JP2001123012A - Composition containing phenol resin and production method of its cured molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition containing a phenol resin prepared by using starch-bearing waste matters by-produced from the starch industry for the reutilization of the waste matters including a corn seed coat by-produced from the starch industry and provide a process for producing a cured molded article obtained by heating and curing the composition. SOLUTION: A resin composition is prepared by reacting starch-bearing waste matters by-produced from the starch industry with phenols in the presence of an acid catalyst at a temperature of 100-220 deg.C to undergo liquefaction and then neutralization to produce a phenol resin and mixing the resulting phenol resin with a curing agent and a filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[Definition of terms] In the present invention, "liquefaction" means that a starch-based substance is liquefied and dissolved from a solid phase to a liquid phase by reaction with phenols.

[0002]

BACKGROUND OF THE INVENTION The present invention aims at reusing starch-based materials, especially corn seed coat, which is a starch industrial waste that has been considered difficult to use with high added value, and uses starch-based materials and phenols. The present invention relates to a phenolic resin-containing composition that is a reaction product, and a method for producing a cured molded article thereof.

[0003]

2. Description of the Related Art In recent years, efforts have been made to produce resin moldings using naturally occurring substances. The use of naturally-occurring substances hinders the use of fossil raw materials such as petroleum to prevent the depletion of limited resources, and the natural biodegradability of natural products means that ecosystems can be used even after they have been destroyed. Attention has been paid to the fact that it can be reduced to a substance that does not harm the earth, and can be a material that is friendly to the earth or the environment. In fact, recently, the renowned green chemistry as a paradigm shift in chemistry has been described as having to use biomass instead of petroleum as a raw material, and on the other hand, the United States on August 12, this year (1999) There are reports that the President has addressed the five ministers and encouraged them to develop bio-based materials. However, in reality, there are many technical problems to be overcome, and very few technologies have been put to practical use. As a technique using a naturally derived substance, use of cellulose (lignocellulose) such as wood was first proposed (see JP-A-61-261358 and JP-A-62-79230). For example, the above publication discloses that lignocellulose is prepared in the presence of phenols or polyhydric alcohols in the presence of 210
It is disclosed that liquefaction is performed by heating and pressurizing at a temperature of up to 260 ° C., and application to adhesives and cured molded articles has also been proposed. Further, JP-A-1-45440, JP-A-1-58021, JP-A-1-58022, JP-A-3-263417,
JP-A-6-226711, JP-A-8-225633 and the like,
In the presence of the lignocellulose phenols or polyhydric alcohols and an acid catalyst, 100 ~ 200 ℃
A method for producing an adhesive or a foam using a material liquefied by heating to a temperature of the above is disclosed.

[0004] Next to cellulose such as wood, attention has recently been focused on the use of starch obtained from cereals. Starch, like cellulose, is the most important polysaccharide, but has no thermoformability per se and is difficult to hot press into boards, sheets and the like. About 3 million tons of starch is produced annually in Japan. The amount of seed coat, germ, protein, etc. by-produced in the manufacturing process reaches about 1 million tons. In addition, a large amount of starch-based waste is generated during starch processing, food preparation and food utilization in the food industry. At present, these wastes are hardly used except for livestock feed, and large quantities are discarded by means such as incineration. If such surplus starch waste can be used for various applications, particularly for molding and other industrial uses as well as thermosetting or thermoplastic resins, it is believed that a biodegradable material will be obtained. As an attempt to convert a starch-based substance into a thermosetting resin, for example, JP-A-6-136168 discloses that starch and corn seed coat, which is an industrial waste thereof, are treated at 30 to 200 ° C. in the presence of an acid catalyst and a polyhydric alcohol. A method for producing a foam by mixing and reacting a liquefied product obtained by heating with a blowing agent or a polyvalent isocyanate is disclosed. The foam obtained in this manner is excellent in biodegradability, so that it is not always necessary to perform waste incineration, and even if it is performed, the amount of heat required for waste incineration can be reduced. However, the invention described in the above publication has a long liquefaction reaction time of starch,
There are drawbacks such as low stability over time of the obtained liquefied product. In addition, the types of resin compositions finally obtained from the liquefied product are also limited.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to overcome the above-mentioned problems and to liquefy a starch-based substance containing corn seed coat, which is industrial waste of starch, by the action of phenol and then to convert it into resin. Thereby, while being able to express chemical and mechanical properties equivalent to or better than ordinary plastic materials, a phenolic resin-containing composition having biodegradability is prepared, and a cured molded article using the same is prepared. It is to provide a manufacturing method.

[0006]

SUMMARY OF THE INVENTION The present invention provides a phenolic resin obtained by reacting a starch-based material with phenols at 100 to 220 ° C. in the presence of an acid catalyst, liquefying the resultant, and neutralizing the resulting phenolic resin. And a phenolic resin-containing composition prepared by mixing a filler. Alternatively, the present invention provides a method in which a starch-based substance is treated with 100
Liquefaction by reacting with phenols at ~ 220 ° C,
Provided is a phenolic resin-containing composition prepared by further adding formaldehyde, copolycondensing, neutralizing, and mixing a curing agent and a filler with the obtained phenolic resin. Further, the present invention also provides a method for producing a cured molded article, which comprises heating and curing the phenolic resin-containing composition, and a cured molded article produced by the production method.

[0007]

According to the present invention, a liquefaction reaction of a starch-based substance can be easily achieved in a short time in the presence of an acid catalyst and phenols. In particular, according to the present invention, not only starch and starch derivatives but also corn seed coat (so-called corn feed) exhibiting high solvolysis and acid hydrolysis properties due to phenol can be used. In the present invention, starch industrial waste, which has conventionally been low in value added and has been disposed of, can be used as a raw material, so that not only resources can be effectively used, but also a high-strength cured molded body can be easily produced. And it can be manufactured at low cost. In particular, corn hulls and the like contain unique components completely different from starch and starch derivatives.In the present invention, the reduction of the molecular weight of these raw materials can proceed more easily and quickly, and as a result, a highly reactive phenol Thus, it is possible to produce a composition containing a chlorinated derivative (that is, a phenolic resin). The cured molded article of the present invention obtained by curing and molding the phenolic resin-containing resin composition obtained as described above has a high crosslink density and a high mechanical strength equivalent to or higher than that of a commercially available novolak resin (for example, bending strength and the like). ) Is also expressed. Furthermore, according to the present invention, the amount of formaldehyde to be copolycondensed with the phenolic resin-containing resin composition can be reduced, which is also effective for environmental protection.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Resin Composition The phenolic resin-containing composition according to the first aspect of the present invention comprises:
Reacting with phenols at ℃ to produce a liquefied product, (2) neutralizing the liquefied product to prepare a phenolic resin, and (3) obtaining a phenolic resin, a curing agent and It is prepared by a method including a step of mixing a filler. As another method, the phenolic resin-containing composition of the present invention is subjected to a copolycondensation reaction by adding formaldehyde to the obtained liquefied product after the step (1), followed by neutralization. Preparing a phenolic resin, and
(3 ′) It may be prepared by a preparation method including a step of mixing a curing agent and a filler with the phenolic resin.

(1): Liquefaction of starch-based material First, the starch-based material is subjected to 100-220 in the presence of an acid catalyst.
React with phenol at ℃ to liquefy. The starch-based substance used as a starting material in the present invention includes various starches such as corn starch, potato starch, tapioca starch, wheat starch, and derivatives thereof (for example, those that have been esterified, etherified, oxidized, or enzymatically decomposed). In addition, corn seed coat, or protein and fat as industrial waste produced in large quantities in the starch production process is included. The seed coat of corn varies depending on the type of corn and the starch manufacturing process to be applied, but usually contains cellulose and hemicellulose as main components and contains protein, residual starch, ash and moisture.

When the above-mentioned esterified or etherified starch is used as a starch-based substance, the degree of substitution, which represents the average number of substituted hydroxyl groups per glucose residue in the esterified or etherified product, is 0. 01 ~
It is preferable to use those having a range of 0.5. Alternatively, as the crosslinked starch derivative, one having the above substitution degree of 0.0003 to 0.01 is preferably used.

[0011] The starch derivative may be prepared using any of the conventionally known esterifying agents, etherifying agents and crosslinking agents. Examples of preferably used esterifying agents include formic acid, formic anhydride, acetic acid, acetic anhydride, vinyl acetate, saturated fatty acids, unsaturated fatty acids, acetyl chloride, ketene, sodium phosphate, sodium tripolyphosphate and the like; Examples of the agent include methyl chloride, ethylene oxide, ethylene chlorohydrin, monochloroacetic acid, diethylaminoethyl chloride, 2,3-epoxypropyltrimethylammonium chloride and the like. On the other hand, examples of the crosslinking agent that can be suitably used include phosphorus oxychloride, trimetaphosphoric acid, acrolein, epichlorohydrin and the like.

The above-mentioned starch derivative is an oxidized starch having a degree of substitution of about 0.000001 to 0.02, which represents the average number of substituted carboxyl groups per glucose residue in the obtained starch derivative; or starch is α-amylase,
β-amylase, glucoamylase, isoamylase,
It may be a starch hydrolyzate degraded by the action of a hydrolase such as α-glucosidase and pullulase.

In the present invention, the above-mentioned starch or its derivative or corn seed coat used as a starch-based substance is easy to handle.
It is preferably in powder or particulate form during use,
The particle size is not particularly limited as long as it can be sufficiently solvolyzed in the liquefaction reaction step with phenols.

In the present invention, a phenol or a phenol derivative having a high solvolysis property is used for the starch-based substance. Examples of such phenols include, for example, phenol, o-, m- or p-cresol, 3,5-, 2,
3- or 2,6-xylenol, o-, m- or p-propylphenol, o-, m- or p-butylphenol, o-, m- or p-sec-butylphenol, o-, m
-Or monovalent phenols such as p-tert-butylphenol, hexylphenol, phenylphenol, octylphenol, naphthol; divalent phenols such as catechol, resorcinol, quinol, acrylresorcinol, bisphenol A, bisphenol F, bisphenol S; and pyroganol , Phloroglucill,
Trivalent phenols such as trihydrobenzene and gallic acid;
And their chlorides. The phenols may be used alone or in combination of two or more.

The acid catalyst preferably used in the present invention includes inorganic acids such as sulfuric acid and hydrochloric acid (so-called mineral acids); organic acids such as toluenesulfonic acid and phenolsulfonic acid; It may be selected from Lewis acids such as zinc chloride and boron trifluoride.

In the present invention, in step (1) relating to the preparation of a liquefied product, preferably 5 to 800 parts by weight, particularly 10 to 500 parts by weight, usually 0.1 to 20 parts by weight, preferably 0 to 20 parts by weight of a starch-based substance is used. It is added to 100 parts by weight of said phenol or phenol mixture in the presence of an acid catalyst in an amount of from 0.5 to 10 parts by weight. Use of 5 starch-based substances
When the amount is less than part by weight, it is difficult to convert the obtained liquid into a resin in the next step. The amount of starch-based material is 800
If the amount is more than 10 parts by weight, the liquefaction does not proceed sufficiently. However, if the preparation of the liquefied product in this step (1) is performed using a twin-screw extruder, it is possible to use more than 800 parts by weight of a starch-based substance. For example, corn may be used as a starch-based substance. When using a seed coat, the liquefaction reaction can proceed sufficiently even when the amount is increased to about 1,000 parts by weight.

In the present invention, the liquefaction reaction in the step (1) is determined according to the following equation by measuring the weight of the unliquefied starch-based substance and the unreacted phenol relative to the used weight of the raw material (that is, the charged weight). The amount of phenol bound to the starch-based material to be obtained: CP (%) is preferably at least 70%, more preferably at least 75%.

CP (%) = (W ₁ −W ₂ ) / (W ₀ −W _r ) × 100 (1) In the above formula (1), W ₁ is a charged weight of phenols,
W ₂ represents the weight of unreacted phenols, W ₀ represents the weight of the starch-based material charged, and W _r represents the weight of the unliquefied starch-based material. Here, W ₂ may be a value obtained by analyzing a sample after the liquefaction reaction by using a high-pressure liquid chromatography (HPLC) method or the like.

The liquefaction in the step (1) is carried out at 100
The reaction is carried out at a temperature of -220 ° C, preferably 130-200 ° C, most preferably 150-200 ° C for 15-300 minutes, preferably 30-120 minutes. In particular, when using corn seed coat as a starch-based substance, by increasing the use weight of the acid catalyst and raising the reaction temperature,
The liquefaction reaction can proceed more effectively.

The liquefaction reaction can proceed more efficiently by appropriately stirring the reaction mixture in addition to heating in the above temperature range. For example, the rotation speed is 30 to 300 rpm
By stirring the inside of the reaction system at m, the liquefaction reaction time when no torque is applied (30 to 300 minutes)
The starch-based substance can be liquefied stably and reliably in a shorter time (for example, in 15 to 200 minutes) with good reproducibility.

In this step (1), in the early stage of the liquefaction reaction, in order to suppress runaway of the reaction due to heat generation and to efficiently discharge the water of the starch-based material as a starting material outside the system, the reaction is carried out at the beginning of the liquefaction. And / or an organic solvent that can azeotrope with water or a solvent that can dissolve the resulting liquefied product during the reaction,
The total reaction system may be added in an amount of 10 to 500 parts by weight based on 100 parts by weight.

The liquefied product obtained in this step (1) is characterized by having reactivity with aldehydes, epoxies or isocyanates.

(2) or (2 ′): Preparation of Phenolic Resin Next, after the liquefaction reaction in the step (1), the acidic liquefied product is added to a generally known neutralizing agent such as MgO, NaOH and imidazole. Is added and the mixture is subjected to a neutralization reaction to prepare a phenolic resin [Step (2)].

Alternatively, a phenolic resin may be prepared by adding formaldehyde to the liquefied product obtained in the above step (1) to cause a copolycondensation reaction, followed by neutralization to obtain a phenolic resin [step (2). ')]. In the step (2 ') of the present invention, formaldehyde is added in an amount of not more than 1.5, preferably 0.2 to 1.0, in a molar ratio to the unreacted phenol residue in the liquefied product. In the step (2 ′) of the present invention, formaldehyde may be added as it is or in the form of an aqueous solution (ie, as formalin). After the aldehyde is added to the liquefied product, the mixture is reacted at about 80 to 105 ° C. within 90 minutes, preferably 10 to 60 minutes, and then a neutralizing agent is added in the same manner as in step (2) to perform a neutralization reaction. Attached. In some cases, after adding formaldehyde to the liquefied product, the product may be immediately subjected to a neutralization reaction without performing the above-described reaction.

Regardless of whether aldehyde is added or not, the above-mentioned neutralized reaction product is heated at a reduced pressure of 5 to 180 mmHg, for example, at 60 to 180 ° C. to obtain unreacted phenols which are not bound to starch-based substances. Or when added, after removing an organic solvent capable of azeotroping with water, a solvent capable of dissolving a liquefied product to be formed, and the like, drying is performed using a drying means known in the art.

The obtained dried product is obtained by using a conventional means such as a grinder, a freeze grinder, a wheely mill or a mortar.
Preferably, it is pulverized (at room temperature) to about 0.01 to 5 mm. However, if desired, the phenols are not completely removed from the neutralized reaction product during drying,
The next step with some unreacted phenol still contained
In the case of (3), it is not necessary to grind.

(3): Preparation of a Phenolic Resin-Containing Composition The phenol of the present invention is obtained by adding and mixing a curing agent and a filler to the phenolic resin obtained in the phenol liquefaction step (2). A resin-containing composition is obtained.

Examples of suitable curing agents used in the present invention include hexamethylenetetramine (so-called hexamine), and in some cases, paraformaldehyde, trioxane and the like can also be used. Further, depending on the properties required of the final product, an epoxy resin may be added to the phenolic resin obtained in the previous step to form an epoxy-phenol resin composition; a diisocyanate compound may be added as a curing agent to form a polyurethane or It may be a polyurea resin composition. Alternatively, it is also possible to add a urea resin, a melamine resin or a urea-melamine resin to the phenolic resin, and perform three-dimensional curing as a mixed resin-containing composition.

Suitable fillers used in this step (3) include wood flour, wood fibers (ie pulp), lignin or lignin compounds, synthetic fibers; and silica stone, diatomaceous earth, glass, alumina, mica, Examples thereof include inorganic substances such as carbon black and silicon carbide, and any of these can be used alone or in combination of two or more.

The curing agent is used in an amount of 1 to 25% by weight, preferably 5% by weight, based on the total weight of the obtained phenolic resin-containing composition.
The filler may be added in an amount of -20% by weight and the filler in an amount of 20-80% by weight, preferably 30-70% by weight, respectively.

Further, in addition to the above-mentioned essential components (a combination of a curing agent and a filler or a filler), various additives necessary for producing a desired product, for example, alkylresorcinol, etc. A crosslinking agent such as a polyvalent epoxy compound or a diisocyanate compound;
A curing accelerator such as calcium oxide, magnesium oxide or calcium hydroxide; a pigment; a flame retardant; a lubricant such as stearic acid or calcium stearate may be added. These additives are desirably in a total amount of 5 to 30% by weight, preferably 8 to 25% by weight, based on the total weight of the resin composition.

In this step (3), means for mixing and kneading each of the above-mentioned additives to the phenolic resin obtained in the preceding step (2) include, for example, a Ripon-type rotary blade inside and a heating jacket outside. , A kneader-type mixer or a Banbury mixer, or a screw extrusion-type kneader, a co-kneader, a heating roll, a ball mill, or the like can be used alone or in combination of two or more.

The resin composition of the present invention prepared through the above steps can be used as a food packaging material in addition to applications such as adhesives, molding materials, and shock absorbers.

Cured Molded Article The present invention also provides, as a second aspect, a method for producing a cured molded article by heat-curing the resin composition of the present invention obtained by the above method. The method of heating and curing the resin composition,
The resin composition is heated to 140 to 200 ° C., preferably 17 ° C., using a hot pressing means such as a hot press using a mold.
0 to 180 ° C, 5 to 100 MPa, preferably 10 to 8
6 seconds to 20 minutes at 0 MPa, preferably 2 to 10
By applying molding conditions such as minutes, it is possible to obtain a cured molded article having a high crosslinking density and a high strength equal to or higher than that of a novolak resin.

The heating and pressure molding conditions and the means used therefor may be appropriately changed according to the desired use of the cured molded article. For example, when the resin composition of the present invention is provided for use as an adhesive, after applying the resin composition to a desired site, the resin composition is cured in a desired range selected from the above-mentioned heating conditions, thereby achieving high adhesion. An adhesive cured product is obtained.

[0035]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. (1) Liquefaction reaction of starch-based material Example 1 10 g of corn seed coat as starch-based material was
An L-volume glass three-necked flask was weighed, and 30 g of phenol obtained by uniformly mixing sulfuric acid was added thereto. The amount of sulfuric acid was 3% by weight of phenol (= 0.9 g).
These were liquefied by heating under reflux at normal pressure and 150 ° C. for 20 minutes. After the liquefaction reaction, the mixture was washed out of the reaction flask with methanol into a 300 mL beaker, and the obtained diluted methanol solution was stirred for 20 minutes, and then filtered under reduced pressure using glass fiber filter paper. After the methanol-insoluble fraction separated by filtration was dried at 105 ° C. for 24 hours, the weight (g) of unliquefied maize seed coat was measured by gravimetric analysis. On the other hand, the filtered methanol-soluble fraction was analyzed by HPLC, and the amount of unreacted phenol was measured. The measured non-liquefied corn pericarp weight was Wr and unreacted phenol amount of W _2, coupled phenol amounts in accordance with the above equation (1): was determined CP (%). Table 1 shows the amount (%) of unliquefied corn seed coat residue and the CP value (%) obtained above with respect to the charged weight (10 g) of the corn seed coat together with the amounts of the respective liquefaction reaction components.

Examples 2 to 7 Except that the liquefaction reaction time was set to 30, 60, 90, 120, 150 or 180 minutes, the corn seed coat was liquefied in the same manner as in Example 1, and then the unliquefied corn seed coat was prepared. The amount of bound phenol: CP (%) was determined by measuring the amount of residue and the amount of unreacted phenol. Table 1 shows the amount (%) of unliquefied corn seed coat residue and the CP value (%) obtained above with respect to the charged weight (10 g) of the corn seed coat together with the amounts of the respective liquefaction reaction components.

Comparative Examples 1-7 Polyethylene glycol 400 instead of phenol:
The use of 30 g of a mixture of glycerin (weight ratio) = 4: 1 and the liquefaction reaction time of 20, 30, 60, 9
The corn coat was liquefied in the same manner as in Example 1 except that the time was set to 0, 120, 150 or 180 minutes. Table 1 shows the residual amount (%) of the unliquefied corn seed coat with respect to the charged weight (10 g) of the corn seed coat together with the amounts of the respective liquefaction reaction components.

[0038]

[Table 1] a): Corn seed coat was used. b1): Phenol was used. b2): A mixture of polyethylene glycol 400: glycerin (weight ratio) = 4: 1 was used. c): concentrated sulfuric acid

In Examples 1 to 7 in which corn husk, which is industrial waste of starch, was liquefied with phenol, the amount of unliquefied corn husk residue after liquefaction for 20 minutes was 13%. A decrease in the amount of the residue was confirmed. That is, the results in Table 1 show that the liquefaction reaction 180
This shows that the reaction is still continuing even after minutes. CP
The value already exceeded 102% in 20 minutes of the liquefaction reaction, and it was also confirmed that this value gradually increased with the liquefaction time. In contrast, in Comparative Examples 1 to 7 in which the corn seed coat was liquefied using a polyhydric alcohol (polyethylene glycol / glycerin mixed system), the amount of unliquefied residue of the corn seed coat was higher than in Examples 1 to 7 above. Has become. From these results, when using corn hulls as starch industrial waste, compared to polyhydric alcohol, the resin composition prepared using phenol is better in terms of reactivity. I understand.

Example 8 10 g of corn starch was weighed into a 50 mL glass three-necked flask, and 0.9 g of sulfuric acid (= 3% by weight of phenol used) was uniformly mixed with phenol 30.
g was added. These were subjected to 20
The mixture was heated under reflux for minutes and liquefied. After the liquefaction reaction, the mixture was washed out of the reaction flask with a methanol into a 300 mL beaker, and the obtained diluted methanol solution was stirred for 20 minutes.
Filtration under reduced pressure was performed using a glass fiber filter paper. After the methanol-insoluble fraction separated by filtration was dried at 105 ° C. for 24 hours, the amount of unliquefied starch residue was quantified by gravimetric analysis. On the other hand, the filtered methanol-soluble fraction was analyzed by HPLC, and the amount of unreacted phenol was measured. The measured amount of unliquefied starch residue is Wr and the amount of unreacted phenol is W _2, and the amount of bound phenol: C according to the above formula (1)
P (%) was determined. Corn starch charge weight (1
Table 2 shows the amount (%) of the unliquefied starch residue and the CP value (%) obtained above with respect to 0 g) together with the amounts of the respective liquefaction reaction components.

Examples 9 to 13 The liquefaction reaction time was 30, 60, 90, 120 or 180
Starch was liquefied in the same manner as in Example 8 except that the amount was changed to minutes, and then the amount of bound phenol: CP (%) was determined by measuring the amount of unliquefied starch residue and the amount of unreacted phenol. Table 2 shows the residual amount (%) of the non-liquefied starch and the CP value (%) obtained above with respect to the charged weight (10 g) of the corn starch together with the amounts of the respective liquefaction reaction components.

[0042]

[Table 2] a): Use corn starch b): Use phenol c): Concentrated sulfuric acid

As shown in Table 2, the reaction of liquefying starch-based corn starch by the method of the present invention was conducted at 150 ° C.
It turns out that it is already completed in 20 minutes. Furthermore, the value of the amount of bound phenol is larger than that of corn husk liquefaction, and it has been shown that the amount of bound phenol increases with the liquefaction reaction time even after the liquefaction reaction seems to be completed. It was confirmed that the reaction was a liquefaction reaction with high reaction efficiency.

(2) Preparation of phenolic resin Example 14 In this example, the weight ratio of corn starch to phenols was
1 shows a preparation example of a phenolic resin oligomer when the ratio is 1: 3. Magnesium oxide was added to the methanol-dissolved fraction (ie, filtrate) of the starch liquefaction (CP = 158.1%) obtained in Example 10 to neutralize it. Next, after methanol was evaporated at 50 ° C., free unreacted phenol was distilled off at 180 ° C. under reduced pressure to obtain a phenolic resin oligomer. The obtained solid resin oligomer was pulverized using a freezing pulverizer or a mortar to obtain a powder. The thermal properties of the powdered resin oligomer were measured using the Shimadzu Flow Tester CFT-
It measured using 500A. Thermal properties are heat softening temperature:
T _s , heat flow temperature T _f , and 130 ° C., 1.225 × 1
0 ⁶ were measured for melt viscosity under shear stress dyn / cm ^2. The results are summarized in Table 3. As shown in Comparative Example 10 below, a commercially available NOV
OLAC resin (manufactured by Hitachi Chemical Co., Ltd .; trade name: HP-700)
NK; number average molecular weight 3814) is shown in Table 3 together with the thermal softening temperature: T _s and the thermal fluidization temperature T _f measured under the same conditions.

Example 15 In this example, corn seed coat and phenols as starch industrial waste were mixed at a weight ratio of 1: 1 and 200 ° C.
For 30 minutes to prepare a phenolic resin. 6 g of corn hulls were placed in a 20 mL stainless steel autoclave (TV, manufactured by Pressure Glass Industry Co., Ltd.).
S-1) was weighed, and 6 g of phenol in which sulfuric acid was uniformly mixed was added thereto. The amount of sulfuric acid was 3% by weight of phenol. These were sealed and heated at 200 ° C. for 30 minutes to liquefy. Immediately after the liquefaction, the mixture was cooled in ice water, the autoclave was opened, and the content was washed out with methanol into a 200 mL beaker. The resulting methanol dilution was stirred for 20 minutes, and then filtered under reduced pressure using glass fiber filter paper. The methanol-insoluble residue separated by filtration was dried at 105 ° C. for 24 hours, weighed, and the weight of unliquefied corn seed coat was measured. After the methanol-insoluble fraction separated by filtration was dried at 105 ° C. for 24 hours, the amount of unliquefied maize seed coat residue was quantified by gravimetric analysis. On the other hand, the filtered methanol-soluble fraction was analyzed by HPLC to measure the amount of unreacted phenol W ₂ ,
The amount of bound phenol: CP (%) determined according to the above formula (1) was 75.9%. The obtained liquid was neutralized by adding magnesium oxide to a methanol-dissolving section (that is, a filtrate). Next, methanol was heated to 50 ° C.
After evaporating under the conditions, free unreacted phenol was distilled off at 180 ° C. under reduced pressure to obtain a phenolic resin.

The obtained solid resin was pulverized using a freezing pulverizer or a mortar to obtain a powder. The thermal properties of the powdered resin were measured using the Shimadzu Flow Tester CFT-50.
It was measured using OA. Thermal properties are heat softening temperature:
T _s , heat flow temperature T _f , and 130 ° C., 1.225 × 1
0 ⁶ were measured for melt viscosity under shear stress dyn / cm ^2. The results are summarized in Table 3.

Example 16 A reaction and filtration were conducted in the same manner as in Example 15 except that 3 g of corn seed coat and 9 g of phenol were used. The methanol-insoluble residue and the methanol-insoluble fraction separated by filtration were treated in the same manner as in Example 15 to obtain 158.7% of bound phenol after liquefaction: CP (%). Methanol dissolution classification of the obtained liquefied product (that is,
The filtrate was neutralized by adding magnesium oxide. next,
After evaporating the methanol at 50 ° C., the free unreacted phenol is distilled off at 180 ° C. under reduced pressure,
A phenolic resin was obtained. The obtained solid resin was pulverized using a freezing pulverizer or a mortar to obtain a powder. The thermal properties of the powdery resin were measured using a flow tester CFT-500A manufactured by Shimadzu Corporation. Thermal properties include thermal softening temperature: T _s , heat flow temperature T _f , and 130 ° C., 1.
The melt viscosity under a shear stress of 225 × 10 ⁶ dyn / cm ² was measured. The results are summarized in Table 3.

COMPARATIVE EXAMPLES 8 AND 9 Instead of cornstarch, wood (birch powder, 20 to 20)
Example 10 except that 10 g was used.
Liquefaction and resin preparation were carried out according to
Wood liquefact-phenolic resins with values of 69% and 88% were obtained. The heat flow temperature _Tf was measured for each resin. The results are summarized in Table 3.

Comparative Example 10 NOVOLAC resin as a control sample (manufactured by Hitachi Chemical Co., Ltd .; trade name HP-700NK; number average molecular weight 3814)
The thermal properties (thermal softening temperature: T _s , thermal fluidization temperature T _f , and 130 ° C., 1.2
The melt viscosity under a shear stress of 25 × 10 ⁶ dyn / cm ² was measured. The results are summarized in Table 3.

[0050]

[Table 3] a1): Corn starch was used. a2): Corn seed coat was used. b): Phenol was used. c): concentrated sulfuric acid d): measured at 130 ° C. under a shear stress of 1.225 × 10 ⁶ dyn / cm ²

[0051] From the results of Table 3, the thermal properties of the phenolic resin oligomer prepared from starch liquefied material in Example 14 as compared to commercially available NOVOLAC resin is a control sample, the thermal softening temperature T _s and heat flow temperature It can be seen that both T _f are low. Furthermore, from the results of Example 15,
When the liquefaction reaction weight ratio between starch industrial waste and phenols is 1: 1, C is lower than in Example 14 where the weight ratio is 1: 3.
It can be seen that the P value decreases. When the resins obtained in Examples 14 to 16 are compared with the resins obtained in Comparative Examples 8 and 9, both of the resins obtained in Examples 14 and 15 are more heat than the commercially available control NOVOLAC resin. It can be seen that the resin has high mechanical properties and is more plastic, and the resin obtained in Example 16 is comparable to the commercially available resin. Regarding the thermal fluidization temperature, the resin obtained in Comparative Example 8 had a CP = 69% and T _f = 125 ° C., and the resin obtained in Comparative Example 9 had a CP = 88% and T _f = 160 ° C. On the other hand, it is understood that all of the resins obtained in Examples 14 to 16 of the present invention can be plasticized at a relatively low temperature in terms of thermal properties.

(3) Production of cured molded product Example 17 37.7 parts by weight of the powdery phenolic resin obtained from Example 16 (from which free unreacted phenol was removed) was added to
49.5 parts by weight of filler (wood flour), 9.4 parts by weight of hexamethylenetetramine, 2.4 parts by weight of calcium hydroxide, and 1.0 part by weight of zinc stearate were added, and Labo Plastmill (Toyo Seiki ( After kneading and mixing using
Using a mold, the composition was cured under the conditions of a compression molding temperature of 170 to 180 ° C., a molding time of 5 minutes, and a molding pressure of 50 MPa. As a result, seven bending test pieces of a novolak resin having dimensions of 10 × 2 × 120 (mm) in accordance with JIS standards were obtained. The obtained seven test pieces were all measured at 20 ° C and 60 ° C.
After humidity control for two days and nights under the condition of% RH, a bending test was performed using Shimadzu Autograph AGS-5kNG (manufactured by Shimadzu Corporation). By this bending test, the bending strength, the bending elastic modulus, and the bending work were measured, and the average of the measured values of the seven samples was determined. Table 4 shows the results. The obtained cured molded article not only had excellent appearance, but also exhibited high flexural strength, flexural modulus and flexural breakage work as shown in Table 4.

[0053]

[Table 4] 1): Wood flour 2): Hexamethylenetetramine ++: A molded test piece was conditioned at 20 ° C. and 60% RH for two days and night, and then a bending test was performed.

From the results shown in Table 4, it can be seen that the cured molded article of the phenolic resin composition of the present invention gives excellent bending test results.

Evaluation of Biodegradability The test piece obtained after the bending test obtained in Example 17 was subjected to the following biodegradability test. The test piece was put into a composting device (Nature Pocket made by Natural Kobo Co., Ltd.), treated for 2 weeks, and then weighed. It was confirmed that biodegradation was progressing. That is, corn seed coat is used as a starch-based material, and a liquefied product of corn seed coat and phenol (weight ratio 1: 1) is used.
It can be seen that the test piece obtained by curing and molding the phenolic resin prepared in 3) has excellent biodegradability.

Example 18 In this example, unreacted phenol in a liquefied product produced using corn husk as a starch industrial waste was prepared.
Formaldehyde was reacted to produce a novolak resin-like resin having a three-dimensional structure. Corn seed coat 3
g was weighed into a 20 mL stainless steel autoclave (TVS-1 manufactured by Pressure Glass Industry Co., Ltd.), and 9 g of phenol obtained by uniformly mixing sulfuric acid was added thereto. The amount of sulfuric acid was 3% by weight of phenol. These are 20
Heat at 0 ° C. for 30 minutes to liquefy. After the liquefaction reaction,
Immediately after cooling in ice water, the autoclave was opened, and the content was washed out with methanol into a 200 mL beaker. The resulting methanol dilution was stirred for 20 minutes, and then filtered under reduced pressure using glass fiber filter paper. A liquefied material-containing filtrate from which a methanol-insoluble residue was removed by filtration was used as a sample (i), and after separately performing the same liquefaction, a liquefied material containing a methanol-insoluble residue without filtration was used as a sample (ii). The methanol-insoluble fraction separated from sample (i) was subjected to 105 ° C.
After drying for 24 hours, the amount of unliquefied maize seed coat residue was measured. Further, the sample (i) was analyzed by HPLC, and the amount of unreacted phenol was measured. The measured amount of unliquefied maize seed coat residue is determined by Wr
The amount of unreacted phenol was W _2, and the amount of bound phenol: CP (%) was determined according to the above formula (1).

Formalin (formaldehyde 37% aqueous solution) was added in an amount of 0.8 molar equivalent of formaldehyde to the amount (mol) of unreacted phenol in the liquefied product sample (ii). The mixture was heated at reflux for 80 or 120 minutes to cause a copolycondensation reaction. After the reaction, each copolycondensate was diluted with acetone and neutralized by adding magnesium oxide. Thereafter, the diluting solvent was distilled off at 50 ° C. under a reduced pressure of about 20 mmHg, and then the free unreacted phenol was distilled off at 180 ° C. to obtain resins A to C. The obtained solid resin was pulverized using a freezing pulverizer or a mortar to obtain a powder. The thermal properties of the powdery resin were measured using a flow tester CFT-500A manufactured by Shimadzu Corporation. Thermal properties were measured for thermal softening temperature: T _s , heat flow temperature T _f, and melt viscosity under a shear stress of 130 ° C. and 1.225 × 10 ⁶ dyn / cm ² . Further, in the curing molding of the resin at 170 ° C., the resins A to
For each of C, the time (minute) required for 90% curing was also measured. Table 5 summarizes these results.
Table 5 also shows the results of measuring the thermal properties of the NOVOLAC resin manufactured by Hitachi Chemical Co., Ltd. used in Comparative Example 10 as a control sample in the same manner as described above.

[0058]

[Table 5] +: Liquefied matter from which methanol-insoluble residue was removed ++: Liquefied matter containing methanol-insoluble residue 1): Corn seed coat was used. a): Sulfuric acid b): Formaldehyde was used in the form of formalin (37% aqueous formaldehyde solution). c): Measured at 130 ° C. under a shear stress of 1.225 × 10 ⁶ dyn / cm ² d): When cured at 170 ° C., the resin composition is 90%.
% Time required for curing (minutes) +++: Commercially available NOVOLAC resin used in Comparative Example 10 (manufactured by Hitachi Chemical Co., Ltd .; trade name HP-700NK; number average molecular weight 3814)

As is clear from the results in Table 5, Example 1
The thermal softening temperature for T.8: T _s was about the same between the liquefied product and the subsequent copolycondensate, but the thermal fluidization temperature: T s
_{Both f} and melt viscosity were higher for the copolycondensate. On the other hand, regarding the liquefied product, the presence or absence of a methanol-insoluble residue containing salts generated after neutralization (samples (i) and (ii))
Since no significant difference is observed in the curing molding time according to Comparative Example 1), it is considered that the presence of the salt is not involved in the curing molding. From the results in Table 5 above, 17
The 90% curing time at 0 ° C. is slightly longer than the curing time of a commercially available NOVOLAC resin shown as a comparative example. However, as for the copolycondensate, the longer the copolycondensation reaction time, the shorter the curing time. 9 in less time than resin
It can be seen that 0% cure can be achieved.

Example 19 Formalin (formaldehyde 37%) was used in an amount equivalent to 0.8 molar equivalent of formaldehyde with respect to the amount (mol) of unreacted phenol in the liquefied product sample (i) prepared in Example 18.
Aqueous solution) and heated under reflux at 105 ° C. for 80 minutes to cause a copolycondensation reaction. After the reaction, each copolycondensate was diluted with acetone and neutralized by adding magnesium oxide. Thereafter, the diluting solvent was distilled off at 50 ° C. and the unreacted phenol liberated at 180 ° C. under reduced pressure of about 20 mmHg, and the solid was pulverized to obtain a powdery resin. The liquefied product sample (i) prepared in Example 18 and the above (i)
And the sample (ii) and the sample (i
i) with the same proportions as in Example 17, except that a wood flour filler is added in an amount of 50% by weight, based on the total weight of each of the copolycondensation resins A, B and C obtained by reacting formaldehyde. Blends a hardening agent (hexamethylenetetramine), a hardening accelerator (calcium hydroxide) and a release agent (zinc stearate) with Labo Plastomill (Toyo Seiki Co., Ltd.)
After kneading and mixing using a mold, the mixture was cured and molded for 5 minutes under the conditions of a compaction molding temperature of 170 to 180 ° C. and a molding pressure of 50 MPa. The molded specimen is
After humidity control at 0 ° C. and 60% RH for two days and nights, a bending test was performed using Shimadzu Autograph AGS-5kNG (manufactured by Shimadzu Corporation) to measure bending strength, bending elastic modulus, and work to be broken. . The results are summarized in Table 6.

[0061]

[Table 6] 1) Wood flour +++: commercially available NOVOLAC resin used in Comparative Example 10 (manufactured by Hitachi Chemical Co., Ltd .; trade name HP-700NK; number average molecular weight 3814)

From the results shown in Table 6, the liquefied product and the phenolic resin which is a copolycondensation reaction product of the liquefied product and formaldehyde are compared. It can be seen that the amount increases. The copolycondensate of the present invention is commercially available NOVOLA
It can also be seen that the resin exhibits the same strength as the C resin.

Example 20 The total weight of the copolycondensation resin B prepared in Example 18 was
Hexamethylenetetramine, calcium hydroxide and zinc stearate were blended in the same proportions as in Example 17, except that a wood flour filler in an amount of 50, 60 or 70% by weight was added, and Labo Plastomill (Toyo Seiki ( After kneading and mixing using a mold, a pressing molding temperature of 170
Curing molding was performed for 5 minutes under the conditions of ~ 180 ° C and molding pressure of 50 MPa. The molded test piece was subjected to
After humidity control for two days and nights under the condition of% RH, a bending test was performed using Shimadzu Autograph AGS-5kNG (manufactured by Shimadzu Corporation) to measure bending strength, bending elastic modulus, and bending work. In addition, as a control sample, wood powder filler in an amount of 50 or 60% by weight with respect to NOVOLAC resin manufactured by Hitachi Chemical Co., Ltd. used in Comparative Example 10 and hexamethylenetetramine, calcium hydroxide and A bending test was also performed on a sample obtained by curing and molding the system to which zinc stearate was added in the same manner as described above. Table 7 summarizes the results.

[0064]

[Table 7] 1) Wood flour +++: commercially available NOVOLAC resin used in Comparative Example 10 (manufactured by Hitachi Chemical Co., Ltd .; trade name HP-700NK; number average molecular weight 3814)

From the results in Table 7, it is found that the copolycondensate B of Example 18 (using corn seed coat as a starch industrial waste) has a higher flexural strength as the filler is added in an increased amount. It can be seen that 70% by weight exhibits almost the same mechanical properties as a commercially available NOVOLAC resin containing 50% by weight of wood powder. The molecular weight of starch industrial waste obtained from corn seed coat is 1230
Dalton and lower than the commercial NOVOLAC resin. That is, when corn husk is used in the present invention, a copolycondensate having a lower molecular weight and a higher affinity with wood powder filler is obtained, so that the dispersibility of the filler is improved, and as a result, excellent It is considered that mechanical properties were obtained.

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Claims (7)

[Claims] 1. A starch-based material is treated with an acid catalyst in the range of 100 to 100.
A phenolic resin-containing composition prepared by reacting with a phenol at 220 ° C., liquefying, neutralizing, and mixing the obtained phenolic resin with a curing agent and a filler. 2. The method according to claim 1, wherein the starch-based substance is treated with
A phenolic resin prepared by reacting with phenols at 220 ° C. to liquefy, co-polycondensing by further adding formaldehyde, neutralizing, and mixing the obtained phenolic resin with a curing agent and a filler. Containing composition. 3. The phenols are selected from substituted or unsubstituted phenols or bisphenols.
Or the phenolic resin-containing composition according to 2. 4. The phenolic resin-containing composition according to claim 1, wherein the starch-based substance is corn seed coat. 5. The phenolic resin-containing composition according to claim 1, wherein the acid catalyst is at least one selected from organic acids, inorganic acids, and Lewis acids. 6. A method for producing a cured molded article, comprising heating and curing the phenolic resin-containing composition according to claim 1. 7. A cured molded article produced by the production method according to claim 6.