JPH0284420A - Polyurethane foam for interior core material and laminate for interior material using the same foam - Google Patents

Abstract

PURPOSE:To obtain the title polyurethane foam having each specified density, compressive strength and closed cell content and outstanding in sound absorptivity, low-temperature moldability and self-retainability by blending a specific polyol, water, foam stabilizer and catalyst followed by adding a specific polyisocyanate component to the system. CONSTITUTION:(A) A mixed polyol comprising (1) a polyol 20-50mgKOH/g in OH value, prepared by polymerization of an ethylenic unsaturated monomer in a polyether polyol 2-4 in the number of functional group, made up of a polymer-dispersed polyol and active hydrogen compound of polyol 2-4 in the number of functional group, (2) a second polyol >=3 in the number of functional group and 400-800mgKOH/g in OH value, and (3) an active hydrogen compound >=2 in the number of functional group and <=200 in molecular weight, at the weight ratio: (1):(2):(3)=(50-90):(10-50):(0.3-10), (B) water, (C) a foam stabilizer, (D) a catalyst, and, if needed, (E) a halogenated alkane-based foaming agent, are mutually blended. The resultant blend is then incorporated with a polyisocyanate component containing >=30wt.% of polyphenylenepolymethylene polyisocyanate, thus obtaining the objective polyurethane foam.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polyurethane foam that is lightweight and has excellent sound absorption, low-temperature moldability, and self-retention properties, and a laminate using this polyurethane foam as a core material.

[Conventional technology]

In recent years, efforts have been made to enhance the functionality of various interior materials with the aim of enhancing and rationalizing livability. For ceiling materials, polyurethane foam with an open-cell structure with good sound absorption properties is being used instead of conventional materials such as cardboard, glass wool, polyethylene foam, or polystyrene foam to improve sound absorption, moldability, and appearance. Molded products with a core structure are increasingly being used.

These products are manufactured by: (1) a method in which polyurethane foam foam material is poured into a mold in which a gelatinous mat or surface material is placed, and foaming, curing, and molding are performed simultaneously in the mold; (2)
A method in which a soft porous material is impregnated with a curable resin raw material, and the reinforcing material and the porous material are bonded together and the porous material is cured by heating, and at the same time/or thereafter, compression molding is performed by heating.

Alternatively, (3) a method has been proposed in which a pre-manufactured foam is processed into a sheet shape and then bonded to a reinforcing material with an adhesive, and simultaneously/or subsequently heat-formed. For example, in the method (1) above, The foam tends to become closed cells and becomes heavy. In method (2), the manufacturing process becomes complicated and strict process control is required to maintain the stability of the raw materials. Furthermore, as shown in British Patent Nos. 1,527,290 and 2,028,714, method (3) requires relatively high temperatures to form the foam, and there are limits to the surface materials that can be used due to energy costs and heat resistance. There are problems such as.

[Problem to be solved by the invention]

The present invention solves the problems of the conventional technology described above, and provides a polyurethane foam that is lightweight and has excellent sound absorption, moldability, and self-retention properties, and a building material using the polyurethane foam as a core material, particularly a laminated material for automobile ceiling materials. It is about the body and more specifically:
A composite laminate for building materials in which a specific polyurethane foam sheet for the core material, reinforcing material, surface material, etc. are bonded together with an adhesive, and/or pressure molded after bonding, which is not conventional. This solves the problems with the product.

[Means for Solving the Problems] The present inventors have studied the formulation of polyurethane foam for core materials, and have developed a laminated layer particularly suitable for interior materials using a specific polyurethane foam obtained as a core material. The present invention relates to the body, that is, the present invention is as follows.

(1) (a) An active hydrogen compound mixture consisting of a polymer-dispersed polyol obtained by polymerizing an ethylenically unsaturated monomer in a polyether polyol having 2 to 4 functional groups and a polyol having 2 to 4 functional groups, Its OH value is 20-50
mgKOH/g of a polyol, (b) a polyol with a functional group number of 3 or more and an O1 value of 400 to 800 mgKOH/g, and (c) an active hydrogen compound with a functional group number of 2 or more and a molecular weight of 200 or less (a): (b): (c)
= 50-90: 10-50: 0.3-10 (
A polyisocyanate component containing 30% by weight or more of polyphenylpolymethylene polyisocyanate is added to a mixed component containing polyol, water, a foam stabilizer, a catalyst, and, if necessary, a halogenated alkane blowing agent, in a proportion of (weight ratio). density 20~35kg/m3, compressive strength 0.3
0 to 0.90 kg/cm", a closed cell ratio of 4 to 12%, an open-cell polyurethane foam for interior material core materials that has sound absorption properties, low-temperature moldability, and excellent self-retention properties.

(2) A method for producing polyurethane foam as described in (1).

(3) The polyurethane foam described in (1) is used as a core material, and a reinforcing material and, if necessary, an organic or inorganic cloth-like or film-like surface material are bonded to one or more sides of the core material with an adhesive. A laminate for interior materials.

In producing the specific polyurethane foam of the present invention,
(Polymer-dispersed polyols in Group 81 are produced by methods known in the art, such as Japanese Patent Publication No. 44-8230 and Japanese Patent Publication No. 52-3439.) As polyols, water, propylene glycol, dipropylene glycol, tripropylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, 1.3
- One or two types of active hydrogen compounds such as butanediol, 14-butanediol, glycerin, trimethylolpropane, penquerythritol, monoethanolamine, jetanolamine, triethanolamine, α-methylglucoside, ethylenediamine, tolylenediamine, etc. Alkylene oxides such as propylene oxide and ethylene oxide may be added alone or in combination with two or more of them to the above mixture.

Examples of ethylenically unsaturated monomers used in the production of the polymer-dispersed polyol are acrylonitrile, styrene, methyl methacrylate, etc., and mixtures of one or more of these monomers are used.

The polyol used to produce the above polymer-dispersed polyol and the polyol mixed into the polymer-dispersed polyol may be of the same kind or different kinds, and the mixing ratio varies depending on the amount of polymer in the polymer-dispersed polyol, but the total polyol The amount of polymer-dispersed polyol contained therein is usually preferably 35 to 45% by weight.

By using this polymer-dispersed polyol, the foam becomes an open-cell structure. If a polymer-dispersed polyol is not blended, the number of closed cells will increase, resulting in various disadvantages.

(Polyols belonging to Group 81 are (a): (b):
(c) = 50~90:10~50:0.3~10
The weight ratio (the same applies hereinafter) is 50 to 90 parts by weight, preferably 60 to 85 parts by weight.

If the amount is less than 50 parts by weight, the resulting foam will be hard and the closed cell ratio will be high. However, problems such as shrinkage after foam formation, cracking during molding, deterioration of mold reproducibility during molding, and further deterioration of sound absorption properties occur.

If the amount exceeds 90 parts by weight, the foam will be soft and the self-retention properties (bending strength) of the resulting laminate will be poor.

Polyols belonging to the above group (a): (b)
): The weight ratio of (c) is 10 to 50 parts by weight, preferably 12 to 40 parts by weight.

If the amount is less than 10 parts by weight, the foam will be soft and the self-retention properties of the laminate will be poor; if the amount exceeds 50 parts by weight, the foam will be hard and the closed cell ratio will be high, and when producing the laminate,
Inconveniences such as cracking of the foam occur.

Examples of polyols belonging to group (b) are glycerin, pentaerythritol, 1,2,6-hexandriol,
Monoethanolamine, jetanolamine, triethanolamine, pentaerythritol, α-methylglucoside, ethylenediamine, tolylenediamine, 4,4
"-Alkylene oxides such as propylene oxide, ethylene oxide, etc. are added alone or to a mixture of two or more of active hydrogen compounds such as diaminodiphenylmethane, diethylenetriamine, sorbitol, sucrose, etc. to produce a compound with a valence of 0! 400~ 800 polyol.

The active hydrogen compounds belonging to group (c) are the above-mentioned (a):
The weight ratio of (b):(c) is 0.3 to 10 parts by weight, preferably 0.5 to 5 parts by weight. 0.3
If the amount is less than 1 part by weight, there will be problems such as collapse during formation of foam, and even if foam is obtained, it will be soft and unsuitable for use in the present invention. If the amount exceeds 10 parts by weight, there will be a large number of closed cells, resulting in disadvantageous phenomena such as shrinkage upon returning to room temperature after foam formation.

Examples of active hydrogen compounds of group (c) are ethylene glycol, propylene glycol, alkylene oxide adducts such as aniline, monoethanolamine, jetanolamine, triethanolamine, pentaerythritol, ethylenediamine, tolylene diamine, and the like. These compounds may be used alone or in combination of two or more.

As the blowing agent, in addition to water, fluorinated hydrocarbons, low-boiling chlorinated hydrocarbons, low-boiling hydrocarbons, etc. are used. Typically, water and optionally fluorinated hydrocarbons are used in combination with water. The amount of water used is 3 to 7 parts by weight per 100 parts by weight of polyol.

The foam stabilizer is a polysiloxane copolymer, such as L-3550, L-3600, L-3601, manufactured by Nippon Unicar Co., Ltd.
Sl+-190, 511-194, 511-200 manufactured by Toray Silicone, such as Shi-5410 and L-5420
There are also F-122 and F-305 manufactured by Shin-Etsu Chemical Co., Ltd.

The amount used is 0.00 parts per 100 parts by weight of the polyol mixture.
It is 3 to 1.5 parts by weight.

Secondary amines such as triethylenediamine, tetramethylhexamethylenediamine, dimethyldichlorohexylamine, and dimethylethanolamine, and tin compounds such as tin octoate and dibutyltin dilaurate are used as catalysts. The amount used is usually 0.1 to 3.0 parts by weight per 100 parts by weight of the polyol mixture.

If the amount of polyphenylpolymethylene polyisocyanate in the polyisocyanate component is less than 30% by weight, the appropriate hardness required for the core material of the laminate cannot be obtained, and in some cases, phenomena such as collapse may occur during foam formation. There is. The preferred amount is 50% by weight or more.

NGO in the above polyisocyanate and (a), [with])
, (c) and the molar ratio with the amount of active hydrogen in water (NCO/
The molar ratio of active hydrogen) is preferably 0.90 to 1.20. When the molar ratio exceeds 1.20, the foam becomes hard and brittle, and cracks may occur during molding. Also, 0
If it is less than 90°, sufficient hardness will not be imparted to the foam.

The polyurethane foam of the present invention contains, in addition to the polyol mixture and polyisocyanate, a blowing agent as described above,
A catalyst and a foam stabilizer are used, and if necessary, a flame retardant, a filler, an antioxidant, a fungicide, a coloring agent, etc. are also used.

When forming polyurethane, the mixing of raw materials is as follows:
The low-pressure foaming method, in which raw materials are mixed and stirred while feeding them at a constant speed into a chamber with a rotating stirrer, or the high-pressure foaming method, in which high-pressure raw materials are mixed by colliding with each other, can be used. It can also be produced by a so-called hand mix method in which the ingredients are weighed into one container and then mixed using a stirrer rotating at high speed.

The laminate of the present invention is manufactured by processing the polyurethane foam produced by the above method into a sheet shape, and bonding a reinforcing material such as glass fiber and an organic or inorganic cloth or film surface material with an adhesive. be done.

The thickness of polyurethane foam is usually 10 to 50 mm.

As the reinforcing material, short or long fibers such as glass may be used as they are or processed into a mat or cloth shape.

As the surface material, which may be used as necessary, organic or inorganic materials, nonwoven fabrics, films, etc. are used.

The thickness of the reinforcing material and the surface material is usually 1 to 3 layers, and the reinforcing material and the surface material are usually bonded to one or two opposing surfaces of the polyurethane foam core material, but may also be bonded to other surfaces if necessary.

The adhesive can be either a solvent type or an emulsion type, and a thermosetting type or a thermoplastic type, but an emulsion type or thermosetting type is preferable from the viewpoint of the molding atmosphere, the heat resistance of the surface material, the environment in which the product is used, etc. .

Adhesion and pressure molding of the polyurethane foam, reinforcing material, and surface material are usually carried out under heating, although processing at room temperature is possible depending on the type of adhesive.

The processing temperature varies depending on the type of adhesive, but it is better not to use high temperatures to avoid deterioration of the urethane foam, surface material, etc. The polyurethane foam used in the present invention usually has 6
Molding processing is possible at 0'C-120'C. Further, the compression time is usually 2 to 5 minutes.

Apply the adhesive to the surface of the polyurethane foam with a sprayer, brush, or roll. The adhesive is the foam and reinforcement,
and apply an amount that will ensure sufficient adhesion of the surface material.

After applying an adhesive to the polyurethane foam and laminating a reinforcing material and, if necessary, a surface material, a laminate is obtained by heat-compressing the seal. At this time, if a mold having a desired shape is used, the shape can be transferred and imparted to the laminate.

〔Example〕

The present invention will be explained in more detail below with reference to Examples and Comparative Examples.

Example 1 40 parts by weight of polyol (a-2), polyol (a-2)
3) 30 parts by weight, 30 parts by weight of polyol (b-1),
Polyol (c-IH, 0 parts by weight, polyol (c-2
) 5 parts by weight of water to a polyol mixture consisting of 2 parts by weight,
A mixture obtained by adding 0.5 parts by weight of a foam stabilizer (L-3600 manufactured by Nippon Unicar Co., Ltd.) and 0.5 parts by weight of N, N, N', N' tetramethylhexamethylenediamine (abbreviated as TMIIDA) and stirring the mixture. 109 parts by weight and isocyanate Al37
．． Three parts by weight were mixed for 10 seconds using a stirrer at 4000 revolutions per minute, and poured into a cardboard box measuring 20 cm in length and width. The mixture started foaming in about 15 seconds, and the foaming stopped after about 2 minutes and 30 seconds. - After standing for day and night, the properties of the obtained foam were measured and were as shown in Table 1.

Example 2 The foam obtained in Example 1 was cut to a thickness of 10 mm, and an acrylic emulsion adhesive with a solid content of 50% was coated on both sides with a roll at a total of 300 g/m2, and the length was 50 nm + m.
100g/m” of glass fiber on each side, and a thickness of 1
One layer of polyester fiber non-woven fabric with a weight of 70 g/m'' was placed on both sides and sandwiched between two aluminum plates with a partially textured pattern heated to 110°C with an 8 mm spacer. After 2 minutes. It was taken out and cooled to obtain a laminate in which the uneven pattern was accurately copied.

The physical properties of the laminate were as listed in Table 1.

Examples 3 to 7 Foams were prepared in the same manner as in Example 1 by changing the type of polyol and the amount of blowing agent, and then a laminate was obtained in the same manner as in Example 2.

The formulation of the raw materials, the obtained foam, and the properties of the laminate were as shown in Table 1.

Comparative Examples 1 to 3 Foams and laminates were produced in the same manner as in Examples 1 and 2 except for using different polyols.

The physical properties of the obtained foam and the laminate using the foam were as shown in Table 1.

Isocyanate A Polyol (a Polyol (a Polyol (a Polyol (b :Polyphenylpolymethylenebo Liisocyanate 60% Containing so-called polymer link Ml) ■ = Glycerin and propylene oxide side and ethylene oxide Hydroxyl value: 34mg KOII/g polyether polio Rules.

:Ac in polyol (a-1) Combine rylonitrile and methylene 011 obtained by combining Polyol with a value of 28 mg KOII/g.

: A polyether polyol with a hydroxyl value of 28 mgKOH/g made by adding propylene oxide and ethylene oxide to propylene glycol.

；Glycerin and propylene oxide Hydroxyl group formed by adding a side Polyether polyol with a value of 560 mgKOH/g.

Polyol (b-2): A polyether polyol with a hydroxyl value of 750 mgKOH/g formed by adding propylene oxide to ethylene diamine.

Polyol (b-3): A polyether polyol with a hydroxyl value of 450 mg KO II/g, which is obtained by adding propylene oxide to a mixture of sucrose and glycerin.

Polyol (c-1) 'jetanolamine.

Polyol (c-2): Triethanolamine.

Polyol (d): Polyether polyol with a hydroxyl value of 160 mg KO1 (/g) by adding propylene oxide to propylene glycol.

TMIIDA: N,N,N',N'-tetramethylhexamethylenediamine.

Freon-11 nitrichloromonofluoromethane.

〔Effect of the invention〕

According to the present invention, a lightweight polyurethane foam with an open cell structure suitable as a core material can be obtained, and a laminate using this polyurethane foam as a core material can be molded without impairing the delicate texture of the surface material etc. It's extremely easy.

In addition, the obtained laminate has appropriate strength and excellent self-retention properties, and is excellent as an interior material such as a ceiling material for vehicles such as automobiles or various buildings.

Claims (3)

[Claims] (1) (a) An active hydrogen compound mixture consisting of a polymer-dispersed polyol obtained by polymerizing an ethylenically unsaturated monomer in a polyether polyol having a functional group number of 2 to 4 and a polyol having a functional group number of 2 to 4, Its OH value is 20-50mg
KOH/g polyol, (b) number of functional groups 3 or more, OH value 400 to 800 mgK
OH/g polyol and (c) active hydrogen compound with functional group number of 2 or more and molecular weight of 200 or less (a):(b):(c)=50-90:10-5
Polyol containing in a ratio of 0:0.3 to 10 (weight ratio),
Density: 20 to 35 kg/m, obtained by adding a polyisocyanate component containing 30% by weight or more of polyphenylpolymethylene polyisocyanate to a mixture of water, a foam stabilizer, a catalyst, and, if necessary, a halogenated alkane blowing agent.
An open-cell polyurethane foam for interior material core materials with a compressive strength of 0.30 to 0.90 kg/cm2, a closed cell ratio of 4 to 12%, sound absorption properties, low-temperature moldability, and excellent self-retention properties. (2) A method for producing polyurethane foam according to claim 1. (3) The polyurethane foam according to claim 1 is used as a core material, and a reinforcing material and, if necessary, an organic or inorganic cloth-like or film-like surface material are bonded to one or more surfaces of the core material with an adhesive. A laminate for interior materials.