JP2001226447A - Resin composition, molding material and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To smoothly cure a phenolic resin at a low temperature while suppressing the generation of free formaldehyde and replenishing free phenol to the system. SOLUTION: A polyvalent isocyanate is dispersed as a curing agent in an aqueous solution of a phenolic resin. The polyvalent isocyanate acts not only as a curing agent of the phenolic resin but also as a replenishing agent for free phenol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition used for, for example, an impregnating material, a binder, a paint, an adhesive, and the like, and a molding material and a molded product using the resin composition.

[0002]

2. Description of the Related Art Conventionally, phenolic resins have been used as impregnating materials such as fiber sheets, wood chips, binders such as fiber materials, paints, adhesives, etc. As a curing agent for curing the phenolic resins, Formaldehyde and formaldehyde donors such as hexamethylenetetramine have been used.

[0003]

However, when the above-mentioned curing agent is used, formaldehyde is easily released at the time of curing, and formaldehyde is easily left in the phenol resin even after the curing. There is a problem that the formaldehyde is released from a molded product or the like obtained by curing the impregnated molding material, thereby polluting the environment. Accordingly, an object of the present invention is to provide a resin composition that does not release formaldehyde during and after curing.

[0004]

In order to solve the above-mentioned problems, the present invention provides a resin composition in which a polyvalent isocyanate is dispersed in an aqueous phenol resin solution.
In the resin composition, since the polyvalent isocyanate acts as a curing agent for the phenolic resin, it is not necessary to use a formaldehyde donor such as formaldehyde or hexamethylenetetramine as a curing agent. It does not release formaldehyde later and there is no risk of polluting the environment.

[0005] In the above resin composition, the polyvalent isocyanate is preferably a block polyvalent isocyanate, and the phenolic resin is preferably a novolak type. ,
Desirably it is sulfomethylated and / or sulfimethylated.

The present invention also provides a molding material comprising a porous material impregnated with the above resin composition. The phenol resin in the resin composition is used in the B state.

[0007] The present invention also provides a molded product which is obtained by heat-molding the above-mentioned molding material into a predetermined shape and thermally curing the resin composition in the molding material.

Further, the present invention provides a molding material comprising a chip and / or a powder and / or a fiber material in which the above resin composition is mixed as a binder, and the above resin composition which is heated and formed into a predetermined shape. Another object of the present invention is to provide a molded product obtained by thermosetting the resin composition in the molding material.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. A. Resin Composition The essential components of the resin composition in the present invention are a phenol resin aqueous solution and a polyvalent isocyanate dispersed in the phenol resin aqueous solution. [Phenol resin] A phenol resin is obtained by condensing a phenol compound with an aldehyde and / or an aldehyde donor. As the water-soluble phenol resin, it is preferable to use a sulfomethylated and / or sulfimethylated phenol resin for improving the stability. The present invention is not limited to the above-mentioned phenolic resin. For example, a novolak resin (JP-A-11-322874) obtained by subjecting a cresol composed of m-cresol and p-cresol to a condensation reaction with a carbonyl compound is also soluble in water. It can also be used as a phenolic resin.

(Phenol Compound) The phenol compound used in the phenol resin may be a monohydric phenol, a polyhydric phenol,
A mixture of a monohydric phenol and a polyhydric phenol may be used, but when only a monohydric phenol is used, formaldehyde is easily released at the time of curing and after the curing. Use a mixture with phenol.

(Monohydric phenol) Examples of the above monohydric phenol include phenol, o-cresol, m-cresol, p-cresol, ethylphenol, isopropylphenol, xylenol, 3,5-xylenol, butylphenol, t-butylphenol, Alkylphenols such as nonylphenol, o-fluorophenol, m-fluorophenol, p-fluorophenol, o-chlorophenol, m-chlorophenol, p
-Chlorophenol, o-bromophenol, m-bromophenol, p-bromophenol, o-iodophenol, m-iodophenol, p-iodophenol, o-aminophenol, m-aminophenol, p
Monosubstituted phenols such as aminophenol, o-nitrophenol, m-nitrophenol, p-nitrophenol, 2,4-dinitrophenol, 2,4,6-trinitrophenol, and polycyclic monophenols such as naphthol And monohydric phenols may be used alone or as a mixture of two or more.

(Polyhydric phenol) Examples of the above polyhydric phenol include resorcin, alkylresorcin, pyrogallol, catechol, alkylcatechol, hydroquinone, alkylhydroquinone, phloroglucin, bisphenol, dihydroxynaphthalene and the like. Alternatively, two or more kinds can be used in combination. Preferred among the polyhydric phenols are resorcinol and alkylresorcinol, and particularly preferred is alkylresorcinol, which has a higher reaction rate with aldehydes than resorcinol.

As the alkylresorcinol, for example, 5-
Methyl resorcinol, 5-ethyl resorcinol, 5-propyl resorcinol, 5-n-butyl resorcinol, 4,5-dimethyl resorcinol, 2,5-dimethyl resorcinol, 4,
5-diethylresorcin, 2,5-diethylresorcin, 4,5-dipropylresorcin, 2,5-dipropylresorcin, 4-methyl-5-ethylresorcinol,
-Methyl-5-ethyl resorcin, 2-methyl-5-propyl resorcin, 2,4,5-trimethyl resorcin, 2,4,5-triethyl resorcin and the like. Polyhydric phenol mixtures obtained by dry distillation of Estonian oil shale are inexpensive and contain a large amount of various highly reactive alkylresorcinols in addition to 5-methylresorcinol, and are therefore particularly preferred polyhydric phenolic raw materials in the present invention.

In the present invention, the phenolic compound is condensed with an aldehyde and / or an aldehyde donor. The aldehyde donor means a compound capable of generating and providing an aldehyde when decomposed, or a mixture thereof. Examples of such aldehydes include formaldehyde, acetaldehyde, propionaldehyde, chloral, furfural, glyoxal, n-butyraldehyde, caproaldehyde, allylaldehyde, benzaldehyde, crotonaldehyde, acrolein, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde and the like. And examples of the aldehyde donor include paraformaldehyde, trioxane, hexamethylenetetramine, tetraoxymethylene and the like.

As described above, in order to improve the stability of the water-soluble phenol resin, it is desirable that the phenol resin is sulfimethylated and / or sulfomethylated. (Sulfimethylating agent) Examples of the sulfimethylating agent that can be used for the sulfimethylation of the phenolic resin include alkali metal sulfoxylates of aliphatic and aromatic aldehydes such as formaldehyde sodium sulfoxylate (Rongalit) and benzaldehyde sodium xylate. , Alkali metal such as sodium hydrosulfite and magnesium hydrosulfite, hydrosulfite (dithionite) of alkaline earth metal, alkyl sulfoxylates such as sodium ethyl sulfoxylate, hydroxymethane sulfinate And the like.

(Sulfomethylating agent) Examples of the sulfomethylating agent that can be used for sulfomethylation of the phenol resin include sulfurous acid, bisulfite or metabisulfite, and alkali metals or quaternary amines such as trimethylamine and benzyltrimethylammonium. Alternatively, examples thereof include water-soluble sulfites obtained by reacting with quaternary ammonium, and hydroxyalkane sulfonates such as hydroxymethane sulfonate obtained by reacting these water-soluble sulfites with aldehydes.

(Third component) In the production of the phenol resin, if necessary, for example, hydrochloric acid, sulfuric acid, orthophosphoric acid, boric acid, oxalic acid, formic acid, acetic acid, butyric acid, benzenesulfonic acid,
Inorganic or organic acids such as phenolsulfonic acid, p-toluenesulfonic acid, naphthalene-α-sulfonic acid, naphthalene-β-sulfonic acid, esters of organic acids such as dimethyl oxalate, maleic anhydride, phthalic anhydride, etc. Acid anhydrides, ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium oxalate, ammonium acetate, ammonium phosphate, ammonium thiocyanate, ammonium imidosulfonate, etc., monochloroacetic acid or its sodium salt, α, α′-dichlorohydrin, etc. Organic halides, triethanolamine hydrochloride, amine hydrochlorides such as aniline hydrochloride, urea adducts such as urea adduct salicylate, urea stearate, urea heptanoate, N-trimethyltaurine, zinc chloride, chloride 2. Oxidation of acidic substances such as iron, ammonia, amines, hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide, barium hydroxide and calcium hydroxide, and alkaline earth metals such as lime. , An alkaline substance such as a weak acid salt of an alkali metal such as sodium carbonate, sodium sulfite, sodium acetate and sodium phosphate may be mixed as a catalyst or a pH adjuster.

(Production of phenolic resin) The phenolic resin (initial condensate) can be produced by a conventional method.
Specifically, (a) a method of condensing a monohydric phenol and / or a polyhydric phenol with an aldehyde, and (b) a method of condensing a monohydric phenol and an aldehyde with an initial condensate and / or a polyhydric phenol. A method of condensing an initial condensate obtained by condensing an aldehyde with a monohydric phenol and / or a polyhydric phenol, (c) an initial condensate obtained by condensing a monohydric phenol, a polyhydric phenol and an aldehyde, A method of condensing monohydric phenol and / or polyhydric phenol, (d) an initial condensate obtained by condensing monohydric phenol with aldehydes and an initial condensate obtained by condensing polyhydric phenol with aldehydes A method of condensation,
(e) condensing a monohydric phenol, a polyhydric phenol, and an aldehyde with an initial condensate obtained by condensing a monohydric phenol and an aldehyde and / or an initial condensate obtained by condensing a polyhydric phenol with an aldehyde; Can be produced by a method of condensing an initial condensate.

For example, the (a) monohydric phenol and / or
Alternatively, in the condensation of a polyhydric phenol with an aldehyde, the aldehyde is generally used in an amount of 0.2 to 0.2 mol per mol of the monohydric phenol.
3 mol, 1 mol of polyhydric phenol, 0.1 to 0.8 mol of aldehydes and, if necessary, a solvent and a third component are added, and the mixture is heated at a liquid temperature of 55 to 100 ° C. for 8 to 20 hours. Let it. At this time, the aldehyde may be added in its entirety at the start of the reaction, or may be added in portions or continuously dropped.

In the condensation reaction between the phenolic compound and the aldehyde and / or the aldehyde donor, the above acidic substance or alkaline substance is used as a catalyst.
In the present invention, it is desirable to use a novolak type phenol resin by using an acidic substance. The novolak type phenol resin uses a small amount of formaldehyde and has good reactivity with polyvalent isocyanate.

When the above-mentioned phenolic resin precondensate is subjected to sulfomethylation and / or sulfimethylation, the precondensate may be added to a phenolic compound and / or a sulfimethylation agent at any stage by adding a sulfomethylation agent and / or a sulfimethylation agent. Sulfomethylating the precondensate and / or
Alternatively, it can be produced by sulfimethylation. The sulfomethylating agent and / or the sulfimethylating agent may be added at any stage before, during, or after the condensation reaction.

The total amount of the sulfomethylating agent and / or sulfimethylating agent is usually 0.001 to 1.5 mol per 1 mol of the phenolic compound. In order to maintain good properties such as physical properties of the cured resin, the amount is preferably about 0.01 to 0.8 mol.

The aqueous solution of the precondensate of the sulfomethylated and / or sulfimethylated phenolic resin is stable in a wide range from acidic (pH 1.0) to alkaline, and can be any of acidic, neutral and alkaline. It can be cured even in areas. In particular, when cured on the acidic side, residual methylol groups are reduced, and there is no danger that the cured product is decomposed to formaldehyde.

[Polyvalent isocyanate] In the present invention, a polyvalent isocyanate is used as a curing agent for the phenol resin. The polyvalent isocyanate is a compound having at least two isocyanate groups in one molecule,
Such polyvalent isocyanates include, for example, 2,4
-Tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, 1,4
-Naphthalene diisocyanate, 4,4'-diphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-diphenyl diisocyanate, 3,3'-dimethyl- 4,4'-
Diphenylmethane diisocyanate, 3,3'-dimethoxy-4,4'-diphenyldiisocyanate, 2-chloro-1,4-phenyldiisocyanate, 1-chloro-2,4-phenylene diisocyanate, m- Phenylene diisocyanate, p-phenylene diisocyanate, 2,2 ', 5,5'-tetramethyl-4,4'-biphenylene diisocyanate, m-xylylene diisocyanate, ω-xylylene diisocyanate, ω And diisocyanates such as' -xylylene diisocyanate. The polyvalent isocyanates are used alone or in combination of two or more.

A block polyvalent isocyanate obtained by blocking the isocyanate group of the polyvalent isocyanate with a blocking agent may be used as a curing agent. The blocking agent is a compound containing various active hydrogens, which can block the isocyanate group of the polyvalent isocyanate compound and can dissociate at a desired temperature to release the isocyanate group. Anything is fine. For example, lower alcohols (methanol, ethanol, etc.), phenols, aliphatic mercaptans (ethyl mercaptan, etc.),
Aromatic mercaptans (such as β-thionaphthol), hydrocyanic acid,
Secondary aromatic amines (eg, N-methylaniline), oximes (eg, acetoxime, cyclohexanone oxime),
Active methylene compounds (such as diethyl malonate, acetylacetone, and ethyl acetoacetate), lactams (such as ε-caprolactam), and bisulfites can be used as blocking agents.

The above polyvalent isocyanate and block polyvalent isocyanate are dissolved in an organic solvent having no active hydrogen, for example, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, and the like. May be added to the aqueous phenolic resin solution, or may be dissolved in the above organic solvent and then added to the aqueous phenolic resin solution as an aqueous dispersion. By making the polyvalent isocyanate or the block polyvalent isocyanate into an aqueous dispersion, the solubility and dispersibility of the block polyvalent isocyanate in an aqueous phenol resin solution are improved. The amount of the polyvalent isocyanate and the block polyvalent isocyanate added is 2 to the phenol resin.
１５０150% by weight.

[Resin Composition] The resin composition of the present invention contains the above-mentioned water-soluble phenol resin and a polyvalent isocyanate, and in the resin composition, the polyvalent isocyanate is obtained by curing the phenol resin. Acts as an agent. Therefore, there is no need to use a formaldehyde donor such as formaldehyde or hexamethylenetetramine as a curing agent for the phenolic resin.
The content of free formaldehyde during and after curing is reduced, and there is no risk of polluting the environment. Further, since the epoxy compound also reacts with free phenol present in the resin composition, generation of offensive odor due to free phenol of the resin compound can be prevented.

The amount of the polyvalent isocyanate to 100 parts by weight of the phenol resin is preferably 2 to 150 parts by weight, more preferably 5 to 100 parts by weight, as solids. If the blending amount of the polyvalent isocyanate is less than 2 parts by weight, the phenol resin will not be sufficiently cured, and if the blending amount of the polyvalent isocyanate exceeds 150 parts by weight, the strength of the molded product will be reduced.

In the resin composition of the present invention, a third component may be added as required. For example, triethylamine, cobalt naphthenate, benzyltrimethylammonium hydroxide, stannous chloride, stannic chloride, tetra-n-butyltin, tri-n-butyltin, which promotes the reaction between a polyvalent isocyanate and a phenol resin Acetate, n-butyltin trichloride, trimethyltin hydroxide, dimethyltin dichloride, dibutyltin dilaurate, triethyldiamine,
Stanas octoate, dibutyltin di-2-ethylhexoate, sodium orthophenylphenate, potassium oleate, potassium oleate, lead nitrate, tetra (2-ethylhexyl) titanate, ferric chloride, ferric 2-ethylhexoate A catalyst such as iron, cobalt 2-ethylhexoate, zinc naphthenate, and antimony trichloride may be added. Also, if necessary, various amino resins such as urea resins and melamine resins; natural rubber or derivatives thereof; styrene-butadiene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, isoprene rubber, isoprene -Synthetic rubber latex such as isobutylene rubber; vinyl acetate, vinyl propionate, styrene, acrylic ester, methacrylic ester, acrylonitrile, acrylic acid, methacrylic acid, maleic acid, vinyl chloride, vinylidene chloride,
Homopolymers of vinyl monomers such as vinylpyridine or copolymers of two or more of these vinyl monomers; polyurethane, polyamide, butyral resin, polyethylene, polypropylene, vinyl acetate-ethylene copolymer, chlorinated polyethylene, Emulsion, latex or aqueous solution of various synthetic resins such as chlorinated polypropylene and polyester; polyvinyl alcohol, sodium alginate, starch, starch derivatives, glue, gelatin, blood powder, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, polyacrylate, polyacrylamide, etc. Water-soluble polymers and natural gums; fillers such as calcium carbonate, talc, gypsum, carbon black, wood flour, walnut flour, coconut husk, wheat flour, rice flour; surfactants; stearic acid, palmitic acid, etc. Higher fatty acid, palmityl alcohol, higher alcohols such as stearyl alcohol; butyryl stearate, esters of fatty acids such as glycerin monostearate; fatty acid amides; natural waxes carnauba wax, synthetic waxes; paraffins,
Release agents such as paraffin oil, silicone oil, silicone resin, fluororesin, polyvinyl alcohol, and grease; hexane, butane, n-pentane, alcohol, ether,
Methylene chloride, carbon tetrachloride, chlorofluoromethane,
Low boiling solvents such as 1,1,2-trichloro-1,2,2-trifluoroethane; azodicarbonamide, dinitrosopentamethylenetetramine, P, P′-oxybis (benzenesulfonylhydrazide), azobis-2,
Organic foaming agents such as 2 ′-(2-methylglopionitrile); inorganic foaming agents such as sodium bicarbonate, potassium bicarbonate and ammonium bicarbonate; n-pentane, isopentane,
Microcapsule type foaming agent containing butane, isobutane, etc. in thermoplastic resin microcapsules; hollow particles such as shirasu balloon, pearlite, glass balloon, foamed glass, hollow ceramics; plastics such as foamed polyethylene, foamed polystyrene, foamed polypropylene Foams and foams; pigments, dyes, flame retardants, flame retardants, water repellents, oil repellents, insect repellents, preservatives, antioxidants, ultraviolet absorbers; DB
A third component such as P, DOP, a phthalate plasticizer such as dicyclohexyl phthalate, or another plasticizer such as tricresyl phosphate may be added.

The resin composition described above comprises a fiber sheet,
It can be used for various purposes such as impregnating a porous body such as a plastic foam sheet to impart rigidity and moldability, mixing it with a wood chip or a fiber material as a binder, or applying a paint or an adhesive.

B. Molding Material The resin composition of the present invention is impregnated into a porous material as an impregnating agent, or mixed with a chip, powder or fiber as a binder. Since a porous material (molding material (1)) impregnated with the resin composition of the present invention or a chip, powder or fiber (molding material (2)) mixed with the resin composition of the present invention has moldability, Useful as a material.

[Porous Material] Examples of the porous material used in the molding material (1) of the present invention include a fiber aggregate, a plastic foam having open cells, and a sintered plastic bead. Examples of the fiber constituting the fiber aggregate include natural fibers such as cotton, hemp, wool, silk, kenaf, coconut fiber, and bamboo fiber, polyamide fiber, polyester fiber, acrylic fiber, viscose fiber, acetate fiber, and vinyl chloride fiber. , Organic synthetic fiber such as vinylidene chloride fiber, asbestos fiber, glass fiber, carbon fiber, ceramic fiber, metal fiber, whisker, inorganic fiber such as rock wool (rock wool),
Alternatively, recycled fibers obtained by defibrating scraps of fiber products using the above fibers, or a mixture of two or more of these fibers, or polyester fibers, polypropylene fibers, and polyethylene having a melting point of 200 ° C. or less with these fibers Fibers and mixtures with low-melting fibers such as polyamide fibers. As the fiber aggregate, a web,
Nonwoven fabrics, felts, knitted fabrics, laminates thereof and the like are included.

Examples of the plastic foam include a polyurethane foam having an open-cell structure, a polyolefin foam such as polyethylene and polypropylene, a polyvinyl chloride foam, a polystyrene foam, a melamine resin, and the like.
There are amino-based resin foams such as urea resin and phenol resin foams. The plastic foam is usually provided in the form of a sheet when used as a raw material for a base material of an interior material of an automobile.

[Production of molding material (1)] Molding material of the present invention
(1) can be produced by a method in which the porous material is impregnated with the resin composition of the present invention, and heated and dried at a temperature not higher than the curing temperature of the resin composition.

As a method for impregnating the porous material with the resin composition, a known method such as a dipping method or a spray method is applied. In the case of the immersion method, for example, by immersing the porous material in an impregnation tank filled with the resin composition, and then pressing the porous material to which the resin composition has adhered with a squeezing roll or a press machine, The porous material can be impregnated with a predetermined amount of the resin composition. The resin composition filled in the impregnation tank may be foamed and / or foamed.

The porous material impregnated with the resin composition is subjected to a heating and drying step. In this step, the phenol resin precondensate contained in the resin composition may be brought into the B state. In order to keep the initial condensate in the B state, the heating temperature, the heating time, and the like may be adjusted. The heating temperature is set to be equal to or lower than the curing temperature of the resin composition. It is about 1 to 5 hours. For the heating and drying, hot-air drying, far-infrared drying, high-frequency heating and the like are usually applied.

By setting the phenolic resin precondensate in the resin composition impregnated in the porous material into the B state, the stability of the resin composition is improved and the molding material can be stored for a long period of time. In addition, since the water content of the resin composition is reduced, the molding time is shortened, and a puncture phenomenon due to moisture vapor does not occur even when the resin composition is molded by hot pressing. Further, after the molding material is subjected to hot press molding, the resin composition is completely cured, so that a molded product excellent in shape retention and heat resistance can be obtained.

[Molding / Molded Article] The resin composition impregnated in the molding material (1) of the present invention is thermosetting and therefore has moldability and is usually used in a lower mold and an upper mold having a desired mold surface shape. By hot pressing using a molding machine.
The hot pressing conditions are set to a temperature and time at which the resin composition is completely cured, and the pressing pressure is usually 1 to 10 kg /.
It is cm ^2. At this time, it may be superimposed on another sheet and hot-pressed to form a laminate.

Since the molding material (1) of the present invention is impregnated with the above resin composition which does not use a formaldehyde donor such as formaldehyde or hexamethylenetetramine as a curing agent, it does not release formaldehyde during and after curing. There is no risk of polluting the environment.

The molded product obtained from the molding material (1) of the present invention is particularly suitable for vehicle interiors such as door trims, dashboards, ceiling materials, insulator hoods, dash inners, dash outers, engine under covers, trunk side trims, and the like. It is useful as a material, a base material or a skin material of the interior material, or a building material such as a floor material, a wall material, and a roof base material.

When the molded article of the present invention is used as a skin material, a wadding material such as a plastic foam or a nonwoven fabric may be backed, and the base material to which the skin material is adhered is, for example, polyurethane. Foam, polyethylene, polyolefin foam such as polypropylene, polyvinyl chloride foam, polystyrene foam, melamine resin foam,
Plastic foam such as urea resin foam, cardboard,
There are resin felt, plywood, particle board, wood cement board and the like.

When the obtained molded product is used as a skin material, it is usually adhered to a substrate by the following three methods. In the first method, as shown in FIG. 1, a base material (11) is formed into a predetermined shape, and a sheet-like molding material (1) is cured and formed into a shape conforming to the shape of the base material (11). And bonding the formed cured sheet (12) to the surface of the substrate (11). In order to attach the cured sheet (12) to the surface of the substrate (11), an adhesive, a hot-melt type adhesive or a hot-melt sheet described later may be used, or the substrate (11) may be heated. When it is made of a plastic material, it may be heated and fused.

In the second method, as shown in FIG. 2, the sheet-shaped molding material (12a) and the base material (11a) before forming the base material are superimposed, and the upper mold (13) having a predetermined shape is formed. ) And the lower mold (14) and hot-press molding the base material (11a) and the molding material (12).
a) is simultaneously molded and the resin composition in the molding material (12a) is cured. At this time, depending on the material of the base material (form), the molding material (12a) and the base material form (11a)
In between, hot melt sheet and natural resin, natural rubber,
An adhesive such as a synthetic resin or a synthetic rubber may be interposed.

In the third method, as shown in FIG. 3, a sheet-like molding material is cured and molded in a predetermined shape in advance, and the molded cured sheet (12) is formed on a mold surface (151) of a molding die (15). In addition, there is a method in which the foamed resin liquid R is injected into the molding die (15) from the resin injection port (152) and cured to form a base material. Examples of the type of the foamed resin liquid R include, for example, polyurethane foamed resin, polyolefin foamed resin such as polyethylene and polypropylene, polyvinyl chloride foamed resin, polystyrene foamed resin, melamine foamed resin, urea foamed resin, and the like. There is a composition.

Since the skin material of the present invention is obtained by impregnating and curing the above resin composition which does not use a formaldehyde donor such as formaldehyde or hexamethylenetetramine as a curing agent, the molding material releases formaldehyde. No risk of polluting the environment. Further, since the skin material of the present invention has high rigidity, the obtained interior material is provided with good shape stability, and the shape can be maintained for a long time.

When the molded article of the present invention is used as a base material for an interior material, a skin material is usually adhered to the surface thereof. Examples of the skin material include artificial leather, leather, fiber knitted fabric, non-woven fabric, and plastic foams such as polyurethane foam, polyethylene foam, polypropylene foam, polystyrene foam, and polyvinyl chloride foam. There are laminated materials and the like.

The skin material is adhered to the above-mentioned base material with an adhesive, a hot melt type adhesive, a hot melt sheet or the like. Examples of the adhesive include an acrylic adhesive, a synthetic rubber adhesive, an elastomer adhesive, a vinyl acetate adhesive, a vinyl chloride adhesive, a urea resin adhesive, a melamine resin adhesive, and an epoxy resin. An adhesive based on the resin composition of the present invention is used as the adhesive, and the skin material is impregnated with a thermosetting synthetic resin in the form of an initial condensate solution as the adhesive, and is used as it is or in the B state. After that, the skin material can be adhered to the base material by superimposing the base material on the base material and molding at the same time, and furthermore, impregnation of such a thermosetting synthetic resin and application of the adhesive. Etc. can be used in combination. As the thermosetting synthetic resin, the resin composition of the present invention can be used.

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 resins and polyurethane resins. Or a mixture of two or more of polyester resins, polyamide resins and the like. The hot melt adhesive is provided as a solution type or an emulsion type, and also as a dispersion type in which the hot melt adhesive powder is dispersed in water. Further, the hot melt adhesive is formed into a sheet and used as a hot melt sheet.

When the above adhesive is formed into an adhesive layer by coating or the like, it may be preferable that the adhesive layer is scattered in a dotted manner on the bonding surface of the skin material and / or the base material. As described above, if the skin material and the base material are bonded by the adhesive layer scattered in a point-like manner, the rigidity of the adhesive layer does not affect the molding shape of the interior material or the uneven shape of the surface, and therefore, The shape and unevenness of the interior material are sharply formed. 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 bonding surface of the skin material and / or the substrate, for example, a spray coating method, a letterpress printing method, a silk screen printing method or the like is applied. After the masking sheet is applied, a method of applying an adhesive with a spray, knife coater, roll coater, flow coater or the like, and then peeling off the masking sheet may be applied. The above skin material and / or
Alternatively, a desirable method of dispersing the adhesive layer in a dot-like manner on the adhesive surface of the base material is a method of spray-coating a hot-melt adhesive powder dispersion.

The skin material is adhered to the surface of the base material by the adhesive layer. When the adhesive is a solution type or an emulsion type, the adhesive layer formed on the bonding surface is completely dried. Before joining, stick them together. When the adhesive layer is of 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 molding of the base material may be performed before the skin material is bonded, at the same time as the skin material is bonded, or at any time after the skin material is bonded.

In the case where the above-mentioned skin material is air-permeable and is molded after bonding the skin material to the base material, the air contained in the base material passes through the point-like adhesive layer at the time of molding and is formed on the skin. Since the material is smoothly discharged to the outside, no puncture phenomenon occurs in the manufactured interior material.

The base material of the interior material comprising the molding material (1) of the present invention is obtained by impregnating and curing the above resin composition which does not use a formaldehyde donor such as formaldehyde or hexamethylenetetramine as a curing agent. Therefore, the interior material does not emit formaldehyde and does not pollute the environment.

The interior material using the molding material (1) of the present invention as a base material has high rigidity and can be used for various applications. For example, it is suitable as an interior material for a trunk room of a car or an interior material for a dashboard. is there. In the interior material,
In particular, when the skin material and the base material are adhered by an adhesive layer scattered in a dotted manner, the rigidity of the adhesive layer does not affect the molding shape of the interior material or the uneven shape of the surface. The molded shape and uneven shape of the 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.

[Chip / Powder / Fiber] The chips used in the molding material (2) of the present invention are mainly wood chips,
Although wood chips such as wood wool and wood fiber bundles are used, plastic pieces, plastic foam pieces and the like can also be used. As the powder used for the molding material (2) of the present invention, there is a woody powder such as wood powder, but other plastic powders are also used. The fibers used in the molding material (2) of the present invention include the above-mentioned natural fibers, organic fibers, inorganic fibers, recycled fibers, and wood fibers such as pulp. The chips, powders, and fibers may be used in combination of two or more and / or two or more of each other.

[Production of molding material (2)] Molding material of the present invention
(2) The chip, powder, the method of dipping the fiber in the resin composition of the present invention, the chip, the powder, the chip by stirring the fiber and adding the resin composition by spraying or the like, The resin composition is added to powder and fiber and mixed. Then, if desired, the mixture is dried at a temperature lower than the curing temperature of the resin composition. In this case, the molding material
Similarly to (1), the phenol resin precondensate in the resin composition may be in the B state.

[Molding / Molded Product] The molding material (2) of the present invention is sprayed on a lower mold having a desired mold surface shape without drying, or after being dried, to form a mat. Then, the mat is hot-pressed by the lower mold and the upper mold. The pressing condition is the same as that of the molding material (1), and it may be superposed on another sheet and hot-pressed to form a laminated molded product.

The molding material (2) of the present invention also contains no formaldehyde donor such as formaldehyde or hexamethylenetetramine as a curing agent, and thus does not release formaldehyde during and after curing. There is no risk of polluting the environment.

The molded product obtained from the molding material (2) of the present invention may be an interior material similar to the molding material (1) or a base material of the interior material, or a building material such as a floor material, a wall material and a roof base material. Useful for

The resin composition of the present invention comprises, in addition to the above molding materials,
It is also useful as an adhesive or paint vehicle. In addition, the molding material is used as a pad material or a cushion material for sheets and mats, for example, in addition to interior materials and building materials.

[0061]

When a polyvalent isocyanate is mixed with a phenol resin, a crosslinking reaction occurs between a hydroxyl group of the phenol resin and an isocyanate group of the polyvalent isocyanate, and the resin composition is cured.

[0062]

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[0063]

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Since the hydroxyl group of the phenol group tends to dissociate as shown in Chemical formula 2, the above curing reaction is carried out at a low temperature, and particularly when the phenol resin is a novolak type, the reaction is carried out quickly and smoothly. In the above-mentioned curing reaction, formaldehyde or a formaldehyde donor is not used as a curing agent, so that the free formaldehyde content is reduced. Furthermore, free phenol contained in the phenol resin also reacts with the isocyanate group of the polyvalent isocyanate compound in the same reaction as described above, so that the free phenol content in the phenol resin is reduced. In the case of a block polyvalent isocyanate, a crosslinking reaction is carried out in the same manner as in Chemical Formula 1 after the blocking agent is released as shown below. The block of the polyvalent isocyanate block is not dissociated in the heating and drying step, but is dissociated by heating in the molding step by hot pressing.

[0065]

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Example 1 A 50% by weight (hereinafter simply referred to as%) aqueous solution 100 of the sulfimethylated phenol-alkylresorcin-formaldehyde initial cocondensate (A)
A 50% aqueous dispersion of hexamethylene diisocyanate (B) using an aromatic mercaptan as a blocking agent was mixed at a weight ratio shown in Table 1 with respect to parts by weight (hereinafter simply referred to as "parts"). Table 1 shows the results of measuring free formaldehyde after forming a film of the mixture and heating and curing at 190 ° C. for 3 minutes.

Comparative Example 1 Table 1 shows the results of measurement of the free formaldehyde of a novolak type phenol resin (mixed with 6% hexamethylenetetramine) powder (a) after heat curing at 190 ° C. for 3 minutes in the same manner as in the example.

[0068]

[Table 1]

According to Table 1, in the case of the resin composition of the present invention, the amount of free formaldehyde is much smaller than that of a conventional phenol resin.

Example 2 Sulfomethylated phenol-
50% of orcinol-formaldehyde initial cocondensate
100 parts aqueous solution, low alcohol as a blocking agent
50% of hexamethylene diisocyanate using
Disperse the aqueous dispersion in 50 parts and 50% carbon black in water
Difficult to disperse in 30% water consisting of 2 parts of liquid, nitrogen and phosphorus containing compound
30 parts of flame retardant, 35% water-soluble fluororesin as oil repellent
A mixture of 5 parts of a liquid is mixed with a polyester fiber.
Porous material (400g / m^Two20g in solid content
/ M ^TwoAfter the impregnation so that the coating amount is
After drying, hot press at 200 ℃ for 3 minutes.
Good molded products were obtained. Also free form of this
Aldehyde is free phenol at less than 0.002 μg / g
Was not detected.

Example 3 Novolak-type sulfomethylated alkylresorcinol-formaldehyde precondensate 5
Methylene diisocyanate 5 per 100 parts of 0% aqueous solution
The resulting mixture was applied at a coating amount of 20% with respect to the wood flour 100, and then heated and pressed at 120 ° C. for 6 minutes to produce a wood board. The wood board had high strength and free formaldehyde was less than 0.002 μg / g.

Example 4 A 50% aqueous dispersion of hexamethylene diisocyanate using an aliphatic mercaptan as a blocking agent was added to 100 parts of a 50% aqueous solution of a sulfimethylated phenol-alkylresorcin-formaldehyde initial cocondensate. 30 parts and a mixture of 15 parts of 50% latex of styrene-isoprene-styrene copolymer were impregnated into a polyester nonwoven fabric having a basis weight of 100 g / m ² at an application amount of 70 g / m ² and dried at 120 ° C. When hot pressing was performed at 200 ° C., a molded product having good moldability was obtained. The product dried at 120 ° C. was allowed to stand at room temperature (about 20 to 25 ° C.) for 30 days, and was similarly heated and pressed to obtain a good molded product. In each case, free formaldehyde was less than 0.002 μg / g and free phenol was not detected.

[0073]

According to the present invention, there is provided a resin composition which has a low content of harmful substances such as free formaldehyde and free phenol during and after curing and can be cured at low temperatures. The composition is useful for molding materials, binders, adhesives, paints and the like.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing an example of a process for producing a molding material of the present invention.

FIG. 2 is an explanatory view showing an example of a process for producing a molding material of the present invention.

FIG. 3 is an explanatory view showing an example of a process for producing a molding material of the present invention.

[Explanation of symbols]

 11 Base member 12 Cured sheet

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Takehiko Kajita 213-5 Minami-Shibata-cho, Tokai City, Aichi Prefecture Inside Nagoya Yuka Co., Ltd. (72) Inventor Kunori Ito Minami-Shibata-cho, Tokai City, Aichi Prefecture 213 No. 5 Nagoya Yuka Co., Ltd. F-term (reference) 4F072 AA04 AA07 AB03 AB04 AB05 AB06 AB08 AB09 AB10 AB11 AB27 AB28 AB29 AB30 AB31 AD13 AD15 AD53 AE01 AF31 AG02 AG14 AH03 AH31 AH53 AJ04 AK05 AK14 AL17 4J0311 DJ HA07 HC11 HC12 HC13 HC22 HC52 HC54 HC61 HC63 HC64 HC66 HC67 HC71 HD02 HD03 HD04 HD05 HD06 HD12 RA07 RA08 4J038 DG151 DG301 GA13 MA08 MA09 NA27 PB05 PB07 PC06 PC08 PC10 4J040 EF141 EF331 GA23 JA03 JB02 LA11 MB01 MB02 MB07 PA30

Claims (9)

[Claims] 1. A resin composition comprising a polyphenolic isocyanate dispersed in an aqueous phenol resin solution. 2. The resin composition according to claim 1, wherein the polyvalent isocyanate is a block polyvalent isocyanate. 3. The resin composition according to claim 1, wherein the phenol resin is of a novolak type. 4. Part or all of the phenolic resin is
The resin composition according to any one of claims 1 to 3, which is sulfomethylated and / or sulfimethylated. 5. A molding material comprising a porous material impregnated with the resin composition according to claim 1. Description: 6. The molding material according to claim 5, wherein the phenolic resin in the resin composition is in a B state. 7. A molded product obtained by heat-molding the molding material according to claim 5 into a predetermined shape and thermally curing the resin composition in the molding material. 8. A molding material comprising a chip and / or a powder and / or a fiber material mixed with the resin composition according to claim 1 as a binder. 9. A molded product obtained by heating and molding the molding material according to claim 8 into a predetermined shape and thermally curing the resin composition in the molding material.