropylene, polyurethane, polyvinyl chloride, polystyrene, polybutadiene, acrylonitrile butadiene, styrene-alkyd resin, acrylate styrene acrylonitrile, cellulose, chlorinated polyether, ethylene vinyl acetate, fluororesin, polyacryl. Foams having an open cell structure such as nitrile, phenolic resin, polyacetal, polyamide, polyester and the like can be mentioned, and among these, polyether urethane foam, polyester urethane foam and polyethylene foam are particularly preferable.

[0008] The plastic foam / silicone rubber composite constituting the bathing cup of the present invention is obtained by impregnating the above-mentioned plastic foam substrate with a curable liquid silicone rubber composition and then curing the liquid silicone rubber composition. be able to.

Such curable liquid silicone rubber compositions include those mainly composed of linear structure diorganopolysiloxane or those mainly composed of varnish structure organopolysiloxane. Use a rubber or silicone rubber foam.

As this liquid silicone rubber composition,
Addition reaction curing type, heat curing type using peroxide,
UV using an initiator that is radically cleaved by ultraviolet light
There are various curing types such as curing type and vulcanization type that uses electron beam or microwave, but considering that it is used by impregnating plastic foam, the addition reaction curing type is easier to work with. preferable.

The addition reaction-curable liquid silicone rubber composition used in the production of the cup for wearing of the present invention includes
(A) A diorganopolysiloxane containing at least two alkenyl groups directly bonded to a silicon atom in one molecule,
(B) A hydrogen atom (≡Si) directly connected to a silicon atom in one molecule.
An organohydrogenpolysiloxane containing at least two —H groups), a platinum-based catalyst (c), and an antibacterial agent (d) are essential components.

Here, as the component (a), those represented by the following formula (1) are preferable.

[0013]

[Chemical 1] (However, in the formula, R ¹ is an alkenyl group such as a vinyl group or an allyl group, R ² is a different or the same kind of a substituted or unsubstituted monovalent hydrocarbon group, p is 50 to 100,000, and q / p = 0 to 0. It is 1.)

In the above formula, R ¹ is an alkenyl group such as vinyl group or allyl group, and vinyl group is particularly preferable. R ² is different or the same kind of substituted or unsubstituted, preferably 1 to 10 carbon atoms.
Is a monovalent hydrocarbon group, and as the monovalent hydrocarbon group,
For example, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group, an aryl group such as a phenyl group and a tolyl group, or a part of a hydrogen atom bonded to a carbon atom of these groups or Chloromethyl group, trifluoropropyl group, which are all substituted with halogen atom, cyano group, etc.
A monovalent hydrocarbon group excluding an aliphatic unsaturated group selected from a cyanoethyl group and the like can be mentioned, and a methyl group is particularly preferable. Further, p is 50 to 100,000, q / p = 0 to
It is 0.1. The viscosity of the diorganopolysiloxane of the component (a) is preferably 100 to 100,000 cp at 25 ° C.

The organohydrogenpolysiloxane (b) acts as a crosslinking agent for the component (a),
It may be linear, cyclic or branched. This organohydrogenpolysiloxane must have at least two ≡Si—H groups in one molecule, and 2
The one having a number of ≡Si—H groups can extend the chain length of the diorganopolysiloxane molecule of the component (a) to lower the hardness or increase the strength of the cured product, while having 3 Those having at least ≡Si—H groups can control the hardness and elastic modulus of the cured product. The amount of the organohydrogenpolysiloxane blended is such that the ≡Si—H group in the organohydrogenpolysiloxane is 0.5 to 4 in molar ratio with respect to the alkenyl group in the diorganopolysiloxane of the component (a). The amount is preferably in the range of 1 to 2.

As the component (b), particularly, the following formula (2) R ³ _a H _b SiO _{(4-ab) / 2} (2) (wherein R ³ is a group excluding an aliphatic hydrocarbon group) Valent hydrocarbon group, a and b are 0 ≦ a ≦ 2, 0 <b ≦ 3, 0 <a + b ≦
It is a positive number that satisfies 3. ) Are preferable.

In the formula, R ³ is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, excluding an aliphatic hydrocarbon group,
For example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group, an aryl group such as a phenyl group and a tolyl group, a chloromethyl group, 3,3,3-
Examples thereof include a substituted monovalent hydrocarbon group such as a trifluoropropyl group, and when a plurality of them are present, they may be the same or different. The monovalent hydrocarbon group is preferably a methyl group or a phenyl group because it is easily available. In addition,
A hydrogen atom directly connected to a silicon atom has a
It may be on the side chain.

As the platinum-based catalyst of (c), a known catalyst for addition reaction can be used in a catalytic amount, specifically, chloroplatinic acid,
Examples thereof include alcoholic solutions of chloroplatinic acid, complexes of chloroplatinic acid with olefins and vinylsiloxanes, platinum black and the like.

The antibacterial agent (d) is a component that imparts antibacterial properties to various bacteria and the like coming from seawater, pool water, etc. to the water-wearing cup of the present invention, and the antibacterial agent is not particularly limited, but is particularly an antibacterial ceramic. Is preferred. As a specific commercially available product of this antibacterial ceramic, Zeomic manufactured by Shinagawa Fuel Co., Ltd. can be mentioned. The amount of the antibacterial ceramic compounded is in the range of 0.1 to 5 parts, preferably 0.5 to 3 parts, per 100 parts (parts by weight, the same applies hereinafter) of the component (a) diorganopolysiloxane. .

Further, the liquid silicone rubber composition used for the production of the cup for wearing of the present invention is also preferably an aqueous emulsion type. The composition of this aqueous emulsion type is (e) a silicone aqueous emulsion obtained by emulsifying an organopolysiloxane having at least two hydroxyl groups bonded to silicon atoms in one molecule with water using an anionic emulsifier, (f) amino A dispersion of a functional silane or a reaction product of a hydrolyzate thereof and an acid anhydride and colloidal silica, (to) an epoxy-functional alkoxysilane, (h) a curing catalyst, and (d) an antibacterial agent. it can.

In this case, in the silicone aqueous emulsion of the component (e), the organopolysiloxane having a hydroxyl group has a hydroxyl group bonding position,
The organic group other than the hydroxyl group, the molecular structure, the degree of polymerization, etc. are not particularly limited, and various conventionally known ones can be used. The molecular weight is preferably 10,000 or more.

In this case, as the organopolysiloxane, an α, ω-dihydroxyorganopolysiloxane represented by the following formula (3) or an organohydroxypolysiloxane represented by the following formula (4) can be used.

[0023]

[Chemical 2] (However, in the formula, R ⁴ and R ⁵ are different or the same kind of substituted or unsubstituted monovalent hydrocarbon groups excluding the aliphatic unsaturated hydrocarbon group, and L represents an integer of 200 to 3000.)

[0024]

[Chemical 3] (However, in the formula, R ⁶ , R ⁷ , R ⁸ , and R ⁹ are respectively different or the same substituted or unsubstituted monovalent hydrocarbon groups excluding aliphatic unsaturated hydrocarbon groups, M is 2 to 20, and N is Indicates an integer of 3 to 20.)

In the formula (3), R ⁴ and R ⁵ are different or the same kind of substituted or unsubstituted, preferably monovalent hydrocarbon groups having 1 to 10 carbon atoms, such as methyl group, ethyl group and propyl group. Groups, alkyl groups such as butyl group, pentyl group and hexyl group, aryl groups such as phenyl group and tolyl group, substituted monovalent hydrocarbon groups such as chloromethyl group and 3,3,3-trifluoropropyl group. be able to. Also, equation (4)
Where R ⁶ , R ⁷ , R ⁸ and R ⁹ are each a different or the same substituted or unsubstituted monovalent hydrocarbon group except for the aliphatic unsaturated hydrocarbon group, preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms. From the viewpoint of ease of use and viscosity of the resulting composition, these are methyl groups,
A phenyl group is preferred.

This organopolysiloxane is a straight-chain or branched-chain organopolysiloxane having a ring-opening reaction of a cyclic siloxane such as octaorganocyclotetrasiloxane, or having a hydrolyzable group such as an alkoxy group or an acyloxy group. Can be synthesized, or a method of hydrolyzing one kind or two or more kinds of organohalogenosilane can be synthesized.

The anionic emulsifier used in the preparation of the component (e) is preferably a conventionally known emulsifier, preferably one having a surface-active action that can serve as an emulsion polymerization catalyst, for example, sulfonic acids, sulfuric acids, Phosphoric acids or salts thereof, specifically, aliphatic sulfates such as sodium lauryl sulfate, aliphatic hydrocarbon group-substituted benzenesulfonic acid such as dodecylbenzenesulfonic acid, aliphatic hydrocarbon group-substituted naphthalenesulfonic acid, polyethylene glycol Examples thereof include sulfate ester salts and lauryl phosphate.

The silicone aqueous emulsion of the component (e) can be prepared by various conventionally known methods. For example, a method in which an organopolysiloxane having at least two ≡Si—OH bonds in one molecule and water are emulsified in the presence of an anionic emulsifier, or a cyclic siloxane such as octaorganocyclotetrasiloxane and water are anionic. After emulsifying with a system emulsifier, a conventionally known ring-opening polymerization catalyst is added to polymerize under heating to synthesize an organopolysiloxane having two or more ≡Si-OH bonds in one molecule, and And a method for obtaining an aqueous emulsion.

In this case, R ¹⁰ Si (OR ¹¹ )
₃ (wherein R ¹⁰ is an alkyl group, an alkenyl group, an aryl group, etc., R ¹¹ is an alkyl group, an acyl group, etc.) is added to the cyclic organopolysiloxane to emulsify it, or This trifunctional silane may be separately emulsified and added to the cyclic siloxane emulsifier.

The amount of the anionic emulsifier used in the preparation of the (e) component aqueous silicone emulsion is 0.3 to 20 parts, preferably 0.5 to 5 parts, relative to 100 parts of the organopolysiloxane. If the amount used is less than 0.3 parts, emulsification becomes difficult, and it becomes difficult to obtain the desired aqueous emulsion. On the contrary, if it exceeds 20 parts, the rubber physical properties (strength, elongation, hardness) of the elastomer finally obtained are obtained. Etc.) may decrease. The amount of water used is 25 to 6 per 100 parts of organopolysiloxane.
It is preferably set to 00 parts.

In the preparation of this silicone aqueous emulsion, the combined use of a nonionic emulsifier such as polyoxyethylene alkyl ether or polyoxyethylene alkylphenyl ether or a fluorine emulsifier does not significantly deteriorate the rubber physical properties. Is optional.

Next, the component (f) is the rubber physical properties of the obtained elastomer and the adhesiveness (adhesion or fixation) to the substrate.
In addition to the above, it is a component added for the purpose of preventing cracks when forming a thick film, and also has an action of enhancing the reinforcing property of colloidal silica with respect to the organopolysiloxane in the component (e).

One of the components constituting this (f) component is
It is a reaction product of an amino-functional silane or a hydrolyzate thereof and an acid anhydride. Amino-functional silanes that can be used in the synthesis of this reaction product include, for example, the formula R ¹² _n Si (O
R ¹³ ) _4-n (In the formula, R ¹² is a 2-aminoethyl group, 3-
Aminopropyl group or N- (2-aminoethyl)
Total carbon number of alkyl groups such as -3-aminopropyl group 1
~ 8 aminoalkyl group, R ¹³ represents an alkyl group or an acyl group having 1 to 4 carbon atoms, and n is 1, 2, 3 or 4). Specifically, 3-aminopropyltriethoxysilane, N- (2-
Aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldiethoxysilane,
N- (2-aminoethyl) -3-triethylenediaminopropylmethyldimethoxysilane and the like can be mentioned, and these (partial) hydrolyzates can also be used.

Examples of the acid anhydride that reacts with the amino-functional silane include methyltetrahydrophthalic anhydride, methylhymic acid anhydride, phthalic anhydride, ethylene glycol bistrimethate, maleic anhydride, and the like.
Pyromellitic anhydride, succinic anhydride, polyazelic polyanhydride, trimellitic anhydride, nadic anhydride, phenylmaleic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, dodecylsuccinic acid An anhydride, a dichloro rendic acid anhydride, etc. are illustrated.

The reaction between the amino-functional silane and the acid anhydride may be achieved by simply mixing the two at room temperature (exothermic reaction), and the desired product can be easily obtained.

The reaction product obtained by this reaction is
It is desirable to carry out the reaction in the presence of one or more organic solvents selected from methanol, ethanol, butanol, isopropanol, acetone, methyl ethyl ketone, tetrahydrofuran, dimethylformamide and the like, because gelation easily occurs.

In this reaction, the reaction molar ratio of the amino-functional silane or its hydrolyzate and the acid anhydride is preferably equimolar, but there is no problem even if one of them is used in excess.

The type of the colloidal silica which is the other component of the component (f) is not limited, but for example, those having a particle size of 10 to 40 mμ and stabilized with sodium or aluminum ions are preferable. As a commercial product,
For example, Snowtex 40 manufactured by Nissan Chemical Co., Ltd. can be easily obtained.

When the component (f) is prepared, the reaction product and the colloidal silica are used in a proportion of 0.1.
The colloidal silica may be used in an amount of 1 to 50 parts, preferably 0.1 to 20 parts, and more preferably 1 to 5 parts, based on 100 parts of the colloidal silica. If the amount of the reaction product used is too small, the effect of improving the adhesiveness to the substrate is small, and if it is too small, the fluidity of the composition may decrease.

The component (f) can be prepared by gradually dropping the reaction product into a required amount of colloidal silica while stirring at room temperature. In this case, insoluble matter is generated at the initial stage of dropping, but if stirring is further continued, the whole becomes a uniform, semitransparent liquid matter having fluidity.

The blending amount of the component (f) is 1 to 6 with respect to 100 parts of the organopolysiloxane in the component (e).
It may be 0 part, preferably 3 to 30 parts.
If the amount of the component (f) used is less than 1 part, the resulting rubber substance may be inferior, while if it exceeds 60 parts, the elongation may be small, and when used as a coating agent, it may form a thick film. If so, cracks may easily occur.

Examples of the epoxy-functional alkoxysilane of component (g) include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycyloxypropyltrimethoxysilane and γ-glycidoxypropylmethyldiethoxysilane. Etc. can be illustrated.

The curing catalyst of the component (h) is a component for curing the silicone composition, and is, for example, dibutyltin dilaurate, dibutyltin diacetate, tin octylate, tin laurate, iron octoate, lead octylate. , Metal salts of organic acids such as tetrabutyl titanate, n-
Examples thereof include amine compounds such as hexylamine and guanidine, and their hydrochlorides.

Before using these curing catalysts, it is desirable to prepare an O / W type emulsion by using an emulsifier and water by a conventional method.

The amount of the curing catalyst blended is 0.01 to 10 parts with respect to 100 parts of the siloxane content in the component (e).
The range of 0.1 to 3 parts is preferable. If it is less than 0.01 part, the curing action may be insufficient, and if it is used in excess of 10 parts, no particular effect on curing may be observed, and the elastomer obtained may be prone to cracking.

As the antibacterial agent as the component (d), the same ones as those described in the addition reaction curable liquid silicone rubber composition can be used.
0.1-5 parts can be used with respect to 0 part.

The liquid silicone rubber composition described above preferably has a low viscosity because of its ability to be impregnated into a plastic foam. Specifically, it has a viscosity of 100 to 1000 at 25 ° C.
00 cp, and more preferably 100 to 5000 cp.

When a high viscosity room temperature curing (RTV) rubber or a millable type rubber having a viscosity of 100,000 cp or more is used, it is dissolved in a low molecular weight organosiloxane having a boiling point of 200 ° C. or less or an organic solvent so that the viscosity is within the above range. It is desirable to use.

In this case, as the low molecular weight organosiloxane having a boiling point of 200 ° C. or less, the following compounds can be listed as typical examples. In the formula below, Me represents a methyl group.

[0050]

[Chemical 4]

On the other hand, examples of the organic solvent include toluene, xylene, benzene, solvent naphtha, industrial gasoline, hydrocarbons such as cyclohexanone, n-hexane, and rebroin, trichlorofluoromethane, trichlorofluoroethane. , Fluorohydrocarbons such as tetrachloride-difluoroethane can be used.

In addition to the above liquid silicone composition, a foamable liquid silicone rubber composition can be used in the present invention. The foamable liquid silicone rubber composition can be composed of the following components. (H) α, ω-dihydroxyorganopolysiloxane represented by the general formula (3), (b) organohydroxypolysiloxane represented by the general formula (4), and (nu) represented by the general formula (2). An organohydrogenpolysiloxane having at least two units in one molecule,
(L) Platinum or platinum-based compound, (D) Antibacterial agent

Here, the α, ω-dihydroxyorganopolysiloxane as the component (H) has a degree of polymerization L of 20 to 3000, preferably 300 to, in order to impart mechanical strength to the silicone rubber foam after curing. A range of 2000 is good. If L is less than 20, the elongation of the silicone rubber foam after curing may not be sufficient, and L is 3000.
If it exceeds, it may not be preferable for handling work.

In the organohydroxypolysiloxane represented by the general formula (4) as the component (i), M is 2 to 2
0, preferably 10 to 20, N is an integer of 3 to 20, preferably 5 to 20. When N is less than 3, the expansion ratio becomes low, and a room-temperature-curable foamed silicone rubber composition having an excellent expansion ratio may not be obtained. The addition amount of the component (i) is 0.01 to 30 parts with respect to 100 parts of the component (h),
The range of 0.1 to 20 parts is preferable. Addition amount is 0.
If the amount is less than 01 parts, the thixotropy of the resulting composition may be deteriorated and the foam stability may be poor, and a cell having fine cells (air bubbles) may not be obtained, and if it exceeds 30 parts. However, the cross-linking speed decreases, and the cell shape may deteriorate.

In addition, in the case of the addition curing type, it is preferable to add acetylene alcohol or a reaction control agent represented by the following formula in order to facilitate the work. In addition, V in the following formula
i represents a vinyl group.

[0056]

[Chemical 5]

The component (g) is an organohydrogenpolysiloxane having at least two units represented by the general formula (2) in one molecule, and the hydrogen atom directly bonded to the silicon atom causes the component Hydrogen gas is generated by the dehydrogenation reaction with the hydroxyl group directly bonded to the silicon atom,
It is also a component that forms crosslinks. The hydrogen atom directly connected to the silicon atom may be at the molecular end or at the side chain. The shape of the molecule may be linear, cyclic or branched. The addition amount of this component (nu) is 0.5 to 20 moles, preferably 2 to 10 moles, of SiH groups per 1 mole of hydroxyl groups in the above components.
If it is less than 0.5 mol, the foaming ratio and the bubble-stabilizing property may not be improved, and if it exceeds 20 mol, the obtained foam may not have sufficient mechanical strength.

The platinum or platinum-based compound as the component (l) and the antibacterial ceramic as the component (d) may be the same as described above.

The amount of component (l) used is (h),
0.1 to 1000 based on the total amount of (i) and (u) components
ppm, (d) component usage is (chi), (ri),
It is preferably 0.1 to 5 parts with respect to 100 parts of the total amount of the (nu) component.

Although the foamable liquid silicone rubber composition is a condensation type, an addition-curable foamable liquid silicone rubber composition comprising the following components is also preferably used. (Wo) Organopolysiloxane containing at least two alkenyl groups in one molecule represented by the above formula (1), (i) Organohydroxypolysiloxane of the above general formula (4), and (nu) The above general formula ( Organohydrogenpolysiloxane having at least two units of 2) in one molecule, (l) platinum or platinum compounds, (d) antibacterial agent

Here, (wo), (ri), (nu),
The components (l) and (d) are the same as above, and the compounding amounts are also the same except that the component (h) is read as the component (wo).

In the present invention, the above liquid silicone rubber composition contains, in addition to the above-mentioned components, an adhesiveness-imparting agent,
Reinforcing fillers can be added. The adhesiveness-imparting agent is not particularly limited, but a silicon compound containing a functional group such as an epoxy group or an alkoxy group which contributes to the adhesiveness in one molecule is preferable, and in addition to these groups, an alkenyl directly bonded to a silicon atom. A group or a hydrogen atom may be contained at the same time. Further, as the reinforcing filler, dry silica (fume method) or wet silica (wet method) is preferable, and this silica is treated with dimethylchlorosilane or hexamethyldisilazane to adjust the activity to improve dispersibility. It may be an improved surface-treated silica.

In addition, the liquid silicone rubber composition contains a filler such as quartz powder, ferric oxide, aluminum oxide, calcium silicate, etc., a heat-resistant material such as ferrous oxide, ferric oxide, cerium oxide, iron octylate and the like. An improver, a pigment such as carbon black, and a colorant such as titanium oxide and red iron oxide can be added within a range that does not affect the physical properties of the rubber that can be obtained.

Further, in the present invention, it is recommended to add a foamed plastic microballoon to the curable liquid silicone rubber composition. As this microballoon, known ones can be used, for example, polyvinyl chloride, polyvinyl acetate, polyester, polycarbonate, polyethylene, polystyrene, polymethyl methacrylate, polyvinyl alcohol, ethyl cellulose, nitrocellulose, benzyl cellulose, epoxy resin,
Interfacial polymerization of materials such as hydroxypropylmethyl cellulose phthalate, polyvinyl formal, vinyl chloride-vinyl acetate copolymer, vinyl acetate-cellulose acetate butyrate copolymer, styrene-maleic acid copolymer, acrylonitrile-styrene copolymer, vinylidene chloride-achloronitrile copolymer, etc. Examples thereof include those obtained by microencapsulation by chemical treatment, physicochemical treatment such as complex coacervation method, pH control method, and mechanical treatment such as spray drying method. It is also possible to use volatile substances such as isobutane under pressure to impart thermal expansion properties, and the size is preferably 1 to 500 μm in diameter. As a specific product, for example, the product name EXPANCEL (manufactured by Nippon Philite Co., Ltd.) can be exemplified.

The blending amount of the microballoon is 0.1 to 50 relative to 100 parts of the curable liquid silicone rubber composition.
Parts, preferably 1 to 30 parts.
If it is less than 0.1 part, a sponge that can be expected to sufficiently reduce the tightening pressure may not be formed in some cases, and if it exceeds 50 parts, the compression set may increase.

The water-drinking cup of the present invention is a plastic foam / impregnated with silicone rubber or silicone rubber foam as described above.
It is formed from a silicone rubber composite. As a method for obtaining this composite, for example, a plastic foam is hot-pressed beforehand or molded into a shape of a water cup by cutting, and a liquid silicone rubber composition is formed in the molded body. It is possible to employ a method in which a curing reaction is caused after impregnation with the composition, or a liquid silicone rubber composition is impregnated in a plastic foam sheet and the curing reaction and the molding are simultaneously performed by hot pressing or the like.

The method for impregnating the liquid silicone rubber composition into the plastic foam is not particularly limited, but for example, an impregnating roll coater, a spray coater, a knife coater, a comma coater, a gravure coater or the like can be adopted.

In this case, the impregnation amount is 0.1 to 0.1 in terms of solid content weight ratio of the plastic foam and the silicone rubber composition.
The range is 50, preferably 0.5 to 10. When it is less than 0.1, the texture, general physical properties and functionality of the cured organopolysiloxane may not be exhibited, and when it exceeds 50, the texture, general physical properties and functionality of the plastic foam may not be exhibited.

As described above, the water-immersive cup of the present invention can be effectively laminated with a woven cloth, a non-woven cloth, a plastic film or a synthetic rubber sheet (FIG. 3). As the lamination method, when the above composite is hot-press molded into a cup shape for water wearing, these are placed in the composite at the time of hot-pressing, and a method of adhesion coating at the same time as molding is adopted. Or, it may be coated with an adhesive (for example, a silicone-based adhesive or a silane coupling agent) on a composite molded in the shape of a cup for wearing water, or may be sewn on a woven cloth or a non-woven cloth. Of course, a method of covering with a plastic film by heat sealing can also be adopted.

As described above, when the woven cloth or the non-woven cloth is laminated, the feeling of the watering cup having the composite material laminated with the woven cloth, the non-woven cloth, the plastic film or the synthetic rubber sheet becomes more preferable. When it is covered with a synthetic rubber sheet, it is excellent in waterproofness and can be more preferable for wearing in water.

Examples of the woven and non-woven fabric materials include cotton, hemp, silk, wool, rayon, cupra, acetate, triacetate, promix, vinylon, nylon, vinylidene, polyvinyl chloride, polyester, acrylic and polypropylene. , Polyurethane, benzoate,
Polyclar and the like can be exemplified, and the form is woven fabric,
Any of knit, braid, neck, felt, fleece, etc. may be used.

The material of the plastic film is not limited as long as it can impart waterproofness to the swimsuit cup, and examples thereof include fluororesin, ABS, nylon, polybutadiene, polyethylene, polypropylene, polyurethane, PVA, polyvinyl chloride and polyester. Its thickness is 1
About 0 to 1000 μm is preferable.

Further, the synthetic rubber sheet may be any one as long as it can impart waterproofness to the cup for water wearing, and examples of the material thereof include butadiene rubber, silicone rubber, urethane rubber, acrylic rubber, NBR, CR, IIR, IR, and fluororubber. For example, silicone rubber is preferable from the viewpoint of safety because of the nature of the cup for wearing, which is used in contact with the human body. The thickness of the synthetic rubber sheet is preferably about 10 to 1000 μm.

In the cup for wearing water of the present invention, the thickness of the peripheral portion of the composite is preferably thin from the viewpoint of appearance (conspicuousness) when viewed from the surface of the swimsuit.
It is about 2 mm, preferably about 0.2 to 1 mm.
If the thickness is less than 0.1 mm, the strength may be insufficient, and it is 2 m.
If it exceeds m, the cup shape may be raised on the surface of the swimsuit, and the appearance may be deteriorated. In addition, the thickness of the top (center part) of the water cup is plastic foam-
The range of 1 to 30 mm, preferably the range of 2 to 15 mm is preferable from the viewpoint of effectively exhibiting the elasticity, cushioning property, and breast shaping property of the organopolysiloxane composite foam. It is desirable that the change in thickness from the peripheral portion to the top be smooth.

In the present invention, a plastic foam / silicone rubber composite, or a laminate obtained by laminating a woven fabric, a non-woven fabric, a plastic film or a synthetic rubber sheet on one or both of the front and back surfaces of the composite is JI.
Regarding the bending resilience according to SL-1096, it is preferable that the loop hardness in the C method is 200 to 3000 gf.
If it is less than 200, the cup may lose its shape due to the stress applied to the bust portion when the swimsuit is worn, and the bust shapeability may deteriorate. On the other hand, when it is 3000 or more, the cup may be too hard and may have an unpleasant sensation of pressure. It is more preferably 400 to 2000 gf. Further, it is preferable that the loop reaction rate (50% compression) is 30% or more. If it is less than 30%, external force is applied to the bust portion, and when the swimsuit cup is deformed, the deformability of the deformed portion is poor and it looks bad. At the same time, the bust shaping may be deteriorated. More preferably, it is 50% or more.

[0076]

EFFECTS OF THE INVENTION The bathing cup of the present invention has good elasticity, shock absorbing property, breast shaping property, soft feeling, good bust protection effect and good usability, as well as heat resistance and washing resistance. Excellent, it does not lose its shape due to washing with warm water and heat drying with a dryer, has excellent weather resistance, does not turn yellow or saturate due to direct sunlight, and has a low water absorption rate, so it has excellent quick-drying properties It satisfies the functions required for.

[0077]

EXAMPLES Hereinafter, the present invention will be specifically shown by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following examples, parts are parts by weight.

[Examples 1 to 3 and Comparative Example 1] An addition reaction curable liquid silicone rubber composition having the following composition was added to the flexible polyurethane foam sheet shown in Table 1 in the amount shown in Table 1 to obtain the antibacterial ceramic (ZAW- 10D, manufactured by Shinagawa Fuel Co., Ltd., was impregnated with an impregnating roll coater,
Hot pressing was performed under a molding pressure of 10 kgf / cm ² and a heating condition of 150 ° C. for 10 minutes to prepare a cup for wearing water as shown in FIG. In this case, in Example 1, the liquid silicone rubber composition-impregnated polyurethane foam sheet was subjected to hot press molding using a composite sheet in which nylon 2 weight recots were laminated on the front and back surfaces to prepare a cup for wearing as shown in FIG. did.

For comparison, a flexible polyurethane foam sheet similar to that used in Example 2 was used, and a composite sheet obtained by laminating nylon 2 weight ricott on the front and back surfaces of the sheet without impregnating the liquid silicone rubber composition was prepared in the same manner as above. hand,
Created a cup for watering. Composition of Liquid Silicone Rubber Composition (1) Dimethylpolysiloxane having a molecular chain end blocked with a dimethylvinylsilyl group (viscosity at 25 ° C .: 500
0cs) 100 copies

[0080]

[Chemical 6] (3) Silica 10 in which the surface of Aerosil 300 (Japan Aerosil Co., Ltd.) is surface-treated with hexamethyldisilazane
Parts (4) 2% by weight chloroplatinic acid solution in isopropyl alcohol 0.1 parts (5) acetylene alcohol (control agent) 0.01 parts

Heat resistance, weather resistance, washing resistance and antibacterial properties of the obtained water-immersed cup were measured by the following methods. The results are also shown in Table 1. <Heat resistance> 10 x 10 mm from the top of the water cup
To obtain a test piece, and JIS-K
Based on -6301, compression set (%) was measured under the conditions of 120 ° C., 22 hours and 50% compression. <Weather resistance> Using a sheet-shaped test piece 120 × 25 mm having the same thickness as the thickness of the top portion of the water-immersed cup, which was hot press molded under the same molding conditions as described above, JIS-B-775.
The tensile strength retention rate (%) was measured according to 2. <Washing resistance> A cup for wearing water is JIS-L-0217-7.
According to the 6103 method, washing was performed under the conditions of a hot water temperature of 60 ° C., and after drying with tumbler warm air for 30 minutes, the deformation of the cup was visually observed and evaluated according to the following criteria. Observation position A: Deformation of projected area from above the sample B: Deformation due to peeling of the sample C: Deformation seen from the shapeability of the entire sample D: Other evaluation criteria 0: No change before and after treatment 1: Deformation before and after treatment Yes 2: Deformation was present before and after treatment 3: Deformation was great before and after treatment <Antibacterial property> The test was performed according to the ASTM-G21 test method. On a test piece (30 × 30 mm) placed on an agar plate, a fixed amount of a mold spore suspension of the test bacteria shown below was sprayed at a temperature of 25.
After culturing at a temperature of 85 ° C. and a humidity of 85% RH or more, the growth state of the mold after one month was observed with a stereoscopic microscope and the naked eye, and the growth of mycelium was evaluated according to the criteria shown below. Test bacterium 1. Aspergillus niger IFO44
14 2. Penicillium funiculosum
IFO6345 Criteria 0: Mold growth is not recognized (stereoscopic microscope) 1: Mold growth is not recognized (visual) 2: Mold growth is slight (25% or less of test surface). 3: Little mold growth (25% to 50% or less of test surface) is recognized. 4: Moderate mold growth (50% -100% of test surface)
Below). 5: Mold growth is severe (the test surface is completely covered).

[0082]

[Table 1]

From the results shown in Table 1, it was confirmed that the water-immersive cups of Examples 1 to 3 were excellent in heat resistance, weather resistance, washing resistance and antibacterial property.

[Examples 4 to 6, Comparative Example 2] A flexible polyurethane foam shown in Table 2 was previously cut into a bust cup shape as shown in FIG. Rubber composition with antibacterial ceramic (ZEOMICS ZAW-1
0D) was blended in the amounts shown in Table 2 using an impregnating roll coater, and dried and cured with a hot air dryer at 150 ° C. for 10 minutes to give a polyurethane foam / silicone rubber composite. Obtained. Polyester knit fabric is placed on the front and back of this composite through Primer C (manufactured by Shin-Etsu Chemical Co., Ltd.) and bonded by heating at 150 ° C. for 30 minutes using a dryer to form a cup for wearing water. did.

For comparison, a polyester knitted cloth was similarly adhered to a polyurethane foam molded body not impregnated with a silicone rubber composition to prepare a cup for wearing water. Liquid silicone rubber composition (water-based silicone emulsion
Down) (A) component: octamethylcyclotetrasiloxane 50
0 part, 25 parts of methyltrimethoxysilane, 465 parts of water and 10 parts of dodecylbenzenesulfonic acid were emulsified using a homomixer, and a homogenizer was passed twice at a pressure of 300 psi to obtain a stable emulsion, which was then placed in a flask. It was charged and heated at 70 ° C. for 12 hours. Then, the mixture was cooled to room temperature, left standing for 24 hours, and adjusted to pH 7.0 with sodium carbonate.

The non-volatile content of this product was 47%, which was 20% of the organopolysiloxane separated using methanol.
% Toluene solution had a viscosity of 7200 cp (25 ° C.). Component (B): 98 parts of maleic anhydride and 31 ethanol
To a mixture of 9 parts, 221 parts of 3-aminopropyltriethoxysilane was added dropwise at room temperature and stirred to obtain a reaction product.

Colloidal silica (manufactured by Nissan Chemical Co., Ltd., Snowtex 40, active ingredient 40%, Na ₂ O amount 0.6%,
When 30 parts of the reaction product obtained above was gradually added dropwise to 1,000 parts of pH 9.3 at room temperature with stirring, a semitransparent uniform dispersion liquid was obtained. The pH of this product is 3.
It was 4. Component (C): 30 parts dioctyltin dilaurate, 1 part polyoxyethylene nonylphenyl ether and 69 water
The part was emulsified by a conventional method. (D) Emulsion composition: Next, (A) component 100
Parts, 9 parts of the component (B) and 1.5 parts of the component (C) are uniformly mixed, and then 0.5 part of γ-glycidoxypropyltrimethoxysilane is further added and uniformly dissolved to obtain a silicone aqueous emulsion. A composition was obtained. The emulsion composition contained 41% curable solids and had a pH of 6.8.
Met.

With respect to the obtained cup for wearing on water, heat resistance, weather resistance, washing resistance and antibacterial property were evaluated in the same manner as above.
The results are also shown in Table 2.

[0089]

[Table 2]

From the results shown in Table 2, it was confirmed that the watering cups of Examples 4 to 6 were excellent in heat resistance, weather resistance, washing resistance and antibacterial property.

[Examples 7-9, Comparative Example 3] Examples 4-6
The same polyurethane foam molded article as above was coated with the foamable 2 liquid silicone rubber composition having the composition shown below and the antibacterial ceramic (Zeomix ZAW-10D) mixed in the amount shown in Table 3, and then the two rolls The mixture was uniformly impregnated by passing it through the rolls, and left at room temperature for 3 minutes to obtain a polyurethane foam / silicone rubber composite. Polyester tricot was added to this composite through a silicone adhesive (KE1820 manufactured by Shin-Etsu Chemical Co., Ltd.) at 120 ° C. for 1 hour.
Bonding was performed for 0 minutes under a hot pressing condition of 1 kgf / cm ² using a mold to prepare a cup for wearing water.

For comparison, a polyester tricot was similarly adhered to a polyurethane foam molded body not impregnated with the liquid silicone rubber composition to prepare a cup for water application. Liquid silicone rubber composition (liquid silicone foam)

[0093]

[Table 3]

The liquid I and the liquid II were mixed at the time of coating using a two-liquid mixed coating robot TR30001 (trade name, manufactured by Auto Machine Co., Ltd.). With respect to the obtained cup for wearing on water, heat resistance, weather resistance, washing resistance and antibacterial property were evaluated in the same manner as above. The results are also shown in Table 4.

[0095]

[Table 4]

From the results shown in Table 4, it was confirmed that the water-immersive cups of Examples 7 to 9 were excellent in heat resistance, weather resistance, washing resistance and antibacterial property.

[Example 10, Comparative Example 4] A high viscosity addition reaction type liquid silicone rubber composition KE1300 (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity 100,000 cs) containing antibacterial ceramic (Zeomic ZAW-10D) was added with hexane. Using the diluted one and the same polyurethane foam sheet as in Examples 1 to 3, the polyurethane foam sheet was impregnated with the liquid silicone rubber composition using an impregnating roll coater, and then dried at 70 ° C. for 30 minutes. Polyurethane foam / silicone rubber composite molded into a water cup shape by drying with a machine to remove the solvent and pressing with a mold at a molding pressure of 10 kgf / cm ² and 150 ° C. for 5 minutes Got A polyester film having a thickness of 12 μm (Diafoil # 12, manufactured by Diafoil Co., Ltd.) was heat-sealed to a sheet molded product using a mold on the obtained composite, and a cup for wearing covered with a polyester film was heat-sealed. Created.

For comparison, a polyurethane foam sheet not impregnated with the liquid silicone rubber composition was similarly molded into a water cup shape and coated with a polyester film to prepare a water cup.

With respect to the obtained cup for wearing on water, heat resistance, weather resistance, washing resistance, antibacterial property and water absorption were evaluated in the same manner as above. The results are also shown in Table 5.

[0100]

[Table 5]

From the results shown in Table 5, it was confirmed that the water-immersive cup of Example 10 was excellent in heat resistance, weather resistance, washing resistance, antibacterial property and non-water absorption.

Example 11 An antibacterial ceramic (100 parts by weight of the addition-curable liquid silicone rubber composition used in Example 1 was added to a polyurethane foam molded article which had been previously hot pressed into a bust cup shape using a mold. Zeomic Z
1 part of AW-10D) and 3 parts of microballoon DU461 (manufactured by Nippon Philite, trade name) were added and impregnated using an impregnation machine. Next, the liquid silicone rubber composition was foamed and cured with a hot air dryer under the conditions of 150 ° C. for 10 minutes to prepare a polyurethane foam / silicone rubber composite. Next, silicone rubber sheet (KE951
A 1 mm thick vulcanized sheet (calendered by Shin-Etsu Chemical Co., Ltd., trade name) is placed on the front and back surfaces of this composite, and a molding pressure of 3 kgf / cm ² , 165 is used using a mold.
Hot pressing was carried out under conditions of ℃ and 10 minutes to prepare a cup for wearing water.

With respect to the obtained cup for wearing on water, heat resistance, weather resistance, washing resistance, antibacterial property and water absorption were evaluated in the same manner as above. The results are also shown in Table 6.

[0104]

[Table 6]

From the results shown in Table 6, it was confirmed that the water-immersive cup of Example 11 was excellent in heat resistance, weather resistance, washing resistance, antibacterial property and non-water absorption.

Further, when the swimsuit cups of Examples 1 to 11 were attached to a nylon one-piece swimsuit, and women in their 20s to 50s tried on them, the wearing feeling was soft and the bust shaping was good. Good results were obtained in practical use.

In Examples 2, 5, 8, 10 and Comparative Example 2, the thickness of the top is ½, and the thickness is 20 × 5.
A 0 mm sheet-shaped test piece was prepared and JIS-L-10
Bending resilience of 96 was measured. The results are shown in FIG. 4 and Table 7.

[0108]

[Table 7]

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing a plastic foam / silicone rubber composite that constitutes a water cup of the present invention.

FIG. 2 is a cross-sectional view showing one embodiment of the water-immersed cup of the present invention.

FIG. 3 is a cross-sectional view showing another embodiment of the swimming cup of the present invention.

FIG. 4 is a graph showing bending resilience of JIS-L-1096 of Examples and Comparative Examples.

[Explanation of symbols]

1 plastic foam 2 skeletal lattice 3 silicone rubber or silicone rubber foam 4 plastic foam / silicone rubber composite 5 water cup 6 woven cloth, non-woven cloth, plastic film or rubber sheet

Front page continued (72) Inventor Tsutomu Yoneyama 1 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (72) Inventor Ryuichi Handa Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture No. 1 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (72) Inventor Shogo Sutonami-ku, Tokyo 5-4-25 Miyamae Flexi Co., Ltd.

Claims (4)

[Claims] 1. A bathing cup formed by molding a plastic foam / silicone rubber composite in which a skeleton lattice surface of a plastic foam base material having an open cell structure is covered with silicone rubber or silicone rubber foam into a bust cup shape. 2. The plastic foam according to claim 1 /
A bathing cup formed by molding a woven cloth, a nonwoven cloth, a plastic film or a synthetic rubber sheet laminated on one or both of the front and back surfaces of the silicone rubber composite into a bust cup shape. 3. The cup for wearing according to claim 1, wherein the plastic foam / silicone rubber composite contains an antibacterial agent. 4. A plastic foam / silicone rubber composite or a laminate in which a woven fabric, a non-woven fabric, a plastic film or a synthetic rubber sheet is laminated on either or both of the front and back surfaces of the composite according to JIS-L-1096. In flexural resilience, the C-method (loop compression method) has a loop hardness of 200 to 3000 gf and a 50% compression loop resilience of 30% or more. cup.