JPS6042431A - Polyurethane foam sheet of excellent heat process-ability and laminate thereof - Google Patents

Abstract

PURPOSE:The titled foam sheet which can be easily formed into a foam sheet of a desired density and a desirable thickness by means of a mold, doctor blade or the like, prepared by adding a thermoplastic substance to a mixture of starting materials. CONSTITUTION:A mixture comprising a compound having at least two active hydrogen atoms, and organic polysocyanate compound, a catalyst, a silicone foam stabilizer and other additives is further mixed with a thermoplastic substance (e.g., PE. PVC, or PS) and the resulting mixture is agitated mechanically to disperse an inert gas uniformly throught the mixture to form a structurally stable foam. This foam is formed into a sheet and heat-cured to produce the titled foam sheet. The dimensional change can be easily pre-estimated and controlled because this process consists of two stages of a foam-forming stage and a curing stage, and neither chemical expansion nor expansion by evaporation of a liquid occurs and only heat expansion occurs. Therefore, a form sheet of a desired density and a desired thickness can be easily formed by means of a mold, doctor blade, or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polyurethane foam sheets with excellent heat processability and multilayer bodies thereof.

Conventional 1. Polyurethane foam is thermosetting, and it has been difficult to perform post-processing and post-molding after producing polyurethane foam.

In order to obtain a polyurethane foam molded product with a curved surface, the polyurethane raw material is injected in liquid form into a mold having that shape in advance, or a large foam pan is used.
After making 14 pieces, they were cut out or molded into the desired shape. An object of the present invention is to provide polyurethane foam sheets and multilayer bodies thereof that have excellent heat processability that could not be obtained by conventionally known methods.

The sheets of the present invention have a foam thickness of 0.2 to 50 mm.
, form density 0.1~x, oy/crr? Adashi,
Refers to gaskets, shoe insoles, sealing materials, mounts, spacers, etc.

Further, the sheet multilayer body of the present invention includes the polyurethane foam sheet and a carrier such as fiber, carpet, car mat, artificial turf, cushion floor-1 synthetic leather, synthetic resin sheet, synthetic resin film, metal film, or nonwoven fabric. refers to the adhesive composite of

The present invention provides the following methods: (1) A mixture of a compound having two or more active hydrogens, an organic polyisocyanate compound, a catalyst, a silicone foam stabilizer, and other additives is uniformly dispersed with an inert gas throughout the mixture by mechanical stirring. to form a substantially structurally stable foam, which is then formed into a sheet;
Polyurethane foam sheets that are heat-cured and have excellent heat processability, characterized in that a thermoplastic substance is blended into the mixture.

(2) Compounds with two or more active hydrogens, organic polyinsyanate compounds 1. A mixture of catalyst, silicone foam stabilizer, and other additives is subjected to mechanical agitation to uniformly disperse an inert gas throughout the mixture to form a substantially structurally stable foam; After carrying the body on a carrier,
A 7-ohm polyurethane sheet multilayer body having excellent heat processability, characterized in that a thermoplastic substance is blended into the mixture of the polyurethane foam sheet multilayer body.

In contrast to the conventional method for producing polyurethane (7 ohm sea) M in which the formation of bubbles, expansion and curing occur almost simultaneously, the present invention normally produces a foam in which an inert gas is dispersed by mechanical stirring. It consists of two stages: a formation stage and then a curing stage in which the foam is heated to complete the reaction. In addition, there is virtually no chemical expansion (i.e., expansion due to gas generated in the liquid phase due to chemical reaction) or expansion due to volatilization of the liquid.
Since substantially only thermal expansion occurs, dimensional changes are easily predicted and easily controlled.

Therefore, according to the present invention, a foam sheet having a desired density and thickness can be easily formed using a mold or a doctor blade. Furthermore, it is also possible to easily form a foam sheet by passing the foam mixture through rollers with release paper kept at regular intervals.

The production of the multilayer body according to the invention is also carried out in the same way as the production of the above-mentioned sheets. That is, the foam mixture is molded and adhered to one surface of a flat carrier.

If necessary, another carrier may be attached to the foam surface. Furthermore, a roller may be used depending on the case.

In short, if the foam before hardening is molded into a 7 ohm sheet, it will become a sheet, and if this foam sheet is integrally molded with the carrier on a carrier, it will become a multilayered product. Particularly in the case of a multilayer body made of thin fabric, the fabric may be adhered not only to one side but also to both sides of the foam sheet. If the sheet is thin, it can also serve as a type of adhesive for multiple carriers.

The sheets or multilayer bodies thus obtained are subjected to secondary processing such as perforation, molding, cutting, attachment to other objects, and adhesion.

The foam of the present invention is formed by mechanically agitating an inert gas such as air or nitrogen gas with a high shear device such as a Hobart mixer or an Oakes mixer.
This is carried out by mixing a compound having at least 1 active hydrogen (hereinafter simply referred to as an active hydrogen-containing compound) into a liquid phase consisting of an organic polyin 7-anate or the like.

After formation of the foam of the present invention, to stabilize the foam,
It is possible to incorporate a foam stabilizer such as an organosilicon surfactant or to use an active hydrogen compound as described in US Pat. No. 3,821,130. In this case, the organosilicon surfactant is 1. For example, Nippon Unicar's L-501, L-520, L-53.
2, L-540, L-544, L-3550, L-53
02, L-5305, L-5320゜L-5340, L
-5350, L-5410, L-5420゜L-571
0, L-5720, etc., and those manufactured by Toray Silicone include 5H-190% 5H-192, 5H-193,
5H-194, 5H-195, 5H-200°5RX-
253 etc., and Shin-Etsu Silicone Co., Ltd. has F-11.
4, F-121, F-122, F-220°F"-23
0, F-258, F-260B, F-305, F-30
6, F-317, F-601, F-606, X-20-
200, X-20-201, etc., and FiTFA-4200, TFA-4202 manufactured by Toshiba Silicone Co., Ltd., as well as those described in JP-A-51-75683.

In order to accelerate the reaction between the active hydrogen-containing compound and the organic polyisocyanate in the heat curing stage after the foam is formed, it is desirable to uniformly mix a catalyst into the reaction system in advance. For such a catalyst, the following formula (1
) and (2).

(Here, M is Ni, Cu, Fe, n is 2 or 3
, R1e and R2 are each an alkyl group or a phenyl group)
(Here, s R3 + R4 are each an alkyl group or a phenyl group) Examples of these include nickel acetylacetonate, copper acetylacetonate, ferrous and ferric acetate fA-7 acetonate, molybdenum oxide acetylacetonate, and derivatives thereof. It is.

Derivatives of nickel acetylacetonate include nickel diacetonitrile diacetylacetonate, nickel diphenylnitrile diacetylacetonate, nickel bis(triphenylphosphine) diacetylacetonate, and the like.

These catalysts are optionally used diluted with a solvent. The solvent used here is most preferably an active hydrogen-containing compound or an organic polyisocyanate used as a raw material for the polyurethane composition, or amines used in combination, but in some cases, other solvents that can dissolve the above catalyst, such as methanol, chloroform, etc. , tetrahydrofuran, dioxane, etc. can be used.

The reaction of the above catalyst is relatively slow below 60°C,
Heating to 70°C or higher has the advantage of accelerating the reaction.

Catalysts that can be used in the present invention include the above-mentioned known urethanization catalysts, such as amine-based urethanization catalysts (triethylamine, tripropylamine, triisopropanolamine, tributylamine, trioctylamine, hexyl decyl Dimethylamine, N-methylmorpholine, N:r-f Lumo k 7-olin, N-offdabcylmorpholine, monoethanolamine, jetanolamine, triethanolamine, N-methyljetanolamine, N,N- Dimethylethanolamine, diethylenetriamine, N, N, N', N'-tetramethylethylenediamine, N, N, N', N
'-tetramethylpropylenediamine, N, N, N
', N'-tetramethylptadiamine, N, N
, N', N'-tetramethyl-1,3-butanediamine, N, N, N', N'-tetramethylhexamethylenediamine, bis(2-(N,N-dimethylamino)ethyl]ether, N, N-dimethylbenzylamine, N, N-dimethylbenzylamine, N, N-dimethylcyclohexylamine, N, N, N', N',
Azacyclic compounds such as N'-pentamethyldiethylenetriamine, triethylenediamine, formates and other salts of triethylenediamine, amino group oxyalkylene adducts of primary and secondary amines, N,N-dialkylpiperazines, various N, N', N' -) 1j Alkylaminoalkylhexahydrotriazines, Japanese Patent Publication No. 1973
2-43517! -Aminocarbonyl catalyst, Special Publication Showa 5
3-14279 β-amine nitrile catalyst, etc.).

Organometallic urethanation catalysts (tin acetate, tin octoate, tin oleate, tin laurate, diptyltin diacetate,
Diptyltin dilaurate, diptyltin dichloride, lead octoate, lead naphthenate.

cobalt naphthenate, etc.).

The amount of these catalysts used is 0.0 parts by weight per 100 parts by weight of the active hydrogen-containing compound.
001 to 10.0 parts.If the above-mentioned catalyst is used in an amount that promotes the reaction in the heat curing stage, if the reaction in the foam formation stage is accelerated, the foam formation stage The organic polyisocyanates used in the present invention are known and are not particularly limited, but include 2.4-) lylene diisocyanate, 2.6-) Lylene diisocyanate, 2.4
−) Rerenjiinokuane),! = 2.6-) mixture of lylene diisocyanate with an isomer ratio of 80/20.65/35, crude tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, dicyclohexylmethane diisocyanate 7,1-), polyphenyl Methylene polyisocyanate (known as crude MDI), various known modified diphenylmethane-4,4'-diisocyanates modified with carbodiimide groups, dianisidine diinocyanate, toluidine diisocyanate, xylylene diisocyanate, bis(2-incyanate), etc. Anatoethyl) fumarate, bis(2-incyanatoethyl) fumarate, bis(2-incyanatoethyl) carbonate, bis(2-4incyanatoethyl) carbonate, 1.6-
hexylylene diisocyanate, 3-isocyanate methyl-3,5,5-)limethylcyclohexyl isocyanate), 1. 4-tetramethylene diincyanate,
1.10-decamethylene diinocyanate, cumene-2
, 4-diincyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-bromo-1,3-722 diisocyanate $-), 4-ethoxy-1 , 3-phenylene diinocyanate, 2,4'-diisocyanat diphenyl ether, 5,6-dimethyl-1,3-phenylene diinocyanate, 2,4-dimethyl-1°3-phenylene diicanate, 4. 4'-Diynecyanatodiphenyl ether, bis5.6-(2-cyanatoethyl)bicycloC2,2,1)hept-2-ene, benzidine diisocyanate, 4.6-dimethyl-1.3-
7-enylene diisocyanate, 9.10-anthracene diisocyanate, 4,4'-diisocyanatodibenzyl, 3,3-dimethyl-4,4'-diyne cyanatodiphenylmethane, 2,6-dimethyl-4,4'-dibenzyl incyanatodiphenyl, 2,4-diisocyanatostilbene, 3.3'-dimethyl-4,4'-diynecyanatodiphenyl, 3.3'-dimethoxy-4,4'-diynecyanatodiphenyl, 1.4 -anthracene diisocyanate, 2,5-fluorene diisocyanate), 1,8-naphthalene diisocyanate, 2,6-diisocyanatobenzfuran, 2,4,6-tolutriene diisocyanate. dimer,
Dimeric NCO-terminated prepolymers from these organic polyisocyanate compounds and their active hydrogen-containing compounds are used alone or in admixture.

Active hydrogen-containing compounds of the present invention include monomeric polyols such as ethylene glycol, glopylene glycol, diethylene glycol, triethylene glycol, diethylene glycol, trimethylene glycol-A/, i, 3- and 1,4-butanediol; Aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, methylene orthochloroaniline, 4.4'
- Aromatic polyamines such as diphenylmethanediamine, 2.4-) lylene diamine, 2.6-) lylene diamine, alkanolamines such as triethanolamine and jetanolamine, water, ethylene glycol,
Globylene glycol, diethylene glycol, triethylene glycol, diethylene glycol, trimethylene glycol, 1,3- and 1,4-butanediol, 1
．． 5-bentanediol, 1,2-hexylene glycol, 1,10-decanediol, 1,2-cyclohexanediol, 2-butene-1,4-diol, 3-cyclohexane-1,1-dimetatool.

4-Methyl-3-cyclohexane-1,1-dimetatool, 3-methylene-1,5-bentanediol, (2-
hydroxyethoxy) -1-7' lovanol, 4-(
2-hydroxyethoxy)-1-butanol, 5-(2
-hydroxypropoxy)-1-pentanol, 1-(
2-hydroxymethoxy)-2-hexanol, 1-(
2- and droxypropoxy)-2-octatool, 3-
Allyloxy-1,5-bentanediol, 2-allyloxymethyl-2-methyl-1,3-bentanediol, [
4,4-Benzyloxy)-methyl)-1,3-propanediol, 3-(o-propenylphenoxy)1,2-
Propanediol, 2,2'-diisopropylidene bis(P-7 22leneoxy)jetanol, glycerin,
1.2.6-hexanediol, 1,1.1-) listyrole ethane, 1゜1.1-) listyrole propane,
3-(2-hydroxyethoxy)-1,2-propanediol, 3-(2-hydroxyalkyl)-1,2-'
lobanediol, 2.4-dimethyl-2-(2-hydroxyethoxy)-methylbentanediol 1°5.1.
1.1-) Lis[2-hydroxyethoxy)methyl]-
Ethane, 1,1.1-)lis[(2-hydroxypropoxy)-methyl]propane, pentaerythritol, nruvit, sucrose, lactose, α-methylglucoside, a-hydroxyalkylglu':1'/'r' ,) Phosic resin, cynic acid, benzenesic acid, polysinic acid (e.g. tripolysinic acid and tetrabovvvnic acid), phenolaniline-
Formaldehyde ternary condensation products, aniline-formaldehyde condensation products, caprolactone, etc., aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, methyleneornochloroaniline, 4.4'-diphenylmethanediamine, 2.4-)
One or more of aromatic polyamines such as lylene diamine and 2,6-lylene diamine, alkanolamines such as triethanolamine and jetanolamine, ethylene oxide, globylene oxide, butylene oxide, tetrahydrofuran, and styrene oxide. or polytetramethylene ether glycol, ethylene glycol, diethylene glycol, trimethylene glycol, 1,2-globylene glycol, dipropylene glycol, trimethylene glycol, 1,3- and 1- .4
- One or 2fi of compounds having at least two hydroxyl groups such as butanediol, tetramethylene glycol, neopentyl glycol, hexamethylene glycol, decamethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, etc.
J! In addition to the above, malonic acid, maleic acid, succinic acid, adipic acid, tartaric acid, pimelic acid, sebacic acid, oxalic acid, phthalic acid, terephthalic acid, hexahydrophthalic acid,
One or two compounds having at least two carboxyl groups, such as aconitic acid, trimetic acid, hemimellitic acid, etc.
Ring-opening polymers of cyclic esters such as polyvarnishes, chill polyols, and polycaprolactones, as well as JP-B No. 39-24737, JP-B No. 41-3473, and JP-B No. 4
3-22108, Special Publication No. 44-8230, Special Publication No. 47-
15108, Special Publication No. 47-47597. Special Public Service 47-4
7999, JP-A-48-34991. Japanese Unexamined Patent Publication 1977-50
398. There are so-called polymer polyol compositions obtained by polymerizing ethylenically unsaturated compounds in polyether polyols and/or polyester polyols as described in JP-A-51-70286, etc., and methods for preparing such compositions. Suitable ethylenically unsaturated compounds include acrylonitrile, styrene, etc. Additionally, 1,2-polybutadiene glycol, polybutadiene glycol, and 4-polybutadiene glycol are used.

The various active hydrogen-containing compounds described above may be used alone or in combination of two or more.

The thermoplastic substances used in the present invention include polyethylene resin, polypropylene resin, acrylic-styrene resin, acrylic-styrene-butadiene resin, ethylene-vinyl chloride copolymer resin, ethylene-vinyl acetate copolymer resin, vinyl chloride resin, and chlorine. chlorinated polyethylene resin, chlorinated polypropylene resin, vinyl acetate resin, phenoxy resin, fluororesin, polyacetal resin, polycarbonate resin,
These resins include polystyrene resins, polysulfone resins, polyurethane resins, heptalate resins, methacrylic resins, petroleum resins, etc., and these resins may be used alone or in combination of two or more. These thermoplastic substances are used after being mixed with an active hydrogen compound or a polyincyanate compound in advance, so that the thermoplastic substances have a particle size of 10 mμ to 1 mm.
It is used in powder form. It is also possible to use two or more thermoplastic substances having different particle size ranges at the same time. If the particle size of the powder is 1 mm or more, there is a risk of clogging the pump, piping, mixing head, etc. of the urethane foaming machine. Such a powdered thermoplastic material is produced by emulsion polymerization or suspension polymerization, or by pulverizing granules at an ultra-low temperature.
00 parts, it is used in an amount of 200 parts or less, preferably 1
00 copies or less.

In the present invention, various known organic and inorganic photonic agents, dyes,
A coloring agent and the like can be mixed therein.

It is also possible to locally improve the hardness and other physical properties of polyurethane sheets by absorbing the plasticizer into the resin powder using the triblend method.

The polyurethane 7 ohm sheets obtained according to the present invention can be formed into a desired shape by hot pressing in a mold, and can be used for furniture with curved surfaces, the outer layer of vehicle cushions, and for use in shock prevention for precision machinery. It can be used as a cover. In addition, these 7 ohm sheets can be laminated with other synthetic resin sheets,
By performing graining, a multilayer sheet with an uneven pattern on the surface and excellent cushioning properties can be produced. Since this multilayer sheet has a beautiful and impressive appearance, it can be widely used as ceiling materials, wall materials, and floor materials for houses, automobiles, etc. Carpets lined with the polyurethane foam of the present invention can also be formed into desired shapes, such as the interior floors of automobiles, by thermal fabrication. As described above, the polyurethane foam sheets and multilayered products thereof according to the present invention have a wide range of uses, and the present invention will now be specifically explained with reference to Examples.

Example 1 Polymer polyol synthesized from polyoxypropylene polyoxyethylene glycol having a photometric value of 39°8, acrylonitrile, and styrene (hydroxyl value 32°0)
), 144 parts of EP-55ON (polyoxypropylene polyoxyethylene polyol water e photometry 54-0 manufactured by Mitsui Hiduru Tsurethane Co., Ltd.) Particle size 0.2-1 to a polyol mixture consisting of 8 parts of diethylene glycol Add 100 parts of .2μ vinyl chloride resin (121 manufactured by Nippon Zeon Co., Ltd.), 1.0 part of nickel acetylacetonate, and 2 parts of L-520 (organosilicon surfactant manufactured by Nippon Unicar Co., Ltd.), and mix these mixtures. A and TDI-80 (Mitsui Nisso Urethane Tolylene Diisocyanate 2.4 integrated 72.6 integrated = 80
/20) and 50 parts of a prepolymer (NCO% = 28ii%) synthesized from MN-1000 (polyoxypropylene polyol manufactured by Mitsui Nisso Tsuretan Co., Ltd., hydroxyl value 168) using an Oakes mixer, and air was mixed in. A fine and uniform foam was formed.

Apply this foam to a thickness of 2 mm on release paper, and
Cured at 0°C for 5 minutes.

The cured sheet is a foam sheet with uniform cells. When this foam sheet was placed in a metal mold with a curved surface and hot-pressed at 100° C. for 2 minutes, it was easily heat-processed, and after returning to room temperature, it was removed from the mold to obtain a molded product.

Example 2 The foam obtained in Example 1 was applied to the back of the carpet to a thickness of 3
mm, and cured at 150°C for 5 minutes. The resulting carpet covered with 7-ohm urethane is used as a car mat for automobiles. The carpet was placed in a mold shaped like the interior floor of an automobile and hot-pressed at 100° C. for 2 minutes. It was easily heat-processed, and after returning to room temperature, the mold was removed to obtain a molded carpet.

Example 3 In Example 1, 120 parts of ethylene-vinyl acetate copolymer resin powder with a particle size of 0.05 to 9.2 mm was added to Mixture 8 in Example 1 and mixed thoroughly, and then A foam sheet with a thickness of 3 mm was obtained by processing in the same manner. This 7 ohm sheet was passed through an embossing machine at the same time as a soft vinyl chloride sheet having a thickness of 11 nm, and then heated, bonded, and embossed to obtain a multilayer body. The obtained multilayer sheet having an uneven pattern on its surface is flexible and elastic, and can be used in a wide range of applications for ceilings, walls, and flooring in houses, vehicles, etc.

patent applicant Mitsui Nisso Urethane Co., Ltd.

Claims (2)

[Claims] (1) An inert gas is uniformly dispersed throughout a mixture of a compound having two or more active hydrogens, an organic polyisocyanate compound, a catalyst, a silicone foam stabilizer, and other additives by mechanical stirring. After forming a substantially structurally stable foam and then molding the foam into a sheet,
Polyurethane foam sheets having excellent heat processability, which are heat-cured polyurethane 7-ohm sheets, characterized in that a thermoplastic substance is blended into the mixture. (2) An inert gas is uniformly dispersed throughout the mixture of a compound having two or more active hydrogens, an organic polyinon77ate compound, a catalyst, a silicone foam stabilizer, and other additives by mechanical stirring. In a polyurethane foam sheet multilayer body, which is formed into a substantially structurally stable foam tq, which is then supported on a carrier, and then thermally cured, a thermoplastic material IRt- is added to the mixture. A multilayer polyurethane foam sheet with excellent heat processability.