JP2021167385A - Resin composition - Google Patents

Abstract

To provide a technique related to a resin composition which can, while reducing an odor, improve kneadability with aggregate and increase an actual carbon ratio when made into a refractory product.SOLUTION: Provided is a resin composition which contains an alkyl-etherified phenol resin having an alkyl ether group bonded to a phenol ring, does not substantially contain a solvent, and does not gel according to a test under the following measurement condition. (Measurement Condition) According to JIS K6910, 2 ml of the resin composition is placed on a hot plate at 150°C and a time is measured until the resin composition hardens. When hardening does not occur after 10 minutes, it is regarded that the resin composition does not gel.SELECTED DRAWING: None

Description

The present invention relates to resin compositions. More specifically, it relates to a resin composition for use as a refractory.

In recent years, the amount of graphite-containing refractories using phenol resin as a binder has been increasing in converters, electric furnaces, pans and the like. Along with this, there are increasing cases where phenolic resin is used as a binder for aggregates such as graphite, magnesia, and alumina in refractories mainly used for repairing the furnace wall and the bottom of the above-mentioned steelmaking equipment. As the phenol resin used, novolak type and resol type liquid or powder phenol resins are used alone or in combination.

To give a typical example of use of phenol resin, in the case of novolak type phenol resin, powder resin containing hexamethylenetetramine may be used together with a wetting agent such as ethylene glycol, glycerin or polyhydric alcohol, or resol type liquid phenol resin. It is used in combination with.
Further, a liquid resin in which a novolak type phenol resin is previously dissolved in a solvent such as ethylene glycol is often used in combination with hexamethylenetetramine at the time of kneading.
On the other hand, in the case of resole-type phenol resin, a solvent-type liquid resin using an aqueous solvent-type liquid resin or a solvent such as ethylene glycol may be used alone, or these liquid resins may be used in combination with a novolak-type powder resin. I'm doing it.

As a technique relating to a phenol resin for refractories, for example, the technique described in Patent Document 1 is known.

Japanese Unexamined Patent Publication No. 10-139845

Since a conventional phenol resin requires a solvent during kneading, volatilization of the solvent causes odor generation, deterioration of the working environment, or an increase in environmental load. Further, even after kneading, there is a problem that the solvent volatilizes from the kneaded product with time, or the reaction of the phenol resin itself proceeds during storage of the kneaded product, and the kneaded product becomes hard and difficult to mold. Further, it is required to further increase the residual carbon ratio for refractories obtained by drying or heating using phenol resin as a binder for aggregates, but it is difficult for conventional phenol resins to meet this demand. It has become.

Therefore, in the present invention, the kneading property with the aggregate and the storage stability of the kneaded material are improved, and the residual coal ratio when the refractory material is used is increased without causing the problems of deterioration of the working environment and increase of the environmental load. It is an object of the present invention to provide a resin composition capable of providing a resin composition capable of providing a resin composition.

According to the present invention, a resin composition containing an alkyl etherified phenol resin having an alkyl ether group bonded to a phenol ring, substantially free of a solvent, and not gelled as a result of a test under the following measurement conditions. Is provided.
(Measurement condition)
According to JIS K 6909, 2 ml of the resin composition is placed on a hot plate at 150 ° C., and the time until the resin composition is cured is measured. If it does not cure after 10 minutes, it is considered not to gel.

Further, according to the present invention, a refractory product obtained by drying or firing the above-mentioned resin composition is provided.

According to the resin composition of the present invention, the kneadability with the aggregate and the storage stability of the kneaded material are improved without causing the problems of deterioration of the working environment and increase of the environmental load, and the residue when made into a refractory material. The charcoal rate can be increased.

Hereinafter, embodiments of the present invention will be described in detail. In the present specification, the notation "a to b" in the description of the numerical range indicates that it is a or more and b or less unless otherwise specified.

The resin composition according to the embodiment contains an alkyl etherified phenol resin having an alkyl ether group bonded to a phenol ring. The resin composition does not substantially contain a solvent and does not gel as a result of a test under the measurement conditions shown below.
(Measurement condition)
According to JIS K 6909, 2 ml of the resin composition is placed on a hot plate at 150 ° C., and the time until the resin composition is cured is measured. If it does not cure after 10 minutes, it is considered not to gel.

The term "substantially free of solvent" means that the content of the solvent in the entire resin composition is 10% by mass or less. The content of the solvent in the entire resin composition is preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 1% by mass or less.

Since the resin composition of the present embodiment does not substantially contain a solvent, the solvent does not volatilize from the resin composition, so that the odor of the solvent is not generated, the working environment can be improved, and the environment can be improved. It does not become a load. Further, since the resin composition of the present embodiment has a high solid content ratio of the alkyl etherified phenol resin, it is possible to increase the residual carbon ratio of the refractory obtained by firing, and to improve the mechanical strength. Can be done.

Further, since the resin composition of the present embodiment has a property of not gelling when heated under the above measurement conditions, it is possible to improve the kneadability with the aggregate, and by extension, the residual coal after drying and firing. The rate can be increased and the mechanical strength can be improved.

Summarizing the above, according to the resin composition of the present embodiment, it is possible to improve the kneadability with the aggregate and the storage stability of the kneaded material without causing the problems of deterioration of the working environment and increase of the environmental load. .. In addition to this, the residual coal rate when used as a refractory can be increased.

(Alkyl etherified phenol resin)
The alkyl etherified phenol resin used in the resin composition of the present embodiment is a phenol resin having an alkyl ether group bonded to a phenol ring (RO-CH _2- , where R represents an alkyl group). In other words, it is a phenol resin in which a part of the methylol groups (methylol groups in the phenol resin) contained in the phenol resin is etherified. That is, it is a phenol resin having an unetherified methylol group (HOCH _2- ) and an etherified _{methylol group (RO-CH 2-} , where R represents an alkyl group). Examples of the alkyl group constituting R include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, a pentyl group, an isopentyl group and a hexyl group. Heptyl group, octyl group, 2-ethylhexyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, Examples thereof include alkyl groups having 1 to 20 carbon atoms such as a nonadesyl group and an eicosyl group. Such an alkyl etherified phenol resin is obtained _{by reacting a phenol resin having a methylol group (HOCH 2-} ) bonded to a phenol ring with alcohols (R-OH) such as methanol and ethanol to form the methylol group of the phenol resin. At least a part of the above is obtained by etherifying with an alkyl group (alkyl etherification). As the alcohols used in the alkyl etherification reaction, methanol is preferably used, and as the alkyl etherified phenol resin, a phenol resin having _{a methyl ether group (CH 3-} O-CH _{2-) bonded to a phenol ring is preferable.}

The alkyl etherification rate of the alkyl etherified phenol resin is preferably 50 mol% or more. Here, the alkyl etherification rate refers to the ratio (mol%) of the alkyl ether groups to the total amount of the methylol groups and the alkyl ether groups contained in the alkyl etherified phenol resin. When the alkyl etherification rate is 50 mol% or more, the activity of the methylol group is controlled, and thus the stability of the alkyl etherified phenol resin over time can be enhanced. If the alkyl etherification rate is less than 50 mol%, the stability over time under temperature conditions of, for example, 30 to 40 ° C. may decrease. From the viewpoint of further improving the stability over time of the alkyl etherified phenol resin, the alkyl etherification rate is more preferably 60 mol% or more, further preferably 70 mol% or more, still more preferably 80 mol% or more. Is.

The alkyl etherification rate can be measured by an NMR apparatus. Specifically, for example, an alkyl etherified phenol resin is acetylated, this is ^{measured by a 1} H-NMR device, and the integrated value of the chemical shift portion of the methylol group, methylene group, and alkyl ether group bonded to the phenol ring is used. Can be calculated.

A phenol resin having a methylol group bonded to a phenol ring is obtained by reacting phenols with formaldehyde in the presence of a basic catalyst. This phenol resin has a form in which a methylene group and a dimethylene ether group are bonded to a phenol ring in addition to a methylol group.
Of these bonding groups, the methylol group mainly contributes to the curing reaction when the phenol resin is used, but since the methylol group has high reaction activity, it suppresses the time-dependent change of the phenol resin having the methylol group. Needed to be stored and handled at low temperatures.

The alkyl etherified phenol resin is obtained by alkyl etherifying (methyl etherifying when methanol is used) the methylol group with an alcohol such as methanol. The alkyl ether group is, so to speak, a state in which the methylol group is blocked by alkyl etherification, can suppress the change with time under a temperature condition of 30 to 40 ° C., and has a neutral pH even at 100 ° C. or lower. If the curing agent does not coexist, the stability is high. On the other hand, by adding a curing agent such as an acidic compound at the time of use, this block can be easily removed and the desired curing reaction can be performed.

The weight average molecular weight of the alkyl etherified phenol resin is preferably 100 to 10,000. More preferably, it is 200 to 5000.
By setting the weight average molecular weight in the above range, a particularly good curing reaction proceeds, so that the mechanical strength and heat resistance of the cured product can be improved, and the viscosity and melting point of the resin can be lowered to work. The effect of improving sex can be enhanced.

The weight average molecular weight was measured by the gel permeation chromatograph method under the following conditions.
1) Device body: "HLC-8120" manufactured by TOSOH
2) Column for analysis: manufactured by TOSOH (G1000HXL: 1, G2000HXL: 2, G3000HXL: 1)
GPC measurement was performed using a differential refractometer as a detector under analytical conditions of a flow rate of 1.0 ml / min, an elution solvent of tetrahydrofuran, and a column temperature of 40 ° C., and the molecular weight was converted by standard polystyrene.

By containing the above-mentioned alkyl etherified phenol resin, the resin composition of the present embodiment has a lower limit of viscosity at 25 ° C., for example, 500 mPa · s or more, preferably 750 mPa · s or more, more preferably 1000 mPa · s. It can be s or more. On the other hand, the upper limit of the viscosity at 25 ° C. is preferably 5000 mPa · s or less, more preferably 4500 mPa · s or less, and further preferably 4000 mPa · s or less. By setting the lower limit of the viscosity at 25 ° C. to the above range, the kneadability when the aggregate is added can be enhanced. By setting the upper limit of the viscosity at 25 ° C. to the above range, the adhesiveness with the aggregate can be enhanced, and the mechanical strength after drying or firing can be enhanced.

The mass of the resin composition of the present embodiment after heating at 135 ° C. for 1 hour is preferably 80% by mass or more, more preferably 85% by mass or more, and 90% by mass, based on the mass before heating. It is more preferably mass% or more.
When the mass after heating at 135 ° C. for 1 hour is within the above range, the residual coal ratio after drying or firing can be increased.

The mass of the resin composition of the present embodiment after heating at 135 ° C. for 1 hour, then heating at 430 ° C. for 30 minutes, and further heating at 800 ° C. for 30 minutes is 40% by mass or more with respect to the mass before heating. Is more preferable, 45% by mass or more is more preferable, and 50% by mass or more is further preferable.
When the mass after the heating conditions is in the above range, the residual coal ratio after drying or firing can be further increased.

(Other ingredients)
The resin composition of the present embodiment may contain additives depending on the intended use and necessity.
In the resin composition of the present embodiment, the cured product can be used as a part of the composition of the molded product. Such a resin composition can be used as a resin composition for a molded product. In this case, the resin composition of the present embodiment may contain a curing agent.

Examples of the additive include a curing agent. The curing agent may be appropriately selected depending on the type of the alkyl etherified phenol resin, but at least one selected from the group consisting of hexamethylenetetramine, isocyanate resin, epoxy resin and hexamethoxymethylol melamine is preferable. Among these, hexamethylenetetramine can be used from the viewpoint of heat resistance of the cured product.

(Manufacturing method of alkyl etherified phenol resin)
The method for producing the alkyl etherified phenol resin is not particularly limited, and examples of the method for producing the alkyl etherified phenol resin include the following methods. Phenols and aldehydes are reacted under a basic catalyst to synthesize a resol-type phenol resin mainly containing a methylol group, the pH is adjusted to 2 to 8 with an acidic substance, methanol is added, and the methylol group is added. And methanol are reacted to obtain an alkyl etherified phenol formaldehyde. The reaction conditions between the methylol group and methanol are preferably in the range of a reaction temperature of 130 to 170 ° C. and a reaction pressure of 1.0 to 2.0 MPa, typically a reaction temperature of 150 ° C. and a reaction pressure of 1.4 MPa.

(Refractory)
The resin composition of the present embodiment can be a resin composition for refractories used for forming refractories. That is, the alkyl etherified phenol resin of the present embodiment can be used as a refractory binder.

The refractory of the present embodiment can be obtained by drying or firing the resin composition for the refractory. The refractory may be an amorphous refractory or a standard refractory.

Such a resin composition for a refractory can include, for example, the above-mentioned curing agent and the above-mentioned aggregate for refractory in addition to the above-mentioned alkyl etherified phenol resin.

Since the resin composition of the present embodiment has a high residual carbon content, it is possible to form a strong carbon bond and to improve high durability.

As the aggregate, for example, alumina; magnesia; dolomite; magnesia; silica; zircon; silicon carbide; graphite such as scaly graphite, lump graphite, earth graphite; and the like can be used. Among these, magnesia can be used. These may be used alone or in combination of two or more.

In the resin composition for fireproof materials, the blending ratio of the aggregate and the alkyl etherified phenol resin is not particularly limited, but for example, 2 parts by mass to 12 parts by mass of the alkyl etherified phenol resin with respect to 100 parts by mass of the aggregate. A part by mass may be blended.

In the present embodiment, an amorphous refractory can be obtained by kneading a compound such as an aggregate or an alkyl etherified phenol resin at a predetermined compounding ratio. As a specific example, a kneaded product can be obtained by mixing the above-mentioned compound such as an alkyl etherified phenol resin, a curing agent, and an aggregate, and then kneading the mixture using a mixer or the like. The conditions for kneading are not particularly limited, but for example, kneading can be performed at 50 ° C. for 30 minutes. Since the resin composition of the present embodiment has good kneadability with the aggregate, kneading can be carried out without using an organic solvent.

Further, in the present embodiment, the obtained kneaded product is filled in a mold or the like, pressed and molded, and then dried at a predetermined temperature to obtain a dried standard refractory (non-fired). By further firing the obtained non-fired standard refractory, a fired standard refractory can be obtained. At this time, the drying treatment may be performed by heating at, for example, 150 ° C. to 300 ° C. As a result, the alkyl etherified phenol resin and the curing agent can be cured. Further, the firing treatment may be performed by heating at, for example, 1000 ° C. to 1500 ° C. This makes it possible to carbonize the phenol skeleton derived from the alkyl etherified phenol resin. In the standard refractory, all of the alkyl etherified phenol resin may be carbonized, but some of the alkyl etherified phenol resin may remain.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted.

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

<Preparation of resole-type phenol resin A>
1000 parts of phenol, 1725 parts of 37% formaldehyde aqueous solution (corresponding to 2.0 mol per 1 mol of phenols), and 180 parts of barium hydroxide were added to a 5 L three-necked flask equipped with a stirrer and a thermometer. , 90 ° C. for 1 hour.
Then, the reaction system was neutralized with a 25% aqueous sulfuric acid solution to adjust the pH to 4.5. Then, the reaction system was depressurized to 5000 Pa, heated to 70 ° C. and distilled under reduced pressure, dehydrated until the water content in the reaction system reached 2.0%, and then 1021 parts of methanol (1 mol of phenols). (Equivalent to 3.0 mol) was added to obtain 2760 parts of a resole-type phenol resin A.
The resulting resol-type phenol resin A was acetylated, ¹ using ^H-NMR apparatus, methylol groups attached to the phenol ring was calculated methyl ether group, dimethylene ether group, the proportion of methylene groups, respectively , 88 mol%, 0 mol%, 2 mol%, 10 mol%.

<Preparation of methyl etherified resol type phenol resin A>
276 parts of the above-mentioned resol type phenol resin A and 306 parts of methanol (amount of methanol: equivalent to 12.0 mol per 1 mol of phenols) were put into a 1 L autoclave device equipped with a stirrer, and the temperature was raised. After reacting at 150 ° C. and 1.4 MPa for 1 hour, the mixture was cooled.
The obtained resin was taken out and placed in a 1 L three-necked flask equipped with a stirrer and a thermometer. Then, vacuum distillation was carried out at a reduced pressure of up to 5000 Pa, and dehydration was carried out until the water content in the reaction system became 1.0% or less to obtain 194 parts of methyl etherified phenol resin A.
The resulting methyl ether of phenol resin A was acetylated in a manner described in detail below, ¹ using ^H-NMR apparatus, methylol group attached to the phenol ring, a methyl ether group, dimethylene ether group, a methylene group As a result of calculating the ratio of, it was 2 mol%, 82 mol%, 1 mol%, and 15 mol%, respectively.

<Preparation of methyl etherified resol type phenol resin B>
Methyl etherified by the same method as the method for producing methyl etherified resol-type phenol resin A, except that the amount of formaldehyde aqueous solution during the resol resin reaction was 1856 parts (corresponding to 2.5 mol per 1 mol of phenols). A resol type phenol resin B was obtained.

<Preparation of methyl etherified resol type phenol resin C>
By the same method as the method for producing methyl etherified resol-type phenol resin A, except that the amount of formaldehyde aqueous solution during the reaction of the resol-type phenol resin A was 1294 parts (corresponding to 1.5 mol per 1 mol of phenols). A methyl etherified resol type phenol resin C was obtained.

<Preparation of methyl etherified resol type phenol resin D>
By the same method as the method for producing methyl etherified resol-type phenol resin A, except that the amount of formaldehyde aqueous solution during the reaction of the resol-type phenol resin A was 2588 parts (corresponding to 3.0 mol per 1 mol of phenols). A methyl etherified resol type phenol resin D was obtained.

<Preparation of resole-type phenol resin E>
Resolated phenol by the same method as the method for producing resol-type phenol resin A, except that the amount of methanol added during the reaction of resol-type phenol resin A was 102 parts (equivalent to 3.0 mol per 1 mol of phenols). Resin E was obtained.

Regarding the methyl etherified resol type phenol resins A to D and resol type phenol resins E obtained above, the number average molecular weight and the weight average molecular weight, and the methylol group, methyl ether group, and dimethylene ether group bonded to the phenol ring , The proportion of methylene groups was measured using the following method. The results are shown in Table 1.

(Measurement of number average molecular weight and weight average molecular weight)
The number average molecular weight and the weight average molecular weight were measured by using a liquid chromatography method. The liquid chromatography method uses GPC (gel permeation chromatography), uses tetrahydrofuran as an elution solvent, and detects a differential refractometer under the conditions of a flow rate of 1.0 ml / min and a column temperature of 40 ° C. The molecular weight was converted by standard polystyrene.
The device is
1) Main body: "HLC-8120" manufactured by TOSOH
2) Analytical column: One "G1000HXL", two "G2000HXL", and one "G3000HXL" manufactured by TOSOH were used.

(Methylol group, methyl ether group, methylene group, dimethylene ether group ratio)
Using acetylated resin the above phenol resin following methods were measured by H ¹ -NMR.

(Acetylation)
2 g of liquid phenol resin was weighed in a 200 ml triangular flask, 10 mL of pyridine was added to dissolve the resin, and then 10 mL of acetic anhydride was added. Then, the Erlenmeyer flask was left at room temperature for 24 hours so as not to be exposed to light. Then, when 100 ml of pure water was added to the Erlenmeyer flask, the acetylated product was precipitated, so that the supernatant water was removed. The precipitate was placed in a vacuum dryer to remove the solvent and water to obtain a resin acetylated product.

^(H 1 -NMR measurement)
The acetylated resin was measured in a deuterated acetone solvent using tetramethylsilane (TMS) as a standard peak at 0 ppm. The device is
Body: "JNM-AL300" manufactured by JEOL Ltd.
It was used.

Methylol group, methyl ether group, a methylene group, methyl ether Karitsu dimethylene ether group, from the integral value of each peak in H ¹ -NMR measurement, was calculated. The calculation method is as follows.
A: Peak integral value of benzene ring around 6.7 to 7.5 ppm B: Peak integral value of methylol group around 5 ppm C: Peak integral value of ether group around 4.5 ppm D: Methylene group peak around 4 ppm Integral value E: Peak integral value of methyl group near 3.3 ppm From the above integral value, molar index of phenol: α = (A + B / 2 + C / 2 + E) / 5
Number of moles of methylol group with respect to phenol: β = B / 2α
Number of moles of methylene group with respect to phenol: γ = D / 2α
Number of moles of methyl ether group with respect to phenol: δ = (D / 3) / 2α
Number of moles of dimethylene ether group with respect to phenol: ε = (C-2 (D / 3)) / 4α
Number of moles of fully bound phenol (formaldehyde / phenol reaction molar ratio): ζ = α + β + γ + δ + ε
Was calculated, and the ratio of each binding group was calculated according to the following formula.
Ratio of methylol groups (mol%): a = β / ζ
Percentage of methylene groups (mol%): b = γ / ζ
Percentage of methyl ether groups (mol%): c = δ / ζ
Percentage of dimethylene ether (mol%): d = ε / ζ.

(Preparation of resin composition)
The resin compositions of Examples 1 and 2 and the resin compositions of Comparative Examples 1 to 4 were obtained with the compounding components and amounts shown in Table 2.
(Example 1)
Practical use of 28 parts of the methyl etherified resol resin A (converted to resin solid content) obtained above, 650 parts of magnesia clinker coarse particles (1 to 3 mm), 200 parts of magnesia clinker fine powder (0.3 mm or less), and 150 parts of scaly graphite. It was charged in a universal test device. The mixture was kneaded at 40 ° C. for 30 minutes to obtain a resin composition for refractories.

(Example 2)
The refractory resin composition is the same as in Example 1 except that 28 g of the methyl etherified resol resin A (converted to the resin solid content) is changed to 28 g of the methyl etherified resol resin B (converted to the solid content) obtained above. Got

(Comparative Example 1)
A refractory resin composition was obtained in the same manner as in Example 1 except that 28 g of the methyl etherified resole resin A (converted to the resin solid content) was changed to 28 g of the resole resin E (converted to the solid content) obtained above. rice field.

(Comparative Example 2)
Refractory in the same manner as in Example 1 except that 28 g of methyl etherified resol resin A (converted to resin solid content) was changed to 11 g of the methyl etherified resol resin A (converted to solid content) obtained above and methanol. A resin composition for use was obtained.

(Comparative Example 3)
The refractory resin composition is the same as in Example 1 except that 28 g of the methyl etherified resol resin A (converted to the resin solid content) is changed to 28 g of the methyl etherified resol resin C (converted to the solid content) obtained above. Got

(Comparative Example 4)
The refractory resin composition is the same as in Example 1 except that 28 g of the methyl etherified resol resin A (converted to the resin solid content) is changed to 28 g of the methyl etherified resol resin D (converted to the solid content) obtained above. Got

The resin compositions obtained in Examples 1 and 2 and Comparative Examples 1 and 4 were measured for the following physical properties. The results are shown in Table 2.

(Viscosity measurement)
The viscosity (mPa · s) of each of the obtained resin compositions was measured at 25 ° C. using a synchronous electric rotary viscometer.

(Content of unreacted phenol)
According to JIS K 6910, the measurement was performed by the internal standard method using a gas chromatography method and 2.5-xylenol as an internal standard substance.

(Content of unreacted formaldehyde)
It was measured by the hydroxylammonium hydrochloride method according to JIS K 6910.

(Gelification time)
For each of the obtained resin compositions, the gelation time was measured under the measurement conditions shown below.
(Measurement condition)
According to JIS K 6910, about 2 ml of liquid phenol resin is placed on a hot plate at 150 ° C., and the time until the resin composition is cured is measured. If it does not cure after 10 minutes, it is considered not to gel.

(amount of water)
It was measured by the Karl Fischer method according to JIS K 0068.

(Resin solid content)
The resin composition was heated at 135 ° C. for 1 hour. The mass before heating and the mass after heating were measured, and the mass reduction rate (mass%) was determined based on the following formula.
Weight reduction rate (mass%) = (mass after heating / mass before heating) x 100

(Residual coal rate)
The resin composition was heated at 135 ° C. for 1 hour, then at 430 ° C. for 30 minutes, and further at 800 ° C. for 30 minutes. The mass before heating and the mass after heating were measured, and the mass reduction rate (mass%) was determined based on the following formula.
Weight reduction rate (mass%) = (mass after heating / mass before heating) x 100
The larger the mass reduction rate, the higher the residual coal rate.

The resin compositions obtained in Examples 1 and 2 and Comparative Examples 1 and 4 were evaluated for the following performance. The evaluation results are shown in Table 2.
(Workability)
The odor of the obtained resin composition was evaluated according to the following evaluation criteria.
When it is judged that the solvent does not volatilize and does not interfere with the work: ○ (No problem with workability)
If it is judged that the work will be hindered due to the volatile solvent: × (There is a problem with workability)

(Kneadability with aggregate)
After kneading, the resin composition and the aggregate are sufficiently familiar with each other as "○" (good kneadability), and the resin composition and the aggregate are partially separated as "x" (poor kneadability). ).

(Storage stability)
After the kneaded product is stored at 25 ° C. for 48 hours, the one in which the hardness of the kneaded product has not changed from that immediately after molding is marked with "○" (good storage stability), and the state in which the kneaded product has hardened is marked with "x"("x"). Storage stability is poor).

As shown in Table 2, in each of the resin compositions of Examples 1 and 2, the mass after heating at 135 ° C. for 1 hour, the heat treatment at 135 ° C. for 1 hour, the heat treatment at 430 ° C. for 30 minutes, and the heat treatment at 800 ° C. It is considered that the mass after the heat treatment for 30 minutes is sequentially carried out is remarkably higher than that of Comparative Example 1, and the residual coal ratio after heating is increased. Further, the resin composition of the example was excellent in workability because the solvent did not volatilize, and was also excellent in kneadability with the aggregate and storage stability.

Claims (4)

Contains an alkyl etherified phenolic resin with an alkyl ether group attached to the phenol ring.
Virtually free of solvents
A resin composition that does not gel as a result of tests under the measurement conditions shown below.
(Measurement condition)
According to JIS K 6910, 2 ml of the resin composition is placed on a hot plate at 150 ° C., and the time until the resin composition is cured is measured. If it does not cure after 10 minutes, it is considered not to gel. The resin composition according to claim 1, wherein the viscosity at 25 ° C. is 500 mPa · s or more and 5000 mPa · s or less. The resin composition according to claim 1 or 2, wherein the mass after heating at 135 ° C. for 1 hour is 80% by mass or more with respect to the mass before heating. Any of claims 1 to 3, wherein the mass after heating at 135 ° C. for 1 hour, then heating at 430 ° C. for 30 minutes, and further heating at 800 ° C. for 30 minutes is 40% by mass or more with respect to the mass before heating. The resin composition according to item 1.