JPH01315413A - Resin composition, vibration damper, thermoforming material and thermoforming method - Google Patents

Abstract

PURPOSE:To obtain the subject composition giving polyurethane form having light weight and excellent workability suitable for vibration damper of automobile or thermoforming material having excellent thermoformability and maintenance by mixing specific polyol and specific amount of organic polyisocyanate. CONSTITUTION:(A) Polyol containing polycaprolactone polyesterpolyol having 100-600 hydroxyl value is mixed with (B) organic polyisocyanate in amount of giving 50-300 NCO index (preferably 2,4-tolylenediisocyanate, etc.), (C) catalyst (e.g., sodium acetate, etc.) and (B) additives to obtain the aimed composition. Besides, containing amount of polycaprolactone polyesterpolyol in component A is preferably >=50wt.%. Furthermore, (condensed) polyesterpolyol is preferable as a polyol other than polycaprolactone polyesterpolyol.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a resin composition, a damping material, a thermoforming material, and a thermoforming method.

[Prior Art] Soundproofing and vibration damping materials include various rubber-like substances, thermoplastic resins, etc. with fillers such as mica, carbon black, and calcium carbonate added, but these are expensive and heavy. There is a problem with this. Also, poly1
Countermeasures have been taken to increase the density and improve the sound insulation performance by adding fillers such as those mentioned above to cretan foam, but even in this case, it results in an increase in cost and a decrease in physical properties, making it unsatisfactory. It wasn't ゛'s. Therefore, for example, viscoelastic foams with high viscosity properties are used, such as foams made by post-processing polyurethane foam lx and impregnating it with asphalt, or foams made by applying asphalt to the polyurethane foam raw material and foaming it integrally. The current situation was that

Furthermore, as a thermoforming material and a molding method, a method is known in which a flexible polyurethane foam is impregnated with an emulsion, an adhesive, a thermoplastic resin, etc., and then hot-pressed.

[Points to be solved by the invention] As mentioned above, asphalt-based foam is extremely inefficient in terms of workability, as the processing equipment is contaminated by asphalt during hot compression molding, and furthermore, it is costly. Furthermore, post-treated asphalt foam has the disadvantage of high impregnation, making it difficult to obtain uniform quality, and it is desirable that it be lightweight as a soundproofing material for use in vehicles, etc. However, the above-mentioned asphalt foam, various rubbers and resins to which fillers are added have a problem that they have a high density and are heavy.

Further, conventional thermoforming materials are soft and have poor shape retention, and the thermoforming method requires a lot of man-hours.

[Means for resolving the problem] In order to solve the above-mentioned problem, the present inventors have intensively studied resin compositions, damping materials, thermoforming materials, and thermoforming methods, and have found that:
We have arrived at the present invention. That is, the present invention provides a polyurethane resin composition in which a polyol and an organic polyisocyanate are reacted in the presence of a catalyst and optionally an additive, in which the polyol has a hydroxyl value of 100 to 600.
A polyurethane resin composition comprising at least a portion of a polyester polyol having an NCO index of ~300, a polyurethane resin composition comprising a polyol and an organic polyisocyanate prepolymer in the presence of a catalyst and optionally an additive. In the method for producing polyurethane foam, the polyol is a polycaprolactone polyester polyol having a hydroxyl value of 100 to 600, and the organic polyisocyanate prepolymer reacts a polyether polyol with a stoichiometrically excess organic polyisocyanate. The polyurethane foam according to claim 2, wherein the polyurethane foam is an organic polyisocyanate 1-prepolymer with an NCO% of 10 to 20% obtained by A soundproofing and damping material for automatic iJi, characterized in that the thermoforming material made of the composition according to claim 1 and the thermoforming material according to claim 4 are molded by heating and pressurizing. It is a thermoforming method.

The polyols used in the present invention include those commonly used in polyurethanes, such as polyether polyols, polyester polyols, polycarbonate polyols, polybutadiene polyols, and the like.

Polyether polyols include active hydrogen atom-containing compounds such as polyhydric alcohols, polyhydric phenols, amines, and polycarboxylic acids.

Examples include compounds with a structure in which an oxide is added.

Examples of polyhydric alcohols include dihydric alcohols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and neopentyl glycol, as well as glycerin, trimethylolpropane, pentaerythryl, and sorbitol. , trivalent or higher polyhydric alcohols such as sucrose, and the like.

Polyhydric phenols include polyhydric phenols such as pyrogallol and hydroquinone, as well as bisphenols such as bisphenol A; condensates of phenol and formaldehyde (novolak), for example, US Pat. No. 3,265,641
Examples include polyphenols described in the specification.

Amine lamps also include ammonia; mono-, di-, and triethanolamine, isopropanolamine,
Alkanolamines such as aminoethylethanolamine; C1-C20 alkylamines; C2-C6 alkylene diamines such as ethylene diamine, propylene diamine, hexamethylene diamine, polyalkylene polyamines such as diethylene triamine, triethylene theramine; aliphatic amines such as aniline; , phenylene diamine, diaminotoluene, xylylene diamine, methylene dianiline, diphenyl ether diamine and other aromatic amines; aliphatic amines such as isothrondiamine, cyclohexylene diamine; aminoethyl piperazine and other special public works 2104
Examples include the heterocyclic amines described in Publication No. 4. Two or more of these active hydrogen atom-containing compounds may be used in combination. Preferred among the stiffeners are polyhydric alcohols.

Examples of polycarboxylic acids include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, maleic acid, and dimer acid, and aromatic polycarboxylic acids such as phthalic acid, terephthalic acid, and trimellit-rft. Two or more kinds of the above-mentioned active hydrogen atom-containing compounds can also be used.

Examples of alkylene oxides to be added to the active hydrogen atom-containing compound include EO, PO, butylene oxide (tetrahydrofuran), and the like. The alkylene oxides may be used alone or in combination of two or more, and in the latter case, block addition or random addition may be used. This JL
Preferred among these fullkylene oxides are tetrahydrofuran, po and EO.

Examples of polyester polyols include condensed polyester polyols obtained by reacting low-molecular polyols (the above-mentioned dihydric alcohols, !-limethylolpropane, t% dicarboxylic M such as glycerin (the above-mentioned polycarboxylic acids, etc.) Gen glycols include those described in Japanese Patent Application Laid-Open No. 55-98220, 11 Rubber Association Journal Vol. 45 (1972), pages 449-450, and Sealand (by Damsis, published by Reinsbold, 1967). can be used.

Examples of the polycarbonate diol include those obtained from the above-mentioned di- or trihydric alcohols and carbonic acid diesters (dimethyl carbonate, diethyl carbonate-1-, etc.).

Among these, preferably polyether polyol,
It is a condensed polyester polyol.

These may be used in combination if necessary.

The hydroxyl value of these polyols is usually 100 to 700, preferably 1°00 to 650. Outside this range, soundproofing, vibration damping properties, and aging formability are poor.

The polycaprolactone polynisal polyol used in the present invention can be obtained by reacting the polyhydric alcohol described above or the polyhydric phenol described above with ε-caprolactone. The hydroxyl nor value of polycaprolactone polynisal polyol is usually 100 to 600.
Preferably 1 is 100-580. If the hydroxyl value is outside this range, the soundproofing, vibration damping properties and thermoformability will be poor.

The content of polycaprolactic polyester polyol in the polyol is usually 30% or more, preferably 50% by weight.
% or more. If it is less than 30%, sound insulation, vibration damping properties and thermoformability are poor.

As the organic polyisocyanate 1 used as a raw material for the thermoforming material of the present invention, those commonly used for polyurethane are used. For example, aromatic polyisocyanates having 6 to 20 carbon atoms (excluding carbon in the NCO group) [2,4- and/or 2,6-dolylene diisocyanate (TDI
), coarse ffTDI, 2,4'- and/or 4,4'
- diphenylmethane diisocyanate (Ml) I), crude iMDI [, 11mdiaminodiphenylmethane (condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof diamino diphenylmethane and a small amount (e.g. 5-20%) of trifunctional or higher functional (polyaryl polyisocyanate (PAPI))]: aliphatic polyisocyanate having 2 to 18 carbon atoms [hexamethylene diisocyanate 1-.
lysine diisocyanate, etc.]: Alicyclic poly-f-socyanate having 4 to 5 carbon atoms (isophorone diisocyanate, dicyclohexylmethane diisocyanate, etc.): Aroaliphatic polyisocyanate having 8 to 15 carbon atoms [xylylene diisocyanate, etc.]: and these Modified products of polyisocyanate (urethane group, carbodiimide group,
allophanate group, urea group, biuret 1-group, uretdione group, uretonimine group, incyanurate group,
Oxazolidone group-containing modified products, etc.): and patent application 1983
Polyisocyanates other than those described in -199160: and mixtures of two or more thereof,
Among these, preferred are 2,4- and 2,6-
-'1'D1. and mixtures of these isomers, 2,4
'- and 4,4'-MDI and mixtures of these isomers, crude MD1. and mixtures of TDI and MDI, and modifications containing urethane groups, carbodiimide groups, 70-phanate groups, urea groups, biuret groups, uretdione groups, uretonimine groups, isocyanurate groups, and oxazolidone groups derived from these polyisocyanate-1- It is poly-r-socyanate.

N00% of organic polyisocyanate-1- is usually 25-50
%, preferably 25-35%. Outside this range, thermoformability is poor.

An example of an organic polyisocyanate prepolymer used as a raw material for soundproofing and vibration damping materials is the organic polyisocyanate 1 described above in stoichiometric excess with polyether polyol.
Obtained by reacting with.

Examples of polyether polyols include those obtained by adding alkylene oxide to the polyhydric alcohol described above. The polyhydric alcohol is usually a dihydric to trihydric alcohol, preferably a dihydric alcohol.

Outside this range, the strength of the polyurethane foam will be low, and the viscosity of the organic polyisocyanate will increase.The hydroxyl value of the polyether polyol is usually from 20 to 600, preferably from 25 to 590. Outside this range, the strength of the polyurethane foam will be low and the viscosity of the organic polyisocyanate brevolimer will increase.

As alkylene oxide, ethylene oxide (E
(abbreviated as O), propylene oxide (abbreviated as Po), butylene oxa, and ido. Preferred among these are EO and/or PO.

N00% of the organic polyisocyanate prepolymer is usually 10 to ZO%, preferably 10 to 18%.

The NCO index of the present invention is usually 50 to 300, preferably 90 to 300, particularly preferably 90 to 250 when used as a soundproofing or vibration damping material. If the NCO index is outside this range, the soundproofing and Φ11@ properties will be poor. Moreover, when used for thermoforming materials, it is usually 50 to 300, preferably 80 to 200. It is possible outside this range. Specifically, metal salts of carboxylic acids, such as sodium acetate, lead octylate, zinc octylate, cobalt naphthenate, etc.; alkoxides and phenoxides of alkali and alkaline earth metals, such as sodium methoxide, sodium phenoxy Tertiary amines, such as 1-helythylamine, triethylenediamine, N-methylmorpholine, dimethylaminomethylphenol, pyridine; Quaternary ammonium bases, such as tetraethylammonium hydroxy; Imidazoles, such as imidazole, 2-ethyl -4-methylimidazole, etc.: Organometallic compounds such as tin and antimony, such as tetraphenyltin,
Examples include 1-butylantimony oxide. Among these, preferred are organic metal compounds such as tin and antimony, tertiary amines, metal salts of carboxylic acids, or mixtures thereof.

The amount of catalyst used is not particularly limited, but the total amount of polyol is 10
Usually 0.1 to 5 parts, preferably 0.3 to 3 parts
Department. Outside this range, an appropriate curing time cannot be obtained.

Additives that may be used as necessary in the present invention include foam stabilizers, blowing agents, and auxiliary agents.

As the foam stabilizer, one for urethane foam is usually used. For example, L-540 (manufactured by Nihon Unicar Co., Ltd.)
, 5I-I-193, 5I-I-190, 5RX-29
4A, 5RX-274G (manufactured by Toray Silicone Co., Ltd.), f1! Although the dosage is not particularly limited, it is usually 0.5 to 5 parts per 100 parts of the total amount of polyol.

Examples of blowing agents include water, Freon, and methylene chloride. The amount used is not particularly limited, but is usually 15 parts or more per 100 parts of the total amount of Beauriol.

Examples of auxiliary agents include thixotropic agents, fillers, and coloring agents.

The polyurethane resin and foam of the present invention do not require special manufacturing equipment, and can be manufactured using conventional equipment by the one-shock method, spray method, molded method, or slab method.

The polyurethane resins described above are useful as thermoforming materials, and thermoforming is accomplished by heating and pressurizing with conventional equipment.

Heating may be performed by microwaves in addition to the usual method.

Heating temperature is usually 50-200℃, preferably 60-15℃
It is 0°C. Outside this range, thermoformability is poor, and the pressure should be generally 0.1 kg/am2 or more, O, ],
If it is less than kg/am2, thermoformability is poor.

Thermoforming materials are particularly useful as exterior or interior materials for automobiles, trains, houses, etc.

Furthermore, the above-mentioned polyurethane foam is useful as a soundproofing and vibration damping material, and is particularly effective as a soundproofing and vibration damping material for transport vehicles such as automobiles, trains, and aerial mines, as well as for transportation vehicles such as factories, machines, and houses, which are particularly susceptible to vibration. . Specific examples include vertical parts such as car doors and dash silencers, and complex parts around the engine.

[Examples] The present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.The compositions of raw materials used in Examples and Comparative Examples will be explained.

Polyol 1: PC which is polycaprolactone polyester polyol; L-303 (Daicel Chemical Industry Co., Ltd.)
fA), with a hydroxyl value of 54.0.

Polyol 2...Polycaprolactone polyester polyol PCL-305 (Daicel Chemical Co., Ltd.)
Co., Ltd.), with a hydroxyl value of 304.

Polyol 3: Polycaprolactone polynisder polyol E-489 (manufactured by Daicel Chemical Industries, Ltd.) with a hydroxyl value of 464.

Polyol 4: Added ■)0 to glycerin and has a hydroxyl value of 561.

Polyol 5: Glycerin with PO and EO added and has a hydroxyl value of 33.

Foam stabilizer 1...5H-193 (Toray Silicone Co., Ltd.)
Foam stabilizer 2...5RX-274G (manufactured by Toray Silicone Co., Ltd.) Catalyst 1...Polycat 42 (San-Apro Co., Ltd.) Catalyst 2...Minico L-1,020 (Mitsui Nisso Co., Ltd.) Co., Ltd.) Isocyanate-1-J,...P in propylene glycol
One that has O added and has a hydroxyl value of 1.12, and one that is reacted with TDI-80 and has an NCO% of 15%.

Isocyane 1-2... Millionate MR (manufactured by Nippon Polyurethane Kogyo Co., Ltd.) Isocyane-1 to:3... Sumidur VT (manufactured by Sumitomo Bayer Urethane Co., Ltd.) Examples 1 to 3, Comparative Example 1 Table 1 Polyurethane foam was manufactured based on the formulation shown in . The resulting polyurethane foam was measured for density, soundproofing, and vibration damping properties [loss coefficient by vibration reed method at 20°C and 40°C].

The results are listed in Table 1.

The soundproofing and vibration damping measurement samples are 200X20XQ,
An 8 mm3 steel plate coated with polyurethane foam was used.

As is clear from the measurement results, the loss coefficients at 20° C. and 40° C. are higher in Examples 1 to 3 than in Comparative Example 1, which indicates that they have excellent soundproofing and vibration damping properties.

Example 4 The formulation of Example 3 was sprayed onto a door panel using a spray device (APW-5000 manufactured by Amita Okuma Sangyo Co., Ltd. ff) to obtain a vibration damping material. It was installed in a car and its vibration damping properties were investigated. The damping properties were good.

Examples 5 to 7, Comparative Examples 2.3 Thermoforming materials of polyurethane resin and polyurethane foam were prepared according to the formulations shown in Table 2, and thermoformed.

The results are also listed in Table 1. Thermoformability is better than comparative examples of conventional technology.

Comparative Example 4 Polyethylene resin powder was sprinkled on the surface of the polyurethane foam prepared in Comparative Example 2 at 150°C for 10k.
6. Shape retention is poor when thermoformed under conditions of g/cm2.

Table 2 [Effects of the Invention] As is clear from the above results, the polyurethane foam produced according to the present invention can be made into an excellent soundproofing and vibration damping material because it uses the specified polyol and organic polyisocyanate. Moreover, since asphalt 1- is not used, processing equipment is not contaminated with asphalt during processing such as hot compression molding, and work efficiency is not reduced. Furthermore, since no filler is used, the polyurethane resin is lightweight and is particularly preferred as a soundproofing and vibration damping material for automobiles.In addition, the polyurethane resin of the present invention can be used as a thermoforming material, and has better thermoformability than conventional thermoforming materials.

It is particularly suitable for exterior or interior materials for automobiles, houses, etc. because of its excellent retention properties.

Furthermore, the polyurethane resin and polyurethane foam of the present invention do not require any special manufacturing equipment, and have the advantage that they can be manufactured using conventional equipment using a one-shot method or a spray method.

Claims (1)

[Claims] 1. A polyol containing at least a portion of a polycaprolactone polyester polyol having a hydroxyl value of 100 to 600, an organic polyisocyanate in an amount giving an NCO index of 50 to 300, a catalyst, and additives. Polyurethane resin composition. 2. A method for producing polyurethane foam in which a polyol and an organic polyisocyanate prepolymer are reacted in the presence of a catalyst and optionally an additive, in which the polyol contains at least a portion of a polycaprolactone polyester polyol having a hydroxyl value of 100 to 600; The organic polyisocyanate is an organic polyisocyanate prepolymer with an NCO% of 10 to 20% obtained by reacting a polyether polyol with a stoichiometric excess of organic polyisocyanate, and an NCO index of 50 to 300. Characteristic polyurethane foam manufacturing method. 3. A soundproofing and vibration damping material for automobiles comprising the polyurethane foam according to claim 2. 4. A thermoformable material comprising the composition according to claim 1. 5. A thermoforming method for thermoforming the thermoforming material according to claim 4 under heating and pressure.