JPH07114780B2 - Polyurethane resin condom and its manufacturing method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plasticized thermoplastic polyurethane resin condom and a method for producing the same. More specifically, a polycarbonate-based or polyether-based thermoplastic polyurethane resin, and a plasticizer, if necessary, vinyl chloride resin and / or fine powder synthetic silica is further added, and the resulting solution is dissolved in a solvent to form a uniform solution. Immerse the male mold in, and gradually pull up from the liquid,
The present invention relates to a polyurethane resin condom and a method for producing the same, which comprises drying by blowing hot air over a mold, followed by boiling or heating with steam, followed by quenching, drying again with warm air, and then demolding.

[0002]

2. Description of the Related Art Condoms have been manufactured exclusively from natural rubber latex except for those using animal bag-shaped or tubular organs. Therefore, there was a limit to reducing the film thickness and improving to a product with less usability, but as with natural rubber products, it has flexibility and strength. Has proposed the use of polyurethane resin, which has several excellent properties (Patent Publication No. 3-761).
44). However, when using this type of thermosetting polyurethane resin, it is practically difficult to obtain a high-strength one, and it is necessary to carry out a reaction between the polyisocyanate and the polyol on the mold. , The polyurethane resin raw material once attached to the mold surface must be kept on the mold until the reaction is substantially completed, and therefore the molding time becomes extremely long, so the process should be put on a smooth series of flows. Since it is not possible to do so, it is extremely economically disadvantageous compared to the case of using natural rubber latex, and the polyurethane resin once formed on the mold cannot be thoroughly purified by a method such as reprecipitation. Since it is possible, the condom formed on the mold will be put to practical use after a slight cleaning after demolding, and the aromatic amine remaining on the surface of the condom will be used. The possibility of carcinogenic effect results in the remaining by, that the products leave Ichimatsunofuan in terms of safety was inevitable. A method of using a thermoplastic polyurethane resin has been proposed as a means for compensating for the drawbacks of the thermosetting polyurethane resin (Japanese Patent Publication No. 47-24947). At present, there are only a few special polyester resins as plastic polyurethane resins that have sufficient strength and satisfactory flexibility, but this polyester polyurethane resin is essentially However, there was a problem that mold and miscellaneous bacteria adhered and propagated during storage.

[0003]

The natural rubber latex conventionally used as a material for producing a condom has a limitation on the film thickness due to the restriction on strength, and as a polyurethane resin to be replaced, the strength is not sufficient. In addition to the thermosetting type which is sufficient and has a problem in safety, or in addition to the thermoplastic polyester-based polyurethane resin in which microbial adhesion and hydrolysis are unavoidable, in terms of having both strength and flexibility, There was nothing satisfactory.

[0004]

The inventors of the present invention have solved these problems, and as a method for producing a material having high safety and the strength and flexibility required for a condom, they are not easily affected by microorganisms. From the point of view, select polycarbonate type and polyether type thermoplastic polyurethane resins, add a plasticizer to them to impart flexibility without significantly reducing the strength, and if necessary, a high polymerization degree polyvinyl chloride resin. The method of applying a material to which a fine powder synthetic silica is added for the purpose of improving the compatibility between the respective material components to the production of a condom, and its boiling or steam heating /
The present invention has been completed through intensive research on the synergistic effect of the quenching treatment and its plasticizer .

[0005]

That is, the present invention relates to a polycarbonate-based or polyether-based thermoplastic polyurethane resin,
If necessary, polyvinyl chloride resin, and / or fine powder synthetic silica and other additives are mixed with the plasticizer and dissolved in a solvent to form a uniform solution. The present invention provides a polyurethane resin condom and a method for producing the same, which are characterized by being sprayed and dried, boiled, quenched, and dried with warm air. Typical polycarbonate-based thermoplastic polyurethane resin raw materials that are usefully used in the condom of the present invention include 4,4'-diphenylmethane diisocyanate (MDI), toluylene diisocyanate (TDI), and isophorone as polyisocyanates. Diisocyanate (IPDI), 4,4'-methylenebis (cyclohexyl isocyanate) (HMDI), hexamethylene-
1,6-diisocyanate (HDI), and the like, one or more polyisocyanates selected from the group are used, and the average molecular weight of the polycarbonate-based polyol is 500 to 5000, and a linear poly ( 1,6-hexamethylene glycol carbonate), poly (1,4-
Tetramethylene glycol carbonate) or poly (diethylene glycol carbonate) as the main component, and some of these structural units are replaced with those with higher molecular weight or bulky structure to improve the flexibility. It can be used after being replaced with a part of the structural unit such as hexamethylene glycol,
Those having a larger molecular weight and a more bulky structure include various isomers such as heptamethylene glycol, octamethylene glycol, 1,4-cyclohexene glycol, xylylene glycol, dimethylolcyclohexane and bishydroxymethyltetrahydrofuran. Some of the main chains can be used by changing them to a structure of a carbonate / glycol copolymer by converting a part of the main chain into an oligoalkylene glycol, and can be used for this purpose. Examples include oligoethylene glycol such as triethylene glycol and tetraethylene glycol, dipropylene glycol, oligopropylene glycol such as tripropylene glycol, di (tetramethylene glycol), and tri (tetoglycol). There are various oligoalkylene glycols such as oligo (tetramethylene glycol) such as methylene glycol), and if the molecular weight of these various polycarbonate glycols is 500 or less, it becomes too rigid as a material for condoms, and if it is 5000 or more, workability is increased. Since it becomes worse, it is necessary to set it to 500 to 5000. Examples of the chain extender that can be used in the present invention include ethylenediamine, 1,2-propylenediamine, tetramethylenediamine, piperazine, 1,4-diaminocyclohexane and isophoronediamine, which are used in the production of ordinary thermoplastic polyurethane resins. 4,4 '
-Various low molecular weight diamines such as dicyclohexylmethanediamine, xylylenediamine, diethylenetriamine, and dibutylenetriamine, and other low molecular weight glycols such as triamine, ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, and octamethylene glycol, There are various low molecular weight active hydrogen compounds such as hydrazine, and if a particularly bulky structure is used among these, the crystallinity of the hard segment is lowered, and therefore the effect of improving the flexibility of the resin can be obtained, which is preferable, It goes without saying that most of the chain extenders used in these polycarbonate-based polyurethane resins can also be used in the polyether-based polyurethane resins. As the diisocyanate used as a raw material of a typical polyether-based thermoplastic polyurethane resin used in the condom of the present invention, those which can be used for producing the above polycarbonate-based thermoplastic polyurethane resin, It can be used almost in the same manner, and the polyether-based polyol has an average molecular weight of 50 because it is completely the same as the case of the polycarbonate-based polyol.
0 to 5000, poly (1,2-propylene glycol), poly (1,4-tetramethylene glycol),
Poly (1,6-hexamethylene glycol), poly (1,8-octamethylene glycol), copolymer glycols of these various glycols, and the like can be similarly used. As a method for producing a polycarbonate-based or polyether-based thermoplastic polyurethane resin that can be used in the present invention, if necessary, in the presence of a suitable solvent, an isocyanate is added to both terminals under heating and stirring by a general method. It can be produced by synthesizing a prepolymer having a nato group and then reacting it with a chain extender, and adding various tertiary amine-based catalysts in addition to organometallic catalysts such as dibutyltin dilaurate to carry out the reaction. The polycarbonate-type or polyether-type thermoplastic polyurethane resin produced in this way is safe after removing low molecular weight impurities through purification by reprecipitation three times or more after synthesis. It is necessary to use the higher one. The polyvinyl chloride resin that can be used in this invention has an average degree of polymerization of at least 1000.
It is preferably at least 1800, more preferably at least 1800 in order to maintain strength, and the addition amount of the vinyl chloride resin is 200 parts or less with respect to 100 parts (parts by weight, the same hereinafter) of the thermoplastic polyurethane resin. It is preferable to maintain the rubber elasticity, and if it is 1 part or less, the effect of addition such as reinforcement and release cannot be obtained. Therefore, it is preferably 1 to 200 parts. As the plasticizer which can be used in the present invention, those having a particularly high safety are selected from those industrially used as a plasticizer for polyvinyl chloride resin.
If chosen, most can be used as well, for example di (2-ethylhexyl) phthalate, dibutylphthalate, diethylphthalate, dimethylphthalate,
Butyl lauryl phthalate, butyl stearyl phthalate, di (2-ethylhexyl) azelaate, di (2-
Ethylhexyl) adipate, tricresyl phosphate, triphenyl phosphate, tributoxyethyl phosphate, dibenzyl ether, epoxidized soybean oil, and any of the following liquid synthetic rubbers: chlorinated polyisoprene, chlorinated polyethylene, butadiene / vinyl. Pyridine rubber, chloroprene rubber, acrylonitrile / butadiene rubber, styrene / butadiene rubber, butyl rubber,
Examples thereof include hydrogenated polybutadiene. Other additives that can be used in this invention include various stabilizers such as antioxidants, ultraviolet absorbers, heat stabilizers, and bactericides, as well as lubricants, colorants, fragrances, spermicides, and particle sizes. It is possible to increase an organic or inorganic filler having a particle size of 50 μm or less. If a filler with a particle size of 50 μm or more is used, pinholes are likely to occur in the condom,
The particle size of the filler is 5 because it easily precipitates in the solution.
It should be 0 μm or less. As a solvent that can be used for molding a condom in the present invention, any solvent that dissolves or disperses various materials at the same time, is chemically stable, and has low toxicity is generally used industrially. It can be used alone or as a mixed solvent of two or more components, for example, dimethyl sulfoxide, dimethylacetamide, dimethylformamide, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene. , Xylene, ethylbenzene, monochlorobenzene, dichlorobenzene, methylene chloride, acetonitrile, isopropyl alcohol and the like. The quenching treatment after boiling of the present invention is one in which a synergistic effect with the addition of a plasticizer is recognized, and the mold is dipped,
A new treatment method that makes it possible to improve the tensile strength and further increase the flexibility by treating a condom that has been pulled up, dried, and molded, especially before demolding. It is heated with steam, then rapidly cooled by means such as pouring into cold water, dried with warm air, and demolded. If the boiling time is less than 0.5 minutes, no sufficient effect can be obtained and 60 minutes or more. However, it is preferable to set the time to 0.5 to 60 minutes because the effect will not change.

[0006]

The present invention will be described in more detail with reference to the following examples. Examples 1 to 3 and Comparative Examples 1 to 2 In Example 1, poly (1,6) having an average molecular weight of 3000 was used.
-Hexamethylene glycol carbonate), MDI,
From 100 parts of a thermoplastic polyurethane resin synthesized in dimethyl sulfoxide in the absence of a catalyst from ethylenediamine via a prepolymer having isocyanate groups at both ends, 20 parts of dibenzyl ether and an average degree of polymerization of 200
0 parts suspension polymerized vinyl chloride resin 0, average particle size 2μ
m, 3 parts of fine powder synthetic silica having a maximum particle size of 20 μm, and 0.02 part of dimethylpolysiloxane-based silicone oil as an antifoaming agent were dissolved in dimethyl sulfoxide / tetrahydrofuran (4/1, volume ratio unless otherwise specified). At most, make a 4.6% solution, use a male mold with Teflon coating on an aluminum core mold, and mold by immersing / blowing hot air at 50 ° C for 15 minutes and drying 3 times, and immerse in boiling water for 5 minutes. Then, it was put into water at 5 ° C. and rapidly cooled, and dried air at 50 ° C. was blown again for 60 minutes to remove the mold, and then the physical properties and transparency were evaluated, and another 27
The rate of change in tensile strength measured after standing at 0 ° C for 3 months was evaluated. Other examples and comparative examples were carried out and compared in the same manner as the examples. Their material compositions are shown in Table 1 and the evaluation results of each example are shown in Table 2.

[0007]

EFFECTS OF THE INVENTION The condoms produced in Examples 1 to 3 are, as shown in the physical property values of Table 2, in terms of strength, compared with conventionally produced natural rubber latex products (Comparative Example 2), Whereas it was proved that it has a performance exceeding this, in the case of using a thermoplastic polyurethane resin based on a low molecular weight polyester polyol and not subjecting to quenching treatment after boiling (Comparative Example 1), PVC
It was difficult to remove the mold because no nyl resin was added.
Its strength is unsatisfactory, and its high tensile stress makes it extremely difficult to apply it to this application. Even during a storage test in saturated steam for 3 months, this material suffers from strength deterioration that is thought to be due to microbial growth. Was recognized. As a comprehensive evaluation, as shown in the rightmost column of Table 2, it was demonstrated that Examples 1 to 3 gave extremely good condoms as compared with Comparative Examples 1 and 2, and thus the usefulness of the present invention. Became clear. As described above, the condom obtained by carrying out the present invention has a significantly improved tensile strength as compared with the conventional natural rubber latex product, and thus has a film thickness of 200 to 250 μm as compared with the conventional product. It is possible to make it extremely thin compared to the product and make it less likely to be worn, have moderate flexibility, and because it is colorless and excellent in transparency, it can also be vividly colored. Since the product is not allergenic and it is a material to which microorganisms do not adhere easily, it makes it possible to manufacture condoms that are extremely superior in terms of safety and storage stability. It can be said that this is a meaningful invention.

Claims (4)

[Claims] 1. A polycarbonate-based or polyether-based thermoplastic polyurethane resin, a plasticizer, and other additives are mixed and dissolved in a solvent to form a uniform solution. A method for producing a polyurethane resin condom , which comprises pulling up, drying by blowing hot air or warm air over a mold, boiling or heating with steam, quenching, drying again with warm air, and then demolding. 2. The other additive comprises vinyl chloride resin and / or finely powdered synthetic silica.
The method for producing a polyurethane resin condom according to claim 1 . 3. Produced by the method of claim 1 .
Condom made of polyurethane resin. 4. Produced by the method of claim 2 .
Condom made of polyurethane resin.