JP3837574B2 - Clay molding production method and clay molding composition - Google Patents

Description

  The present invention relates to a method for producing a clay molded product and a composition for clay molding.

Clay is widely used as a molding material because it has plasticity and adhesiveness. As a method for obtaining a molded product using this clay, a method is used in which water is added to clay to form a paste, which is molded into a predetermined shape and then dried and cured.
However, such a method has problems such as long time for drying and curing after the molding and insufficient strength of the molded product.

  It is an object of the present invention to provide a method for producing a clay molded product that is easy to dry and harden after formation and has excellent molded product strength, and a composition for clay molding.

  According to the present invention, the following methods and compositions are provided.

(1) (i) carboxyl group-containing saccharide compounds Mono及 beauty / or carboxyl group-containing lignin substance, (ii) a polyvalent epoxy compound, consists (iii) polyhydric alcohol and (iv) clay, at least a clay A method for producing a clay molded article, comprising molding a mixture containing 40% by weight and then spraying the catalyst solution for curing the epoxy compound on the surface of the molded article.
(2) (i) carboxyl group-containing saccharide compounds Mono及 beauty / or carboxyl group-containing lignin substance, (ii) a polyvalent epoxy compound, (iii) the epoxy compound curing reaction catalyst, (iv) a polyhydric alcohol and ( v) A method for producing a clay molded product comprising molding a clay comprising at least 40% by weight and curing the mixture.
(3) The method according to (1) or (2), wherein the polyvalent epoxy compound is an aliphatic epoxy compound.
(4) (i) carboxyl group-containing saccharide compounds and / or carboxyl group-containing lignin substance, (ii) a polyvalent epoxy compound, (iii) the epoxy compound curing reaction catalyst, (iv) a polyhydric alcohol and ( v) A clay molding composition comprising clay.
(5) The composition according to (4), wherein the polyvalent epoxy compound is an aliphatic epoxy compound.

  According to the present invention, it is possible to easily and efficiently produce a clay molded article having excellent strength. Moreover, since the clay molded article of the present invention contains a sugar compound and / or lignin substance excellent in biodegradability, it will collapse when discarded in the natural environment.

In the carboxyl group-containing sugar compound used in the present onset bright, as the sugar compound, conventionally known various soluble it is used. Such substances include monosaccharides, oligosaccharides, polysaccharides, sugar alcohols, and the like, and any are usable as long as they are soluble in polyol. Such sugar compounds include, for example, molasses, molasses, glucose, galactose, xylose, lactose, mannose, talose, rhamnose, arabinose, glucosyl mannose, lyxose, allose, altrose, gulose, idose, ribose, erythrose, threose , Psicose, fructose, sorbose, tagatose, pentulose, tetrose, sucrose, maltose, isomaltose, cellobiose, lactose, trehalose, kojibiose, sophorose, nigerose, laminaribiose, isomaltose, gentiobiose, melibiose, blanteobiose, Vicianose, agarobiose, sylabiose, rutinose, primeproose, xylobiose, rosigenaviose, erythritol Mesoerythritol, maltitol, lactitol, D-threitol, D-arabinitol, ribitol, xylitol, sorbitol, galactitol, D-mannitol, allitol, higher alditol, etc., starch, dextran, mannan, pectin, pectic acid, alginic acid , Chitosan and the like.

In the carboxyl group-containing lignin substance used in the present invention, the lignin substance includes lignin and modified products thereof. This lignin substance is a polymer having a molecular weight of 800 to 10,000 formed by condensation of structural units having phenylpropane as a skeleton, separated from wood, bamboo, straw, etc., and is a conventionally known substance. is there. The thing is, usually, are'll handling in powder form.

  In the present invention, the saccharide compound containing carboxy group and the lignin substance (hereinafter also simply referred to as carboxy group-containing product) are dissolved in a polyhydric alcohol (polyol) and used in the form of a solution. The polyol used in the present invention is a liquid compound containing at least two hydroxyl groups in the molecule, and examples thereof include ethylene glycol, diethylene glycol, 1.4-butanediol, 1.6- Low molecular weight polyols such as hexanediol, neoventyl glycol, trimethylol bropan, glycerin, triethanolamine, sorbitol: polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide / propylene oxide copolymer: Examples include polycaprolactone, poly-β-methyl-δ-ptyrolactone, polyesters from diols and dibasic acids, and the like. Other examples include hydroxyl group-containing liquid polybutadiene, polycarbonate diol, and acrylic polyol.

The polyvalent epoxy compound used in the present invention has at least two epoxy groups in the molecule, and those used as epoxy resins can be generally used. As such an epoxy compound, various conventionally known compounds that are solid or liquid at room temperature are used. Examples of such a resin include diglycidyl ether type epoxy resins such as alkylene glycol type epoxy resins, bisphenol A type epoxy resins, and bisphenol F type epoxy resins; novolak types such as phenol novolac type epoxy resins and cresol novolak type epoxy resins. Examples thereof include epoxy resins; glycidyl ester type epoxy resins; glycidyl amine type epoxy resins; linear aliphatic type epoxy resins;
In the present invention, in view of biodegradability, it is preferable to use an aliphatic structure (having an alkylene group, an alkenylene group or the like). Examples of such aliphatic epoxy resins include alkylene glycol type epoxy resins, aliphatic glycidyl ether type epoxy resins, aliphatic glycidyl ester type epoxy resins, aliphatic glycidyl amine type epoxy resins, and aliphatic oil-modified epoxy resins. Examples thereof include resins.

Carboxyl group-containing saccharide compounds and / or lignin compounds are prepared by introducing a carboxyl group into the sugar compound and / or lignin compounds. As a method for introducing a carboxyl group in this case, a method of subjecting a hydroxy (OH) group of a sugar compound or a lignin substance to an esterification reaction with a polyvalent carboxylic acid anhydride (Japanese Patent Laid-Open No. 2002-284791) can be used.

前記式中、Ｒは２価脂肪族基及び２価芳香族基等の２価有機基を示す。２価脂肪族基には、鎖状又は環状のものが包含され、鎖状のものには、炭素数１〜１２、好ましくは２〜８のアルキレン基が包含され、環状のものには、炭素数５〜１２、好ましくは６〜８のシクロアルキレン基が包含される。２価芳香族基には、アリーレン基及びアリールジアルキレン基が包含される。これらの２価脂肪族基及び２価芳香族基には、置換基、例えば、カルボキシル基や、酸無水物基、アミノ基等が結合していてもよい。前記多価カルボン酸無水物の具体例を示すと、例えば、マロン酸無水物、コハク酸無水物、グルタル酸無水物、アジピン酸無水物、ピメリン酸無水物、スベリン酸無水物、アゼライン酸無水物、メチルナジック酸無水物、アルケニルコハク酸無水物、ヘキサヒドロフタル酸無水物等の脂肪族多価カルボン酸無水物や、トリメリット酸無水物、ピロメリット酸無水物、ベンゾフェノンテトラカルボン酸無水物、フタル酸無水物等の芳香族多価カルボン酸無水物等が挙げられる。
本発明においては、生分解性の点から、脂肪族系多価カルボン酸無水物の使用が好ましい。 The polyvalent carboxylic acid anhydride includes divalent to hexavalent, preferably divalent to tetravalent carboxylic acid anhydrides, and divalent carboxylic acid anhydrides are preferably used. Such a polyvalent carboxylic acid anhydride is a conventionally known substance and can be represented by, for example, the following general formula (1).

In the above formula, R represents a divalent organic group such as a divalent aliphatic group and a divalent aromatic group. The divalent aliphatic group includes a chain or cyclic group, the chain group includes an alkylene group having 1 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and the cyclic group includes carbon. A cycloalkylene group of 5 to 12, preferably 6 to 8 is included. The divalent aromatic group includes an arylene group and an aryl dialkylene group. A substituent such as a carboxyl group, an acid anhydride group, an amino group, or the like may be bonded to these divalent aliphatic group and divalent aromatic group. Specific examples of the polyvalent carboxylic acid anhydride include, for example, malonic acid anhydride, succinic acid anhydride, glutaric acid anhydride, adipic acid anhydride, pimelic acid anhydride, suberic acid anhydride, azelaic acid anhydride , Aliphatic polycarboxylic acid anhydrides such as methyl nadic acid anhydride, alkenyl succinic acid anhydride, hexahydrophthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic acid anhydride, Aromatic polyhydric carboxylic acid anhydrides such as phthalic anhydride and the like.
In the present invention, it is preferable to use an aliphatic polycarboxylic acid anhydride from the viewpoint of biodegradability.

  In the first method for introducing a carboxyl group into a sugar compound or lignin substance, first, the sugar compound and / or lignin substance (hereinafter also referred to as sugar compound or the like) and a polyol are mixed, and the sugar compound and / or lignin substance are mixed. Is prepared in a dissolved state. In this case, the ratio of the sugar compound used is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 1 part by weight of the polyol. When the ratio of the sugar compound or the like is too large, it becomes difficult to uniformly dissolve in the polyol, and a uniform polyol solution cannot be obtained.

  Next, a polyvalent carboxylic acid anhydride is mixed with a polyol solution containing the sugar compound and the like in a dissolved state, and an esterification reaction is performed. In this case, it is preferred that a catalyst is present in the reaction mixture. As the catalyst in this case, a conventionally known esterification reaction catalyst can be used. The reaction temperature is 30 to 150 ° C., preferably 50 to 100 ° C., and normal pressure or reduced pressure is adopted as the reaction stress.

前記式中、［Ａ］は多糖化合物及び／又はリグニン物質からそれに含まれるヒドロキシル基を除いた残基を示す。Ｒは２価有機基を示す。 The esterification reaction of the polyvalent carboxylic acid anhydride with respect to the sugar compound or the like can be represented by the following formula.

In said formula, [A] shows the residue remove | excluding the hydroxyl group contained in a polysaccharide compound and / or a lignin substance. R represents a divalent organic group.

  As can be seen from the above reaction formula, the polyvalent carboxylic acid is contained in 1 mol of the hydroxyl group contained in the polyol solution (that is, the total amount of hydroxyl groups contained in the sugar compound and the hydroxyl group contained in the polyol). When 1 mole of acid anhydride is reacted, an esterification reaction product containing 1 mole of free carboxyl group (—COOH) is obtained. The ratio of the free carboxyl group contained in the reaction product can be adjusted by the amount of polyvalent carboxylic anhydride used. In the case of the present invention, the usage ratio of the polyvalent carboxylic acid anhydride is calculated by converting one carboxylic acid anhydride group to 2 equivalents with respect to the equivalent number of all free hydroxyl groups (—OH groups) contained in the polyol solution. Then, it is 1.6 to 4 times equivalent, preferably 2 to 3 times equivalent. The esterification reaction product is liquid or solid at normal temperature.

In the second method of producing the carboxyl group-containing sugar compound and / or lignin material, firstly, a sugar compound and / or mixing the lignin material and the polyol to produce a polyol solution containing a sugar compound such as in solution. In this case, the ratio of the sugar compound used is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 1 part by weight of the polyol.

  Next, a polycarboxylic acid anhydride is added and mixed to the mixture obtained as described above, and an esterification reaction is performed. The reaction temperature is 30 to 150 ° C., preferably 50 to 100 ° C., and normal pressure or reduced pressure is adopted as the pressure. The use ratio of the polyvalent carboxylic acid anhydride is 1.6 to 4 times the equivalent number of carboxyl group equivalents of the polyvalent carboxylic acid anhydride, with respect to the equivalent number of all hydroxyl groups contained in the polyol, sugar compound, etc. Preferably it is 2-3 times equivalent.

  The esterification reaction product thus obtained is a solid or solid-liquid mixture containing a free carboxyl group. The ratio of the free carboxyl group contained in the reactive organism can be adjusted by the amount of polyvalent carboxylic anhydride used. In the case of the present invention, the usage ratio of the polyvalent carboxylic acid anhydride is calculated by converting one carboxylic acid anhydride group to 2 equivalents with respect to the equivalent number of all free hydroxyl groups (—OH groups) contained in the reaction raw material. Then, it is 1.6 to 4 times equivalent, preferably 2 to 3 times equivalent. The esterification reaction product is liquid or solid at normal temperature.

Carboxyl group-containing lignin material may also be obtained by oxidizing lightly lignin. Such lignin oxidation methods are known.

The sugar compounds and lignin substances according to the invention contains a biodegradable product fraction in the molecule, which has excellent biodegradability, it can be applied to various applications as a biodegradable reactants .

  In the composition comprising the polyvalent epoxy compound and the carboxyl group (epoxy resin composition), various auxiliary components, for example, a curing accelerator, a filler, a colorant, a flame retardant, a release agent are used as necessary. Molding agents and the like can be blended. As a hardening accelerator, a conventional thing, for example, an imidazole compound, diazabicycloundecene and its phenol salt, a triphenylphosphine, a tertiary amine, an amine adduct latent hardening accelerator, dicyandiamide, etc. are used. Examples of the filler include alumina, silica, magnesia, antimony trioxide, magnesium carbonate, calcium carbonate, mica, and clay.

  The compounding quantity of the carboxyl group-containing material in the epoxy resin composition is 0.8 to 2 times equivalent, preferably 1 to 1.5 times equivalent to the number of epoxy group equivalents of the epoxy resin.

  In the epoxy resin composition, the carboxyl group-containing product acts as a curing agent, and by heating this, the carboxyl group-containing product reacts with the epoxy resin, and the cured product having the carboxyl group-containing product as a crosslinking agent is obtained. Obtainable. Since this cured product has a biodegradable carboxyl group-containing part in its structure, it is microbially degradable and produces biodegradability from that part.

  Examples of the epoxy compound curing reaction catalyst used in the present invention include conventionally known ones such as amino catalysts such as dimethylbenzylamine, dimethylaniline, 2,4,6-tris (dimethylaminomethyl) phenol, and diethylbenzylamine. Tin and titanium-based catalysts such as tin 2-ethylhexanoate (II), dibutyltin laurate, titanium 2-ethylhexanoate (IV) and the like are used. These are used as a polyol solution. In this case, the catalyst concentration in the solution is 0.05 to 5 wt%, preferably 0.1 to 2 wt%.

  Examples of the clay in the present invention include various conventionally known clays such as white clay, kaolin, bentonite, kibushi clay, gyrome clay, and talc.

  In order to produce a clay-formed product according to the present invention, first, a liquid epoxy resin composition comprising a carboxyl group-containing material, a polyvalent epoxy compound and a polyhydric alcohol is prepared, and clay is added thereto, and the mixture is uniformly kneaded and kneaded. The kneaded product is formed into a predetermined shape using a molding method such as manual labor, a mold, an extruder, or the like.

The proportion of the clay may be an amount that enables the kneaded product to be molded, and is at least 40% by weight, preferably 50 to 80% by weight in the entire kneaded product or molded product.
The polyhydric alcohol as the solvent is 5 to 30% by weight, preferably 10 to 20% by weight, in the entire kneaded product or molded product.

Next, a catalyst solution is apply | coated to the surface of this molded object, and it hold | maintains under room temperature or 30-60 degreeC heating. As a result, the catalyst solution penetrates into the molded product from the surface of the molded product, and the epoxy resin and the carboxyl group-containing product undergo a curing reaction to obtain a cured molded product.
In the present invention, the epoxy resin curing reaction catalyst can be contained in the epoxy resin composition in a liquid form instead of being contained in the spray solution.

  The shape of the molded product is not particularly limited, and may be various shapes such as a container shape, a hollow body shape, a plate shape, a block shape, and a column shape.

  Next, the present invention will be described in further detail with reference to examples.

Reference example 1
0.5 g of acidolysis lignin was dissolved in 1.55 g of ethylene glycol at 50 ° C., 6.3 g of succinic anhydride and 5 drops of dimethylaniline were added thereto, and the mixture was stirred at 80 ° C. for 3 hours. In the infrared absorption spectrum of the obtained esterified product (carboxyl group-containing product) (polyvalent carboxylic acid product), peaks were observed at 1740 cm (ester) and around 1800 cm (carboxylic acid).

Reference example 2
In Reference Example 1, polyvalent carboxylic acid was obtained in the same manner using kraft lignin instead of acidolysis lignin. The IR spectrum confirmed that the structure contained an ester group and a carboxyl group.

Reference example 3
In Reference Example 1, polyvalent carboxylic acid was obtained in the same manner using glucose instead of acidolysis lignin. It was confirmed by IR vector that the structure contained an ester group and a carboxyl group.

Reference example 4
In Reference Example 1, a polyvalent carboxylic acid was obtained in the same manner using fructose instead of acidolysis lignin. The IR spectrum confirmed that the structure contained an ester group and a carboxyl group.

Reference Example 5
In Reference Example 1, a polyvalent carboxylic acid was obtained in the same manner using sucrose instead of acidolysis lignin. The IR spectrum confirmed that the structure contained an ester group and a carboxyl group.

Reference Example 6
In Reference Example 1, polyvalent carboxylic acid was obtained in the same manner using molasses instead of acidolysis lignin. It was confirmed by IR spectrum that the structure contained an ester group and a carboxyl group.

Reference Example 7
After soaking 0.5 g of lintercellulose in water, it was replaced with ethylene glycol and mixed to 1 g of ethylene glycol. To this was added 4.8 g of succinic anhydride and 5 drops of dimethylaniline, and the mixture was mixed at 80 ° C. Stir for hours. In the infrared absorption spectrum of the obtained polyvalent carboxylic acid product, peaks were observed at 1740 cm (ester) and around 1800 cm (carboxylic acid).

Reference Example 8
In Reference Example 7, starch was used instead of lintercellulose, and a polyvalent carboxylic acid was obtained in the same manner.

Reference Example 9
In Reference Example 7, a polyvalent carboxylic acid was obtained in the same manner using chitin instead of lintercellulose.

Reference Example 10
In Reference Example 7, polyvalent carboxylic acid was obtained in the same manner using chitosan instead of lintercellulose.

Reference Example 11
In Reference Example 7, wood powder was used in place of lintercellulose, and a polyvalent carboxylic acid was obtained in the same manner.

Reference Example 12
In Reference Example 7, a polyvalent carboxylic acid was obtained in the same manner using coffee beans instead of lintercellulose.

Reference Example 13
In Reference Example 7, bagasse was used in place of lintercellulose, and a polyvalent carboxylic acid was obtained in the same manner.

Example 1
10 parts of a carboxyl group-containing lignin sulfonate obtained by lightly oxidizing lignin sulfonate was dissolved in 10 parts of ethylene glycol, and 6.5 parts of ethylene glycol glycidyl ether was added thereto to obtain a solution. To this solution, 50 parts of white clay was added and mixed well, and the resulting mixture was formed into a plate shape. An amine-based catalyst and an ethylene glycol solution of a tin-based catalyst were sprayed on the surface of the molded body, and left at room temperature for 1 day to obtain a plate-shaped cured body.

Example 2
10 parts of a carboxyl group-containing lignin sulfonate obtained by lightly oxidizing lignin sulfonate was dissolved in 10 parts of ethylene glycol, and 6.5 parts of ethylene glycol glycidyl ether was added thereto to obtain a solution. To this solution, 50 parts of white clay and 0.1 part of amine-based catalyst and tin-based catalyst were added and mixed well, and the resulting mixture was formed into a plate shape. The plate-like cured body was obtained by leaving it at room temperature for 1 day.

Example 3
A derivative mixture obtained by reacting 10 parts of glucose and 10 parts of ethylene glycol with succinic anhydride to undergo ester carboxyl oxidation was obtained. 10 parts of this derivative mixture was dissolved in 10 parts of ethylene glycol, and 10 parts of ethylene glycol glycidyl ether was added thereto to obtain a solution. To this solution, 50 parts of white clay and 0.1 part of an amine catalyst and tin catalyst are added and mixed well. The resulting mixture is formed into a plate shape and allowed to stand at room temperature for one day. Obtained.

Example 4
A derivative mixture obtained by reacting 10 parts of molasses and 10 parts of ethylene glycol with succinic anhydride to undergo ester carboxylation was obtained. 10 parts of this derivative mixture was dissolved in 10 parts of ethylene glycol, and 10 parts of ethylene glycol glycidyl ether was added thereto to obtain a solution. To this solution, 50 parts of white clay and 0.1 part of an amine catalyst and tin catalyst are added and mixed well. The resulting mixture is formed into a plate shape and allowed to stand at room temperature for one day. Obtained.

Example 5
A derivative mixture obtained by reacting 10 parts of kraft lignin and 10 parts of ethylene glycol with succinic anhydride to undergo ester carboxylation was obtained. 10 parts of this derivative mixture was dissolved in 10 parts of ethylene glycol, and 10 parts of ethylene glycol glycidyl ether was added thereto to obtain a solution. To this solution, 50 parts of white clay and 0.1 part of an amine catalyst and tin catalyst are added and mixed well. The resulting mixture is formed into a plate shape and allowed to stand at room temperature for one day. Obtained.

Example 6
In Example 1, a plate-like cured body was obtained in the same manner except that the esterification product shown in Reference Example 1 was used as the carboxyl group-containing substance.

Example 7
In Example 1, a plate-like cured body was obtained in the same manner except that the esterification product shown in Reference Example 4 was used as the carboxyl group-containing substance.

Example 8
In Example 1, a plate-like cured body was obtained in the same manner except that the esterification product shown in Reference Example 5 was used as the carboxyl group-containing substance.

Claims (5)

(I) carboxyl group-containing saccharide compounds Mono及 beauty / or carboxyl group-containing lignin substance, (ii) a polyvalent epoxy compound, (iii) consists of polyhydric alcohols and (iv) clay, clay at least 40 wt% A method for producing a clay molded product, comprising molding the mixture containing the mixture, and spraying the epoxy compound curing reaction catalyst solution on the surface of the molded product. (I) carboxyl group-containing saccharide compounds Mono及 beauty / or carboxyl group-containing lignin substance, (ii) a polyvalent epoxy compound, (iii) the epoxy compound curing reaction catalyst, (iv) a polyhydric alcohol and (v) Clay And forming a mixture containing at least 40% by weight of the clay and curing the mixture.   The method according to claim 1 or 2, wherein the polyvalent epoxy compound is an aliphatic epoxy compound. (I) carboxyl group-containing saccharide compounds Mono及 beauty / or carboxyl group-containing Gurinin substance, (ii) a polyvalent epoxy compound, (iii) the epoxy compound curing reaction catalyst, (iv) a polyhydric alcohol and (v) Clay A clay molding composition comprising:   The composition according to claim 4, wherein the polyvalent epoxy compound is an aliphatic epoxy compound.