JPH05255467A - Rigid polyurethane foam and its production - Google Patents

Abstract

PURPOSE:To prevent the shrinkage of a closed-cell rigid polyurethane foam in the production process. CONSTITUTION:A rigid polyurethane foam is produced by compounding an isocyanate compound, an active hydrogen compound having >=2 active hydrogen groups and a 1,2-added polybutadiene as a shrinkage-preventing agent and foaming the obtained composition. A foaming agent substituting fluorocarbons and meeting the fluorocarbon restriction can be used in the above process and a rigid polyurethane foam having high quality can be produced while preventing abnormal shrinkage of the foam.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a closed cell type rigid polyurethane foam which can be used for building materials, structural materials, heat insulating materials or other applications. More specifically, the present invention relates to a rigid polyurethane foam that solves the problem of foam shrinkage or dimensional stability after foaming that occurs when a foaming agent other than CFCs, for example, a foaming agent other than CFCs is used with the strengthening of CFC regulations.

[0002]

2. Description of the Related Art Generally, a rigid polyurethane foam comprises a polyisocyanate compound having at least two isocyanate groups as a main raw material, and at least two.
Produced by mixing active hydrogen compounds having individual active hydrogen-containing groups with auxiliary raw materials such as foaming agents, catalysts, foam stabilizers and other additives, and foaming and curing, building materials, lightweight structural materials, heat insulation for heat insulation It is used in various industrial fields such as wood. Conventionally, a halogenated hydrocarbon compound represented by trichlorofluoromethane (hereinafter referred to as CFC-11) (hereinafter referred to as CFC) has been used as a foaming agent for polyurethane. The reason is that CFC has an appropriate boiling point. It is excellent in many points as a foaming agent, such as that it has a flame retardancy and is easy to handle due to its flame retardancy, and that the performance of the obtained foam is good. However, in recent years, CFCs have been legally restricted or banned in various countries because they are the cause of the destruction of the earth's ozone layer. Therefore, in the production of urethane foam products, it has been necessary to switch some or all of the CFCs to another blowing agent. However, when trying to make a closed cell type rigid polyurethane foam by using a large amount of water as the main foaming agent instead of CFC, the foam will abnormally shrink and deform within a few days after the completion of foam curing, so application as a product. In some cases, it becomes unusable. Generally, polyurethane foam has a structure in which cells (hereinafter referred to as cells) are embedded in polyurethane resin, and each of the cells is an independent "closed cell type" or a continuous cell type "open cell type".
Is either. If the cell is a communicating bubble, the internal gas is gradually exchanged with the outside air through the bubble, while if the cell is a closed bubble, the gas is likely to remain in the cell.

The mechanism by which the above-mentioned abnormal contraction occurs is presumed from the experiments by the present inventors as follows. That is, carbon dioxide remains in the closed cell type cell obtained by water foaming immediately after foaming, but originally carbon dioxide has a good affinity with polyurethane resin and has a large gas permeation coefficient, so carbon dioxide is Due to the difference in carbon dioxide partial pressure between the inside and the atmosphere, it is gradually permeated to the outside through the cell membrane and discharged.On the other hand, air with a low permeability coefficient does not enter from the outside, so the inside of the cell is decompressed and eventually forms. Contracts.
The abnormal shrinkage peculiar to such a closed-cell foam is
Carbon dioxide generated as a result of the reaction of isocyanate with water or carbon dioxide dissolved in a polyol or isocyanate in advance is not a unique phenomenon, but any foaming agent that easily permeates polyurethane resin can occur. .. Alternatively, even in the case of a foaming agent having a relatively high boiling point, the foaming agent gas may be condensed and liquefied inside the cell by natural cooling after foaming and hardening, and the inside may be depressurized to cause abnormal shrinkage. As described above, the contraction occurs in any case because the air does not enter from the outside when the pressure inside the cell is reduced.

There are few precedents in documents and patents that describe a method for solving such abnormal shrinkage in a method for producing a closed-cell type rigid polyurethane foam.
JP-B-61-29609 discloses a closed-cell type having improved low-temperature dimensional stability by using a polyol obtained by polymerizing an ethylenically unsaturated monomer in a low-molecular weight polyol (hereinafter referred to as polymer polyol). Of rigid polyurethane foams are described. However, in this method, the viscosity of the polyol is generally high and the mixing of the isocyanate and the polyol becomes poor,
If the low molecular weight polyol as the base, the type of the monomer and the polymerization conditions are not properly selected, there is a problem that the polymer component is easily separated in the produced polymer polyol. On the other hand, some methods for producing open-celled rigid polyurethane foam have been proposed. For example, JP-A-49-105
No. 899, a petroleum oily hydrocarbon compound is disclosed in
-80436 discloses metal salts of higher fatty acids and amides,
JP-A-63-89519 describes a method using a metal salt of an acidic phosphoric acid ester.

[0005]

When a certain type of foaming agent such as water is used in the production of closed cell type rigid polyurethane foam, abnormal foam shrinkage occurs after the completion of foaming and curing.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted diligent studies to find a closed cell type rigid polyurethane foam which does not cause abnormal shrinkage after foam formation and has good dimensional stability. As a result, a certain polybutadiene is added. A novel rigid polyurethane foam was found by preventing abnormal shrinkage by mixing and foaming. That is, the present invention provides (a) a component containing a polyisocyanate compound having at least two isocyanate groups, and (b) a component containing an active hydrogen compound having at least two active hydrogen-containing groups,
And (c) a 1,2-addition type liquid polybutadiene having a molecular weight of 800 to 4000 as a shrinkage inhibitor, and a closed cell type obtained by foaming and curing the composition using a foaming agent. Rigid polyurethane foam.

The method of the present invention will be described in detail below. The closed cell type rigid polyurethane foam defined in the present invention is a rigid polyurethane foam having a cell closed cell rate (hereinafter referred to as a closed cell rate) of 50% or more. Furthermore, the closed cell rate defined in the present invention is a measurement method that is usually used in a rigid polyurethane foam, that is,
It is an apparent volume ratio (%) measured by the method described in ASTM D-2856 using a "pneumatic apparent volume measuring device". The component (c) polybutadiene used in the process of the present invention is a 1,2-addition type polybutadiene having a molecular weight of 800 to 4000. Although 1,4-addition type polybutadiene is known in addition to 1,2-addition type polybutadiene, 1,4-addition type polybutadiene has no effect of preventing shrinkage. The molecular weight is 800 to 4000. If it is lower than this range, there is no shrinkage-preventing effect. The amount thereof used is 0.001 to 0.03 part per 100 parts by weight of the total amount of the component (a) containing the isocyanate compound and the component (b) containing the active hydrogen compound according to claim 1. preferable. If it is less than this amount, the effect of preventing shrinkage is weak, and if it is more than this amount, the closed cell ratio cannot be maintained at 50% or more.
In these polybutadienes, a hydrogen atom or a functional group such as a hydroxyl group or a carboxylic acid is usually bonded to the end of the molecule. The polybutadiene used in the present invention is usually used by mixing it with the component (b), but it may be used by mixing it with the component (a). However, the effect decreases when it is used in the form of an isocyanate prepolymer obtained by mixing it with the component (a) and previously reacting it with an isocyanate compound such as TDI at a high temperature. The shrinkage-preventing effect of these shrinkage-preventing agents can be obtained only under the above-mentioned limited conditions, but the characteristic is that the foaming gas and the external air are gradually exchanged and 50% or more of the cells are independent. It is to be a bubble. Therefore, the effect of preventing shrinkage is considered to be the result of the addition of the shrinkage preventive agent to create very fine voids in each cell membrane during the foaming process.

The blowing agent used in the method of the present invention is a specific blowing agent such that the foam shrinks after foam hardening. Typical examples include water and carbon dioxide gas, but in addition to these, there are those having a good affinity with polyurethane resin, and halogenated hydrocarbon compounds having a high boiling point. That is, methylene chloride, chlorodifluoromethane (hereinafter abbreviated as CFC-22), dichlorotrifluoroethane (hereinafter abbreviated as CFC-123), dichlorofluoroethane (hereinafter abbreviated as CFC-141), trichlorotrifluoroethane ( Hereinafter, CFC-113), chlorodifluoroethane (hereinafter CFC-142), and the like. However, any other foaming agent that causes shrinkage may be used. Since these foaming agents cause shrinkage if used in a certain amount or more, the method of the present invention also when other foaming agents other than the above-mentioned foaming agents that do not cause shrinkage (for example, Freon-11) are used in combination. include.

Component (a) used in the method of the present invention
As the polyisocyanate compound having at least two isocyanate groups therein, those generally used in conventional rigid polyurethane foams are used. Specifically, 4,4'-diphenylmethane diisocyanate (hereinafter
4,4'-MDI), 2,4'-diphenylmethane diisocyanate (hereinafter 2,4'-MDI), 2,4-diisocyanate toluene (hereinafter 2,4-TDI), 2,6-diisocyanate toluene ( Hereinafter referred to as 2,6-TDI), and dimers, trimers or multimers thereof, or a mixture thereof, which is referred to as crude TDI, crude MDI, and a mixture thereof. Further, an isocyanate prepolymer which is a reaction product of the above-mentioned isocyanate with an active hydrogen compound which reacts with an isocyanate such as polyol, amine or mercaptan is also included.

The component (b) used in the present invention is
It is a component containing a compound having at least two active hydrogen-containing groups such as OH group, primary amino group, secondary amino group and SH group. Specifically, it is usually a low molecular weight compound having two or more hydroxyl groups and having a hydroxyl value of 200 to 600 mg-KOH / g. Such a compound is obtained, for example, by adding an alkylene oxide to a low molecular weight hydroxyl group-containing compound or amine compound which is an initiator. More specifically, for example, low molecular weight polyols (initiators) such as ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, α-methylglycoside, sorbitol, sucrose, or ethylenediamine, diethylenetriamine, piperazine, 4 , 4'-Diaminodiphenylmethane (4,4'-MDA), 2,4'-Diaminodiphenylmethane
(2,4'-MDA), 2,4-diaminotoluene (2,4-TDA), 2,6-diaminotoluene (2,6-TDA) and other amine compounds (initiators), propylene oxide, ethylene oxide,
There is a polyether polyol obtained by adding an alkylene oxide such as butylene oxide. Alternatively, even a low molecular weight or high molecular weight polyol having a hydroxyl value outside the above range can be used by mixing an amount not too much with the above polyol. Specifically, as the low molecular weight polyol, there is an initiator of the above polyol, and as the high molecular weight polyol, a high molecular weight polyether polyol obtained by addition-polymerizing propylene oxide or ethylene oxide to the above initiator is used. is there. Furthermore, a compound having a low molecular weight or a high molecular weight primary or secondary amino group can be mixed with the above polyol and used. In addition, any low molecular weight polyol that can be used in the production of urethane resin may be used. Specifically, there are a polyester polyol obtained by esterification of a dicarboxylic acid such as adipic acid and a low molecular weight glycol, or polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran. Further, as the SH group-containing active hydrogen compound, specifically, there are thioglycol, mercaptan obtained by esterification of β-mercaptopropionic acid and pentaerythritol, and the like.

As the catalyst used in the method of the present invention, those conventionally used in rigid polyurethane foams are used. Specifically, tertiary amines such as triethylenediamine, tetramethylpropanediamine and pentamethyldiethylenetriamine, metal catalysts such as dibutyltin dilaurate and stannas octoate, and isocyanate trimerization catalysts such as potassium octylate and potassium acetate ( Isocyanurate forming catalyst) and the like. As the foam stabilizer used in the method of the present invention, a commonly used silicone derivative for rigid polyurethane foam (having an alkoxy group or an active OH group at the end of an alkylene oxide-modified polydimethylsiloxane) is used. To be done. Further, so-called nonionic surfactants such as polyoxyethylene octadecylamine, polyoxyethylene beef tallow alkylamine, and long-chain fatty acid alkylol amide can also be used as the foam stabilizer.

As the method for producing the rigid polyurethane foam of the present invention, all methods conventionally used in the production of rigid foam can be applied. The simplest method is to use a mixture (premix resin) in which the above-mentioned polyol, catalyst, foam stabilizer, shrinkage-preventing agent and foaming agent are mixed in advance, and polyisocyanate at 6000 to 9000 rp.
There is a method in which a high speed rotating lab stirrer of m 3 is used to vigorously stir and mix and foam in a specific container. However, an actual production method is a method in which the above two liquids are collision-mixed with a commercially available high-pressure foaming machine for urethane and then injected into a mold. As the high-pressure foaming machine, for example, many machines such as HK-270 manufactured by Maruka Kakoki Co., Ltd. are commercially available. The rigid polyurethane foam obtained by the method of the present invention does not shrink while maintaining a high closed cell ratio even when a foaming agent such as water or carbon dioxide is used which causes abnormal shrinkage after completion of foaming and curing in the conventional method. It won't happen.

[0013]

EXAMPLES Next, the present invention will be described in detail with reference to Examples. Raw material used Polyol A; Hydroxyl value obtained by adding propylene oxide to triethanolamine and sucrose is 370 mg-KOH
/ g of polyol. Polyol B; a polyol having a hydroxyl value of 388 mg-KOH / g, which is a mixture of pentaerythritol, glycerin, and triethanolamine, each of which is obtained by adding propylene oxide at a weight ratio of 60:20:20. Silicone foam stabilizer: L-5340, a polydimethylsiloxane derivative manufactured by Nippon Unicar Co., Ltd. Catalyst A; Kao No. Kalyzer No-1 with N, N, N ', N'-
Tetramethylhexamethylenediamine. Catalyst B; Kao Co., Ltd. Kaolizer No-3 with N, N, N ', N ",
N "-pentamethyldiethylenetriamine. Freon 11; trichlorofluoromethane manufactured by Mitsui DuPont Fluorochemical Co., Ltd. Freon 123; dichlorotrifluoroethane manufactured by Mitsui DuPont Fluorochemical Co., Ltd. Freon 113; Mitsui DuPont Fluorochemical ( Co., Ltd. Trichlorotrifluoroethane Cosmonate M-200; Polyisocyanate from Mitsui Toatsu Chemicals Co., Ltd., crude MDI, NCO% = 31.0. Polybutadiene A; Polybutadiene G from Nippon Soda Co., Ltd.
-1000, molecular weight 1000, vinyl group content 90%,
Terminal hydroxyl type 1,2-addition type polybutadiene. Polybutadiene B: Polybutadiene G of Nippon Soda Co., Ltd.
-3000, molecular weight 3000, vinyl group content 90%,
Terminal hydroxyl type 1,2-addition type polybutadiene. Polybutadiene C: Polybutadiene C of Nippon Soda Co., Ltd.
-1000, molecular weight 1000, vinyl group content 90%,
Terminal carboxylic acid type 1,2-addition type polybutadiene.

Examples 1 to 6 The polyol resin raw materials (shown in units of gram) shown in Table 1 were placed in a 1-liter polypropylene cup and mixed, and then isocyanate M-200 was added to give an index of 110.
In addition to 5000 ~ 70 with a high-speed rotating lab stirrer
High speed stirring and mixing was performed at 00 rpm for about 5 seconds, and this mixture was quickly put into a wooden box (20 cm x 20 cm x 20 cm) with a scissor-shaped paper bag to foam polyurethane. After 1 day, the produced foam was cut into 10 cm cubes with a slitter and the density (unit: Kg /) was examined. Also, using a Beckman type pneumatic apparent specific gravity meter manufactured by Beckman Toshiba Corporation, ASTM D-2
According to the method of 856, the closed cell ratio (unit:%) was examined. Furthermore, the degree of abnormal contraction of the foam was examined until several months later. As a result, no abnormal shrinkage of the foam was observed in any of the examples.

Comparative Examples-1 to 4 Polyurethane was foamed in the same manner as in Example without adding the shrinkage inhibitor. As a result, in each case, abnormal contraction was observed 3 days after the foam was cut, and the foam contracted to about 2/3 one week later.

[0016]

[Table 1]

[0017]

By using the shrinkage-preventing agent of the present invention, it is possible to obtain a closed cell type hard polyurethane foam having fine cells in which shrinkage does not occur.

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Claims (5)

[Claims] 1. At least two components: (a) a component containing a polyisocyanate compound having at least two isocyanate groups, and (b) a component containing an active hydrogen compound having at least two active hydrogen-containing groups. And (c)
1,2-with a molecular weight of 800-4000 as a shrinkage inhibitor
A closed cell type rigid polyurethane foam obtained by foaming and curing a composition containing an addition type liquid polybutadiene with a foaming agent. 2. The amount of the polybutadiene used as the component (c) is 0. 0 based on 100 parts by weight of the total of the components (a) and (b).
The rigid polyurethane foam according to claim 1, which is 001 to 0.03 part. 3. The foaming agent is at least one selected from water, carbon dioxide, methylene chloride, chlorodifluoromethane, dichlorotrifluoroethane, dichlorofluoroethane, trichlorotrifluoroethane and chlorodifluoroethane. The rigid polyurethane foam according to the item. 4. A component as component (b) and / or component (a)
(c) is premixed and then component (a) and component
The method for producing a rigid polyurethane foam according to claim 1, wherein (b) is mixed by high-speed stirring and then injected into a specific container to foam and cure. 5. A component as component (b) and / or component (a)
(c) is premixed and then component (a) and component
The method for producing a rigid polyurethane foam according to claim 1, wherein (b) is subjected to collision mixing with a high-pressure foaming machine, and then injected into a specific container to foam and cure.