JP2023077164A - polyurethane foam - Google Patents

Abstract

To provide a polyurethane foam that can reduce influences on environment as compared to conventional polyurethane foams containing antimicrobial agents such as silver compounds.SOLUTION: Provided is a polyurethane foam containing a plant-derived antimicrobial agent which uses a plant as a raw material. The plant-derived antimicrobial agent is preferably a quaternary ammonium salt-based antimicrobial agent. The polyurethane foam is formed from a polyurethane-forming composition containing a plant-derived antimicrobial agent which uses a plant as a raw material. The polyurethane-forming composition contains, as a polyol, only a polyether polyol derived from petroleum, or a polyether polyol derived from petroleum and a plant-derived polyol which uses a plant as a raw material.SELECTED DRAWING: Figure 2

Description

The present invention relates to polyurethane foams containing antimicrobial agents.

Polyurethane foams are used in various applications such as kitchens, clothing, bedding, furniture, and construction materials.
Polyurethane foam containing an antibacterial agent such as a silver compound is used for applications such as kitchen sponges that require antibacterial properties (Patent Document 1).

JP 2016-180078 A

However, in recent years, the impact on the environment has come to be emphasized, and polyurethane foams with less impact on the environment have been demanded.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polyurethane foam containing an antibacterial agent that has less impact on the environment.

A first invention is a polyurethane foam containing a plant-derived antibacterial agent made from a plant.

A second invention is characterized in that in the first invention, the plant-derived antibacterial agent is a quaternary ammonium salt antibacterial agent.

In a third invention, in the first or second invention, the polyurethane foam is formed from a polyurethane-forming composition containing the plant-derived antibacterial agent, and the polyurethane-forming composition includes: It is characterized by containing 15 to 100 parts by weight of polyether polyol in 100 parts by weight of polyol.

In a fourth invention, in the first or second invention, the polyurethane foam is formed from a polyurethane-forming composition containing the plant-derived antibacterial agent, and the polyurethane-forming composition includes: It is characterized by containing a plant-derived polyol whose raw material is a plant.

A fifth aspect of the invention is a polyurethane foam formed from a polyurethane-forming composition containing a plant-derived polyol whose raw material is a plant and a quaternary ammonium salt-based antibacterial agent.

A sixth invention is characterized in that in any one of the first to fifth inventions, the degree of biomass determined by the AMS method is 1% or more.

Since the polyurethane foam of the present invention contains a plant-derived antibacterial agent, it has less impact on the environment than conventional polyurethane foams containing an antibacterial agent such as a silver compound.
Moreover, when the polyol contains a plant-derived polyol, the biomass degree (plant-derived degree) of the polyurethane foam is increased, and the effect of reducing the load on the global environment can be enhanced.

It is a structural formula of a quaternary ammonium salt-based antibacterial agent having a trimethoxy group. 1 is a table showing measurement results of formulations, physical properties, etc. of Comparative Examples and Examples of the present invention.

The polyurethane foam containing the plant-derived antibacterial agent of the present invention is produced by stirring a polyurethane-forming composition containing a polyol, a polyisocyanate, a catalyst, a blowing agent, and a vegetable oil-derived antibacterial agent to react the polyol and the isocyanate to foam. obtained by The polyurethane foam of the present invention may be either flexible or rigid, and flexible polyurethane foams are suitable for use in kitchens, clothing, bedding, furniture, and the like.

Polyols for polyurethane foams can be used as polyols, and examples thereof include polyether polyols, polyester polyols, polyether ester polyols, plant-derived polyols made from plants, and the like. may be used. Among them, polyether polyol alone or a combination of polyether polyol and plant-derived polyol is preferable in order to make the polyurethane foam resistant to hydrolysis. The average functionality of hydroxyl groups in the polyol should be greater than 1.0. Preferred ranges for the average functional group number of hydroxyl groups in the polyol are 1.5 to 5.0, 1.8 to 4.5, and 2 to 4.0.

Polyether polyols include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, pentaerythritol, trimethylolpropane, sorbitol and sucrose, ethylene oxide (EO), Petroleum-derived polyether polyols to which alkylene oxides such as propylene oxide (PO) are added can be mentioned.
The polyether polyol has a hydroxyl value (OHV) of 15 to 100 mgKOH/g (more preferably 30 to 80 mgKOH/g), a functional group number of 2.0 to 3.5, and a molecular weight of 100 to 10,000 (more preferably 1,000 to 5000) is preferred.
The blending amount of the polyether polyol is preferably 10 to 100 parts by weight, more preferably 15 to 90 parts by weight, and even more preferably 20 to 85 parts by weight, based on 100 parts by weight of the polyol.

Polyester polyols are obtained by polycondensation of 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. and petroleum-derived polyester polyols.
The polyester polyol preferably has a hydroxyl value (OHV) of 15 to 100 mgKOH/g, a functional group number of 2 to 3.5, and a molecular weight of 100 to 10,000 (more preferably 1,000 to 5,000).
Examples of polyether ester polyols include those obtained by reacting polyether polyols with polybasic acids to form polyesters, and those having both polyether and polyester segments in one molecule.

Examples of plant-derived polyols using plants as raw materials include soybean oil-based, coconut oil-based, rapeseed oil-based, coconut oil-based, sunflower oil-based, and castor oil-based polyols. Among them, castor oil polyol is a preferred plant-derived polyol because of its availability and the like.
Castor oil polyols include unmodified castor oil polyols and modified castor oil polyols, both of which can be used, and their combined use is more preferred.

The unmodified castor oil polyol may be any of refined castor oil polyol, semi-refined castor oil polyol, and unrefined castor oil polyol, and among them, refined castor oil polyol is preferred.
Further, the unmodified (refined) castor oil polyol preferably has a functional group number of 2.7 and a hydroxyl value of 155 to 165 mgKOH/g.
Modified castor oil polyols include, for example, ester-modified castor oil polyols obtained by esterifying castor oil with organic acids such as carboxylic acids. The modified castor oil polyol preferably has a functional group number of 2.0 to 3.5 and a hydroxyl value of 40 to 180 mg KOH/produced.

The blending amount of the plant-derived polyol is preferably 5 to 85 parts by weight per 100 parts by weight of the polyol, and the lower limit is more preferably 10 parts by weight or more, further preferably 15 parts by weight or more. Considering the impact on the environment, the blending amount of the plant-derived polyol can be 30 parts by weight or more and 40 parts by weight or more.
When the unmodified (refined) castor oil polyol and the modified castor oil polyol are used in combination, the weight ratio is unmodified (refined) castor oil polyol:modified castor oil polyol=1:1 to 4:1, preferably 1.5:1. ~3:1 is more preferred.

As the polyisocyanate, 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 is preferably 70-140, more preferably 80-130, even more preferably 90-120. If the isocyanate index is less than 70, good foam cannot be obtained. On the other hand, if the isocyanate index exceeds 150, the foam becomes too hard and brittle, resulting in poor durability. On the other hand, if the isocyanate index exceeds 120, the internal exothermic temperature becomes high, making large-scale foaming difficult. The isocyanate index is calculated by [(isocyanate equivalent in the polyurethane-forming composition/active hydrogen equivalent in the polyurethane-forming composition)×100].

As the catalyst, those known for polyurethane foam can be used. For example, amine catalysts such as triethylamine, triethylenediamine, diethanolamine, dimethylaminomorpholine, N-ethylmorpholine and tetramethylguanidine; tin catalysts such as stannus octoate and dibutyltin dilaurate; phenylmercuric propionate and lead octoate. metal catalysts (also referred to as organometallic catalysts) such as

Examples of foaming agents include water, hydrocarbons, halogen compounds, and the like, and one or more of these may be used. Examples of hydrocarbons include cyclopentane, isopentane, normal pentane, and the like. Halogen compounds include methylene chloride, trichlorofluoromethane, dichlorodifluoromethane, nonafluorobutylmethylether, nonafluorobutylethylether, pentafluoroethylmethylether, heptafluoroisopropylmethylether and the like. Among these, water is particularly suitable as the foaming agent. Water may be ion-exchanged water, tap water, distilled water, or the like. The blending amount of water as a foaming agent is preferably 0.5 to 10 parts by weight, more preferably 1 to 8 parts by weight, and even more preferably 1.5 to 5 parts by weight with respect to 100 parts by weight of the polyol.

Examples of antibacterial agents derived from plant oils derived from plants include derivatives of fatty acids derived from plants obtained by refining coconut oil, olive oil, perilla seed oil, safflower oil, sesame oil, soybean oil, rapeseed oil, cedar oil, and the like. be done.
Among them, suitable antimicrobial agents derived from vegetable oils include quaternary ammonium salt antimicrobial agents.
The quaternary ammonium salt antibacterial agent includes a silyl group-containing quaternary ammonium salt antibacterial agent, an alkoxy group-containing quaternary ammonium salt antibacterial agent, an alkoxysilyl group-containing quaternary ammonium salt antibacterial agent, A quaternary ammonium salt antibacterial agent having a trimethoxysilyl group, a quaternary ammonium salt antibacterial agent having a triethoxysilyl group, and the like.

As an example of a quaternary ammonium antibacterial agent, FIG. 1 shows the structural formula of a quaternary ammonium salt antibacterial agent having a trimethoxysilyl group. In the structural formula of FIG. 1, n is preferably 8-20.
[3-(trimethoxysilyl)propyl]dimethyl(octadecyl)ammonium chloride, where n=17, is an example of a quaternary ammonium salt antibacterial agent having a trimethoxysilyl group.
The quaternary ammonium salt antibacterial agent may be used by dissolving it in a solvent such as glycol.

The content of the antibacterial agent derived from vegetable oil is preferably 0.2 to 3.0 parts by weight, more preferably 0.25 to 2.5 parts by weight, and more preferably 0.3 to 1.5 parts by weight per 100 parts by weight of polyol. More preferred. When the vegetable oil-derived antibacterial agent is dissolved in a solvent, a cross-linking agent, a plasticizer, or the like, the amount is higher than the above-mentioned content range, taking into consideration the ratio of the solvent and the like.

The polyurethane-forming composition is blended with other adjuvants as appropriate. Other auxiliary agents include cross-linking agents, foam stabilizers, flame retardants, colorants, stabilizers, plasticizers, and the like.
Examples of cross-linking agents include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1-4-butanediol, 1,6-hexanediol and the like.

As the foam stabilizer, those known for polyurethane foam can be used. Examples thereof include silicone foam stabilizers, fluorine foam stabilizers and known surfactants.

Flame retardants include halogenated polymers such as polyvinyl chloride, chloroprene rubber, and chlorinated polyethylene; phosphoric esters and halogenated phosphoric ester compounds; organic flame retardants such as melamine resins and urea resins; Inorganic flame retardants such as aluminum can be used.

The polyurethane foam of the present invention preferably has a biomass content of 1% or more as measured by the AMS method (accelerator mass spectrometry) defined in ASTM D6866-20.
The degree of biomass refers to the ratio of naturally-derived raw materials contained in a product, and by measuring the amount of radioactive carbon C14 that is contained only in naturally-derived substances, the degree of biomass of the product can be determined. can be measured. Specifically, it is obtained by measuring the C14 concentration of the polyurethane foam by the AMS method and calculating the ratio (%) of the current 100% naturally-derived substance to the C14 concentration.

Examples of the present invention will be specifically described together with comparative examples. Polyurethane-forming compositions of Comparative Examples and Examples, each of which had the following raw materials blended as shown in the table of FIG.

<Polyol>
・ Petroleum-derived polyol; polyether polyol, functional number 3, hydroxyl value 56.1 mgKOH / g, molecular weight 3000, product name: GP-3050NS, manufactured by Sanyo Chemical Industries, Ltd. ・ Plant-derived polyol 1; refined castor oil polyol (ester-based polyol) , Proportion of plant-derived substances in this polyol (plant content) 100%, number of functional groups 2.7, hydroxyl value 155 mgKOH / g, molecular weight 977, product name: H-30, manufactured by Ito Oil Co., Ltd. Plant-derived polyol 2; modified Castor oil polyol (ester-based polyol), ratio of plant-derived substances in this polyol (vegetable content) 100%, number of functional groups 3.5, hydroxyl value 90 mgKOH/g, molecular weight 2181

<Catalyst>
- Catalyst 1; N,N-dimethylaminohexanol, product name: Kaolyzer No. 25, manufactured by Kao Corporation ・Catalyst 2; Aliphatic tertiary amine composition, product name: DABCO 33LSI, manufactured by Evonik Japan ・Catalyst 3; Foam agent>
・Foam stabilizer 1; silicone, product name: L-595, manufactured by Momentive Performance Materials Japan ・Foam stabilizer 2; silicone, product name: SZ-1136, manufactured by Dow Corning Toray Co., Ltd. <Antibacterial agent ＞
Plant-derived antibacterial agent, [3-(trimethoxysilyl)propyl]dimethyl(octadecyl)ammonium chloride 50% dipropylene glycol, product name: EF4850 (HF), manufactured by Freshe Bioscience <Blowing agent>
・Water <Polyisocyanate>
2,4-TDI/2,6-TDI = 80/20 toluene diisocyanate, product name: Coronate T-80, manufactured by Tosoh Corporation

The degree of biomass, foamability, antibacterial properties, density, elongation, air permeability, and distortion of the polyurethane foams of Comparative Examples and Examples were measured or observed. Those results are shown in FIG.

The degree of biomass was determined by the AMS method based on ASTM D6866-20.
In addition, ASTM D6866-20 stipulates that the current concentration of carbon 14 in the atmosphere is increasing year by year, so a coefficient is applied for correction, and the 2020 atmospheric correction coefficient REF (pMC )=100.0 was used to calculate the degree of biomass.
In addition to the biomass degree by the AMS method, FIG. 2 also shows the biomass degree (ratio of plant-derived substances, weight %) calculated by the following formula. In addition, in the column of biomass degree (AMS method) in Examples 2 to 4, no plant-derived antibacterial agent is blended, and the other raw materials are the values measured for the polyurethane foam produced with the formulation shown in FIG. listed as a value.
Biomass degree (percentage of plant-derived substances) = number of parts of plant-derived polyol added / (total number of parts added of composition for forming polyurethane - gas loss) x 100
It was calculated by gas loss=number of parts added with water/18×44.
"18" in the above gas loss calculation formula is the molecular weight of water, and "44" is the molecular weight of carbon dioxide.

The foamability was determined by visually observing the appearance of the polyurethane foam, and evaluating the foaming state as "X" when there were rough cells or punctures, and as "O" when the foaming was normal without roughening or punctures.
For antibacterial activity, the antibacterial activity value against Staphylococcus aureus was measured according to JIS K 6400-9. Escherichia coli was also measured in some examples.
The antibacterial activity values for both Staphylococcus aureus and Escherichia coli are preferably 1.0 or more, more preferably 2.0 or more. The antibacterial activity was evaluated as "X" when the antibacterial activity value against Staphylococcus aureus was less than 1.0, "O" when it was 1.0 or more, and "A" when it was 2.0 or more.

Density was measured according to JIS K 6400, elongation according to JIS K 6400-55, air permeability according to JIS K 6400-7, and strain according to JIS K6400-4 4.5.2A.
Stretch and air permeability are important physical properties when the polyurethane foam is used as a cleaning sponge. Strain is an important physical property when the polyurethane foam is used for load bearing applications such as mattresses.
The elongation was evaluated as "X" when less than 120%, and "O" when 120% or more.
The ventilation was evaluated as "x" for 50 l/min and "good" for 50 l/min or more.
The distortion was evaluated as "×" when it was 10% or more, and as "◯" when it was less than 10%.

The formulations and results of Comparative Examples and Examples will be described below.
Comparative Example Comparative Example is an example in which the plant-derived polyol in the polyol was 0 parts by weight and the plant-derived antibacterial agent was 0 parts by weight.
As a result of the comparative example, the biomass degree (AMS method) was 1%, the biomass degree (ratio of plant-derived substances) was 0% by weight, and since it did not contain an antibacterial agent, antibacterial properties were not obtained, and antibacterial properties were evaluated. was "x". The foamability, elongation, air permeability and distortion were all evaluated as "◯".

・Example 1
Example 1 is an example in which the plant-derived polyol in the polyol was 0 parts by weight and the plant-derived antibacterial agent was 0.65 parts by weight.
As a result of Example 1, the biomass degree (proportion of plant-derived substances) was 0% by weight, the evaluation of antibacterial property was "⊚", and the foaming state, elongation, ventilation and strain were all evaluated as "◯".

・Example 2
Example 2 is an example in which the plant-derived polyol in the polyol was 80.0 parts by weight and the plant-derived antibacterial agent was 0.65 parts by weight.
As a result of Example 2, the biomass degree (AMS method) was 57% (reference value for polyurethane foam produced without blending an antibacterial agent), the biomass degree (ratio of plant-derived substances) was 53% by weight, and antibacterial evaluation was performed. "◯", and the evaluation of foaming state, elongation, ventilation and distortion were all "◯".

・Example 3
Example 3 is an example in which the plant-derived polyol in the polyol was 80.0 parts by weight and the plant-derived antibacterial agent was 0.50 parts by weight.
As a result of Example 3, the biomass degree (AMS method) was 57% (reference value for polyurethane foam produced without adding an antibacterial agent), the biomass degree (ratio of plant-derived substances) was 53% by weight, and the antibacterial property was evaluated. "◯", and the evaluation of foaming state, elongation, ventilation and distortion were all "◯".

・Example 4
Example 4 is an example in which the plant-derived polyol in the polyol was 80.0 parts by weight and the plant-derived antibacterial agent was 1.00 parts by weight.
As a result of Example 4, the biomass degree (AMS method) was 57% (reference value for polyurethane foam produced without adding an antibacterial agent), the biomass degree (ratio of plant-derived substances) was 53% by weight, and antibacterial evaluation was performed. "A", and the foaming state, elongation, ventilation and distortion were all evaluated as "O".

・Example 5
Example 5 is an example in which the plant-derived polyol in the polyol was 40.0 parts by weight and the plant-derived antibacterial agent was 0.65 parts by weight.
The results of Example 5 were as follows: biomass degree (ratio of plant-derived substances) was 28% by weight;

・Example 6
Example 6 is an example in which the plant-derived polyol in the polyol was 40.0 parts by weight and the plant-derived antibacterial agent was 1.00 parts by weight.
The results of Example 6 were as follows: biomass degree (ratio of plant-derived substances) was 28% by weight;

・Example 7
Example 7 is an example in which the plant-derived polyol in the polyol was 15.0 parts by weight and the plant-derived antibacterial agent was 0.65 parts by weight.
The results of Example 7 were as follows: biomass degree (ratio of plant-derived substances) was 11% by weight;

・Example 8
Example 8 is an example in which the plant-derived polyol in the polyol was 15.0 parts by weight and the plant-derived antibacterial agent was 1.00 parts by weight.
The results of Example 8 were as follows: biomass degree (ratio of plant-derived substances) was 11% by weight;

As described above, the polyurethane foam of the present invention has antibacterial properties because it contains a plant-derived antibacterial agent, and can reduce the impact on the environment compared to conventional polyurethane foams containing an antibacterial agent such as a silver compound. can.
In addition, a polyurethane foam containing a plant-derived polyol as a polyol can enhance the effect of reducing the load on the global environment.
It should be noted that the present invention is not limited to the embodiments, and can be modified without departing from the gist of the invention.

Claims (6)

A polyurethane foam containing a plant-derived antibacterial agent made from a plant. The polyurethane foam according to claim 1, wherein the plant-derived antibacterial agent is a quaternary ammonium salt antibacterial agent. The polyurethane foam is formed from a polyurethane-forming composition containing the plant-derived antibacterial agent,
3. The polyurethane foam according to claim 1, wherein the polyurethane-forming composition contains 15 to 100 parts by weight of polyether polyol per 100 parts by weight of polyol. The polyurethane foam is formed from a polyurethane-forming composition containing the plant-derived antibacterial agent,
3. The polyurethane foam according to claim 1, wherein the polyurethane-forming composition contains a plant-derived polyol. A polyurethane foam formed from a polyurethane-forming composition containing a plant-derived polyol whose raw material is a plant and a quaternary ammonium salt antibacterial agent. 6. The polyurethane foam according to any one of claims 1 to 5, having a biomass content of 1% or more according to the AMS method.

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