JPH04185624A - Method of curing - Google Patents

Abstract

PURPOSE:To cure a resin compsn. to be used esp. as a binder of fiber, wood flour, ceramic powder, etc., at a low temp. in a short time by using a specific curing catalyst to cure a mixture of a phenol resin with a novolac polyphenol resin. CONSTITUTION:A mixture of a phenol resin with a novolac polyphenol resin is cured using a curing catalyst comprising a salt of a nitrogenous base with an org. or inorg. acid. Thus, a phenol resin mixture to be used esp. as a binder for fiber, wood flour, ceramic powder, molding sand, etc., can be cured at a low temp. in a short time.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a method for curing phenolic resin mixtures at low temperatures and in a short time, particularly for curing phenolic resin mixtures used as binders for fibers, wood flour, ceramics, foundry sand, etc. low temperature,
This relates to a method of curing in a short time.

[Conventional issues]

Conventionally, as this type of binder, a mixed powder of resol type phenolic resin powder or novolac type phenol ml and an aldehyde donor such as hexamethylenetetramine has been used. However, such phenolic resins have a high curing temperature of approximately 200°C, and when used as a binder for felt, the fibers deteriorate and become brittle due to heat, and in the case of low-melting fibers such as polypropylene fibers, they cannot be used as a binder at all. do not have. Even when used as a binder for ceramics or foundry sand, curing at such high temperatures requires a large heating device and wastes thermal energy.

For this reason, high-ortho type fast-curing phenolic resins are sometimes used, but when cured at low temperatures and in a short time, the apparent curing is fast, but the strength of the resin after curing is lower than that of ordinary phenolic resins. The drawback was that it became significantly weaker.

[Means to solve the problem]

The present invention, as a means for solving the above-mentioned conventional problems,
A curing method in which a mixture of a phenolic resin and a novolak type polyphenol resin is cured using a curing catalyst that is a salt of an organic acid or an inorganic acid and a nitrogen-containing base; The present invention provides a curing method in which a mixture of the above and an aldehyde donor added as a curing agent is cured using a curing catalyst that is a salt of an organic or inorganic acid and a nitrogen-containing base.

The present invention will be explained in detail below.

[Phenol resin cophenol resin is obtained by reacting one or a mixture of two or more phenols such as phenol, cresol, and xylenol with formaldehyde.1 For example, phenol and 0-cresol,
■-Cresol, P-cresol, ethylphenol,
1so-propylphenol, xylenol, 3,5-
Alkylphenol such as xylenol, butylphenol, nonylphenol, 0-fluorophenol, etc.
Fluorophenol, P-fluorophenol, Ω-chlorophenol, intestinal chlorophenol, P-chlorophenol, 0-bromophenol, I-bromophenol, P-bromophenol, 0-iodophenol, ■
-iodophenol, P-iodophenol, 0-aminophenol, Peng-aminophenol, P-aminophenol, 0-nitrophenol, Section-nitrophenol, P-nitrophenol, 2,4-dinitrophenol, 2.4. It is obtained by the reaction of one or a mixture of two or more monovalent phenols such as substituted monovalent phenols such as 6-dolinitrophenol and naphthol with an aldehyde donor such as formaldehyde, and ammonia, Either a resol type phenol resin using an alkali catalyst such as caustic soda or a novolac type phenol resin using an acid catalyst such as sulfuric acid or hydrochloric acid can be used as the phenol resin of the present invention.

In the present invention, if desired, the phenolic resin may include resorcinol, alkylresorcinol, catechol, alkylcatechol, hydroquinone, alkylhydroquinone, pyrogallol, phloroglycine, urea, melamine, thiourea, benzoguanamine, toluene, xylene, coumaron, cyclohexanone, cashew. Oils, tannins, dammar, shellac, rosin or rosin derivatives, petroleum resins, methanol, ethanol, isopropanol,
It may be modified using one or more of butanol, ethylene glycol, glycerin, furfuryl alcohol, linseed oil, tung oil, castor oil, and the like.

[Novolak-type polyhydric phenol resin What is conovolac-type polyhydric phenol resin? One or two types of polyhydric phenols such as resorcinol, alkylresorcinol, pyrogallol, catechol, alkylcatechol, hydroquinone, alkylhydroquinone, phloroglycine, bisphenol, and dihydroxynaphthalene. It is obtained by reacting the above mixture with an aldehyde donor, and an acid catalyst such as sulfuric acid, hydrochloric acid, formic acid, acetic acid, or oxalic acid is used as a reaction catalyst.

Particularly desirable among the above polyhydric phenols are alkylresorcinols. The polyhydric phenol resin using the above alkylresorcinol has excellent storage stability, and when heated and reacted with an aldehyde donor, it cures at low temperature and in a short time, and the cured product has excellent water resistance, heat resistance, and weather resistance. It has flexibility.

Examples of the alkylresorcins mentioned above 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
．． There are 5-triethylresorcin, etc., but especially 5
- Methylresorcin is particularly desirable as a raw material for the polyhydric phenol resin of the present invention because it has good low-temperature curability and provides a cured product with excellent water resistance, heat resistance, weather resistance, and flexibility. Furthermore, mixed alkyl resorcinol (shale oil resorcinol) obtained by dry distillation of oil mother shale produced in Estonia is particularly desirable because it can be obtained at a lower cost and has further excellent low-temperature curing properties, flame resistance, water resistance, heat resistance, weather resistance, etc.

In the present invention, if desired, the novolac type polyhydric phenol resin may include urea, melamine, thiourea, phenol, alkylphenol, catechol, alkylcatechol, hydroquinone, alkylhydroquinone, pyrogallol, phloroglycine, benzoguanamine, toluene, and xylene.

Coumarone, cyclohexanone, cashew oil, tannins, dummer, shellac, rosin or rosin derivatives, petroleum resins, methanol, ethanol, isopropanol, butanol, ethylene glycol, glycerin, furfuryl alcohol.

It may be modified using one or more of linseed oil, tung oil, castor oil, etc.

[Curing Catalyst] In the present invention, a salt of an organic acid or an inorganic acid and a nitrogen-containing base is used as a curing catalyst. Examples of the above organic acids include side 1 acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, succinic acid, maleic acid, tartaric acid, caproic acid, caprylic acid,
Fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linuric acid, picric acid, phenylacetic acid, benzoic acid.

o-toluic acid, -monotoluic acid, p-toluic acid,
o-chlorobenzoic acid 1m-chlorobenzoic acid, P-chlorobenzoic acid, 0-bromobenzoic acid, ■-bromobenzoic acid,
P-bromobenzoic acid, 0-nitrobenzoic acid, -nitrobenzoic acid, P-nitrobenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, P-hydroxybenzoic acid, anthranilic acid, 0-aminobenzoic acid, So-aminobenzoic acid, P-aminobenzoic acid, 0-methoxybenzoic acid,
- Aromatic carboxylic acids such as monomethoxybenzoic acid and P-methoxybenzoic acid, and cyclobutanecarboxylic acid, cyclobutane-1,2-dicarboxylic acid, and cyclobutane-1,3
-dicarboxylic acid, cyclopropanecarboxylic acid, cyclopropane-1,1-dicarboxylic acid, cyclopropane-1,
2-dicarboxylic acid, cyclopropane-1,1,2-)-
Dicarboxylic acid, cyclopropane-1,2,3-)-dicarboxylic acid, 1,3-cyclohexadiene-1-carboxylic acid, 1,3-cyclohexadiene-1°2-dicarboxylic acid, 1,3-cyclo Hexadiene-1,3-dicarboxylic acid, 1,3-cyclohexadiene-1,4-dicarboxylic acid, 1,3-cyclohexadiene-1,6-dicarboxylic acid, 1,3-cyclohexadiene-2, 3-dicarboxylic acid, 1,3-cyclohexadiene-2,5-dicarboxylic acid, ], 3-cyclohexadiene-3,5-dicarboxylic acid, 1,3-cyclohexadiene-5,6-dicarboxylic acid, 1 .4-cyclohexadiene-1,2-dicarboxylic acid, 1,4-cyclohexadiene-1,4-dicarboxylic acid, 1,4-cyclohexadiene-1,6-dicarboxylic acid, 1,4-cyclo Xadiene-3,6-dicarboxylic acid, cyclohexanol-2-carboxylic acid, cyclohexanonecarboxylic acid, cyclohexanecarboxylic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexane-
1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid.

Cyclohexanehexacarboxylic acid, cyclohexyl acetic acid, cyclohexenecarboxylic acid, cyclohexene-1,2
-dicarboxylic acid, cyclohexene-1,3-dicarboxylic acid, cyclohexene-1,4-dicarboxylic acid.

Cyclohexene-1,5-dicarboxylic acid, cyclohexene-1,6-dicarboxylic acid, cyclohexene-3,4-
dicarboxylic acid, cyclohexene-3,5-dicarboxylic acid, cyclohexene-3,6-dicarboxylic acid, cyclohexene-4,5-dicarboxylic acid, cyclopentanecarboxylic acid, cyclopentane-1,1-dicarboxylic acid, cyclopentane-1, 2-dicarboxylic acid, cyclopentane-1,
Examples include alicyclic carboxylic acids such as 3-dicarboxylic acid and cyclopentene-3-carboxylic acid, and examples of the inorganic acids include sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid. Nitrogen-containing bases include ammonia and ammonia derivatives such as hydroxylamine, phenylhydrazine, semicarbazide, hydrazine, methylamine, dimethylamine, trimethylamine.

Ethylamine, diethylamine, triethylamine, n
-Propylamine, di-n-propylamine.

tri-n-propylamine, 1so-propylamine.

di-1so-propylamine, n-butylamine, 1
so-butylamine, 5ec-butylamine, ter-
Butylamine, benzylamine, α-phenylethylamine, β-phenylethylamine, ethylenediamine,
Aliphatic amines such as tetramethylenediamine, tetraethylenediamine, hexamethylenediamine, tetramethylammonium hydroxide, aniline, methylaniline, ethylaniline, dimethylaniline, diethylaniline, diphenylamine, triphenylamine, 0-toluidine, toluidine, P-toluidine, 0-anisidine,
■-Anisidine, P-anisidine, O-chloroaniline, 厘-chloroaniline, P-chloroaniline, 0-bromoaniline, ■-bromoaniline, P-bromoaniline, 0-nitroaniline, 0-phenylenediamine, -1 Phenyl diamine, P-phenylene diamine, 1,2
．． Aromatic amines such as 3-triaminobenzene, 1,2.4-triaminobenzene, 1,2.5-triaminobenzene, 1-naphthylamine, 2-naphthylamine and their derivatives, cyclobutylamine, cyclohexylamine, cyclo Examples include bases such as alicyclic amines such as propylamine, cyclohebutylamine, and cyclopentylamine, and heterocyclic compounds such as piperidine, pyridine, quinoline, and imidazole.

[Aldehyde donor When a novolak type cophenol resin is used, an aldehyde donor is added as a curing agent. The aldehyde donor is formalin.

Formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, caproaldehyde, benzaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde , -tolualdehyde, p-tolualdehyde, salicylaldehyde, or a mixture of two or more thereof.

[Formulation] The curing method of the present invention is to cure a mixture of the above phenolic resin A and the novolac type polyhydric phenol resin B using a salt C of an organic acid or an inorganic acid and a nitrogen-containing base as a curing catalyst. The polyhydric phenol resin B is added in a weight ratio of 1 part or more to the phenol resin A, but preferably the blending ratio of the phenol resin A and the polyhydric phenol resin B is 99:1 to 99:1 by weight. 40:6
It is considered to be about 0. The amount of the salt C is about 0.05 to 30 parts by weight based on 100 parts by weight of the mixture of the phenol resin A and the polyhydric phenol resin B. The above-mentioned phenol resin A and the above-mentioned polyhydric phenol tree DB may be co-condensed in advance.

The method of blending the salt C into the mixture of the phenol resin A and the polyhydric phenol resin B includes (1) a method of mixing the phenol resin A, the polyhydric phenol resin B, and the salt C together in a powder state; (2) A method in which phenol resin A is produced, salt C is added to the solution state before it is made into a solid powder, and then the solid powder is made, and polyhydric phenol resin B powder is mixed therein.

(3) Adding salt C in a solution state before producing polyhydric phenol resin B and making it into a solid powder, and then making it into a solid powder,
A method of mixing phenol resin A powder with this, (4) a method of mixing and dissolving salt C in a mixed solution of the above-mentioned phenol resin A and the above-mentioned polyhydric phenol resin B, etc. are adopted. The above methods (1) to (3) yield a powder composition, and the method (4) yields a solution composition.

When the phenolic resin A is a novolac type, an aldehyde donor is added as a curing agent.

The aldehyde donor is usually used in an amount of 0.5 to 30 parts by weight per 100 parts by weight of the mixture of the phenolic resin A and the polyhydric phenol resin B.

Even when the phenol resin A is a resol type phenol resin, it is desirable to add 0.5 to 30 parts by weight of an aldehyde donor to 100 parts by weight of the novolac type polyhydric phenol resin B.

[Third Substance] In the present invention, a third substance may be further added to the above-mentioned formulation if necessary. Examples of the third substance include natural rubber and its derivatives, 5BR-NBR, CR, EP
Synthetic rubber such as T, vinyl acetate resin, ethylene-vinyl acetate copolymer resin, acrylic resin, methacrylic resin, vinyl chloride resin, vinylidene chloride resin, polystyrene, polyethylene, polypropylene, chlorinated polyethylene, chlorinated polypropylene, polyester resin, urethane resin.

Polyamide resin, epoxy resin, butyral resin, polyacrylic acid, polyacrylamide, polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose,
Cellulose derivatives such as hydroxymethyl cellulose and hydroxyethyl cellulose, sodium alginate, starch, starch derivatives, gelatin, glue, protein such as blood powder,
Calcium carbonate, talc, carbon black, silica,
Fillers such as wood flour, walnut flour, coconut flour, wheat flour, pigments,
Dyes, preservatives, insect repellents, anti-aging agents, ultraviolet absorbers, antioxidants, flame retardants such as antimony trioxide, aluminum hydroxide, bromine compounds, and waxes.

These include mold release agents such as silicone resins, water repellents, etc., and one or a mixture of two or more of these may be blended.

[Effect]

In the present invention, when the phenol resin A or a mixture of the phenol resin A and the salt C is mixed with an aldehyde donor when the phenol resin A is a novolac type, the salt C is hardly cured at room temperature, but when heated, the salt C is hardly cured. acts catalytically, rapidly curing the mixture of phenolic resin A and novolac type polyhydric phenol resin B, and curing is completed in a short time at low temperature, and the resulting resin is similar to the case of commercially available high ortho type phenolic resins. No significant decrease in strength will occur.

〔Example〕

Examples 1-5. Comparative Example 1 Novolac type phenolic resin powder (hereinafter referred to as resin NB-A) and novolac type resorcinol resin (hereinafter referred to as resin NR-
Cyclohexylamine hydrochloride was used as a curing catalyst for the salt of an acid and a nitrogen-containing base, and hexamethylenetetramine was used as an aldehyde donor in the mixture ratio shown in Table 1. A curable composition was prepared, and the gelation time was measured.

The results are shown in Table 1.

do.

Examples 6-10. Comparative Example 2 A curable composition was prepared using the same resins NB-A and NR-B as in the above example, and using cyclohexylamine hydrochloride as a curing catalyst for the salt of an acid and a nitrogen-containing base, with the blending ratio shown in Table 2. A gelation test was conducted using the following methods.The results are shown in Table 2.

Table 2 Examples 11 to 15 Novolac type 5 as novolac type polyhydric phenol resin
- A gelation test was conducted using a curable composition having the same components as in Examples 6 to 10 and the blending ratio shown in Table 3, except that methyl resorcin resin (NR-B2) powder was used.

The results are shown in Table 3.

Table 3 Examples 16-17. Comparative Examples 3 to 5 Novolak type shale oil resorcin resin powder (NR-83) was used as a novolac type polyhydric phenol resin, and a curing catalyst of a salt of an acid and a nitrogen-containing base and a salt of an acid and a non-nitrogen-containing base were added. A curable composition having the blending ratio shown in Table 4 was used, and a gelation test and a moldability test were conducted.

The results are shown in Table 4.

(Left below) 1. According to JIS-6909 powder phenolic resin gelation time measurement method.

Chin 22 The above phenolic resin mixture was applied to felt.
The mixture was mixed uniformly to a coating amount of 0%, molded by heat press at the specified temperature and time to a thickness of 5 cm and a density of 0.09 g/ffl, and then left at room temperature for 10 minutes. Measure the thickness of the molded felt.

Examples 18-21. Comparative Examples 6 to 7 The novolac type phenol resin (NB-A) and novolac type high orthophenol resin (NB-A2) used in Examples 1 to 5 were used as the phenol resin, and the novolac type shale oil was used as the novolac type polyhydric phenol resin. Using resorcinol resin powder (NR-B3) and adding benzylamine benzoate as a curing catalyst for a salt of an acid and a nitrogen-containing base, a curable composition with the blending ratio shown in Table 5 was prepared, and gelling test and moldability test were performed. , flexibility and stress tests were conducted using a culastometer.

The results are shown in Table 5.

(Margin below) Table 5 do.

-2: The above phenolic resin compound was applied to felt at 1
Mix uniformly to a coating amount of 5%, mold by heat press at a specified temperature for 1 hour to a thickness of 20 g/-, and a density of 0.09 g/-, then leave at room temperature for a specified period of time. Measure the thickness of the molded felt 6-3 2. Mix the above phenolic resin mixture evenly with the wood flour so that the coating amount is 200% by heat press.
After molding at 0° C. x 2 minutes to a thickness of 5 m+ and a density of 0.2 g/cd, it was left at room temperature for 24 hours and then bent at 90° and the state was observed.

X: It breaks and cracks. There are some cracks, but it doesn't break.
: Flexible and unbreakable 4: Hardening test using JSR type Curastometer (
Measurement conditions: temperature 150°C, amplitude ±1/4°) Example 22
．． Comparative Example 8 Novolac type resorcinol resin (N
10 parts by weight of a 50% methanol solution of R-B) and a salt as a curing catalyst with a nitrogen-containing base! Add 5 parts of lp-toluidine and uniformly impregnate the felt to a coating amount of 20% as a solid content. After drying at room temperature to remove methanol, heat press to a thickness of 5 m and a density of 0.25 g #
It was molded under the predetermined temperature and time conditions shown in Table 6 so that Also, novolac type resorcinol resin (NR-B)
As a comparative example, a molded product without using . The thickness of the molded felt after being left for 10 minutes after molding was measured.

The results are shown in Table 6.

Table 6 [Effects of the Invention] Therefore, in the present invention, since the curing temperature of the phenol resin is lowered, it is possible to use the phenol resin as a binder for fibers with low heat resistance, and the thermal energy during curing is greatly reduced. will be saved. In the present invention, the strength of the phenol resin after curing is equal to or higher than that of a normal phenol resin.

Patent applicant: Nagoya Yuka Co., Ltd.

Claims (1)

[Claims] 1. A curing method characterized by curing a mixture of a phenol resin and a novolak type polyhydric phenol resin with a curing catalyst that is a salt of an organic acid or an inorganic acid and a nitrogen-containing base.2. A curing method characterized by curing a mixture of a novolac type polyhydric phenol resin and an aldehyde donor as a curing agent using a curing catalyst that is a salt of an organic acid or an inorganic acid and a nitrogen-containing base.