JP2007002032A - Modified phenol resin, method for producing the same, and modified phenol resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a phenol resin modified by a compound having an aliphatic double bond, capable of furnishing a composition with high mechanical strength, when mixed into an elastomer, such as a rubber, and an unsaturated polyester, to provide a method for producing the same, and to provide the modified phenol resin composition. <P>SOLUTION: This modified phenol resin comprises the phenol resin modified by the compound having the aliphatic double bond and has the aliphatic double bond in a molecule of the modified phenol resin itself. The method for producing the modified phenol resin comprises together reacting phenols, aldehydes, and the compound having the aliphatic double bond under an acidic condition of a pH 1 to 4 at a temperature of ≤200°C. The modified phenol resin composition contains the modified phenol resin and a curing agent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a modified phenolic resin having an aliphatic double bond in the molecule, a method for producing the same, and a modified phenolic resin composition.

Cashew nut shell-modified phenolic resins and tall oil-modified phenolic resins are used in various applications such as blending into tires for automobiles and aircraft, civil engineering and construction materials, various industrial product materials, general-purpose daily necessities. Among these, rubber materials used for automobile tires, etc. are composite materials made by adding various additives to raw rubber, and required wear resistance, crack resistance, trauma resistance, low heat generation Various characteristics have been improved.
For example, rubber, which is the main raw material of tires, is made of synthetic rubber such as BR (butadiene rubber) and SBR (styrene-butadiene rubber) and natural rubber, and these rubber materials have wear resistance suitable for tire applications. In order to give performance and mechanical strength, a method of blending a high-modulus thermosetting resin such as phenol resin, or blending a large amount of compounding agents such as sulfur, vulcanization accelerator, carbon black, etc. Etc. are being implemented.

  When a phenolic resin is blended with various materials such as rubber materials, a novolac type phenolic resin is usually used together with a hexamethylenetetramine as a curing agent. However, a novolac type phenolic resin is generally poorly compatible with a substance having low polarity. However, it is difficult to improve the desired material properties simply by blending into a so-called sea-island structure. For this reason, as a novolac type phenol resin, an alkylphenol-modified novolac type phenol resin using an alkylphenol typified by octylphenol or nonylphenol is used, and a relatively long chain alkyl group is introduced into the phenol resin skeleton, which is a raw material. Attempts have been made to improve the compatibility with the components (see, for example, Patent Document 1).

  However, among alkylphenols that are raw materials for such modified novolak-type phenolic resins, use of paranonylphenol, paraoctylphenol, and the like is being restricted from the viewpoint of environmental improvement. On the other hand, the improvement in strength by blending hexamethylenetetramine may lead to an increase in viscosity at the time of kneading the blend and a decrease in mechanical strength, and there is a problem that it becomes difficult to satisfy the required characteristics when blended in a large amount. .

  As a method for solving these problems and improving strength, a method of blending a phenol resin modified with various oils and improved in compatibility with rubber or the like has been known for a long time (for example, see Patent Document 2). ). However, although a certain degree of strength improvement can be expected by improving the compatibility, it is necessary to increase the blending ratio of the resin in order to further improve the strength, but in this case, there is a problem that toughness and elongation decrease. .

JP 2003-292784 A JP 2002-105249 A

  The present invention is a phenol resin modified with a compound having an aliphatic double bond capable of imparting high mechanical strength to these blends and molded articles when blended with an elastomer such as rubber or unsaturated polyester, An object of the present invention is to provide a production method and a modified phenolic resin composition.

Such an object is achieved by the following present inventions (1) to (8).
(1) A modified phenol resin, which is a phenol resin modified with a compound having an aliphatic double bond, and has an aliphatic double bond in the molecule of the modified phenol resin.
(2) The modified phenolic resin according to (1), wherein the integral ratio of the aliphatic double bond proton peak by 1H-NMR analysis is 0.001 or more when that of the aromatic ring is 1. Modified phenolic resin.
(3) The modified phenolic resin according to (1) or (2), wherein the compound having an aliphatic double bond is one or more unsaturated oils selected from cashew nut shell oil, tall oil, and linseed oil. .
(4) The modified phenolic resin according to any one of (1) to (3), wherein the number average molecular weight is 400 to 1100.
(5) The modified phenol resin according to any one of (1) to (4), wherein the compound having an aliphatic double bond is cashew nut shell oil.
(6) The content of the compound having an aliphatic double bond in the modified phenol resin is 20 to 50% by weight based on the whole modified phenol resin. The modified phenolic resin as described.
(7) A method for producing the modified phenolic resin according to any one of (1) to (6) above, wherein a phenol, an aldehyde, and the compound having an aliphatic double bond are pH 1-4. A process for producing a modified phenolic resin, characterized by reacting at 200 ° C. or lower under acidic conditions.
(8) A modified phenolic resin composition comprising the modified phenolic resin according to any one of (1) to (6) and a curing agent.

  The present invention relates to a phenol resin modified with a compound having an aliphatic double bond, and a modified phenol resin containing an aliphatic double bond in the molecule. By using this modified phenol resin, mechanical strength is improved. A high molding can be obtained. The present invention is also a method for producing such a modified phenolic resin, which comprises reacting phenols, aldehydes, and a compound having an aliphatic double bond at 200 ° C. or lower under acidic conditions of pH 1-4. The modified phenolic resin can be effectively obtained. Furthermore, this invention is the modified phenol resin composition containing the said modified phenol resin and a hardening | curing agent, and can obtain hardened | cured material with a high crosslinking density.

The present invention is a phenolic resin modified with a compound having an aliphatic double bond, wherein the modified phenolic resin contains an aliphatic double bond in the molecule of the modified phenolic resin.
Moreover, this invention is a manufacturing method of the modified phenol resin characterized by reacting phenols, an aldehyde, and the compound which has an aliphatic double bond under the acidic of pH 1-4 at 200 degrees C or less.
Furthermore, the present invention is a modified phenolic resin composition containing the modified phenolic resin and a curing agent.

First, a phenol resin modified with a compound having an aliphatic double bond of the present invention (hereinafter sometimes simply referred to as “modified phenol resin”) will be described. The modified phenolic resin of the present invention is characterized by containing an aliphatic double bond in the molecule.
When the modified phenolic resin of the present invention contains an aliphatic double bond in its molecule, it is blended into a resin or elastomer containing an aliphatic double bond such as polybutadiene or unsaturated polyester and cured, The aliphatic double bond portion of the modified phenolic resin reacts with the double bond portion such as polybutadiene or unsaturated polyester to be strongly bonded. Thereby, a cured product (molded product) having high mechanical strength can be obtained.

In the modified phenolic resin of the present invention, the amount (ratio) of the aliphatic double bond is 0.001 or more when the integral ratio of the aliphatic double bond proton peak by 1H-NMR analysis is 1 in the aromatic ring. Preferably there is. Thereby, at the time of curing, a strong cross-linked structure can be formed by reacting with an aliphatic double bond such as polybutadiene or unsaturated polyester, and strength, elastic modulus, hardness and the like can be improved. When the ratio of the aliphatic double bond proton peak is less than 0.001, formation of a crosslinked structure is rare, and effects such as strength improvement may be reduced.
When such a modified phenolic resin does not substantially contain an aliphatic double bond, it does not bind to polybutadiene or unsaturated polyester, but only disperses, resulting in a great difference in the effect of improving strength and elastic modulus. This difference is obvious. For example, even if only one aliphatic double bond is included in a phenol resin molecule having a molecular weight of several thousand, it becomes a large molecule when the blended composition is cured, and the strength and elastic modulus are improved. It becomes possible.

  The phenols used for obtaining the modified phenolic resin of the present invention are not particularly limited, but phenol and various phenols other than phenol, for example, cresol, xylenol, other alkylphenols, resorcinol, etc., alone or in combination of two or more thereof Can be used.

  Aldehydes used in the modified phenolic resin of the present invention are not particularly limited. For example, formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butyl. Examples include aldehyde, caproaldehyde, allyl aldehyde, benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-toluylaldehyde, salicylaldehyde and the like. Among these, it is preferable to use one or more aldehydes selected from formaldehyde and paraformaldehyde. Thereby, a modified phenol resin can be obtained with a good yield.

  In order to obtain the modified phenolic resin of the present invention, the molar ratio (F / P) of phenols (P) and aldehydes (F) is not particularly limited, but is preferably 0.5 to 1.0, particularly 0. .6 to 0.9 is preferable. If the molar ratio is less than the lower limit, a solid modified phenolic resin may not be obtained, and if it exceeds the upper limit, a gelled product may be generated due to an abnormal reaction.

  The modifier used for obtaining the modified phenolic resin of the present invention is a compound having an aliphatic double bond. The compound having an aliphatic double bond is not particularly limited, and examples thereof include unsaturated oils such as cashew nut shell oil (hereinafter referred to as cashew oil), tall oil, and linseed oil. The above can be used. Among these, cashew oil is preferable because it has many aliphatic double bonds. Therefore, when cashew oil is used as a phenol resin modifier, a modified phenol resin substantially having an aliphatic double bond can be effectively obtained by selecting reaction conditions. Also, the price is relatively inexpensive and easy to obtain.

Cashew oil contains cardanol as a main component. Therefore, cardanol obtained by distilling cashew oil can also be used.
The amount of modification of the compound having an aliphatic double bond is not particularly limited, but is preferably in the range of 20 to 50 parts by weight, particularly preferably 30 to 45 parts by weight, with respect to 100 parts by weight of the obtained modified phenolic resin. . If the amount added is less than the lower limit, a sufficient effect may not be obtained.If the amount exceeds the upper limit, the product may not be solidified and difficult to handle, or the gelled product may be caused by an abnormal reaction. May generate.

In order to obtain the modified phenolic resin of the present invention, an acidic catalyst is used. Such acidic catalyst is not particularly limited, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and phosphorous acid, organic acids such as oxalic acid, diethyl sulfuric acid, paratoluenesulfonic acid, and organic phosphonic acid, and zinc acetate. Metal salts etc. are mentioned. These can be used alone or in combination of two or more.
The addition amount of the acidic catalyst is not particularly limited, but is preferably in the range of 0.05 to 5 parts by weight, particularly preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of phenols. If the amount added is less than the lower limit, the reaction may not proceed sufficiently. If the amount exceeds the upper limit, a gelled product may be generated due to an abnormal reaction as in the case where the molar ratio is high.

  In order to obtain the modified phenolic resin of the present invention, a reaction solvent is usually used. Although it does not specifically limit as this reaction solvent, For example, although water and an organic solvent can be used, water is used normally. Moreover, you may carry out without using a reaction solvent, using paraformaldehyde as aldehydes. Examples of the organic solvent include, but are not limited to, alcohols such as methanol, ethanol, propanol, butanol, and amyl alcohol; ketones such as acetone and methyl ethyl ketone; glycols such as ethylene glycol, diethylene glycol, triethylene glycol, and glycerin; Examples include glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and triethylene glycol monomethyl ether, ethers such as 1,4-dioxane, and aromatics such as toluene and xylene. These can be used alone or in combination of two or more. Among these, in order to obtain a solvent-soluble type product, it is preferable to use a polar solvent such as acetone or DMF.

400-1100 are preferable and, as for the number average molecular weight of the modified phenol resin of this invention, 500-1000 are more preferable. Thereby, resin with good handleability is obtained. When the number average molecular weight is lower than the lower limit, it may become a highly viscous material, or even solidify, it may become a material that solidifies during summer storage, which may make handling difficult. Moreover, when it exceeds the said upper limit, it may become difficult to melt | dissolve in solvents, and compatibility with a formulation may fall.
The liquid chromatography method, which is a method for measuring the number average molecular weight, uses GPC (gel permeation chromatography), uses tetrahydrofuran as an elution solvent, has a flow rate of 1.0 ml / min, and a column temperature of 40 ° C. Under the conditions, a differential refractometer was measured as a detector, and the molecular weight was converted with standard polystyrene. The equipment used is as follows.
-Body: manufactured by TOSOH-"HLC-8120"
・ Analytical column: manufactured by TOSOH ・ One "G1000HXL", two "G2000HXL", one "G3000HXL"

Next, a method for producing a phenol resin modified with a compound having an aliphatic double bond of the present invention will be described.
The method for producing a modified phenolic resin of the present invention is characterized in that a phenol, an aldehyde, and a compound having an aliphatic double bond are reacted at 200 ° C. or lower under an acidic pH of 1 to 4. Such a method can effectively produce a modified phenolic resin containing an aliphatic double bond.

Like the reaction for producing a conventional modified phenolic resin, under an acidic pH of 1-4,
When the reaction temperature is higher than 200 ° C., the disappearance of the aliphatic double bond is promoted, and the aliphatic double bond is substantially lost in the obtained resin. When the reaction temperature is increased from 200 ° C. for the purpose of reducing the viscosity during the reaction, the disappearance of the aliphatic double bond can be prevented by adjusting the pH to be higher than 4 and not higher than 7. A modified phenolic resin containing bonds can be obtained, but is not efficient and tends to have a too high molecular weight. On the other hand, when the reaction temperature is 200 ° C. or lower and the pH is higher than 4, since the polymerization reaction of the phenol resin is suppressed, a sufficient increase in molecular weight cannot be expected, and a softening point of 70 ° C. or higher is difficult to consolidate during storage. Resins may not be obtained. Moreover, when pH is lower than 1, the disappearance of the aliphatic double bond is promoted, and the resin may be gelled.
In addition, when the maximum reaction temperature is lower than 100 ° C., even if the pH is 1 to 4, the reaction between the phenol and the compound having an aliphatic double bond is slow and not efficient, so the maximum reaction temperature is 100 degreeC or more is preferable.

  The above-described modified phenolic resin of the present invention or the modified phenolic resin obtained by the production method of the present invention can be blended with elastomer such as rubber or unsaturated polyester to obtain a resin composition with high mechanical strength. it can. The resin composition can be obtained by, for example, preliminarily mixing the modified phenolic resin with a kneading machine or roll, a melt mixing method, a dry mixing method such as pulverization mixing, or a preliminary mixing, without mixing both during the kneading. There are methods such as blending and kneading, but there is no particular limitation.

  As an example, a method for obtaining a rubber composition by blending a modified phenolic resin according to the present invention with rubber will be described. For example, a modified phenolic resin and its curing agent, various rubbers, carbon black and other resins are kneaded in advance at around 150 ° C. with a Banbury mixer etc., and subsequently sulfur and a curing accelerator are added at around 100 ° C. There is a method of kneading, or a method of kneading the above-mentioned compound at around 100 ° C. with a roll or the like, and it is not particularly limited.

  As another example, the method of obtaining the unsaturated polyester composition by blending the modified phenolic resin according to the present invention with the unsaturated polyester includes pulverizing and blending the modified phenolic resin, unsaturated polyester, polymerization initiator, filler and the like. For example, there is a method in which the mixture is preliminarily mixed and then pressed and molded at around 150 ° C., or the above compound is once dissolved in a solvent and dried and then cured, but it is not particularly limited.

  The present invention is a modified phenol composition containing the modified phenolic resin and a curing agent such as hexamethylenetetramine. By containing a curing agent, when cured, a crosslink density is increased, and a resin composition with improved mechanical strength and elastic modulus can be obtained.

  Examples of the curing agent include hexamethylenetetramine and hexamethylolmelamine. The amount of the curing agent is preferably 1 to 30% by weight with respect to the modified phenolic resin. If it is less than 1% by weight, the effect of improving the mechanical strength and elastic modulus may be insufficient, and if it exceeds 30% by weight, the crosslinking density tends to be too high and become brittle.

  Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited to the examples. Further, “parts” and “%” described in the text all indicate “parts by weight” and “% by weight”.

First, an example in which cashew oil is used as a compound having an aliphatic double bond is shown.
<Example 1>
A 3 L three-necked flask was charged with 1000 parts of phenol, 690 parts of 37% formalin (reaction molar ratio 0.8), 400 parts of cashew oil and 10 parts of sulfuric acid, and reacted at 100 ° C. for 1 hour under reflux. The pH during this reaction was about 1.6. Subsequently, while distillation under reduced pressure at 5000 Pa, the temperature was raised to 190 ° C. to obtain 1110 parts of cashew oil-modified phenol resin A. The number average molecular weight of this resin was 920, and the softening point was 88 ° C. In NMR measurement, the integral ratio of the aliphatic double bond proton peak was 0.004 when the aromatic ring double bond proton peak was 1.

<Example 2>
A 3 L three-necked flask was charged with 1000 parts of phenol, 690 parts of 37% formalin (reaction molar ratio 0.8), 500 parts of cashew oil, and 10 parts of sulfuric acid, and reacted at 100 ° C. under reflux for 1 hour. The pH during this reaction was about 1.6. Then, it heated up at 190 degreeC, distilling under reduced pressure at 5000 Pa, and obtained cashew oil modification phenol resin B1210 part. The number average molecular weight of this resin was 820, and the softening point was 85 ° C. In the NMR measurement, the integral ratio of the aliphatic double bond proton peak was 0.003 when the aromatic ring double bond proton peak was 1.

<Example 3>
A 3 L three-necked flask was charged with 1000 parts of phenol, 690 parts of 37% formalin (reaction molar ratio 0.8), 600 parts of cashew oil, and 10 parts of sulfuric acid, and reacted at 100 ° C. for 1 hour under reflux. The pH during this reaction was about 1.6. Subsequently, while distillation under reduced pressure at 5000 Pa, the temperature was raised to 190 ° C. to obtain C1280 parts of cashew oil-modified phenol resin. The number average molecular weight of this resin was 760, and the softening point was 81 ° C. In NMR measurement, the integral ratio of the aliphatic double bond proton peak was 0.012 when the aromatic ring double bond proton peak was 1.

<Example 4>
A 3 L three-necked flask was charged with 1000 parts of phenol, 776 parts of 37% formalin (reaction molar ratio 0.9), 500 parts of cashew oil, and 10 parts of sulfuric acid, and reacted at 100 ° C. under reflux for 1 hour. The pH during this reaction was about 1.6. Subsequently, the temperature was raised to 190 ° C. while distillation under reduced pressure at 5000 Pa to obtain 1180 parts of cashew oil-modified phenol resin D1180. The number average molecular weight of this resin was 880, and the softening point was 89 ° C. In NMR measurement, the integral ratio of the aliphatic double bond proton peak was 0.003 when the aromatic double bond proton peak was 1.

<Example 5>
A 3 L three-necked flask was charged with 1000 parts of phenol, 690 parts of 37% formalin (reaction molar ratio 0.8), 500 parts of cardanol and 10 parts of sulfuric acid, and reacted at 100 ° C. under reflux for 1 hour. The pH during this reaction was about 1.6. Then, it heated up at 190 degreeC, distilling under reduced pressure at 5000 Pa, and obtained 1180 parts of cashew oil modified phenolic resins. The number average molecular weight of this resin was 870, and the softening point was 91 ° C. In NMR measurement, the integral ratio of the aliphatic double bond proton peak was 0.028 when the aromatic ring double bond proton peak was 1.

<Example 6>
A 3 L three-necked flask was charged with 1000 parts of phenol, 690 parts of 37% formalin (reaction molar ratio 0.8), 500 parts of cashew oil, and 20 parts of oxalic acid, and reacted at 100 ° C. under reflux for 1 hour. The pH during this reaction was about 1.7. Then, it heated up at 190 degreeC, distilling under reduced pressure at 5000 Pa, and obtained cashew oil modified phenol resin F1220 part. The number average molecular weight of this resin was 850, and the softening point was 87 ° C. In NMR measurement, the integral ratio of the aliphatic double bond proton peak was 0.003 when the aromatic double bond proton peak was 1.

<Comparative Example 1>
A 3 L three-necked flask was charged with 1000 parts of phenol, 500 parts of cashew oil, 690 parts of 37% formalin (reaction molar ratio 0.8) and 10 parts of sulfuric acid, and reacted at 100 ° C. under reflux for 1 hour. The pH during this reaction was about 1.6. Subsequently, the temperature was raised to 230 ° C. while distillation under reduced pressure at 5000 Pa to obtain 1140 parts of cashew oil-modified phenol resin G1140. The number average molecular weight of this resin was 1040, and the softening point was 98 ° C. Further, in the NMR measurement, an aliphatic double bond proton peak was not observed.

<Comparative example 2>
A 3 L three-necked flask was charged with 1000 parts of phenol, 500 parts of cardanol, 690 parts of 37% formalin (reaction molar ratio 0.8) and 10 parts of sulfuric acid, and reacted at 100 ° C. under reflux for 1 hour. The pH during this reaction was about 1.6. Subsequently, while distillation under reduced pressure at 5000 Pa, the temperature was raised to 230 ° C. to obtain 1140 parts of cashew oil-modified phenol resin H1140. The number average molecular weight of this resin was 950, and the softening point was 95 ° C. Further, in the NMR measurement, an aliphatic double bond proton peak was not observed.

Next, an example in which tall oil is used as a compound having an aliphatic double bond is shown.
<Example 7>
A 3 L three-necked flask was charged with 1000 parts of phenol, 690 parts of 37% formalin (reaction molar ratio 0.8), 400 parts of tall oil, and 10 parts of sulfuric acid, and reacted at reflux at 100 ° C. for 3 hours. The pH during this reaction was 1.6. Subsequently, while distillation under reduced pressure at 5000 Pa, the temperature was raised to 190 ° C. to obtain 1110 parts of tall oil-modified phenol resin A. The number average molecular weight of this resin was 900, and the softening point was 88 ° C. In NMR measurement, the integral ratio of the aliphatic double bond proton peak was 0.003 when the aromatic double bond proton peak was 1.

<Example 8>
A 3 L three-necked flask was charged with 1000 parts of phenol, 690 parts of 37% formalin (reaction molar ratio 0.8), 500 parts of tall oil, and 10 parts of sulfuric acid, and reacted at reflux at 100 ° C. for 3 hours. The pH during this reaction was 1.6. Subsequently, the temperature was raised to 190 ° C. while distillation under reduced pressure at 5000 Pa to obtain 1210 parts of tall oil-modified phenol resin B. The number average molecular weight of this resin was 850, and the softening point was 85 ° C. In NMR measurement, the integral ratio of the aliphatic double bond proton peak was 0.004 when the aromatic double bond proton peak was 1.

<Example 9>
A 3 L three-necked flask was charged with 1000 parts of phenol, 690 parts of 37% formalin (reaction molar ratio 0.8), 600 parts of tall oil and 10 parts of sulfuric acid, and reacted at reflux at 100 ° C. for 3 hours. The pH during this reaction was 1.6. Subsequently, while distillation under reduced pressure at 5000 Pa, the temperature was raised to 190 ° C. to obtain 1280 parts of tall oil-modified phenol resin C. The number average molecular weight of this resin was 800, and the softening point was 81 ° C. In NMR measurement, the integral ratio of the aliphatic double bond proton peak was 0.006 when the aromatic ring double bond proton peak was 1.

<Example 10>
A 3 L three-necked flask was charged with 1000 parts of phenol, 776 parts of 37% formalin (reaction molar ratio 0.9), 500 parts of tall oil, and 10 parts of sulfuric acid, and reacted at reflux at 100 ° C. for 3 hours. The pH during this reaction was 1.6. Subsequently, the temperature was raised to 190 ° C. while distillation under reduced pressure at 5000 Pa to obtain 1180 parts of tall oil-modified phenol resin D1180. The number average molecular weight of this resin was 900, and the softening point was 89 ° C. In NMR measurement, the integral ratio of the aliphatic double bond proton peak was 0.004 when the aromatic ring double bond proton peak was 1.

<Comparative Example 3>
A 3 L three-necked flask was charged with 1000 parts of phenol, 500 parts of tall oil, 690 parts of 37% formalin (reaction molar ratio 0.8), and 10 parts of sulfuric acid, and reacted at 100 ° C. under reflux for 3 hours. The pH during this reaction was 1.6. Subsequently, the temperature was raised to 230 ° C. while distillation under reduced pressure at 5000 Pa to obtain 1140 parts of tall oil-modified phenol resin E1140. The number average molecular weight of this resin was 1050, and the softening point was 98 ° C. Further, in the NMR measurement, an aliphatic double bond proton peak was not observed.

<Confirmation of double bond>
About the modified phenol resin obtained in the said Examples 1-10 and Comparative Examples 1-3, the aliphatic double bond was confirmed by the peak which appears in about 5 ppm by 1H-NMR. NMR measurement was performed using JNM-ECX manufactured by JEOL Ltd. with a total number of 64 times. The measured values are as described above. The NMR chart of the modified phenolic resin obtained in Example 2 and Comparative Example 1 is shown in FIG.

<Characteristics of modified phenolic resin-containing composition>
In order to observe the characteristics of the composition containing the modified phenolic resin, the rubber and unsaturated polyester were respectively mixed and cured, and the physical properties of the cured product were measured.

1. Rubber compounding test Various rubber compositions obtained by kneading the compounding composition (parts by weight) shown in Table 1 with a heating roll at 100 ° C. were vulcanized at 180 ° C. for 5 minutes with a hydraulic press to obtain a vulcanized rubber sheet having a thickness of 2 mm. Produced. Using this rubber sheet, hardness (Shore A) and 25% tensile modulus were measured according to JIS K 6301, and elastic modulus was measured according to JIS K 6394. The hardness was measured with a durometer manufactured by Toyo Seiki Co., Ltd. The tensile modulus was measured at a pulling speed of 50 mm / min using a Toyo Seiki strograph. In addition, the elastic modulus was measured by using a DMS6100 manufactured by Seiko Instruments Inc. under the tensile conditions of 60 ° C. and 10 Hz.

2. Unsaturated polyester blending test The blending composition (parts by weight) shown in Table 2 was cured at 150 ° C. for 1 hour to produce a sheet having a thickness of 2 mm. Using this sheet, hardness and bending strength were measured. The hardness was measured with a durometer manufactured by Toyo Seiki Co., Ltd. according to JIS K 7060 (Barcol hardness). The bending strength was measured according to JIS K 7060 using a Tensilon UTM-500 manufactured by Orientec Corp. under conditions of a span of 50 mm and a speed of 5 mm / min.

（表の注）
天然ゴム：東知社製
カーボンブラック：三菱化学社製、ＨＡＦ
亜鉛華：堺化学社製、酸化亜鉛
加硫促進剤：Ｎ−オキシジエチレン−２−ベンゾチアゾールスルフェンアミド

(Note to table)
Natural rubber: Carbon black manufactured by Tochisha: HAF manufactured by Mitsubishi Chemical
Zinc flower: manufactured by Sakai Chemical Industry Co., Ltd., zinc oxide vulcanization accelerator: N-oxydiethylene-2-benzothiazole sulfenamide

（表の注）
不飽和ポリエステル：ジャパンコンポジット社製、ポリホープ８２０Ｐ

(Note to table)
Unsaturated polyester: Polyhope 820P, manufactured by Japan Composite

The measurement results are shown in Tables 3 and 4.

  As is clear from Table 3, the modified phenolic resins of the present invention obtained in Examples 1 to 10 have an aliphatic double bond in the molecule, and the composition containing this is Comparative Example 1. The elastic modulus, hardness, modulus, and bending strength were improved as compared with the case where the modified phenol resin substantially free of aliphatic double bond obtained in -3 was blended.

Since the phenol resin modified with the compound having an aliphatic double bond of the present invention contains an aliphatic double bond in the molecule, a resin or elastomer containing an aliphatic double bond such as polybutadiene or unsaturated polyester. Can give high strength to products using these resins and elastomers. Furthermore, since the elastic modulus and hardness are improved, it can be suitably used as a hard rubber compound or a high-strength unsaturated polyester compound. Therefore, it can be widely applied in applications such as tires and FRP. Moreover, the modified phenol resin composition of this invention can obtain the hardened | cured material (molded object) from which the crosslinking density became high and the mechanical strength and elastic modulus improved more by containing a hardening | curing agent.
Furthermore, the method for producing a modified phenolic resin of the present invention can effectively obtain the modified phenolic resin containing an aliphatic double bond in the molecule.

3 is an NMR chart of cashew oil-modified phenol resins obtained in Example 2 and Comparative Example 1. In the cashew oil-modified phenol resin obtained in Example 2, an aliphatic double bond peak was observed at about 5 ppm.

Explanation of symbols

A Peak due to aliphatic double bond proton B Peak due to aromatic double bond proton

Claims (8)

A modified phenolic resin, which is a phenolic resin modified with a compound having an aliphatic double bond, and has an aliphatic double bond in the molecule of the modified phenolic resin. The modified phenolic resin according to claim 1, wherein the modified phenolic resin has an aliphatic double bond proton peak integral ratio of 0.001 or more when the aromatic ring is 1 as determined by 1H-NMR analysis. The modified phenolic resin according to claim 1 or 2, wherein the compound having an aliphatic double bond is one or more unsaturated oils selected from cashew nut shell oil, tall oil, and linseed oil. The modified phenolic resin according to any one of claims 1 to 3, having a number average molecular weight of 400 to 1100. The modified phenolic resin according to any one of claims 1 to 4, wherein the compound having an aliphatic double bond is cashew nut shell oil. The modified phenolic resin according to any one of claims 1 to 5, wherein a content of the compound having an aliphatic double bond in the modified phenolic resin is 20 to 50 wt% with respect to the entire modified phenolic resin. A method for producing the modified phenolic resin according to any one of claims 1 to 6, wherein a phenol, an aldehyde, and the compound having an aliphatic double bond are heated at 200 ° C under an acidic condition of pH 1-4. The manufacturing method of the modified phenol resin characterized by reacting below. A modified phenolic resin composition comprising the modified phenolic resin according to any one of claims 1 to 6 and a curing agent.

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