JP2009173808A - Hydrophilic phenolic resin, moldable material using the same and molded material and interior material using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To stabilize an aqueous solution of a phenolic resin over a broad pH range and to provide a moldable material which enables molding a molded material having uniform properties. <P>SOLUTION: The phenolic resin is a condensate of a phenolic compound and an aldehyde and/or an aldehyde donor, and a hydrophilic group other than a sulfomethyl group and/or a sulfimethyl group is introduced into part of the phenolic resin or the entire phenolic resin to improve the hydrophilicity of the phenolic resin. A porous material is impregnated with an aqueous solution of an initial condensate of such a hydrophilic phenolic resin to form a moldable material. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a hydrophilic phenol resin used for, for example, automobile interior materials and building materials, moldable materials using the same, molded materials and interior materials using them.

For example, as a moldable material used for automobile interior materials and building materials, a molding material in which a porous material such as a fiber sheet is impregnated with a phenol-based synthetic resin has been conventionally used (see Patent Document 1).
JP 2007-015386 A

The conventional moldable material is produced by impregnating a porous body with an aqueous solution of an initial condensate of a phenolic resin, and heating and drying the porous body impregnated with the initial condensate.
However, since the conventional aqueous solution of the initial condensate of phenolic resin is unstable, it is usually necessary to make the pH strong alkali in order to improve the standing stability. Further, when the pH of the initial condensate is set to the acidic side, the water solubility is lost, and the water dilutability is deteriorated, and there is a possibility that white turbid separation occurs.
When the porous body is impregnated with such an unstable initial condensate aqueous solution, the amount of the initial condensate impregnated in the porous body varies, and such a moldable material is heated and molded. When the initial condensate in the moldable material is cured, there arises a problem that partial variations occur in physical properties such as rigidity, water resistance and heat resistance of the obtained molded product.
Therefore, an object of the present invention is to provide an aqueous solution of an initial condensate of a hydrophilic phenol resin that is stable over a wide pH range for a long period of time. Another object of the present invention is to provide a moldable material using the hydrophilic phenolic resin, a molding material and an interior material using the moldable material.

As a means for solving the above-mentioned problems, the present invention provides a phenolic resin that is a condensate of a phenolic compound and an aldehyde and / or an aldehyde donor, and a sulfomethyl group is present in part or all of the phenolic resin. And / or a hydrophilic phenol-based resin into which a hydrophilic group other than a sulfymethyl group is introduced.
Further, it comprises a porous material impregnated with an initial condensate of a hydrophilic phenolic resin, and the initial condensate provides a moldable material in a B state.
The moldable material is preferably in the form of a sheet.
Further comprising a base material and a cured sheet obtained by curing an initial condensate of a hydrophilic phenolic resin in the sheet-like moldable material attached to a part or all of the surface of the base material, and having a predetermined shape An interior material comprising a base material comprising a cured sheet obtained by curing a hydrophilic phenolic resin in the moldable material, and a skin material adhered to the surface of the base material. Is to provide.
It is desirable that the base material and the skin material are bonded to each other by an adhesive layer scattered in the form of dots on the bonding surface.

In general, the moldable material is provided in the form of a sheet, and if the sheet-shaped moldable material is used, the base material and the sheet-shaped moldable material attached to a part or all of the surface of the base material It is possible to provide a molding material characterized by comprising a cured sheet obtained by curing the initial hydrophilic phenol-based resin composition therein and molded into a predetermined shape.
If the sheet-like moldable material is used, a base material comprising a cured sheet obtained by curing the hydrophilic phenolic resin initial composition in the moldable material, and a skin material adhered to the surface of the base material It is also possible to provide an interior material characterized in that, in this case, the base material and the skin material are bonded by an adhesive layer scattered in a dotted manner on the bonding surface. desirable.

[Action]
In the hydrophilic phenolic resin of the present invention, a phenolic resin has high hydrophilicity because a hydrophilic group other than a sulfomethyl group and / or a sulfymethyl group is introduced into a part or all of the phenolic resin. And forms a stable aqueous solution over a wide pH range.
〔effect〕
Since the hydrophilic phenol resin of the present invention can be uniformly impregnated into a porous material, it is possible to provide a moldable material that gives a molding material having uniform physical properties.
Therefore, according to the present invention, a door trim, a dashboard, a ceiling material, a floor material, an insulator hood, a dash inner, a dash outer, an engine under cover, a trunk side can be obtained by using a moldable material using a hydrophilic phenolic resin. It is possible to provide molding materials useful as interior materials for vehicles such as trims, building materials such as wall materials, core materials such as beds, cushion materials such as chairs, sofas and seats, and various pads.

Hereinafter, the present invention will be described in detail.
[A. Moldable material)
[Phenolic resin]
The phenolic resin used in the present invention is usually provided as an aqueous solution of an initial condensate or an organic solvent-water mixed solution.
The phenolic resin of the present invention is a condensate of a phenolic compound and an aldehyde and / or aldehyde donor.

[Phenolic compounds]
The phenolic compound may be a monohydric phenol, a polyhydric phenol, or a mixture of a monohydric phenol and a polyhydric phenol. In addition, the phenolic resin in the present invention includes an initial condensate obtained by condensing a monohydric phenol and an aldehyde and / or an aldehyde donor, and an initial condensate obtained by condensing a polyhydric phenol and an aldehyde and / or an aldehyde donor. May be an initial cocondensate obtained by co-condensation.

[Monohydric phenol]
Monohydric phenols include phenol, alkylphenols such as o-cresol, m-cresol, p-cresol, ethylphenol, isopropylphenol, xylenol, 3,5-xylenol, butylphenol, t-butylphenol, nonylphenol, or o-fluoro. Phenol, m-fluorophenol, p-fluorophenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-bromophenol, m-bromophenol, p-bromophenol, o-iodophenol, m-iodo Phenol, p-iodophenol, o-aminophenol, m-aminophenol, p-aminophenol, o-nitrophenol, m-nitrophenol, p-nitrophenol, 2,4-dini Examples include monohydric phenol substitutes such as rophenol and 2,4,6-trinitrophenol, and polycyclic monohydric phenols such as naphthol. These monohydric phenols may be used alone or in combination of two or more. Can be used.

[Polyphenol]
Examples of the polyhydric phenol include resorcin, alkylresorcin, pyrogallol, catechol, alkylcatechol, hydroquinone, alkylhydroquinone, phloroglucin, bisphenol, dihydroxynaphthalene, and the like. These polyhydric phenols are used alone or in combination of two or more. can do. Among the polyhydric phenols, preferred is resorcin or alkylresorcin, and particularly preferred is alkylresorcin, which has a higher reaction rate with aldehyde than resorcin.
Examples of the alkyl resorcin include 5-methyl resorcin, 5-ethyl resorcin, 5-propyl resorcin, 5-n-butyl resorcin, 4,5-dimethyl resorcin, 2,5-dimethyl resorcin, 4,5-diethyl resorcin, 2 , 5-diethyl resorcin, 4,5-dipropyl resorcin, 2,5-dipropyl resorcin, 4-methyl-5-ethyl resorcin, 2-methyl-5-ethyl resorcin, 2-methyl-5-propyl resorcin, 2 , 4,5-trimethylresorcin, 2,4,5-triethylresorcin and the like.
A polyhydric phenol mixture obtained by dry distillation of an Estonia oil shale is inexpensive and contains a large amount of highly reactive various alkylresorcins in addition to 5-methylresorcin. Therefore, it is a particularly preferable polyhydric phenol raw material in the present invention.

[Aldehyde and / or aldehyde donor]
The aldehyde and / or aldehyde donor means an aldehyde, a compound that generates an aldehyde when decomposed or a mixture thereof. Examples of such a compound include formalin, formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, Polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, caproaldehyde, allylaldehyde, benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, etc. Or the mixture of 2 or more types is illustrated.

[Curing agent]
The condensation of the phenolic compound with the aldehyde and / or aldehyde donor is usually carried out in the presence of an acidic curing agent (acid catalyst) or an alkaline curing agent (alkali catalyst). When an acidic curing agent is used, a novolak is first obtained, and the novolak is cured using a curing agent such as hexamethylenetetramine. When an alkaline curing agent is used, a resol is first obtained, and the resol is heated and pressurized, or is cured using an acid catalyst.
Examples of the acidic curing agent include hydrochloric acid, sulfuric acid, orthophosphoric acid, boric acid, succinic 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 dimethyl oxalate, acid anhydrides such as maleic anhydride, phthalic anhydride, or ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium oxalate, ammonium acetate , Ammonium salts such as ammonium phosphate, ammonium thiocyanate, ammonium imide sulfonate, monochloroacetic acid or its sodium salt, organic halides such as α, α'-dichlorohydrin, triethanolamine hydrochloride, anil hydrochloride Amines hydrochloride equal or salicylic acid urea adduct, urea adduct of stearic acid, urea adduct such as heptanoic acid urea adduct, or N- trimethyl taurine, zinc chloride, ferric chloride and the like are exemplified.
Examples of the alkaline curing agent include alkali metals such as sodium hydroxide, potassium hydroxide, barium hydroxide and calcium hydroxide, hydroxides of alkaline earth metals, oxides of alkaline earth metals such as lime, or Examples include alkali metal weak acid salts such as sodium carbonate, sodium sulfite, sodium acetate and sodium phosphate, and amines such as ammonia, trimethylamine, triethylamine, hexamethylenetetramine and pyridine.

[Hydrophilic group]
In the present invention, as the hydrophilic group introduced into the phenolic _{resin, -SO 3 H, -SO 3 M} , -OSO 3 H, -OSO 3 M, -COOM, -NR 3 X, -COOH, -NH ₂ , —CN, —OH, —NHCONH ₂ , — (OCH ₂ CH ₂ ), —SO ₃ NH ₂ , CO—, ═N—SO ₃ H, a phosphate group, and the like.
These hydrophilic groups may be introduced alone or in combination of two or more.

[Third component]
In addition to the above curing agents, for example, formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, caproaldehyde, allylaldehyde, Aldehydes such as benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, methylolurea, methylated methylolurea, urea resin, methylolmelamine, methylated methylolmelamine, alkylolated triazone derivatives A compound that generates an aldehyde upon decomposition may be mixed as a curing agent.

  In addition to the curing agent, if necessary, amino resins such as monohydric phenol resins, polyhydric phenol resins, urea resins, melamine resins, or natural rubber or derivatives thereof such as styrene-butadiene rubber, acrylonitrile. -Synthetic rubbers such as butadiene rubber, chloroprene rubber, ethylene-propylene rubber, isoprene rubber, isoprene-isobutylene rubber, vinyl, vinyl propionate, styrene, acrylic ester, methacrylic ester, acrylonitrile, acrylic acid, methacrylic acid, maleic acid , Homopolymers of vinyl monomers such as vinyl chloride, vinylidene chloride and vinylpyridine, or copolymers of two or more of these vinyl monomers, polyurethane, polyamide, epoxy resin, butyral resin, polyethylene, polypropylene, Acetate Emulsions, latexes or aqueous solutions of various synthetic resins such as nyl-ethylene copolymer, chlorinated polyethylene, chlorinated polypropylene, and polyester, as well as polyvinyl alcohol, sodium alginate, starch, starch derivatives, glue, gelatin, blood powder, methylcellulose, carboxy Filling with water-soluble polymers such as methylcellulose, hydroxyethylcellulose, polyacrylate, polyacrylamide, natural gums, calcium carbonate, talc, gypsum, carbon black, wood powder, walnut powder, coconut powder, wheat flour, rice flour, etc. Agents, other surfactants, higher fatty acids such as stearic acid and palmitic acid, higher alcohols such as palmityl alcohol and stearyl alcohol, fatty acid esters such as butyryl stearate and glycerin monostearate, etc. Fatty acid amides, other natural waxes such as carnauba wax, synthetic waxes, other paraffins, paraffin oil, silicone oil, silicone resin, fluororesin, polyvinyl alcohol, release agents such as grease, hexane, Low boiling solvents such as butane, n-pentane, alcohol, ether, methylene chloride, carbon tetrachloride, chlorofluoromethane, 1,1,2-trichloro-1,2,2-trifluoroethane, and other azodicarbonamides , Dinitrosopentamethylenetetramine, p, p′-oxybis (benzenesulfonyl hydrazide), azobis-2,2 ′-(2-methylgropionitrile), etc. Substances that react with acid hardeners, such as carbon or sodium bicarbonate, potassium, ammonium or Lucium, foaming agents such as thermoplastic expansible microspheres microencapsulated with n-pentane, isopentane, butane, isobutane, etc., and hollow particles such as shirasu balloon, pearlite, glass balloon, foamed glass, hollow ceramics, etc. In addition, foams and expanded particles such as expanded polyethylene, expanded polystyrene, expanded polypropylene, pigments, dyes, flame retardants, flame retardants, insecticides, antiseptics, anti-aging agents, UV absorbers, DBP, The curable resin may be modified by co-condensation or mixing by adding a third component such as a phthalate plasticizer such as DOP or dicyclohexyl phthalate or other plasticizer such as tricresyl phosphate. .

[Production of phenolic resins]
The above phenolic resin can be produced by a conventional method. In particular, an initial condensate obtained by condensing a phenolic compound and an aldehyde and / or an aldehyde donor in the presence of a curing agent is used as the phenolic resin. The initial condensate may comprise: (a) condensing a monohydric phenol and / or polyhydric phenol and an aldehyde and / or aldehyde donor in the presence of a curing agent; or (b) a monohydric phenol and an aldehyde. And / or polycondensation B and / or polyhydric phenol with aldehyde and / or aldehyde donor in the presence of a curing agent. It can be produced by co-condensing the initial condensate C.

  In the condensation of the monohydric phenol and / or polyhydric phenol and the aldehyde and / or aldehyde donor (a) above, the aldehyde and / or aldehyde donor is usually 0.2 to 3 moles per mole of the monohydric phenol. , 0.1 mol to 0.8 mol of aldehyde and / or aldehyde donor, and if necessary, a solvent, a third component, and a curing agent are added to 1 mol of polyhydric phenol. The reaction is carried out at 100 ° C. for 8 to 20 hours. At this time, the aldehyde and / or aldehyde donor may be added all at the start of the reaction, or may be added in portions or continuously.

In the case of performing the two-stage cocondensation of (b) above, the initial condensate A produced by the method (a) above is added to the polyphenol B and / or the initial condensate produced by the method (a) above. C, aldehyde and / or an aldehyde donor, a solvent, a complexing agent, a third component, a catalyst, and a curing agent are added as necessary, and the temperature is 1 to 10 at a liquid temperature of 60 to 100 ° C. The reaction is heated for an hour.
The total amount of polyhydric phenol added at this time is preferably 0.01 to 3 moles per mole of monohydric phenol. Moreover, it is preferable that the addition amount of a hardening | curing agent is 0.01 to 20 weight% with respect to a phenolic compound, and it is especially preferable that it is 0.01 to 15 weight%.
The complexing agent may be added to reduce the reactivity between the polyhydric phenol and the aldehyde. As such a complexing agent, a compound having a ketone group or an amide group having a complexing ability with respect to a hydroxyl group of a polyhydric phenol can be used, and examples thereof include acetone, caprolactam, and the like. preferable. The addition amount of the complexing agent is not particularly limited, but usually about 0.4 to 0.8 mol of the complexing agent is preferable per 1 mol of polyhydric phenol. This complexing agent may be added when the initial condensate C is produced.

Water is usually used as the solvent, but if necessary, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, s-butanol, t-butanol, n-amyl alcohol, isoamyl alcohol, n -Alcohols such as hexanol, methylamyl alcohol, 2-ethylbutanol, n-heptanol, n-octanol, trimethylnonyl alcohol, cyclohexanol, benzyl alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, abiethyl alcohol, diacetone alcohol Or acetone, methyl acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, diethyl ketone, di-n-propyl Tones, diisobutyl ketone, acetonyl acetone, methyl oxide, cyclohexanone, methyl cyclohexanone, acetophenone, camphor and other ketones, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, polyethylene glycol and other glycols, or ethylene Glycol ethers such as glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol isopropyl ether, diethylene glycol monomethyl ether and triethylene glycol monomethyl ether, or esters of the above glycols such as ethylene glycol diacetate and diethylene glycol monoethyl ether acetate And its derivatives Is an ether such as 1,4-dioxane, or a water-soluble or hydrophilic organic solvent such as diethyl cellosolve, diethyl carbitol, ethyl lactate, isopropyl lactate, diglycol diacetate, dimethylformamide, or two or more of them. Mixtures can be added and used.
Acetone or the like acts as a complexing agent for alkylresorcin at the same time as a solvent, so that a milder reaction is brought about.

The introduction of the hydrophilic group into the phenolic resin may be performed before, during or after the condensation reaction of the monohydric phenol and / or polyhydric phenol with the aldehyde and / or aldehyde donor, The precondensation product A and the polyhydric phenol B and / or the initial condensation product C may be subjected to any stage before, during, or after the reaction.
The introduction amount of the hydrophilic group is usually 0.001 to 1.5 mol with respect to 1 mol of the phenol compound, but the properties such as the curability of the initial condensate to be produced and the physical properties of the resin after curing are improved. In order to maintain it satisfactorily, it is preferably about 0.01 to 0.8 mol.
The initial condensate of the phenolic resin having a hydrophilic group introduced in this manner has good stability as an aqueous solution over a wide pH range, hardly causes phase separation or the like, and increases the curing rate.

[Porous material]
Examples of the porous material used in the present invention include a fiber aggregate, a plastic foam having open cells, and a sintered body of plastic beads.
The fibers constituting the fiber aggregate include natural fibers such as cotton, hemp, wool, silk, kenaf, palm fiber, bamboo fiber, polyamide fiber, polyester fiber, acrylic fiber, viscose fiber, acetate fiber, vinyl chloride fiber. , Organic synthetic fibers such as vinylidene chloride fibers, asbestos fibers, glass fibers, carbon fibers, ceramic fibers, metal fibers, inorganic fibers such as whiskers, or recycled products obtained by weaving scraps of textile products using the above fibers Examples thereof include fibers, a mixture of two or more of these fibers, or a mixture of these fibers with low melting point fibers such as polyester fiber, polypropylene fiber, polyethylene fiber, polyamide fiber having a melting point of 200 ° C. or lower.
The fiber assembly may be in the form of a sheet such as a nonwoven fabric, felt, knitted fabric, or a laminate thereof, or a small piece of fiber obtained by cutting the sheet-like fiber assembly into small pieces, or in the form of cotton. Or a sliver-like one. The fiber assembly may be mixed with hot melt powder such as polyethylene powder, polyamide powder, polyvinylidene chloride powder, low melting point polyester resin powder, and the like.
Examples of the plastic foam include polyurethane foam having an open cell structure, polyolefin foam such as polyethylene and polypropylene, polyvinyl chloride foam, polystyrene foam, amino resin foam such as melamine resin and urea resin, phenol, and the like. There are resin foams and the like. The plastic foam is usually provided in the form of a sheet when used as a raw material for an automobile interior material base material, but may be formed into an arbitrary shape such as a block or a granule depending on the application.

[Manufacture of moldable materials]
In order to produce the moldable material of the present invention, the porous material is impregnated with the aqueous solution of the initial condensate of the hydrophilic phenol resin. As the impregnation method, a known method such as a dipping method or a spray method is applied, and the porous material is dipped and suppressed in the aqueous solution of the initial condensate that has been foamed and / or foamed in advance. The material is preferably impregnated with the aqueous solution of the initial condensate.
If the aqueous solution of the initial condensate thus foamed and / or foamed is used, the amount of the initial condensate impregnated into the porous material can be adjusted without diluting the aqueous solution of the initial condensate with water or a solvent. Therefore, the amount of water or water-soluble solvent in the porous material can be reduced to shorten the drying time.
In order to foam the initial condensate aqueous solution, air is blown into the initial condensate aqueous solution or the initial condensate aqueous solution is agitated, but preferably both of them are performed simultaneously, particularly preferably further foaming. Add agent, foam stabilizer, foam stabilizer, etc. Examples of the foaming agent and foam stabilizer include alkylbenzene sulfonate, alkyl sulfate ester salt, fatty acid salt, alkyl naphthalene sulfonate, alkyl sulfosuccinate, alkyl diphenyl ether disulfonate, alkyl phosphate, and polyoxyethylene. Anionic surfactants such as alkyl or alkylallyl sulfate esters, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester, special polycarboxylic acid type polymer surfactant, polyoxyethylene alkyl ether, polyoxyethylene Alkyl allyl ether, polyoxyethylene derivative, oxyethylene excipropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbi Nonionic surfactants such as oleic fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, alkylalkanolamide, octadecylamine acetate, imidazoline derivative acetate, polyalkylene polyamine derivative or salt thereof, octadecyltrimethyl Surfactants such as ammonium chloride, trimethylaminoethylalkylamido halide, alkylpyridinium sulfate, alkyltrimethylammonium halide, and other cationic surfactants and amphoteric surfactants, silicone surfactants, fluorosurfactants, Penetration agents, natural oil derivatives, glycols, etc. are used, and foam stabilizers include polyacrylic acid, polymethacrylic acid, polyacrylic acid and polymethacrylic acid. Sodium salt or potassium salt, polyvinyl alcohol, polyvinyl pyrrolidone, partially saponified product of polyvinyl acetate resin, water-soluble polymer such as carboxymethyl cellulose, hydroxyethyl cellulose, saccharide, stearic acid, zinc stearate, palmitic acid, long chain fatty acid amide Oil lubricants etc. are used. Two or more of the foaming agents, foam stabilizers, and foam stabilizers may be used in combination.
In order to foam the aqueous solution of the initial condensate, the aqueous solution of the initial condensate includes, for example, an inorganic compound such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, an azide compound, a nickelo compound, an azo compound, a sulfonyl compound, etc. Or a low boiling point solvent such as n-pentane, methanol, methyl ether, ethyl ether, methylene chloride, carbon tetrachloride, chlorofluoromethane, or the like. Are added and mixed, and heated to the boiling point of the solvent or higher to cause foaming. In this case, it is desirable to stir the aqueous solution of the initial condensate, and the same foaming agent, foam stabilizer, penetrant, foam stabilizer and the like as in the case of foaming may be added.
You may perform foaming by the said air blowing and / or stirring, and foaming by this foaming agent simultaneously.
The foaming or foaming ratio of the aqueous solution of the initial condensate is usually 0.8 to 50 times, preferably 2 to 20 times. Generally, the porous material impregnated with the initial condensate solution has a low density. The bubbles may be coarse, but in the case of high density, finer bubbles are desirable.
In order to impregnate the porous material with the initial condensate aqueous solution, for example, the foamed and / or foamed initial condensed water solution is filled in an impregnation tank, and the porous material is immersed in the impregnation tank. Then, the porous material to which the initial condensate aqueous solution is adhered is suppressed by a squeeze roll or a press disk. Alternatively, immediately before the porous material is fed to the drawing roll, the foamed and / or foamed initial condensate aqueous solution is supplied to one side or both sides of the porous material. In this case, one or two or more squeezing rolls may be arranged after the squeezing roll. Further, the arrangement of the squeezing rolls may be in the vertical direction or in the horizontal direction.
By such pressing, the foamed and / or foamed initial condensate aqueous solution adhering to the porous material penetrates into the porous material.
The porous material impregnated with the aqueous solution of the initial condensate is subjected to a heat drying step. In this step, the initial condensate is brought into a B state. In order to keep the initial condensate in the B state, the amount of the curing catalyst added to the initial condensate aqueous solution, the heating temperature, the heating time, etc. may be adjusted. The heating temperature is usually about 40 to 170 ° C., and the heating time is About 0.1 to 5 hours. For the heat drying, usually hot air drying, far-infrared drying, high-frequency heat drying, or the like is applied.

  Thus, by making the initial condensate of the hydrophilic phenolic resin impregnated in the porous material into the B state, the stability of the phenolic resin is improved and the molding material can be stored for a long time, Since the moisture content of the phenolic resin is reduced, the molding time is shortened, and the puncture phenomenon due to moisture vapor does not occur even when molded by hot pressing. Further, since the phenolic resin is completely cured after the molding material is hot press molded, a molded product having excellent shape retention and heat resistance can be obtained.

[Molding]
Since the moldable material of the present invention is impregnated with a B-type hydrophilic phenolic resin initial condensate, it has moldability and is usually molded by hot pressing using a lower mold and an upper mold having desired shapes. The The conditions for hot pressing are set to a temperature and time for completely curing the phenolic resin in the B state, and the pressing pressure is usually 1 to 10 kg / cm ² . At this time, it is good also as a laminated molded material by superposing | stacking with another sheet | seat and hot-pressing.
The resulting molding material is particularly useful for vehicle interior materials such as door trims, dashboards, ceiling materials, flooring materials, insulator hoods, dash inners, dash outers, engine under covers, trunk side trims, and building materials. is there.

[B. Molded material)
The molding material of the present invention is obtained by adhering the above-mentioned formable material in a sheet form to a part or all of the surface of the base material and molding it into a predetermined shape. The hydrophilic phenolic resin in the moldable material is cured, so that the sheet-shaped molding material is a cured sheet.
The base material may be any material as long as it has moldability. For example, various plastic foams, particle boards, fiber boards, felts, plastic sheets, low-melting fiber-containing nonwoven fabrics, glass wool, asbestos Etc.
Examples of the plastic foam include polyurethane foam, polyolefin foam such as polyethylene and polypropylene, polyvinyl chloride foam, polystyrene foam, melamine resin foam, urea resin foam, and phenol resin foam.

As a method for producing the molding material, first, as shown in FIG. 1, the base material 11 is molded into a predetermined shape, and the sheet-formable material is cured into a shape suitable for the shape of the base material 11. There is a method of molding and sticking the molded cured sheet 12 to the surface of the substrate 11.
In order to adhere the cured sheet 12 to the surface of the base material 11, an adhesive may be used, or when the base material 11 is made of a thermoplastic material, it may be heat-sealed.
Secondly, as shown in FIG. 2, the sheet-shaped moldable material 12a and the base material 11a before molding of the base material are superposed, and hot pressing is performed between the upper mold 13 and the lower mold 14 having a predetermined shape. There is a method of molding. At this time, depending on the material of the base material (base material), an adhesive such as a hot melt sheet, natural resin, natural rubber, synthetic resin, or synthetic rubber may be used between the cured sheet 12a and the base material base 11a. It may be interposed.
Thirdly, as shown in FIG. 3, the sheet-formable material is cured and molded into a predetermined shape in advance, and the molded cured sheet 12 is set on the mold surface 151 of the molding die 15 and the resin injection port 152. There is a method in which the foamed resin liquid R is injected into the mold 15 and cured.
Examples of the foamed resin liquid R include polyurethane foam resins, polyolefin foam resins such as polyethylene and polypropylene, polyvinyl chloride foam resins, polystyrene foam resins, melamine foam resins, urea foam resins, and phenol foam resins.
The molding material of the present invention obtained as described above can be used for various applications, for example, as wall materials; bed core materials; cushion materials such as chairs, sofas, seats; interior materials; Is preferred.
Since the cured sheet adhered to the surface of the base material in the molding material of the present invention is excellent in moldability unlike a simple fiber sheet, the molding material can be molded into a desired shape.

[C. Interior material)
The interior material of the present invention comprises a base material obtained by curing the hydrophilic phenol resin initial condensate in the moldable material, and a skin material adhered to the surface of the base material.
Examples of the skin material include artificial leather, leather, fiber knitted fabric, nonwoven fabric, and plastic foams such as polyurethane foam, polyethylene foam, polypropylene foam, polystyrene foam, and polyvinyl chloride foam. There are laminated materials.
The skin material is adhered to the substrate by an adhesive. Examples of the adhesive include acrylic adhesives, synthetic rubber adhesives, elastomer adhesives, vinyl acetate adhesives, vinyl chloride adhesives, urea resin adhesives, melamine resin adhesives, and phenol resin adhesives. It is a commonly used adhesive such as an adhesive or an epoxy resin adhesive. The adhesive is provided as a solution type or an emulsion type.
Furthermore, there exists a hot-melt-type adhesive as an adhesive used for the said adhesive bond layer. Examples of the hot melt adhesive include polyolefin resins such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, and ethylene-ethyl acrylate copolymer, or modified products of the polyolefin resin, polyurethane resins, and polyester resins. A single resin or a mixture of two or more of resins, polyamide resins and the like is used.
The hot melt adhesive is provided as a solution type or an emulsion type, and is also provided as a dispersion type in which the hot melt adhesive powder is dispersed in water.
The adhesive layer is preferably scattered in the form of dots on the surface of the skin material and / or the base material. In this way, if the skin material and the base material are bonded by the adhesive layer scattered in the form of dots, the rigidity of the adhesive layer does not affect the molding shape of the interior material and the uneven shape of the surface, and therefore the The molded shape of the interior material and the uneven shape of the surface are molded sharply. When the skin material has air permeability, the adhesive layer also has air permeability, so that an interior material having excellent soundproofing properties can be obtained.
In order to disperse the adhesive layer in the form of dots on the adhesive surface of the skin material and / or base material, for example, a spray coating method, a relief printing method, a silk star printing method, etc. are applied. A method of applying an adhesive with a spray, a knife coater, a roll coater, a flow coater or the like after the coating, and then peeling the masking sheet may be applied.
A desirable method of dispersing the adhesive layer in the form of dots on the surface of the skin material and / or the base material is a method of spray-coating a hot melt adhesive powder dispersion.

  The hot melt adhesive powder used in the hot melt adhesive powder dispersion is usually a powder having a size of about 20 to 400 mesh, and the hot melt adhesive powder is usually in the range of 5 to 60% by weight in water. Distributed. Examples of the water include one or more thickeners such as methyl cellulose, methoxy cellulose, ethyl cellulose, ethoxy cellulose, and carboxymethyl cellulose, such as higher alcohol sulfate (Na salt or amine salt), alkyl allyl sulfonate (Na salt or Amine salts), alkyl naphthalene sulfonates (Na salts or amine salts), alkyl naphthalene sulfonate condensates, alkyl phosphates, dialkyl sulfosuccinates, rosin soaps, fatty acid salts (Na salts or amine salts), etc. Activator, polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene alkyl ester, polyoxyethylene alkylamine, polyoxyethylene alkylolamine, polyoxyethylene Nonionic surfactants such as lenalkylamide, sorbitan alkyl ester, polyoxyethylene sorbitan alkyl ester, octadecylamine acetate, imidazoline derivative acetate, polyalkylene polyamine derivative or salt thereof, octadecyltrimethylammonium chloride, trimethylaminoethylalkylamide halogen One or more surfactants such as cationic surfactants such as nido, alkylpyridinium sulfate, and alkyltrimethylammonium halide may be added as a dispersant. As the dispersant, it is particularly desirable to use a spinnable thickener. Examples of the spinnable thickener include alkali metal salts such as sodium, potassium and lithium such as polyacrylic acid, polymethacrylic acid and alginic acid, water-soluble synthetic polymers such as polyethylene oxide, troal mallow, gluten, and bellows. There are water-soluble natural polymers made of plant mucilage such as Noritsugi, and sodium polyacrylate is a particularly desirable spinnable thickener. The addition amount of the spinnable thickener depends on the molecular weight, and is usually added so that the viscosity of the hot melt adhesive powder dispersion during spraying is 50 to 10,000 cps / 25 ° C. For example, the addition amount in the case of sodium polyacrylate having a viscosity average polymerization degree of about 38000 is about 0.01 to 1.0% by mass.

Further, the hot melt adhesive powder dispersion includes, for example, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, vinyl chloride resin, vinylidene chloride resin, styrene resin, vinyl acetate resin, Thermosetting resins such as fluorine resins, thermoplastic acrylic resins, thermoplastic polyesters, thermoplastic polyamides, thermoplastic urethane resins, epoxy resins, melamine resins, urea resins, phenol resins, resorcin resins, alkyl resorcin resins, acrylonitrile Synthetic resin emulsions such as butadiene copolymer, styrene-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylic rubber, butyl rubber, silicon rubber, urethane rubber, fluoride rubber, polysulfide rubber, graft rubber , Butaj Rubber, isoprene rubber, chloroprene rubber, polyisobutylene rubber, polybutene rubber, isopten-isoprene rubber, acrylate-butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, pyridine-butadiene rubber, styrene-isoprene rubber, acrylonitrile-chloroprene rubber , Styrene-chloroprene rubber, styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-hydrogenated polyolefin-styrene copolymer and butadiene-styrene block copolymer, styrene-rubber intermediate block-styrene Synthetic rubbers such as block copolymers such as copolymers, elastomer powders and emulsions may be added. Furthermore, if necessary, fillers such as calcium carbonate, talc, gypsum, carbon black, wood powder, walnut powder, and coconut powder, thickeners, pigments, dyes, flame retardants, flame retardants, insecticides, preservatives, anti-aging Agents, ultraviolet absorbers, fluorescent dyes, surfactants, foaming agents, softeners such as paraffin, wax, silicone, water repellents, release agents, plasticizers, and the like may be added.
When spraying the hot melt adhesive powder dispersion onto the adhesive surface of the skin material and / or substrate, the hot melt adhesive powder is sprayed by sucking the skin material and / or substrate from the back side. It is desirable to prevent rebound due to impact and to adsorb the hot melt adhesive powder to the bonding surface. The spray coating amount of the hot melt adhesive powder dispersion is usually 5 to 100 g / m ² as a solid content. When the above spinnable thickener is used, the hot melt adhesive powder dispersion has a spinnable structural viscosity, so when sprayed, it is not dispersed in a mist form and becomes a conglomerate droplet on the adhesive surface. Adhere to. Such a nodule droplet does not enter between the fuzz (fuzz) even if there is a fuzz (fuzz) on the bonding surface, and adheres to the fuzz (fuzz) surface. Therefore, after drying, a state in which the hot melt adhesive powder is efficiently attached to the surface of the adhesive surface can be obtained.

As described above, after the hot melt adhesive powder dispersion is spray-coated on the adhesive surface of the skin material and / or substrate, the skin material and / or substrate is heated and dried, and the hot melt adhesive powder is bonded. Fusing to the surface. The conditions for the heat drying are about 100 to 200 ° C. and about 5 seconds to 5 minutes at a temperature equal to or higher than the melting point of a commonly used hot melt adhesive.
The skin material is adhered to the surface of the base material by the adhesive layer, but when the adhesive is a solution type or an emulsion type, before the adhesive layer formed on the adhesive surface is completely dried. Bond them together. When the adhesive layer is a hot melt type, the adhesive surface is heated to soften the adhesive layer formed on the adhesive surface, and then the two are bonded together.
The base material may be formed before the skin material is bonded, simultaneously with the bonding of the skin material, or at any point after the skin material is bonded.
In the case where the skin material is breathable and molded after the skin material is bonded to the base material, the gas generated from the air contained in the base material or the synthetic resin contained in the base material (For example, formalin gas in the case of phenol resin, water or carbon dioxide gas in the case of polyvalent isocyanate) passes through the point-like adhesive layer during molding and is smoothly discharged from the skin material to the outside world. The interior material does not puncture, and the problem of odor due to residual gas is also eliminated.
The interior material of the present invention can be used for various applications, and is suitable, for example, as an automobile trunk room interior material or a dashboard interior material. In the interior material, in particular, when the skin material and the base material are bonded by an adhesive layer scattered in the form of dots, the rigidity of the adhesive layer affects the molded shape of the interior material and the uneven shape of the surface. Therefore, the molded shape and uneven shape of the interior material are sharply formed. When the skin material is breathable, the adhesive layer also has breathability, so that the obtained interior material has excellent soundproofing properties.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to these examples.

[Example 1]
In a reaction vessel equipped with a thermometer, condenser, and stirrer, 1 mol of phenol, 1.8 mol of 37% formaldehyde, 0.02 mol of sodium hydroxide, and 0.2 mol of sodium sulfanilate as a hydrophilic group. Mole was added, reacted at 70 ° C. for 5 hours, 0.2 mol of alkylresorcinol was added, and further reacted at 70 ° C. for 2 hours to obtain an initial condensate (A).

[Example 2]
In a reaction vessel similar to that in Example 1, 1 mol of p-cresol, 2.0 mol of 37% formaldehyde, 0.1 mol of ammonia, and sodium n-tetradecyl sulfate as a hydrophilic group were added, at 65 ° C. After the reaction for 8 hours, 0.3 mol of 5-ethylresorcin and 0.15 mol of acetone as a complexing agent were added and further reacted at 60 ° C. for 3 hours to obtain an initial condensate (B).

[Comparative Example 1]
The initial condensate (C) was obtained in the same manner as in Example 1 except that the hydrophilic group was removed.

[Verification of water solubility and stability]
Using the initial condensates (A), (B), and (C) obtained in Examples 1 and 2 and Comparative Example 1, each pH was adjusted using acetic acid and caustic soda as pH adjusting reagents. And about the thing adjusted to each pH, while examining water dilutability and verifying water solubility, stability was verified. The results are shown in Table 1.

  From the results in Table 1, it was found that the solution according to the present invention was excellent in water solubility and stability on the acidic to alkaline side.

Example 3
A 50% by mass aqueous solution of the initial condensate (A) obtained in Example 1 and 0.5% by mass of lauryl dimethylamine oxide are added and dissolved, and filled in a foaming tank 21 shown in FIG. The aqueous solution S is bubbled by blowing air from the air blowing nozzle 23 while being stirred by the stirrer 22 in the foaming tank 21. In this case, the expansion ratio is 8 times.
The aqueous solution S thus foamed is supplied to the immersion tank 26 from the discharge pipe 25 by opening the valve 24. The porous material 211 is a needle punched nonwoven fabric made of a mixed fiber of polyester fiber: bamboo fiber = 6: 4, and has a basis weight of 500 g / m ^{2. The} porous material 211 passes through the guide rolls 27A, 27B, 27C, 27D. Then, the aqueous solution S in the immersion bath 26 is crushed and adhered to the aqueous solution S, and is then pressed by the squeeze roll 28 and adhered to the porous material 211. It penetrates into the inside.
The porous material 211 impregnated with the aqueous solution S is then introduced into the drying chamber 29 where it is heated and dried for 10 minutes with hot air at 80 ° C. and impregnated in the porous material 211. -The formaldehyde precondensate is slightly condensed into the B state. The synthetic resin impregnation amount of the porous material 211 is 15% by mass.
The obtained moldable material 211A is heat-dried, then cut to a predetermined size by a cutter 210, and set in a hot-pressure molding machine 215 including an upper mold 215A and a lower mold 215B together with a skin material 212 as shown in FIG. . The skin material 212 is made of a polypropylene needle punched nonwoven fabric, and a polyethylene film 213 is lined on the back surface.
The moldable material 211A is hot-pressed by the hot-press molding machine 215, and at the same time, the skin material 212 is pressed through a polyethylene film 213. The hot press conditions are a press temperature of 180 ° C., a press pressure of 3 g / m ² , and a press time of 0.5 minutes.
Thus, the automobile ceiling material 214 as shown in FIG. 6 is manufactured.

Example 4
1% by weight of sodium lauryl sulfate and titanium oxide 0.2% by weight, polyvinyl alcohol 0.5% by weight, hexamethylene as a curing agent in the 98.5% by weight aqueous solution of the initial condensate (B) obtained in Example 2 4% by mass of tetramine is added and mixed, filled into a foaming tank 21 shown in FIG. 4, and air is blown from the air blowing nozzle 23 while stirring by a stirrer 22. In this case, the expansion ratio is 3 times.
The foamed material was infiltrated into a polyurethane foam sheet, which is a porous material, in the same manner as in Example 3, and then heated and dried with hot air at 60 ° C. for 5 minutes to slightly condense the impregnated initial cocondensate. Let B state. The impregnation amount of the co-condensate in the B state with respect to the polyurethane foam sheet was 15% by mass.
When the obtained molding material was thermoformed at 200 ° C. for 1 minute, a molded article having good rigidity was obtained.

Example 5
An initial cocondensate of phenol-alkylresorcinol-formaldehyde was added to a 65% by mass aqueous solution of a hydrophilic initial condensate in which 1 mol of —COOH group was introduced with respect to 1 mol of the total of the phenol and alkylresorcinol. 1% by mass of hydrochloric acid and 0.5% by mass of lauryldimethylamine oxide are added and dissolved, and filled in a foaming tank 21 shown in FIG. The aqueous solution S is bubbled by blowing air from the air blowing nozzle 23 while being stirred by the stirrer 22 in the foaming tank 21. In this case, the expansion ratio is 6 times.
The foamed material was infiltrated into the same porous material 211 as in Example 3 in the same manner as in Example 3, and then heated and dried with hot air at 80 ° C. for 5 minutes to slightly condense the impregnated initial cocondensate. To state B. The amount of impregnation of the B-state cocondensate into the porous material 211 is 20% by mass.
The obtained molding material 211 is hot-pressed in the same manner as in Example 3 except that it is cut into a predetermined size by the cutter 210 after being heated and dried, and then the press temperature is set to 200 ° C.
Thus, the automobile ceiling material 214 as shown in FIG. 6 is manufactured.

Example 6
10.0% by mass of the initial condensate (B) obtained in Example 2, 60% by mass of vinylpyridine-styrene-butadiene copolymer rubber latex (solid content 40%), and 15% by mass of formaldehyde (37%). After immersing a polyester fiber non-woven fabric by a spunbond method having a basis weight of 50 g / m ^{2 in} a mixed resin solution containing 15% by mass of water so as to have an adhesion amount of 20% of the polyester fiber, at 120 ° C. It was dried for 2 minutes to obtain a resin fiber sheet. Next, the resin fiber sheet is polymerized on both surfaces of a 2 mm thick unvulcanized rubber sheet made of natural rubber, and the unvulcanized rubber is pressurized with 145 ° C. × 15 minutes and 20 kg / cm ² with a hot press machine. When vulcanized, a molded sheet having excellent adhesion between the resin fiber sheet and rubber was obtained. In Example 6, even when the processing liquid was prepared by mixing various additives with the initial condensate (B), the processing liquid was stable regardless of the change in pH.

It is explanatory drawing which shows an example of the process of manufacturing the molding material of this invention. It is explanatory drawing which shows an example of the process of manufacturing the molding material of this invention. It is explanatory drawing which shows an example of the process of manufacturing the molding material of this invention. It is explanatory drawing which shows the process of manufacturing the molding material of this invention. It is explanatory drawing which shows the process of shape | molding the molding material of this invention. It is a perspective view of the molding (automobile ceiling material) obtained by shape | molding the molding material of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 Base material 11a Base material 12 Hardened sheet 12a Sheet-formable material 13 Upper mold 14 Lower mold 15 Mold 151 Mold surface 152 Resin inlet 21 Foaming tank 22 Stirrer 23 Air blowing nozzle 24 Valve 25 Exhaust pipe 26 Dipping tank 211 Porous material 27A-27D Guide roll 28 Drawing roll 29 Drying chamber 210 Cutter 211A Moldable material 212 Skin material 213 Polyethylene film 214 Automotive ceiling material 215 Hot press machine 215A Upper mold 215B Lower mold R Foamed resin liquid S aqueous solution

Claims (6)

  A phenolic resin which is a condensate of a phenolic compound and an aldehyde and / or an aldehyde donor, wherein a hydrophilic group other than a sulfomethyl group and / or a sulfymethyl group is introduced into part or all of the phenolic resin A hydrophilic phenolic resin characterized by that.   A moldable material comprising a porous material impregnated with the initial condensate of the hydrophilic phenolic resin according to claim 1, wherein the initial condensate is in a B state.   The moldable material according to claim 2, wherein the moldable material is in sheet form.   From the base material, and the cured sheet obtained by curing the initial condensate of the hydrophilic phenolic resin in the sheet-like moldable material of claim 3 attached to a part or all of the surface of the base material And a molded material characterized by being molded into a predetermined shape.   An interior material comprising: a base material comprising a cured sheet obtained by curing the hydrophilic phenolic resin in the moldable material according to claim 3; and a skin material adhered to the surface of the base material. . The interior material according to claim 5, wherein the base material and the skin material are bonded to each other by an adhesive layer scattered in the form of dots on the bonding surface.