JPH08176403A - Resin composition for pultrusion - Google Patents

Abstract

PURPOSE: To obtain a resin compsn. for continuous pultrusion which is excellent in releasability, heat resistance, and flame retardance. CONSTITUTION: A resin compsn. having a good pultrudability is prepd. by compounding a novolak phenol resin having an ortho-para ratio of 3 or higher with a divinylbenzene compd., a perfluoroalkyl-contg. fluorinous mold lubricant, and a curative and pref. further with a filler and a flame retardant.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a resin composition for continuous pultrusion.

[0002]

2. Description of the Related Art Continuous pultrusion molding is a method in which a thermosetting resin is impregnated into a reinforcing fiber base material mainly composed of thread-like fibers, such as glass fiber roving, and introduced into a heated mold, It is molded by pulling it out with a pulling device while being heated and cured by.

As the thermosetting resin, unsaturated polyester resin, epoxy resin and phenol resin are mainly used.

[0004]

However, although the above unsaturated polyester resin and epoxy resin are excellent in moldability and mechanical strength, they are inferior in heat resistance and flame retardancy.

Phenolic resins are excellent in terms of heat resistance and flame retardancy, but have a drawback that mechanical strength, particularly normal state strength, is poor due to generation of condensation gas. In addition, when the above thermosetting resin is used, the releasability is generally poor, and a wax or the like is added to the resin, but the releasability is not satisfactory. , Which had a negative effect on flame retardancy.

An object of the present invention is to provide a resin composition for pultrusion molding which is excellent in heat resistance, flame retardancy and releasability.

[0007]

The inventors of the present invention have made diligent studies in view of the above circumstances and found that a phenol resin,
It was found that a resin composition containing divinylbenzenes, a fluorine-based mold release agent, and a curing agent as essential components is excellent in heat resistance, flame retardancy, and mold release property, and is suitable as a resin for pultrusion molding. It came to completion.

That is, the present invention contains a phenolic resin (A), divinylbenzenes (B), a fluorine-based releasing agent (C) and a curing agent (D), and preferably further contains a filler (E) and a flame retardant. Provided is a resin composition for pultrusion molding, which is characterized by using (F) together.

Phenolic resin (A) used in the present invention
Is a structure in which an aromatic ring derived from a novolac type phenolic compound is crosslinked by a methylene bond, but there is no particular limitation, and all of the following can be used.

As the starting phenolic compound, any of the known and conventional compounds can be used. For example, phenol, bisphenol F, bisphenol A, cresol, P
-Alkyl-substituted phenols such as tert-butylphenol, halogen-substituted phenols such as bromophenol, compounds containing two or more phenolic hydroxyl groups such as resorcin, 1-naphthol, 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, etc. Examples thereof include aromatic compounds having a phenolic hydroxyl group such as naphthols, and unsaturated group-containing phenols such as paravinylphenol and isopropenylphenol. These may be used alone or as a mixture of two or more of these compounds.

Other phenolic resins include phenol-dimethoxyxylylene resin obtained by reaction of phenol and dimethoxyxylylene, phenol-divinylbenzene resin obtained by reaction of phenol and divinylbenzene, and phenol and dicyclopentadiene. The phenol-dicyclopentadiene resin obtained by the above reaction is also contained in the phenol resin.

The method of crosslinking the methylene bond of the novolac type phenolic resin is as follows: crosslink between ortho positions with respect to hydroxyl groups of each aromatic ring; crosslink between ortho positions and para positions; There are three cases where the para positions are cross-linked. Thus, the number of methylene bonds cross-linked between para-positions and para-positions relative to the hydroxyl group of the aromatic ring and the number of methylene bonds bonded at ortho-para-positions is 1 /
The ortho-para ratio is the ratio of the number of methylene bonds bridging between ortho positions to the sum of 2 and the sum of 1/2 of the number of methylene bonds bridging between ortho positions and para positions. Hereinafter referred to as o / p ratio).

The novolac type phenolic resin of the present invention is
A novolac type phenol resin having an o / p ratio of 3 or more is preferably used. Novolak type phenolic resins with an o / p ratio of 3 or more are usually synthesized by reacting phenols with paraformaldehyde, which is a formaldehyde source, in an aromatic hydrocarbon solvent using a metal salt or metal oxide as a catalyst. The conditions in the synthesis of are not particularly limited.

As described above, as the novolak type phenolic resin, generally-known high ortho novolac, in which a large number of phenolic compounds having an o / p ratio of 3 or more are bound at the ortho-position bonding portion, is preferable. The reason is that the resin composition of the present invention has good compatibility with divinylbenzenes serving as a crosslinking agent. Out of this
It is more preferable that the / p ratio is 4 or more.

The novolac type phenolic resin of the present invention preferably has a softening point of 60 to 130 ° C, more preferably 60 to 100 ° C. Softening point is 60
When the temperature is lower than 0 ° C, the molecular weight of novolac is low and the heat resistance is poor, and when the temperature is higher than 130 ° C, it is difficult to dissolve in divinylbenzene, which is not preferable.

The molecular weight of the novolac type phenol resin used in the present invention is not particularly limited, but the number average molecular weight is preferably 300 to 2000, and more preferably 400 to 900. When the number average molecular weight is 300 or less, heat resistance is poor, and when it is 2,000 or more, it is difficult to dissolve in divinylbenzene, which is not preferable.

The novolac type phenolic resin of the present invention is
The catalyst such as a metal salt or a metal oxide can be used even if it remains, but it is preferable to reduce the amount of the catalyst remaining by a step such as washing with water. This is because the acids serving as the curing accelerator are consumed by the residual metal compound, and it is admitted that the one having less residual catalyst is preferable in terms of performance.

Among the above-mentioned phenol resins (A), the novolac type phenol resin is excellent in flame retardancy and the dicyclopentadiene-phenol resin is excellent in heat resistance. Examples of the divinylbenzenes (B) used in the present invention include divinylbenzene, divinylbenzene compounds such as alkyldivinylbenzene and halogen-substituted compounds, and are not particularly limited, but the reactivity and workability are not limited. Considering the above, divinylbenzene is preferable.

The divinylbenzenes used in the present invention may be a mixture thereof, or a mixture containing other third component, that is, impurities. The blending ratio of the component (A) and the component (B) in adjusting the synthetic resin composition used in the present invention varies depending on the types of the phenol resin and divinylbenzenes used,
50 to 150 parts by weight of divinylbenzene per 100 parts by weight of the phenol resin. Preferably, the total amount of the reactive bonds of the unsaturated double bond of the methylene group in the phenol resin and the divinylbenzene is equal to or less than the number of bonds of the phenolic resin skeleton in the basic resin, that is, the number of bonds of the phenolic skeleton. It should be. That is, equivalent weight to 0.
8 equivalents are preferred.

Although the divinylbenzenes can be polymerized by heating, the compounding object can be carried out at room temperature or under heating since the compounding object is a phenolic substance acting as a polymerization inhibitor. . However, considering safety, they should be mixed at a temperature as close to room temperature as possible.

If there is no problem even if a solvent is contained in the final method of use, a solvent can be added if necessary. The synthetic resin composition of the present invention may be blended in the same reactor immediately after synthesizing the basic resin, or may be taken out of the reactor once and blended in a new container. .

Fluorine-based release agent (C) used in the present invention
Examples thereof include perfluoroalkyl group / lipophilic group-containing oligomers, perfluoroalkyl group / lipophilic group-containing urethanes, perfluoroalkyl group-containing oligomers, perfluoroalkyl phosphates and the like. These may be diluted with terpen, ethyl acetate or the like, if necessary.

The amount of the fluorine-based releasing agent is not particularly limited, but is 0.1 to 5.0 parts by weight per 100 parts by weight of the synthetic resin composition containing the phenol resin (A) and the divinylbenzenes (B). Parts are preferred.

Examples of the curing agent (D) used in the present invention include metal chlorides such as aluminum chloride and stannous chloride, inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, benzenesulfonic acid and paratoluenesulfonic acid. And organic phenolic acid such as acetic acid, oxalic acid, and maleic acid, as well as phenolic resin (A).
Derived from sulphonides, halides, phosphites such as phosphorous monophenyl, specifically p
Also included are so-called latent catalysts, such as methyl toluene sulfonate, ammonium chloride or benzylsulfonium salts, which decompose at a certain temperature to produce an acidic component. These curing agents may be used alone or in combination. Among these curing agents, it is preferable to use a benzylsulfonium salt which has a life of a compounding liquid.

The amount of the curing agent used is not limited, but the phenol resin (A) and the divinylbenzenes (B) are used.
0.1 to 5.0 parts by weight is preferable per 100 parts by weight of the synthetic resin composition consisting of.

When a benzylsulfonium salt is used as a curing agent, it is difficult to dissolve in a synthetic resin composition consisting of a phenol resin (A) and a divinylbenzenes (B) because it is a solid, so that it is cured uniformly. It is preferably dissolved in a phenolic monomer and used in a diluted state.

When flame retardancy is required as the required performance of the pultruded product, it is preferable to further add a filler (E) and a flame retardant (F). The filler (E) used in the present invention is not particularly limited, and an organic filler or an inorganic filler can be used, but an inorganic filler is preferable. Examples of the inorganic filler include silica, aluminum hydroxide, titanium oxide, calcium carbonate, talc, kaolin clay, mica, alumina and the like. The amount of the filler (E) used is not limited, but is 1 per 100 parts by weight of the synthetic resin composition comprising the phenol resin (A) and divinylbenzene (B).
˜50 parts by weight is preferred.

Here, the flame retardant (F) used in the present invention
As, for example, red phosphorus, triphenyl phosphate, cresyl phenyl phosphate, tricresyl phosphate, triallyl phosphate, tris chloroethyl phosphate, antimony trioxide, boric acid,
Aluminum borate, tetrabromobisphenol A,
Common flame retardants such as hexabromocyclodecane can be mentioned. Among these, red phosphorus having a large flame retardant effect is preferable. The amount used is not limited, but is preferably 1 to 50 parts by weight per 100 parts by weight of the synthetic resin composition comprising the phenol resin (A) and the divinylbenzenes (B).

A resin composition containing the above-mentioned phenol resin (A), divinylbenzenes (B), a fluorine-based releasing agent (C) and a curing agent (D), or a filler (E).
A resin composition containing a resin and a flame retardant (F) is impregnated into rovings or mats of glass, carbon, etc., and molded while being drawn into a mold, thereby providing excellent heat resistance, flame retardancy, and release properties. A molded product can be obtained.

Pultrusion molding means that long reinforcing materials such as roving, spun roving, continuous strand mat, chop mat, etc. are passed through a uniform resin impregnation tank to impregnate them, and excess resin is squeezed to obtain a heated gold. It is a molding method in which it is continuously drawn after it is passed through a mold and cured. In general, unsaturated polyesters, epoxies, and phenol resins are the mainstream resins, but no resin has excellent mechanical strength, heat resistance, flame retardancy, and releasability.

[0031]

[Examples] Examples will be described below. Hereinafter, "parts" means "parts by weight" and "%" means "% by weight" unless otherwise specified.

Synthesis Example 1 (Synthesis of novolac type phenolic resin) In a four-necked 3 liter flask equipped with a stirrer, condenser, thermometer and dropping funnel, 940 g of phenol (1
(0 mol) and 470 g of xylene and 281.3 g (7.5 mol) of 80% paraformaldehyde were added and stirring was started. As a catalyst, 4.7 g of zinc acetate dihydrate was added, and the temperature was raised to the reflux temperature. After xylene and water are distilled off for 4 hours and the reaction is performed while removing only the outflowing water layer, distillation is started to remove residual water and xylene as a solvent, and the temperature is raised to 130 ° C. Then, it was kept at 130 ° C. for 2 hours. Water (940 g) was added, the mixture was cooled to 80 ° C., and stirring was stopped. The separated upper aqueous layer was extracted, water was further added, and zinc acetate as a catalyst was washed and separated by the same operation. Then, the resin layer was heated to remove residual moisture and heated to 170 ° C. After partially removing the free phenol at 170 ° C. under reduced pressure, the free phenol was taken out from the reaction vessel, and the softening point (ring and ball method) was 85 ° C. and the number average molecular weight was 852 (G.
A solid novolac resin (confirmed by PC) was obtained. 13C-
It was confirmed by NMR that the ortho-para ratio was 4.3.

To 100 parts of the obtained novolak resin, 80 parts of divinylbenzene (purity 80%, impurities of ethylstyrene) were dissolved at 90 ° C. to obtain a viscosity of 750 cp.
A yellowish brown resin liquid (1) of s (25 ° C.) was obtained.

Synthesis Example 2 100 parts of divinylbenzene (purity: 80%, impurities: ethylstyrene) per 100 parts of DPP-H (dicyclopentadiene-phenol resin softening point: 103 ° C.) manufactured by Nippon Petrochemical Co., Ltd. Dissolve at ℃, viscosity 520
A uniform dark brown resin solution (2) with cps (25 ° C.) was obtained.

Examples 1 to 5 and Comparative Examples 1 and 4 A resin mixed solution prepared by mixing a predetermined amount of a resin liquid, a release agent, a curing agent, a filler, and a flame retardant was put in an impregnation layer, and the glass content became 80 wt%. Adjust the amount of glass roving so that
For a rod mold with a diameter of 10 mm and a length of 50 cm, 1
A molded product was obtained by curing at a temperature of 70 ° C. while pulling in at a speed of 20 cm / min.

Comparative Examples 2 to 3 A resin mixed solution prepared by mixing predetermined amounts of a resin liquid, a curing agent, a filler and a flame retardant was put in an impregnation layer, and the glass content was 80 wt.
Adjust the amount of glass roving so that
A 50 mm long metal mold having a rod size of 50 mm was drawn in and cured at a temperature of 150 ° C. at a speed of 20 cm / min to obtain a molded product.

Examples of the formulations of these resins are shown in Tables 1 and 2.
The physical property evaluations and the like are shown in Table 3.

[0038]

[Table 1] Megafac F-178: Dainippon Ink and Chemicals, Inc.
Perfluoroalkyl group / lipophilic group-containing oligomer PX-33: Xylene sulfone sulfonic acid / phenol = 1/2 mixture CR85-50: Benzyl sulfonium salt / m-cresol = 1/1 mixture Silica: Micron Harimic S-0 Average particle size 3 μm Red phosphorus: Phosphorus Chemical Co., Ltd., Norverwell FST
-100 average particle size 2-5 μm

[0039]

[Table 2] Polylite HN-235: Dainippon Ink and Chemicals, Inc.
Made polyester resin (containing 50% benzoyl peroxide powder 2%) Dythric 300X: Phenolic resin made by Dainippon Ink and Chemicals, Inc. Moldwith INT-1850: Accelerator Plastic Research Laboratories release agent (alkylaryl, polyethylene glycol) , Hop fatty acid ester,
Hydrogenated animal and vegetable oils and fats, fatty acid mono- or dialkanolamide mixtures)

[0040]

[Table 3] <Test method> Strength: JIS K-6911 Oxygen index: JIS K-7201 UL: V-0, V-1 according to UL standard As shown in Table 3, the resin composition of the present invention is pulled out as compared with the conventional composition. It is possible to provide a material excellent in heat resistance (flame release property), heat resistance, and flame retardancy.

[0041]

The resin composition of the present invention has improved releasability, which is a problem in continuous pultrusion.
It also has excellent heat resistance, flame retardancy, and strength.

Claims (9)

[Claims] 1. A pultrusion resin composition comprising a phenol resin (A), divinylbenzenes (B), a fluorine-based mold release agent (C) and a curing agent (D). 2. The composition according to claim 1, further comprising a filler (E) and a flame retardant (F) in combination. 3. The composition according to claim 1 or 2, wherein the phenol resin (A) is a novolac type phenol resin having an orthopara ratio of 3 or more. 4. The softening point of the novolac type phenolic resin is
The composition according to claim 3, which has a temperature of 60 to 130 ° C. 5. The composition according to claim 1 or 2, wherein the phenol resin (A) is a dicyclopentadiene-phenol resin. 6. The composition according to claim 1, wherein the fluorine-based releasing agent (C) is a perfluoroalkyl group-containing oligomer. 7. The curing agent (D) is a benzylsulfonium salt, as claimed in any one of claims 1 to 6.
The composition according to the item. 8. The composition according to claim 2, wherein the filler (E) is silica. 9. The composition according to claim 2, wherein the flame retardant (F) is red phosphorus.