JPH08199040A - Synthetic resin composition - Google Patents

Abstract

PURPOSE: To obtain a synthetic resin composition which can give a cured product having excellent processability and heat resistance and high strengths and water absorptivity by using a specified novolac phenolic resin and an ethylenically unsaturated compound as essential components. CONSTITUTION: This composition essentially consists of a novolac phenolic resin (A) having ethylenic unsaturations in the molecule and compound (B) having at least two ethylenic unsaturations. It is desirable that the component A is a resin leaving an ortho/para isomer ratio of 3 or above. It is more desirable that the component A is a phenolic resin obtained by a reaction of phenol with dicyclopentadiene and desirably having a number-average molecular weight of 200-2000. It is desirable that component B is divinylbenzene.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified phenolic resin, and more particularly to a modified phenolic resin which is excellent in workability and heat resistance and gives a cured product having high strength and high water absorption resistance.

[0002]

2. Description of the Related Art Phenolic resins are mainly used for molding materials, laminates and industrial resins (adhesives or binders), and demands for them are expected in the future due to their excellent physical properties.

However, in recent years, the usage conditions of materials in each of these applications tend to become more and more severe, and in particular, the workability and heat resistance of materials have become important characteristics. The present inventor has found a technique for obtaining a cured product having good performance under mild conditions without condensation water or volatile components resulting from a curing agent, which is a problem when molding (= curing) a phenol resin. is suggesting. (JP-A-5-51516, JP-A-5-51516)
That is, it is a synthetic resin composition comprising a novolac type phenol resin and a compound having at least two ethylenically unsaturated double bonds, and provides a cured product having high strength and high water absorption resistance.

[0004]

However, recent severe conditions for using materials require further improvement in heat resistance, and in some cases, the technique proposed by the present inventor may not be sufficient.

An object of the present invention is to provide a synthetic resin composition which is excellent in heat resistance and which gives a cured product having high strength and high water absorption resistance.

[0006]

Means for Solving the Problems Accordingly, the present inventors have:
As a result of extensive studies in view of the above circumstances, a novolac-type phenol resin, by using a phenol resin having an ethylenically unsaturated double bond, a cured product having significantly superior heat resistance as compared with a cured product of the above composition. The present invention has been completed and the present invention has been completed.

[0007] That is, the present invention is, firstly, that the novolac type phenol resin and the ethylenically unsaturated double bond are at least 2
In a synthetic resin composition containing as an essential component a compound having a novolac type, a novolak type phenolic resin (A) containing an ethylenically unsaturated double bond in the molecule is used as the novolak type phenolic resin. The present invention relates to a synthetic resin composition.

Secondly, the present invention relates to a synthetic resin composition characterized by using a resin having an ortho / para ratio of 3 or more as the novolac type phenolic resin (A). Further, the present invention relates to a synthetic resin composition characterized by using a phenol resin obtained by a reaction of phenol and dicyclopentadiene as the novolac type phenol resin (A), and the number average of the novolac type phenol resin (A). The present invention relates to a synthetic resin composition having a molecular weight of 200 to 2000.

Further, the present invention is a synthetic resin composition characterized in that the compound having at least two ethylenically unsaturated double bonds is divinylbenzene, and the compound has at least a phenolic hydroxyl group. I have one,
The present invention also relates to a synthetic resin composition characterized by using a compound having at least three ethylenically unsaturated double bonds, which has a novolac type phenol resin (A) and at least two ethylenically unsaturated double bonds. The ratio with the compound (B) is (A) / (B) = 70/3 by weight.
It is related with the synthetic resin composition characterized by being 0-40 / 60.

[0010]

[Structure] The novolac type phenolic resin (A) having an ethylenically unsaturated double bond used in the present invention is not particularly limited.

As the starting phenolic compound, a phenolic compound having at least one ethylenically unsaturated double bond is used alone, or a usual phenolic compound having no ethylenically unsaturated double bond is used in combination therewith. It is necessary to use it.

At least one ethylenically unsaturated double bond
The phenolic compound having one is not particularly limited, but for example, arylphenol (o-, m-
Or p-), vinylphenol (o-, m- or p)
-), Propenylphenol (o-, m- or p-), isopropenylphenol (o-, m- or p-), arylresorcinol, diarylresorcinol, arylcatechol, diarylcatechol, arylhydroquinone, diarylhydroquinone, arylpyrogallol Etc.

Usual phenol compounds include phenol, phenol dimers such as bisphenol A, bisphenol F and biphenol, alkylphenols such as cresol and p-tert.butylphenol, phenolic hydroxyl groups such as resorcinol and hydroquinone. And compounds such as naphthols such as naphthol and dihydroxynaphthalene. Moreover, you may use these compounds individually or in mixture of 2 or more types.

The novolac type phenol resin (A) having an ethylenically unsaturated double bond of the present invention can be obtained by reacting the above phenolic compound with formaldehyde and the like. The molecular weight of the novolac type phenol resin (A) is not particularly limited, but the number average molecular weight is preferably 200 to 2000, more preferably 30.
It is 0 to 1000.

The novolac type phenol resin is an aromatic hydrocarbon resin having a similar structure such as xylene / formaldehyde resin, a reaction product of xylene resin and phenol, and phenol aralkyl synthesized by the reaction of phenol and dimethoxyxylylene. Examples thereof include resins, phenol / dicyclopentadiene resins obtained by the reaction of phenol and dicyclopentadiene, and resins obtained by polymerizing p-vinylphenol, isopropenylphenol and the like.

The above-mentioned novolac type phenolic resins modified may also be used. These may be used alone or in combination of two or more.
The novolac-type phenol-formaldehyde resin of the present invention includes not only those generally referred to as a phenol compound bound only by a methylene bond but also those bound by a methylene bond and a dimethylene ether bond.

Further, among the above-mentioned novolak type phenolic resins, the compatibility with the compound having at least two ethylenically unsaturated double bonds as the crosslinking agent is good,
Highly ortho novolac type phenolic resin in which a lot of phenolic compounds are bonded at the ortho position bonding portion and novolac type phenolic resin synthesized from phenol having a substituent at the meta position are preferable, and particularly high ortho It is preferable that the orientation (o / p ratio) between the ortho position and the para position of the novolac type phenol resin is 3 or more.

In addition to the high ortho novolac type phenolic resin, a phenol / dicyclopentadiene resin obtained by the reaction of phenol and dicyclopentadiene can be preferably used. Of these, a number average molecular weight is particularly preferable. Those of 300 to 1000 are more preferable.

The compound (B) having at least two ethylenically unsaturated double bonds used in the present invention is not particularly limited, and examples thereof include divinylbenzene, alkyldivinylbenzene and halogen substitution products thereof. However, divinylbenzene is preferable among these in consideration of reactivity and workability. The divinylbenzenes used in the present invention may be a mixture of two or more kinds thereof, and further, those containing ethylbenzene, styrene or the like having one ethylenically unsaturated double bond as an impurity.

As the compound (B), a compound having at least one phenolic hydroxyl group and at least three ethylenically unsaturated double bonds can be used.

The compound having at least one phenolic hydroxyl group and at least three ethylenically unsaturated double bonds is not particularly limited, and examples thereof include triarylphenol, trivinylphenol and tripropenyl. Examples thereof include phenol, triisopropenylphenol, triarylresorcinol, trivinylresorcinol and the like.

The mixing ratio of the synthetic resin composition used in the present invention is such that the novolac-type phenol resin (A) having an ethylenically unsaturated double bond to be used and at least two or more ethylenically unsaturated double bonds are used. It depends on the kind of the compound (B), but usually (A) / (B) ratio is 70.
/ 30-40 / 60 (weight ratio) is applied.

If the (A) / (B) ratio is greater than 70/30, the viscosity of the product composition becomes too high, which makes it difficult to handle, and further, the solubility becomes insufficient and a solution cannot be formed. On the other hand, when the (A) / (B) ratio is less than 40/60, the production amount of the homopolymer consisting only of the (B) component increases, and it becomes difficult to realize the original performance of the phenol resin. Particularly preferably, although depending on the types of (A) and (B), the bond of the aromatic hydrocarbon skeleton (eg, phenolic skeleton) in the component (A) is
A range in which the sum of the methylene group or norbornyl group, which is the bonding group in the component (A), and the reactive bond (that is, the ethylenically unsaturated double bond) in the component (B) is equivalent to 0.8 equivalent. Is.

These blending processes are carried out at room temperature or under heating as they are, but if there is no problem even if a solvent is contained in the final use method, a solvent may 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 (A), or the basic resin (A) may be taken out from the reactor once and newly added. You may mix | blend in another container.

The synthetic resin composition of the present invention can be cured by adding a curing accelerator and heating at room temperature or heating. Examples of the curing accelerator include metal chlorides such as aluminum chloride and stannous chloride, inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, organic sulfonic acids such as benzenesulfonic acid and p-toluenesulfonic acid, acetic acid and oxalic acid. , An organic carboxylic acid such as maleic acid, or the like can be used, and a peroxide can also be applied. Of these, a uniform solution is easily obtained,
In addition, organic sulfonic acid is preferable because the curing rate can be easily adjusted.

The amount of the curing accelerator used is not particularly limited, but is preferably 0.1% to 5.0% (based on the weight of the composition). It is also possible to mix and use a curing accelerator. As the curing accelerator, in addition to the above compounds, a sulfonated compound derived from the novolak type aromatic hydrocarbon-formaldehyde resin shown above can also be used.

Further, latent catalysts represented by phosphite esters such as phosphorus monophenyl, esters derived from sulfuric acid and organic sulfonic acids, such as salts of methyl p-toluenesulfonate and ammonium chloride ( Those which decompose at a certain temperature to generate an acidic component) can be used, and these may be mixed and used.

It is also effective in some cases to use a mixture of the above-mentioned ordinary curing accelerator and the latent catalyst.
Further, not only the above curing accelerators but also their halides and the like can be used.

The curing time varies depending on the type and proportion of the resin compound and the type and amount of the curing accelerator. The synthetic resin composition obtained by the present invention can be handled as an easy-to-handle solution, and unlike ordinary phenol resins, it can be cured uniformly without generating volatile components and at room temperature. It is possible and the composition proposed by the present inventor (JP-A-5-51516, JP-A-5-11
A cured product having heat resistance superior to that of JP 7337) is obtained.

The synthetic resin composition and cured product of the present invention are flame retardant, low smoke-producing, heat-resistant, which are advantages of the phenol resin.
While maintaining strength, etc., it has the disadvantages of workability, curability,
It improves moldability, shrinkage, distortion, color tone and the like.

Further, the synthetic resin composition of the present invention can be used not only by curing the resin composition alone, but also by curing it together with the reinforcing material and the filler, which is useful for various purposes. .

Therefore, the resin composition of the present invention is, for example, various molding materials, glass fiber sizing agents, binders for foundry sand, binders for abrasive wheels, adhesives, binders for friction materials, binders for refractory materials. , Binders for heat insulating materials, foam materials, resin concrete, rubber reinforcing agents, paints for various applications, coating agents, etc., not only in the fields where novolac type phenolic resins were conventionally used, but also resole type phenolic resins, unsaturated polyester It can be used in the fields where resins and the like have been used, and can be expected to improve performance.

The novolac type phenolic resin composition of the present invention can be molded by crosslinking and curing the resin composition alone or by compounding with a reinforcing material or a filler. The molding method includes injection molding method, RIM method, SMC method,
A method such as a hand lay-up method or a pultrusion molding method can be adopted, but the molding method is not particularly limited.

[0035]

EXAMPLES The embodiments of the present invention will now be described with reference to specific examples, but the present invention is not limited to these examples. Parts and% in the examples are based on weight unless otherwise specified.

[Synthesis Example 1] 752 g (8 mol) of phenol, 268 g (2 mol) of O-arylphenol and 470 g of xylene were added to a 4-necked 3 liter flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel.
243.8 g (6.5 mol) of 0% paraformaldehyde
Was added and stirring was started. 4.7 g of zinc acetate dihydrate was added as a catalyst, and the temperature was raised to the reflux temperature. After refluxing xylene and water for 4 hours and reacting while removing only the outflowing water layer, distillation is started to remove residual water and xylene, which is a solvent, at 130 ° C. for 2 hours. Held
Water (940 g) was added, the mixture was cooled to 80 ° C., and stirring was stopped. The separated upper water layer was extracted, water was further added, and zinc acetate as a catalyst was washed and separated by the same operation. After that, the resin layer is heated to remove residual moisture, and
The temperature was raised to 0 ° C. After partially removing free phenol at 170 ° C. under reduced pressure, it was taken out from the reaction vessel to obtain a solid novolac resin having a softening point (ring and ball method) of 65 ° C. and a number average molecular weight of 723 (confirmed by GPC). It was confirmed by ₁₃ C-NMR that the ortho / para ratio was 4.9.

[Synthesis Examples 2 to 6] Synthetic Examples 1 to 6 except that a phenol-based compound having at least one phenol and an ethylenically unsaturated double bond was used as shown in Table-1. Various novolak type phenolic resins were synthesized in the same manner as in 1. Their softening points, number average molecular weights and ortho / para ratios are as shown in Table 1.

[Synthesis Example 7] A novolac type phenol resin was synthesized in the same manner as in Synthesis Example 1 except that 864 g of m-cresol was used instead of 752 g of phenol in Synthesis Example 1. The softening point, number average molecular weight and ortho / para ratio are shown in Table 1.

Comparative Synthetic Example 1 A novolak type phenol resin was synthesized in the same manner as in Synthetic Example 1, except that the unsaturated group-containing phenolic compound was not used and the amount of phenol used was 940 g. Their softening points, number average molecular weights and ortho / para ratios are as shown in Table 1.

[0040]

[Table 1]

Example 1 100 parts of the novolac type phenolic resin obtained in the above Synthesis Example 1 was dissolved in 50 parts of divinylbenzene (purity 80%, impurities of ethylstyrene), which is also a crosslinking agent, at 50 ° C. Let the viscosity be 710 cps
A uniform green-brown liquid (25 ° C.) was obtained.

Xylene sulfonic acid as a curing accelerator was added to the above composition in an amount of 0.5% relative to the composition, and crosslinked at 80 ° C. for 1 hour to obtain a cured product. [Examples 2 to 9] The same as Example 1 except that as shown in Table 2, various novolac type phenolic resins and divinylbenzene (impurities are all ethylstyrene) were used. As a result, various green-brown or yellow-brown liquids were obtained. Their viscosities were as shown in Table 2, respectively.

The above composition was cured by treating it in each of Examples 2 to 8 in the same manner as in Example 1 and in Example 9 by crosslinking at 120 ° C. for 30 minutes, although the curing accelerator was the same. I got a thing.

[0044]

[Table 2]

Example 10 100 parts of the novolak type phenolic resin obtained in Comparative Synthesis Example 1 was dissolved in 100 parts of triarylphenol at 50 ° C. instead of divinylbenzene to obtain a viscosity of 1290 cps (25 ° C.). A uniform green-brown liquid was obtained.

A cured product was obtained by treating the above composition in the same manner as in Example 1. Example 11 100 parts of the novolac type phenolic resin obtained in Synthesis Example 1 was mixed with divinylbenzene (purity 80%,
Impurity is dissolved in 80 parts of ethyl styrene) and 20 parts of triarylphenol at 50 ° C., and the viscosity is 595 cps.
A uniform green-brown liquid (25 ° C.) was obtained. A cured product was obtained by treating this composition in the same manner as in Example 1.

[Example 12] In Example 11, instead of the novolac type phenol resin obtained in Synthesis Example 1, a special phenol resin DP manufactured by Nippon Petrochemical Co., Ltd. was used.
P-3H (phenol dicyclopentadiene resin, softening point 112 ° C, number average molecular weight 625) was used, except that
A uniform green-brown liquid was obtained in exactly the same manner as in Example 11.
The viscosity was 320 cps (25 ° C).

A cured product was obtained by treating the above composition in the same manner as in Example 1. The cross-linking curing conditions and performance evaluation results of the cured products of Examples 1 to 12 are shown in Table 3.

Comparative Example 1 The procedure of Example 12 was repeated except that triarylphenol was not used and divinylbenzene (purity 80%, impurities of ethylstyrene) was 100 parts. A uniform reddish brown liquid was obtained. The viscosity was 220 cps (25 ° C). A cured product was obtained by treating this composition in the same manner as in Example 1.

Comparative Example 2 Synthesis Example 1 in Example 1
A uniform yellow-brown liquid was obtained in the same manner as in Example 1 except that the novolac type phenolic resin obtained in Comparative Synthesis Example 1 was used instead of. Viscosity is 730 cps (25
℃).

A cured product was obtained by treating the above composition in the same manner as in Example 1. The cross-linking curing conditions and performance evaluation results of the cured products of Comparative Examples 1 and 2 are as shown in Table 3.

[0052]

[Table 3]

From Table 3, the cured product of the synthetic resin composition of the present invention is superior to the synthetic resin compositions previously proposed by the present inventor (Japanese Patent Laid-Open Nos. 5-51516 and 5-117337). It has heat resistance, and it is further found that the bending strength, bending elastic modulus, Rockwell hardness and moisture absorption resistance are also good.

[0054]

INDUSTRIAL APPLICABILITY The novolac type phenol resin composition of the present invention can be handled as a uniform solution, and can be cured without generating volatile components and at room temperature, and is particularly heat resistant. It is possible to obtain a cured product having excellent strength and high water absorption resistance. The obtained resin cured product retains the advantages of phenolic resin, such as flame retardancy, low smoke generation, heat resistance, and strength, while at the same time has the disadvantages of workability, curability, moldability, shrinkability, distortion, and color tone. And so on.

The synthetic resin composition of the present invention can be applied to applications to which ordinary phenol resins are applied, but various molding materials, laminates and industrial resins (adhesives or adhesives) which require particularly severe heat resistance. Best suited for use as a binder.

Claims (8)

[Claims] 1. A synthetic resin composition comprising a novolac type phenol resin and a compound (B) having at least two ethylenically unsaturated double bonds as essential components, wherein the novolac type phenol resin is contained in the molecule. A synthetic resin composition comprising a novolac type phenolic resin (A) having an ethylenically unsaturated double bond. 2. The composition according to claim 1, wherein a resin having an ortho / para ratio of 3 or more is used as the novolac type phenolic resin (A). 3. The composition according to claim 1, wherein a phenol resin obtained by reacting phenol with dicyclopentadiene is used as the novolac type phenol resin (A). 4. The composition according to claim 1, wherein the novolac type phenolic resin (A) has a number average molecular weight of 200 to 2,000. 5. At least 2 ethylenically unsaturated double bonds
The composition according to any one of claims 1 to 4, wherein the individual compound (B) is divinylbenzene. 6. An ethylenically unsaturated double bond at least 2.
5. A compound having at least one phenolic hydroxyl group and at least three ethylenically unsaturated double bonds is used as the compound (B) having at least one, and any one of claims 1 to 4 is used. Composition. 7. The composition according to claim 6, wherein the compound having at least one phenolic hydroxyl group and at least three ethylenically unsaturated double bonds is triarylphenol. 8. The weight ratio of the novolac type phenolic resin (A) to the compound (B) having at least two ethylenically unsaturated double bonds is (A) / (B) = 70/3.
The composition according to any one of claims 1 to 6, which is 0 to 40/60.