JPH08108509A - Structural material, manufacture thereof and interior finish material for vehicle - Google Patents

Abstract

PURPOSE: To provide the light weight, the rigidity and to mold at a low temperature or the ambient temperature by molding of sole coconut fiber, blended fiber of the coconut fiber and other fiber, and cured material of polyvalent phenol aldehyde condensate. CONSTITUTION: The structural material is formed in a predetermined shape of sole coconut fiber or mixed fiber of coconut fiber and other fiber, and cured material of polyvalent phenol aldehyde condensate for bonding the fiber. With the structural material used as a reinforcing material, it is laminated on a base material 1 such as synthetic resin foamed material, etc., and used, for example as an interior finish material for a vehicle. The material 1 is, for example, formed by setting a facing material 2 obtained by lining polyvinyl chloride leather with polypropylene foamed sheet coated at the rear surface with polyester hot-melt adhesive 3, vacuum press-bonding the material 2 to the front surface of the material 1, and then pressing it. Thus, a door trim 7 for a vehicle which has a light weight, high rigidity and excellent heat resistance is, for example, obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a structural material used as an interior material for a vehicle such as an automobile and a building material.

[0002]

2. Description of the Related Art As a structural material of this type, a synthetic resin, glass fiber, wood fiber, recycled fiber or the like is mixed with a phenol resin as a binder, and the mixture is heat-molded into a predetermined shape and the phenol resin is cured. Is provided.

[0003]

However, the curing temperature of the phenol resin as a binder is a high temperature of about 200 ° C., the efficiency of heat energy in the manufacturing process is poor, and the heat resistance of polyvinyl chloride leather or polypropylene nonwoven fabric is low. It is difficult to superimpose an outer covering material or the like having poor properties at the same time and to form the fibers at the same time, and the fibers or the like may be deteriorated due to the high temperature during the forming. Furthermore, the cured product of the phenol resin was too hard and had brittle defects. Further, in the conventional structural material, it is necessary to increase the density in order to obtain rigidity, which increases the weight of the structural material. Especially, when the structural material is used as a vehicle interior material, this is a problem. It becomes an important issue.

[0004]

[Means for Solving the Problems] As a means for solving the above-mentioned conventional problems, the present invention comprises a coconut fiber alone or a mixed fiber of a coconut fiber and another fiber, and a polyvalent resin which binds the fiber. A structural material comprising a cured product of a phenol / aldehyde condensate, which is molded into a predetermined shape. The polyhydric phenol / aldehyde-based condensate is a condensate of a polyhydric phenol with an aldehyde and / or an aldehyde donor, or with a polyhydric phenol,
It is a cocondensation product of a monohydric phenol and / or amino compound monomer with an aldehyde and / or an aldehyde donor. The structural material is a palm fiber alone or in a mixed fiber of a palm fiber and other fibers, the polyhydric phenol / aldehyde condensate is present with or without the addition of a curing agent, and heat molded into a predetermined shape. It is produced by a method of curing the condensate. Further, the present invention provides a vehicle interior material comprising the above structural material and a vehicle interior material obtained by laminating the above structural material on a base material such as a synthetic resin foam as a reinforcing material.

The present invention will be described in detail below. [Polyhydric Phenol] In the polyhydric phenol / aldehyde condensate of the present invention, the polyhydric phenol used for condensation with the aldehyde is resorcin, alkylresorcin, pyrogallol, catechol, alkylcatechol,
Hydroquinone, alkylhydroquinone, phloroglucin, bisphenol, is a polyhydric phenol such as dihydroxynaphthalene, or a mixture of two or more,
Of these polyhydric phenols, preferred is resorcin or alkylresorcin, and particularly preferred is alkylresorcin, which has a faster reaction rate with aldehyde than resorcin. Examples of the above alkylresorcin include 5-methylresorcin, 5-ethylresorcin, and 5
-Propylresorcin, 5-n-butylresorcin,
4,5-dimethylresorcin, 2,5-dimethylresorcin, 4,5-diethylresorcin, 2,5-diethylresorcin, 4,5-dipropylresorcin, 2,5-
Dipropylresorcin, 4-methyl-5-ethylresorcin, 2-methyl-5-ethylresorcin, 2-methyl-5-propylresorcin, 2,4,5-trimethylresorcin, 2,4,5-triethylresorcin, etc. is there. The polyhydric phenol mixture obtained by dry distillation of Estonian oil shale is inexpensive, and contains a large amount of various highly reactive alkylresorcins in addition to 5-methylresorcin, and is therefore the most preferable polyhydric phenol raw material for the present invention. .

[Aldehyde and / or Aldehyde Donor] The aldehyde and / or aldehyde donor used in the present invention means an aldehyde and / or a compound which produces and provides an aldehyde when decomposed,
Formalin, formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-
Examples thereof include butyraldehyde, caproaldehyde, allyl aldehyde, benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, saltylaldehyde and the like, or a mixture of two or more thereof.

[Acid catalyst and alkali catalyst] In the present invention, in the condensation of a polyhydric phenol with an aldehyde and / or an aldehyde donor, or with a polyhydric phenol and / or a polyhydric phenol condensate and a monohydric phenol. And / or during the co-condensation of the monohydric phenol-based condensate and / or the amino-based compound monomer and / or the amino-based condensate with the aldehyde and / or the aldehyde donor, if necessary, an acid catalyst or an alkali catalyst is added. . The amount thereof added is a few wt% or less of the total amount of the polyhydric phenol, monohydric phenol and / or amino compound monomer, and usually 6 wt% (hereinafter simply referred to as%) or less. Examples of the acid catalyst include hydrochloric acid, sulfuric acid, orthophosphoric acid, boric acid, oxalic acid, formic acid, acetic acid, butyric acid, benzenesulfonic acid, phenolsulfonic acid, paratoluenesulfonic acid, naphthalene-α-sulfonic acid, naphthalene-β.
-Inorganic or organic acids such as sulfonic acid, or esters of organic acids such as oxalic acid dimethyl ester, maleic anhydride, acid anhydride such as phthalic anhydride, ammonium chloride,
Ammonium sulfate, ammonium nitrate, ammonium oxalate, ammonium acetate, ammonium phosphate, ammonium thiocyanate, ammonium salts such as ammonium imidosulfonate, monochloroacetic acid and its sodium salt, organic halides such as α, α'dichlorohydrin,
There are triethanolamine hydrochloride, hydrochlorides of amines such as aniline hydrochloride, urea adducts such as salicylate urea adduct, stearic acid urea adduct, heptanoic acid urea adduct, N-trimethyltaurine, zinc chloride and ferric chloride. . Examples of the alkaline catalyst include sodium hydroxide, potassium hydroxide, barium hydroxide, hydroxides of alkaline earth metals such as calcium hydroxide, oxides of alkaline earth metals such as lime, sodium carbonate, Weak acid salts of alkali metals such as sodium sulfite, sodium acetate, sodium phosphate, ammonia, trimethylamine, triethylamine, triethanolamine,
Examples of amines include hexamethylenetetramine and pyridin. You may use together 2 or more types of the said acid catalyst or alkali catalyst.

[Polyhydric phenol / aldehyde condensate]
In the present invention, the polyhydric phenol / aldehyde condensate used as the binder of the palm fiber alone or the mixed fiber of the palm fiber and the other fiber means the polyhydric phenol and the aldehyde and / or the aldehyde donor as described above. A single condensate or a mixture of two or more condensates condensed in the presence of an acid or alkali catalyst or in the absence of a catalyst;
Alternatively, polyhydric phenol and monohydric phenol and / or amino compound monomer and aldehyde and / or aldehyde donor were co-condensed with or without acid or alkali catalyst under heating or at room temperature. The co-condensate is a single or a mixture of two or more, or the above condensate is a single or two or more and the above co-condensate is a single or a mixture of two or more. The condensate or cocondensate may be sulfomethylated with a sulfomethylating agent, and the polyhydric phenol may be complexed with a complexing agent during condensation of the condensate or cocondensate. . Further, in the co-condensation of the polyhydric phenol with the monohydric phenol and / or the amino compound monomer, a part or all of the monomer is replaced with the polyhydric phenol and the monohydric phenol and / or the amino compound monomer with the aldehyde and / or the aldehyde donor. An initial condensation product with the body may be used. Examples of the polyhydric phenol / aldehyde condensate of the present invention include polyhydric phenol / aldehyde condensate, monohydric phenol / polyhydric phenol / aldehyde cocondensate, urea / polyhydric phenol / aldehyde cocondensate, urea / Monohydric phenol / polyhydric phenol / aldehyde co-condensation product, melamine / polyhydric phenol / aldehyde cocondensation product, melamine / monohydric phenol / polyhydric phenol / aldehyde cocondensation product, urea / melamine / polyhydric phenol / aldehyde cocondensation product Compounds, urea, melamine, monohydric phenols, polyhydric phenols, aldehyde co-condensates, etc., or their sulfomethylated products or their complexed products. To obtain a cocondensation product of polyhydric phenol with monohydric phenol and / or amino compound monomer with aldehyde and / or aldehyde donor, polyhydric phenol and / or polyhydric phenol / aldehyde condensate and monohydric phenol And / or a monohydric phenol / aldehyde condensate and / or an amino compound monomer and / or an amino compound monomer / aldehyde condensate are preferably co-condensed with an aldehyde and / or an aldehyde donor if necessary. However, the order of addition and the like is arbitrary and is usually 1 to 24 at room temperature to 100 ° C.
Perform condensation for about an hour. In addition, a polyhydric phenol and / or a polyhydric phenol and / or polyhydric acid are added to a monohydric phenol / aldehyde condensate partially or wholly methylolated or an amino compound monomer / aldehyde condensate partially or wholly methylolated or methylated methylolated. The polyphenol / aldehyde condensate may be added and mixed, and if necessary, an aldehyde and / or an aldehyde donor may be added for cocondensation. When the polyhydric phenol / aldehyde-based condensate of the present invention is condensed or co-condensed, polyhydric phenol, monohydric phenol, amino compound monomer, aldehyde and / or aldehyde donor, condensation catalyst, solvent, sulfomethylating agent, In addition to the complexing agent, as the third component,
If desired, toluene, xylene, coumarone, cyclohexanone, cashew oil, tannins, dammers, shellac, rosin or rosin derivatives, petroleum resin, methanol, ethanol, isopropanol, n-butanol,
Isobutanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerin, furfuryl alcohol, linseed oil, tung oil, castor oil, etc. alone or in combination of two or more as a co-condensation agent or modifier, at the start of the condensation or co-condensation reaction, during the reaction , Or after the reaction ends,
It may be added or modified. Further, the polyhydric phenol / aldehyde condensate of the present invention may be used as a solid powder which is solidified and pulverized by a method such as room temperature or heat evaporation, vacuum evaporation, spray dryer, precipitation drying of resin by salt folding, pH adjustment, etc. Absent.

[Monohydric Phenol] Monohydric phenol co-condensed with the above-mentioned polyhydric phenol means phenol or o-
Cresol, m-cresol, p-cresol, ethylphenol, iso-propylphenol, xylenol, 3,5-xylenol, butylphenol, t-butylphenol, alkylphenols such as nonylphenol, o-fluorophenol, m-fluorophenol, p-fluoro. Phenol, o-chlorophenol,
m-chlorophenol, p-chlorophenol, o-bromophenol, m-bromophenol, p-bromophenol, o-iodophenol, m-iodophenol, p-iodophenol, o-aminophenol, m
-Monophenol substitution products such as -aminophenol, p-aminophenol, o-nitrophenol, m-nitrophenol, p-nitrophenol, 2,4-dinitrophenol, 2,4,6-trinitrophenol and naphthol Such monohydric phenols are used alone or as a mixture of two or more kinds.

[Amino compound monomer] The amino compound monomer which is co-condensed with the above polyphenol is
Means a single or a mixture of two or more amino compounds that form a curable resin through a condensation reaction with an aldehyde such as carbamide and / or aminoazine.
Examples thereof include thiourea, melamine, thiomelamine, dicyandiamide, guanidine, guanamine, acetoguanamine, benzoguanamine, and 2,6-diamino-1,3-diazine.

[Sulfomethyl Agent] The above polyhydric phenol / aldehyde condensate is added with a sulfomethylating agent, if necessary, when the monohydric phenol, polyhydric phenol or amino compound monomer and aldehyde are condensed or co-condensed. However, the condensate or the cocondensate can be partially sulfomethylated to improve the water solubility on the neutral and acidic sides and delay the curing rate. As the sulfomethylating agent, a water-soluble sulfite salt of sulfite, bisulfite or metabisulfite and a quaternary amine or quaternary ammonium such as alkali metal or trimethylamine or benzyltrimethylammonium, or a water-soluble sulfite salt or aldehyde thereof. Examples thereof include hydroxyalkanesulfonic acid such as hydroxymethanesulfonic acid salt and / or alkali metal salt of hydroxyalkanesulfonic acid obtained by the reaction with.

[Complexing Agent] The complexing agent of the polyhydric phenol / aldehyde condensate of the present invention is used for relaxing the reactivity between the polyhydric phenol and the aldehyde,
Examples of such a complexing agent include compounds having a ketone group or an amide group capable of forming a complex with a hydroxyl group of a polyhydric phenol. Examples thereof include acetone and caprolactam. Acetone is particularly preferable. Is.

[Solvent] The polyhydric phenol / aldehyde condensate of the present invention is mainly provided in the form of a solution, and water is usually used as the solvent for the solution.
If necessary, alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol, diethylene glycol, polyethylene glycol and the like, water-soluble organic solvents such as acetone and ketones such as methyl ethyl ketone, or a mixture of two or more thereof can be used. Acetone and the like act as a solvent and, at the same time, as a complexing agent for alkylresorcin, and bring about a milder curing reaction. However, in the present invention, a powdery polyhydric phenol / aldehyde condensate obtained by removing the solvent from the above-mentioned solution by a method such as vacuum drying and pulverizing the obtained dry solid is also used.

[Third component] In addition to the above components, the polyhydric phenol / aldehyde condensate of the present invention may contain amino compounds such as monohydric phenol, polyhydric phenol, urea, thiourea, melamine and thiomelamine, if desired. Monomers, monohydric phenol resins, urea resins, amino resins such as melamine resins, natural rubber and its derivatives, styrene-butadiene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, isoprene rubber, isoprene- Homopolymers of synthetic rubber such as isobutylene rubber, vinyl acetate, vinyl propionate, styrene, acrylic ester, methacrylic ester, acrylonitrile, acrylic acid, methacrylic acid, maleic acid, vinyl chloride, vinylidene chloride, vinylidyne, etc. Or these bi Two or more copolymers of Le monomer,
Polyurethane, polyamide, epoxy resin, butyral resin, polyethylene, polypropylene, vinyl acetate-ethylene copolymer, chlorinated polyethylene, chlorinated polypropylene, emulsion or latex of various synthetic resins such as polyester, polyvinyl alcohol, sodium alginate, Starch, starch derivatives, glue, gelatin, blood meal, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, polyacrylic acid, polyacrylamide and other water-soluble polymers and natural gums, as well as calcium carbonate, talc, gypsum, carbon black, Fillers such as wood flour, walnut flour, coconut husk flour, wheat flour and rice flour, surfactants, higher fatty acids such as stearic acid and palmitic acid, higher alcohols such as palmityl alcohol and stearyl alcohol Esters of fatty acids such as ruthel, butyl stearate, glycerin monostearate, fatty acid amides, natural waxes such as carnauba wax, synthetic waxes, paraffins, paraffin oil, silicone oil, silicone resin, fluororesin, polyvinyl Releasing agents such as alcohol and grease, pigments, dyes, flame retardants, flame retardants, insect repellents, preservatives, anti-aging agents, UV absorbers and DB
A third component such as a phthalate ester plasticizer such as P, DOP or dicyclohexyl phthalate, or another plasticizer such as tricresyl phosphate is added to the polyhydric phenol / aldehyde condensate to co-condensate or mix. The condensate may be modified by, for example,

[Fiber] As the fiber used in the structural material of the present invention, palm fiber alone, or palm fiber and polyester fiber, aliphatic or aromatic polyamide fiber, acrylic fiber, polyethylene fiber, polyolefin fiber such as polypropylene fiber, Vinylidene fiber, polyvinyl chloride fiber, polyurethane fiber, chemical fiber such as vinylon, rayon, cupra and acetate, wood fiber such as pulp and wood chips, natural fiber such as cotton, bamboo fiber, wool and silk, or the above-mentioned chemical fiber and natural There are mixed fibers in which fibers such as organic fibers such as recycled fibers, glass fibers, rock wool, ceramic fibers, and inorganic fibers such as carbon fibers are mixed. The above examples do not limit the present invention. The coconut fiber can be degreased with a caustic soda aqueous solution, a surfactant, a solvent or the like in advance, or can be subjected to a pretreatment such as an ultraviolet treatment.

[Manufacturing of Structural Material] The structural material of the present invention is manufactured mainly by the following method. (1) Polyhydric phenol / aldehyde condensate is mixed as a binder with coconut fiber alone or a mixed fiber of coconut fiber and other fibers, and dried at that temperature or 120 ° C or less, preferably 60 to 100 ° C. After that, heat-molding into a predetermined shape. In this method, a solution of the polyhydric phenol / aldehyde condensate is generally sprayed onto the fibers and mixed. (2) In the method of (1), preforming is performed before heat forming into a predetermined shape, and the preform is heat formed into a predetermined shape. The preform is usually fleece, felt, non-woven fabric,
It is provided in a sheet state such as a fiber knitted fabric. The sheet-shaped preform is generally produced by a fleece making machine, an entanglement machine, a needle punching machine, a paper making machine, a forming machine, a roll press, etc., but if desired, the above drying temperature is used when producing the preform. The preformed product may be used as a prepreg by heating to the above temperature to make the polyhydric phenol / aldehyde condensate that is the binder into a semi-cured state. (3) Palm fiber alone or a mixed fiber of palm fiber and other fibers is molded into a predetermined shape and then impregnated with a solution of a polyhydric phenol / aldehyde condensate as a binder by dipping, spraying, etc. Or 120
It is dried at a temperature of ℃ or below and then heat-cured. (4) A palm fiber alone or a mixed fiber of palm fiber and another fiber is formed into a sheet-shaped preform by the method of (2), and a solution of a polyhydric phenol / aldehyde condensate is dipped into the preform. , Impregnate with spray, etc., and then heat-mold. The amount of the polyhydric phenol / aldehyde condensate mixed or impregnated with the above-mentioned coconut fiber alone or a mixed fiber of coconut fiber and another fiber, or a molded product thereof or a preformed product thereof is usually 100 parts by weight of the fiber (hereinafter simply referred to as "part 1 to 500 parts, preferably 3 to 100 as solid content
Parts, more preferably 5 to 50 parts, usually 5 to 25 parts. The polyhydric phenol / aldehyde condensate is cured by heat molding to bind the fibers. In the production of the structural material, the coconut fiber alone or a mixed fiber of coconut fiber and other fibers may be added to the polyhydric phenol / aldehyde condensate prior to impregnation, or the polyhydric phenol.
After impregnation with aldehyde condensate, phenol resin, amino resin, epoxy resin, urethane resin, xylene resin, ketone resin, polyester resin, alkyd resin,
Silicone resin, thermosetting resin such as furan resin, polyethylene, polypropylene, polyolefin, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, polyethylene terephthalate, One or a mixture of two or more thermoplastic resins such as a thermoplastic acrylic resin, a thermoplastic polyester, a thermoplastic polyamide and a nylon may be mixed or impregnated in a powder form or a solution form.

[Curing of Polyhydric Phenol / Aldehyde Condensate] Curing of the polyhydric phenol / aldehyde condensate of the present invention is carried out with sufficient methylol groups or methylated methylol groups necessary for curing in the molecule of the condensate. If the quantity is included,
It can be cured by heating without adding a curing agent. However, usually, in the case of the above-mentioned aldehyde and / or aldehyde donor, about 0 to 100 parts of the alkylolated triazone derivative is used per 100 parts of the condensate using an aldehyde and / or an aldehyde donor or an alkylolated triazone derivative as a curing agent. In this case, about 0 to 500 parts are added and mixed, and the mixture is cured at room temperature or by heating. When hexamethylenetetramine and / or an alkylolated triazone derivative is added as the above-mentioned curing agent, it usually does not cure for a long period of time at 90 ° C or lower, but it rapidly cures when heated to 130 to 140 ° C or higher. Therefore, when the structural material of the present invention is obtained, when the resin is mixed with the palm fiber alone or a mixed fiber of the palm fiber and other fiber, or the resin is impregnated by dipping, spraying or the like and then immediately molded, at room temperature of the resin. Since a high curing speed of the above may be practically acceptable, an ordinary curing agent such as paraformaldehyde or formalin is used. However, when a long storage period after mixing is required, the above hexamethylenetetramine and / or alkyl It is desirable to use rolled triazone derivatives. Further, an acid catalyst or an alkali catalyst as used in the production of the polyhydric phenol / aldehyde condensate may be added and used together with a curing agent. The amount of the acid catalyst or alkali catalyst added is usually 0.05 per 100 parts of the resin.
It is about 50 parts.

[Alkylolated Triazone Derivative] The alkylolated triazone derivative used as the above-mentioned curing agent is a urea compound, an amine, an aldehyde and / or
Alternatively, it is obtained by reaction with an aldehyde donor. Urea compounds used in the production of alkylolated triazone derivatives include urea, thiourea, alkylurea such as methylurea, alkylthiourea such as methylthiourea, phenylurea, naphthylurea, halogenated phenylurea, nitrated alkylurea. And the like, or a mixture of two or more thereof is exemplified, and a particularly desirable urea compound is urea or thiourea. Also, as amines, aliphatic amines such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, and amylamine, amines such as benzylamine, furfurylamine, ethanolamine, ethylenediamine, hexamethylenediamine, hexamethylenetetramine, and ammonia. Are exemplified, and these are used alone or as a mixture of two or more kinds. The aldehyde and / or aldehyde donor used in the production of the above alkylolated triazone derivative are the same as those used in the polyhydric phenol / aldehyde condensate of the present invention. For the synthesis of the alkylolated triazone derivative of the present invention, usually, amines and / or ammonia 0.1 to 1.2 mol, aldehyde and / or aldehyde donor 1.5 per mol of the urea compound is used.
The reaction is carried out at a ratio of ˜4.0 mol. The order of addition during the reaction is arbitrary, but the preferred reaction method is that the required amount of the aldehyde donor is first added to the reactor, and the required amount of the amines and / or ammonia is usually maintained at a temperature of 60 ° C. or lower. It is to add gradually the required amount of urea compound, and to stir and heat at 80 to 90 ° C. for 2 to 3 hours to react. As the aldehyde and / or the aldehyde donor, 37% formalin is usually used, but part of it may be replaced with paraformaldehyde in order to increase the concentration of the reaction product. The use of hexamethylenetetramine as the aldehyde donor also gives higher solids reaction products. The reaction of the urea compound, the amines and / or ammonia with the aldehyde and / or the aldehyde donor is usually carried out in an aqueous solution, but some or all of the water is methanol, ethanol, isopropanol, n-butanol, ethylene. Alcohols such as glycol and diethylene glycol may be used singly or as a mixture of two or more kinds, and water-soluble organic solvents such as ketones such as acetone and methyl ethyl ketone may be used alone or as a mixture of two or more kinds.

[Laminated Material] The structural material or preformed body manufactured as described above may be formed by laminating two or more layers of the same kind or different kinds, or reinforced on both sides or one side of the structural material or preformed body. You may laminate another material, such as a material, a covering material, and a base material. As the reinforcing material, the surface covering material, the substrate, etc., the organic or inorganic fiber knitted fabric or non-woven fabric, garment cloth, mesh such as wire mesh, metal frame, metal material such as metal plate, waste paper, cardboard, resin felt, Examples include plastic sheets, carpets, synthetic leather, and plastic foam sheets. Examples of the synthetic leather include polyvinyl chloride leather, polyamide leather, and amino acid leather, and examples of the plastic foam sheet include a polyethylene foam sheet, a polypropylene foam sheet, a polyurethane foam sheet, and a melamine resin foam sheet. The non-woven fabric or synthetic leather may be lined with the plastic foam sheet as a cushioning material. Further, a reinforcing material and a facing material may be laminated together on the structural material or preform. In the case of the above method (3) or (4), that is, when the above-mentioned structural material or preform is impregnated with the polyhydric phenol / aldehyde condensate by dipping, spraying or the like, the reinforcing material or the covering material is used. Other materials such as the above are laminated before or after coating and impregnating the condensate. When the reinforcing material, the covering material and the like are porous materials, the condensate may be applied and impregnated on the reinforcing material and the covering material. Further, when the structural material or preform has a relatively weak strength against pulling such as a cotton-like body or an entangled body, the structural material or preform is preliminarily provided with the reinforcing material,
When the condensate is impregnated after adhering another material such as a surface covering material with an adhesive or the like, there is no deviation or peeling between the structural material or the preformed body and the reinforcing material, the surface covering material or the like during the impregnation work, Further, when the condensate is a solution, the solution does not cause displacement or peeling due to swelling of the structural material or preform, and continuous work is possible, and displacement or peeling during drying is also possible. It is particularly preferable because the occurrence of Further, when another material such as the reinforcing material or the covering material is laminated on the structural material or the preformed body, the structural material or the preformed material when the reinforcing material, the covering material or the like is made of a directional fiber substance. It is, of course, possible to change the directionality of the fibers and change the directionality of the layers in the same way, or to laminate two or more layers of the structural material or preforms having the directionality. In this case, the strength of the structural material is further improved. For laminating the structural material or preform with another material such as the reinforcing material and the covering material, an adhesive, a hot-melt adhesive, a hot-melt sheet, an ordinary adhesive or the like is used. When impregnating a material or the like with the polyhydric phenol / aldehyde condensate or another synthetic resin, an adhesive is not always necessary.

[Heat Forming] As described above, the structural material of the present invention is the same as or preformed by mixing the polyhydric phenol / aldehyde condensate with the coconut fiber alone or the mixed fiber of the coconut fiber and other fibers. Immediately after, or after laminating two or more layers with each other, or immediately after laminating another material such as a reinforcing material and a covering material, or after storing for a required period, cut into a predetermined shape, or by hot pressing without cutting. Perform molding. When forming by laminating another material such as a reinforcing material and a covering material, if the other material such as a reinforcing material and a covering material is a non-breathable material such as a metal plate or a plastic sheet, other than hot press Vacuum forming is also possible. Further, as described above, other materials such as a reinforcing material and a facing material may be laminated after molding. Since the polyhydric phenol / aldehyde-based condensate of the present invention can be cured at a low temperature of 200 ° C. or lower, preferably 140 ° C. or lower, the heat molding temperature is accordingly reduced to 200 ° C. or lower, and if desired, 140 ° C. or lower. Even if the surface material is poor in heat resistance, such as polypropylene nonwoven fabric or polyvinyl chloride leather, it can be molded before or simultaneously with the molding of the structural material or the preform.

[Use] As described above, the structural material of the present invention is lightweight and has rigidity, and therefore, it is a structural building material such as an outer wall material, an inner wall material, a soundproof material, a ceiling material for a vehicle such as an automobile, a door trim, and a dash. Used for interior materials such as boards, tonneau boards, and lining materials for luggage compartments. In the interior materials for vehicles such as automobiles, the structural material of the present invention is used as a base material or as a reinforcing material for a base material instead of glass fiber. As the base material on which the structural material of the present invention is laminated as a reinforcing material, a polyurethane foam, a polystyrene foam,
There are plastic foams such as polyethylene foams, polypropylene foams, phenol resin foams, melamine resin foams, amino resin foams such as urea resin foams, cardboard, resin felt, waste paper boards and the like. The base material includes polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, fluororesin, thermoplastic acrylic resin, thermoplastic polyester, Thermoplastic polyamide, thermoplastic urethane resin, acrylonitrile-butadiene copolymer, styrene-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, ethylene-propylene copolymer, ethylene-propylene terpolymer, ethylene-vinyl acetate copolymer Thermoplastic synthetic resins such as polymers, natural rubber,
Natural or synthetic rubber such as chloroprene rubber, nitrile rubber, butyl rubber, urethane resin, melamine resin, thermosetting acrylic resin, urea resin, benzoguanamine resin, ketone resin, phenol resin, polyphenol resin, epoxy resin, thermosetting Thermosetting synthetic resin such as type polyester, allyl resin, silicone resin, alkyd resin,
Polycarbonate resin, acetal resin, coumarone indene resin, petroleum resin, or urethane resin prepolymer, epoxy resin prepolymer, melamine resin prepolymer, urea resin prepolymer, phenol resin prepolymer, diallyl phthalate prepolymer that produces the above synthetic resin. , Acrylic oligomer, polyvalent isocyanate, methacrylic ester monomer, prepolymer such as diallyl phthalate monomer, oligomer, monomer and polyvinyl alcohol, sodium alginate, starch, starch derivative, glue, gelatin, blood powder, methyl cellulose,
Carboxymethyl cellulose, hydroxyethyl cellulose, polyacrylic acid, may be applied or impregnated with water-soluble polymers such as polyacrylamide, natural gums, further calcium carbonate, talc, gypsum, carbon black,
Fillers such as wood flour, walnut flour, coconut husk flour, wheat flour and rice flour, surfactants, higher fatty acids such as stearic acid and palmitic acid, higher alcohols such as palmityl alcohol and stearyl alcohol, butyl stearate, glycerin monostearate Fatty acid esters such as, fatty acid amides, natural waxes such as carnauba wax, synthetic waxes, paraffins, paraffin oil, silicone oil, silicone resin, fluororesin, polyvinyl alcohol, release agents such as grease, pigments , Flame retardants such as dyes, flame retardants, antimony trioxide, aluminum hydroxide and bromine compounds, insect repellents, preservatives, anti-aging agents, UV absorbers, water repellents, chemical foaming agents, capsule foaming agents and DBPs. , DOP,
One or more co-condensates or mixtures of phthalic acid ester plasticizers such as dicyclohexyl phthalate and other plasticizers such as tricresyl phosphate may be applied, impregnated or mixed. Further, the structural material of the present invention does not cause the work environment to deteriorate due to scattering of small pieces unlike glass fiber, and is lighter than glass fiber, and thus is extremely useful as a reinforcing material.

[0022]

In the structural material of the present invention, the polyhydric phenol / aldehyde condensate or the sulfomethylated product of the condensate is stable in a wide pH range, has room temperature curability, and has a long pot life and a short reaction time. To cure. Therefore, the structural material of the present invention can be efficiently formed by heating at a low temperature, and the cured product thereof is extremely excellent in flexibility, water resistance, heat resistance, weather resistance and the like. Further, the coconut fiber constituting the structural material has a high rigidity, and a structural material having a high rigidity can be obtained even if the density is roughened to reduce the weight.

[0023]

【Example】

[Example 1] 1 mol of resorcin and 37% formalin 0.
0.1 mol of caustic soda was added to 5 mol and reacted 50
% Polyhydric phenol / aldehyde condensate 100 parts and 20 parts of hexamethylenetetramine as a curing agent were added to the liquid binder mixture and spray-mixed to the coconut fiber at a solid content of 12%. dry. The palm fiber mixed with the liquid binder mixture is pressed at room temperature using a fleece manufacturing machine to form a mat-shaped preform, and the preform is 170 ° C. and 2.5 kg / cm 2.
Hot press at a pressure of ² for 40 seconds, specific gravity 0.3 thickness 5
It was formed into a mm plate. In this way, a plate-like structural material that is lightweight, highly rigid and excellent in heat resistance was obtained.

Example 2 1 mol of phenol, 0.4 mol of 5-methylresorcinol, 2.1 mol of 37% formalin at a ratio of 0.1 mol of caustic soda and 50% monohydric phenol / polyhydric phenol / aldehyde Cocondensate 100
Part, 45% paraffin emulsion as a release agent.
A liquid binder mixture containing 5 parts and 1 part of 40% ammonium phosphate as a flame retardant was mixed with 80% palm fiber and 2 hemp fibers.
Spray-mix to 0% mixed fiber so that the added amount of solid content is 10%, dry at 100 ° C or less, and then press at room temperature using a fleece maker to preform a mat-like shape. The preformed body at 170 ° C, 2 kg / cm
Hot pressed at a pressure of ² for 50 seconds, specific gravity 0.7 thickness 3
It was formed into a mm plate. In this way, a plate-like structural material that is lightweight, highly rigid and excellent in heat resistance was obtained.

Example 3 Alkylresorcin (boiling point 270 to 290 ° C.) 1 obtained by purifying shale oil resorcin obtained by dry distillation of Estonian oil shale 1
Mol, urea 0.8 mol, 37% formalin 0.5 mol and caustic soda 0.1 mol added and condensed to 60% polyhydric phenol / urea / aldehyde cocondensate 100 parts hexamethylenetetramine 15 parts as a curing agent Liquid binder mixture added, 90% palm fiber, polyester fiber 1
A mixed fiber consisting of 0% is spray-mixed so as to have a solid content of 8%, and then entangled by a needle punch to form a mat-shaped fiber entangled body.
Hot pressing was carried out at a temperature of 3 kg / cm ² for 40 seconds to form a plate having a specific gravity of 0.9 and a thickness of 2.5 mm. In this way, a plate-like structural material that is lightweight, highly rigid and excellent in heat resistance was obtained.

[Example 4] 1,5-dimethylresorcinol 1 mol, phenol 0.7 mol, melamine 0.3 mol,
To 100 parts of sulfomethylated 60% polyphenol / monophenol / melamine / aldehyde cocondensate reacted with 37% formalin (1 mol) and sodium sulfite (0.4 mol), urea, methylamine and A liquid binder mixture prepared by adding 100 parts of 50% alkylolated triazone derivative obtained by the reaction of 37% formalin, 80% coconut fiber and 20% polypropylene fiber
Spray-mixed to the mixed fiber consisting of 10% solid content, dried at 60 ° C., and then pressed at room temperature using a fleece maker to give a mat-shaped preform. The preform is pressed at 130 ° C. for 30 seconds to give a mat-like prepreg, which is stored at room temperature for 7, 30, and 60 days, and then the prepreg is kept at 180 ° C. for 3 kg /
It was hot pressed at a pressure of cm ² for 1 minute to form a plate having a thickness of 2.5 mm and a specific gravity of 0.8. In this way lightweight and rigid,
A plate-like structural material having excellent heat resistance and bending strength was obtained. In the plate-shaped structural material of this example, the polypropylene fibers contained during the hot pressing are softened and the coconut fibers are entangled with each other to improve the rigidity.

[Example 5] 1 mol of 5-ethylresorcin, 0.2 mol of m-cresol, 0.8 mol of urea, 0.2 mol of sodium sulfite, 2.1 mol of 37% formalin and adjusted to pH 5.1. The sulfomethylated polyhydric phenol / monohydric phenol / urea / aldehyde cocondensate was dried by vacuum evaporation at 60 ° C. or lower and pulverized to about 100 mesh. A powdery binder mixture prepared by adding 20 parts of paraformaldehyde as a curing agent to 100 parts of the powder of the polyhydric phenol / aldehyde condensate produced in this manner was used to prepare 70% coconut fiber and 10% recycled fiber.
The mixture was added to a mixed fiber of 20% pulp so as to be 12% and entangled into a sheet by an entanglement machine, and the fiber entangled body was hot pressed at 100 ° C. and a pressure of 2.5 kg / cm ² for 30 seconds. Then, it was formed into a sheet having a thickness of 1 mm and a specific gravity of 0.6. In this way, a lightweight sheet-like structural material having excellent heat resistance, rigidity and strength was obtained.

[Example 6] 90% coconut fiber and 10 bamboo fiber
%, The liquid binder mixture of Example 1 is spray-mixed to the mixed fibers so that the added amount of solid content is 15%, and the mixture is dried at 60 ° C. or lower.
The mixed fiber mixed with the liquid binder mixture is sprinkled on a mold to form a mat, and the mat is heated to 170 ° C.
Hot press for 40 seconds, thickness 0.5mm, specific gravity 0.2
When formed into a sheet, a sheet-like structural material having good weight and high rigidity was obtained.

Comparative Example 1 50% consisting of 1 mol of phenol, 2 mol of 37% formalin and 0.2 mol of caustic soda
Using a resol-type phenol / aldehyde condensate as a binder, spray coating was applied to coconut fiber so that the coating amount was 12% in terms of solid content, followed by drying at 60 ° C. and then thermocompression molding. At this time, when the hot pressing temperature was 180 ° C., the required hardening was 1 minute or more, and when the hot pressing temperature was 170 ° C., the hardening was insufficient and the rigidity and strength were insufficient even after hot pressing for 3 minutes.

[Embodiment 7] In the hot press of Embodiment 1, the plate-shaped structural material is formed into a base material shape of an automobile door trim. As shown in FIG. 1, the base material (1) is a vacuum pressure bonding machine (4).
Set on the lower mold (5) and covered with polyvinyl chloride leather and polypropylene foam sheet.
Set the back surface of (2) with polyester hot melt adhesive (3) applied, press the surface mounting material (2) on the surface of the base material (1) and press it with the upper mold (6). .
In this way, the automobile door trim (7) as shown in FIG. 2, which is lightweight, highly rigid and excellent in heat resistance, is manufactured.

Example 8 The fiber entangled body of Example 3 was set as a base material (11) on the lower mold (15) of the automobile molding ceiling press molding machine (14) shown in FIG. A surface material (12) made of polypropylene needle non-woven fabric lined with a polyethylene hot melt sheet (13) is set, and 150 ° C. between the lower mold (15) and the upper mold (16) of the press molding machine (14), 3 kg /
Hot press for 30 seconds at a pressure of cm ² . After that, trimming is performed to form a molded ceiling material for automobiles as shown in FIG.
Get (17). The molded ceiling material (17) is lightweight and highly rigid, and has excellent heat resistance and shape retention.

[Embodiment 9] The sheet-like structural material of Embodiment 5 is set as a reinforcing material (21) on the lower mold (25) of the automobile forming ceiling vacuum forming machine (24) shown in FIG. The base material (23), which is a polystyrene foam plate heat-softened at 150 ° C., and a polypropylene fiber non-woven fabric, and an exterior material (22) lined with an ethylene-vinyl acetate copolymer are overlaid, vacuum-molded, and a lower mold ( The stack is clamped between 25) and the upper mold (26). In this way, a molded ceiling material for an automobile having the same shape as that shown in FIG. 4 of Example 7 is obtained. Since the molded ceiling material is reinforced by the reinforcing material (21), it is lightweight, highly rigid, and excellent in heat resistance and shape retention.

[Embodiment 10] As shown in FIG. 6, a polyvinyl chloride sheet (31) is molded into the shape of an automobile dashboard, and the polyvinyl chloride sheet (31) is preformed with a preform of Example 2 using an acrylic resin. 150 by pressing with an adhesive
The polyhydric phenol / aldehyde condensate in the preformed product is polymerized and cured by heating at 1 ° C. for 1 minute to obtain an insulator (32). In this way, the automobile dashboard (33) is manufactured.

[Embodiment 11] In the hot press of Embodiment 3, the plate-like structural material is molded so as to conform to the shape of the floor of the automobile to produce a carpet underlay (42) having the shape shown in FIG. 7. The underlay (42) is set on the lower die (45) of the carpet molding machine (44), and the carpet (41) in which the lined polyethylene sheet (43) is heated and softened is placed on the underlay (42). The carpet (41) is molded by sandwiching the mold (45) and the upper mold (46), and at the same time, the underlay (42) is pressure-bonded through the polyethylene sheet (43). In this way, the molded carpet (47) for automobile floor covering as shown in FIG. 8 is manufactured.

[Embodiment 12] On the lower die (57) of the automobile molding ceiling press molding machine (56) shown in FIG. 9, diphenylmethane-4.
The polyurethane foam sheet (52) impregnated with 4% -diisocyanate (MDI) was laminated on both sides with the sheet-like structural material of Example 6 as the reinforcing material (51, 51), and the polyamide hot melt nonwoven fabric was further laminated thereon. (55) lined polypropylene needle punched non-woven surface material (54) is set, the press molding machine (56) between the lower mold (57) and the upper mold (58) 150 ℃, 3kg / cm Hot press at a pressure of ² for 1 minute. Sheet-shaped reinforcing material (51,
51) is a polyurethane foam sheet (52) impregnated with M
It is adhered by the exudation of DI, and the covering material (54) is adhered by softening the polyamide hot melt nonwoven fabric (55). After that, trimming is performed to obtain a molded ceiling material for automobiles having a shape similar to that shown in FIG. Since the molded ceiling material is reinforced by the reinforcing material (51, 51), it is lightweight and highly rigid, and has excellent heat resistance and shape retention.

[Example 13] Figs. 10 to 12 relate to a molded carpet (67) for floor covering of an automobile, and (61) is the mat-shaped fiber entangled body produced in Example 3. A hemp fiber sheet (62, 63) in which hemp fibers are entangled by a needle punch is polymerized on the upper and lower sides of the united body (61). The hemp fiber sheets (62, 63) are mixed with the liquid binder of Example 3 so that the solid content is 10%. As shown in FIG. 10, the polymer was set in a press molding machine (68) consisting of an upper mold (69) and a lower mold (70), and hot pressed at 150 ° C. and a pressure of 3 kg / cm ² for 1 minute. Manufacture carpet underlay (64). The carpet underlay (64) is then shown in FIG.
As shown in 1, set in the crimping mold (68A) consisting of the upper mold (69A) and the lower mold (70A), and the polyethylene sheet (66) on the back side.
The carpet (65) in the heat-softened state is overlaid and pressure-bonded. In this way, a molded carpet (67) for automobile floor covering as shown in FIG. 12 is manufactured. In this example, the hemp fiber sheet (62, 63) having a dense structure is formed on the front and back surfaces of the carpet underlay (64). ) Is provided, a molded carpet (67) having a high surface smoothness can be obtained.

[Embodiment 14] A heat insulating material (72) made of the structural material of Embodiment 1 between the concrete formwork (77, 77) shown in FIG.
The concrete and the reinforcing bars (76) are inserted, and then concrete is poured to form the concrete skeleton wall (73) having the heat insulating material (72) attached to the inner surface as shown in FIG. After releasing the mold (77, 77), the mortar cement layer (7
4) is applied, and a decorative sheet (75) is attached to the inner surface of the mortar cement layer (74) to construct a building wall (71).
Since the heat insulating material (72) is porous, the concrete skeleton (73)
And the adhesion of the mortar cement layer (74) to the heat insulating material (72) is extremely excellent.

In addition to the above-mentioned examples, the structural material of the present invention is used for various automobile interior materials such as seat cushions, seat back pad materials, visor pad materials, trunk room lining materials, and trunk room lining materials. However, it is also used as a heat insulating material for floors of buildings.

[0039]

Therefore, according to the present invention, there is provided a structural material which is light in weight, rich in rigidity, and moldable at low temperature or room temperature.

[Brief description of drawings]

 1 and 2 relate to the seventh embodiment.

FIG. 1 is a sectional view of a vacuum pressure bonding process.

FIG. 2 is a perspective view of a door trim. FIGS. 3 and 4 show an eighth embodiment.
It is about.

FIG. 3 is a sectional view of a molding process.

FIG. 4 is a perspective view of an automobile molded ceiling.

FIG. 5 is a sectional view of a molding process in Example 9.

FIG. 6 is a perspective view of a dashboard according to a tenth embodiment. FIGS. 7 and 8 relate to the eleventh embodiment.

FIG. 7 is a sectional view of a carpet molding process.

FIG. 8 is a sectional view of a molded carpet.

FIG. 9 is a cross-sectional view of the molding process in Example 12;
12 and 12 relate to Example 13.

FIG. 10 is a cross-sectional view of the underlay molding process.

FIG. 11 is a sectional view of the carpet pressure bonding step.

FIG. 12 is a sectional view of the molded carpet.
Relates to Example 14.

[Fig. 13] Sectional view of concrete formwork

FIG. 14 is a sectional view of the wall

[Explanation of symbols]

 1,11,23,52 Base material 7 Door trim 17 Molded ceiling material 33 Dashboard 42 Carpet underlay 21,51 Reinforcement material 62 Insulation material

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C08L 61/04 LMX 97/02 LSW // B29K 61:00 105: 04 201: 00

Claims (12)

[Claims] 1. A coconut fiber alone or a mixed fiber of coconut fiber and another fiber, and a polyhydric phenol binding the fiber.
A structural material comprising a cured product of an aldehyde-based condensate and formed into a predetermined shape. 2. The structural material according to claim 1, wherein the polyhydric phenol / aldehyde condensate is a condensate of a polyhydric phenol with an aldehyde and / or an aldehyde donor. 3. The polyhydric phenol / aldehyde-based condensate is a co-condensate of a polyhydric phenol, a monohydric phenol and / or an amino compound monomer, and an aldehyde and / or an aldehyde donor. Structural material described in 4. The structural material according to claim 1, wherein a part or all of the polyhydric phenol is alkylresorcin. 5. The structural material according to claim 1, wherein the cocondensate is sulfomethylated. 6. A polyhydric phenol / aldehyde condensate is added to a coconut fiber alone or a mixed fiber of coconut fiber and another fiber with or without a curing agent,
A method for producing a structural material, which comprises heat-molding into a predetermined shape and curing the condensate. 7. A coconut fiber alone or a mixture of coconut fiber and another fiber in which the polyhydric phenol / aldehyde condensate is present is preformed into a sheet and then heat-formed into a predetermined shape. Item 6. A method for manufacturing a structural material according to item 6. 8. The polyphenol / aldehyde-based condensate is provided as a solution, and the solution is mixed with the coconut fiber alone or a mixed fiber of coconut fiber and other fibers. Structural material manufacturing method 9. The method for producing a structural material according to claim 6, 7 or 8, wherein the curing agent is hexamethylenetetramine and / or an alkylolated triazone derivative. 10. A vehicle interior material comprising the structural material according to claim 1. 11. An interior material for a vehicle, characterized in that the structural material according to claim 1 is laminated on a base material as a reinforcing material. 12. The base material is a synthetic resin foam.
1. Interior material for vehicle according to 1.