JPH0760928A - Phenol frp molded article and production thereof - Google Patents

Abstract

PURPOSE:To obtain a fire-retardant molded article generating no gas at the time of the trial combustion of a car material and passing fire retardancy standards by constituting the liquid phenol resin of a phenol FRP molded article of a resorcinol component and a phenol/resol component both of which respectively have specific compsns. CONSTITUTION:A phenol FRP molded article is produced by impregnating a fiber base material with a phenol resin soln. containing a liquid phenol resin, a filler and other additives and curing the impregnated base material. In this case, the liquid phenol resin is constituted of a component (a) being resolcinol or a resolcinol component containing a resorcinol novolac resin being a reaction product of resorcinol and aldehyide in the presence of an acid catalyst and a phenol resol resin component being a reaction product of formaldehyde and/or paraformaldehyde and at least one phenol compd. selected from a group consisting of compds. represented by chemical formulae.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly flame-retarded phenol FRP molded article and a method for producing the same. The phenol FRP molded product according to the present invention is mainly used for vehicle parts,
It has excellent flame retardancy as aircraft parts, ducts, ceiling materials, wall materials, ship parts, tanks, pipes, silos, etc. and is applied to various industrial uses.

[0002]

2. Description of the Related Art In recent years, phenol FRP moldings have not been obtained with thermosetting resin FRP moldings such as unsaturated polyester resin and epoxy resin, or thermoplastic resin FRP moldings such as polypropylene resin, polyethylene resin and polystyrene resin. Since it has various excellent properties such as heat resistance, fire resistance, and low smoke generation, its usefulness has attracted great attention. However, conventional phenol resole resin is added with inorganic filler such as calcined gypsum, clay, aluminum hydroxide, antimony trioxide, paraffin chloride, etc., and resin containing decapromodiphenyl is impregnated and laminated on the fiber base material. There is a method of curing to produce a phenol FRP molded product. However, in these methods, gas is generated by the heat from the phenolic resin, which causes blister on the surface, deformation due to cissing, ignition, etc., resulting in "noncombustibility" in the Ministry of Transport's material combustion test for railway vehicles (hereinafter referred to as vehicle material combustion test). It was not possible to obtain a phenol FRP molded product that passed the standard.

Further, on the surface of a gel coat layer in which aluminum hydroxide is mixed with unsaturated polyester resin, vinyl ester resin is mixed with any one of aluminum hydroxide, aluminum powder, aluminum particles, aluminum fibers or aluminum coated glass fibers. There has been developed a method for solving the above problem by providing the above-mentioned primer on the phenol FRP layer (JP-A-1-105735). However, it is economically problematic to use the above-mentioned costly method even for a phenol FRP molded article for which surface makeup is unnecessary.

[0004]

SUMMARY OF THE INVENTION Therefore, the inventors of the present invention have a problem in the prior art, that is, it is difficult to pass the "nonflammability" test for car materials in phenol FRP made of a conventional phenol resol resin. The present invention has been completed for the purpose of improvement. According to the present invention, the application of the phenol FRP molded product having excellent flame retardancy is expanded, and a highly flame retarded phenol FRP molded product is provided.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors impregnated a fiber base material with a compounding component of a specific resorcinol component and a phenol resole resin and molded it. The obtained phenolic FRP molded product is "non-combustible" for car materials depending on the curing conditions and composition.
No gas is generated due to heat in the test, ignition, flame,
We succeeded in obtaining a phenol FRP molded product that does not undergo carbonization deformation and that passes the "non-combustible" standard for vehicle fuel tests. That is,
The present invention includes (1) after impregnating a fibrous base material with a phenolic resin solution containing a liquid phenolic resin, a filler, and other additives to cure it,
In the method for producing the obtained phenol FRP molded article,
The phenol resin is (a) resorcinol and / or
Or a resorcinol component containing a resorcinol novolac resin which is a reaction product of the resorcinol and an aldehyde in the presence of an acid catalyst, and (b) formaldehyde and / or paraformaldehyde and a group represented by the following formula [Chemical formula 3] Phenol resole resin component which is a reaction product with at least one phenol compound

[0006]

[Chemical 3] (Wherein R, R ′, R ″, and R ″ ′ are reaction products with OH or a chain or cyclic hydrocarbon group having a saturated or unsaturated bond having 1 to 6 carbon atoms) (2) A total amount of the resorcinol component of the component (a) and the phenol resole resin component of the component (b) is 100.
(3) Methylene, which is a reaction product obtained by reacting 0.01 to 40 parts by weight of a methylene donor with respect to parts by weight. The donor is furfural, furfuryl alcohol, oxazolidine and / or acrolein, and the phenol FRP molded article according to (2) above, (4) the resorcinol component of (a) above is 30
The phenol FRP molded article according to (1) or (2) above, which is obtained by reacting 5 to 15 parts by weight of formaldehyde with respect to 80 parts by weight of resorcinol, (5) the component (b) above. The phenol resole resin component is obtained by reacting 40 to 75 parts by weight of the above phenol compound with 20 to 55 parts by weight of paraformaldehyde, and the phenol FRP molded article according to (1) or (2) above, That is the manufacturing method. The present invention will be described below. The reaction of the resorcinol component of the component (a) and the phenol resole resin component of the component (b) used in the present invention is desirably carried out in the presence of an alkali catalyst, but the reaction is possible even in the absence thereof. Alkali catalysts can be selected from the group consisting of metal hydroxides, metal oxides and amino compounds containing amino groups as suitable catalysts, sodium hydroxide, ammonium hydroxide, and potassium hydroxide, calcium hydroxide. , Magnesium hydroxide, magnesium oxide, calcium oxide, sodium oxide, potassium oxide, zinc acetate and the like and the alkali catalysts described later are exemplified. Aminosilane-based amino compounds are also suitable. Acid-catalyzed phenol F
Compared with the method for producing an RP molded article, the method for producing an FRP molded article of the present invention is preferably adjusted to pH 6 to 10, and as a result, even when a filler is used in combination, the alkalinity is not strong, so the filler There is a wide range of choices.

In the method for producing a phenol FRP molded article of the present invention, the reaction can be initiated and cured at room temperature within an appropriate range. For example, at a temperature of 15 to 120 ° C, a pH of 6 to 1
It can be cured within a range of 0 to 1 hour to 24 hours. An appropriate mixing ratio is selected so that the above-mentioned pH is adjusted in the range of 6 to 10, and preferably 50 to 150 parts by weight relative to 100 parts by weight of the resorcinol component of the component (a). It is preferable to mix the phenol resole resin component as the component (b).

The resorcinol component (a) is 30 to
For example, it can be obtained by reacting 80 parts by weight of resorcinol with 5 to 15 parts by weight of formaldehyde, at this time, 0.025 to 0.3 parts by weight (preferably 0.0
3 to 0.1 part by weight) of an organic acid solution, for example, a resorcinol novolak resin which can be obtained by reacting in the presence of a catalyst such as p-toluenesulfonic acid or oxalic acid, or the resorcinol alone or a mixture of the above. Can be used as appropriate.

The phenolic resole resin as the component (b) is 20 to 40 parts by weight of the phenolic compound.
It can be obtained by reacting ˜55 parts by weight of paraformaldehyde, and it is not necessary to use it as a powder, and paraformaldehyde can be dissolved and reacted without using a solvent. Therefore, the quality of the product is good in that no solvent is used. It is desirable to carry out in the presence of the same alkali catalyst as above, but the reaction is possible in the absence thereof.

Since the reaction time between the resorcinol component which is the component (a) of the present invention and the phenol resole resin component which is the component (b) is short, the paraformaldehyde used as the component (b) is a phenol compound. Before the reaction, at least a part of the material is dissolved and reacted with the formaldehyde used in the component (a). Such a reaction system of the component (a) and the component (b) can be used even when the curing agent used is liquid, and the amount of mixing may be small. In the present invention,
By adding a methylene donor, it is also possible to reduce the viscosity of the so-called mix, ie the mixture, to improve the reaction process and the wetting with the fibrous base material. Furthermore, cross-lin
k) It has the effect of increasing the density, which results in phenol F
The strength of the RP molded product can be improved. About 0.01 to 40 parts by weight, preferably 10 to 2 parts, based on 100 parts by weight of the total reaction mix of the components (a) and (b).
It is also possible to add 0 parts by weight of aldehyde to the reaction mix. The methylene donor can be preferably selected from the group consisting of furfural, furfuryl alcohol, oxazolidine, acrolein, and combinations thereof, but is not necessarily limited thereto. As the phenol compound used in the phenol resin of the present invention, those represented by the following general formula [Chemical Formula 4] are preferable.

[0011]

[Chemical 4] (Here, R, R ′, R ″, and R ″ ′ are OH or a chain or cyclic hydrocarbon group having a saturated or unsaturated bond having 1 to 6 carbon atoms) Specific examples include phenol, o-
Cresol, m-cresol, p-cresol, thymol, p-ter-butylphenol, ter-butylcatechol, catechol, isoeugenol, o-methoxyphenol, 4,4'-dihydroxyphenyl-2,
2-propane, isoamyl salicylate, benzyl salicylate, methyl salicylate, 2,6-di-t-butyl-p
-Cresol, xylenolic acid, etc. More preferred are phenol, 4,4-dihydroxyphenyl-2,2-propane and 2,6-di-t-butyl-p-cresol, and preferred xylenolic acid is 2,3-xylenol, 2,2. 4-xylenol, 2,6-xylenol, 3,4-xylenol,
Examples include 3,5-xylenol and the like.

Formaldehyde, paraformaldehyde, polyoxymethylene, trioxane and the like can be used as the aldehydes as one raw material. This aldehyde is reacted with resorcinol in the presence of an acidic catalyst to obtain a resorcinol novolak resin. The phenol resol resin as the component (b) is a liquid phenol resin obtained from the phenol compound and the aldehyde compound formaldehyde and / or paraformaldehyde in the presence or absence of the alkali catalyst.
The phenol compound may be phenol and homologues such as cresols and xylenols, or a mixture thereof.

As the aldehydes of the component (a), for example, not only formaldehyde, acetaldehyde, furfural, and other aldehydes and their compounds, but also compounds which produce aldehydes can be used. Formaldehyde, hexamethylenetetramine, methylol, trioxane, tetraoxymethane and other compounds that decompose to generate formaldehyde, and mixtures thereof can also be used.

Examples of the methylene donor used in the present invention include furfural, furfuryl alcohol,
1 or 2 selected from oxazolidine and acrolein
That is all. Various acids can be used as the acid catalyst for obtaining the phenol resole resin component (b). For example, inorganic acids such as phosphoric acid, hydrochloric acid, sulfuric acid, organic sulfonic acids such as phenol sulfonic acid, toluene sulfonic acid, benzene sulfonic acid, and meta sulfonic acid, organic polymer acids obtained by sulfonation of toluene resin, xylene resin, naphthalene resin, etc. Is used. These acids may be used alone or in combination of two or more.
Further, it may be used as an aqueous solution or another solvent. The amount of the acid catalyst added is 1 to 50 parts by weight, preferably 10 to 30 parts by weight, based on 100 parts by weight of the liquid phenol resin. Examples of the fiber base material that can be used in the present invention include inorganic fibers such as glass and carbon, and organic fibers such as Kevlar, nylon and vinylon. Inorganic fibers such as glass and carbon are preferably used.

As the filler used in the present invention, known fillers such as barium sulfate, talc, clay, mica, aluminum hydroxide, calcium carbonate, gypsum, hemihydrate gypsum, glass beads, etc. may be blended as necessary and used. To be In addition, known pigments, flame retardants, release agents, other additives, and the like can be added as necessary. The alkali catalyst used as necessary in the present invention may be, for example, any of the alkali catalysts used in the method for producing a phenol resole resin. Specific examples include NaOH, KOH, MgOH ₂ , Ca (O
H) ₂ , NH ₄ OH, NaO ₂ , K ₂ O, MgO, Ca
Strong alkalis such as O, ZnO and Zn (CH) ₂ or salts of these alkalis such as zinc acetate can also be used. Aminosilane-based amino compounds are also suitable.

As the molding method used in the present invention, a known fiber base material is spread on a mold, and a thermosetting resin containing additives such as a curing catalyst and a filler is applied and impregnated and cured. After that, a hand lay-up molding method, which is a method for molding a fiber-reinforced plastic to be removed from the mold, a spray-up molding method in which the fiber base material and the above-mentioned compounded resin are simultaneously sprayed onto the mold to cure and then demolded, 1 set A resin that spreads the fiber base material inside the mold and mixes the thermosetting resin and the curing agent from the nozzle provided in the mold in advance or injects the mixed resin to cure and then removes the mold. A known molding method for a reinforced fiber plastic such as an injection molding method is used. In the present invention, among the above-mentioned raw materials, the raw materials excluding the fiber base material are uniformly mixed and impregnated into the fiber base material by any of the above-mentioned molding methods,
After curing, the molded product is removed from the mold to obtain a phenol FRP molded product. The curing process can be performed in a heating atmosphere even at room temperature. When mixing the raw materials excluding these fiber base materials, a stirrer such as a disperser is used when batch mixing, and a known other component mixer is used when continuously mixing.

[0017]

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples. Synthesis Example (a) (Synthesis of Resorcinol Component) 445 parts by weight of resorcinol, 162 parts by weight of 37%
A formalin aqueous solution and 3 parts by weight of a 20% p-toluenesulfonic acid aqueous solution were reacted in a flask at 100 ° C. for 2 hours, and 295 parts by weight of resorcinol was added to the reaction product and mixed, and a 50% sodium hydroxide aqueous solution was added. It was neutralized and diluted with acetone and methanol to obtain about 1000 parts by weight of a resorcinol component as the component (a).

Synthesis Example (b-1) (Phenol Resol Component-1) 630 parts by weight of 90% phenol solution, 400 parts by weight of 91% paraformaldehyde and 5 parts by weight of zinc acetate hydrate were mixed in a flask. The reaction product was dehydrated under reduced pressure, and 275 parts by weight of furfural was added and mixed to obtain about 1000 parts by weight of (b-
1) A phenol resole resin as a component was obtained.

Synthesis Example (b-2) (Phenol Resol Component-2) 600 parts by weight of m-cresylic acid, 360 parts by weight of 91
% Paraformaldehyde and 5 parts by weight of zinc acetate hydrate were mixed in a flask and reacted at 90 ° C. for 1 hour, the reaction product was dehydrated under reduced pressure, and 250 parts by weight of furfural was added and mixed to obtain about 1000 parts. Phenol resole resin as the component (b-2) was obtained.

Synthesis Example (b-3) (Phenol Resol Component-3) 590 parts by weight of xylenolic acid, 360% by weight of 91%
Paraformaldehyde and 5 parts by weight of zinc acetate hydrate were mixed in a flask and reacted at 70 ° C. for 1 hour, the reaction product was dehydrated under reduced pressure, and further 230 parts by weight of furfural was added and mixed to obtain about 1000 parts by weight. To obtain a phenol resole resin as a part (b-3) component.

Examples 1 to 7 The resorcinol component according to the above-mentioned synthesis example (a) and the phenol resole component according to the synthesis examples (b-1), (b-2) and (b-3) were mixed in the amounts shown in Table 1. A chopped strand glass mat was impregnated with a filler and an alkali catalyst and cured at room temperature for 24 hours to obtain a phenol FRP plate of A4 size. This phenol FRP plate was after-cured under the after-cure (post-cure) conditions shown in Table 1, and then cut into a B5 plate to carry out a combustion test of a car material fuel test. The test results are summarized in Table 1.

Comparative Examples 1 to 3 Chopped strand glass mats with the blending amounts shown in Table 1 were used in the same manner as in Example 1 except that the conventional resole resin was trade name XPL-4852B manufactured by Gunei Chemical Co., Ltd. Phenol FRP
I got a plate. This phenol FRP plate was subjected to a combustion test of a vehicle material combustion test in the same manner as in Example 1. The test results are shown in Table 1.

As a result of this test, Examples 1 to 5 did not generate gas during the combustion test and passed the regulations of "nonflammability", but Comparative Examples 1 to 3 generated gas, and Comparative Example 3 was the standard. Although it passes the above test, in the test of a public institution, the generation of gas changes the direction of the alcohol flame during the combustion test, so it may be judged as ignition, and in many cases it does not pass the "nonflammability" standard.

[0024]

[Table 1] However, the following materials were used as the filler and the alkali catalyst. Filler: Barium Sulfate (Sakai Chemical Industry Co., Ltd., Barium Sulfate BA): Magnesium hydroxide (Showa Denko KK, Hydilite-32) Catalyst: Magnesium oxide (Kyowa Chemical Co., Ltd., Kyowamag 20) Caseras Mat: Chopped Strand glass mat (Central Glass Co., Ltd. ECM-501P-450)

[0025]

EFFECTS OF THE INVENTION The phenol FRP molded product according to the present invention can be cured at room temperature and after curing at room temperature or under heating, no gas is generated during a combustion test of a vehicle material combustion test, and the product is in the "nonflammable" standard. It is possible to provide a highly flame-retardant phenol FRP molded product that passes, and it has excellent flame retardancy as a vehicle part, an aircraft part, an automobile part, a building material, etc., and is an industrially useful invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroshi Makiguchi 3-2-5 Kasumigaseki, Chiyoda-ku, Tokyo Mitsui Toatsu Chemicals, Inc.

Claims (6)

[Claims] 1. A method for producing a phenol FRP molded product obtained by impregnating a fiber base material with a phenol resin solution containing a liquid phenol resin, a filler, and other additives, and curing the liquid phenol resin, wherein the liquid phenol resin is (a). A resorcinol component containing a resorcinol novolak resin which is a reaction product of the resorcinol and an aldehyde in the presence of resorcinol and / or an acid catalyst; and (b)
Phenol resole resin component which is a reaction product of formaldehyde and / or paraformaldehyde and at least one phenol compound selected from the group represented by the following formula [Chemical formula 1] (Wherein R, R ′, R ″, and R ″ ′ are reaction products with OH or a chain or cyclic hydrocarbon group having a saturated or unsaturated bond having 1 to 6 carbon atoms) Phenol FRP molded product. 2. The total amount 1 of the resorcinol component of the component (a) and the phenol resole resin component of the component (b) described above.
The phenol FRP molded article according to claim 1, which is a reaction product obtained by reacting with 0.01 to 40 parts by weight of a methylene donor with respect to 00 parts by weight. 3. The phenol FRP molded product according to claim 2, wherein the methylene donor is furfural, furfuryl alcohol, oxazolidine and / or acrolein. 4. The resorcinol component of the component (a) is 5 to 1 with respect to 30 to 80 parts by weight of resorcinol.
The phenol FRP according to claim 1 or 2, which is obtained by reacting 5 parts by weight of formaldehyde.
Molded product. 5. The phenol resole resin component as the component (b) is 20 to 55 with respect to 40 to 75 parts by weight of at least one phenol compound selected from the group represented by the following formula [Chemical formula 2]. The phenol FRP molded product according to claim 1 or 2, which is obtained by reacting parts by weight of paraformaldehyde. [Chemical 2] (Here, R, R ′, R ″, and R ″ ′ are OH or a chain or cyclic hydrocarbon group having a saturated or unsaturated bond having 1 to 6 carbon atoms) 6. The method for producing a phenol FRP molded product according to any one of claims 1 to 5.