JP2007153987A - Aqueous dispersion and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous dispersion of a curable resin composition obtained by oxidative polymerization of a vegetable oil containing a phenolic compound, and to provide a method for producing the same. <P>SOLUTION: The aqueous dispersion comprises a curable resin composition dispersed in water, the curable resin composition being formed by polymerizing an oxidatively polymerizable compound comprising a vegetable oil containing a phenolic compound. The aqueous dispersion can be obtained by using a fatty acid as a surfactant in a weight ratio relative to a solid content of 10% or more and neutralizing the fatty acid with a basic substance. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an aqueous dispersion of a curable resin composition and a method for producing the same, and relates to a coating film forming material, a recording material compound, an ink raw material, a coating raw material, a photoresist raw material, a molding material, a laminate material, and an adhesive material. The present invention relates to an aqueous dispersion of a curable resin composition useful as a raw material, a raw material for a binder, a raw material for a phenol resin for casting, and a raw material for a phenol resin for fiberboard, and a method for producing the same.

Various production methods are known for oxidation polymers containing phenols as a raw material, but a resin formed by polymerizing an oxidation polymerizable compound containing a vegetable oil containing a phenol compound in WO 01/000702 A1 pamphlet A curable resin composition containing and a method for producing the same have been reported.
However, this resin composition is generally synthesized in a volatile organic solvent and is insoluble in water, and its application is limited due to environmental load problems.
WO01 / 000702A1 pamphlet

  The present invention relates to a vegetable oil oxidation polymer containing a phenolic compound, a coating film forming material, a recording material compound, an ink raw material, a coating raw material, a photoresist raw material, and a molding material in a state not containing a volatile organic solvent. An aqueous dispersion of a curable resin composition that can be used as a raw material for laminated materials, a raw material for adhesive materials, a raw material for binders, a raw material for phenolic resins for casting, and a raw material for phenolic resins for fiberboard, and a method for producing the same The purpose is to do.

The present invention relates to an aqueous dispersion in which a curable resin composition formed by polymerizing an oxidative polymerizable compound containing a vegetable oil containing a phenol compound is dispersed in water. The present invention relates to an aqueous dispersion which is used at a weight ratio of 10% or more and can be obtained by neutralizing the fatty acid with a basic substance.
Moreover, the said aqueous dispersion whose acid value before neutralization is 30 or more is preferable. The aqueous dispersion is preferably a natural product or a derivative of a natural product.
An aqueous dispersion in which the basic substance is aqueous ammonia is preferred.

  Next, the present invention provides an aqueous dispersion in which a curable resin composition formed by polymerizing an oxidatively polymerizable compound containing a vegetable oil containing a phenol compound is dispersed in water, and a fatty acid as a surfactant, The present invention relates to a method for producing an aqueous dispersion, wherein the fatty acid is neutralized with a basic substance at a weight ratio of 10% or more based on solid content.

  According to the present invention, an aqueous dispersion that is inferior to a volatile organic solvent varnish in terms of physical properties can be provided by dispersing a curable resin composition formed by polymerizing a vegetable oil containing a phenol compound in water. . As a result, it can be expected to expand applications by reducing the environmental load.

  The present invention relates to a curable resin composition formed by polymerizing an oxidatively polymerizable compound containing a vegetable oil containing a phenolic compound, water such as tap water, ion-exchanged water, and distilled water using a fatty acid as a surfactant. An aqueous dispersion dispersed in Production methods include emulsification and suspension dispersion, which can be produced by any method. The emulsification method may be any of the known forced emulsification method, phase inversion emulsification method, D phase emulsification method, gel emulsification method, etc., and the equipment used is a single agitation with a stirring blade, a disper, a homogenizer, etc. and a combination thereof. Combined stirring, sand mill, and multi-screw extruder can be used.

  Various vegetable oils containing phenolic compounds are known (for example, those shown in Chem. Soc. Rev., 8, 499 (1979)), and Anacardicae , Gymnospermae, Compositae, Richens, and Proteaacae can be used. Specific examples of phenolic compounds in vegetable oils that contain phenolic compounds include anacardic acid, anagiganic acid, perangic acid, ginkgoic acid, ginkgolic acid, cardanol, cardol, methylcardol, urushiol, thiol, ranger, and lackol. Can be mentioned. The content of various phenol compounds in these vegetable oils used in the present invention is usually 50% by weight or more, preferably 70% by weight or more in total. Specific examples of such vegetable oil include cashew nut shell liquid obtained from cashew tree (Anacardium occidentale).

  This cashew nut shell liquid includes all high-viscosity liquids extracted from cashew nuts that bear fruit on cashew trees. The cashew nut shell liquid component is not particularly limited, and examples include compounds such as anacardic acid, cardanol, cardol, and methyl cardol. Preferably, it is obtained by treating cashew oil containing anacardic acid as a main component at a high temperature. Examples include cashew nut shell liquid containing cardanol as a main component. These components are alkyl or alkenyl derivatives of monohydric phenols, and the side chain alkenyl group is composed of monoene, diene, or triene. However, in the present invention, they may be used as a mixture thereof. In the present invention, a high-viscosity liquid extracted from cashew nuts may be used as it is, or may be used after treatment such as purification or denaturation.

Moreover, in the manufacturing method of this invention, it is preferable to use the vegetable oil containing a phenolic compound derived from nature like cashew nut shell liquid as a vegetable oil containing a phenolic compound.
Furthermore, it is possible to carry out a copolymerization reaction by containing various oxidatively polymerizable compounds such as phenols, naphthols and aromatic amines in addition to the above vegetable oil. The phenols, naphthols, aromatic amines used in the copolymerization reaction, and the amount used thereof are appropriately determined in various physical properties required according to the purpose of use of the vegetable oil polymer containing the obtained phenol compound. It is possible to select one, or two or more kinds can be used. Although the ratio of the compound used as such a copolymerization reaction component is arbitrary, with respect to the vegetable oil containing a phenol compound (with respect to the sum total of the phenol compound contained in it), phenols and naphthols Is usually 5000 mol% or less, preferably 500 mol% or less, and particularly preferably 100 mol% or less. Moreover, aromatic amines are 5000 mol% or less normally, Preferably it is 500 mol% or less, Most preferably, it is 100 mol% or less.

  Specific examples of such phenols include o-cresol, m-cresol, p-cresol, p-octylphenol, p-dodecylphenol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5- Dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, o-ethylphenol, m-ethylphenol, 2,4,6-dimethylphenol, pt-butylphenol, 2 , 4-di-t-butylphenol, alkylphenols such as 2,6-di-t-butylphenol, pt-amylphenol, polyhydric phenols such as hydroquinone, catechol, resorcinol, virogallol, urushiol, thiol, and raccol, o -Chlorophenol, m-c Lophenol, p-chlorophenol, 2,4,6-trichlorophenol, o-bromophenol, m-bromophenol, p-bromophenol, o-fluorinated phenol, m-fluorinated phenol, p-fluorinated phenol, etc. Aminophenol such as halogenated phenol, o-aminophenol, m-aminophenol, p-aminophenol, bisphenol A, p- (α-cumyl) phenol, p-phenylphenol, guaiacol, guetol, phenol, etc. Can do. Specific examples of naphthols include α-naphthol, β-naphthol, 1,4-dihydroxynaphthalene and the like.

  Specific examples of aromatic amines include aniline, o-anisidine, p-anisidine, 2,4-xylidine, 3,4-xylidine, p-cresidine, 4,4｀-diamino-3,3｀-diethyldiphenylmethane. 4,4｀-diaminobenzanilide, diaminodiphenyl ether, 3,3｀-dimethyl-4,4｀-diaminodiphenylmethane, sulfanilic acid and the like.

  Although the curable resin composition is obtained by the oxidative polymerization reaction of the vegetable oil, the embodiment of this reaction is not particularly limited. For example, methods such as suspension polymerization, dispersion polymerization, and emulsion polymerization can be used in addition to solventless polymerization and solution polymerization. Moreover, the catalyst, enzyme, etc. which were used for the polymerization reaction may remain.

Next, the fatty acid which comprises the aqueous dispersion of this invention is demonstrated.
As a method for mixing fatty acids, in the production process of the aqueous dispersion of the curable resin composition, there are a method of mixing with the resin composition and then mixing with water, and a method of mixing with water and then mixing with the resin composition. Yes, either method is acceptable.

  Examples of fatty acids include sorbic acid, butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, vegetable fatty acids (tung oil fatty acid, coconut oil fatty acid, Safflower fatty acid, soybean oil fatty acid, rapeseed oil fatty acid, regenerated oil fatty acid, sunflower oil fatty acid, rice sugar fatty acid, cottonseed oil fatty acid, corn oil fatty acid, peanut fatty acid, Hyelsinic acid rapeseed oil fatty acid, tall oil fatty acid, castor oil fatty acid, dehydrated castor oil Fatty acids, palm oil fatty acids, coconut oil fatty acids, palm kernel oil fatty acids, olive oil fatty acids, etc.), fish oil fatty acids, various high oleic acid fatty acids, medium chain fatty acids, lard fatty acids, beef tallow fatty acids, lanolin fatty acids, etc. , Preferably vegetable fatty acid, fish oil fatty acid, lard fatty acid, beef tallow fatty acid, lanolin Naturally derived fatty acids such as fatty acid and the like.

  Fatty acid is used as a surfactant in dispersing the curable resin composition in water. The fatty acid is preferably used in a weight ratio of 10% or more based on the solid content of the curable resin composition. When used at a weight ratio of less than 10%, the curable resin composition is not dispersed in water but floats.

Next, the basic substance constituting the aqueous dispersion of the present invention will be described.
In this invention, when using a fatty acid, it is preferable to neutralize by adding a basic substance so that it may become a neutralization rate 70% or more after an aqueous-ized process or aqueous-ized.
Basic substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonium carbonate, potassium carbonate, ammonia, methylamine, propylamine, hexylamine, octylamine, ethanolamine, propanolamine, diethanolamine, N-methyldiethanolamine, dimethyl Examples include amine, ethylamine, diethylamine, triethylamine, N, N-dimethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, and morpholine. Ammonia is preferable, and it is more preferable to add it as an aqueous solution.

  Various additives such as a stabilizer such as an antioxidant and an ultraviolet absorber can be added to the resin composition of the present invention within a range not inhibiting the effects of the present invention. Furthermore, additives such as fillers, plasticizers, thickeners, preservatives, antifoaming agents and leveling agents can be used in combination as required.

  Hereinafter, the present invention will be described in more detail with reference to examples. In the text, parts and% represent parts by weight and% by weight unless otherwise specified.

<Example 1>
In a 500 ml three-necked separable flask, 30 g of cashew nut shell liquid and 70 g of toluene were added and dissolved, and then 457 mg of iron salen was added. A stir bar was attached and placed in a 30 ° C. water bath and stirred at 250 rpm. Thereafter, 1.62 ml of 30% aqueous hydrogen peroxide was added 10 times every 15 minutes. The reaction was terminated 3 hours after the first hydrogen peroxide solution was added, and the reaction solution was concentrated to obtain a curable resin composition toluene varnish having a solid content of 80.0%.
48.0 parts of linseed oil fatty acid was added to 100 parts of the curable resin composition toluene varnish and well kneaded to give an acid value of 78.0. To this was added 116 parts of 2.5% aqueous ammonia (at this time, 100% neutralization rate), and after stirring well, stirring was continued while gradually adding 396 parts of water. While reducing the pressure at 90 ° C., toluene was distilled off to obtain an aqueous dispersion having a solid content of 20%.

<Example 2>
48.0 parts of linseed oil fatty acid was added to 100 parts of the curable resin composition toluene varnish obtained in Example 1 and kneaded well to give an acid value of 78.0. To this was added 81 parts of 2.5% aqueous ammonia (at this time, neutralization rate 70%), and after stirring well, stirring was continued while gradually adding 431 parts of water. While reducing the pressure at 90 ° C., toluene was distilled off to obtain an aqueous dispersion having a solid content of 20%.

<Example 3>
48.0 parts of linseed oil fatty acid was added to 100 parts of the curable resin composition toluene varnish obtained in Example 1 and kneaded well to give an acid value of 78.0. To this was added 151 parts of 2.5% aqueous ammonia (at this time, neutralization rate 130%, ammonia excess), and after stirring well, stirring was continued while gradually adding 361 parts of water. While reducing the pressure at 90 ° C., toluene was distilled off to obtain an aqueous dispersion having a solid content of 20%.

<Example 4>
80.0 parts of linseed oil fatty acid was added to 100 parts of the curable resin composition toluene varnish obtained in Example 1 and kneaded well to give an acid value of 104. To this was added 193 parts of 2.5% aqueous ammonia (at this time, neutralization rate 100%), and after stirring well, stirring was continued while gradually adding 447 parts of water. While reducing the pressure at 90 ° C., toluene was distilled off to obtain an aqueous dispersion having a solid content of 20%.

<Example 5>
16.0 parts of linseed oil fatty acid was added to 100 parts of the curable resin composition toluene varnish obtained in Example 1 and kneaded well to give an acid value of 34.7. To this was added 38.7 parts of 2.5% aqueous ammonia (at this time, neutralization rate 100%), and after stirring well, stirring was continued while gradually adding 345 parts of water. While reducing the pressure at 90 ° C., toluene was distilled off to obtain an aqueous dispersion having a solid content of 20%.

<Example 6>
An aqueous dispersion having a solid content of 20% was obtained in the same manner as in Example 1 except that soybean oil fatty acid was used instead of linseed oil fatty acid.

<Example 7>
An aqueous dispersion having a solid content of 20% was obtained in the same manner as in Example 1 except that coconut oil fatty acid was used instead of linseed oil fatty acid.

<Comparative Example 1>
7.5 parts of linseed oil fatty acid was added to 100 parts of the curable resin composition toluene varnish obtained in Example 1 and kneaded well to give an acid value of 17.8. To this was added 18.1 parts of 2.5% aqueous ammonia (at this time, neutralization rate 100%), and after stirring well, stirring was continued while gradually adding 332 parts of water, but the kneaded material was dispersed in water. I did not.

<Evaluation of coating film>
The viscosity of the aqueous dispersion of the curable resin composition toluene varnish obtained in Example 1 and the curable resin composition obtained in Examples 1 to 7 was measured with an E-type viscometer. Further, these dispersions were applied to an aluminum plate with an applicator and heated in an oven at 150 ° C. for 3 hours to be cured. A 3 mil applicator was used for the toluene varnish and a 16 mil applicator for the aqueous dispersion to keep the membrane pressure constant.

＊＊：測定不能
The obtained resin coating film was evaluated by the following method.
Pencil hardness test: JIS standard “pencil scratch test” (JIS K5400) was used.
Gloss measurement: 60 ° gloss was measured using BYK Micro Trigloss.
The evaluation results are shown in Table 1.

**: Measurement not possible

  According to the present invention, it is possible to make a curable resin composition containing a resin formed by polymerizing an oxidative polymerizable compound containing a vegetable oil containing a phenol compound, and to obtain a coating liquid with a small environmental load. done.

Claims (5)

  In an aqueous dispersion in which a curable resin composition formed by polymerizing an oxidatively polymerizable compound containing a vegetable oil containing a phenol compound is dispersed in water, a fatty acid as a surfactant is 10% by weight based on the solid content. An aqueous dispersion that can be obtained as described above and neutralized with a basic substance.   The aqueous dispersion according to claim 1, wherein the acid value before neutralization is 30 or more.   The aqueous dispersion according to claim 1 or 2, wherein the fatty acid is a natural product or a derivative of a natural product.   The aqueous dispersion according to any one of claims 1 to 3, wherein the basic substance is aqueous ammonia. In an aqueous dispersion in which a curable resin composition formed by polymerizing an oxidatively polymerizable compound containing a vegetable oil containing a phenol compound is dispersed in water, a fatty acid as a surfactant is 10% by weight based on the solid content. A method for producing an aqueous dispersion, wherein the fatty acid is neutralized with a basic substance.