JP7001505B2 - Polyurethane foam resin composition and polyurethane foam resin - Google Patents

Description

The present invention relates to a polyurethane foam resin composition and a polyurethane foam resin.

Conventionally, a foamed polyurethane resin (polyurethane foam, foamed polyurethane elastomer, etc.) has been used as a cushioning material, a shock absorbing material, a vibration absorbing material, a cushioning material, a mattress material, a sound absorbing material, and the like.

As a method for producing such a foamed polyurethane resin, for example, it is known that a polyurethane resin composition containing a polyisocyanate component and a polyol component is injected into a mold, then foamed and cured, and molded into a desired shape. There is.

For example, a polyurethane composition is prepared by mixing a polyisocyanate component containing an isocyanate group-terminated prepolymer obtained by a reaction of polyphenylmethane polyisocyanate with a polyether polyol and a polyol component, and the polyurethane composition is prepared. A method for producing a foamed polyurethane elastomer, which is injected into a mold and foamed, has been proposed (see, for example, Patent Document 1).

In such a method for producing a foamed polyurethane elastomer, the polyurethane composition flows in the mold and foams until the rise time of the polyurethane composition elapses.

Japanese Unexamined Patent Publication No. 2016-204403

However, in the method for producing a foamed polyurethane elastomer described in Patent Document 1, it is desired to improve the rise time of the polyurethane resin composition from the viewpoint of suppressing molding defects of the foamed polyurethane elastomer.

Therefore, it is considered to add a reaction retarder to the polyurethane resin composition to improve the rise time of the polyurethane resin composition.

However, when a reaction retarder is added to the polyurethane resin composition, the reactivity between the polyisocyanate component and the polyol component is lowered, so that there is a problem that the time required for curing the polyurethane resin composition (curing time) becomes long. .. As a result, there is a problem that the time required for producing the foamed polyurethane resin increases and the production efficiency of the foamed polyurethane resin decreases.

Therefore, the present invention provides a polyurethane foam resin composition and a polyurethane foam resin that can reduce the curing time while improving the rise time.

The present invention [1] comprises a polyisocyanate component containing a terminal isocyanate group-containing prepolymer which is a reaction product of polyphenylmethane polyisocyanate and a polyol, a polyol component, water, an organic metal catalyst, and the following general formula. A foamed polyurethane resin composition containing the reaction retarder shown in (1) and having a mol ratio of the reaction retarder to 1 mol of the organic metal catalyst of 0.50 or more and 2.10 or less.

(In the general formula (1), A represents an aliphatic ring or an aromatic ring. R ¹ represents a hydrocarbon group having 1 carbon atom constituting the ring A. R ² represents a carbon bonded to the ring A. The aliphatic hydrocarbon group of No. 1 is shown. R ³ is a hydrogen atom or an alkyl group bonded to a nitrogen atom contained in the ring A. R ⁴ is a hydrogen atom or a carboxyl group bonded to the ring A. m is 1 or 2, n is 0 or 1, and the sum of n and m is 2 or less.)
The present invention [2] includes the polyurethane resin composition according to the above [1], wherein the reaction retarder is picolinic acid.

The present invention [3] includes the foamed polyurethane resin composition according to the above [1] or [2], wherein the organometallic catalyst contains an organotin compound.

The present invention [4] includes the foamed polyurethane resin composition according to any one of the above [1] to [3], wherein the polyol contains polytetramethylene ether glycol.

The present invention [5] includes a foamed polyurethane resin containing a foamed cured product of the foamed polyurethane resin composition according to any one of the above [1] to [4].

In the foamed polyurethane resin composition of the present invention, since the mol ratio of the reaction retarder to 1 mol of the organic metal catalyst is equal to or higher than the above lower limit, the initial reaction between the polyisocyanate component containing the terminal isocyanate group-containing prepolymer and the polyol component. Can be suppressed, and the rise time of the foamed polyurethane resin composition can be improved.

Further, since the reaction retarder is a specific compound represented by the above general formula (1) and the mol ratio of the reaction retarder to 1 mol of the organic metal catalyst is not more than the above upper limit, the rise time has elapsed (that is, the foamed polyurethane resin). After the composition has fully swelled), the reaction between the polyisocyanate component and the polyol component can proceed smoothly, and the curing time of the foamed polyurethane resin composition can be reduced.

Therefore, the foamed polyurethane resin composition can have a well-balanced rise time and curing time, and can be suitably used for producing the foamed polyurethane resin.

Since the polyurethane foam resin of the present invention contains the foamed cured product of the above-mentioned polyurethane foam resin composition, it can be efficiently produced.

<Polyurethane foam resin composition>
The foamed polyurethane resin composition of the present invention contains, as essential components, a polyisocyanate component, a polyol component, water, an organic metal catalyst, and a reaction retarder represented by the following general formula (1).

1. 1. Polyisocyanate component The polyisocyanate component contains a terminal isocyanate group-containing prepolymer which is a reaction product of polyphenylmethane polyisocyanate and a polyol.

Polyphenylmethane polyisocyanate (p-MDI) is produced by a known method, specifically, for example, by phosgenating polypeptide methylene dianiline obtained by a condensation reaction of aniline and formalin. .. In addition, polyphenylmethane polyisocyanate is also generally referred to as Polymeric MDI, Crude MDI, Polymethylene polyphenyl polyisocyanate and the like.

Polyphenylmethane polyisocyanate usually contains diphenylmethane diisocyanate (monomer) and a condensate of diphenylmethane diisocyanate (oligomer, polymer). That is, the polyphenylmethane polyisocyanate is a composition containing diphenylmethane diisocyanate (MDI) and a condensate of diphenylmethane diisocyanate.

Examples of the diphenylmethane diisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate and the like.

The isocyanate group content (NCO%) of the polyphenylmethane polyisocyanate is, for example, 10% by mass or more, preferably 20% by mass or more, for example, 50% by mass or less, preferably 40% by mass or less. The isocyanate group content can be measured by the n-butylamine method based on JIS K-1603-1 (2007) using a potentiometric titrator (the same applies hereinafter).

Examples of the polyol include a low molecular weight polyol having a number average molecular weight of less than 250, a high molecular weight polyol having a number average molecular weight of 250 or more, and the like. The polyol can be used alone or in combination of two or more.

The low molecular weight polyol is a compound having two or more hydroxyl groups and having a number average molecular weight of 60 or more and less than 250, preferably 200 or less. Examples of low molecular weight polyols include dihydric alcohols (eg, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5). -Pentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, 3-methyl-1,5-pentanediol, isosorbide, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof. , 1,4-Cyclohexanediol, hydride bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A, etc.), trihydric alcohols (eg, bisphenol A, etc.) Glycerin, trimethylol propane, etc.), tetrahydric alcohols (eg, tetramethylolmethane (pentaerythritol), diglycerin, etc.), pentahydric alcohols (eg, xylitol, etc.), hexahydric alcohols (eg, sorbitol, etc.), 7-valent alcohols. (For example, persetol, etc.) and the like. The low molecular weight polyols can be used alone or in combination of two or more.

The high molecular weight polyol is a compound having two or more hydroxyl groups and having a number average molecular weight of 250 or more, preferably 400 or more, more preferably 500 or more, for example, 10,000 or less, preferably 5000 or less, still more preferably 1500 or less. be.

Examples of the high molecular weight polyols include polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, silicone polyols, fluorine polyols, vinyl monomer modified polyols and the like. The high molecular weight polyol can be used alone or in combination of two or more.

Examples of the polyether polyol include polyoxy (C2 to 3) alkylene polyol (for example, polyoxyethylene glycol, polyoxypropylene glycol (PPG), polyoxyethylene polyoxypropylene copolymer, etc.), polytetramethylene ether glycol (PTMEG). ), Polyethylene ether glycol and the like.

Examples of the polyester polyol include an adipate-based polyester polyol, a phthalic acid-based polyester polyol, and a lactone-based polyester polyol.

Examples of the polycarbonate polyol include a ring-opening polymer of ethylene carbonate using the above-mentioned low molecular weight polyol as an initiator, and an amorphous polycarbonate polyol obtained by copolymerizing the above-mentioned dihydric alcohol and the ring-opening polymer.

Examples of the polyurethane polyol include a polyester polyurethane polyol, a polyether polyurethane polyol, a polycarbonate polyurethane polyol, a polyester polyether polyurethane polyol, and the like.

Examples of the epoxy polyol include a reaction product of the above-mentioned low molecular weight polyol and polyfunctional halohydrin (for example, epichlorohydrin, β-methylepichlorohydrin, etc.).

Examples of the vegetable oil polyol include hydroxyl group-containing vegetable oil (for example, castor oil, coconut oil, etc.), ester-modified castor oil polyol, and the like.

Examples of the polyolefin polyol include a polybutadiene polyol and a partially Ken-valent ethylene-vinyl acetate copolymer.

As the acrylic polyol, for example, a hydroxyl group-containing acrylate (for example, 2-hydroxyethyl (meth) acrylate, etc.) and a copolymerizable vinyl monomer copolymerizable therewith (for example, alkyl (meth) acrylate, aromatic vinyl monomer, etc.). And the copolymer with.

Examples of the silicone polyol include an acrylic polyol in which a silicone compound containing a vinyl group (for example, γ-methacryloxypropyltrimethoxysilane) is blended as the copolymerizable vinyl monomer in the above-mentioned copolymerization of the acrylic polyol. Be done.

Examples of the fluorine polyol include an acrylic polyol in which a fluorine compound containing a vinyl group (for example, tetrafluoroethylene, chlorotrifluoroethylene, etc.) is blended as the copolymerizable vinyl monomer in the above-mentioned copolymerization of the acrylic polyol. Be done.

Examples of the vinyl monomer-modified polyol include a reaction product of the above-mentioned high molecular weight polyol and a vinyl monomer (for example, an alkyl (meth) acrylate).

Among such polyols, a high molecular weight polyol is preferable, a polyether polyol is more preferable, and a polytetramethylene ether glycol is particularly preferable. That is, the polyol preferably contains polytetramethylene ether glycol.

When the polyol contains polytetramethylene ether glycol, the rise time and curing time of the foamed polyurethane resin composition can be more reliably secured in a well-balanced manner, and the foamed polyurethane resin described later includes polyphenylmethane polyisocyanate and polytetramethylene. A soft segment generated by the reaction with ether glycol can be imparted.

The average number of functional groups of the polyol is, for example, 2 or more, for example, 5 or less, preferably 4 or less. The average hydroxyl value of the polyol is, for example, 33.7 mgKOH / g or more, preferably 56.1 mgKOH / g or more, for example, 187 mgKOH / g or less, preferably 112.1 mgKOH / g or less. The average number of functional groups of the polyol component can be calculated from the charged components, and the average hydroxyl value can be measured by an acetylation method or a phthalation method based on JIS K-1557-1 (2007) ( The same applies below).

Then, the terminal isocyanate group-containing prepolymer is prepared by reacting the above-mentioned polyphenylmethane polyisocyanate with the above-mentioned polyol at a ratio in which free isocyanate groups remain.

The terminal isocyanate group-containing prepolymer has at least free isocyanate groups at both ends of the molecule.

The average number of functional groups of isocyanate groups in the terminal isocyanate group-containing prepolymer is, for example, 2 or more, for example, 5 or less, preferably 4 or less.

The isocyanate group content (NCO%) in the terminal isocyanate group-containing prepolymer is, for example, 1% by mass or more, preferably 5% by mass or more, for example, 30% by mass or less, preferably 20% by mass or less, still more preferably. It is 10% by mass or less.

As such a terminal isocyanate group-containing prepolymer, a commercially available product can also be used.

Such a polyisocyanate component may contain other isocyanates (eg, carbodiimide-modified MDI derivative, o-MDI, etc.) in addition to the terminal isocyanate group-containing prepolymer, but is preferably a terminal isocyanate group-containing prepolymer. Consists of.

2. 2. Polyol component Examples of the polyol component include the above-mentioned low molecular weight polyol and the above-mentioned high molecular weight polyol. The polyol component can be used alone or in combination of two or more.

Among the polyol components, a low molecular weight polyol is preferable, a dihydric alcohol is more preferable, and 1,4-butylene glycol is particularly preferable. That is, the polyol component preferably contains a low molecular weight polyol, and more preferably consists of a low molecular weight polyol.

When the polyol component contains a low molecular weight polyol, a hard segment generated by the reaction between the terminal isocyanate group-containing prepolymer and the low molecular weight polyol can be imparted to the foamed polyurethane resin described later. Further, when the polyol component is composed of a low molecular weight polyol and does not contain a high molecular weight polyol, it is possible to surely reduce the curing time of the foamed polyurethane resin composition.

The average number of functional groups of the polyol component is, for example, 2 or more, for example, 5 or less, preferably 4 or less. The average hydroxyl value of the polyol component is, for example, 33.7 mgKOH / g or more, preferably 56.1 mgKOH / g or more, for example, 187 mgKOH / g or less, preferably 112.1 mgKOH / g or less.

3. 3. Water Water is a chemical foaming agent that reacts with the isocyanate groups of the polyisocyanate component to generate carbon dioxide.

The content ratio of water is, for example, 0.01 part by mass or more, preferably 0.10 part by mass or more, for example, 1.0 part by mass or less, preferably 0.30 with respect to 100 parts by mass of the polyisocyanate component. It is 0 parts by mass or less, more preferably 0.23 parts by mass or less.

4. Organometallic catalyst The organometallic catalyst is a known urethanization catalyst, and examples thereof include organic tin compounds, organic lead compounds, organic nickel compounds, organic copper compounds, organic bismuth compounds, and potassium salts. The organometallic catalyst can be used alone or in combination of two or more.

Examples of the organotin compound include tin acetate, tin octylate, tin oleate, tin laurate, monobutyl tin trioctate, dibutyl tin diacetate, dimethyl tin dilaurate, dibutyl tin dilaurate, dibutyl tin dimercaptide, dibutyl tin maleate, and dibutyl tin di. Examples thereof include neodecanoate, dioctyl tin dimercaptide, dioctyl tin dilaurylate, and dibutyl tin dichloride.

Examples of the organic lead compound include lead octanate and lead naphthenate. Examples of the organic nickel compound include nickel naphthenate and the like. Examples of the organic cobalt compound include cobalt naphthenate. Examples of the organic copper compound include copper octeneate and the like. Examples of the organic bismuth compound include bismuth octylate and bismuth neodecanoate.

Examples of the potassium salt include potassium carbonate, potassium acetate, potassium octylate and the like.

Among such organometallic catalysts, an organotin compound is preferable.
That is, the organometallic catalyst preferably contains an organotin compound, and more preferably comprises an organotin compound.

When the organometallic catalyst contains an organotin compound, the curing time of the foamed polyurethane resin composition can be surely reduced.

The content ratio of the organic metal catalyst (converted to 100% of the active component amount) is, for example, 0.010 parts by mass or more, preferably 0.015 parts by mass or more, for example, 0.10 with respect to 100 parts by mass of the polyisocyanate component. By mass or less, preferably 0.05 parts by mass or less, more preferably 0.025 parts by mass or less.

5. Reaction retarder The reaction retarder is a heterocyclic compound represented by the following general formula (1).

(In the general formula (1), A represents an aliphatic ring or an aromatic ring. R ¹ represents a hydrocarbon group having 1 carbon atom constituting the ring A. R ² represents a carbon bonded to the ring A. The aliphatic hydrocarbon group of No. 1 is shown. R ³ is a hydrogen atom or an alkyl group bonded to a nitrogen atom contained in the ring A. R ⁴ is a hydrogen atom or a carboxyl group bonded to the ring A. m is 1 or 2, n is 0 or 1, and the sum of n and m is 2 or less.)
In the general formula (1), R ¹ represents a hydrocarbon group having 1 carbon atom constituting the ring A, and specifically, represents a methylene group (-CH _2- ) or a methine group (-CH =). Further, in the general formula (1), m is 1 or 2.

Therefore, in the general formula (1), A is a 5-membered heteroaliphatic ring (pyrrolidin ring) or a 5-membered heteroaromatic ring (pyrrole ring) when m is 1, and when m is 2. It is a 6-membered heteroaliphatic ring (piperidine ring) or a 6-membered heteroaromatic ring (pyridine ring).

In the general formula (1), R ² represents an aliphatic hydrocarbon group having 1 carbon atom bonded to the ring A, and specifically, represents a methylene group (-CH _2- ). In the general formula (1), R ² is bound to R ¹ , and the binding site of R ² is the α-position (2nd position) or β-position (3rd position) of the ring A. Further, in the general formula (1), n is 0 or 1, and the sum of n and m is 2 or less.

Therefore, in the general formula (1), when n is 1, the carboxyl group (-COOH) is ringed via the methylene group (R ² ) bonded to the carbon atom (R ¹ ) at the α-position of the ring A. When it is bonded to A and n is 0, it is directly bonded to the carbon atom (R ¹ ) at the α-position or β-position of the ring A.

In the general formula (1), R ³ represents a hydrogen atom or an alkyl group bonded to a nitrogen atom contained in the ring A. In the general formula (1), the alkyl group represented by R ³ includes, for example, an alkyl group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, etc.). ). In the general formula (1), R ³ is preferably a hydrogen atom.

In the general formula (1), R ⁴ represents a hydrogen atom or a carboxyl group bonded to the ring A, and preferably represents a hydrogen atom.

Specific examples of the reaction retarder represented by the general formula (1) include picolinic acid, 2-pyridinyl acetic acid, 2-piperidincarboxylic acid, nicotinic acid, 2,6-pyridinedicarboxylic acid, and proline. Such a reaction retarder represented by the general formula (1) can be used alone or in combination of two or more.

Among such reaction retarders represented by the general formula (1), picolinic acid, nicotinic acid and proline are preferable, and picolinic acid is more preferable. That is, the reaction retarder preferably comprises at least one selected from the group consisting of picolinic acid, nicotinic acid and proline, more preferably picolinic acid, and particularly preferably picolinic acid.

When the reaction retarder contains picolinic acid, nicotinic acid, proline, particularly picolinic acid, the rise time of the foamed polyurethane resin composition can be further improved.

The mol ratio of the reaction retarder to 1 mol of the organometallic catalyst is 0.50 or more, preferably 0.80 or more, 2.10 or less, preferably 2.00 or less, still more preferably 1.50 or less, and particularly preferably. Is 1.00 or less.

When the mol ratio of the reaction retarder is at least the above lower limit, the rise time of the foamed polyurethane resin composition can be improved. When the mol ratio of the reaction retarder is not more than the above upper limit, the curing time of the foamed polyurethane resin composition can be reduced.

The content ratio of the reaction retarder is, for example, 0.0010 parts by mass or more, preferably 0.0030 parts by mass or more, for example, 0.010 parts by mass or less, preferably 0.010 parts by mass or more, based on 100 parts by mass of the polyisocyanate component. , 0.0080 parts by mass or less, more preferably 0.0050 parts by mass or less.

6. Additives Further, the foamed polyurethane resin composition can further contain a known additive as an optional component in an appropriate ratio.

Known additives include, for example, amine-based catalysts, foam stabilizers (eg, silicone-based foam stabilizers), processing aids (eg, acrylic copolymer solutions), thermal stabilizers (eg, hindered phenolic oxidation). Examples thereof include heat-resistant stabilizers (eg, phosphite esters, etc.), antioxidants, ultraviolet absorbers, light-resistant stabilizers, flame retardants, colorants, and the like.

<Polyurethane foam resin>
Such a foamed polyurethane resin composition is configured as, for example, a two-component resin material having an agent A containing the above-mentioned polyisocyanate component and an agent B containing the above-mentioned polyol component. Each of the organometallic catalyst, the reaction retarder and the known additive may be contained in any of the agents A and B, but is preferably contained in the agent B. Further, water is contained in the agent B.

The polyurethane foam resin composition is a raw material for the polyurethane foam resin, and is suitably used for producing the polyurethane foam resin.

In order to produce a polyurethane foam resin, for example, first, the above-mentioned agents A and B are mixed to prepare a mixture thereof (polyurethane foam resin composition).

The agent A and / or the agent B are preferably heated to reduce the viscosity before being mixed.

The heating temperature of the agent A is, for example, 25 ° C. or higher, preferably 50 ° C. or higher, for example, 120 ° C. or lower, preferably 100 ° C. or lower. The heating temperature of the agent B is, for example, 25 ° C. or higher, preferably 30 ° C. or higher, for example, 100 ° C. or lower, preferably 80 ° C. or lower. Further, the heating temperature of the agent B is preferably lower than the heating temperature of the agent A.

Further, the agent A and the agent B have, for example, an isocyanate index (NCO / (OH + H ₂ O)) × 100 (that is, the ratio of the total isocyanate group of the polyisocyanate component to the total hydroxyl group of the polyol component and the total water) as follows. It is mixed so as to be in the range of.

That is, the isocyanate index is, for example, 75 or more, preferably 90 or more, more preferably 100 or more, for example, 300 or less, preferably 200 or less, still more preferably 150 or less.

Next, a mixture of the agent A and the agent B (foamed polyurethane resin composition) is injected into a predetermined mold to be preheated, if necessary.

The preheating temperature of the mold is, for example, 50 ° C. or higher, preferably 60 ° C. or higher, for example, 130 ° C. or lower, preferably 100 ° C. or lower, and more preferably 90 ° C. or lower.

Then, in the mold, the polyisocyanate component and the polyol component are reacted (urethanization reaction), and the mixture of the agent A and the agent B (foamed polyurethane resin composition) is foamed.

As a result, the foamed polyurethane resin composition is foamed and cured to form the foamed polyurethane resin, and the foamed polyurethane resin is formed into a predetermined shape.

The range of the reaction temperature (molding temperature) is the same as the range of the preheating temperature described above.

The reaction time (molding time) is, for example, 5 minutes or more, preferably 10 minutes or more, for example, 60 minutes or less, preferably 30 minutes or less, and more preferably 15 minutes or less.

Next, the foamed polyurethane resin is removed from the mold. Then, if necessary, the polyurethane foam resin may be heated at the above reaction temperature within about 24 hours.

As described above, the foamed polyurethane resin is manufactured.

The foamed polyurethane resin contains a foamed cured product of the foamed polyurethane resin composition, and preferably consists of a foamed cured product of the foamed polyurethane resin composition.

Such a foamed polyurethane resin preferably comprises a soft segment formed by the reaction of polyphenylmethane polyisocyanate with a high molecular weight polyol, a terminal isocyanate group-containing prepolymer (polyphenylmethane polyisocyanate), and a low molecular weight polyol. It contains a hard segment formed by the reaction and is configured as a foamed polyurethane elastomer.

The hardness (C hardness) of the foamed polyurethane resin (foamed polyurethane elastomer) is, for example, 40N / 100cm ² or more, preferably 60N / 100cm ² or more, for example, 90N / 100cm ² or less, preferably 80N / 100cm ² or less. be. The hardness (C hardness) can be measured according to the Asker C hardness based on JIS K7312 (1996) (the same applies hereinafter).

Further, the density of the foamed polyurethane resin (foamed polyurethane elastomer) is higher than the density of the polyurethane foam (for example, 0.2 g / cm ³ or less), for example, 0.3 g / cm ³ or more, preferably 0.4 g / cm / cm. cm ³ or more, more preferably 0.5 g / cm ³ or more, for example 0.8 g / cm ³ or less, preferably 0.7 g / cm ³ or less, still more preferably 0.6 g / cm ³ or less. ..

Examples of applications of such foamed polyurethane resin include various industrial products, and specific examples thereof include cushioning materials, shock absorbers, vibration absorbers, cushioning materials, mattress materials, and sound absorbing materials.

<Action effect>
In the above-mentioned foamed polyurethane resin composition, the mol ratio of the reaction retarder to 1 mol of the organometallic catalyst is at least the above lower limit. Therefore, the initial reaction between the polyisocyanate component containing the terminal isocyanate group-containing prepolymer and the polyol component can be suppressed, and the rise time of the foamed polyurethane resin composition can be improved.

Further, since the reaction retarder is a compound represented by the above general formula (1) and the mol ratio of the reaction retarder to 1 mol of the organic metal catalyst is not more than the above upper limit, the rise time has elapsed (that is, the foamed polyurethane resin composition). After the swelling is complete), the reaction between the polyisocyanate component and the polyol component can proceed smoothly, and the curing time of the foamed polyurethane resin composition can be reduced.

Therefore, the foamed polyurethane resin composition can have a well-balanced rise time and curing time, and can be suitably used for producing the foamed polyurethane resin.

The foamed polyurethane resin is produced by foaming and curing the above foamed polyurethane resin composition. Therefore, even if the foamed polyurethane resin composition is heated to the above reaction temperature, the fluidity of the foamed polyurethane resin composition can be ensured until the rise time of the foamed polyurethane resin composition elapses. Then, after the rise time elapses, the foamed polyurethane resin composition can be smoothly cured. Therefore, the foamed polyurethane resin can be efficiently produced.

Further, since the reaction retarder is a compound represented by the above general formula (1), the foamed polyurethane resin can suppress coloring.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. Specific numerical values such as the compounding ratio (content ratio), physical property values, parameters, etc. used in the following description are the compounding ratios (content ratios) corresponding to those described in the above-mentioned "Mode for carrying out the invention". ), Physical property values, parameters, etc. can be replaced with the upper limit value (value defined as "less than or equal to" or "less than") or the lower limit value (value defined as "greater than or equal to" or "excess"). can. In addition, "part" and "%" are based on mass unless otherwise specified.

<Preparation of raw materials>
<< Preparation of polyisocyanate component >>
Preparation Example 1 (Isocyanate (1))
A reaction product of polyphenylmethane polyisocyanate (p-MDI) and polytetramethylene ether glycol (PTMEG1000) having a number average molecular weight of 1000 (isocyanate group content = 8% by mass, average number of functional groups = 2, commercially available product). Prepared as isocyanate (1).

Preparation Example 2 (Isocyanate (2))
A reaction product of polyphenylmethane polyisocyanate (p-MDI) and polytetramethylene ether glycol (PTMEG2000) having a number average molecular weight of 2000 (isocyanate group content = 8% by mass, average number of functional groups = 2, commercially available product). Prepared as isocyanate (2).

<< Preparation of polyol component >>
Preparation Example 3 (Polyformer (1))
1,4-butylene glycol (1,4-BG) was prepared as the polyol (1).

Preparation example 4 (polypoly (2))
Polytetramethylene ether glycol (PTMEG1000) having a number average molecular weight of 1000 was prepared as the polyol (2).

Preparation Example 5 (Polyformer (3))
Polytetramethylene ether glycol (PTMEG2000) having a number average molecular weight of 2000 was prepared as the polyol (3).

<< Preparation of catalyst >>
Preparation Example 6 (Catalyst (1))
DBTDL (organic metal catalyst, dibutyltin dilaurate (IV) (dibutyltin dilaurate), manufactured by Nitto Kasei Co., Ltd.) was prepared as the catalyst (1).

Preparation example 7 (catalyst (2))
Dabco 33LV (amine-based catalyst, 33% by mass dipropylene glycol solution of triethylenediamine, manufactured by Air Products Japan, Inc.) was prepared as the catalyst (2).

<< Preparation of reaction retarder >>
Preparation Example 8 (Delayant (1))
Picolinic acid (a reaction retarder contained in the general formula (1)) was prepared as a retarder (1).

Preparation example 9 (delaying agent (2))
Niacin (a reaction retarder contained in the general formula (1)) was prepared as a retarder (2).

Preparation Example 10 (Delayant (3))
Proline (a reaction retarder contained in the general formula (1)) was prepared as a retarder (3).

<< Preparation of additives >>
Y-10366 (Silicone-based defoaming agent, Momentive Performance Materials Japan), P9908 (Processing aid, Acrylic copolymer solution, BYK), IRG1135 (Heat stabilizer, Hindered phenol-based antioxidant) Agent, manufactured by BASF), JPP100 (heat stabilizer, phosphite esters, manufactured by Johoku Chemical Industry Co., Ltd.) were prepared.

<Manufacturing of polyurethane foam resin composition and polyurethane foam resin>
Examples 1 to 6 and Comparative Examples 1 to 5
In the components (raw materials) shown in Table 1, each component other than the polyisocyanate component was weighed, blended according to the formulation in Table 1, and stirred and mixed so as to be uniform to prepare Agent B. .. The temperature of Agent B was adjusted to 50 ° C.

The polyisocyanate component prepared separately was weighed according to the formulation in Table 1 to prepare Agent A. The temperature of Agent A was adjusted to 80 ° C.

Then, Agent A was added to Agent B, and the mixture was stirred with a high-speed stirrer for 10 seconds while degassing under vacuum to prepare a foamed polyurethane resin composition.

Then, the polyurethane resin composition is quickly injected into a closed mold (depth 50 mm, length × width 280 mm × 180 mm) preheated to 80 ° C., and foamed and cured at 80 ° C. in 15 minutes to obtain the foamed polyurethane resin. Manufactured.

<Evaluation>
<< Rise time (minutes) >>
The rise time of the foamed polyurethane resin composition of each Example and each Comparative Example was measured by the following method and evaluated according to the following criteria. The results are shown in Tables 1 and 2.

The polyurethane foam resin composition was inserted into a 500 mL polycup, and the swelling time of the polyurethane foam composition was visually measured.

The rise time measurement was started at the moment when the mixing of the agent A (polyisocyanate component) and the agent B (polyol component) was started.
◯: Rise time is 1 minute or more.
×: Rise time is less than 1 minute.

<< Tack Free Time (TFT, Minutes) >>
The tack free time of the foamed polyurethane resin composition of each Example and each Comparative Example was measured by the following method. The results are shown in Tables 1 and 2.

The surface dryness time of the polyurethane foam resin composition inserted into the above polycup was measured. The measurement was started at the moment when the mixing of the agent A (polyisocyanate component) and the agent B (polyol component) was started.

<< 15-minute demolding property >>
The 15-minute demolding property of the foamed polyurethane resin of each Example and each Comparative Example was evaluated by the following method. The results are shown in Tables 1 and 2.

After injecting each foamed polyurethane resin composition into the above-mentioned sealed mold, foaming and curing were performed at 80 ° C. for 15 minutes, and then the foamed polyurethane resin was taken out from the mold, and the state of the foamed polyurethane resin at this time was confirmed. ..
◯: Completely cured, the polyurethane foam resin can be smoothly removed from the mold.
Δ: No uncured portion is observed, but the curing is insufficient and the polyurethane foam resin is slightly brittle.
×: Adhering resin was observed on the uncured liquid resin part or the inner surface of the mold, and the foamed polyurethane resin could not be removed from the mold.

Claims (4)

Polyphenylmethane A polyisocyanate component containing a terminal isocyanate group-containing prepolymer, which is a reaction product of polyisocyanate and a polyol,
The polyol component and
water and,
Organometallic catalyst and
Contains a reaction retarder,
The reaction retarder is picolinic acid, nicotinic acid or proline.
A foamed polyurethane resin composition, wherein the mol ratio of the reaction retarder to 1 mol of the organometallic catalyst is 0.50 or more and 2.10 or less. The foamed polyurethane resin composition according to claim 1, wherein the organometallic catalyst contains an organotin compound. The foamed polyurethane resin composition according to claim 1 or 2 , wherein the polyol contains polytetramethylene ether glycol. A foamed polyurethane resin comprising a foamed cured product of the foamed polyurethane resin composition according to any one of claims 1 to 3 .