JPH02214763A - Thermosetting molding material - Google Patents

Abstract

PURPOSE:To obtain molding material of filler-containing, phenol-modified aromatic hydrocarbon aldehyde resin suitable for wear-resistant material, friction material or insulating coating, etc., having improved mechanical strength and heat resistance by mixing with cyanic acid ester compound. CONSTITUTION:(A) 100 pts.vol. phenol-modified aromatic hydrocarbon aldehyde resin composition composed of A1: 76-95 pts.wt. novolak-type phenol-modified aromatic hydrocarbon aldehyde resin, A2: 5-15 pts.wt. curing agent and A3: 0.3-10 pts.wt. cyanic acid ester compound (e.g. 1,3- or 1,4-dicyanatobenzene) is mixed with (B) 40-240 pts.vol. filler (e.g. glass fiber or rock wool fiber). Preferably, A1 is mixed with A3, then A2 is added, thus further B is mixed to afford the aimed thermosetting molding material.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a filled phenol-modified aromatic hydrocarbon aldehyde resin molding material with improved mechanical strength and heat resistance. This material can be subjected to compression molding, transfer molding, etc., and can also be used as a powder coating, and the cured product is used for various purposes such as insulating coatings, body wear materials, heat insulating materials, and brakes.

[Conventional technology and its problems]

The cured product of thermosetting phenol-modified aromatic hydrocarbon aldehyde resin is known as a molding material with excellent heat resistance and body abrasion resistance, but it can also be mixed with fillers (materials) to make composite materials and molding materials. When used, it has the drawback of poor adhesion to fillers, hardness and brittleness, and poor mechanical strength.

In order to solve this problem, methods are known in which improvements are made by blending flexibility-imparting resins such as nonylphenol, rubbers, etc., but this method has the drawback of deteriorating heat resistance.

[Means to solve the problem]

The present invention has been made as a result of intensive studies to obtain a filler-containing thermosetting phenol-modified aromatic hydrocarbon aldehyde resin that has excellent mechanical strength and has improved these drawbacks. The present invention was completed based on the discovery that a molding material with significantly improved mechanical strength could be obtained by the above method.

That is, the present invention provides a thermosetting molding material comprising (a), 1 part of 100 vol of a phenol-modified aromatic hydrocarbon aldehyde resin), and 40 to 240 vol parts of a filler, in which the resin (a) (c) is a thermosetting molding material with improved mechanical strength characterized by containing 0.3 to 10 wt% of a cyanate ester compound; in a preferred embodiment, the resin (a) is a novolac type Phenol-modified aromatic hydrocarbon aldehyde resin (a-1
) 76-95wt part and its curing agent (a-2) 5-
15wt part and cyanate ester compound (c) 0.3~
In addition, after mixing the resin (a-1) and the cyanate ester compound (c), the curing agent (a
-2) is a thermosetting molding material with improved mechanical strength.

The configuration of the present invention will be explained below.

The phenol-modified aromatic hydrocarbon aldehyde resin of component (a) of the present invention includes toluene, xylene, mesitylene,
Aromatic nuclei obtained by reacting aromatic hydrocarbons such as alkyl tephthalene with aldehydes such as formaldehyde and paraformaldehyde in the presence of an acid catalyst form methylene bonds (-CI2-) and methylene ether bonds (-C).
1. -0-C1,-) or acetal bond (-CH*
It is a resin in which a methylol group (-CH2DH) is bonded to a part of the aromatic nucleus, and toluene resin, xylene resin, etc. depending on the main aromatic hydrocarbon used. resin, mesitylene resin,
What is called a naphthalene resin; it also mainly consists of resol type or novolak type resins produced by reacting phenol or alkylphenol.

Further, the ratio of aromatic hydrocarbon and phenol in the phenol-modified aromatic hydrocarbon aldehyde resin is preferably 3 to 7:3.

Furthermore, when the phenol-modified aromatic hydrocarbon aldehyde resin of the present invention is a resol type, it is easily cured by mere heating and does not require a particular curing agent. 5 to 15 w of hardening agent such as or rose formaldehyde.
t% of the mixture to make it thermosetting.

The cyanate ester compound (c) of the present invention is an organic compound containing one, preferably two or more cyanato groups (-0CN) in the molecule, and the above-mentioned (a) component 100w
0.3 to 10 wt% relative to t%, preferably 0.5 to 10 wt%
It is used in a range of 5 wt%. If the amount added is less than 0.3 wt%, the strength improvement effect - the effect of improving adhesion with the filler - is insufficient, and if it is used in an amount exceeding 10 wt%, it is unnecessary from the viewpoint of the strength improvement effect, and This is not preferable because it may cause problems such as foaming of the molded product. As the cyanate ester compound, known curable resins containing a cyanate ester compound as an essential component, such as cyanato resin (Japanese Patent Publication No. 41-1928, No. 45-11712, No. 44-1222, German Patent No. M1190184) !
>, cyanate ester-maleimide resin, cyanate ester-maleimide-epoxy resin (Japanese Patent Publication No. 54-30
440 etc., Special Publication No. 52-31279, ll5P-4
110364, etc.), cyanate ester epoxy resin (Japanese Patent Publication No. 46-41112), etc. - all can be used as component (e) of the present invention.

Moreover, those suitable as the cyanate ester compound (c) of the present invention have the general formula (1); R(OCN) m ---(1
) (in the formula, m is an integer of 2 or more and usually 5 or less, R is an aromatic organic group, and the cyanato group is bonded to the aromatic ring of the organic group) It is a compound. To give a concrete example, 1゜3-
or 1,4-dicyanatobenzene, 1.3.5-) licyanatobenzene, 1.3-, 1.4-, 1.6-, 1
．． 8-, 2.6- or 2°7-dicyanatonaphthalene,
1.3.6-) lycyanatonaphthalene, 4,4°-dicyanatobiphenyl, bis(4-cyanatophenyl)methane, 2,2-bis(4-cyanatophenyl)propane,
2,2-bis(3,5-dichloro-4-cyanatophenyl)propane, 2,2-his(3,5-dichloro-4-cyanatophenyl)
Cyanatophenyl)propane, bis(4-cyanatophenyl)ether, bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl)sulfone, tris(4-cyanatophenyl)phosphite, tris(4-cyanatophenyl)propane,
(USP-40
26913), cyanic acid esters obtained by the reaction of novolacs with cyanogen halides (USP-4022
755, USP-3448079). In addition to these, Special Publications No. 41-1928, No. 43-18468
, 44-4791, 45-11712, 46-
41112, 47-26853, JP-A-51-631
49, USP-3553244, 3755402, 37
40348,3595900.

Cyanic acid esters described in US Pat. No. 3,694,410 and No. 4,116,946 may also be used.

In addition, a prepolymer obtained by polymerizing the above-mentioned polyfunctional cyanate ester in the presence or absence of a mineral acid, a Lewis acid, a salt such as sodium carbonate or lithium chloride, a phosphate ester such as tributylphosphine, etc. used as. These prepolymers are formed by trimerization of cyanide groups in the cyanate ester (sym-)
Generally has a riazine ring in the molecule.

Furthermore, the polyfunctional cyanate esters described above can also be used in the form of prepolymers with amines. Examples of amines that can be suitably used include meta- or para-phenylenediamine;
meta- or baraxylylene diamine, 1,4- or 1
．． 3-cyclohexanediamine, hexahydroxylylenediamine, 4,4°-diaminobiphenyl, bis(4
-aminophenyl)methane, bis(4-aminophenyl)ether, bis(4-aminophenyl)sulfone, bis(4-amine-3-methylphenyl)methane, bis(
4-amino-3,5-dimethylphenyl)methane, bis(4-aminophenyl)cyclohexane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-
Amino-3-methylphenyl)propane, 2,2-bis(4-amino-3-chlorophenyl)propane, bis(
4-amino-3-chlorophenyl)methane, 2.2-bis(4-amino-3,5-dibromophenyl)propane, bis(4-aminophenyl)phenylmethane, 3.4
-diaminophenyl-4-aminophenylmethane, l,
1-bis(4-aminophenyl)-1-phenylethane and the like.

The polyfunctional cyanate esters, prepolymers thereof, and prepolymers with amines mentioned above can be used alone or in the form of mixtures, and the number average molecular weight of the individual and mixtures is preferably l, 700 or less, especially 300 to 1.500. A range of is preferred.

Cyanate ester-maleimide resin (Special Publication No. 54-30
440, etc.), cyanate ester-maleimide-epoxy resins (Japanese Patent Publication No. 52-31279, etc.), and cyanate ester-epoxy resins (Japanese Patent Publication No. 46-41112, etc.). Maleimide, which is a compositional component, is a compound represented by the following formula (2) and its prepolymer.

(In the formula, R1 is an aromatic or alicyclic organic group having a valence of 2 or more and usually a valence of 5 or less, X, , X.

is hydrogen, halogen, or an alkyl group, and n is usually an integer of 2 to 5. ) Maleimides represented by the above formula are produced by a method known per se in which maleic anhydride and polyamines containing 2 to 5 amino groups are reacted to prepare maleamic acid, and then maleamic acid is cyclized by dehydration. can do. The polyamines used are preferably aromatic polyamines in terms of the heat resistance of the final resin, but if flexibility and flexibility of the resin are desired, alicyclic amines may be used alone or in combination. good. Further, it is desirable that the polyamines be primary amines from the viewpoint of reactivity, but secondary amines can also be used. Suitable amines include those exemplified as those used as prepolymers with cyanate esters, and melamines having an S-) lyazine ring;
These are polyamines made by reacting aniline with formalin and linking benzene rings with methylene bonds.

In addition, the epoxy resin can be any resin that has been conventionally used as a molding material, and specifically, bisphenol A type epoxy resin, phenol novolac type epoxy resin, Talesol novolac type epoxy resin, etc. Epoxy resins) Halogenated bisphenol A type epoxy resins, halogenated phenol novolak type epoxy resins, triglycidoxybenzene, and other tri- or higher-functional known polyfunctional epoxy resins, etc., either alone or as a mixture of two or more types. Can be used. In the present invention, it is preferable to use trifunctional or higher functional functional groups.

The filler (material) of the present invention refers to fillers in various forms such as known fibers, short fibers, powder, chips, scales, etc. used for reinforcing materials, etc., depending on the purpose of use of the molding material. The blending amount is selected from the range of 40 to 240 VO 1 part per 100 vol parts of the resin.

The fibrous filler is mainly used to improve strength, and in the present invention, fibers made of inorganic, metal, or heat-resistant resins with a fiber diameter of 0.1 m or more are preferable. Specifically, glass fiber, rock wool fiber, steel fiber, carbon fiber, novoloid fiber, potassium titanate fiber, fully aromatic polyamide fiber (aramid fiber, Nomex fiber), polyphenylene sulfide fiber, polyether ether ketone fiber, Examples include etherimide fiber. These fibrous reinforcing base materials may be treated with a silane coupling agent, titanate coupling agent, or other surface treatment agent as appropriate. In addition, powdered fillers include graphite, molybdenum disulfide, lead, calcium difluoride,
Sliding materials such as phthalocyanine, copper phthalocyanine, and fluororesin (Teflon); rubber powder, phenol, etc.
Frictional powders at low temperatures such as cured novolac resins, other heat-resistant cured resin powders with no melt flowability, cashew dust, organic powders such as wood flour; alumina, silica, short glass fibers, rock wool short fiber, mullite,
Other hardness and wear modifiers for ceramics, etc.: inorganic powders such as barium sulfate, calcium carbonate, talc, clay, mica, diatomaceous earth, lime, copper, brass, bronze, iron, zinc,
Metal powders and chips such as tin and aluminum, copper oxide, antimony trioxide, magnesium oxide, zirconium oxide,
Examples include auxiliary fillers such as fillers such as metal oxides such as ferric oxide.

Examples of the mold release agent include internal mold release agents such as petroleum wax, carnauba wax, montan wax, and others.

The present molding material is manufactured by uniformly mixing the components described above. The mixing is carried out using a known Banbury mixer 1 Henschel mixer, roll, extruder, etc., by dividing the mixture in batches or sequentially so that each component is uniform and does not deteriorate due to mutual reactions, etc. In particular, when blending a novolak type phenol-modified aromatic hydrocarbon aldehyde resin (a-1) as a resin component, hexamine as its curing agent (a-2), and a cyanate ester compound (c), hexamine and (c) JIi It is preferable to uniformly mix component (a-1) and component (c) before blending component (a-2). In addition, when blending a resin component and a fibrous filler, for example, a method such as mixing powder such as barium sulfate with the resin powder and blending the fibrous filler with this can be used to uniformly mix the resin component. Select the mixing order to match. The mixing conditions range from room temperature to 150°C or less, preferably 100°C.
℃ or less for 1 to 30 minutes, preferably 3 to 10 minutes.

The above-prepared thermosetting molding material of the present invention is suitably preformed, a reinforcing material is used, an adhesive layer is suitably formed on the surface to be integrated with the reinforcing material, and then the thermosetting molding material of the present invention is molded under heat and pressure. Obtain the molded article of the invention.

Here, as the reinforcing material, in addition to iron plates, glass fiber or other fiber reinforced plates, composites of iron and fiber reinforced plates, fiber fabrics, etc. can be used as appropriate.

The molding conditions are a pressure of 100 to 800 kg/c++f, preferably 150 to 700 kg/caf, and a temperature of 140 to 700 kg/caf.
Molding is carried out at 300°C, preferably 160-200°C, for 1-120 minutes, preferably 3-15 minutes. After molding, usually 150-300°C, preferably 170-250°C
by post-curing for 2 to 24 hours, preferably 5 to 16 hours.

〔Example〕

The present invention will be explained below with reference to Examples.

In addition, unless otherwise specified, parts in Examples, etc. are based on weight.

Example 1 Phenol-modified xylene resin (manufactured by Mitsubishi Gas Chemical ■, Nicanol P-100. Hereinafter referred to as resin 1), hexamethylenetetramine (hereinafter referred to as curing agent 1), bisphenol A cyanate monomer (hereinafter referred to as BPA- (denoted as CN) were each made into a powder with a throughput of 200 mesh.

Carbon fiber chopped strands (length 3mm) 300g 1 natural graphite (particle size 10,
ca) 200g, 1600g of the above resin and BPA-
After adding 6 g of CN and mixing for 10 seconds at room temperature, 160 g of the above curing agent was added and further mixed for 10 seconds (volume ratio in the mixture was resin/filler = 100/44).

The mixture was put into a mold and preformed at 65℃, 300kg/cot for 1 minute, then heated in an oven at 120℃ for 9 minutes, put into the mold again, and preformed at 170℃, 400kg/cot.
After molding for 4 minutes at nf, the molded parts were removed from the mold and post-cured in an oven at 220° C. for 2 hours.

Table 1 shows the results of measuring the bending strength of the obtained cured product.

Comparative Example 1 A cured product was obtained in the same manner as in Example 1 except that BPA-CN was not used in the preparation of the molding material.

Table 1 shows the results of measuring the bending strength of the obtained cured product.

Example 2 Phenol-modified xylene resin (manufactured by Mitsubishi Gas Chemical ■, Nikanol P-140, hereinafter referred to as resin 2), prepolymer of bisphenol A cyanate (number average molecular weight 700
, hereinafter referred to as P-CN7) were each made into a powder with a mesh throughput of 200.

Glass fiber 1 with a diameter of 13-1 and a length of 3 mm is placed in a ball mill.
After adding 50 parts of the above resin, 2100 parts of the above resin, and 72 parts of P-CN and mixing at room temperature for 30 minutes, 110 parts of the curing agent used in Example 1, 3 parts of stearic acid, and 1.0 part of the epoxy silane coupling agent were added. and further mixed for 1 hour at room temperature (
The volume ratio in the mixture is resin/filler = 100/60).

The mixture was put into a mold and preformed at 65℃, 300kg/caf for 1 minute, then heated in an oven at 120℃ for 9 minutes, put into the mold again, and preformed at 170℃, 300kg/caf.
After molding for 4 minutes at af, the molded article was removed from the mold and post-cured in an oven at 220° C. for 2 hours. Table 2 shows the results of measuring the bending strength of the obtained cured product.

Comparative Example 2 Table 2 shows the results of measuring the bending strength of a cured product obtained in the same manner as in Example 2 except that P-CN7 was not used in the preparation of the molding material.

Example 3 Bismaleimide-modified cyanate resin (Mitsubishi Gas Chemical Co., Ltd., BT 2680, Bismaleimide/Siaho)
=60/40, number average molecular weight 450) and barium sulfate were mixed at a weight ratio of 1:1, and this was made into a 200 mesh through powder.

12 parts of this powder, 100 parts of phenol-modified xylene resin (manufactured by Mitsubishi Gas Chemical ■, Nikanol GP300), and 500 parts of rock wool (varnish fiber, manufactured by Nippon Steel Chemical @, diameter 3 to 10-1, length 50 m or less) were mixed in a Henschel mixer. and mixed for 30 seconds. This was placed in a ball mill, 110 parts of the curing agent used in Example 1 was added, and the mixture was further mixed for 15 seconds (the volume ratio in the mixture was resin/filler = 100/
182).

Table 3 shows the results obtained in the same manner as in Example 2 except that the obtained mixture was used.

Comparative Example 3 The molding material was prepared in the same manner as in Example 3 except that BT2680 was not used. The results are shown in Table 3.

[Operation and effects of the invention]

As is clear from the above detailed description of the invention, examples, and comparative examples, the thermosetting molding material containing the cyanate ester compound of the present invention has significantly improved strength compared to the case where the cyanate ester compound is not blended. It is what was done.

Moreover, the cyanate ester compound of the present invention is a compound that allows a cured product to be obtained that exhibits extremely high heat resistance.
There is no deterioration in heat resistance at all.

From the above, the thermosetting molding material of the present invention is a heat-resistant material with excellent mechanical strength, and by appropriately selecting the type of filler, etc., the thermosetting molding material of the present invention can be used as a wear-resistant material, a friction material (brake material),
It is understood that it can be suitably used in various applications such as heat insulating materials, insulating paints, and the like.

Claims (1)

[Claims] 1 (a) 100 vol parts of phenol-modified aromatic hydrocarbon aldehyde resin and (b) 40 to 240 vol of filler
In the thermosetting molding material, the resin (a) contains (c) a cyanate ester compound of 0.3 to 1 part.
A thermosetting molding material with improved mechanical strength, characterized in that it contains 10 wt%. 2. The resin (a) contains 76 to 95 wt parts of a novolac type phenol-modified aromatic hydrocarbon aldehyde resin (a-1), 5 to 15 wt parts of its curing agent (a-2), and 0. 2. The thermosetting molding material according to claim 1, comprising 3 to 10 parts by weight. 3 The resin (a-1) and the cyanate ester compound (c)
Claim 2: After mixing, the curing agent (a-2) is added.
The thermosetting molding material described.