JPH04146916A - Polyol composition for flexible polyurethane foam and production of flexible polyurethane foam - Google Patents

Abstract

PURPOSE:To form a polyol composition having good moldability at a mold temperature of 35-60 deg.C and being desirable for the production of a polyurethane foam of low foam hardness by mixing two specified polyether polyols with a specified monool. CONSTITUTION:This composition comprises a polyether polyol (a) having a functionality of 2 or above and a molecular weight of 800-1700 per hydroxyl group, a polyether polyol (b) having a functionality of 3 or above and a molecular weight of 300-800 per hydroxyl group and a monool (c) having a functionality of 1 and a molecular weight of 100-2000. Component (b) is used in an amount of about 40-5wt.% based on the whole polyol composition. A compound of a structure derived by effecting an addition reaction of a hydrocarbon alcohol having one active hydrogen atom with an alkylene oxide is desirable as component (c), and it is used in an amount of about 20-0.1% based on the whole polyol composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polyol composition for flexible polyurethane foam and a method for producing flexible polyurethane foam. More specifically, we manufacture polyurethane foam that has good moldability over a wide range of mold temperature (hereinafter simply referred to as mold temperature) from 35°C to 60°C when urethane foaming liquid is injected, and has soft foam hardness. The present invention relates to a polyol composition for molded polyurethane foam and a method for producing flexible polyurethane foam.

[Prior art] Methods for lowering the hardness of polyurethane foam include using Freon 11, lowering the number of functional groups in polyols, and using polyether polyols with a large number of oxyethylene moieties (for example, 4IA, as described in Japanese Patent Publication No. 4G-28793, Kosho 5
No. 8-3488, Special Publication No. 5313700, Special Publication No. 5
There are methods disclosed in Japanese Patent Publication No. G-43247 and Japanese Patent Publication No. 54-17360, and methods of increasing the mold temperature.

[Problem to be solved by the invention] However, these methods have advantages and disadvantages.

In other words, the method of using fluorocarbons has an environmental problem in that the fluorocarbons destroy the ozone layer, and the method of lowering the number of functional groups in the polyol requires a longer curing time for the foam and significantly deteriorates the compression set, making it impractical. poor. Methods of molding polyurethane foam using a one-shot method using a polyether polyol with a large amount of oxyethylene moieties, and methods of increasing the mold temperature, result in poor foaming stability and molding defects such as cracks, resulting in the production of polyurethane foam Molded products of Ft. cannot be obtained.

[Means for Solving the Problems] The present inventors have solved these problems and reduced the mold temperature to 35
As a result of intensive studies on a polyol composition suitable for producing polyurethane foam with good moldability and soft hardness over a wide range of temperatures from °C to 60 °C, and a method for producing polyurethane foam, the present invention was developed. reached.

That is, the present invention provides: (a) a polyether polyol having a functional group number of 2 or more and a molecular weight per hydroxyl group of 800 to 1700; and (b) a polyether polyol having a functional group number of 3 or more and a molecular weight per hydroxyl group of 300 to 800. and (c) a polyether polyol with a functional group number of 1 and a molecular weight of 100 to
A polyol composition for flexible polyurethane foam characterized by comprising a monool of 2000: a polymer polyol comprising the above polyol composition and a vinyl monomer polymer, the polymer comprising (a), (b) and (
c) A polymeric polyol composition obtained by polymerizing a vinyl monomer in at least one of the above; and a desorbing polyisocyanate and a polyol are reacted in the presence of a catalyst, a blowing agent, and a foam stabilizer to form a flexible polyurethane. In the method for producing foam, as the polyol,
A method for producing a flexible polyurethane foam, characterized in that the composition according to any one of Item 3 and/or the composition according to Claim 4 is used.

Examples of the polyether polyol (a) used in the present invention include compounds having a structure in which an alkylene oxide is added to a compound having two or more active hydrogen atoms (eg, alcohols and amines).

Examples of alcohols include dihydric alcohols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and neopentyl glycol, and glycerin.
trimethylolpropane, pentaerythritol,
Examples include trihydric or higher alcohols such as sorbitol and sugar.

Amines include ammonia; alkanolamines such as mono- and triethanolamine, impropaturamine, and aminoethylethanolamine;
+-C29 alkylamines; C2-C6 alkyl diamines such as ethylene diamine and hexamethylene diamine; polyalkylene polyamines such as diethylene triamine and triethylene tetramine; aniline, phenylene diamine, diamino]-lueno, quinolyl diamine, methylene dianiline , aromatic amines such as diphenyl ether diamine; alicyclic amines such as isophorone diamine and nochlorohexylene diamine; aminoethylpiperazine, and heterocyclic amines described in UB 55-21044. Two or more of these active hydrogen atom compounds may be used in combination. Among these, alcohols are preferred.

As the alkylene oxide to be added to the above active hydrogen atom compound, ethylene oxide (hereinafter abbreviated as EO)
, propylene oxide (hereinafter abbreviated as PO), 1. 2
-1. Examples include 3-L 4- 2<3-butylene oxide, etc., and combinations of two or more thereof, preferably EO and PO in combination, and the addition format may be block addition or random addition.

The number of functional groups in polyol (a) is y;'> 2 or more,
Preferably 2.5 to 4. It is 0. If the number of functional groups is less than 2, the compression set will be poor and the curing time will be long.

The number of molecules per hydroxyl group in polyol (a) is usually 8
00-1700. Preferably it is 900-1500. If the molecular weight per hydroxyl group is less than 800, the foam will collapse and the compression set will be poor, and if it exceeds J700, the compression set will be poor and the curing time will be longer.

The polyether polyol (b) includes a structure in which an alkylene oxide is added to a compound having three or more active hydrogen atoms (for example, alcohols and amines).

Examples of alcohols include trihydric or higher alcohols such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, and sucrose.

Amines include ammonia; alkanolamines such as mono- and triethanolamine, isopropanolamine, and aminoethylethanolamine;
C2 such as ethylenediamine and hexamethylenediamine
~C6 alkylenediamine; diethylenetriamine,
Polyalkylene polyamines such as triethylenetetramine; Aromatic amines such as aniline, phenylene diamine, diaminotoluene, xylylene diamine, methylene dianiline, diphenyl ether diamine; Alicyclic amines such as isophorone diamine and cyclohexylene diamine; Aminoethyl Piperazine, Special Publication 55-2
Examples include the heterocyclic amines described in No. 1044. Two or more of these active hydrogen atom compounds may be used in combination. Among these, alcohols are preferred.

The alkylene oxide to be added to the active 1 (1 hydrogen atom compound) is EOl PO, J, 2-1,
3-1. 4-2. Examples include 3-butylene oxide and the like, and combinations of two or more of these, preferably for 01 of EO and PO, and the addition format may be block addition or random addition.

The number of functional groups in the polyol (b) is usually 3 or more, preferably 3.0 to 6.0. If the number of functional groups is less than 3, compression set will be poor.

The molecular weight per hydroxyl group (p1) of polyol (b) is usually 300 to 800, preferably 400 to 700. If the molecular weight per hydroxyl group is 300, the foam will collapse, and if it exceeds 800, compression set will occur. Deteriorate.

Examples of the monol (c) include compounds having a structure in which an alkylene oxide is added to a hydrocarbon alcohol having one active hydrogen atom or a phenol. Among these, preferred is a compound having a structure in which an alkylene oxide is added to a hydrocarbon alcohol.

Examples of hydrocarbon alcohols include monohydric alcohols having 1 to 18 or more carbon atoms (e.g., methanol, ethanol, n- and 15O-propanol, phthanol,
Examples include aliphatic, alicyclic and aromatic alcohols such as 2-ethylhexyl alcohol, cyclohexyl alcohol, and benzyl alcohol.

Examples of phenols include monohydric phenols (eg, phenol, alkylphenols such as nonylphenol), and the like.

Examples of the alkylene oxide to be added to the above active hydrogen atom compound include EO, POll, 2-1゜4-2.
Examples include 3-butylene oxide and a combination of two or more thereof, preferably EO and PO, and the addition format may be either block or random.

Molecule I of monool (c) usually has a molecular weight of 100 to 2000, preferably 400 to 1600. If the number of molecular groups is less than 100, the foam will collapse, and if it exceeds 2,000, the foam hardness, which is the object of the present invention, will not soften, and when the mold temperature is raised (45°C to 60°C), the molded foam will have loose skin, Cracks occur.

The polyol composition of the present invention consists of the above (a), (b) and (c). The amount of each is usually 40 to 95%, preferably 5% (a), based on the weight of the total polyol composition.
0-80%, (b) usually 40-5%, preferably 3
(c) is usually 20-0.1%, preferably 15-3%.

If (a) is less than 40%, impact resilience and compression set will be poor, and if it exceeds 95%, moldability will be poor and the foam hardness will be difficult to soften. When (b) is 5% ungrooved, the compression set becomes poor, and when it exceeds 40%, cracks appear,
Resilience deteriorates. If (c) is 0.1% ungrooved, the foam hardness becomes soft<<, and if the mold temperature is raised, cracks will occur, and if it exceeds 20%, the compression set will be poor and the curing property will be poor.

A polymer polyol composition comprising the polyol composition of the present invention and a vinyl monomer polymer also belongs to the present invention.

The polymer polyol composition is one in which vinyl monomers such as acrylonitrile and styrene are polymerized and stably dispersed in at least one of 1. (a), (b) and (c) in the presence of a radical initiator, The content of vinyl polymer in the polymer polyol is generally 45% or less, preferably 30% or less, based on the total polymer polyol weight.

The present invention also includes a method for producing flexible polyurethane foam by reacting an organic polyisocyanate with the above polyol composition and/or polymer polyol composition in the presence of a catalyst, a blowing agent, and a foam stabilizer.

As the organic polyisocyanate used in the present invention, those commonly used for polyurethane are used. For example, aromatic polyisocyanate having 6 to 20 carbon atoms (excluding the carbon number in the NGO group) [2,4-2,E3-) lylene diisocyanate (TDI), crude TDL 2.4-
- 4,4-diphenylmethane diisonanate (MD
I), crude MDI [crude diaminophenylmethane (a condensation product of formaldehyde and an aromatic amine (aniline) or a mixture thereof; a mixture of diaminodiphenylmethane and a small amount (e.g. 5-20% by weight) of a trifunctional or higher functional polyamine) polyisonoanate obtained by phosgenation of ); polyaryl polyisonoanate (PAP
Aliphatic isonanates having 2 to 18 carbon atoms (hexamethylene diisocyanate, lylene diisocyanate, etc.); Alicyclic polyisocyanates having 4 to IS (inlon diisocyanate, dicyclohexylene isonanate, etc.); Aroaliphatic polyisocyanates having 8 to 15 carbon atoms [such as xylylene diisocyanate; modified products of these polyisocyanates (urethane group, carbodiimine group, allophanate group, urea group, biuret group, uretdione group, uretonimine group, isocyanurate group) , oxazolidone group-containing modified products, etc.); polyisocyanates other than the above described in Japanese Patent Application No. 199180/1980; and mixtures of two or more of these. Among these, preferred are 2.4
- and 2.6-TDI, and mixtures of these isomers.

As the foam stabilizer, those for soft urethane foam are usually used. For example, dimethylroxane-based foam stabilizers are mentioned, and specifically, Nippon Unicar Co., Ltd.
-294A etc.

Any known catalyst can be used. Specifically, gold R 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 phenoxide, etc. )-tertiary amines (e.g. triethylamine, triethylenediamine, N-methylmorpholine, dimethycyleaaminomethylphenol, pyridine, etc.); quaternary ammonium bases (e.g. tetraethylammonium hydroquine, etc.); imidazoles (e.g. imidazole, (2-ethyl-4-methylimidazole, etc.); and metal compounds such as tin and antimony (eg, tetraphenyltin, tributylantimony oxide, stannath octoate, etc.). Among these, preferred are metal compounds such as tin and antimony, and tertiary amines.

As the blowing agent, those commonly used for polyurethane foam can be used, and water alone or a combination of long-term methylene chloride is preferably used, and water alone is preferable.Also, according to the present invention, foams with soft hardness can be obtained without using fluorocarbons. If you need a softer material that can be replaced, you can also use Freon.

In the production method of the present invention, when a polyol composition and a polymer polyol composition are used together, the amount of the polymer polyol composition used is usually 50 parts or less, preferably 20 parts or less, when the total of both is 100 parts by weight. It is.

In the present invention, the amounts of each additive (foaming agent, foam stabilizer, and catalyst) to be used per 1 part of 100 ml of polyol are as follows.

There is no particular restriction on the amount of blowing agent used, but in the case of water, it is usually 2
-8 parts, preferably 3-7 parts. The amount of foam stabilizer used is usually 0. 5 to 5 parts, preferably 1 to 3 parts. The amount of catalyst used is usually 0.01 to 3 parts, preferably 0.0 parts.
5 to 2 parts.

The usage amount of Isona Fuichito is usually 70~ as the NGO index.
120, preferably 80-110.

The production method of the soft polyurethane 1 in the present invention can be carried out by a so-called slab, hot cure or cold cure method, but among these, the slab and hot cure method is preferred, and the hot cure method is particularly preferred.

In the hot cure one-way method, the mold temperature is 35 to 60°C.
It has good moldability over a wide range of temperatures, and the mold temperature can be selected depending on the desired density and manufacturing conditions.

[Examples] Hereinafter, the present invention will be further explained with reference to Examples, but the present invention is not limited thereto.

Examples 1 to 6, Comparative Examples 1 to 2 After foaming urethane foam in a mold using the foaming recipe shown in Table 1.2 (numbers in the table indicate parts by weight),
The urethane foam was taken out of the mold to obtain a flexible polyurethane foam, and its physical properties were added for t.

(Development conditions) Mold shape 2 300mmX 300mmX I O0m
Material: Aluminum Mold temperature: 35~60″C Mixing method: Low pressure machine mixing Raw material temperature: 25
±2°C Cure conditions: 150″C x 10 minutes (raw materials used) Polyol (a)-1: PO-EO adduct of glycerin, molecular weight 3000° Polyol (b): PO adduct of pentaerythritol, molecular weight 2000° Monool (c)-1: PO-E0 adduct of n-butanol, molecular weight 600° Monool (c)-2: PO-E0 adduct of n-butanol, molecular weight 1200° T-80: Manufactured by Nippon Polyurethane Co., Ltd. Polymer polyol composition 1 (abbreviated as P-1): 1 polyol (a)-1so azobisisoisoben Tyronitrile 1
4 parts of acrylonitrile and 4 parts of styrene are polymerized and dispersed in the presence of 1 part of acrylonitrile and 4 parts of styrene.

The abbreviations in the table are as follows.

DABCO33LV: )Lyethylenediamine 33%
Dipropyrenoglycol solution 5RX-294A: Toray/Rikonoa Kiku dimethyl chloride/based foam stabilizer The measurement method for foam properties is JIS KG401, and the units are core density...kg/m3 25% ILD...Kg/314cm2 Compression permanent Strain...(A) Repulsion elasticity...(%).

Moldability was determined by visually observing the presence or absence of loose skin and cracks.

Table 1 Table 2 "Effects of the invention" By using the polyol composition for flexible polyurethane foam of the present invention, a low boiling point halogenated hydrocarbon blowing agent such as Freon 11, which is essential in conventional polyether polyols, can be used. By using only water as a foaming agent, it is possible to obtain soft polyurethane foam with the same hardness as conventional foams, and it also solves the problem of environmental destruction. However, it is possible to produce polyurethane foam with good moldability, low density, and soft foam hardness.

prisoner

Claims (1)

[Scope of Claims] 1. (a) A polyether polyol having a functional group number of 2 or more and a molecular weight per hydroxyl group of 800 to 1,700; (b) A polyether polyol having a functional group number of 3 or more and a molecular weight per hydroxyl group of 800 to 1,700; 30
A polyol composition for flexible polyurethane foam, comprising a polyether polyol having a molecular weight of 0 to 800 and (c) a monool having a functional group number of 1 and a molecular weight of 100 to 2,000. 2. The amount of (b) is 40 to 40% by weight of the total polyol composition.
A composition according to claim 1, wherein the composition is 5%. 3. (c) is a compound having a structure in which alkylene oxide is added to a hydrocarbon alcohol having one active hydrogen atom, and the amount of (c) is 2% based on the weight of the total polyol composition.
The composition according to claim 1 or 2, wherein the content is 0 to 0.1%. 4. A polymer polyol comprising the polyol composition according to any one of claims 1 to 3 and a vinyl monomer polymer, the polymer comprising at least one of (a), (b) and (c). A polymer polyol composition obtained by polymerizing a vinyl monomer. 5. Organic polyisocyanate and polyol as a catalyst,
In a method for producing flexible polyurethane foam by reaction in the presence of a blowing agent and a foam stabilizer, the composition according to any one of claims 1 to 3 and/or the composition according to claim 4 is used as a polyol. A method for manufacturing flexible polyurethane foam.