JP2022113909A - Antifungal polyurethane foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antifungal polyurethane foam that allows an antifungal agent to be uniformly dispersed in polyurethane foam to show a high antifungal effect, wherein the antifungal polyurethane foam can be easily produced and is suitable for cushion materials such as a mattress prone to mildew.

SOLUTION: An antifungal polyurethane foam is obtained by mixing and reacting polyurethane foam raw material containing a polyol, an isocyanate, a foamer, a catalyst, and an antifungal agent. As the antifungal agent, added is a liquid antifungal agent such as an isothiazoline-based antifungal agent. The liquid antifungal agent is uniformly dispersed in polyurethane foam and the polyurethane foam raw material is reacted to produce the antifungal polyurethane foam.

SELECTED DRAWING: Figure 1

COPYRIGHT: (C)2022,JPO&INPIT

Description

The present invention relates to an antifungal polyurethane foam and a method for producing the same.

Polyurethane foams are widely used in clothing padding, furniture, bedding, and the like.
Polyurethane foams used in bedding mattresses have the problem of mold growing due to the sweat and body heat of the user during sleep.

Conventionally, polyurethane foams for gaskets and mats for growing seedlings are known to be obtained by adding antifungal agents to polyurethane foam raw materials and foaming them.

Japanese Patent Application Laid-Open No. 2007-16070 JP-A-61-5510

However, antifungal agents added to polyurethane foam for gaskets and seedling mats are in the form of granules or powder. There is a problem that is difficult to get the effect. Moreover, the addition of the granular or powdery antifungal agent increases the viscosity of the polyurethane foam raw material, making it difficult to discharge the polyurethane foam raw material from the injection machine. Therefore, in order to obtain a polyurethane foam having a good foaming state and physical properties, the amount of the granular or powdery fungicide to be added is limited to a small amount, and the antifungal effect cannot be enhanced.

In particular, polyurethane foam for mattresses has a large thickness and a large planar size, so the antifungal agent is likely to be unevenly distributed. Furthermore, the state and physical properties of polyurethane foams for mattresses have a great effect on sleep, so polyurethane foams with poor foam state and poor physical properties are not preferable.

The present invention has been made in view of the above points, and provides a mold-resistant polyurethane foam which has a high mold-resistant effect by uniformly dispersing the mold-resistant agent in the polyurethane foam, and which can be produced satisfactorily. The purpose is to provide a manufacturing method.

The invention of claim 1 relates to an antifungal polyurethane foam in which an isothiazoline antifungal agent is dispersed.

The invention of claim 2 is characterized in that, in claim 1, the isothiazoline fungicide is dispersed in the polyurethane foam in an amount of 0.2 to 0.6 wt %.

According to a third aspect of the invention, there is provided a method for producing a polyurethane foam by mixing and reacting polyurethane foam raw materials containing a polyol, an isocyanate, a blowing agent, a catalyst, and an antifungal agent, wherein the antifungal agent is a liquid antifungal agent. It relates to a method for producing an antifungal polyurethane foam characterized by:

The invention of claim 4 is characterized in that, in claim 3, the liquid antifungal agent comprises an isothiazoline antifungal agent.

The invention according to claim 5 is characterized in that, in claim 4, the amount of the isothiazoline antifungal agent is 0.2 to 0.8 parts by weight with respect to 100 parts by weight of the polyol.

According to the present invention, it is possible to obtain a mold-proof polyurethane foam having a high mold-proof effect by uniformly dispersing the mold-proof agent in the polyurethane foam. In particular, the present invention is suitable as a polyurethane foam for mattresses, which has a large thickness and a large planar size, and whose foam state and physical properties greatly affect sleep, and a method for producing the same.

1 is a table showing formulations and physical properties of Examples and Comparative Examples, and measurement results of mold resistance tests. FIG. 4 is a diagram showing the acquisition position of a sample for mold resistance test.

The antifungal polyurethane foam of the present invention is produced by mixing and reacting polyurethane foam raw materials containing polyol, isocyanate, blowing agent, catalyst and antifungal agent, and the antifungal agent is dispersed in the polyurethane foam. ing.

Polyols for polyurethane foams can be used as polyols, and for example, any of polyether polyols, polyester polyols, and polyether ester polyols can be used, and one or more of them can be used.

Examples of polyether polyols include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, pentaerythritol, trimethylolpropane, sorbitol, sucrose, and ethylene oxide (EO ) and polyether polyols to which alkylene oxides such as propylene oxide (PO) are added.

Examples of polyester polyols include polycondensation from aliphatic carboxylic acids such as malonic acid, succinic acid and adipic acid, aromatic carboxylic acids such as phthalic acid, and aliphatic glycols such as ethylene glycol, diethylene glycol and propylene glycol. Polyester polyols obtained by
Examples of polyether ester polyols include those obtained by reacting the above polyether polyols with polybasic acids to form polyesters, and those having both polyether and polyester segments in one molecule.

As for the polyol, it is preferable to use one or a plurality of polyols having a hydroxyl value (OHV) of 20 to 300 mgKOH/g, a functional group number of 2 to 6, and a weight average molecular weight of 500 to 15,000.

As the isocyanate, aliphatic or aromatic polyisocyanates having two or more isocyanate groups, mixtures thereof, and modified polyisocyanates obtained by modifying them can be used. Examples of aliphatic polyisocyanates include hexamethylene diisocyanate, isophorone diisocyanate, and dicyclohexamethane diisocyanate. Examples of aromatic polyisocyanates include toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate, xyloxy Examples include diisocyanate, polymeric MDI (crude MDI), and the like. In addition, other prepolymers can also be used.

The isocyanate index (INDEX) is preferably 70 or more, more preferably 80-120. The isocyanate index is a value obtained by dividing the number of moles of isocyanate groups in isocyanate by the total number of moles of active hydrogen groups such as hydroxyl groups in polyol and multiplying it by 100. Calculated.

Water is preferred as the blowing agent. Water generates carbon dioxide gas when polyol reacts with isocyanate, and the carbon dioxide gas causes foaming. The amount of water as a foaming agent is preferably 1 to 5.5 parts by weight with respect to 100 parts by weight of polyol.

As a catalyst, a known urethanization catalyst can be used in combination. For example, amine catalysts such as triethylamine, triethylenediamine, diethanolamine, dimethylaminomorpholine, N-ethylmorpholine, and tetramethylguanidine; tin catalysts such as stannus octoate and dibutyltin dilaurate; and phenylmercuric propionate or lead octoate. metal catalysts (also called organometallic catalysts) such as amine catalysts and metal catalysts, or both may be used in combination. The amount of amine catalyst is preferably 0.01 to 3 parts by weight with respect to 100 parts by weight of polyol. The amount of metal catalyst is preferably 0 or 0.01 to 1 part by weight.

A liquid antifungal agent is used as the antifungal agent. As the liquid antifungal agent, an isothiazoline antifungal agent is suitable. Examples of isothiazoline fungicides include 2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, Nn-butyl-1, 2-benzisothiazolin-3-one (BBIT) and the like can be mentioned, and one or more of them can be used in combination. The amount of the isothiazoline fungicide is preferably 0.2 to 0.8 parts by weight, more preferably 0.3 to 0.7 parts by weight, per 100 parts by weight of the polyol. The addition rate (weight ratio) of the antifungal agent in the polyurethane foam can be calculated from the following antifungal agent addition rate, and is preferably 0.2 to 0.6 wt% (% by weight), more preferably 0.3. ~0.6 wt%.
Antifungal agent addition rate (wt%) = [addition amount of antifungal agent ÷ total amount of compounding × 100]

Other auxiliary agents may be added to the polyurethane foam raw material. Examples of auxiliary agents include foam stabilizers and coloring agents. As the foam stabilizer, those known for polyurethane foam can be used. Examples thereof include silicone foam stabilizers, fluorine foam stabilizers and known surfactants. As the coloring agent, those suitable for the use of the polyurethane foam can be used.

Foaming in the production of polyurethane foam is preferably slab foaming. Slab foaming is a method in which raw materials for polyurethane foam are mixed, discharged onto a belt conveyor, and foamed at room temperature under atmospheric pressure, and a semicylindrical polyurethane foam with a square or round cross section is obtained.

The following components were mixed according to the formulation shown in the table of FIG. 1, reacted and foamed to produce polyurethane foams for each example and each comparative example. The formulations of each example and each comparative example are the same except for the type or amount of antifungal agent added.
· Polyol; polyether polyol, molecular weight: 3000, number of functional groups: 3, hydroxyl value: 56.1 mgKOH / mg, product number: GP-3000, manufactured by Sanyo Chemical Industries, Ltd. · Blowing agent; water · amine catalyst; product number: DABCO 33LV manufactured by Evonik Metal catalyst; Product number: Stannous octoate, MRH110, manufactured by Johoku Chemical Industry Co., Ltd. Foam stabilizer; Silicone foam stabilizer, Product number: B8110, manufactured by Evonik Antifungal agent A (isothiazoline, liquid); 2-Butyl-1,2-benzothiazol-3(2H)-one, manufactured by Lonza Japan Antifungal agent B (triazole type, powder); (RS)-1-P-chlorophenyl-4,4- Dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol, manufactured by Sinanen Zeomic Co. Antifungal agent C (pyridine type, powder); 2-mercaptopyridine N-oxide zinc , manufactured by Lonza Japan ・Isocyanate; 2,4-TDI/2,6-TDI = 80/20, product number: Coronate T-80, manufactured by Nippon Polyurethane Industry Co., Ltd.

Cream time and rise time were measured during production of the polyurethane foam in each example and each comparative example. The cream time is the time it takes for the polyurethane foam raw material to change from a liquid state to a resin state when mixed and discharged. On the other hand, the rise time is the time from the time of mixing/discharging until the maximum foaming height is reached. In addition, health bubbles and foam conditions were visually observed. Health bubble means that carbon dioxide gas generated at the time of foaming is bubbling out from the surface of the polyurethane foam. The state of the foam was evaluated as "◯" when there was no problem such as shrinkage in the polyurethane foam, and as "X" when there was a problem.

For the polyurethane foam of each example and each comparative example, density (JIS K7222), 25% ILD hardness (JIS K6400-2 D method), and air permeability (JIS K6400-7 A method) were measured as physical property values.

In addition, the polyurethane foam of each example and each comparative example was subjected to a mold resistance test <mold growth state> in accordance with JIS Z2911:2010 Annex A (regulation), test method B for plastic products. As shown in FIG. 2, the test samples of each example and each comparative example were obtained by measuring the four corners of the polyurethane foam (slab foam) of each example and each comparative example in a vertical cross section perpendicular to the length direction. 1, 2, 4, 5 and central part no. 3 was cut to a size of 50×50×10 mm. In addition, the test bacteria are Aspergillus niger NBRC 105649, Penicillium pinophilum NBRC 33285, Paecilomyces variotii NBRC 33284, Trichoderma virens NBRC 6355, and Chaetomiumium 6 NBRC 6 NBRC 7.

The results of the mold resistance test <mold growth state> were classified into stages [0] to [5] according to the following criteria.
<Judgment Criteria>
0: No fungal growth was observed with the naked eye or under a microscope.
1: Growth of mold is not observed with the naked eye, but can be clearly confirmed under a microscope.
2: The growth of fungi is observed with the naked eye, and the area of the grown portion is less than 25% of the total area of the sample.
3: The growth of fungi is observed with the naked eye, and the area of the grown part is 25% or more and less than 50% of the total area of the sample.
4: The mycelium grows well, and the area of the growing part is 50% or more of the total area of the sample.
5: Mycelium grows rapidly and covers the entire surface of the sample.
Test sample no. 1 to No. 5 measured values, their average values, and the standard deviation as a variation index were obtained.

If both the health bubble and foam state are "○", the average value of the mold resistance test (mold growth state) is [1] or less, and the standard deviation is [0.4] or less, the overall judgment is "◎ ”, Both the health bubble and foam states are “O”, the average value of the mold resistance test (mold growth state) is [2] or less, and the standard deviation is [0.8] or less, When the comprehensive judgment was other than "◎", the comprehensive judgment was "○". If both the health bubble and foam state are "○", the average value of the mold resistance test (mold growth state) is [2] or less, and the standard deviation is greater than [0.8], the overall judgment is "△ ", and when at least one of the health bubble state and foam state is "x", or when the average value of the mold resistance test (mold growth state) is greater than [2], the overall judgment is "x". The measurement results are shown in the table of FIG.

Comparative Example 1 is an example in which none of the antifungal agents A to C is added (the antifungal agent addition rate is 0 wt %). Comparative Example 1 has a cream time of 18 seconds, a rise time of 107 seconds, a health bubble of "◯", a foam state of "◯", a density of 35 kg/m ³ , a 25% ILD hardness of 175 N, and a ventilation rate of 26 L/min. The results of the mold resistance test <mold growth state> were obtained from the test sample No. 1, 2, 4, 5 are [2], test sample no. 3 was [3], the average value was "2.2", the standard deviation was 0.45, and the overall judgment was "x".

Example 1 is an example in which 0.27 parts by weight of antifungal agent A (liquid) was added (addition rate of antifungal agent: 0.2 wt %). Example 1 has a cream time of 18 seconds, a rise time of 107 seconds, a health bubble of "◯", a foam state of "◯", a density of 34.8 kg/m ³ , a 25% ILD hardness of 173 N, and a ventilation rate of 30 L/min. Further, the results of the mold resistance test <mold growth state> were obtained from the test sample No. 1, 2, 4, and 5 are [0], test sample no. 3 was [1], the average value was [0.2], the standard deviation was 0.45, and the overall judgment was "◯". Example 1 can suppress the growth of mold and has a high antifungal effect compared to Comparative Example 1 in which the addition rate of the antifungal agent is 0 wt %.

Example 2 is an example in which 0.41 parts by weight of antifungal agent A (liquid) was added (addition rate of antifungal agent: 0.3 wt%). Example 2 has a cream time of 18 seconds, a rise time of 109 seconds, a health bubble of "◯", a foam state of "◯", a density of 35.4 kg/m ³ , a 25% ILD hardness of 176 N, and a ventilation rate of 35 L/min. Further, the results of the mold resistance test <mold growth state> were obtained from the test sample No. All of 1 to 5 were [0], the average value was [0], the standard deviation was 0, and the overall judgment was "⊚". In Example 2, growth of fungi was not observed with the naked eye or microscope in all of the test samples, and the antifungal effect was even higher than in Example 1 in which the addition rate of antifungal agent A was 0.2 wt%. In addition, since the standard deviation was 0 in the result of the mold resistance test <mold growth state>, it is assumed that the antifungal agent A is uniformly dispersed in the polyurethane foam. It is presumed that the antifungal effect is high.

Example 3 is an example in which 0.68 parts by weight of antifungal agent A (liquid) was added (addition rate of antifungal agent: 0.5 wt%). Example 3 has a cream time of 18 seconds, a rise time of 108 seconds, a health bubble of "◯", a foam state of "◯", a density of 35.2 kg/m ³ , a 25% ILD hardness of 172 N, and a ventilation rate of 31 L/min. Further, the results of the mold resistance test <mold growth state> were obtained from the test sample No. All of 1 to 5 were [0], the average value was [0], the standard deviation was 0, and the overall judgment was "⊚". In Example 3, growth of fungi was not observed with the naked eye or microscopically in all of the test samples, and the antifungal effect was as high as in Example 2. In addition, since the standard deviation was 0 in the result of the mold resistance test <mold growth state>, it is assumed that the antifungal agent A is uniformly dispersed in the polyurethane foam. It is presumed that the antifungal effect is high.

Comparative Example 2 is an example in which 0.41 parts by weight of antifungal agent B (powder) was added (antifungal agent addition rate: 0.3 wt%). Comparative Example 2 has a cream time of 18 seconds, a rise time of 110 seconds, a health bubble of "◯", a foam state of "◯", a density of 35.2 kg/m ³ , a 25% ILD hardness of 175 N, and a ventilation rate of 26 L/min. In addition, the results of the mold resistance test <mold growth state> were obtained from the test sample No. 1 is [0], No. 2 is [1], No. 3 is "2", No. 4 is "0", No. 5 was [1], the average value was [0.8], the standard deviation was 0.84, and the overall judgment was "Δ". Comparative Example 2 has an antifungal effect as compared with Comparative Example 1 in which the addition rate of the antifungal agent is 0 wt %, but the antifungal effect is lower than that of Examples 1 to 3. In Comparative Example 2, the standard deviation of the result of the mold resistance test <mold growth state> was 0.84, so it is presumed that the antifungal agent B was unevenly dispersed in the polyurethane foam. In addition, since the standard deviation of Example 2, in which the addition rate of antifungal agent A (liquid) is equal to the addition rate of antifungal agent B (powder) in Comparative Example 2, is 0, the powder antifungal agent B found to be difficult to disperse uniformly within the polyurethane foam.

Comparative Example 3 is an example in which 0.27 parts by weight of antifungal agent C (powder) was added (addition rate of antifungal agent: 0.2 wt %). Comparative Example 3 has a cream time of 20 seconds, a rise time of 130 seconds, a health bubble of "x", a foam state of "x", a density of 35 kg/m ³ , a 25% ILD hardness of 155 N, and a ventilation rate of less than 5 L/min. Comparative Example 3 was not subjected to the mold resistance test due to its poor foam condition. Since the foam state of Comparative Example 1 in which the addition rate of the antifungal agent was 0 wt% was "O", Comparative Example 3 was obtained by adding 0.27 parts by weight of the antifungal agent C (powder). It is presumed that a viscosity increase, etc., occurred during mixing of the raw materials for the polyurethane foam, hindering good reaction and foaming.

As described above, the antifungal polyurethane foams of Examples 1 to 3 have a high antifungal effect because the antifungal agent is uniformly dispersed in the polyurethane foam, and can be produced satisfactorily.

A first aspect of the invention relates to an antifungal polyurethane foam in which an isothiazoline antifungal agent is dispersed.

A second aspect of the invention is characterized in that, in the first aspect of the invention, the isothiazoline antifungal agent is dispersed in the polyurethane foam at 0.2 to 0.6 wt %.

A third aspect of the invention is a method for producing a polyurethane foam by mixing and reacting polyurethane foam raw materials containing a polyol, an isocyanate, a blowing agent, a catalyst, and an antifungal agent, wherein the antifungal agent is a liquid antifungal agent. It relates to a method for producing an antifungal polyurethane foam characterized by:

A fourth aspect of the invention is characterized in that, in the third aspect of the invention, the liquid antifungal agent comprises an isothiazoline antifungal agent.

A fifth aspect of the invention is characterized in that, in the fourth aspect of the invention, the amount of the isothiazoline antifungal agent is 0.2 to 0.8 parts by weight with respect to 100 parts by weight of the polyol. .

Claims (5)

An anti-mold polyurethane foam in which isothiazoline-based anti-mold agent is dispersed. 2. The antifungal polyurethane foam according to claim 1, wherein the isothiazoline antifungal agent is dispersed in the polyurethane foam in an amount of 0.2 to 0.6 wt %. A method for producing a polyurethane foam by mixing and reacting polyurethane foam raw materials containing a polyol, an isocyanate, a blowing agent, a catalyst, and an antifungal agent,
A method for producing an antifungal polyurethane foam, wherein the antifungal agent is a liquid antifungal agent. 4. The method for producing an anti-mold polyurethane foam according to claim 3, wherein the liquid anti-mold agent comprises an isothiazoline anti-mold agent. 5. The method for producing an antifungal polyurethane foam according to claim 4, wherein the amount of the isothiazoline antifungal agent is 0.2 to 0.8 parts by weight with respect to 100 parts by weight of the polyol.

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