KR20180138263A - Composition for forming eco-friendly polyurethane foam with improved air permeability and antioxidant properties and method for preparing the polyurethane foam - Google Patents

Abstract

Disclosed are a composition for forming environmentally friendly polyurethane foam having enhanced air breathability and antioxidation properties, a manufacturing method of the polyurethane foam, and the like. More specifically, the present invention relates to a polyol premix composition capable of manufacturing the environmentally friendly polyurethane foam improved in breathability and the antioxidation properties while maintaining excellent physical properties including foam state of foam by containing anhydrosugar alcohol derived from natural materials, especially isosorbide, a composition for forming two-component polyurethane foam comprising the same as a component, the manufacturing method of the polyurethane foam using the same, and the environmentally friendly polyurethane foam so manufactured.

Description

TECHNICAL FIELD [0001] The present invention relates to a composition for forming an environmentally friendly polyurethane foam having improved air permeability and antioxidation properties, and a process for producing a polyurethane foam,

The present invention relates to a composition for forming an environmentally friendly polyurethane foam having improved breathability and antioxidation properties, and a process for producing a polyurethane foam. More particularly, the present invention relates to a process for producing a polyurethane foam by incorporating an anhydrosugar alcohol derived from a natural product, A polyol premix composition capable of producing an environmentally friendly polyurethane foam having improved breathability and antioxidation properties while maintaining excellent physical properties including a state, and a composition for forming a two-component polyurethane foam comprising the polyol premix composition as one component, A method for producing a polyurethane foam, and an environmentally friendly polyurethane foam so produced.

Flexible polyurethane foam is lightweight, has a long life and soft elasticity, and is widely used in automobiles, household furniture, interior materials, insulation materials and soundproofing materials. In the case of automobiles and home furnishings, comfort and comfort are required, and environmental regulations are being strengthened. As a result, the automobile and furniture materials, which are able to respond to environmental changes in the automobile and furniture materials markets and meet consumer needs quickly Research is underway to cope with technology development, quality improvement, and environmental regulation. In this regard, automotive and furniture manufacturers recognize that manufacturing products made from environmentally friendly materials is one of the key capabilities of the product. In addition, there is an increasing interest in biomaterials capable of reducing carbon dioxide and harmful gas in preparation for carbon dioxide reduction, prevention of global warming, and exhaustion of fossil fuels. Biomaterials are known to be able to reduce the generation of carbon dioxide and volatile organic compounds, have excellent biodegradability and can reduce the use of fossil fuels.

The polyurethane is produced by a polymerization reaction comprising isocyanate and a polyol as main components, wherein the isocyanate group of the isocyanate compound reacts with the hydroxyl group of the polyol. The polyurethane foam may be prepared by a method of simultaneously foaming isocyanate, polyol, water, additives, etc. Alternatively, a polyol and a diisocyanate are reacted to prepare a prepolymer, followed by mixing a catalyst, a foaming agent, Or by a prepolymer method.

Representative isocyanate compounds used in the production of polyurethane foams include toluene diisocyanate (TDI) compounds and methylene diphenyl diisocyanate (MDI) compounds. TDI is a mixture of 2,4-TDI and 2,6-TDI isomers in an amount of 80:20 wt%, TDI and MDI have some similar properties and also have unique physicochemical properties. Thus, polyurethane TDI and MDI may be selectively used depending on the use of the foam, and they may be mixed or used in combination with derivatives thereof. On the other hand, due to various reasons such as accelerated depletion of petroleum resources, demand for reduction of greenhouse gas due to climate change, increase of raw material price, increase of need for renewable raw materials, polyether polyol, polyester There is a demand for a method of partially or completely replacing existing petroleum-based raw materials with environmentally friendly components in the polyol field such as polyol and isocyanate field.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made keeping in view the above problems occurring in the prior art, and an object of the present invention is to provide a composition for forming a polyurethane foam capable of producing an environmentally friendly polyurethane foam having improved breathability and anti- And a method for producing a polyurethane foam using the same.

According to a first aspect of the present invention, there is provided a polyol premix composition comprising a polyol mixture composed of a polyhydric alcohol and a polyol other than anhydrosugar alcohol, an organometallic catalyst, an amine catalyst, a foam stabilizer and a foaming agent / RTI >

According to a second aspect of the present invention, there is also provided a polyol composition comprising the polyol premix composition as a first component; And a polyisocyanate as a second component. The composition for forming a two-component type polyurethane foam is provided.

According to a third aspect of the present invention, there is also provided a process for producing a polyurethane foam, which comprises mixing and reacting the polyol premix composition and a polyisocyanate.

According to a fourth aspect of the present invention, there is provided a polyurethane foam produced by reacting the polyol premix composition with a polyisocyanate.

By using the polyol premix composition or the composition for forming a polyurethane foam of the present invention, it is possible to produce an environmentally friendly polyurethane foam with improved air permeability and antioxidation property while maintaining excellent physical properties including the foam state of the foam.

Hereinafter, the present invention will be described in more detail.

The polyol premix composition of the present invention comprises a polyol mixture consisting of anhydrosugar alcohol and a polyol other than anhydrosugar alcohol, an organometallic catalyst, an amine catalyst, a foam stabilizer and a foaming agent.

The anhydrosugar alcohol used in the present invention is prepared from hydrogenated sugars derived from natural products.

Hydrogenated sugar (also referred to as " sugar alcohol ") refers to a compound obtained by adding hydrogen to the reducing end group of a saccharide, generally HOCH ₂ (CHOH) _n CH ₂ OH (wherein n is an integer of 2 to 5 ), And classified into tetritol, pentitol, hexitol and heptitol (C 4, 5, 6 and 7, respectively), depending on the number of carbon atoms.

Among them, hexitol having 6 carbon atoms includes sorbitol, mannitol, iditol, galactitol and the like, and sorbitol and mannitol are particularly useful substances.

Anhydrous alcohol has a diol form with two hydroxyl groups in the molecule and can be prepared using hexitol derived from starch. Since alcohol-free alcohol is an eco-friendly substance derived from renewable natural resources, there has been much interest for a long time and studies on the manufacturing method have been carried out. Among these alcohol-free alcohols, isosorbide prepared from sorbitol has the widest industrial application currently.

The use of anhydrous alcohol is widely used in the treatment of cardiovascular diseases, patches, adhesives, oral cleansers and the like, solvents for compositions in the cosmetics industry, and emulsifiers in the food industry. In addition, it is possible to increase the glass transition temperature of a polymer substance such as polyester, PET, polycarbonate, polyurethane, and epoxy resin, to improve the strength of these materials, and to be an environmentally friendly material derived from natural materials. useful. It is also known to be used as an environmentally friendly solvent for adhesives, environmentally friendly plasticizers, biodegradable polymers, and water-soluble lacquers. As such, alcohol-free alcohol has attracted a great deal of attention due to its versatility and its use in real industry is increasing.

In the present invention, as the alcohol without sugar, dianhydrohexitol, which is a dehydrate of hexitol, may be used, more preferably isosorbide (1,4-3,6-dianhydroisorbitol), isomannide 1,4,3,6-dianhydro- mannitol), isoidide (1,4-3,6-dianhydroiditol) and mixtures thereof, and most preferably isosorbide is used .

The polyol other than the anhydropolydanol used in the present invention is usually a polyol having an average number of active hydrogens of 2 or more (preferably 2 to 4) and an active hydrogen equivalent of 600 to 7000, The polyol used can be used.

More specifically, a polyether polyol, a polyester polyol, a polymer polyol obtained by polymerizing the polyol and the vinyl compound, and a combination thereof can be used. According to one embodiment, a polyether polyol or polyether polymer polyol obtained by polymerizing a polyether polyol and a vinyl compound can be preferably used.

The polyol other than the alcohol without anhydride may be used alone or in combination, and preferably the polymer polyol may be used for controlling the physical properties of the flexible polyurethane foam. For example, polyether polymer polyol can be obtained in the form of a stable suspension by grafting a polyvinyl filler to a polyether polyol. Examples of the vinyl compound that can be used in the production of the polymer polyol include acrylonitrile, styrene monomer, methylmethacrylonitrile, and the like. Preferably, acrylonitrile may be used alone or in combination with a styrene monomer. The vinyl compound content in the polymer polyol may be 20 to 50 wt%.

In one embodiment, 100 weight parts of the polyol mixture may contain 1 to 10 weight parts of anhydrous alcohol, more preferably 1 to 8 weight parts, and even more preferably 1 to 5 weight parts. If the content of anhydrosugar alcohol in the polyol mixture is too small, the polyurethane foam may not be foamed or the polyurethane foam may have insufficient air permeability and antioxidation effect. On the contrary, if the polyol foam is excessively large, A foam having a reduced physical property may be formed, or a foam may not be formed.

The organometallic catalyst used in the present invention promotes the reaction between the polyol and the isocyanate compound.

The organometallic catalyst used in the present invention may be an organometallic catalyst commonly used in the production of a polyurethane foam. Examples thereof include organic tin catalysts (more specifically, dibutyltin dilaurate (DBTDL) or tin bis [2-ethylhexanoate]), but is not limited thereto.

The amine catalyst used in the present invention promotes the reaction between the polyol and the isocyanate compound. In the present invention, the kind of the amine catalyst is not particularly limited, but one or a mixture of two or more thereof may be used in the tertiary amine catalyst. More specifically, triethylene diamine, triethylamine Triethylamine, N-methyl morpholine, N-ethyl morpholine, and combinations thereof may be used.

In the polyol premix composition of the present invention, the organometallic catalyst and the amine catalyst may be independently included in an amount of 0.01 to 5 parts by weight, more preferably 0.1 to 2.5 parts by weight, based on 100 parts by weight of the polyol mixture. If the amount of these catalysts to be used is too small, the reaction may be delayed, resulting in poor curing, or a problem of sagging during the formation of the foam. On the contrary, if the amount is too large, the reaction may become too rapid or shrinkage may occur.

The foam stabilizer used in the present invention functions to prevent the cells generated when the cells are formed in the polyurethane foam foam from being united or broken and to adjust the cells to have uniform shapes and sizes . In the present invention, the foam stabilizer can be used without any particular limitations as long as it is commonly used in the production of polyurethane foam foam, and for example, silicon based foam stabilizer can be generally used. The silicon-based foaming agent may be at least one kind selected from silicone oil and derivatives thereof, and specifically may be a polyalkylene oxide methyl siloxane copolymer.

In the polyol premix composition of the present invention, the foaming agent may be contained in an amount of 0.01 to 5 parts by weight, more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the polyol mixture. If the amount of the foam stabilizer used is too small, the foam may be unevenly formed. On the contrary, if the foam stabilizer is used in an excessively large amount, the foam may be shrunk.

As the foaming agent to be used in the present invention, a known foaming agent component conventionally used for the production of flexible polyurethane foam can be appropriately selected and used in consideration of various physical properties of the foamed foam required. In the present invention, water is typically used as the foaming agent. In addition, water may be used as the foaming agent from the group consisting of methylene chloride, n-butane, isobutane, n-pentane, isopentane, dimethyl ether, acetone, carbon dioxide, You can use the selected one. These foaming agents can be suitably used according to known methods of use and depending on the density and other properties of the foam foam desired.

There is no particular limitation on the amount of the foaming agent used in the polyol premix composition of the present invention. For example, 0.1 to 30 parts by weight, more specifically 0.5 to 25 parts by weight, of the foaming agent may be used based on 100 parts by weight of the polyol mixture But is not limited to. According to one embodiment of the present invention, as a foaming agent based on 100 parts by weight of polyol, 0.8 to 5.0 parts by weight of water alone or a mixture of this and 0.1 to 18 parts by weight of methylene chloride may be used.

The polyol premix composition of the present invention may further comprise an auxiliary additive selected from the group consisting of flame retardants, colorants, UV stabilizers, thickeners, foam stabilizers, fillers, and combinations thereof, in addition to the above components.

According to another aspect of the present invention, there is provided a composition comprising the polyol premix composition as a first component; And a polyisocyanate as a second component. The composition for forming a two-component type polyurethane foam is provided.

In the present invention, the polyisocyanate can be used without any particular limitation as long as it can be used in the production of a polyurethane foam. Thus, for example, polyisocyanates selected from aliphatic polyisocyanates, cycloaliphatic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, heterocyclic polyisocyanates, and combinations thereof may be used, and also unmodified polyisocyanates or modified Can be used as the polyisocyanate.

Specifically, the polyisocyanate is at least one compound selected from the group consisting of methylene diisocyanate, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1-12-dodecane diisocyanate, cyclobutane- Cyclohexane-1,4-diisocyanate, isophorone diisocyanate, 2-4-hexahydrotoluene diisocyanate, 2,6-hexahydrotoluene diisocyanate, dicyclohexylmethane-diisocyanate, 4,4'-diisocyanate (HMDI), 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane- , 4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, polydiphenylmethane diisocyanate (PMDI), naphthalene-1,5-diisocyanate and combinations thereof Luer binary may be selected from the group. In one embodiment, as the polyisocyanate, toluene diisocyanate (2,4- / 2,6-isomer ratio = 80/20) in which 2,4-toluene diisocyanate and 2,6-toluene diisocyanate are mixed can be used have.

In the present invention, the amount of polyisocyanate to be used is preferably 70 to 130 in terms of isocyanate index, more preferably 80 to 120, and even more preferably 90 to 110. The isocyanate index refers to the amount of isocyanate used relative to the theoretical equivalent, as a ratio of the number of hydroxy equivalents present in the polyol to the number of equivalents of isocyanate in the urethane reactant. An isocyanate index of less than 100 means that an excess of polyol is present, and an isocyanate index of more than 100 means that an excess of isocyanate is present. When the isocyanate index is less than 70, there is a problem in that the reactivity is slowed and the gelation reaction is delayed and the hardening is not performed. When the isocyanate index is more than 130, the hard segment is excessively increased and the shrinking phenomenon occurs .

In the composition for forming a two-component type polyurethane foam of the present invention, the first component and the second component may be present separately without contact, and they may be mixed immediately before use or in situ .

According to another aspect of the present invention, there is provided a process for producing a polyurethane foam, which comprises mixing and reacting the polyol premix composition and a polyisocyanate, and a polyurethane foam, such as a flexible polyurethane foam, .

When the polyol premix composition of the present invention is used in the production of the polyurethane foam, a polyisocyanate is added to the polyol premix composition and stirred, and then the mixture is poured into a mold to allow curing and foaming to proceed. have.

When the composition for forming a two-component polyurethane foam of the present invention is used for the production of the polyurethane foam, the first component and the second component contained in the composition are mixed and stirred, And the foaming proceeds, whereby a polyurethane foam can be produced.

There are no particular restrictions on equipment or conditions (temperature, time, etc.) used in the production of the polyurethane foam, and the equipment or conditions that are usually employed may be used as is or modified appropriately.

In one embodiment, the polyurethane foam can be cured at elevated temperatures due to the urethane foaming reaction heat, and can be cured preferably at 100 占 폚 to 180 占 폚, or at 120 占 폚 to 180 占 폚, and more preferably at 160 占 폚 to 180 占 폚 But is not limited thereto.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the scope of the present invention is not limited by these examples.

[ Example ]

Comparative Example  And Example  1-5

Isobarbide (ISB), a polyol (TF-3000) other than anhydrous alcohol, a catalyst, a foam stabilizer and a foaming agent were mixed as an alcohol without anhydride according to the components and content ratios shown in Table 1 below and stirred at a stirring speed of 3000 rpm And thoroughly mixed for 1 to 3 minutes to prepare a polyol premix composition.

Polyisocyanate was added to the prepared polyol premix composition and stirred at a stirring speed of 3000 rpm for 7 to 10 seconds to prepare a composition for forming polyurethane foam.

A polyethylene film was laid in a square shape in a 250 mm x 250 mm square box mold, and the polyurethane foam forming composition prepared above was poured thereon. At this time, the cream time, maximum rise time and gel time were measured and recorded using a stopwatch to observe whether health bubbles occurred. The heat of curing reaction of the polyurethane foam was confirmed by a bar thermometer to be 120 ° C. Mold density (measurement method: KS-M-6672) and air permeability (measurement method: ASTM D 3574-01) of the foam specimen thus prepared were measured. Observation and measurement results are shown in Table 1 below.

[Ingredients Used]

1) Polyol

ISB: Free alcohol, isosorbide (Samyang)

TF-3000: no allowance and the polyol, the active hydrogen equivalent of 3,000 other than alcohol, a trifunctional polyether polyol has a hydroxyl value of 54~58mgKOH / g (Mitsui chemicals & SKC polyurethanes, TF-3000 product)

2) Foaming agent

L-580K: a silicone foam stabilizer, a polyalkylene oxide methyl siloxane copolymer (Momentive, NIAX L-580K)

3) Catalyst

A-1: An amine-based catalyst, a bis- (20 dimethylaminoethyl) ether / propylene glycol solution (Momentiva, Naikac catta list A-1)

L-33: amine catalyst, triethylenediamine / dipropylene glycol solution (TEDA L-33, manufactured by Tosoh Corporation) at a concentration of 67 wt%

DBTDL: Organometallic catalyst, dibutyltin dilaurate (Sigma Aldrich)

4) Foaming agent

water

5) Isocyanate

T-80: Toluene diisocyanate (2,4- / 2,6-isomer ratio = 80/20) in which 2,4-toluene diisocyanate and 2,6-toluene diisocyanate were mixed -80 products)

- Cream Time (sec): It means the time taken from when the polyurethane foam stock solution is mixed until the stock solution begins to swell.

- Rise time (seconds): The time taken from when the polyurethane foam stock solution is mixed until the foam reaches maximum swelling.

- Gel time (sec): It refers to the time from when the polyurethane foam raw solution is mixed until the time when the undiluted solution has a gel strength capable of withstanding a light impact and has a stable spatial shape. Specifically, It means when the pellets are pushed into the reaction, at least 3 to 4 urethane fibers are added.

From the above Table 1, it can be seen that the specimens of Examples 1 to 5 maintained the foaming state and physical properties of the foam excellent, and the breathability was remarkably improved as compared with the specimen of Comparative Example 1 prepared without using isosorbide .

On the other hand, as shown in Table 1, since the curing temperature in the actual process rises to 160 ° C or higher, the polyurethane foam samples of Comparative Example 1 and Examples 1 to 5 are post cured in an oven at 160 ° C for 2 hours, As a result of confirming the change, increase in air permeability compared to air permeability at 120 ° C was observed by the cell opening effect. In this case, compared with the specimen of Comparative Example 1 which was manufactured without using isosorbide, It can be seen that the air permeability of the specimens 1 to 5 is remarkably improved.

In addition, since the curing temperature in the actual process rises to 160 ° C or more, the polyurethane foam specimens of Comparative Example 1 and Examples 1 to 5 are post-cured in an oven at 160 ° C for 2 hours, and the YI (Yellow Index) Method: ASTM E313-96). As a result, the YI values of the specimens of Examples 1 to 5 were found to be smaller than those of Comparative Example 1 prepared without using isosorbide. That is, as the content of isosorbide increased, the YI value decreased, indicating that the antioxidant property was improved with increasing isosorbide content.

Claims (13)

A polyol premix composition comprising a polyol mixture consisting of a polyol other than anhydrosugar alcohol and anhydrosugar alcohol, an organometallic catalyst, an amine catalyst, a foam stabilizer and a blowing agent. The polyol as claimed in claim 1, wherein the polyol other than the alcohol without anhydride is selected from the group consisting of a polyether polyol, a polyester polyol, a polymer polyol obtained by polymerizing the polyether polyol or polyester polyol with a vinyl compound, Polyol premix composition. The polyol premix composition of claim 1, wherein the anhydrosugar alcohol is selected from the group consisting of isosorbide, isomannide, isoidide, and mixtures thereof. The polyol premix composition according to claim 1, wherein anhydrous alcohol is contained in an amount of 1 to 10 parts by weight based on 100 parts by weight of the polyol mixture. The polyol premix composition of claim 1, wherein the organometallic catalyst is an organotin catalyst. The polyol premix composition of claim 1, wherein the amine catalyst is a tertiary amine catalyst. The polyol premix composition according to claim 1, wherein the foam stabilizer is a silicone foam stabilizer. The polyol premix composition according to claim 1, wherein the blowing agent is selected from the group consisting of water, methylene chloride, n-butane, isobutane, n-pentane, isopentane, dimethyl ether, acetone, carbon dioxide and combinations thereof. The polyol premix composition of claim 1, further comprising an auxiliary additive selected from the group consisting of a flame retardant, a colorant, a UV stabilizer, a thickener, a foam stabilizer, a filler, and combinations thereof. The polyol premix composition of any one of claims 1 to 9 as a first component; And a polyisocyanate as a second component. The composition for forming a two-component polyurethane foam according to claim 1, 11. The composition of claim 10 wherein the polyisocyanate is selected from the group consisting of methylene diisocyanate, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1-12-dodecane diisocyanate, Diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, 2-4-hexahydrotoluene diisocyanate, 2,6-hexahydrotoluene diisocyanate, dicyclohexyl Methane-4,4'-diisocyanate (HMDI), 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane Diisocyanate, diphenylmethane-4,4'-diisocyanate, polydiphenylmethane diisocyanate (PMDI), naphthalene-1,5-diisocyanate, and combinations thereof. A two-component type polyurethane foam forming composition is selected from the group eojin. A process for producing a polyurethane foam, which comprises mixing and reacting a polyisocyanate with the polyol premix composition of any one of claims 1 to 9. A polyurethane foam produced by reacting a polyisocyanate with the polyol premix composition of any one of claims 1 to 9.