JPH0925469A - Thermosetting resin composition, curing method, wood material and molded product - Google Patents

Abstract

(57) [Summary] [Object] An object of the present invention is to provide a thermosetting resin composition having a long pot life and being rapidly cured by heating at a low temperature. [Structure] A uron-based compound is added as a curing agent to an initial condensation product of a monohydric phenol and / or a polyhydric phenol and an aldehyde.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a binder, a non-woven fabric, a fiber knitted fabric, a coating or impregnating agent for paper, or an adhesive for wood, which is used in the production of molded articles of fibers, wood chips or inorganic powder. The present invention relates to a useful thermosetting resin composition, a method for curing the same, a wood material and a molded article using the thermosetting resin composition.

[0002]

2. Description of the Related Art Conventionally, as a coating or impregnating agent for water-soluble binders, non-woven fabrics, fiber knitted fabrics, papers, etc., or adhesives for wood, which are used in the production of moldings of fibers, wood chips or inorganic powders. , Resol type phenol
Aldehyde-based initial condensates and phenol / resorcin / aldehyde-based initial cocondensates are used.

[0003]

However, the above-mentioned resol-type phenol / aldehyde-based initial condensate is unstable at room temperature and must be stored at a low temperature, so that it has a short shelf life. Moreover, it usually takes 18 to cure it.
High temperature heating of 0 to 200 ° C. is required, and such high temperature heating causes thermal deterioration of molding materials such as fibers and wood chips, and also increases heat energy cost. In the case of monohydric phenol / polyhydric phenol / aldehyde initial cocondensate such as phenol / resorcinol / aldehyde initial cocondensate, it is necessary to add aldehyde as a curing agent when using, such as formalin and paraformaldehyde. When using such aldehyde as a curing agent, the pot life at room temperature after addition of the curing agent is short because the reactivity is too high, and the pot life is 2-3 hours at the longest, and the workability is very high. It has the drawback of being bad. Also formalin,
When heat-reactive hexamethylenetetramine is used as a curing agent instead of paraformaldehyde, the monohydric phenol / polyhydric phenol / aldehyde initial cocondensate is mixed as a binder or coated or coated as an impregnating agent. Curing progressed considerably even in the pre-drying stage after impregnation, and further, the pre-dried product had a problem that it rapidly progressed to cure at room temperature, lost its moldability, and could not be stored for a long period of time. In order to improve the pot life of resorcinol resin after the addition of a curing agent, amino acids such as methylol urea, urea formaldehyde resin, methylated methylol urea, methylol melamine, melamine formaldehyde resin, and methylated methylol melamine are used instead of aldehyde as a curing agent. A curing method has been disclosed in which a system resin is added and the composition is heated and cured at a pH of 7 or more (JP-A-57-053).
536). However, if this method is applied to the above-mentioned monohydric phenol / polyhydric phenol / aldehyde-based initial cocondensate, the pot life after addition of the curing agent is extended, but heating at 180 ° C or higher is required for curing, and heating There is a problem in that the effect of accelerating curing, that is, at a lower temperature and shorter time, cannot be expected.

[0004]

As a means for solving the above-mentioned conventional problems, the present invention provides a monohydric phenol and / or
Alternatively, a thermosetting resin composition, a method for curing the thermosetting resin composition, and the thermosetting resin, which are mainly composed of a mixture of an initial condensation product of a polyhydric phenol and an aldehyde and a uronic compound Provided is a molded product using the resin composition.

The present invention will be described in detail below. The thermosetting resin composition of the present invention is a monohydric phenol / aldehyde-based initial cocondensate and / or a polyhydric phenol / aldehyde-based initial cocondensate and / or a monohydric phenol / polyhydric phenol / aldehyde-based initial cocondensate. It is mainly composed of a mixture of (hereinafter referred to as an initial cocondensate A) and a uronic compound B. [Monohydric phenol] Monohydric phenol used in the initial cocondensation product A of the present invention is exemplified by phenol, o-cresol, m-cresol, p-cresol, ethylphenol, iso-propylphenol, xylenol,
3,5-xylenol, butylphenol, t-butylphenol, alkylphenols such as nonylphenol, o-fluorophenol, m-fluorophenol, p-fluorophenol, o-chlorophenol,
m-chlorophenol, p-chlorophenol, o-bromophenol, m-bromophenol, p-bromophenol, o-iodophenol, m-iodophenol, p-iodophenol, o-aminophenol, m
-Monophenol substitution products such as -aminophenol, p-aminophenol, o-nitrophenol, m-nitrophenol, p-nitrophenol, 2,4-dinitrophenol, 2,4,6-trinitrophenol and naphthol Such monohydric phenols are used alone or as a mixture of two or more kinds.

[Polyhydric Phenol] Examples of the polyhydric phenol used in the initial cocondensation product A of the present invention include resorcin, alkylresorcin, pyrogallol, catechol,
It is a single or a mixture of two or more polyhydric phenols such as alkylcatechol, hydroquinone, alkylhydroquinone, phloroglucin, bisphenol, and dihydroxynaphthalene. Among these polyhydric phenols, desirable one is resorcin or alkylresorcin, and particularly desirable one is alkylresorcin which has a higher reaction rate with aldehyde than resorcin. Examples of the alkylresorcin include 5-methylresorcin, 5-ethylresorcin, 5-propylresorcin,
5-n-butylresorcin, 4,5-dimethylresorcin, 2,5-dimethylresorcin, 4,5-diethylresorcin, 2,5-diethylresorcin, 4,5-dipropylresorcin, 2,5-dipropylresorcin , 4
-Methyl-5-ethylresorcin, 2-methyl-5-ethylresorcin, 2-methyl-5-propylresorcin, 2,4,5-trimethylresorcin, 2,4,5-
Examples include triethylresorcin. The polyhydric phenol mixture obtained by dry distillation of Estonian oil shale is inexpensive and contains a large amount of highly reactive alkylresorcin in addition to 5-methylresorcin, and is therefore the most preferable polyphenol raw material in the present invention.

[Aldehyde and / or aldehyde donor] To prepare the initial cocondensate A of the present invention, the above 1
Condensing the hydric phenol and / or polyhydric phenol with the aldehyde and / or aldehyde donor. The above-mentioned aldehyde donor means a compound that produces and provides an aldehyde when decomposed. Examples of the above aldehyde and aldehyde donor include formalin, formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene,
Chloral, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, caproaldehyde, allylaldehyde, benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde,
A salicyl aldehyde or the like is used alone or as a mixture of two or more kinds.

[Condensation catalyst] In the present invention, a monohydric phenol and / or a polyhydric phenol and an aldehyde and / or
Alternatively, during condensation with an aldehyde donor, an acidic or alkaline condensation catalyst is added if necessary. The addition amount is usually 6% by weight (hereinafter simply referred to as%) or less based on the monohydric phenol and / or the polyhydric phenol. Examples of the acidic catalyst include 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, paratoluenesulfonic acid, naphthalene-α-sulfonic acid, naphthalene-β-sulfonic acid, or esters of organic acids such as oxalic acid dimethyl ester, and acid anhydrides such as maleic anhydride , Manganese hydroxide, chromium hydroxide, iron hydroxide, lead hydroxide, copper hydroxide, zinc acetate, zinc formate, zinc benzoate, zinc chloride, ferric chloride, manganese acetate, cadmium acetate,
Ammonium salts such as ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium oxalate, ammonium acetate, ammonium phosphate, ammonium thiocyanate and ammonium imidosulfonate, monochloroacetic acid and its sodium salt, organic halides such as α, α'dichlorohydrin, tris Examples include ethanolamine hydrochloride, amine hydrochlorides such as aniline hydrochloride, urea adducts such as salicylate urea adduct, stearic acid urea adduct, heptanoic acid urea adduct, and N-trimethyltaurine. Examples of the alkaline catalyst include sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, calcium oxide, barium oxide, magnesium oxide, zinc oxide, cobalt oxide, lead oxide, nickel oxide,
Hydroxides and oxides of metals such as aluminum oxide, weak acid salts of alkali metals such as sodium carbonate, sodium sulfite, sodium acetate, sodium phosphate, and amines such as ammonia, trimethylamine, triethanolamine, hexamethylenetetramine, and pyridine. It is illustrated. Two or more of the above acidic or alkaline catalysts may be used in combination.

[Solvent] In the present invention, water is usually used as a solvent for the initial cocondensate A, but if necessary, further methanol, ethanol, isopropanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol is used. , T-butanol, n-amyl alcohol, iso-amyl alcohol, n-hexanol, methylamyl alcohol, 2-ethylbutynol, n-heptanol, n-octanol, trimethylnonyl alcohol, cyclohexanol, benzyl alcohol, furfuryl alcohol. , Tetrahydrofurfuryl alcohol, abiethyl alcohol, alcohols such as diacetone alcohol, acetone, methylacetone,
Methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, diethyl ketone, di-n-propyl ketone, diisobutyl ketone, acetonylacetone, methyl oxide, cyclohexanone, methylcyclohexanone, acetophenone, camphor such as camphor Ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, polyethylene glycol, and other glycols, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol isopropyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether Glycol ethers such as ethylene glycol Esters and derivatives of the above glycols such as diacetate and diethylene glycol monoethyl ether acetate, ethers such as 1,4-dioxane, diethyl cellosolve, diethyl carbitol, ethyl lactate, isopropyl lactate, diglycol diacetate, dimethylformamide. Water-soluble organic solvents such as the above can be used alone or as a mixture of two or more thereof. Acetone and the like act as a solvent and, at the same time, also act as a complexing agent when using alkylresorcin, and bring about a milder reaction.

[Precondensate A] Precondensate A of the present invention
Is obtained by subjecting a monohydric phenol and / or a polyhydric phenol and an aldehyde and / or an aldehyde donor to a condensation reaction under heating or at room temperature in the presence of an acidic or alkaline condensation catalyst or without the presence of a condensation catalyst. . The addition amount of the aldehyde and / or aldehyde donor at this time is usually 0.2 to 3 mol per 1 mol of the monohydric phenol, and usually about 0.1 to 0.8 mol per polyphenol. . When the monohydric phenol and the polyhydric phenol are co-condensed, it is preferable that the polyhydric phenol is usually co-condensed in an amount of about 0.1 to 2 mol per mol of the monohydric phenol. For co-condensing a monohydric phenol with a polyhydric phenol with an aldehyde and / or an aldehyde donor, a monohydric phenol with a polyhydric phenol with an aldehyde and / or an aldehyde in the presence or absence of an alkali or acidic catalyst Method of simultaneously condensing with a donor A polyhydric phenol and / or a polyhydric phenol / aldehyde precondensate and, if necessary, an aldehyde and / or an aldehyde donor are added to a monohydric phenol and / or a monohydric phenol / aldehyde precondensate. Although any method such as co-condensation may be used, the preferable method is 1
Of a phenol and an aldehyde and / or an aldehyde donor in the presence of an alkali catalyst to give a methylol group-containing resol-type phenol / aldehyde initial condensate, which is then added to the polyhydric phenol and / or the polyhydric phenol / aldehyde. In this method, an initial condensate of the system is added, and if necessary, an aldehyde and / or an aldehyde donor is added to carry out cocondensation. Monohydric phenol 1 in this case
Co-condensation is carried out at a ratio of 0.2 to 6.0 mol of aldehyde and 0.1 to 2.0 mol of polyhydric phenol per mol. The aqueous solution of the initial condensate A is usually stable on the alkaline side having a pH of 8 to 9 or more, but is unstable on the neutral or acidic side and causes a problem of layer separation. To solve this problem, it is desirable to introduce a sulfomethyl group and / or a sulfimethyl group into the initial condensate A. A wide pH range from alkaline to acidic of the initial condensate A by the introduction of the sulfomethyl group and / or the sulfimethyl group.
The thermosetting resin composition of the present invention is obtained in which the water solubility in the region is remarkably improved and which is stable.

If desired as the third component of the initial condensate A, urea, melamine, thiourea, benzoguanamine, toluene, xylene, coumarone, cyclohexanone, cashew oil, tannins, dammers, shellac, rosin or rosin derivatives, petroleum resin. , Methanol, ethanol, isopropanol, n-butanol, isobutanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerin, furfuryl alcohol, linseed oil, tung oil, castor oil, acetone, methyl ethyl ketone and the like as a co-condensation agent or The modifier or the complexing agent may be modified by adding and cocondensing or mixing at the start of the condensation or cocondensation reaction, during the reaction, or after the completion of the reaction.

[Sulfomethylated and Sulfimethylated] Phenol / aldehyde based precondensate A of the present invention
The sulfomethylated products and sulfimethylated products of 1 are
When a polyhydric phenol and / or a polyhydric phenol is condensed with an aldehyde and / or an aldehyde donor, a sulfomethylating agent and / or a sulfimethylating agent may be added and reacted at the start of the condensation reaction or during or after the reaction. Sulfomethylated precondensate or initial cocondensate or sulfimethylated precondensate or initial cocondensate. The sulfomethylating agent or sulfimethylating agent is preferably added when the monohydric phenol is condensed with an aldehyde and / or an aldehyde donor in the presence of an alkali catalyst to form a phenol / aldehyde precondensate. The polyhydric phenol may be previously sulfomethylated and / or sulfimethylated and then condensed or co-condensed with the aldehyde and / or the aldehyde donor. When the above-mentioned initial condensate A is sulfomethylated and / or sulfimethylated, the reaction activity of the initial condensate A with an aldehyde is lowered and the pot life is extended when an aldehyde and / or an aldehyde donor is added as a curing agent. It
Further, the introduction of the sulfomethyl group and / or the sulfimethyl group increases the water solubility of the initial condensate A, and the good water solubility is exhibited in a wide pH range on the neutral or acidic side. When the acidity is kept slightly acidic, the reaction activity of the cocondensate with the aldehyde is the lowest, and the pot life is the longest. When the initial condensate A is a monohydric phenol initial condensate, the reaction activity with an aldehyde may be significantly reduced due to sulfomethylation and / or sulfimethylation, and the curing is too slow even if the urone compound described below is added. Therefore, in the present invention, it is preferable to select a monohydric phenol / polyhydric phenol / aldehyde initial cocondensate as the initial condensate A. In the sulfomethylation, it is desirable that the sulfomethyl group is in the range of 0.05 to 0.5 mol with respect to 1 mol of the monohydric phenol. When the sulfomethyl group is 0.05 mol or less, there is a drawback that the reaction activity with the aldehyde is not sufficiently lowered and the pot life is too short. Further, if the sulfomethyl group is 0.5 mol or more, the reaction activity with the aldehyde is excessively reduced, and
When heated at 0 to 140 ° C. or lower, a cured product having sufficient strength cannot be obtained, and the cured product has poor water resistance. Also in the case of sulfimethylation, for the same reason as in the case of sulfomethylation, it is desirable to set the sulfimethyl group in the range of 0.05 to 0.5 mol with respect to 1 mol of monohydric phenol. When the precondensate A is sulfomethylated and / or sulfimethylated, a stable mixed composition with a uronic compound is obtained even under neutral and acidic conditions. That is, the mixed composition can be used in a pH range where the reaction activity of the uron-based compound becomes higher, and there is an advantage that the curing reaction can proceed by heating at a lower temperature for a shorter time.

[Sulfomethylating Agent and Sulfimethylating Agent] Examples of the sulfomethylating agent used in the present invention include sulfurous acid, bisulfite or metabisulfite and an alkali metal, or a quaternary amine such as trimethylamine or benzyltrimethylammonium, or a quaternary amine. Examples thereof include water-soluble sulfites with a quaternary ammonium, and hydroxyalkanesulfonic acids such as hydroxymethanesulfonic acid salts obtained by reacting these water-soluble sulfites with aldehydes. Examples of the sulfimethylating agent to be used in the present invention include formaldehyde sodium sulfoxylate (Rongalit), alkali metal sulfoxylates of aliphatic and aromatic aldehydes such as benzaldehyde sodium xylate, sodium hydrosulfite, magnesium hydrosulfite. Examples thereof include alkali metal and alkaline earth metal hydrosulfites, sodium ethyl sulfoxylate and other alkyl sulfoxylates, and the like. When an alkali metal dithionite is used as the sulfimethylating agent, the sulfomethylation reaction proceeds in parallel with the sulfimethylation reaction, so that a sulfomethylated product is generated together with the sulfimethylated product.

[Uron-based compound] In the thermosetting resin composition of the present invention, a uron-based compound B is added to the initial condensate A as a curing agent. The uronic compound B is urea and / or thiourea and aldehyde and / or
Alternatively, it is a reaction product with an aldehyde donor and usually has a structural formula of the following chemical formula 1. Here, R is an alkyl group or an aryl group, and depends on the kind of the raw material aldehyde used. Further, the ROH group may be alkoxylated as shown in the structural formulas 2 and 3 below. Here, R'is an alkyl group or an aryl group.

Embedded image

Embedded image

Embedded image A typical example of the uronic compound B of the present invention is dimethylolurone, which is a reaction product of 1 mol of urea and 4 mol of formaldehyde, and a dimethoxylated product thereof. Uron compound B is relatively stable at room temperature, but when it is heated to several tens of degrees Celsius or more, it starts to activate, and when it is carried out under acidic condition, it activates more actively, and it becomes more active than phenol / aldehyde initial condensation products. Acts as a curing agent. And its curing activity is significantly higher than other alkylol group-containing urein, ethyleneurea, propyleneurea, heterocyclic ring compounds such as triazone, or methylolurea, urea formaldehyde resin, methylolmelamine, melamineformaldehyde resin, etc. There is a characteristic. Therefore, the uron-based compound becomes an extremely effective curing agent that heat-cures the phenol / aldehyde-based initial condensate at a low temperature in a short time.

[0015]

[Curing catalyst] A thermosetting resin composition of the present invention comprising an initial condensate A having a sulfomethyl group and / or a sulfimethyl group introduced therein and a uron-based compound B is added to the uron-based compound B at the time of curing. Further, an acidic or alkaline compound may be added as a curing catalyst.
Examples of the acid curing catalyst are hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, sulfonic acid, hydrobromic acid, hydroiodic acid, trichloroacetic acid, benzenesulfonic acid, chlorosulfonic acid, and paratoluene. Sulfonic acid, phenolsulfonic acid, ethanesulfonic acid, mixed alkanesulfonic acid, metabenzenedisulfonic acid, naphthalene α-
Sulfonic acid, 1-naphthol-8-sulfonic acid, metaxylenesulfonic acid, xylenesulfonic acid, polymeric sulfonic acid, styrenesulfonic acid, anthraquinone-2
-Sulfonic acid, anthraquinone-2,7-disulfonic acid, brombenzene-4-sulfonic acid, meta-cresol sulfonic acid, resorcinol sulfonic acid and other strongly acidic inorganic acids or organic acids, boric acid, oxalic acid, formic acid, acetic acid, lactic acid, butyric acid Inorganic or organic acids such as, or esters of organic acids such as oxalic acid dimethyl ester, maleic anhydride, acid anhydrides such as phthalic anhydride, ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium oxalate, ammonium acetate, ammonium phosphate , Ammonium salts such as ammonium thiocyanate and ammonium imidosulfonate, monochloroacetic acid and its sodium salt, α,
Organic halides such as α'dichlorohydrin, triethanolamine hydrochloride, amine hydrochlorides such as aniline hydrochloride, urea adducts such as salicylic acid urea adducts, stearic acid urea adducts and heptanoic acid urea adducts, N-trimethyltaurine, An acidic curing catalyst such as zinc chloride or ferric chloride may be used. Further, for example, hydroxides, oxides, carbonates, amines, etc. of alkali metals, alkaline earth metals, etc. are used, and sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, sodium carbonate, lime, sulfite are used. Amine or a mixture of two or more kinds of amines such as sodium, sodium acetate, sodium phosphate, ammonia, trimethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, hexamethylenetetramine and pyridine. When the above-mentioned acidic curing catalyst is added, the curing reaction of the thermosetting resin composition proceeds rapidly, so that the thermosetting resin composition is easily cured even at low temperature heating or at room temperature.
Particularly when a strong acid curing catalyst is used, the thermosetting resin composition cures extremely quickly even at room temperature, and a uniform and high-quality cured product can be obtained. When the initial condensate A of the thermosetting resin composition of the present invention is sulfomethylated and / or sulfimethylated, even if such a strong acid curing catalyst is added, the amino resin or the water-soluble resol-type phenol resin is added. It does not cause problems such as phase separation and solidification that occur in the case of other thermosetting resins such as. A latent curing catalyst may be used in the thermosetting resin composition of the present invention. Here, the latent curing catalyst refers to one that liberates a substance that exhibits acidity or alkalinity when heated, or one that liberates an acidic substance by a reaction with an aldehyde or a methylol group in a condensate generated by heating and pressurizing. , Formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, oxalic acid,
Aliphatic carboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, benzoic acid, toluic acid, chlorobenzoic acid, bromobenzoic acid, nitrobenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, P-hydroxybenzoic acid, ammonium salts of aromatic carboxylic acids such as anthranilic acid, amine salts, aniline salts, mono,
Di, trialkylaniline salt or phthalanilide,
It is one or a mixture of two or more of urea adducts such as phthalamide, phthalamic acid, ammonium chloride, ammonium sulfate, salicylic acid urea adduct, stearic acid urea adduct, heptanoic acid urea adduct, and N-trimethyltaurine.

[Thermosetting Resin Composition and Curing thereof] In the thermosetting resin composition of the present invention, the above uronic compounds 1 to 500 are usually added to 100 parts by weight of the initial condensate A (hereinafter simply referred to as “part”). Parts are added and mixed, and if necessary, the acidic or alkaline curing catalyst is usually added in an amount of 0.1 to 50.
Part added. The thermosetting resin composition is relatively stable at room temperature, usually has a pot life of several tens of hours or more,
The composition is mixed with fibers, wood chips, or inorganic powder, or is applied or impregnated on non-woven fabric, fiber knitted fabric, paper, wood veneer, etc., and then heated to 120 to 140 ° C. or higher for curing. Furthermore, if necessary, mixing of the thermosetting composition,
After being applied or impregnated, it is relatively stable at room temperature even if it is pre-dried at a temperature of several tens of degrees Celsius or less, and after being stored for a long period of several days to several weeks or more, it is again stored at 120 to 14 ° C.
It is also possible to heat-cure at 0 ° C. or higher. For heating, high-frequency heating is also effective in addition to normal heating using a heating furnace or hot press.

In the thermosetting resin composition of the present invention, in addition to the initial condensate A, uronic compound B, acidic or alkaline curing catalyst, if necessary, a solvent, an aldehyde and / or an aldehyde donor, and a complexing agent. , Amino resins such as urea resins and melamine resins, natural rubber and its derivatives,
Styrene-butadiene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, isoprene rubber, isoprene-isobutylene rubber, and other synthetic rubbers, vinyl acetate, vinyl propionate, styrene, acrylic ester, methacrylic ester, acrylonitrile, acrylic acid, Homopolymers of vinyl monomers such as methacrylic acid, maleic acid, vinyl chloride, vinylidene chloride and vinyl pyridine, or copolymers of two or more of these vinyl monomers, polyurethane, polyamide, epoxy resin, butyral resin, polyethylene ,polypropylene,
Vinyl acetate-ethylene copolymer, chlorinated polyethylene,
Emulsion, latex or aqueous solution of various synthetic resins such as chlorinated polypropylene, polyester, polyvinyl alcohol, sodium alginate, starch, starch derivative, glue, gelatin, blood powder, methyl cellulose,
Filling of water-soluble polymers such as carboxymethyl cellulose, hydroxyethyl cellulose, polyacrylic acid salt, polyacrylamide and natural gums, as well as calcium carbonate, talc, gypsum, carbon black, wood powder, walnut powder, coconut powder, wheat flour, rice powder, etc. Agents, 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 butyl stearate and glycerin monostearate, fatty acid amides, carnauba wax, etc. Natural waxes, synthetic waxes, paraffins, paraffin oil, silicone oil, silicone resin, fluororesin, polyvinyl alcohol, mold release agents such as grease, hexane, butane, n-pentane, alcohol, ether, methylene chloride, tetrachloride Arsenide, chloro fluoro methane, methylene dichloride, 1,1,2-trichloro-1,2,2-and low-boiling solvent such as trifluoroethane, azodicarbonamide, dinitrosopentamethylenetetramine, P, P '
-Oxybis (benzenesulfonylhydrazide), those which generate gas such as azobis-2,2 '-(2-methylpropionitrile), and substances which react with the acidic curing agent while generating carbon dioxide gas, such as carbon or Sodium bicarbonate, potassium, ammonium or calcium,
Foaming agent such as thermoplastic expansive microspheres in which n-pentane, isopentane, butane, isobutane, etc. are microencapsulated, hollow particles such as shirasu balloon, pearlite, glass balloon, foam glass, hollow ceramics, foam polyethylene, foam styrene , Foams such as expanded polypropylene, expanded granules, pigments, dyes, flame retardants, flame retardants, insect repellents, preservatives, anti-aging agents, UV absorbers, and phthalate ester plastics such as DBP, DOP, dicyclohexyl phthalate A third component such as an agent or other plasticizer such as tricresyl phosphate may be added to the condensate to modify the cocondensate by cocondensation or mixing.

[0018]

The mixture of the initial condensate A and the uronic compound B of the present invention has a long pot life, a long pot life and good workability. The mixture is mixed with fibers, wood chips, inorganic powder, non-woven fabric, fiber knitted fabric, paper, wood veneer, plywood, hard board, particle board, fiber board,
After coating or impregnation, it is heated and cured to 120 to 140 ° C or higher, but the dried material of the above-mentioned mixed, coated or impregnated material at a low temperature is relatively stable. Dry at room temperature for several days
After storing for several weeks or more, a two-step method in which the curing is completed by heating again to 120 to 140 ° C. or more can be adopted. When the uron-based compound B is heated to several tens of degrees Celsius or more, it is activated and changes the methylol group of the uron-based compound mainly, and reacts with the active hydrogen of the benzene nucleus of the methylolphenol and / or polyhydric phenol to crosslink and cure. Is expected to progress. At this time, the uron-based compound is much more active than other amino-based resins such as methylol urea, urea formaldehyde resin, methylated methylol urea, methylol melamine, melamine formaldehyde resin, and methylated methylol melamine, and at a lower temperature and a shorter time. The curing reaction proceeds. The resulting cured product has a small amount of residual formalin and is unlikely to generate free formalin. Further, the uron-based compound is more likely to be activated under acidic conditions, so that the thermosetting resin composition of the present invention is hard to be cured.
It is desirable to carry out at H3 to 7. Therefore, in order to make the thermosetting resin composition a stable solution even in the neutral and acidic regions, it is recommended to use the sulfomethylated product and / or sulfimethylated product of the initial condensate A in the thermosetting resin composition. To be done. When a monohydric phenol / polyhydric phenol / aldehyde-based initial cocondensate is selected as the initial condensate A, the thermosetting resin composition cures extremely quickly under acidic conditions.

[0019]

【Example】

[Examples 1 to 5] Resin mixture compositions having the compounding ratios shown in Table 1 were prepared, and the gel times at 35 ° C and 140 ° C of each composition were measured according to JIS-K6802.

[Table 1] Blend (1) Phenol / formaldehyde initial condensate (2) Sulfomethylated phenol / formaldehyde initial condensate (3) Phenol / resorcin / formaldehyde initial cocondensate (4) Phenol / 5-methylresorcin / formaldehyde initial cocondensate ( 5) Sulfimethylated phenol / shale oil alkylresorcin / formaldehyde initial cocondensate (solid content of the above initial condensate is 55% in each case) (6) 50% dimethyloluron

[Comparative Examples 1 to 5] Resin mixture compositions having the compounding ratios shown in Table 2 were prepared, and the gel times at 35 ° C. and 140 ° C. of each composition were measured according to JIS-K6802.

[Table 2] Blend (1) Phenol / formaldehyde initial condensate (2) Sulfomethylated phenol / formaldehyde initial condensate (3) Phenol / resorcin / formaldehyde initial cocondensate (4) Phenol / 5-methylresorcin / formaldehyde initial cocondensate ( 5) Sulfimethylated phenol / shale oil alkylresorcin / formaldehyde initial cocondensate (solid content of the above initial condensate is 55% in each case) (7) 50% dimethylol urea (8) 50% melamine formaldehyde resin (9) paraform (10) Hexamethylenetetramine From Table 1 and Table 2, when dimethylolurone is added as a curing agent, storage stability at room temperature is superior to that when dimethylolurea or melamine-formaldehyde resin is used as a curing agent. In the case of heat curing at 0 ° C., Examples 1 to 5 were cured in a shorter time than Comparative Examples 1 to 5, and the properties of the cured products were insufficient in all cases of Comparative Examples 1 to 5, In particular, the strength, water resistance and boiling resistance were inferior to those of the examples.

Example 6 Examples 1 to 5 shown in Table 1
50 parts of water is added to 50 parts of the resin mixture composition having a mixing ratio of
After uniformly dissolving, 100% of mixed fibers consisting of 80% bamboo fiber and 20% glass fiber, the above aqueous solution of 9% in solid content was evenly applied and mixed by spraying, and dried at 70 ° C. for 1 hour. The mixed mixture was stored immediately after mixing and at room temperature for 7 days and 14 days, and then hot-pressed at 140 ° C. and a pressure of 3 kg / cm ² for 40 seconds to form a plate having a density of 0.9 and a thickness of 2.5 mm and bending. The strength (unit: kgf / cm ² ) was measured and the results shown in Table 3 were obtained.

[Table 3]

Comparative Example 6 Comparative Examples 1 to 5 shown in Table 2
Using the resin mixture composition with the compounding ratio of, a plate having a density of 0.9 and a thickness of 2.5 mm was molded in the same manner as in Example 6, and the bending strength (unit: kgf / cm ² ) was measured, The results shown in Table 4 were obtained.

[Table 4]

From the results of Example 6 and Comparative Example 6, the resin composition according to the present invention has excellent stability at room temperature after predrying and good strength after completion of curing. You can see that you can save.

[Example 7] A resin mixture composition having the compounding ratio of Table 1 Example 4 was coated with 20 mm-thick pine (water content 7%) at a coating amount of 220 g / m ² to form 5 layers. After stacking and pressing, high-frequency heating was performed at an output of 3 kW and a current of 0.5 A for 5 minutes, and the normal state of the bonded laminated wood and the compressive shear strength after repeated boiling were measured according to JIS6802.
The results were 15 kgf / cm ² (100% wood breaking rate) and boiling strength of 68 kgf / cm ² (100% wood breaking rate).

[Example 8] Using the resin mixture composition having the compounding ratio of Table 1 and Example 2, plywood was prepared as follows and the adhesive strength thereof was measured. Blending Example 2 Resin mixture composition 100 parts Wheat flour 20 Ammonium chloride 1 Adhesion conditions Veneer material Lauan veneer moisture 10% Veneer composition 1.0-1.5-1.0 mm 3 plies Adhesive coating amount 30 g / 30 x 30 cm ² Cold pressure 10 kgf / cm ² Hot pressure 120 ° C; 10 kgf / cm ² ; 3 minutes Test result of structural plywood according to Japanese Agricultural Standards Normal adhesive strength 10.3 kgf / cm ² (broken rate 100%) Repeated boiling Adhesive strength 10.0 kgf / cm ² (100% wood breaking rate) 72-hour continuous boiling test 8.5 kgf / cm ² (95% wood breaking rate)

Comparative Example 7 Adhesives having the same compounding ratios as in Example 8 were prepared by using the resin mixture compositions having the compounding ratios shown in Table 2 Comparative Examples 1 to 5, respectively. And was unusable.

Example 9 Sulfimethylated phenol / shale oil alkylresorcin / formaldehyde initial cocondensation product (solid content 55%, pH 5.0) 100 parts, 50% paraffin emulsion 10 parts, 20% ammonium chloride aqueous solution 10 parts In addition, the uniformly mixed adhesive was applied to chips made of Japanese red pine with a water content of 4% at a rate of 11% face and 7% core, and immediately after and after leaving at room temperature for 7 days, it was hot pressed at 150 ° C for 10 minutes. (35 kgf /
cm ² × 3 minutes +15 kgf / cm ² × 3 minutes +5 kgf / cm ² × 4
After molding, a particle board having a thickness of 15 mm having a bending strength of 510 kgf / cm ² immediately after hot pressing and a bending strength of 500 kgf / cm ² after 7 days was obtained.

Example 10 A polyester non-woven fabric having a basis weight of 30 g / m ² was impregnated with the resin mixture composition having the blending ratio of Example 1 shown in Table 1 so that the polyester non-woven fabric had a coating amount of 5%. 20 dried at 80 ℃
When the sheets were laminated and thermocompressed at 120 ° C. for 1 minute, a laminate having a good bending strength of 120 kgf / cm ² was formed.

[Comparative Example 8] A load was manufactured in the same manner as in Example 10 except that the resin mixture composition having the blending ratio of Example 1 shown in Table 1 was used in Comparative Example 1 shown in Table 2. However, curing was insufficient and molding could not be performed. From the results of Example 10 and Comparative Example 8, it is recognized that the resin composition according to the present invention cures at a low temperature.

[Example 11] 10 parts of 10% p-toluenesulfonic acid to 100 parts of the resin composition of Example 2 shown in Table 1, and 5 parts of polyethylene ether sorbitan monolaurate (Tween 20) as a foam stabilizer,
When 10 parts of normal pentane was added as a foaming agent and uniformly mixed, the mixture was poured into a predetermined mold and heated at 70 ° C. to obtain a uniform foamed molded product.

[Example 12] 15 parts of the resin compound composition of Example 5 listed in Table 1 in an inorganic fine powder consisting of 80 parts of talc and 20 parts of calcium silicate, 30 parts of vermiculite as a lightweight aggregate, and shirasu balloon After adding 20 parts and mixing uniformly and drying at 60 ° C, water was evaporated and thermocompression molding was performed at 140 ° C for 5 minutes. Thickness 25 mm, density 0.5 kg / cm
³ lightweight moldings were obtained.

Example 13 To 100 parts of glass short fiber, the resin compound composition of Example 2 shown in Table 1 was added in a solid content of 3 parts.
When spray-coated so as to have a solid content of 0.1%, it was thermoformed at 130 ° C. for 1 minute, and a uniform molded product was obtained. In addition, glass short fibers spray-coated with the resin composition are used at room temperature for 3 days.
The one left for 0 days was molded in the same manner, but was sufficiently cured to obtain a uniform molded product.

[Example 14] To 100 parts of No. 7 silica sand
Add 3 parts of the resin blend composition of Example 5 listed in Table 1,
Fill the mixture with stirring into a predetermined mold and cure,
It was a shell mold. The shell mold is 60 at room temperature
 kgf / cm^Two, After firing at 300 ℃, 50 kgf / cm ^TwoBig of
The bending strength was shown.

Example 15 10 parts of the resin compound composition of Example 5 shown in Table 1 was mixed with 5 parts of a foaming agent in which butane was microencapsulated, and bamboo fiber / hemp fiber was mixed with 10/9.
The needle punched non-woven fabric having a ratio of 0% was impregnated so as to have a solid content of 10%, and then dried at 60 ° C. to evaporate water. The needle punched non-woven fabric was thermocompressed at 140 ° C. for 60 seconds to give a specific gravity of 0.3 and a thickness of 10
When molded to a size of mm, a lightweight and highly rigid structural material was obtained.

[0035]

Therefore, in the present invention, a thermosetting resin composition having a long pot life and good workability can be obtained,
The resin composition can be stored at room temperature for a long period of time even after being mixed, coated or impregnated with the material and then pre-dried if necessary, and the resin composition can be heated to 120 to 140 ° C. or higher. Can be cured quickly. Further, when the pH of the resin composition is cured under neutral or acidic conditions, the curing reaction is further accelerated. The resulting cured resin has high strength and is extremely good in water resistance, oil resistance, and weather resistance. When a sulfomethyl group and / or a sulfimethyl group is introduced into the initial condensate A, the resulting cured resin is much lighter in color than ordinary phenol resins. Therefore, the thermosetting resin composition of the present invention, from the curability and physical properties of the resulting cured resin, as a molding material or foam molding material for cast molding or injection molding, or wood, bamboo,
Plywood, laminated wood, particle board, fiber board,
Organic materials such as OSB, paper, cardboard, felt, non-woven fabric, knitted fabric, bamboo fiber, hemp fiber, palm fiber, glass fiber, rock wool, aramid fiber, ceramic fiber or carbon fiber
Products such as inorganic fibers or non-woven fabrics of organic / inorganic fibers, knitted fabrics, molded products of synthetic resin, sheets, films, foams, ceramic powder, cement, blast furnace slag, fly ash, stone powder, metal powder, glass powder, Inorganic / organic powders such as plastic powders, various organic materials such as metals, adhesives for inorganic materials, binders, coating agents, paint vehicles,
Alternatively, it can be used as a binder for grindstones, shell molds, brake linings, and for compounding rubber. In particular, a fiber molding made of a fiber material and the thermosetting resin composition of the present invention is used for vehicles such as door trims, dashboards, ceiling materials, floor materials, insulator hoods, dash inners, dash outers, engine undercovers and trunk side trims. It is particularly useful for manufacturing interior materials, building materials, etc.

Claims (11)

[Claims] 1. A thermosetting resin composition comprising a mixture of a monocondensation product of a monohydric phenol and / or a polyhydric phenol and an aldehyde and a uronic compound as a main component. 2. A thermosetting resin composition characterized in that a sulfomethyl group and / or a sulfimethyl group are introduced into the initial condensation product of the monohydric phenol and / or polyhydric phenol with an aldehyde of claim 1. 3. A method for curing a thermosetting resin composition, which comprises curing the thermosetting resin composition according to claim 2 under neutral or acidic conditions. 4. Wood veneer and / or wood chips and / or wood chips and / or wood flakes and / or wood wool and / or wood flour adhered by the cured product of the thermosetting resin composition of claim 1. Wood material characterized by being made of 5. A fiber molded product comprising fibers bound by the cured product of the thermosetting resin composition according to claim 1 and molded into a predetermined shape. 6. An inorganic powder molded product comprising an inorganic powder bound by the cured product of the thermosetting resin composition according to claim 1 and molded into a predetermined shape. 7. A porous body molded product, which is a porous body impregnated with a cured product of the thermosetting resin composition according to claim 1, and is molded into a predetermined shape. 8. A thermosetting resin molded product comprising a cured product of the thermosetting resin composition according to claim 1, which is molded into a predetermined shape. 9. The thermosetting resin molded product according to claim 9, wherein an inorganic filler is added to the thermosetting resin molded product. 10. A thermosetting resin foam-molded product, which is a foam-molded product impregnated with a cured product of the thermosetting resin composition according to claim 1, and is molded into a predetermined shape. 11. The thermosetting resin foam molded article according to claim 10, wherein an inorganic filler is added to the thermosetting resin foam molded article.