WO2005052057A1

WO2005052057A1 - Method for producing flexible polyurethane foam

Info

Publication number: WO2005052057A1
Application number: PCT/JP2004/016987
Authority: WO
Inventors: Naoyuki Ohmori; Hitoshi Yaguchi; Yoshiaki Maeda
Original assignee: Nippon Polyurethane Industry Co., Ltd
Priority date: 2003-11-25
Filing date: 2004-11-16
Publication date: 2005-06-09
Also published as: WO2005052057A8; JP2005154533A

Abstract

Disclosed is a method for producing a flexible polyurethane foam with excellent mildew resistance and antibacterial properties wherein a mechanical frothing process is used. The method for producing a flexible polyurethane foam is characterized in that an isocyanate liquid (A) composed of an organic polyisocyanate (a), a polyol liquid (B) wherein a polyol (b1), a catalyst (b2), a foam stabilizer (b3) and colemanite (b4) are mixed in advance, and an inert gas (C) are mixed and dispersed by mechanical stirring and then the resulting mixture is foamed and cured.

Description

Specification

Method for producing flexible polyurethane foam

Technical field

The present invention relates to a method for producing a flexible polyurethane foam, and more particularly, to a method for producing a flexible polyurethane foam having excellent antifungal and antibacterial properties by a mechanical floss method. Background art

[0002] Conventionally, flexible polyurethane foam has been used for relatively directly in contact with the human body, such as kitchen cleaners, body sponges, cosmetic applicators (figure puffs), filter elements, mattresses, pillows, and seat cushions. Often done. In such applications, antifungal and antibacterial properties are often required. For example, flexible polyurethane foams for cosmetic applicators (cosmetic puffs) include (1) open-cell dry polyurethane foam (Patent Document 1 and the like), and (2) open-cell wet polyurethane foam (Patent Document 2). And (3) composite materials (Patent Document 3 and the like) in which these foamed elastic bodies are combined with cloth, flocking, and the like are known.

[0003] Patent Document 1: JP-A-9-1188777

Patent Document 2: JP-A-58-189242

Patent Document 3: Japanese Patent Application Laid-Open No. 2002-262929

[0004] However, when liquid cosmetics, particularly low-viscosity cosmetics, are applied to a cosmetic applicator using a conventional flexible polyurethane foam, most of the cosmetics pass through open cells and puff. It is absorbed inside. As a result, the cosmetics hardly adhered to the skin, and waste of cosmetics only increased, and satisfactory makeup could not be obtained. There were also hygiene problems, such as the cosmetics absorbed inside the puff oozing out on the back and sticking to the clothes, and the cosmetics in the puff spoiled.

[0005] In order to solve such a problem, there is a method of reducing the cell diameter of open cells of the polyurethane foam or reducing the expansion ratio. This prevents the absorption of the cosmetic into the puff to some extent, but on the other hand, it impairs the flexibility, which is an important property of the cosmetic puff, and causes a problem that the commercial value is greatly reduced. [0006] Flexible polyurethane foams incorporating a force-proofing agent are known, and include, for example, those using a quaternary ammonium salt as a fungicide and those using a silver-based force-proofing agent (Patent Document 5, etc.). It has been known.

Patent Document 4: JP-A-11-56741

[0008] However, quaternary ammonium salts have a problem of poor heat resistance. In addition, the silver-based fungicide has a problem that it is colored black due to oxidation of silver and its appearance is deteriorated. Disclosure of the invention

The invention's effect

[0009] According to the present invention, an easy and simple manufacturing method, which has a soft skin contact and a mildew-proof property

-It has become possible to provide flexible polyurethane foam with excellent antibacterial properties.

Problems to be solved by the invention

[0010] The present invention relates to a method for producing a flexible polyurethane foam for cosmetic puffs by a mechanical floss method, which is an easy and simple method for producing a soft polyurethane foam having a soft skin contact.

• To provide flexible polyurethane foam with excellent antibacterial properties.

Means for solving the problem

[0011] The present invention has been found as a result of earnest studies to solve the above-mentioned problems, that is, an isocyanate liquid (A) comprising an organic polyisocyanate (a), a polyol (bl) The polyol liquid (B) in which the catalyst (b2), the foam stabilizer (b3), and the colemanite (b4) are previously mixed, and the inert gas (C) are mixed and dispersed by mechanical stirring, and then the mixed liquid is mixed. Is a method for producing a flexible polyurethane foam, characterized by being foamed and cured. BEST MODE FOR CARRYING OUT THE INVENTION

The organic polyisocyanate (a) used in the present invention includes diphenylmethane diisocyanate (hereinafter abbreviated as “MDI”), polyphenylenepolymethylene polyisocyanate (hereinafter “MDI”). Abbreviated as "MDI polynuclear condensate"), tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, naphthalenediene Isocyanate, hydrogenated diphenylmethane diisocyanate , Hydrogenated xylylene diisocyanate, etc., and part of these isocyanate groups of compounds having an isocyanate group into urethane, biuret, arophanate, carbodiimide, uretonimine, oxazolidone, amide, imide, isocyanurate, uretdione, etc. Modified ones may be mentioned. These can be used alone or in combination of two or more, if necessary.

[0013] MDI, polymeric MDI will be described in more detail.

MDI¾, 4, A'—diphenylmethane diisocyanate (hereinafter, abbreviated as 4, —MDI), 2, 4′—diphenylmethane diisocyanate (hereinafter, abbreviated as 2, —MDI), 2,2'-Diphenylmethane diisocyanate (hereafter abbreviated as 2,2'-MDI) in the form of a mixture (in some cases, single or miscellaneous) of any three types of isomers Exists in.

[0014] The MDI-based polynuclear mixture has three or more benzene rings having an isocyanate group bonded in one molecule, and exists in the form of a mixture of compounds having different degrees of condensation. Usually, it is not supplied in the form of an MDI-based polynuclear mixture alone, but in the form of a mixture with MDI (a mixture of MDI and an MDI-based polynuclear mixture is abbreviated as "polymeric MDI").

[0015] Polymeric MDI is obtained by converting a condensed mixture (polyamine) obtained by a condensation reaction between aniline and formalin from an amino group to an isocyanate group by phosgenation or the like. MDI polynuclear mixture with different degrees of condensation. The composition of MDI and polymeric MDI can be changed by changing the raw material composition ratio and reaction conditions during condensation, and by partially removing MDI by distillation. The MDI content of polymeric MDI and the isomer composition ratio of MDI can be determined from a calibration curve based on the area percentage of each peak obtained by gel permeation chromatography / gas chromatography.

[0016] In the present invention, considering the working environment during foam production, formability of the foam, physical properties of the obtained polyurethane foam, and the like, the MDI having an MDI content of 50 to 100% by mass, '—Polymeric MDIs containing MDI with an MDI content of 50-100% by weight, and urethane prepolymers terminated with isocyanate groups, are preferred.

[0017] The polyol (bl) used in the present invention comprises a polymer polyol and a chain extender. High molecular polyols include polyether polyols, polyester polyols, polycarbonates Bonate polyol, hydrophobic polyol and the like can be mentioned. Here, as the polyether polyol, for example, those obtained by addition-polymerizing an alkylene oxide starting from propylene glycol, ethylene glycol, glycerin, trimethylolpropane, hexanetriol, or the like are preferable.Especially, ethylene oxide or ethylene oxide is added to glycerin. Those obtained by addition polymerization of propylene oxide and propylene oxide are preferred. Examples of the polyester polyol include a condensed polyester polyol obtained by condensation of a dicarboxylic acid with a diol or a triol, a rataton-based polyester polyol obtained by ring-opening polymerization of a diol or a triol, and a polyether polyol. A polyol such as an ester-modified polyol obtained by ester-modifying the above with rataton is preferably used. Examples of the polycarbonate carbonate polyol include those obtained by a transesterification reaction between a low molecular weight polyol such as butanediol and hexanediol and a low molecular weight carbonate such as propylene carbonate and getyl carbonate. Further, as the hydrophobic polyol, polyisoprene polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, or the like is used. These polymer polyol components may be used alone or in combination of two or more.

[0018] The above-mentioned polymer polyol has a substantial average number of functional groups of 2 to 4 and a number average molecular weight of 1,000 to 10,000 (particularly preferably 2 to 4) in consideration of the softness and the like of the obtained flexible polyurethane foam. , 000- 8, 000 Okishiechiren group content) of Ru Ah at 50 mass ^_0/0 following poly (O key dipropylene) polio one Norre or poly (Okishiechiren O carboxymethyl propylene) polyol. The poly (oxyethylene oxypropylene) polyol includes, for example, a block copolymer type or a random copolymer type, or a product obtained by adding an ethylene oxide to the terminal of a poly (oxypropylene) polyol. If the substantial average number of functional groups is too small or if the number average molecular weight is too large, the physical properties of the foam tend to be too small. If the substantial average number of functional groups is too large or if the number average molecular weight is too small, the foam becomes hard and the feel is poor.

[0019] Examples of the chain extender include ethylene glycol, propylene glycol, 1,4-butanediol, trimethylolpropane, tetramethylene ether glycol, polyethylene glycol and the like. These chain extenders may be used alone or in combination of two or more. They may be used together. In the present invention, 1,4-butanediol is preferred. This is because 1,4-butanediol has a primary hydroxyl group and therefore has good reactivity.It is a liquid at room temperature, so it has excellent workability, and it has a moderate molecular weight, so it has excellent mechanical strength. Is obtained.

[0020] Examples of the catalyst (b2) used in the present invention include monoamines such as triethylamine and dimethylcyclohexylamine; diamines such as tetramethylethylenediamine, tetramethylpropanediamine and tetramethylhexanediamine; and pentane. Triamines such as methylethylenetriamine, pentamethyldipropylenetriamine and tetramethyldanidine, triethylenediamine, dimethylbiperazine, methylethylbiperazine, methinolemonorephorin, dimethylaminoethylmorpholine, dimethyl Cyclic amines such as imidazole, alcohol amides such as dimethinoleaminoethanol, dimethylaminoethoxyethanol, trimethylaminoethylethanolamine, methylhydroxyethylpiperazine and hydroxyethylmorpholine , Ether amines such as bis (dimethylaminoethyl) ether, ethylene glycol bis (dimethyl) aminopropyl ether, stannasoctoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin marker peptide, dibutyltin thiocarboxylate Known catalysts such as organic metal compounds such as dibutyltin dimaleate, dioctyltin marker peptide, dioctyltin thiocarboxylate, phenylmercuric propionate and otatenate can be used alone or in combination of two or more.

[0021] The foam stabilizer (b3) used in the present invention is an organic silicon-based surfactant known in the art, for example, L-520, L-540, L_5309, L_5366, and L_5366 manufactured by Nippon Tunicer. SZ-1306, SH-193 and SRX-274C manufactured by Toray Dow Corning, and B-4113 manufactured by Goldschmidt.

The present invention is most characterized by using colemanite (b4). Cholemanite is a calcium-boron based natural mineral represented by the general formula: Ca [B O (OH)] · Η〇. Also

Koremanai HCa〇 '2B O) obtained by calcining this is also preferably used. In the present invention, calcined colemanite having a high boron content is preferred. The use amount of colemanite (b4) is preferably 0.110% by mass relative to the polyol (bl), and particularly preferably 0.55% by mass. In the present invention, other conventionally known additives can also be used, if necessary. For example, antioxidants, ultraviolet absorbers, flame retardants, coloring agents, conductive agents, insulating agents, luminescent agents, antibacterial agents Agents, fragrances and the like.

In order to produce the flexible polyurethane foam of the present invention using these raw materials, the polyisocyanate component, the polyol component, the catalyst, and other additives stored or prepared in separate containers. Into a single mixing head while mixing the inert gas, mix the mixture to make it homogeneous, pour the mixture over a conveyor lined with a formwork and base paper, and heat and harden it. A method in which the composition is cast into a predetermined mold and cured by heating is used. The foam obtained by such a method is a polyurethane foam having uniform fine cells and moderate hardness.

At this time, the isocyanate index (isocyanate group Z active hydrogen group X 100) is preferably from 60 to 120, particularly preferably from 80 to 110. If the index is too low, the foam surface tends to stick to the surface. If the index is too high, the foam may not be foamed or may collapse to obtain a flexible foam.

[0026] The flexible polyurethane foam thus obtained has a density of 0.1-0.9 g / cm ³ , a Asker hardness F of 30-90 °, and is a uniform foam having fine cells. .

[0027] The flexible polyurethane foam obtained by the present invention has open cells, is fine in cells, and has excellent antifungal and antibacterial properties, and has a cosmetic puff, bedding (pillow, mat), cushion, and microphone. 'Easy for headphone covers and clothing.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In Examples and Comparative Examples, ratios are mass ratios and “%” is “mass%” unless otherwise specified.

[Synthesis of urethane prepolymer terminated with isocyanate group]

Synthesis example

A reactor equipped with a stirrer, a cooling pipe, a nitrogen inlet pipe, and a thermometer: A 1,000-ml reactor was charged with 308 g of MDI-1, 1 lg of reactive silicon, and 581 g of polyol-11, and stirred for 80 minutes. Reaction at 4 ° C for 4 hours to obtain NCO-1 It was. The isocyanate content of NCO-1 was 7.9%.

[0030] In the synthesis example

MDI-1:

Diphenylmethane diisocyanate (MDI) containing 50% MDI isomer mixture Reactive silicon:

Hydroxyl-containing silicone foam stabilizer

Polio one _1:

Poly (oxypropylene) polyol with a nominal oxyethylene cap with a nominal average number of functional groups = 3, number average molecular weight = 3,000, and oxyethylene group content = 11%

* MDI isomer mixture:

Mixture of isomers other than 4, 4'-MDI (2, 2'-MDI and 2, -MDI)

[Preparation of Polyol Premix]

Formulation Example 1-1 4

A polyol premix OH-1-4 was prepared by charging as shown in Table 1 into a 2,000 ml reactor.

[Table 1]

[0033] Formulation Examples 1-4, in Table 1

Polyol—2:

Nominal average number of functional groups = 3, number average molecular weight = 6,000, oxyethylene group content = 17% Poly (oxypropylene) polyol polyols with terminal oxyethylene caps

Poly (oxypropylene) polyol with a nominal average number of functional groups = 4, number average molecular weight = 4,000, and oxyethylene group content = 0%

1, 4-BD:

1, 4_ Butaneji

Amin—1:

Reactive amine catalyst

[Production of flexible polyurethane foam]

Example 1

Liquid temperature: 25 ° C polyol premix OH-1 mixed with the isocyanate index shown in Table 2 and liquid temperature: 25 ° C polyisocyanate NCO-1 were mixed and stirred for 1 minute. Pour the mixed solution mixed with dry air into a mold (10 cm x 10 cm x 10 cm, open top), and then place the mold into which the mixture has been poured in a hot air oven adjusted to 80 ° C. For 2 hours to cure the foamed polyurethane raw material. The cured polyurethane foam was removed from the mold to produce a polyurethane foam.

Examples 2-3, Comparative Example 1

Using the raw materials shown in Table 2, a polyurethane foam was produced in the same procedure as in Example 1.

[Table 2]

(Evaluation of flexible polyurethane foam) The evaluation items of the form and the measuring method are as follows.

density:

It was determined according to JIS K 6401.

Hardness:

ASKER hardness tester Measured by F type

Antifungal test:

A 5 mm-thick foam sample was placed in a Petri dish, planted with mold spores, placed in an atmosphere of 25 ° C x 90% RH for 5 days, and the degree of mold growth was visually evaluated.

〇: No mold growth was observed.

△: Mold growth area is less than 1Z3 or less of surface area

X: The area of the mold growing part is 1Z3 or less of the surface area

Experiment:

A 5 mm-thick foam sample was placed in a Petri dish, and one drop of cultured E. coli was added thereto. Thereafter, the cells were placed in an atmosphere of 35 ° C. × 90% RH for 24 hours, and the viable cell count was measured.

〇: Viable bacteria count 10 or less

Δ: Number of viable bacteria-1.1.5 X 10 ⁵

X: viable cell count 1.5 X 10 ⁵ —

From Table 2, it was found that the foams of the examples using colemanite had fungicidal and antibacterial properties, but the foams of the comparative examples not using colemanite were poor in fungicidal and antibacterial properties.

Claims

The scope of the claims

An isocyanate liquid (A) composed of an organic polyisocyanate (a), a polyol (bl), a polyol liquid (B) obtained by roughly mixing a polyol (bl), a catalyst (b2), a foam stabilizer (b3), and colemanite (b4); A method for producing a flexible polyurethane foam, comprising mixing and dispersing an inert gas (C) by mechanical stirring, and then subjecting the mixture to foaming and curing.