JP2022103495A - Urethane resin composition including renewable resources and curing agent for urethane resin composition - Google Patents

Abstract

To use plant-derived raw materials composed of renewable resources in the development of a urethane resin composition used in a thermal barrier, contributing to achievement of SDGs (sustainable development goals).SOLUTION: A urethane resin composition contains a base agent containing a polyisocyanate compound that is mixed with a curing agent containing a plurality of polyol compounds, the urethane resin composition belonging to A type 3 in JIS9526. The plurality of polyol compounds include a first polyol compound that does not contain palm oil and a second polyol compound that has been blended with palm oil in advance.SELECTED DRAWING: Figure 1

Description

The present invention is a field spray type urethane resin composition used for a heat insulating layer of a building and a curing agent for the urethane resin composition, and particularly contributes to the achievement of SDGs (sustainable development targets). The present invention relates to a urethane resin composition and a curing agent for a urethane resin composition.

As a heat insulating layer of a building, a hard urethane resin composition (also referred to as "urethane foam") is used, in which a main agent containing a polyisocyanate compound and a curing agent containing a polyol compound are sprayed and mixed at a construction site to foam. ing.
As described in the following patent documents, these urethane resin compositions are based on predetermined criteria such as density, closed cell ratio, thermal conductivity, moisture permeability coefficient, flame retardancy, and anti-termite property according to the application. The ingredients are adjusted to meet.

Japanese Patent No. 4919449 Japanese Patent No. 6150539 Japanese Patent No. 6200435 Japanese Patent No. 6725606 Japanese Patent No. 6775472

The main agent and the curing agent used for forming the urethane resin composition described in each of the above-mentioned patent documents are generally produced by using a chemical product mainly composed of fossil resources, and the fossil resources are regenerated. There was room to work on the SDGs (Sustainable Development Goals), which have been attracting attention in recent years, from the perspective of replacing them with producible resources.

Therefore, it is an object of the present invention to contribute to the achievement of SDGs (Sustainable Development Goals) by using plant-derived raw materials consisting of reproducible resources in the development of urethane resin compositions used for heat insulating layers. It is one of the above.

The first invention of the present application, which has been made to solve the above problems, is obtained by mixing a main agent containing a polyisocyanate compound and a curing agent containing a polyol compound, and has a foaming ratio of 120 times or more and JIS9526 type A. A urethane resin composition belonging to No. 3, wherein the curing agent is composed of a mixture containing at least a plurality of polyol compounds, and the plurality of polyol compounds are a first polyol compound containing no palm oil. It is characterized by comprising a second polyol compound containing palm oil in advance.
Further, the second invention of the present application is for constituting a urethane resin composition having a foaming ratio of 120 times or more and belonging to Class A 3 of JIS9526 by mixing with a main agent containing a polyisocyanate compound. A first polyol compound which is a curing agent and is composed of a mixture containing at least a plurality of polyol compounds, and the plurality of polyol compounds does not contain palm oil, and contains palm oil in advance. It is characterized by being composed of 2 polyol compounds.

According to the present invention, the following effects are obtained.
(1) By using palm oil, which is a plant-derived raw material consisting of reproducible resources, as a part of the curing agent used for urethane foam, it is possible to contribute to the realization of SDGs (Sustainable Development Goals). ..
(2) By mixing the first polyol compound that does not contain palm oil and the second polyol compound that contains palm oil in advance, a curing agent that ensures storage stability can be obtained. Can be done.
(3) Since palm oil is considered to function as a slimming agent, it leads to a reduction in the amount of other slimming agents used.

Table (1) showing the results of comparative tests of urethane resin compositions Table (2) showing the results of comparative tests of urethane resin compositions

<1> Overall Structure The urethane resin composition according to the present invention is for forming a foam constituting a heat insulating material of a building, and contains a main agent containing a polyisocyanate compound and a curing agent containing a polyol compound. A heat insulating layer is formed on the building by a method of mixing and spraying while spraying with a spray gun or the like, or a method of spraying while mixing both.
In the present invention, it is premised that the foam of the urethane resin composition obtained by the above composition belongs to Class A 3 of JIS9526.

Hereinafter, details of each raw material of the urethane resin composition according to the present invention will be described. The composition of each raw material shall satisfy the criteria such as density, closed cell ratio, thermal conductivity, moisture permeability coefficient, flame retardancy, and anti-termite property required for urethane resin compositions used for specific purposes. It may be adjusted appropriately.

<2> Polyisocyanate compound The polyisocyanate compound is a material used as a main agent of the urethane resin composition according to the present invention.
Examples of the polyisocyanate compound include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates.

Examples of the aromatic polyisocyanate include phenylenediocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate.
Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate and the like.
The polyisocyanate compound may be used alone or in combination of two or more.
The main agent of the urethane resin composition is preferably diphenylmethane diisocyanate because it is easy to use and easily available.

<3> Polyol compound The polyol compound is a material used as a curing agent for the urethane resin composition according to the present invention.
The polyol compound consists of any one of an ester-based polyol compound, an ether-based polyol compound, and other polyol compounds, or a combination thereof.

<3.1> Ester-based polyol compound As the ester-based polyol compound, for example, a polymer obtained by dehydration condensation of a polybasic acid and a polyhydric alcohol, a lactone such as ε-caprolactone and α-methyl-ε-caprolactone. Examples thereof include a polymer obtained by ring-opening polymerization, and a condensate of hydroxycarboxylic acid and the above polyhydric alcohol.
Here, specific examples of the polybasic acid include adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, succinic acid and the like. Terephthalic acid denaturation is preferable in terms of flame retardancy, and fatty acid denaturation is preferable in terms of adhesiveness.

<3.2> Ether-based polyol compound The ether-based polyol compound is obtained by ring-opening addition polymerization of an alkylene oxide to an initiator having 2 to 8 functional groups such as glycol, glycerin, and pentaerythritol, and has a hydroxyl value of 30. It is a polyol having a value of ~ 900 mgKOH / g.
The polyol can be produced by a method known in the art using an initiator having 2 to 8 functional groups, a polymerization catalyst, and an alkylene oxide.
As the initiator used in the production of the polyol, polyhydric alcohols, aromatic amine compounds, aliphatic amine compounds, Mannig compounds and the like can be used.
Examples of the polymerization catalyst used for producing the polyol include an alkali metal catalyst, a cesium catalyst, a phosphate-based catalyst, and a composite metal cyanide complex catalyst (DMC catalyst).
Preferable examples of alkylene oxides used in the production of polyols include propylene oxide and ethylene oxide.
Therefore, the alkylene oxide is preferably a combination of ethylene oxide and propylene oxide. The ratio of ethylene oxide to the total amount of alkylene oxide is 0 to 80% by mass, preferably 0% by mass to 50% by mass, and more preferably 5 to 50% by mass. When ethylene oxide is used, most of the hydroxyl groups of the polyol become primary hydroxyl groups, the reactivity of the polyol becomes high, and the reactivity with isocyanate becomes high, which is preferable in spray applications.
Further, it is preferable that the proportion of ethylene oxide is within the above range in order to prevent shrinkage of the foam. Further, setting the proportion of ethylene oxide within the above range improves the compatibility between the polyol and water used as a foaming agent.

<3.3> Other Polyol Compounds Examples of other polyol compounds include polylactone polyols, polycarbonate polyols, aromatic polyols, alicyclic polyols, aliphatic polyols, polymer polyols, and polyether polyols.
Examples of the polylactone polyol include polypropiolactone glycol, polycaprolactone glycol, polyvalerolactone glycol and the like.
The polycarbonate polyol can be obtained by a dealcohol reaction between a hydroxyl group-containing compound such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol or nonanediol and diethylene carbonate, dipropylene carbonate or the like. Examples include polyols.
Examples of the aromatic polyol include bisphenol A, bisphenol F, phenol novolac, cresol novolak and the like.
Examples of the alicyclic polyol include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, and dimethyldicyclohexylmethanediol.
Examples of the aliphatic polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.
Specific examples of the polyhydric alcohol include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexaneglycol, neopentyl glycol and the like. ..
Specific examples of the hydroxycarboxylic acid include castor oil and reaction products of castor oil and ethylene glycol.
Aromatic polyols are desirable in terms of flame retardancy.

<4> Foaming agent The foaming agent is a material for improving the foaming action when the main agent and the curing agent are mixed.
In the present invention, water is used as the foaming agent and is added to the curing agent.
The content of the foaming agent may be appropriately determined within a range in which foaming is promoted and the density of the obtained molded product can be reduced.

<5> Palm oil Palm oil is a vegetable oil obtained from the fruits of oil palm, and since it is a plant-derived raw material, it can be treated as a reproducible resource.
In the present invention, it is preferable to use the palm oil of RSPO certification (Roundtable on Sustainable Palm Oil: Roundtable for Sustainable Palm Oil).

<5.1> Functions of palm oil Since palm oil is considered to function as a thickener for the polyol compound in the curing agent, diethylene glycol, ethylene glycol, etc., which are generally used as a thickener for the polyol compound, etc. Contributes to the reduction of usage.

<5.2> Target of mixing palm oil When palm oil is mixed with a polyol compound in advance, a polyol compound containing a highly viscous polyol (for example, a polyol having sucrose as an initiator) is used as a mixing target. If it is set aside, the thickening effect of palm oil can be expected, and when the final curing agent is obtained, each polyol compound can be mixed in a reduced viscosity state.

<6> Others In addition, in the urethane resin composition according to the present invention, the following materials may be added to the formulation.

<6.1> Solubilizer The compatibilizer is a material for solving the problem of deterioration of storage stability when palm oil is included in the curing agent.
For example, if an attempt is made to increase the foaming ratio (for example, 120 times or more) of the urethane resin composition, when water is used as the foaming agent, the amount of water in the curing agent also increases, so that palm oil can be easily separated. , Deterioration of storage stability of the curing agent may occur.
In this case, if a predetermined amount of the compatibilizer is added, the raw materials can be uniformly dispersed without separating water and palm oil, and a curing agent having excellent storage stability can be obtained. As the compatibilizer, for example, TERGITOR NP-9 manufactured by Dow, ECOSURF EH-6 and EH-9 manufactured by Dow, DABCO EM400 manufactured by Evonik, and the like can be used.
The compatibilizer may be used alone or in combination of two or more.

<6.2> Defoaming agent A defoaming agent is a material for making bubbles at the time of foaming uniform and stabilizing, and preventing non-uniformity and coarsening of bubbles.
As the defoaming agent, a silicone-based defoaming agent can be used.
The foam stabilizer may be used alone or in combination of two or more.

<6.3> Flame Retardant A flame retardant is a material for imparting flame retardancy.
The flame retardant is preferably a phosphorus-based flame retardant, and suitable examples include tricresyl phosphate (TCP), triethyl phosphate (TEP), tris (β-chloroethyl) phosphate (TCEP), and tris (β-chloropropyl). ) Phosphate (TCPP) or the like can be used.
The flame retardant may be used alone or in combination of two or more.

<6.4> As the catalyst catalyst, an amine catalyst, a lead catalyst, a bismuth catalyst and the like can be mentioned, but it is preferable to use a non-volatile reactive amine catalyst.
A non-volatile amine catalyst is preferable in order to avoid eye rainbow (eye haze), toxicity, and deterioration of moldability.
Further, in the present invention, the amine catalyst is preferably a reactive amine catalyst of a type having a higher foaming activity, and specific examples thereof include an isocyanate reactive catalyst.
Therefore, the catalyst of the present invention preferably contains an isocyanate-reactive catalyst. Here, the isocyanate-reactive catalyst is a reactive amine catalyst having one or more isocyanate-reactive active hydrogen groups in the molecule. The use of an isocyanate-reactive catalyst is advantageous in improving the open-cell property of the foam, reducing the density, and improving the workability (spray thickness amount, sagging property) in spray foaming.
Suitable specific examples of the isocyanate reactive catalyst include N, N, N'-trimethylaminoethylethanolamine, dimethylaminoethoxyethanol, N, N, N'-trimethyl-N'-hydroxyethyl-bisaminoethyl ether and the like. Can be mentioned.

<1> Raw Materials Used Hereinafter, each raw material of the polyol compound constituting the urethane resin composition according to the present invention will be described.

<1.1> Polyisocyanate compound

<1.2> Polyol compound

<2> Outline of each example (Fig. 1)
The outline of Example 1 and Comparative Examples 1 and 2 shown in FIG. 1 is as follows.
Example 1: A curing agent mixed with C3135 and C2020 (first polyol compound) which are polyol compounds containing no palm oil and R8240 (second polyol compound) containing 25% of palm oil in advance is used. What was there.
Comparative Example 1: A product using a curing agent mixed with C3135, C2020 and SR-500, which are polyol compounds containing no palm oil.
Comparative Example 2: A curing agent in which C2020 and SR-500, which are polyol compounds containing no palm oil, and RBD palm oil are separately mixed are used.

<2> Evaluation of storage stability (Fig. 1)
Example 1 using a curing agent in which C3135 and C2020 (first polyol compound), which are polyol compounds not containing palm oil, and R8240 (second polyol compound) containing 25% palm oil in advance are mixed. Then, it was possible to obtain the same storage stability as in Comparative Example 1 using a curing agent mixed with C3135, C2020 and SR-500 which are polyol compounds containing no palm oil.
From this result, polyoxypropylene glyceryl ether ([CH2O (C3H6O) nH] [CHO (C3H6O) nH] [CH2O (C3H6O), which is contained in SR-500 of Comparative Example 1 and is considered to function as a thickener. ) nH]), it is considered that the palm oil contained in R8240 of Example 1 exerts a thickening effect on the curing agent and contributes to ensuring storage stability.

On the other hand, in Comparative Example 2 in which a curing agent in which palm oil-free polyol compounds C3135, C2020 and SR-500 were separately mixed with RBD palm oil was used, the curing agent was separated and the storage stability was improved. The result was a decline. It is considered that this is because the storage stability of the curing agent is adversely affected in the embodiment in which palm oil is newly added to the usual compounding of the curing agent.
As a method for solving the above problem in Comparative Example 2, it is conceivable to increase the amount of the compatibilizer, decrease the amount of palm oil, decrease the amount of water, etc., all of which are compatible with SDGs, which is the object of the present invention. It is not preferable because it works disadvantageously for forming a urethane resin composition having a foaming ratio of 120 times or more.

<3> Spray test Next, the mixed solution of the above polyol premix and polyisocyanate (polypolypremix: polyisocyanate component = 1: 1 (volume ratio)) is installed vertically assuming a wall surface under the following conditions. Rigid urethane foam was manufactured in accordance with JIS A9526 by the method of spraying on the plywood, and the physical properties were evaluated (thermal conductivity, flammability, density measurement).
・ Spray foamer: Reactor A-25 manufactured by Graco
-Spray gun: Graco AP gun (chamber size 4242)
-Discharge pressure: 6.0 MPa

<4> Quality evaluation of JIS A9526 Class A 3 (Fig. 2)
In each of Examples 1 and Comparative Examples 1 and 2, a good foam having a foaming ratio of 120 times or more could be obtained without causing a large shrinkage after molding.
As for Example 1, as a result of measuring the raw material viscosity, thermal conductivity, and flammability, it was confirmed that the quality of JIS A9526 Class A 3 was satisfied as in Comparative Example 1.
However, with respect to Comparative Example 2, the flammability could not satisfy the quality of JIS A9526 Class A3.

<5> Summary From the above results, among the urethane resin compositions according to the present invention, particularly when a urethane resin composition having a foaming ratio of 120 times or more is obtained, as a method of containing palm oil in the polyol compound, storage is performed. From the viewpoint of stability and quality assurance of JIS A9526 Class A3, it is preferable to obtain a curing agent using a polyol compound containing palm oil in advance.

Claims (2)

A urethane resin composition having a foaming ratio of 120 times or more and belonging to Class A 3 of JIS9526, which is obtained by mixing a main agent containing a polyisocyanate compound and a curing agent containing a polyol compound.
The curing agent consists of a mixture containing at least a plurality of polyol compounds.
The plurality of polyol compounds are
The first polyol compound, which does not contain palm oil,
It is characterized by comprising a second polyol compound pre-containing palm oil.
Urethane resin composition. A curing agent for constituting a urethane resin composition having a foaming ratio of 120 times or more and belonging to Class A 3 of JIS9526 by mixing with a main agent containing a polyisocyanate compound.
Consists of a mixture containing at least multiple polyol compounds,
The plurality of polyol compounds are
The first polyol compound, which does not contain palm oil,
It is characterized by comprising a second polyol compound pre-containing palm oil.
A curing agent for urethane resin compositions.

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