JPH09208657A - Manufacture of polyurethane foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polyurethane foam that overcomes problems of the prior art, does not require the use of a physical foaming agent, does not emit a foul odor or the like, does not discolor or deteriorate a material, such as polyvinyl chloride and ABS resin, that is placed in contact with the polyurethane foam, and can be foamed in situ by a spray foamer or the like. SOLUTION: This method of producing a polyurethane foam is to react a polyol component containing a benzilic ether phenol resin having a hydroxymethyl group with an organic polyisocyanate component in the presence of an organotin urethanizing catalyst, a tertiary amine urethanizing catalyst having a functional group reactive with an isocyanate in the molecule, and water.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyurethane foam, more specifically, it is not necessary to use a physical foaming agent, and moreover, a bad odor is generated, polyvinyl chloride or ABS is used. The present invention relates to a method for producing a polyurethane foam which does not cause discoloration or deterioration of the material even when it is used in contact with a resin or the like and can be foamed in situ by a spray foaming machine or the like.

[0002]

2. Description of the Related Art Conventionally, for the purpose of preventing dew condensation of buildings, heat insulation, etc., a rigid polyurethane foam produced by spray foaming at a construction site has been applied, and the polyurethane foam produced by this conventional method is manufactured. The undiluted solution for use contains fluorine-containing halogenated hydrocarbons (CFC and H) as a foaming agent.
CFC) is used in a proportion of about 15-40% by weight of the total stock solution. However, it is said that the fluorine-containing halogenated hydrocarbon will be totally prohibited in the near future due to the problem of ozone layer depletion.

[0003]

Therefore, water or the like has been studied as a foaming agent to replace the above-mentioned fluorine-containing halogenated hydrocarbon, but with water or the like, a free foaming density (for example, 20 kg / m) comparable to that of conventional products is obtained. ^{If 3} ) is to be achieved under the condition that the liquid ratio of the isocyanate component and the polyol component, which is generally adopted in spray foaming, is 1: 1, about 80% of the whole isocyanate component used together with the polyol component has a urea bond. Since it is used for production, the adhesiveness of the foam will be reduced, and the physical properties such as brittleness will be reduced.

When water is used as a foaming agent, two-stage foaming (lateral expansion phenomenon) is caused by the difference between the reaction rate between the isocyanate component and the polyol component and the reaction rate between the isocyanate component and water. Occurs, a gap is likely to occur between the surface of the object to which the foam is adhered and the foam, and as a matter of course, in the winter when the reaction between the isocyanate component and water does not proceed, the required low density The above foam cannot be obtained, and further problems such as an increase in liquid ratio [ratio of NCO component to OH component] and an increase in viscosity of the undiluted liquid occur in controlling foaming in spray foaming.

In order to prevent the above-mentioned two-stage foaming, an amine catalyst called a foaming catalyst, which promotes the reaction between an isocyanate component and water, is used in a further stage. However, this catalyst is volatile and produces an unpleasant odor. In case of construction in a place where exhaust equipment such as foaming is not installed, or when the worker does not equip the armor, it causes discomfort to the worker, and when working for a long time in a very narrow place. May cause an amine rainbow phenomenon (a phenomenon in which the vapor of the catalyst blinds the eyes). In particular, since the stock solution for spray foaming is required to have fast hardening, the proportion of the amine catalyst in the stock solution is high. There are many problems.

Further, when the conventional polyurethane foam is used in contact with other plastics such as polyvinyl chloride and ABS resin, the amine catalyst that volatilizes or sublimes causes the plastics to be colored or discolored. This phenomenon is remarkable especially when polyvinyl chloride is used as other plastics.

The object of the present invention is to solve the above-mentioned drawbacks of the prior art, and (1) it is not necessary to use fluorine-containing hydrogen halide or the like which has a great influence on ozone layer destruction and global warming as a foaming agent, 2) No bad odor or amine rainbow phenomenon is generated, and (3) the material is not discolored or deteriorated even when it is used in contact with polyvinyl chloride or ABS resin. ) It is to provide a method for producing a polyurethane foam capable of in-situ foaming by a spray foamer or the like.

[0008]

In order to achieve the above object, the constitution adopted by the present invention is such that a polyol component containing a benzylic ether type phenolic resin having a hydroxymethyl group and an organic polyisocyanate component are It is characterized by reacting in the presence of a tin-based urethane-forming catalyst, a tertiary amine-based urethane-forming catalyst having a functional group that reacts with an isocyanate group in the molecule, and water.

That is, the inventors of the present invention have the following reaction formula A:
As shown in, a phenol (1) having a hydroxymethyl group at the o-position reacts with an organic isocyanate (2) in the presence of an organotin urethanization catalyst to generate carbon dioxide gas (for example, Hybrid Phenolic / Urethane Foams, Anthon
y J. Papa and Frank E. Critchfield, Journal of Cellu
lar Plastics, 258, September / October (1979)). Similarly, a phenol resin having a hydroxymethyl group at the o-position is used as a polyol component to form a polyurethane foam, and the generated carbon dioxide gas is foamed. An attempt was made to use it as a foaming agent for body formation.

Embedded image Reaction formula A

However, since a novolac phenolic resin, which is a phenolic resin having a hydroxymethyl group at the o-position, is generally solid and insoluble in a solvent, it is difficult to use it as a polyol component.
Resol-based phenol resin, which is a phenol resin having a hydroxymethyl group at the position, usually has a large amount of water of 20% or more, and when used as a polyol, a large amount of water reacts with isocyanate and controls the reaction. Becomes difficult. Further, if the water content is lowered, the resin viscosity rises, and the stirring efficiency is lowered. Therefore, the inventors of the present invention have found that among the phenolic resins, for example, the water content is 0.5% or less and the viscosity is 1000 to 20000 cp.
As a result of repeated experiments focusing on the benzylic ether type phenolic resin, it was found that this phenolic resin can be used as a polyol component in the production of polyurethane foam.

However, the carbon dioxide gas generated from the reaction between the hydroxymethyl group of the benzylic ether type phenol resin and the organic isocyanate is not sufficient for foaming, and a foam having a desired low density (high foaming ratio) can be obtained. I found it difficult. Therefore, as a result of further studies by the inventors, a tertiary amine urethane having a functional group that reacts with an isocyanate group in the molecule is added in order to add water as a foaming auxiliary agent and further promote the reaction between water and an isocyanate. In addition to the reaction represented by the above-mentioned reaction formula A, the carbon dioxide generating reaction accompanying the urea bond formation represented by the following reaction formula B can be utilized by adding the oxidization catalyst, and the target low-density polyurethane foam is produced. I found that I could do it.

Embedded image Reaction formula B

In addition, the tertiary amine urethanization catalyst having a functional group that reacts with an isocyanate group in the molecule is capable of reacting water with an isocyanate (urea) and reacting a polyol with an isocyanate (urethane). The present invention has been completed by discovering that the bad odor immediately after foaming and the influence of amine vapor on the human body (particularly eyes) are small since they are consumed by being reacted with isocyanate after being accelerated.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.

The present invention is characterized in that a benzylic ether type phenolic resin having a hydroxymethyl group is used as at least a part of the polyol component essential for producing a polyurethane foam, and the "hydroxymethyl group" is used here. The "benzylic ether type phenolic resin having" is obtained by reacting phenol and an aldehyde at a temperature of 100 to 130 ° C using a catalyst composed of a divalent metal naphthenate, a carboxylate or the like. It is a kind of phenol resin, and its properties can be changed depending on the polymerization conditions, ranging from viscous liquids to semi-solids and solids. For example, it is produced according to the method described in Japanese Patent Publication No. 47-50873. Is something that can be done.

The benzylic ether type phenolic resin having such a hydroxymethyl group (hereinafter, may be simply referred to as benzylic ether type phenolic resin in this specification) has a hydroxyl value of, for example, 300 to 300.
700 mg KOH / g, preferably 450-600 mg
It can be used as a part of the polyol component within the range of KOH / g.

In the present invention, the benzylic ether type phenol resin may be used alone as the polyol component, but when used alone, the curing speed becomes too fast and cracks are formed inside the formed foam. Is likely to occur, or a foam having open cells is likely to be formed, so that it is generally desirable to use it in combination with another polyol. As other polyols that can be used in combination, those conventionally used in the production of polyurethane can also be used in the present invention as well, and examples thereof include ethylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol 1,4-butane. Dihydric alcohols such as diols; trihydric or higher alcohols such as glycerin, trimethylolpropane, tris (2-hydroxyethyl) isocyanurate, pentaerythritol, sucrose, sorbitol; ethylenediamine, tolylenediamine, or ethylene oxide, Polyether polyols obtained by ring-opening addition polymerization of propylene oxide; polybasic acids such as adipic acid, succinic acid, phthalic acid, fumaric acid and polyhydrogens such as ethylene glycol and propylene glycol And polyester polyols obtained by polycondensation reaction or ring-opening polymerization of lactones with shea compound.

The above-mentioned other polyols other than the benzylic ether type phenol resin may be used alone or in combination of two or more kinds, and ethylenediamine type polyol, tolylenediamine type polyol and phthalic acid ester type polyol are particularly preferable. .

When these other polyols are used in combination with the benzylic ether type phenolic resin, the amount of the benzylic ether type phenolic resin used is not strictly limited, and the physical properties desired for the foam to be formed are not limited. ,
Although it can be changed over a wide range depending on the type of other polyols used in combination, it is usually convenient to use it within the range of 20 to 100% by weight, particularly 30 to 80% by weight, based on the total amount of polyols. is there.

On the other hand, as the organic polyisocyanate component which reacts with the above-mentioned polyisocyanate component, any of those conventionally used for producing polyurethane foams can be used. As such a polyisocyanate compound, , For example 2,4- and / or 2,
6-Tolylene diisocyanate (TDI), crude TD
I, 2,2'- and / or 2,4'- and / or 4,
4'-diphenylmethane diisocyanate (MDI),
Aromatic polyisocyanates such as polymethylene polyphenylene (crude MDI), crude diaminodiphenylmethane phosgene, polyallyl polyisocyanate, etc., or aliphatic polyisocyanates such as hexamethylene diisocyanate, and aromatic araliphatic polyisocyanates such as xylene diisocyanate , Or urethane bond, carbodiimide bond, allophanate bond, urea bond, burette bond, uretdione bond, uretoimine bond,
Examples include modified products of the above polyisocyanates containing one or more types of isocyanurate bonds, oxazolidone bonds, and the like, and mixtures of two or more types thereof.

Among them, 2,4- and / or 2,6 are aromatic polyisocyanates because of their high reactivity with the polyol component, and among them, 2,4- and / or 2,6 because they are commercially available at low cost.
-Tolylene diisocyanate (TDI), 2,2'- and / or 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), polymethylene polyphenylene (crude MDI), and of these polyisocyanates Modified products and mixtures of two or more thereof are preferred.

The NCO content of the organic isocyanate component that can be used is such that the composition liquid ratio of the organic polyisocyanate component and the polyol component in a spray foaming machine is 1: 1 to.
When used in the range of 2: 1, if the NCO content is too low, the desired low-density foam cannot be obtained, and if it is too high, the composition liquid itself becomes unstable. Is preferred and 20 to 35% by weight is particularly preferred.

The ratio of the organic polyisocyanate component to the polyol component used is NCO / OH equivalent of l. The range of 0 to 3.5 can be exemplified as a suitable one.

In the present invention, an organotin urethanization catalyst is used in order to promote the reaction between the hydroxymethyl group of the benzylic ether type phenol resin and the isocyanate group of the organic polyisocyanate component. As the organotin-based urethane-forming catalyst, those generally used in the urethane-forming reaction can be used.
Examples thereof include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dialkylmalate, tin stearate, tin octylate and the like. The amount of these organotin urethanization catalysts to be used is not particularly limited, but is usually 0.1% based on the total amount of the benzylic ether type phenol resin used. It is suitable to use it in the range of 1 to 14% by weight, particularly 0.4 to 9% by weight.

In the present invention, in order to accelerate the water-isocyanate reaction, a tertiary amine urethane catalyst having a functional group which reacts with an isocyanate group in the molecule (hereinafter referred to as a reactive tertiary amine urethane catalyst). Sometimes called). Here, the functional group that reacts with isocyanate is, for example, —OH group, —COOH group, or —NH ₂
Group, —CHO group, —SH group, etc., and as the catalyst,
N, N, N'-triethyl-N'-hydroxyethylethylenediamine, N, N-dimethylethanolamine,
N, N-dimethylpropanolamine, N, N, N'-
Trimethyl-N'-hydroxyethylbis (aminoethyl) ether, dimethylaminoethylamine, dimethylaminopropylamine, dibutylaminoethylamine,
Dimethylaminooctylamine, dipropylaminopropylamine, 3-quinuclidinol (3-hydroxyazabicyclo [2,2,2] octane), dimethylethanolamine, N, N, N'-trimethylaminoethylethanolamine, dimethylaminotri Oxyethylene,
Examples thereof include dimethylaminoethoxyethanol and the like.

The above catalyst may be used alone, but in order to control the reactivity and enhance the stability of the composition (low volatility, no precipitation occurs), it may be in the form of a salt (complex) with an acid. The acid for forming the salt includes, for example, carboxylic acid, phenol, boric acid, carbonic acid and the like.

In the present invention, water is used as a foaming auxiliary agent, but when used in a large amount, the physical properties such as brittleness and adhesiveness are deteriorated, or two-stage foaming occurs during in-situ foaming, which causes cracks and floating. Due to the tendency, it is desirable to use an amount of 4% by weight or less, especially 2% by weight or less, based on the organic polyisocyanate component.

Further, in the present invention, in order to control the reaction rate, if necessary, other urethane-forming catalysts other than the organotin-based urethane-forming catalyst and the reactive tertiary amine-based urethane-forming catalyst, such as an organic polyisocyanate component, may be used. It can be used in the range of 0.1 to 5% by weight based on the standard. still,
When the amount is 0.1% by weight or less, the effect of controlling the reaction rate is small, and when 5% by weight or more is used, the mechanical strength of the foam produced is lowered and the discoloration of PVC resin, ABS resin, etc. becomes large. It is not preferable.

With the other urethanization catalysts, since the internal temperature of the polyurethane foam during the production of the polyurethane foam of the present invention is 100 to 145 ° C., evaporation and volatilization of these urethanization catalysts are prevented during production. Therefore, the boiling point is preferably 150 ° C. or higher, and examples of such other urethanization catalysts include 1,4-diazabicyclo [2,2,2] octane and 2-methyl-1,4.
-Diazabicyclo [2,2,2] octane, N, N-dimethylaminoethylmorpholine, N, N, N ', N'
-Tetramethylhexamethylenediamine, trimethylaminoethylpiperazine, N, N'-dimethylcyclohexylamine, N, N'-dimethylbenzylamine, N-
Trioxyethylene-N, N dimethylamine, N, N,
N ', N ", N" -pentamethyldiethylenetriamine, bis-2-dimethylaminoethyl ether, 1,8
-Diazabicyclo (5,4,0) undecene-7,1,
Tertiary amine catalysts such as 5-diazabicyclo (4,3,0) nonene-5 and derivatives thereof, and salts of these with acids such as carboxylic acid and carbonic acid, or organometallic salt urethanization catalysts Specific examples include cobalt naphthenate, tetra (2-ethylhexyl) titanate, cobalt-2-ethylhexoate, zinc naphthenate and lead octylate.

In addition, in the present invention, in order to enhance the flame retardancy of the foam, an isocyanurate-forming catalyst is added, if necessary, in an amount of 100% by weight or less, preferably 50% by weight or less of the reactive tertiary amine catalyst. In addition to the range, it can be converted to isocyanurate. The isocyanurate-forming catalyst is 1
When it is used in an amount of more than 00% by weight, isocyanurate-forming reaction precedes urethane formation and urea formation, and the temperature inside the foam during the foam production rises rapidly, causing cracks and scorch inside the foam. It is not preferable because it occurs and the mechanical strength of the foam decreases.

As the above-mentioned isocyanurate-forming catalyst, for example, 1,3,5-tris (N, N-zincylaminoalkyl) -S-hexahydrotriazine and its alkylene oxide and water adduct are preferable. N,
Tertiary amine catalysts such as N ′, N ″ -tris (dimethylaminopropyl) hexahydro-S-triazine and 2,4,6-trisdimethylaminomethylphenol; potassium acetate, potassium octanoate, potassium 2-ethylhexanoate , Potassium propionate, potassium formate, potassium isobutyrate, potassium methacrylate, potassium sorbate, sodium acetate, sodium 2-ethylhexanoate, sodium propionate, sodium butyrate, sodium formate, sodium caprylate, sodium carbonate, iron oxalate Examples thereof include organic metal salt-based catalysts; quaternary amine organic acid salt catalysts, and the like.

Further, in the present invention, a carbodiimidization catalyst may be added, if necessary, in order to increase the foaming ratio of the foamed product or flame retardancy, and a reactive tertiary amine-based catalyst may be used.
Carbodiimidization can also be performed by adding in an amount of 0% by weight or less, preferably 50% by weight or less. When 100% by weight or more of the carbodiimidization catalyst is used, the carbodiimidization reaction precedes the urethanization and urea formation, so that the free foaming density of the foam is extremely reduced, and the closed cell ratio is also reduced. Therefore, it is not preferable.

Examples of the carbodiimidization catalyst that can be used include 1-phenyl-2-phospholen-1-oxide, 3-methyl-2-phospholen-1-oxide, and 1-phenyl-2-phospholen-1-oxide.
-Ethyl-3-methyl-2-phospholen-1-oxide, 1-ethyl-2-phospholen-1-oxide, 3-
Phosphorene oxides such as methyl-1-phenyl-2-phospholen-1-oxide or 3-phosphorene isomers thereof; 1,3,5-tris (N, N-dialkylaminoalkyl) -S-hexahydrotriazine derivative Examples thereof include triazine ring-containing tertiary amine compounds; organometallic compounds such as titanium tetrapropoxide and zirconia tetrapropoxide.

Further, in the present invention, other additives which may be used in the production of polyurethane foams, for example, ethylene oxide of dimethyl silicone, a propylene oxide adduct, a cationic surfactant, an anionic surfactant, Foam stabilizer such as nonionic surfactant; tris (2,3-dibromopropyl phosphate), tri-
Organic phosphorus and halogenated esters such as 2-chloroethyl phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate; bisphenol A, bisphenol S, bisphenol F,
Flame retardants such as bisphenols such as tetrabromobisphenol A; Thickeners such as dibutyl phosphate, dioctyl phosphate, polypropylene carbonate; Fillers such as antimony trioxide, diolite, and hajlite; Colorants such as pigments and dyes You may mix suitably.

As a method for producing a polyurethane foam using the above-mentioned various components, for example, all the components other than the organic polyisocyanate component are mixed to prepare a polyol composition in advance, and the polyol composition is mixed with the organic polyisocyanate. An example is a method in which an isocyanate component is added and mixed, poured into a mold, or sprayed on the surface of a base material using, for example, a spray foamer, and then foamed and cured. The time required for foam hardening is usually about 5 to 30 seconds.

[0035]

Next, the present invention will be described more specifically with reference to examples.

Example 1 Benzylic ether type phenolic resin having a hydroxymethyl group (hydroxyl value = 596 mgKOH / g) 1
2.5 g and ethylenediamine-based polyol (hydroxyl value = 300 mgKOH / g, Asahi Glass Co., Ltd. FD-19
0) 28.08 g and an organotin urethane formation catalyst (dibutyltin dilaurate, manufactured by Sankyo Air Program Co., Ltd.)
2.0 g of a tertiary amine urethane catalyst having a functional group that reacts with an isocyanate group in the molecule (carbonate of dimelaminopropylamine, moisture content 14% by weight, U-CAT2790 manufactured by San-Apro Co., Ltd.) And silicone-based foaming agent (CF201 manufactured by Toray Dow Corning Silicon Co., Ltd.)
2) 0.5 g and flame retardant (triethyl phosphate,
Each component of 6.5 g of Daihachi Chemical Co., Ltd. and 0.32 g of water was weighed in a 750 ml container and pre-stirred, and then crude polymethylene polyphenyl isocyanate (Crude MDI, Nippon Polyurethane ( Co., Ltd. Millionate MR-200) (50 g) was added, and the mixture was stirred at room temperature with a basket-type stirrer at 2000 r. p. It was vigorously stirred for 1 to 2 seconds at m, and cup-free foam-cured as it was. The cream time, rise time and density (free foam density) of the obtained foam are shown in Tables 1 and 2 below.

According to the above composition, a gasmer foaming machine (H
A foam was obtained by F-100 type). The spray foamability, foaming state, self-adhesion strength, closed cell ratio, amine odor and discoloration of vinyl chloride of the obtained foam are shown in Tables 1, 2 and 3 below.

The spray foamability, foaming state, adhesive strength, closed cell ratio, amine odor and discoloration of vinyl chloride in Tables 1, 2 and 3 were evaluated according to the following criteria.

Spray Foamability The workability of spray foaming was evaluated as follows, and the results are shown in three stages. 1: Good workability (the foam does not extend laterally, there are no two-stage foaming or liquid sagging, and the finished state is good) 2: Workable (the foam has a lateral extension, there are some two-step foaming or liquid sagging, but the foam physical properties There is no problem) 3: Cannot be installed (cannot be installed due to lateral expansion of foam, two-stage foaming and liquid sag)

Foamed state The foamed state was evaluated as follows, and the results are shown in three stages. 1: Foamed state is good (Dimensional change rate is 1% or less (25 ° C / 1 day later), no cracks or cracks) 2: Foamed state is almost good (Dimensional change rate is 3% or less (25 ° C /
(1 day later), cracks and some cracks) 3: Poor foaming state (dimensional change rate of 3% or more (25 ° C / 1 day later), cracks and cracks)

Adhesive Strength Spray application was performed on a gypsum board, and the adhesive strength with the gypsum board was evaluated by a tensile strength test (JIS-A-9526), and the results are shown in three levels. 1: Adhesive state is good (adhesive strength is 2 kgf / cm ² or more) 2: Adhesive state is almost good (some peeling, etc., adhesive strength 1 to
2 kgf / cm ² ) 3: Poor adhesion state (adhesion strength is 1 kgf / cm ² or less)

Closed Cell Rate The state of the cells in the foam after foaming was evaluated, and the result was 3
Shown in stages. The lower this value, the higher the thermal conductivity,
Insulation effect is poor. 1: Nearly closed cells (closed cell ratio is 70% or more) 2: Less closed cells (closed cell rate is 40 to 70% or more) 3: Many open cells (closed cell rate is 40% or less)

Amine odor 2500 × 3300 in an atmosphere of 25 ° C. and 65% relative humidity
Hard urethane foam was continuously sprayed to a thickness of 25 mm on 30 gypsum boards having a spray surface area of 1 m ^{2 in} a room with poor ventilation of × 2600 mm (21.45 m ³ ). Immediately after the spraying, the amine odor was evaluated based on the sensory test of 5 persons, and the results are shown in 5 levels. 1: Odorless 2: Almost odorless 3: Slightly odorous 4: Fairly bad odor 5: Unbearable bad odor

Discoloration of vinyl chloride Hard urethane foam was sprayed onto a vinyl chloride sheet (thickness 0.3 mm) to a thickness of 25 mm, and this was used as a sample.
This sample piece was wrapped in aluminum foil and treated at 120 ° C. for 48 days to screen the discoloration of the vinyl chloride sheet. The degree of discoloration was evaluated according to the following four grades. 1: Slightly colored 2: Orange-colored 3: Red-colored 4: Black-colored Incidentally, when only the vinyl chloride sheet was treated under the same conditions, the degree of coloring was 1.

Examples 2 to 22 Polyurethane foams were produced in the same manner as in Example 1 according to the compositions and blending ratios shown in Table 1. The obtained foam has a cream time, a rise time, a density (free foaming degree) in a cup-free state, and a spray foaming property, a foaming state, an adhesive strength, a closed cell ratio, an amine odor and a vinyl chloride content in spray foaming. The discolored state is shown in Tables 1 and 2.

[0046]

[Table 1]

[Table 2]

[Table 3]

Examples 23 to 25 Polyurethane foams were produced in the same manner as in Example 1 except that the crude MDI in Example 1 was replaced with the organic polyisocyanate component shown in Table 4 below. Evaluated to. The results are shown in Table 4 below (however, the evaluation in Table 4 complied with the judgment criteria in Table 1, Table 2 and Table 3).

[Table 4]

Comparative Examples 1 to 6 Polyurethane foams were produced in the same manner as in Example 1 according to the compositions and blending ratios shown in Table 5 below. Cream time of the obtained foam in a cup-free state,
Table 5 below shows rise time, density (free foaming degree), and spray foamability during spray foaming, foaming state, adhesive strength, closed cell ratio, amine odor, and discoloration state of vinyl chloride (however, Table 5 The evaluation in 5 complied with the judgment criteria in Table 1, Table 2 and Table 3).

[Table 5]

As can be seen from Tables 1 to 5, the foams produced according to the present invention exhibit superior physical properties to the foams of the comparative examples, especially regarding amine odor and discoloration of vinyl chloride during spray foaming. Was excellent.

The raw materials used in Examples and Comparative Examples are as follows.・ Coarse MDI Nippon Polyurethane Industry Co., Ltd. Millionate MR-2
00, NCO content 31% -TDI mixture Sumitomo Bayer Urethane Co., Ltd. Sumidule T-8
0,2,4-TDI: 2,6-TDI = 80: 20, N
CO content 48% -Mixture of crude MDI and TDI Mixture of crude MDI 50% and TDI mixture, NCO content 39.5% -MDI prepolymer Sumitomo Bayer Urethane Co., Ltd. Desmodur E-2
7, NCO content rate 8% -Hydroxymethyl group-containing phenolic ether type phenol resin Hodogaya Chemical Co., Ltd. BEP-1000 OH type 596 mgKOH / g-Polyol Asahi Glass Co., Ltd. FD190: ethylenediamine type, O
H value 300 mg KOH / g manufactured by Takeda Pharmaceutical Co., Ltd. DT300: tolylenediamine type, OH value 300 mg KOH / g manufactured by Toho Rika Co., Ltd. PL108: phthalate ester type,
OH value 224 mgKOH / g-Organotin-based urethane-forming catalyst Sankyo Air Products Co., Ltd. T-12: Dibutyltin dilaurate-Reactive tertiary amine-based urethane-forming catalyst (San Apro Co., Ltd., U-CAT2790: Dimethylaminopropyl) Amine carbonate (water content 14%) ZF-10: N, N, manufactured by San Techno Chemical Co., Ltd.
N "-trimethyl-N'-hydroxyethylbis (aminoethyl) ether-other urethanization catalyst DABCO 33LV manufactured by Sankyo Air Products Co., Ltd .:
1,4-diazabicyclo [2,2,2] octane Sankyo Air Products Co., Ltd. DABCO PMDET
A: N, N, N ', N ", N" pentamethyldiethylenetriamine-trimerization catalyst manufactured by San-Apro Co., Ltd., Polycat 41: N, N,
N "-tris (dimethylamino) propyl-hexahydro-S-toazine Sankyo Air Products Co., Ltd. DABCO TMR-
5: Quaternary amine formate DABCO K-15 manufactured by Sankyo Air Products Co., Ltd .:
Potassium 2-ethylhexanoate-Carbodiimidization catalyst 3-Methyl-1-phenyl-2-phosphorene-1-oxide-Foam stabilizer SH-193 manufactured by Toray Dow Corning Silicon Co., Ltd.
Silicone-based flame retardant TEF: triethyl phosphate manufactured by Daihachi Chemical Co., Ltd.

[0051]

According to the method of the present invention, a benzylic ether type phenol resin, an organotin urethanization catalyst, a tertiary amine urethanization catalyst having a functional group capable of reacting with an isocyanate group in the molecule, water, etc. By controlling the amount, the expansion ratio of the polyurethane foam to be formed can be freely adjusted, and for example, it is possible to produce a foam having a large expansion ratio of free expansion density of 40 kg / m ³ or more. .

The polyurethane foam produced by the method of the present invention contains CFC, HC which causes ozone depletion.
Not only does it need to use fluorine-containing halogenated hydrocarbons such as FC, but it is also used for spray foaming, in addition to improving the physical properties such as low adhesion and arm strength, which have been problems with conventional foams made by water foaming. In doing so, it is possible to greatly reduce the amine odor due to the amine catalyst that has been conventionally used and the influence of the amine rainbow on the worker.

Further, by foaming using water according to the conventional method,
For example, when a spray foaming machine is used, the liquid ratio (ratio of isocyanate component to polyol component) is usually fixed at 1: 1 or 2: 1. It is necessary to increase the proportion of water, and for that reason, it is necessary to use a high molecular weight polyol having a large hydroxyl value as the other polyol component, and in such a case, it is possible to use a spray foaming machine. Since a large amount of thinning agents (flame retardants, etc.) must be used in order to reduce the viscosity to a predetermined level (500 CP or less), the resin strength of the foam is reduced and the dimensional stability is deteriorated and the adhesion strength to the core is reduced. However, according to the method of the present invention, it is possible to produce a foam that does not cause the above problems only by mixing 5 to 10% of the flame retardant.

Further, in the polyurethane foam produced by the conventional method, when it is used in contact with other plastic resin or metal, such as ABS resin, vinyl chloride resin or aluminum, the above-mentioned fluorine-containing halogenated hydrocarbon or amine is used. The above-mentioned other plastic resins and metals are eroded by the catalyst, and there have been problems such as deterioration and discoloration of the coating film, but according to the method of the present invention, other plastic resins that do not have these defects It is also possible to produce a complex of

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Eiji Sasaki 1-18-1 Nishiarai-cho, Adachi-ku, Tokyo Nisshin Spinning Co., Ltd. Tokyo Research Center

Claims (12)

[Claims] 1. A polyol component containing a benzylic ether type phenolic resin having a hydroxymethyl group, and an organic polyisocyanate component, an organotin urethanization catalyst, and a functional group capable of reacting with an isocyanate group in a molecule. A method for producing a polyurethane foam, which comprises reacting in the presence of a primary amine-based urethane-forming catalyst and water. 2. The method for producing a polyurethane foam according to claim 1, wherein the hydroxymethyl group-containing benzylic ether type phenolic resin contained in the polyol component has a hydroxyl value of 300 to 700 mgKOH / g. 3. The proportion of the benzylic ether type phenolic resin having a hydroxymethyl group contained in the polyol component is 20 based on the total amount of the polyol components.
The method for producing a polyurethane foam according to claim 1, wherein the content is -100% by weight. 4. The production of a polyurethane foam according to claim 1, wherein the proportion of the organotin urethanization catalyst is 0.1 to 14% by weight based on the benzylic ether type phenolic resin having a hydroxymethyl group. Method. 5. The method for producing a polyurethane foam according to claim 1, wherein the tertiary amine urethanization catalyst having a functional group that reacts with an isocyanate group in the molecule is a salt with an acid. 6. The proportion of the tertiary amine urethanization catalyst having a functional group that reacts with an isocyanate group in the molecule is 1 to 10% by weight based on the organic polyisocyanate component.
2. The method for producing a polyurethane foam according to claim 1. 7. The method for producing a polyurethane foam according to claim 1, wherein the proportion of water is 4% by weight or less based on the organic polyisocyanate component. 8. The polyurethane foam according to claim 1, which further uses a urethane-forming catalyst other than the organotin-based urethane-forming catalyst and the tertiary amine-based urethane-forming catalyst having a functional group that reacts with an isocyanate group in the molecule. Manufacturing method. 9. The proportion of the urethane-forming catalyst other than the organotin-based urethane-forming catalyst and the tertiary amine-based urethane-forming catalyst having a functional group that reacts with an isocyanate group in the molecule is 0. The method for producing a polyurethane foam according to claim 8, wherein the content is 1 to 5% by weight. 10. The polyurethane foam according to claim 1, wherein the isocyanurate-forming catalyst is used in an amount of 100% by weight or less based on the tertiary amine-based urethane-forming catalyst having a functional group which reacts with an isocyanate group in the molecule. Body manufacturing method. 11. The polyurethane foam according to claim 1, wherein the carbodiimidization catalyst is used in an amount of 100% by weight or less based on a tertiary amine urethanization catalyst having a functional group that reacts with an isocyanate group in the molecule. Manufacturing method. 12. A polyurethane method in which the method for producing a polyurethane foam according to any one of claims 1 to 11 is carried out by a spray foaming machine.