JP2002012644A - Method for producing urethane-modified polyisocyanurate foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for the production of a urethane-modified polyisocyanurate foam having improved initial adhesivity to a face material, especially a soft face material while keeping excellent flame-retardancy, heat- resistance and smoking tendency by using water as a foaming agent. SOLUTION: The objective foam is produced by reacting a polyisocyanate compound component, a polyol component, water and a solubilizing agent in the presence of an isocyanate trimerization catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The heat resistance, flame retardancy,
The present invention relates to a method for producing a foam which maintains excellent performance of low smoke emission and has improved initial adhesion to a soft surface material.

[0002]

2. Description of the Related Art A urethane-modified polyisocyanurate foam has been known as a heat insulating material having excellent flame retardancy, heat resistance and low smoke generation. In this case, the conversion of the specific fluorocarbon used as the blowing agent and the alternative fluorocarbon compound is indispensable due to the problem of depletion of the ozone layer, and a production method using water as a blowing agent instead of them has been studied. .
In the case of foaming with water (carbon dioxide), when continuous production of a laminate board, siding, etc. is performed, the initial adhesiveness with a surface material, particularly a soft surface material, is reduced. Was.

[0003]

DISCLOSURE OF THE INVENTION The present invention relates to a water-based material having excellent characteristics such as flame retardancy, heat resistance, and low smoke emission, and improved initial adhesion to a surface material, particularly a soft surface material. It is an object of the present invention to provide a method for producing a urethane-modified polyisocyanurate foam which does not use a specific freon or a substitute freon compound by using as a foaming agent.

[0004]

Means for Solving the Problems The present inventors have used water as a blowing agent in the production of urethane-modified polyisocyanurate foams, while maintaining excellent characteristics of flame retardancy, heat resistance and low smoke generation. As a result of intensive studies on the improvement of the initial adhesiveness with a surface material, particularly a soft surface material, the present inventors have found that a specific compatibilizer improves the initial adhesiveness with a soft surface material, and reached the present invention.

That is, the present invention comprises reacting a polyisocyanate compound component (A), a polyol component (B), water (C), and a compatibilizer (D) in the presence of an isocyanate trimerization catalyst (E). A method for producing a urethane-modified polyisocyanurate foam, characterized in that: The compatibilizer (D) is used in an amount of 3 to 20 parts by weight based on 100 parts by weight of the polyol component (B).
Parts by weight, the isocyanate trimerization catalyst (E) is used in an amount of 0.35 to 15 parts by weight based on 100 parts by weight of the polyol component (B), and the water (C) is used in an amount of 2 to 100 parts by weight of the polyol component (B). It is characterized by being used up to 30 parts by weight.

Further, according to the present invention, the compatibilizer (D) may be a nitrogen-containing, sulfur-containing, phosphorus-based, halogen-based, hydrocarbon-based,
One or more selected from ether-based, ester-based, and carbonate-based organic compounds, wherein the polyol component (B) is a polyhydric alcohol or a benzylic ether-type phenol resin or / and a benzylic ether-type phenol resin. It is characterized by containing a modified phenol resin obtained by reacting the alkylene oxide adduct.

The method for producing a urethane-modified polyisocyanurate foam of the present invention uses these compatibilizers. Therefore, even if water is used as the foaming agent, the produced foam has flame retardancy. While maintaining the excellent characteristics of heat resistance and low smoke emission, the initial adhesion to a face material, particularly a soft face material, is improved.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The polyol component used in the present invention is a mixture of polyols generally used for producing urethane foam. As the polyol, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, polytetramethylene glycol, 1,4-butanediol, and the like, or one or more of these alkylene oxides are addition-polymerized. Bifunctional polyol, trimethylolpropane, glycerin, etc., or trifunctional polyol obtained by addition polymerization of alkylene oxide thereto, pentaerythritol, sorbitol, sugar, etc., or polyfunctional polyol obtained by addition polymerization of alkylene oxide thereto, other alkanols Examples thereof include those obtained by addition polymerization of an alkylene oxide to an amine, and aromatic polyester polyols and acrylic polyol resins. As the polyol, a phenol resin, a modified phenol resin, a benzylic ether type phenol resin, a method disclosed in Japanese Patent Publication No. 7-30155 (polyhydric alcohol or alkylene thereof with respect to 100 parts by weight of the benzylic ether type phenol resin). (Addition of 20 to 100 parts by weight of an oxide adduct and heating under reduced pressure), and these may be used alone or in combination of two or more.

As the polyisocyanate compound used in the present invention, those generally used for the production of urethane foams can be used, and are not particularly limited, and m- or p-phenylene diisocyanate, p- -Xylene diisocyanate, ethylene diisocyanate, tetramethylene-1,4-diisocyanate, hexamethylene-1,6-
Diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethyl-diphenylmethane-4,4'-
Diisocyanate, 3,3-dichloro-4,4'-biphenylene diisocyanate or 1,5-naphthalenediisocyanate, 2,4- and 2,6-tolylene diisocyanate and mixtures thereof, crude tolylene diisocyanate Nart, 4,4'-
Examples thereof include diphenylmethane diisocyanate and crude diphenylmethane diisocyanate. These isocyanate compounds are used alone or in combination of two or more. The amount of the isocyanate group and the equivalent ratio of active hydrogen in the polyol component mixed solution are 1.5 to 10.0, preferably 1.
It is in the range of 75-4.5. If the equivalent ratio is less than 1.50, the flame retardancy, heat resistance, and low smoke emission will be poor, and if it is more than 10.0, the brittleness of the foam will be severe and the adhesion to the face material will be poor.

The compatibilizer used in the present invention is not particularly limited, but includes nonylphenol ethylene glycol diglycidyl ether, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone,
Examples include morpholine, pyridine, dibutyl phthalate, dioctyl phthalate, ethylene carbonate, propylene carbonate, trimethyl phosphate, triethyl phosphate and the like, and these can be used alone or in combination of two or more. The amount used is 3 to 20 parts by weight based on 100 parts by weight of the polyol component (B).

As the foam stabilizer used in the present invention, an organic polysiloxane copolymer generally used as a foam stabilizer during the production of a urethane foam can be used as it is. Examples of the organic polysiloxane copolymer include SH-190, SH-192, and SH-19 manufactured by Toray Silicone Co., Ltd.
3, SH-194, M505, M507, M509, S
RX253, manufactured by Nippon Unicar, L-520, L
-540, L-580, L-582, L-5340, L
-5410, L-5420, L-5470, SZ-11
27, manufactured by Toshiba Silicone Co., TFA-4200,
TFA4205, TFA7241, B-8404, B-8017 manufactured by Goldschmidt, and the like.

The amount of the foam stabilizer used in the present invention is 0.5 to 1 with respect to 100 parts by weight of the polyol component (B).
0 parts by weight is suitable.

As the isocyanate trimerization catalyst used in the present invention, an isocyanate trimerization catalyst conventionally used for production of polyisocyanurate resins and the like can be used. Specific examples of the isocyanate trimerization catalyst include the following. In the organic metal salt system,
Potassium acetate, potassium octenoate, iron oxalate and the like. Tertiary amine salts include 2,4,6-tris (dimethylaminomethyl) -phenol, N, N ', N "-tris (dimethylaminopropyl) hexahydrotriazine and the like.

The amount of the urethane-forming catalyst and trimerization catalyst used in the present invention is 0.35 to 15 parts by weight, preferably 0.1 to 15 parts by weight, based on 100 parts by weight of the polyol component (B).
70 to 10 parts by weight.

As a catalyst for performing a urethane modification reaction,
What is generally known as a urethanization catalyst can be used. For example, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylpropane-1,3-diamine, N, N, N ', N'-tetramethylhexene- 1,6-diamine, N, N, N ', N ", N" -pentamethyldiethylenetriamine, N, N-dicyclohexylmethylamine, bis (N, N-dimethylaminoethylpiperazyl) ethane, N, N', Tertiary amines such as N "-tris (diethylaminopropyl) hexahydrotriazine and dibutyltin dilaurate, dibutyltin diacetate and the like can be used alone or in combination.

The water used in the present invention reacts with the polyisocyanate compound to generate carbon dioxide and acts as a blowing agent. The amount of the water used is determined by the density of the target foam, and the amount of the polyol component (B) 100
A suitable amount is 2 to 30 parts by weight based on parts by weight. If the amount of water used is less than 2 parts by weight, the density of the foam becomes too high, and if it exceeds 30 parts by weight, the mechanical strength is reduced and the foam cannot be used.

In the present invention, a flame retardant and a crosslinking agent can be used as required. As the flame retardant, triphenyl phosphate, tricresyl phosphate, trichloroethyl phosphate, tris-β-chloroethyl phosphate can be used alone or in combination of two or more. As the crosslinking agent, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, triethanolamine, ethylenediamine, and the like can be used alone or in combination. These additives and other additives may be mixed in advance with the mixture containing the polyol component (B), or may be added during the reaction.

[0018]

The present invention will be specifically described below with reference to examples and comparative examples. “Parts” and “%” are based on weight. The density was measured according to JISA-9514 using a foam obtained by free foaming. The initial adhesion test is
In a 400 x 400 x 20 mm aluminum mold kept at 60 ° C,
Aluminum kraft paper was installed as a face material on both sides and foamed into a board shape. Thirty seconds after the release, a 10 cm-wide peel test was performed to measure the adhesive strength.

Example 1 PL-107 (Toho Rika Co., Ltd.)
Made, aromatic polyester polyol, OH value 190) 70
Parts, 20 parts of SOR220 (manufactured by Takeda Pharmaceutical Co., Ltd., sorbitol-based polyol, OH value 200), MF-78 (manufactured by Takeda Pharmaceutical Co., Ltd., glycerin-based polyol, OH value of 37) 1
0 parts, dimethylformamide (hereinafter abbreviated as DMF) 3 parts, tris- (monomethyl-2-chloropropyl) phosphate (hereinafter abbreviated as TMCPP, manufactured by Daihachi Chemical Co., Ltd., flame retardant) 15 parts, SH-193 (Toray Dow Silicone Co., Ltd., foam stabilizer) 5 parts, water 6 parts, PELCAT95
40 parts (Pelron Co., trimerization catalyst) 3 parts and TOYOCAT DT (Tosoh Corporation, urethanization catalyst) 1 part were mixed, and DRC was mixed.
340 parts of -535 (manufactured by Nippon Polyurethane Industry Co., Ltd., crude diphenylmethane diisocyanate, NCO content: 31.0%) was added and stirred, and the mixture was transferred to a 1-liter paper cup for foaming. The obtained foam had a good foam state and a density of 34.5 kg / m3.

In the initial adhesion test, the above mixture was poured into an aluminum mold for adhesion test, foaming was performed, and 30 seconds after demolding, a 10 cm-wide peel test was performed, and a result of 1.0 kg was obtained.

Examples 2 to 7 Foaming was carried out in the same manner as in Example 1 using various polyols, foam stabilizers, and compatibilizers, and density and initial adhesion tests were performed. [Table 1] shows the mixing ratio and the measurement results.

[0022]

[Table 1]

The raw materials used are listed below. BEP: Modified phenolic resin (Hodogaya Chemical Industry Co., Ltd.)
PL-107: aromatic polyester polyol (manufactured by Toho Rika Co., Ltd., OH value 190) Terol 236: aromatic polyester polyol (Ox)
id Co., OH number 245) SOR220: propylene oxide adduct of sorbitol (OH value 200, manufactured by Takeda Pharmaceutical Co., Ltd.) MF-78: glycerin-based ethylene / propylene oxide adduct (Takeda Pharmaceutical Co., Ltd.) DOH: dimethylformamide PC: propylene carbonate NMP: N-methylpyrrolidone TMCPP: tris (monomethyl-2-chloropropyl) phosphate (flame retardant manufactured by Daihachi Chemical Industry Co., Ltd.) TOP: trioctyl phosphate (Flame retardant manufactured by Daihachi Chemical Industry Co., Ltd.) SH-193: silicone foaming agent (manufactured by Toray Dow Silicone Co., Ltd.) DRC-535: crude diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd.) NCO content 3
1.0%) PELCAT9540: Potassium octenoate trimerization catalyst (Pelr
on Co.) TOYOCAT DT: Urethane conversion catalyst: (Tosoh Corporation)

Comparative Example 1 From the composition of Example 1, DMF
, Except for foaming, and an adhesion test was performed. Initial adhesive strength
It was as small as 0.1 kg / 10 cm.

[Comparative Examples 2 to 5] Initial adhesion tests were performed when the amount of the compatibilizer was changed. Initial adhesion was less than 1.0kg / 10cm

[0026]

According to the polyurethane foam of the present invention,
Uses water as a foaming agent and has excellent flame retardancy, heat resistance, and low smoke emission characteristics without using specific CFCs or alternative CFC compounds. A method for producing a urethane-modified polyisocyanurate foam having improved properties can be provided.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J034 AA04 DA01 DB03 DC02 DN03 HA07 HC03 HC12 HC13 HC35 HC61 HC64 HC67 KB03 KC02 KC35 KD01 KD02 KD11 KE01 KE02 MA12 MA14 MA15 MA16 MA24 NA03 QB17 QC01

Claims (6)

[Claims] 1. A polyisocyanate compound component (A),
A method for producing a urethane-modified polyisocyanurate foam, comprising reacting a polyol component (B), water (C), and a compatibilizer (D) in the presence of an isocyanate trimerization catalyst (E). 2. The urethane-modified polyisocyanurate foam according to claim 1, wherein the compatibilizer (D) is used in an amount of 3 to 20 parts by weight based on 100 parts by weight of the polyol component (B). Production method. 3. The above isocyanate trimerization catalyst (E) is added in an amount of 0.35 to 100 parts by weight of the polyol component (B).
The method for producing a urethane-modified polyisocyanurate foam according to claim 1 or 2, wherein the foam is used in an amount of from 15 to 15 parts by weight. 4. The urethane-modified polyisocyanurate foam according to claim 1, wherein the water (C) is used in an amount of 2 to 30 parts by weight based on 100 parts by weight of the polyol component (B). How to make the body. 5. The method according to claim 1, wherein the compatibilizer (D) is a nitrogen-containing compound,
The urethane-modified polyisocyanurate according to claim 1, wherein the urethane-modified polyisocyanurate is at least one selected from sulfur-containing, phosphorus-based, halogen-based, hydrocarbon-based, ether-based, ester-based, and carbonate-based organic compounds. A method for producing a foam. 6. The polyol component (B) contains a benzylic ether-type phenolic resin and / or a modified phenolic resin obtained by reacting a polyhydric alcohol or an alkylene oxide adduct thereof with a benzylic ether-type phenolic resin. Claims 1 to
6. A method for producing the urethane-modified polyisocyanurate foam according to claim 5.