JP4060694B2 - Foamable resol-type phenolic resin composition and phenolic resin foam using the same - Google Patents

Description

【００３７】
【表２】

【００３８】
【表３】

【００３９】
［注］１）レゾール型フェノール樹脂中にビスフェノールＡ型ジグリシジルエーテル及びネオデカン酸グリシジルエステルを配合したが、ビスフェノールＡ型ジグリシジルエーテルの溶解が不十分で、樹脂液の安定性が悪く、発泡評価できなかった。
【００４０】
【表４】

【００４１】
［注］
２）酸性硬化剤中にビスフェノールＡ型ジグリシジルエーテル及びネオデカン酸グリシジルエステルを配合したが、ビスフェノールＡ型ジグリシジルエーテルの溶解が不十分で、硬化剤液の安定性が悪く、発泡評価できなかった。
３）発泡時に破泡現象が生じ、発泡体の外観不良により、測定せず。
【００４２】
【発明の効果】
本発明によれば、経時的に安定した低吸水性及び金属板との良好な接着性などを有するフェノール樹脂発泡体を与え、かつ発泡硬化反応性に優れる発泡性レゾール型フェノール樹脂組成物を提供することができる。
また、前記発泡性レゾール型フェノール樹脂組成物を発泡硬化させることにより、前記の優れた特性を有するフェノール樹脂発泡体を得ることができる。[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to a foamable resol-type phenol resin composition and a phenol resin foam using the same. More specifically, the present invention provides a phenolic resin foam having a low water absorption that is stable over time, good adhesion to a metal plate, and the like, and is excellent in foam curing reactivity, And a phenol resin foam having the above-mentioned excellent properties obtained by foam-curing the composition.
[0002]
[Prior art]
  Phenol resin foam is lightweight and has superior flame resistance, heat resistance, low smoke generation, solvent resistance, mechanical strength, etc., compared to thermoplastic resin foam. Widely used for interior materials such as clean room panels and partition panels as lightweight insulation materials, or for external wall materials such as metal siding and metal panels, ceiling materials, roof base materials, underfloor insulation materials, fire doors, etc. .
This phenol resin foam is generally produced by mixing a resol type phenol resin with a foam stabilizer, a foaming agent, and an acidic curing agent, and foaming and curing at about room temperature to 120 ° C.
  However, since the phenol resin foam uses a strong acid as an acidic curing agent, and remains as a free acid in the phenol resin foam after foaming, the free acid intervenes with water so that an iron plate, an aluminum plate, etc. There was concern about rust prevention by corroding the metal of the metal or causing corrosion of metal fasteners such as nails. In addition, the residual acid has a strong affinity with water, and as a result, the foam water absorption is higher than that of other plastic foams (polystyrene foam, urethane foam, polyethylene foam, etc.), resulting in high mechanical strength. There were drawbacks such as lowering and peeling due to weak interfacial strength between the iron plate and the foam. In addition, there are disadvantages such as contamination (correlated with corrosion) on the metal surface due to the acid flowing out of the foam system.
[0003]
  On the other hand, as a method for producing a phenol resin foam, for example, an aliphatic polyhydric alcohol di- or triglycidyl ether compound (the main chain excluding glycidyl groups and side chains has 6 or less carbon atoms) alone or a mixture of the compounds, There has been disclosed a method using a glycidyl ether compound-blended phenolic resin that is blended with a phenolic resin and subjected to a heat reaction treatment (see, for example, Patent Document 1). In this method, as the glycidyl ether compound, neopentyl glycol, 1,6-hexanediol diglycidyl ether, butyl glycidyl ether, or the like (the number of carbons in the main chain excluding the glycidyl group and side chain is 6 or less) is used. Yes. However, although the glycidyl ether compound is good in terms of compatibility with the phenol resin, most of the glycidyl ether compound is liquid, so that it is easy to separate with time, and unreacted glycidyl ether is eluted from the phenol resin foam. There is a problem that the product quality tends to be unstable and the product is unstable, and that glycidyl ether tends to adversely affect the foam curing reaction.
[0004]
  In addition, an acid catalyst containing resorcinol as a curing accelerator is used as a resole type phenol resin, which is modified with at least one of di- and triglycidyl ether compounds of alkylene glycol or alkylene ether glycol having 2 to 6 carbon atoms. A phenolic resin foam having improved corrosion resistance and moisture absorption resistance has been disclosed (see, for example, Patent Document 2). In this phenol resin foam, as in Patent Document 1, neopentyl glycol, 1,6-hexanediol diglycidyl ether, butyl glycidyl ether, etc. (mainly excluding glycidyl groups and side chains) are used as glycidyl ether compounds. The number of carbon atoms in the chain is 6 or less), but although it is good in terms of compatibility with the phenolic resin, most of them are liquid and have the same problems as described above. Also, when resorcinols are blended in an acidic catalyst, it is difficult to adjust the timing of the foam curing reaction due to heat generated from the high reaction activity of resorcinol, and it is difficult to supply a stable phenol resin foam. It is believed that there is.
  Therefore, it has been required to develop a phenol resin foam that is stable in quality, having low water absorption that is stable over time, good adhesion to a metal plate, good foam curing reactivity, and the like.
[0005]
[Patent Document 1]
JP 59-122522 A
[0006]
[Patent Document 2]
JP 59-124940 A
[0007]
[Problems to be solved by the invention]
Under such circumstances, the present invention provides a foamed resol-type phenol which gives a phenolic resin foam having low water absorption that is stable over time and good adhesion to a metal plate, and is excellent in foam curing reactivity. It aims at providing the resin composition and the phenol resin foam using the same.
[0008]
[Means for Solving the Problems]
  As a result of intensive studies to achieve the above object, the inventors of the present invention include an acid curing agent, a foaming agent, and a foam stabilizer together with a resol type phenol resin, and also has a specific molecular weight as a modifier. It has been found that the object can be achieved by a composition comprising a mono and / or polyglycidyl ether compound having an epoxy equivalent, preferably a glycidyl ether compound having an aromatic ring or a cycloalkane ring in the molecule in a predetermined ratio. The present invention has been completed based on such findings.
[0009]
  That is, the present invention
(1) (A) resol type phenol resin, (B) acidic curing agent, (C) foaming agent, (D) foam stabilizer, (E) modifierAnd (F) liquid stabilizerAnd a mono- and / or polyglycidyl ether compound having a weight average molecular weight of 200 to 3000 and an epoxy equivalent in the range of 150 to 2500 as a modifier of the component (E). It contains in the range of 0.2-20 weight part with respect to 100 weight part,Contains a glycidyl ester compound as a liquid stabilizer for the component (F).A foamable resol-type phenolic resin composition characterized by that.
(2) The glycidyl ether compound of component (E) has 8 or more carbon atoms in the main chain excluding epoxy groups and side chains, and has an aromatic ring and / or a cycloalkane ring in the main chain.(1) aboveFoamable resol-type phenolic resin composition,
(3) The glycidyl ester compound of component (F) is neodecanoic acid glycidyl ester and / or hexahydrophthalic acid glycidyl ester.(1) or (2) aboveFoamable resol-type phenolic resin composition,
(4)The foamable resol-type phenol according to any one of claims 1 to 3, comprising glycidyl ester compound (F) in an amount of 25 to 400 parts by weight with respect to 100 parts by weight of glycidyl ether compound (E). Resin composition.
(5) The foamable resole of (1) to (4), wherein the foaming agent of component (C) is at least one fluorine-containing foaming agent selected from HFC-365mfc, HFC-245fa, and HFE-7100 Type phenolic resin composition,
(6) The foaming of the above (1) to (4), wherein the foaming agent of component (C) is at least one hydrocarbon-based foaming agent selected from n-pentane, isopentane, cyclopentane and 2-methylpentane. Resol type phenolic resin composition, and
(7) A phenol resin foam obtained by foam-curing the foamable resol-type phenol resin composition of (1) to (6) above,
Is to provide.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
  The foamable resol-type phenol resin composition of the present invention (hereinafter sometimes referred to as a foamable composition or simply a composition) includes (A) a resol-type phenol resin, (B) an acidic curing agent, and (C) a foaming agent. , (D) a foam stabilizer, (E) a modifier, and (F) a liquid stabilizer.
  In the composition of the present invention, the resol type phenol resin used as the component (A) is not particularly limited, and known methods conventionally used for the production of resol type phenol resins, such as phenols and aldehydes, It can be produced by reacting in the presence of an alkaline catalyst in an excessive amount and dehydrating and concentrating. Examples of phenols include phenol, various cresols, various xylenols, and among these, phenol and m-cresol are preferable from the viewpoint of reactivity and curability. These phenols may be used alone or in combination, and may be used in combination with o-cresol, p-cresol, bisphenol and the like. As aldehydes, formaldehyde, paraformaldehyde, polyoxymethylene, trioxane and the like can be used. These aldehydes may be used alone or in combination. Examples of the alkaline catalyst include sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, magnesium hydroxide and the like.
[0011]
  In the composition of the present invention, examples of the acidic curing agent used as the component (B) include inorganic acids such as phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, hydrochloric acid and sulfuric acid, Organic acids such as aryl sulfonic acids such as phenol sulfonic acid, toluene sulfonic acid, xylene sulfonic acid and benzene sulfonic acid, and alkyl sulfonic acids such as methane sulfonic acid are used, but not limited thereto. These acidic curing agents can be used alone or in combination of two or more. Although the usage-amount of an acidic hardening | curing agent is not specifically limited, It is 1-50 weight part normally with respect to 100 weight part of resol type phenol resin of the said (A) component, Preferably it is the range of 5-30 weight part. is there.
[0012]
  In the composition of the present invention, as the foaming agent used as the component (C), HFC-365mfc (1,1,1,3,3-pentafluorobutane, manufactured by Solvay Japan), which is a fluorine-containing foaming agent, HFC-245fa (1,1,1,3,3-pentafluoropropane, manufactured by Central Glass Co., Ltd.) and HFE-7100 (nonafluorobutyl methyl ether, manufactured by 3M Co.) are used alone or in combination of two or more. can do. The combination ratio is not particularly limited. Moreover, n-pentane, isopentane, cyclopentane, 2-methylpentane, etc. which are hydrocarbon-type foaming agents can be used individually or in combination of 2 or more types. The combination ratio is not particularly limited. The amount of these foaming agents used is usually in the range of 1 to 20 parts by weight, preferably 1.5 to 15 parts by weight with respect to 100 parts by weight of the resol type phenolic resin as component (A). When the amount of the foaming agent used is less than 1 part by weight, vaporization is rapid, and the foam curing is not balanced, making it difficult to obtain a uniform cell structure. On the other hand, if it exceeds 20 parts by weight, the foaming pressure in the cell and the foam regulating force cannot be balanced, the cell wall is broken, and it is difficult to obtain a homogeneous cell structure. In addition to these blowing agents, volatile organic liquids of about -20 to 100 ° C., which are known blowing agents, such as fluorinated hydrocarbons, chlorinated hydrocarbons, aliphatic hydrocarbons, or a mixture of two or more of them are used. These are blowing agents that promote the destruction of the global environment, such as trichloromonofluoromethane (F-11), trichlorotrifluoroethane (F-113), dichlorotetrafluoroethane (F-114), and the like. Carbon chloride, trichloroethane and the like are not preferred in practice.
  Further, these blowing agents and carbonates that generate carbon dioxide, nitroso compounds that generate nitrogen gas, azo compounds, hydrazine derivatives, and the like can be used in combination.
[0013]
  Examples of the foam stabilizer used as the component (D) in the composition of the present invention include a surfactant such as a silicone-based ethylene oxide-propylene oxide copolymer, or a polyoxyalkylene adduct such as sorbitan, alkylphenol, castor oil, and the like. Is mentioned. These may be used alone or in combination. The amount used is preferably in the range of usually 0.5 to 10 parts by weight per 100 parts by weight of component (A) resol type phenol resin. If the amount of the foam stabilizer used is less than 0.5 parts by weight, bubbles cannot be stably formed, and a homogeneous cell structure is difficult to obtain (cell size variation and voids are generated). On the other hand, when the amount exceeds 10 parts by weight, the foam regulating force becomes excessive, the bubble wall becomes too thick and becomes stiff and causes cracking.
[0014]
  In the composition of the present invention, a monoglycidyl ether compound or a polyglycidyl ether compound is used as a modifier for the component (E). The polyglycidyl ether compound is not particularly limited as long as it has two or more glycidyl groups in the molecule, and examples thereof include diglycidyl ether, triglycidyl ether, and tetraglycidyl ether. These glycidyl ether compounds may be used singly or in combination of two or more.
  In the present invention, a glycidyl ether compound having a weight average molecular weight of 200 to 3000 and an epoxy equivalent in the range of 150 to 2500 is used.
[0015]
  By using such a glycidyl ether compound, it is possible to prevent elution from the phenol resin foam, and to compound a relatively large amount of the compound, and to exert an adhesive effect with a metal plate, a low water absorption effect of the foam, The foamable composition also exhibits good foam curing reactivity. Furthermore, an increase in the viscosity of the foamable composition can be moderated, and the filling property with a metal panel or the like is improved.
  The addition amount of this glycidyl ether compound is 0.2-20 weight part with respect to 100 weight part of resol type phenol resin of (A) component, Preferably it is the range of 0.5-15 weight part. If the amount of glycidyl ether compound added is less than 0.2 parts by weight based on 100 parts by weight of the resol type phenol resin, reaction heat sufficient to shorten the foam curing time cannot be obtained, or the familiarity and adhesion to the metal plate. Improvement may not be obtained or water absorption may not be reduced. Moreover, when the addition amount of a glycidyl ether compound exceeds 20 weight part, a bubble breaking phenomenon will occur at the time of foaming, and it will cause the appearance defect.
[0016]
  In the present invention, this glycidyl ether compound has an aromatic group and / or a cycloalkane ring in the main chain having 8 or more carbon atoms in the main chain excluding the epoxy group and the side chain, from the viewpoint of performance. preferable. One or more aromatic rings or cycloalkane rings may be introduced into the main chain, or both the aromatic ring and cycloalkane ring may be introduced. Here, examples of the aromatic ring include a benzene ring and a naphthalene ring. Among these, a benzene ring is preferable, and examples of the cycloalkane ring include a cyclopentane ring, a cyclohexane ring, and a cyclooctane ring. Of these, the cyclohexane ring is preferred.
Examples of such glycidyl ether compounds include monoglycidyl ether compounds such as butylphenyl glycidyl ether, phenol ethylene oxide adduct glycidyl ether, phenol propylene oxide adduct glycidyl ether, and phenol ethylene oxide adduct hydrogenated products. Examples include diglycidyl ether, glycidyl ether of hydrogenated product of propylene oxide adduct of phenol, and diglycidyl ether compounds such as bisphenol A type diglycidyl ether, phenylene diglycidyl ether, tolylene glycidyl ether, and cyclohexylene diglycidyl ether. Bis (glycidoxymethyl) cyclohexane, bis (glycidoxymethyl) benzene, etc. Examples of the silyl ether compound include tris (glycidoxy) benzene, tris (glycidoxy) cyclohexane, tris (glycidoxymethyl) benzene, and tris (glycidoxymethyl) cyclohexane. Examples of the tetraglycidyl ether compound include 1, Examples include 2,4,5-tetrakis (glycidoxymethyl) benzene and 1,2,4,5-tetrakis (glycidoxymethyl) cyclohexane. Furthermore, examples of the polyglycidyl ether compound include glycidyl ethers of phenol novolac resins. These glycidyl ether compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
[0017]
  In the composition of the present invention, a glycidyl ester compound is used as a liquid stabilizer for the component (F). This glycidyl ester compound is considered to have a function of assisting compatibility of the glycidyl ether compound with a resol type phenol resin and an acidic curing agent when used in combination with the glycidyl ether compound. A liquid containing a polyglycidyl ether compound such as glycidyl ether, triglycidyl ether, or diglycidyl ether may be accompanied by an increase in viscosity due to polymerization, but the viscosity can be adjusted by using a glycidyl ester compound in combination.
  The glycidyl ester compound is not particularly limited as long as it is a glycidyl ester compound of an organic acid, but neodecanoic acid glycidyl ester and hexahydrophthalic acid glycidyl ester are preferable. This glycidyl ester compound may be used individually by 1 type, and may be used in combination of 2 or more type. The addition amount is not particularly limited, but is usually selected in the range of 25 to 400 parts by weight with respect to 100 parts by weight of the glycidyl ether compound of component (E).
[0018]
  Various additives can be blended in the foamable resol-type phenol resin composition of the present invention within the range where the object of the present invention is not impaired. For example, it is possible to add an inorganic filler as a flame retardant. Specifically, aluminum hydroxide, aluminosilicate fine hollow particles, talc, clay, calcium hydroxide, boric acid and the like can be used. Boric acid and aluminosilicate fine hollow particles may be added to the acidic curing agent. Also, hardening accelerators such as resorcinol and alkylresorcinol, Shirasu balloon, glass balloon, multi-hard aggregate, inorganic and organic fillers such as metal powder and wood powder, fiber reinforcement such as glass fiber, carbon fiber and aramid fiber You may mix | blend materials etc.
[0019]
  In the foamable resol-type phenolic resin composition of the present invention, there is no particular limitation on the blending method of the glycidyl ether compound and the glycidyl ester compound, but when preparing the composition industrially, (1) glycidyl ether compound single solution Alternatively, a glycidyl ester compound is used in combination as a liquid mixture in advance and blended at the production stage of the resol type phenol resin. (2) In front of the foam mixing device, the phenol resin and the glycidyl ether compound alone or the glycidyl ester compound A method of premixing in the same line and leading to a foam mixing device. (3) A glycidyl ether compound alone or a glycidyl ester compound is used in combination with a curing agent during the production of an acidic curing agent to form a curing agent composition. Method, (4) with an acidic curing agent in front of the foam mixing device A method of premixing in the same line by using a lysidyl ether compound alone or in combination with a glycidyl ester compound, and leading to a foam mixing device. And the like, and a method of leading from a separate line to a foam mixing device.
[0020]
  The foamable resol-type resin composition of the present invention is blended with such a blending method, a resole-type phenol resin, a glycidyl ether compound and an optionally used glycidyl ester compound, or an acidic curing agent. It can be prepared by blending various additives used as required.
  The phenolic resin foam of the present invention is obtained by pouring the foamable resol type phenolic resin composition into a frame or a mold and foaming and curing it at a temperature in the range of ordinary temperature to 120 ° C.
  The phenol resin foam thus obtained has good adhesion to a metal plate and exhibits a stable low water absorption over time. The reason for exhibiting good adhesiveness with the metal plate is that the foamable composition has better compatibility with the metal plate, and the effect due to the epoxy resin appears. The reason why the foam has low water absorption is that the acid remaining in the foam is protected by a glycidyl ether compound or a glycidyl ester compound, thereby reducing the affinity with water, and uniform and strong. It is thought to make a closed cell.
[0021]
  Furthermore, when considering productivity, foam curing reaction characteristics are required. However, when the glycidyl ether compound and the glycidyl ester compound used in some cases and the acidic curing agent are in contact with each other, a rapid heat generation due to the reaction occurs. Thus, by increasing the internal heat generation of the foam compounding liquid, it is possible to shorten the foam curing time and improve the productivity.
[0022]
【Example】
  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
[0023]
Example 1
A four-necked flask was charged with 2000 g of phenol, 2930 g of 37% by weight formalin (formaldehyde / phenol molar ratio 1.7) and 60 g of a 20% by weight aqueous sodium hydroxide solution as a catalyst. The aqueous solution was neutralized to pH 7.0 with a% p-toluenesulfonic acid aqueous solution and dehydrated under reduced pressure to make the water content in the resin 10% by weight or less. The obtained resol type phenol resin had a solid content of 80% by weight, a viscosity of 4000 mPa · s (25 ° C.), a specific gravity of 1.250 (25 ° C.), and a weight average molecular weight of 300. For 100 parts by weight of this resol type phenol resin, 3 parts by weight of L-5420 (silicone surfactant manufactured by Nippon Unicar) as a foam stabilizer and bisphenol A type diglycidyl ether having a weight average molecular weight of 350 as a modifier (Japan) Epoxy Co., Epoxy Equivalent 190) 3.5 parts by weight, Neodecanoic acid glycidyl ester 1.5 parts by weight as a liquid stabilizer, HFC-365mfc (manufactured by Nippon Solvay) 6 parts by weight as a foaming agent, and high speed stirring After mixing, the liquid temperature was adjusted to 30 ° C.
[0024]
  Thereafter, 25 parts by weight of 70 wt% p-toluenesulfonic acid as an acidic curing agent was added at 30 ° C., and the mixture was stirred and mixed at high speed for 10 seconds with a homodisper, and then heated to 65 ° C. using the upper and lower surface materials as iron plates. The mixture was immediately poured into a 400 × 400 × 25 mm mold container. The time when the liquid level of the poured liquid starts to rise is cream time (CT), the time when the stick is put inside the foaming liquid and the resistance sharply increases is gel time (GT), and the time when the liquid level finishes rising is the rise time (RT), the foam hardening behavior was confirmed with the tack free time (TFT) as the time when the foam surface layer did not become sticky. After 3 minutes from the start of stirring of the blended stock solution, the foam was taken out, weighed, and the weight of the iron plate was subtracted to obtain the foam density. For the measurement of the adhesive strength between the steel plate and the foam, the test piece was cut out to 50 × 50 × 25 mm, a jig for tensile test was attached to the surface of the iron plate, and the tensile test was performed with a total of 6 at a crosshead speed of 1 mm / min. The adhesive strength was calculated from the average value of the four samples excluding the minimum value. The foam water absorption was measured by cutting a test piece into 100 × 100 × 20 mm (the iron plate portion was cut out) and measuring the water absorption after immersion for 1 month. The above results are shown in Table 1.
[0025]
Example2
  In Example 1, 1.5 parts by weight of neodecanoic acid glycidyl esterInstead toThis was carried out in the same manner as in Example 1 except that 1.5 parts by weight of hexahydrophthalic acid glycidyl ester was added. The results are shown in Table 1.
[0026]
Example3
  In Example 1, 2.5 parts by weight of bisphenol A type diglycidyl ether (manufactured by Japan Epoxy Co., Ltd., epoxy equivalent 1000) having a weight average molecular weight of 1600 as a modifier, and HFC-365mfc (manufactured by Solvay Japan Co., Ltd.) as a foaming agent Example 1 except that a mixture of 4 parts by weight and 0.6 part by weight of HFE-7100 (manufactured by Nippon Solvay) was used and the amount of neodecanoic acid glycidyl ester was changed to 2.5 parts by weight. Carried out. The results are shown in Table 1.
[0027]
Example 4
  3.5 parts by weight of bisphenol A type diglycidyl ether (manufactured by Japan Epoxy Co., Ltd., epoxy equivalent 190) having a weight average molecular weight of 350 as a modifier, 30 parts by weight of 70% by weight p-toluenesulfonic acid as an acid curing agent, and liquid stabilization After mixing 1.5 parts by weight of neodecanoic acid glycidyl ester as an agent to produce 35 parts by weight of an acidic curing agent blend, the temperature was adjusted to 30 ° C..
  On the other hand, with respect to 100 parts by weight of the same resol type phenolic resin as in Example 1, 3 parts by weight of L-5420 (above) and 6 parts by weight of HFC365mfc (above) as a foam stabilizer are added and mixed at high speed. After that, the liquid temperature was adjusted to 30 ° C. Next, this was mixed with 35 parts by weight of the acidic curing agent blend at high speed with a homodisper for 10 seconds, and then the same as in Example 1. The results are shown in Table 1.
[0028]
Example5
  Example4In Example 1, except that the amount of 70% by weight p-toluenesulfonic acid was changed to 25 parts by weight and resole-type phenol resin, diglycidyl ether and 70% by weight p-toluenesulfonic acid were added separately.4It carried out like. The results are shown in Table 1.
[0029]
Example6
  In Example 1, it implemented like Example 1 except having used 6 weight part of n-pentane as a foaming agent. The results are shown in Table 1.
[0030]
Example7
  In Example 1, it carried out like Example 1 except having changed the quantity of bisphenol A type diglycidyl ether into 15 weight part, and changing the quantity of neodecanoic acid glycidyl ester into 7.5 weight part. The results are shown in Table 1.
[0031]
Comparative Example 1
  In Example 1, it implemented like Example 1 except not having added bisphenol A type diglycidyl ether and neodecanoic acid diglycidyl ester. The results are shown in Table 1.
[0032]
Comparative Example 2
  In Example 1, 3.5 parts by weight of bisphenol A type diglycidyl ether having a weight average molecular weight of 3700 (manufactured by Japan Epoxy Co., Ltd., epoxy equivalent 2800) was used as a modifier, and the amount of neodecanoic acid glycidyl ester added was 3.5. It implemented like Example 1 except having changed into the weight part. The results are shown in Table 1.
[0033]
Comparative Example 3
  Example4In this, 3.5 parts by weight of bisphenol A type diglycidyl ether (manufactured by Japan Epoxy Co., Ltd., epoxy equivalent 2800) having a weight average molecular weight of 3700 was used as a modifier, and the amount of neodecanoic acid glycidyl ester was 3.5 parts by weight and 70 parts by weight. The same operation as in Example 6 was carried out except that the amount of weight% p-toluenesulfonic acid was changed to 25 parts by weight. The results are shown in Table 1.
[0034]
Comparative Example 4
  In Example 1, it carried out like Example 1 except having changed the quantity of bisphenol A type diglycidyl ether into 0.1 weight part, and not using neodecanoic acid glycidyl ester. The results are shown in Table 1.
[0035]
Comparative Example 5
  In Example 1, it carried out like Example 1 except having changed the quantity of bisphenol A type diglycidyl ether into 25 weight part, and not using neodecanoic acid glycidyl ester. The results are shown in Table 1.
[0036]
[Table 1]

[0037]
[Table 2]

[0038]
[Table 3]

[0039]
[Notes] 1) Although bisphenol A type diglycidyl ether and neodecanoic acid glycidyl ester were blended in the resol type phenol resin, the bisphenol A type diglycidyl ether was not sufficiently dissolved, the stability of the resin liquid was poor, and foam evaluation could not.
[0040]
[Table 4]

[0041]
[note]
2) Although bisphenol A type diglycidyl ether and neodecanoic acid glycidyl ester were blended in the acidic curing agent, the dissolution of bisphenol A type diglycidyl ether was insufficient, the stability of the curing agent liquid was poor, and foaming evaluation was not possible. .
3) Bubble measurement occurred during foaming and was not measured due to poor appearance of the foam.
[0042]
【The invention's effect】
  According to the present invention, a foamable resol-type phenolic resin composition that gives a phenolic resin foam having low water absorption that is stable over time, good adhesion to a metal plate, and the like, and is excellent in foam curing reactivity is provided. can do.
  Moreover, by foaming and curing the foamable resol-type phenol resin composition, a phenol resin foam having the above-described excellent characteristics can be obtained.

Claims (7)

(A) resol type phenol resin, (B) acidic curing agent, (C) foaming agent, (D) foam stabilizer , (E) modifier and (F) liquid stabilizer , and (E) As a component modifier, a mono and / or polyglycidyl ether compound having a weight average molecular weight of 200 to 3000 and an epoxy equivalent of 150 to 2500 is added to 0.1 parts by weight of 100 parts by weight of the component (A). A foamable resol-type phenol resin composition comprising 2 to 20 parts by weight and containing a glycidyl ester compound as a liquid stabilizer for the component (F) . (E) a glycidyl ether compound of the component is, is the number of carbon atoms in the main chain except the epoxy group and the side chain of 8 or more, and according to claim 1, wherein those having an aromatic ring and / or cycloalkane ring in the main chain Foamable resol type phenolic resin composition. The foamable resol-type phenol resin composition according to claim 1 or 2 , wherein the glycidyl ester compound of component (F) is neodecanoic acid glycidyl ester and / or hexahydrophthalic acid glycidyl ester. The foamable resol-type phenol according to any one of claims 1 to 3, which contains 25 to 400 parts by weight of the glycidyl ester compound of (F) component with respect to 100 parts by weight of glycidyl ether compound of (E) component. Resin composition . The foamable resol type according to any one of claims 1 to 4, wherein the foaming agent of component (C) is at least one fluorine-containing foaming agent selected from HFC-365mfc, HFC-245fa, and HFE-7100. Phenolic resin composition. The foaming agent according to any one of claims 1 to 4, wherein the foaming agent of component (C) is at least one hydrocarbon-based foaming agent selected from n-pentane, isopentane, cyclopentane and 2-methylpentane. Resol type phenolic resin composition. A phenol resin foam obtained by foam-curing the foamable resol-type phenol resin composition according to any one of claims 1 to 6.