JPH0578552A - Synthetic resin composition - Google Patents

Abstract

PURPOSE:To prepare the subject compsn. which gives a cured article excellent in flexibility by compounding a novolac arom. hydrocarbon-formaldehyde resin with a curative comprising a compd. having two ethylenically unsatd. double bonds. CONSTITUTION:The objective compsn. is prepd. by compounding a novolac arom. hydrocarbon-formaldehyde resin with a curative comprising a compd. of the formula (wherein R1 is a residue of an optionally substd., oxygen- terminated arylene or alkylene oxide polymer unit) having two ethylenically unsatd. double bonds [e.g. hydroquinone bis(vinylbenzyl) ether]. The obtd. compsn. generates no gas during curing and gives a cured article which is not only excellent in flexibility but also has advantages characteristic of a divinylbenzene-cured article such as high flame retardance, low smoke generation, high heat resistance, high strengths, good workability, good curability, low stress, and good color.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a synthetic resin composition.

[0002]

2. Description of the Related Art U.S. Pat. No. 4,200,706 describes a curable synthetic resin composition comprising a novolac type phenolic resin and divinylbenzene.

[0003]

However, a cured product obtained by curing a novolac type phenolic resin with divinylbenzene has a drawback that flexibility is insufficient.

Moreover, when a curing accelerator is added to a mixture of a novolak type phenolic resin and divinylbenzene to accelerate the curing, the reaction proceeds unless it is used immediately, and the storage stability is extremely poor.

[0005]

Means for Solving the Problems The inventors of the present invention have made extensive studies in view of the above situation. In addition to the above, as a compound having at least two ethylenically unsaturated double bonds instead of divinylbenzene, the following specific structure It was found that the above problem can be solved by using the compound of 1), and the present invention has been completed.

That is, the present invention provides a synthetic resin composition comprising a novolac-type aromatic hydrocarbon-formaldehyde resin (A) and a curing agent (B) as the curing agent (B).
The ethylenically unsaturated double bond represented by the following general formula 1 is replaced by 2
The present invention relates to a synthetic resin composition, which is characterized by using a compound having an individual. General formula 1

[0007]

[Chemical 2]

(However, R ₁ is an arylene group which may have a substituent or a terminal oxygen residue of an alkylene oxide polymerized unit.) The novolac type aromatic hydrocarbon-formaldehyde resin (A ) Is not particularly limited, but preferably has a softening point of 60 to
The temperature is 130 ° C., and more preferably 80 to 100 ° C.

The resin (A) is typically a novolac type phenol resin. The novolac type phenol resin can be produced by a known and commonly used method. For example, it can be easily obtained by dehydration condensation of phenols and formaldehyde supplying substance in the presence of a catalyst, if necessary.

As the formaldehyde supplying substance, any of the generally known aqueous formaldehyde solution and paraformaldehyde can be used. Any known catalyst may be used as the catalyst, and the catalyst is not particularly limited.

The raw material of the resin (A) is not particularly limited, and any of the known and conventional phenols can be used. For example, phenol and bisphenols such as bisphenol F, bisphenol A and bisphenol AF can be used. , A compound containing two or more phenolic hydroxyl groups such as alkyl-substituted phenols such as cresol and P-tert-butylphenol, halogen-substituted phenols such as bromophenol, resorcin and the like, 1
-Aromatic compounds having a phenolic hydroxyl group such as naphthols such as naphthol, 2-naphthol, 1,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene, and unsaturated group-containing phenols such as paravinylphenol and isopropenylphenol Etc. These may be used alone, or two or more kinds of these compounds may be mixed and used.

If necessary, furfural, melamine, acetoguanamine, benzoguanamine and the like may be used in combination. Of course, the above novolac-type phenol resin includes not only those in which an aromatic ring of phenols is bonded only by a general methylene bond but also those containing a methylene bond and a dimethylene ether bond.

Aromatic hydrocarbon resins such as xylene-formaldehyde resin having a structure similar to the above novolak type phenol resin, reaction products of xylene resin and phenol, and phenol aralkyl synthesized by the reaction of phenol and dimethoxyxylylene. resin

[0014]

[Chemical 3]

A phenol / dicyclopentadiene resin obtained by the reaction of phenol and dicyclopentadiene, a resin obtained by polymerizing paravinylphenol or isopropenylphenol, and a phenol aralkyl resin obtained by the reaction of phenol and divinylbenzene.

[0016]

[Chemical 4]

And the like are also included in the resin (A) according to the present invention. The above-mentioned novolac type aromatic hydrocarbon-formaldehyde resin (A) may be modified, or a mixture of several kinds may be used.

The resin (A) may be in the form of solid, liquid, organic solvent solution, organic solvent dispersion liquid, aqueous solution or water dispersion liquid, but solid one is preferable for molding materials. The curing agent (B) used in the present invention is represented by the following general formula 1.

[0019]

[Chemical 5]

(However, R ₁ is an arylene group which may have a substituent or a terminal oxygen residue of an alkylene oxide polymer unit.) Examples of the curing agent represented by the above general formula 1 include hydroquinone bis ( Vinylbenzyl) ether, resorcin bis (vinylbenzyl) ether,
2-methylresorcin bis (vinylbenzyl) ether, 2-tachary butylresorcin bis (vinylbenzyl) ether, 2-bromoresorcin bis (vinylbenzyl) ether, 2-perfluoromethylresorcin bis (vinylbenzyl) ether, 2, 6-dimethylresorcin bis (vinylbenzyl) ether, 2,6-dibromoresorcin bis (vinylbenzyl) ether,
2,6-ditert-butylresorcin bis (vinylbenzyl) ether, 2,3,5,6-tetrabromoresorcin bis (vinylbenzyl) ether, 1,6-dihydroxynaphthalenebis (vinylbenzyl) ether,
2,7-dihydroxynaphthalene bis (vinylbenzyl)
Ether, ethylene glycol bis (vinyl benzyl)
Ether, propylene glycol bis (vinyl benzyl) ether, diethylene glycol bis (vinyl benzyl) ether, dipropylene glycol bis (vinyl benzyl) ether, triethylene glycol bis (vinyl benzyl) ether, tripropylene glycol bis (vinyl benzyl) ether, etc. Can be mentioned.

The curing agent (B) itself may be obtained by binding a compound having two alcoholic hydroxyl groups or a compound having two phenolic hydroxyl groups to, for example, metachloromethylstyrene or parachlorostyrene by a Williamson reaction. Can be easily obtained. Usually, when using a compound having two alcoholic hydroxyl groups, alkali hydroxide or alkali hydride is used, and when using a compound having two phenolic hydroxyl groups, alkali carbonate or the like is used as a condensation catalyst with chloromethylstyrene. Of course, when a compound having two phenolic hydroxyl groups is used, this can be reacted as a phenolate.

The curing agent (B) may be used alone or as a mixture of two or more kinds. Other curing agents such as hexamethylenetetramine and divinylbenzene may be used in combination with the curing agent (B), if necessary.

The synthetic resin composition of the present invention can be easily obtained by mixing the resin (A) and the curing agent (B) as essential components. The mixing ratio of the resin (A) and the curing agent (B) is not particularly limited and may be appropriately selected depending on the types of the resin (A) and the curing agent (B) used, but the resin (A) 5 to 100 parts by weight of the curing agent (B) with respect to 100 parts by weight
It is used in an amount of 20 parts by weight, preferably 20 to 50 parts by weight.

When the curing agent (B) is solid, the resin (A) and the curing agent (B) may be mixed and pulverized to be mixed, or may be simply a mixture of powders. It can also be used after being dissolved by using a solvent. The composition of the present invention in which the resin (A) and the curing agent (B) are both solid is particularly suitable for a molding material. The composition of the present invention is
Generally, a curing accelerator is added and used.

As the curing accelerator used at this time, metal chlorides such as aluminum chloride and stannous chloride, inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, benzenesulfonic acid,
Organic sulfonic acids such as paratoluene sulfonic acid, organic carboxylic acids such as acetic acid, oxalic acid and maleic acid can be used. The curing accelerator may be simply mixed in the mixture of the resin (A) and the curing agent (B), but is preferably dispersed or mixed in the resin (A).

Further, as the curing accelerator, for example, a sulfonated compound derived from a novolac type aromatic hydrocarbon-formaldehyde resin as described above can also be used. Further, represented by phosphite such as phosphorus monophenyl, esters derived from sulfuric acid and organic sulfonic acid, for example, methyl p-toluenesulfonate, salts such as ammonium chloride, or halides thereof. You may use together with what is called a latent catalyst which decomposes | disassembles at a predetermined temperature and produces | generates an acidic component. The curing accelerator may be added to the mixture of the resin (A) and the curing agent (B), or may be previously reacted in the presence of the curing accelerator during the production of the resin (A). However, when a liquid hardening accelerator is added to the solid composition of the present invention, it is preferred that the hardening accelerator is present in the composition by the latter method.

The curing accelerator can be used not only by itself but also by 2
You may use it in mixture of 2 or more types. The amount of the curing accelerator used is not limited, but is 0.1 to 0.1% by weight of the curing agent.
5.0% by weight is preferred.

The curing time of the synthetic resin composition of the present invention can be appropriately adjusted depending on the type of resin (A), the type of curing agent (B), their mixing ratio, the type and amount of curing accelerator used. Is.

The synthetic resin composition of the present invention gives a cured product having excellent flexibility, which cannot be obtained from a cured product cured with divinylbenzene. Moreover, as with the case of using divinylbenzene, the synthetic resin composition is harmful and has a bad odor. It can be cured without generating ammonia or formaldehyde gas.

The synthetic resin composition of the present invention may be cured by using the resin (A) and the curing agent (B) as essential components. If necessary, a reinforcing material and a filler may be mixed with the composition. It can also be used. This composition can be cured by heating under normal pressure or under pressure, and the cured product is extremely excellent in flexibility.

As the reinforcing material, any known and commonly used fiber reinforcing material can be used. For example, glass fiber, ceramic fiber, asbestos fiber, carbon fiber, inorganic fiber such as stainless fiber, natural fiber such as cotton and hemp. Examples thereof include fibers, synthetic organic fibers such as polyester and polyamide. The shape of the reinforcing material is not particularly limited, and may be any of short fibers, long fibers, yarns, mats, sheets and the like.

As the filler, any known filler can be used, and examples thereof include silica, calcium carbonate, aluminum hydroxide, talc, clay and graphite. These reinforcing materials and fillers can be used not only alone but also as a mixture of two or more kinds, and the amount to be used should be adjusted depending on the application and required performance.

The synthetic resin composition of the present invention is used, for example, in various molding materials, binders for molding sand, binders for grinding wheels, adhesives, binders for friction materials, binders for refractory materials, foam materials, and the like.
It can be used in fields where novolac type aromatic hydrocarbon-formaldehyde resins have been conventionally used, such as resin concrete and rubber reinforcing agents, and is expected to improve performance.

The synthetic resin composition of the present invention can be crosslinked and cured by molding the resin composition alone or by compounding with a reinforcing material and a filler, but the molding method is not particularly limited.

The cured product of the synthetic resin composition of the present invention thus obtained improves the flexibility, which is a drawback of the novolac type aromatic hydrocarbon-formaldehyde resin, divinylbenzene and the cured product, and It is also excellent in flame retardancy, low smoke generation, heat resistance, strength, workability, curability, moldability, shrinkability, distortion, and color tone, which are advantages.

[0036]

EXAMPLES The present invention will be described below with reference to synthesis examples of novolac type phenolic resins, preparation of curable resin compositions, and application examples. All parts and% in the examples are based on weight. Synthesis Example 1 In a four-necked 2 liter flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 940 g of phenol (1
0 mol) and 41% aqueous formaldehyde solution 542 g
(7.5 mol) was added and stirring was started. 98 as a catalyst
% Sulfuric acid was added and the temperature was raised to the reflux temperature. After reacting under reflux for 3 hours, the dehydration circuit was switched to heating to remove water, and the temperature was raised to 150 ° C. After partially removing the free phenol under reduced pressure at 150 ° C., it was taken out from the reaction vessel to obtain a solid novolac type phenol resin having a softening point (ball & ring method) of 95 ° C. Synthesis Example 2 A 4-neck 2 liter flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel was charged with 940 g of phenol (1
0 mol) and 576 g (8 mol) of 41% formaldehyde were added and stirring was started. 2.4 g of zinc acetate dihydrate was added as a catalyst, and the temperature was raised to the reflux temperature. After reacting for 5 hours under reflux, while starting distillation to remove water,
The temperature was raised to 130 ° C. After holding at 130 ° C. for 1 hour, the temperature was raised to 150 ° C. while distilling. After further removing some of the free phenol under reduced pressure, 2.4 g of xylensulphonic acid was added and stirred to uniformly dissolve and take out,
A solid novolac type phenolic resin having a melting point of 88 ° C. was obtained. Synthesis Example 3 Metacresol 1080 was placed in a 4-neck 2 liter flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel.
g (10 mol) and 41% formaldehyde aqueous solution 50
6 g (7.5 mol) was added and stirring was started. 2.7 g of 50% aqueous paratoluenesulfonic acid solution was added as a catalyst, and the temperature was raised to the reflux temperature. After reacting under reflux for 3 hours, dehydration was started to remove water and the temperature was raised to 170 ° C. Further, after free metacresol was partially removed under reduced pressure, it was taken out of the reaction vessel to obtain a solid metacresol novolac type resin having a softening point of 97 ° C. Example 1 1 of the novolac type phenolic resin obtained in Synthesis Example 1
20 parts of hydroquinone bis (vinylbenzyl) ether, which is a curing agent, was mixed with 00 parts and pulverized to obtain a powder resin composition.

This composition was reacted in a mold at 150 ° C. for 20 minutes to obtain a cured product. This cured product was extremely excellent in flexibility. The cured product was also measured for flexural strength, flexural modulus, hardness, heat distortion temperature, hygroscopicity, and color tone of the cured product. The results are shown in Table-1. In addition, in Table-1,
* 1) and * 2) represent the weight increase rate after standing for 2 hours in boiling water and the weight increase rate after standing for 4 hours in boiling water, respectively.

[0038]

[Table 1]

Comparative Example 1 1 of the novolac type phenolic resin obtained in Synthesis Example 1
10 parts of hexamethylenetetramine as a curing agent was mixed with 00 parts and pulverized to obtain a powder resin composition.

This composition was reacted at 150 ° C. for 20 minutes in a mold to obtain a cured product. However, when cured,
Generation of odorous gas was remarkable and workability was extremely poor. Moreover, a large amount of air bubbles remain in the cured product,
The flexural strength, flexural modulus and hygroscopicity were considerably inferior to the cured product of the composition of Example 1. Comparative Example 2 1 of the novolac type phenol resin obtained in Synthesis Example 1
20 parts of divinylbenzene, which is a curing agent, was mixed with 00 parts to obtain a liquid resin composition.

After holding this composition at 80 ° C. for 10 minutes,
Reaction was carried out for 20 minutes in a mold at 150 ° C. to obtain a cured product.
This cured product was significantly inferior in flexibility to the cured product of Example 1. Example 2 1 of novolak type phenolic resin obtained in Synthesis Example 2
20 parts of hydroquinone bis (vinylbenzyl) ether, which is a curing agent, was mixed with 00 parts and pulverized to obtain a powder resin composition.

This composition was reacted at 150 ° C. for 20 minutes in a mold to obtain a cured product. This cured product was as flexible as the cured product of Example 1. Example 3 1 of the novolac type phenolic resin obtained in Synthesis Example 3
20 parts of hydroquinone bis (vinylbenzyl) ether, which is a curing agent, was mixed with 00 parts and pulverized to obtain a powder resin composition.

This composition was reacted at 150 ° C. for 20 minutes in a mold to obtain a cured product. This cured product was as flexible as the cured product of Example 1. Example 4 1 of novolac type phenolic resin obtained in Synthesis Example 1
20 parts of resorcin bis (vinylbenzyl) ether, which is a curing agent, was mixed with 00 parts and pulverized to obtain a powder resin composition.

This composition was reacted at 150 ° C. for 20 minutes in a mold to obtain a cured product. This cured product was as flexible as the cured product of Example 1. Example 5 100 parts of the synthetic resin composition obtained in Example 1 above,
A solution prepared by adding 100 parts of methyl ethyl ketone as a solvent was impregnated into a glass non-woven fabric (manufactured by Japan Vilene; Cumulus 5003) so that the resin adhesion amount was 75%, and dried in a dryer at 80 ° C. for 10 minutes, Eight resin-bonded glass nonwoven fabrics were stacked and compression molded at 150 ° C. for 10 minutes under a pressure of 20 kg / cm ² to obtain a glass-containing resin laminated plate.

[0045]

The synthetic resin composition of the present invention contains at least 2 ethylenically unsaturated double bonds having a specific structure as a curing agent.
Since the individual compound is used, a particularly remarkable effect that a cured product having extremely excellent flexibility can be obtained is exhibited.

Moreover, the obtained resin cured product can be cured without the generation of gas, which is an advantage of the cured product cured with divinylbenzene, which is low water absorption, flame retardancy, low smoke generation, and heat resistance. It also has properties, strength, workability, curability, moldability, shrinkability, distortion, color tone and the like.

Claims (1)

[Claims] 1. A synthetic resin composition comprising a novolac type aromatic hydrocarbon-formaldehyde resin (A) and a curing agent (B), wherein the curing agent (B) has the following general formula 1.
A synthetic resin composition comprising a compound having two ethylenically unsaturated double bonds represented by: General formula 1 (However, R ₁ is an arylene group which may have a substituent or a terminal oxygen residue of an alkylene oxide polymer unit.)