JPH0995549A - Production of polyurethane foam integrated with skin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a polyurethane foam integrated with a skin and excellent in vibration characteristics in a low to medium frequency region from a raw material of low viscosity with high productivity by reacting a polyol component and an organic isocyanate component in a mold having a skin set therein. SOLUTION: A foam layer and a skin comprising, e.g. a sheet formed from, e.g. a vinyl chloride resin having a filler added thereto are molded in a mold to produce an integral article. 100 pts.wt. polyol component comprising a mixture of a polyether polyol having an average functionality of 2.5 to 6.0 and an active hydrogen equivalent of 1,500 to 3,000 and a polyoxyalkylene monool at a weight ratio of (65 to 99):(35 to 1), an organic isocyanate component comprising a modified diphenylmethane diisocyanate and/or a polymethylene polyphenylene polyisocyanate and tolylene diisocyanate, and 1-50 pts.wt. liquid hydrocarbon resin are reacted with water, etc.

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 skin-integrated polyurethane foam having excellent vibration characteristics (sound-proofing performance) particularly in a low / mid-frequency region.

[0002]

2. Description of the Related Art Conventionally, as a polyurethane foam molded product having a vibration characteristic (soundproof performance), a polyurethane foam molded product containing a viscous substance such as asphalt or urethane oligomer has been known. (For example, JP-A-62-205115).

[0003]

However, when the above-mentioned material is poured into a mold due to the high viscosity of the raw material,
There are problems such as poor flowability of the raw material in the mold and poor moldability of the urethane foam; it takes a long time to cure the urethane foam, and the productivity is poor.

[0004]

Means for Solving the Problems The present inventors have found that particularly low
As a result of intensive studies to find a method of producing a skin-integrated polyurethane foam mold molded article having excellent vibration characteristics (sound insulation performance) in the medium frequency range, relatively low viscosity of the raw material, and high productivity, the present invention Reached.

That is, according to the present invention, the polyol component (a) and organic

1. A skin-integrated polyurethane foam is produced by reacting a polyol component (a) and an organic isocyanate component (b) in a mold in which a skin is set in the presence of water and other auxiliaries. In the method, (a) has an average number of functional groups of 2.5 to 6.0 and an active hydrogen equivalent of 1500.
A polyether polyol (a1) and a polyoxyalkylene monol (a2)
The weight ratio of (a1) :( a2) is (99 to 65) :( 1 to
35) using a polyol mixture which is
Use a polyisocyanate composed of modified diphenylmethane diisocyanate (b1) and / or polymethylene polyphenylene polyisocyanate (b2) and tolylene diisocyanate (b3), wherein the amount of (b3) in (b) is 50 to 90 parts by weight. And 1 to 50 parts by weight of the hydrocarbon resin (c) which is liquid at room temperature with respect to 100 parts by weight of (a).
A method for producing a skin-integrated polyurethane foam, characterized by using parts by weight.

[0006] There is no particular limitation on the skin constituting the molded molded product using the method of the present invention, and a material for the skin usually used for the production of a polyurethane molded foam integral with the skin, for example, vinyl chloride resin, Examples include sheets formed by adding various fillers to a resin such as an ethylene vinyl acetate resin as required. The molded article produced by the method of the present invention has a structure in which the skin and the foam layer are integrated by molding in a mold.

The polyether polyol (a1) used in the present invention includes, for example, alkylene oxide adducts such as alcohols and amines. Examples of alcohols include dihydric alcohols (ethylene glycol, polypropylene glycol, etc.); trihydric alcohols (glycerin, trimethylolpropane, etc.);
Polyhydric alcohols (such as pentaerythritol and methyl glucoside); hexahydric alcohols (such as sorbitol); and octahydric alcohols (such as sucrose). As amines, divalent amines (methylamine, ethylamine,
Aniline, etc.)); trivalent amines (monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, etc.); tetravalent amines (ethylenediamine, hexamethylenediamine, etc.); and these 2
Mixtures of more than one species are mentioned. Examples of the alkylene oxide include ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2-, 1,4- or 2,3-butylene oxide and a combination of two or more thereof. Of these, preferred are PO and / or EO. When used in combination, the addition form may be either block or random, but a block adduct having an oxyethylene group at the end is preferred.

The average number of functional groups in the above (a1) is usually 2.5
To 6.0, preferably 3.0 to 6.0, and more preferably 3.0 to 4.0. When the average number of functional groups is less than 2.5, the curing property is deteriorated, and when it exceeds 6.0, the liquid flowability is deteriorated and the moldability is deteriorated. The active hydrogen equivalent of (a1) is usually 1500 to 3000, preferably 1600.
２2500. If the amount of active hydrogen is less than 1500, the foam tends to be a single-handed foam, and the vibration characteristics deteriorate.
If it exceeds 0, the viscosity of the raw material increases, and the moldability at the time of producing the skin integral foamed polyurethane foam deteriorates.

The polyoxyalkylene monool (a2) used in the present invention includes, for example, methanol,
Examples include PO and / or EO adducts of aliphatic monoalcohols such as ethanol, propanol, butanol, and 2-ethylhesanol. PO and EO in case of co-addition
May be block or random.

The active hydrogen equivalent of (a2) is usually from 200 to
3000, preferably 500 to 2000, and more preferably 700 to 1500. When the active hydrogen equivalent is less than 200, the curing property is deteriorated, and when it exceeds 3000, the vibration characteristics of the molded article are deteriorated. The weight ratio of (a1) to (a2) constituting the polyol component (a) used in the present invention is usually (65 to 99) :( 35 to 1), preferably (75 to 99).
95): (25-5), more preferably (80-9)
5): (20 to 5). If the ratio of (a2) is less than 1, good vibration characteristics cannot be obtained, and the moldability during the production of the skin-integrated polyurethane foam deteriorates, and if it exceeds 35, the curability deteriorates.

The organic polyisocyanate (b) used in the present invention is a modified diphenylmethane diisocyanate (b1) containing a urethane group, a carbodiimide group, a urea group or the like and / or a polymethylene polyphenylene polyisocyanate (b2) and a tolylene diisocyanate. (B3). The amount of (b3) in (b) is usually from 50 to 90, usually 90% by weight. (B3) in (b)
If the amount is less than 50% by weight, the liquid flowability deteriorates, the moldability deteriorates, and the vibration characteristics of the foam also decrease.
If it exceeds, the curing property will deteriorate.

The hydrocarbon resin (c) which is liquid at normal temperature used in the present invention is, for example, Nippon Petrochemical Co., Ltd.
“Nisseki Hisol S-LH” (3-ring aromatic hydrocarbon, viscosity 190 cst / 40 ° C.), “Nisseki Hisol S”
AS-296 "(bicyclic aromatic hydrocarbon, viscosity 5.1 cs)
t / 40 ° C.). The amount of (c) used is
(A) It is usually 1 to 50 parts by weight, preferably 5 to 20 parts by weight based on 100 parts by weight. If the amount is less than 1 part by weight, the effect of improving the vibration characteristics is poor, and if it exceeds 50 parts by weight, the moldability of the skin-integrated urethane foam deteriorates and the curing property also deteriorates.

A catalyst is usually used in the process of the present invention. As the catalyst, known catalysts usually used for polyurethane foams, for example, metal salts of carboxylic acids (sodium acetate, lead octylate, zinc octylate, cobalt naphthenate, stannas octoate); alkali metals or alkaline earths Metal alkoxides or phenoxides (sodium methoxide, sodium phenoxide, etc.); tertiary amines (triethylamine, triethylenediamine, N-methylmorpholine, dimethylaminomethylphenol, pyridine); quaternary ammonium salts (tetraethylhydroxylammonium, etc.); imidazole (Such as imidazole and 2-ethyl-4-methylimidazole); and organometallic compounds containing metals such as tin and antimony (such as tetraphenyltin and tributylantimony oxide). And the like. Preferred among these are tertiary amines and metal salts or organometallic compounds of carboxylic acids containing tin or antimony.

Water is used alone as a blowing agent, but if necessary, a low-boiling compound such as methylene chloride can be used in combination. The amount of the blowing agent is usually 10 parts by weight or less based on 100 parts by weight of the polyol component (a).

In the method of the present invention, a foam stabilizer can be used if necessary. As the foam stabilizer, those which can be generally used for producing a polyurethane foam are used,
As a specific example, a dimethylsiloxane-based foam stabilizer, for example,
"SZ-1306" and "L-5" manufactured by Nippon Unicar Co., Ltd.
20 "," L-540 "," L-5309 "and" L
-5366 ";" SH-190 "," SH-193 ", and" SRX-274C "manufactured by Dow Corning Toray Silicone Co., Ltd.

The polyurethane foam can be produced by any method of slab, hot cure or cold cure, but cold cure is preferred.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be further described below with reference to examples, but the present invention is not limited thereto. The numerical values in the foaming prescription column in Examples and Comparative Examples indicate parts by weight.

[0018]

【Example】

Accordance foam formulations shown in Examples 1-3 and Comparative Examples 1-3 Table 1, was premixed components of (b) other than vigorously stirred, the 3 kg / m ² 8 seconds by adding component (b) A mold made of aluminum at 55 to 65 ° C with a vinyl chloride resin mat set in the lower mold [50 × 60
× 2 (cm)] for foaming. After curing at 60 ° C. for a predetermined time, the mold was released to obtain a molded article of polyurethane foam integrated with the skin. After standing all day and night, vibration characteristics and foam properties were measured. Table 2 shows the measurement results of the physical properties of each foam, and FIGS. 1 and 2 show the measurement results of the vibration characteristics.

[0019]

[Table 1]

[0020]

[Table 2]

[0021]

[Figure 1]

[0022]

FIG. 2

[Description of Raw Materials Used] Polyol (a1) (a1-1): A polyether polyol having a terminal hydroxyl group content of 80% and a molecular weight of 5,000 obtained by sequentially adding PO and EO to glycerin (a1-1) : Polyether polyol monool (a2) having a terminal hydroxyl group content of 75% and a molecular weight of 7000 obtained by sequentially adding PO and EO to glycerin (a2-1): Obtained by sequentially adding PO and EO to butanol Monool organic polyisocyanate (b) having a terminal hydroxyl group content of 10% and a molecular weight of 700 (b2-1): "MR-" manufactured by Nippon Polyurethane Industry Co., Ltd.
200 "(polymethylene polyphenylene polyisocyanate) (b3-1): Nippon Polyurethane Industry Co., Ltd." Coronate T-80 "(toluene diisocyanate; 2,4 /
2,6 isomer weight ratio = 80/20) Adhesive (c) (c-1): Nippon Petrochemical Co., Ltd., "Nisseki Hisol SAS-LH" Crosslinking agent Diethanolamine Catalyst U1000: San Apro Co., Ltd. Tetramethylhexamethylenediamine 33LV: "DABCO" manufactured by Sankyo Air Products
33LV "(a solution of triethylenediamine in dipropylene glycol) foam stabilizer SRX-274C: manufactured by Toray Dow Corning Silicone Co., Ltd., silicone-based foam stabilizer Coloring agent PU-6678: manufactured by Dainippon Ink and Chemicals, Colorant

[Test Methods for Form Physical Properties and Vibration Characteristics] Total density (Kg / m ³ ): Foam weight / apparent volume of foam Tensile strength (Kg / cm ² ): JIS K-6301 Elongation ( %): JIS K-6301 Tear strength (Kg / cm): JIS K-6301 Hardness (Kgf): JIS K-6401 Compression residual strain (%): JIS K-6401 Air permeability (ft ³ / min): Dow Measured with an airflow meter (the test piece is 50 × 50 × 2 mm) Rebound resilience (%): JIS K-6401 Vibration characteristics: Excitation frequency 0-500 Hz Excitation level 0.1-0.2G, 0. The foam and vinyl chloride resin mat were placed on the aluminum plate of the vibration source in the order of 2 to 0.3 mm, and the acceleration displacement between the aluminum plate and the vinyl chloride resin mat was determined. FIG. 1 shows the vibration characteristics of Examples 1 to 3. Further, FIG. 2 shows the comparative vibration characteristics of Comparative Examples 1 to 3.
The lower the vibration transmissibility, the better the sound insulation performance.

[0025]

The molded article of the polyurethane-integrated polyurethane foam obtained by using the method of the present invention has excellent vibration characteristics (sound-proofing properties), especially sound-insulating properties for solid-borne sounds in low and medium frequency regions. In addition, the method of the present invention is excellent in productivity and economical because it is a skin-integrated molding method. Due to the above-mentioned effects, the polyurethane foam molded article obtained by the method of the present invention is useful as a sound insulation (sound insulation) material used for dash silencers of automobiles, lining of floor carpets, and the like.

[Brief description of drawings]

FIG. 1 is a diagram (graph) showing the vibration characteristics of the foams of Examples 1 to 3.

FIG. 2 is a diagram (graph) showing the vibration characteristics of the foams of Comparative Examples 1 to 3.

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[Procedure amendment]

[Submission date] July 1, 1996

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0005

[Correction method] Change

[Correction contents]

That is, the present invention is a method for producing a polyurethane foam integrated with a skin by reacting a polyol component (a) and an organic isocyanate component (b) in the presence of water and other auxiliaries in a mold in which a skin is set. In (a), the average number of functional groups is 2.5 to 6.0,
It consists of a polyether polyol (a1) having an active hydrogen equivalent of 1500 to 3000 and a polyoxyalkylene monol (a2), and the weight ratio of (a1) :( a2) is (99 to 65) :( 1 to 35) Using a polyol mixture of the following formula (b), which comprises modified diphenylmethane diisocyanate (b1) and / or polymethylene polyphenylene polyisocyanate (b2) and tolylene diisocyanate (b3), and the amount of (b3) in (b) Is 50 to 90% by weight of a polyisocyanate,
The hydrocarbon resin (c) which is liquid at room temperature and is (a) 100
A method for producing a skin-integrated polyurethane foam, wherein 1 to 50 parts by weight is used per part by weight.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction contents]

The polyether polyol (a1) used in the present invention includes, for example, alkylene oxide adducts such as alcohols and amines. Examples of alcohols include dihydric alcohols (ethylene glycol, polypropylene glycol, etc.); trihydric alcohols (glycerin, trimethylolpropane, etc.);
Polyhydric alcohols (such as pentaerythritol and methyl glucoside); hexahydric alcohols (such as sorbitol); and octahydric alcohols (such as sucrose). As amines, monovalent amines (methylamine, ethylamine,
Aniline, etc.)); alkanolamines (monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, etc.); divalent amines (ethylenediamine, hexamethylenediamine, etc.); and mixtures of two or more thereof. Examples of the alkylene oxide include ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2-, 1,
4- or 2,3-butylene oxide and their 2
Combinations of two or more species are included. Of these, preferred are PO and / or EO. When used in combination, the addition form may be either block or random, but a block adduct having an oxyethylene group at the end is preferred.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C08G 101: 00) C08L 75:04

Claims (1)

[Claims] 1. A skin-integrated polyurethane foam is produced by reacting a polyol component (a) and an organic isocyanate component (b) in a mold in which a skin is set in the presence of water and other auxiliaries. In the method, (a) has an average number of functional groups of 2.5 to 6.0 and an active hydrogen equivalent of 1500.
A polyether polyol (a1) and a polyoxyalkylene monol (a2)
The weight ratio of (a1) :( a2) is (65-99) :( 35
(1) using a polyol mixture of (1)
Use a polyisocyanate composed of modified diphenylmethane diisocyanate (b1) and / or polymethylene polyphenylene polyisocyanate (b2) and tolylene diisocyanate (b3), wherein the amount of (b3) in (b) is 50 to 90 parts by weight. And 1 to 50 parts by weight of the hydrocarbon resin (c) which is liquid at room temperature with respect to 100 parts by weight of (a).
A method for producing a skin-incorporated polyurethane foam, which comprises using parts by weight.