JPH06157872A - Synthetic resin composition - Google Patents

Abstract

PURPOSE:To obtain a synthetic resin composition suitable for continuous molding, not causing the dropping out of resin during molding, and having good moldability. CONSTITUTION:This resin composition is prepared by adding a thickener comprising a vinyl polymer having cyclic acetal bonds to a thermosetting resin composition comprising a novolac phenolic resin of an ortho/para ratio of 3 or above and a thermosetting resin comprising divinylbenzene, ethylstyrene and xylenesulfonic acid, and is used in pultrusion. In this way, a molding which very scarcely causes the dropping out of resin during continuous molding and so has a desired resin adhesion can easily be obtained.

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 thermosetting resin composition in which divinylbenzene is added to a novolak type phenol resin obtained by reacting phenol with formalin and an acidic catalyst is used. Has been done.

[0003]

The resin composition described in the above specification is a thermosetting liquid resin composition having a relatively low viscosity. It has a low viscosity and is easy to handle, but
For example, in the case of continuous molding methods such as pultrusion molding, if the viscosity is too low, the composition may spill from the substrate, and it may not be possible to attach the required amount of the composition. On the contrary, there are many cases in which problems occur.

Therefore, in order to increase the viscosity of the composition, the applicant tried to thicken it by adding various thickening agents. However, depending on the type of the thickener, there is a drawback that the composition is not uniformly mixed with the composition, or even if the composition can be mixed, the physical properties of the cured product are significantly impaired.

[0005]

Means for Solving the Problems The inventors of the present invention have made extensive studies in view of the above situation, and by using a vinyl polymer having a cyclic acetal bond as a thickener, the viscosity of the composition can be remarkably increased, Moreover, they have found that a cured product having good physical properties can be obtained, and completed the present invention.

That is, the present invention relates to a phenolic resin (A)
And a vinyl polymer (C) having a cyclic acetal bond and divinylbenzenes (B) as essential components.

In the present invention, the phenolic resin (A)
Is a generic name for synthetic resins obtained by reacting phenols as essential components, synthetic resins obtained by reacting phenols with formaldehyde supply substances as essential components, synthetic resins obtained by the reaction of phenols and dimethoxyxylylene. , A synthetic resin obtained by the reaction of phenols and divinylbenzene and a synthetic resin obtained by the reaction of phenols and dicycloalkadienes.

The resin (A) used in the present invention is
Any known and commonly used one can be used, but one having a number average molecular weight of 200 to 2000 is preferable, and one having a number average molecular weight of 400 to 1000 is particularly preferable.

Further, according to the findings of the present inventors, a novolac type phenolic resin having an ortho-para ratio of 3 or more is excellent in compatibility with the divinylbenzenes (B) as the resin (A). I understood.

As the phenols used in the production of the resin (A) used in the present invention, any of the known and commonly used phenols can be used. For example, phenol and bisphenols such as bisphenol F, bisphenol A and bisphenol AF can be used. , Cresols, alkyl-substituted phenols such as P-tert-butylphenol, halogenophenols such as bromophenol, aromatic hydrocarbons containing two or more phenolic hydroxyl groups such as resorcin,
Examples thereof include naphthols such as 1-naphthol, 2-naphthol, 1,6-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene. These phenols may be used alone or as a mixture of two or more kinds.

Examples of the formaldehyde supplying substance include an aqueous formaldehyde solution and paraformaldehyde.

The catalyst for obtaining the synthetic resin obtained by reacting the phenols as the resin (A) with the formaldehyde supplying substance as essential components is not particularly limited, but examples thereof include sulfuric acid, oxalic acid, zinc acetate and the like.

In producing the resin (A), furfural, urea, melamine, acetoguanamine, benzoguanamine and the like may be used in combination with phenols, if necessary. Further, a co-condensation may be carried out by further adding a formaldehyde supply source such as paraformaldehyde.

The above reaction may be carried out in the presence of an organic solvent, or an organic solvent may be added to the obtained reaction product.
The organic solvent used at this time is not particularly limited. The reaction may be carried out in a batch kettle or in a tubular reactor with static mixing elements. The resin (A) may be used alone, but it is also possible to use a mixture of several different types.

As the divinylbenzenes (B) used in the present invention, any known one can be used,
For example, divinylbenzene, alkyldivinylbenzene,
Examples thereof include halogen-substituted compounds, but divinylbenzene is most preferable in consideration of reactivity, workability and the like.

The divinylbenzenes (B) used in the present invention may be used alone, or may be used as a mixture of two or more kinds and further containing other third component.

Examples of the other third component in this case include aromatic monovinyl compounds such as styrene, methylstyrene, ethylstyrene, and monobromostyrene, (meth) acrylic acid methyl ester, (meth) acrylic acid stearyl ester, ( Examples thereof include aliphatic monovinyl compounds such as (meth) acrylic acid, N-methylol (meth) acrylamide, and γ-mercaptopropyltrimethoxysilane.
These third components may be used alone or in combination of two or more. The preferred third component to be used in combination is an aromatic monovinyl compound having good cationic polymerizability.

The vinyl polymer (C) having a cyclic acetal bond in the present invention is usually used as a thickener. The cyclic acetal bond has the following structure.

[0019]

[Chemical 1]

(R is hydrogen or an alkyl group.) In the above vinyl-based polymer (C), for example, one in which R in the cyclic acetal bond is hydrogen is polyvinyl formal, and one in which R is a propyl group is polyvinyl butyral. Is.

According to the knowledge of the present inventors, surprisingly, the cured product cured with the vinyl polymer (C) has an improved tensile strength as compared with the cured product cured without it. Was found. It was also found that polyvinyl butyral has extremely excellent solubility in a mixture of components (A) and (B).

The vinyl polymer (C) may be any vinyl polymer having the above-mentioned cyclic acetal bond, and may further have a hydroxyl group or an acetyl group. Further, it is effective to use a vinyl polymer having a high molecular weight as much as possible within a range in which the components (A) and (B) can be sufficiently mixed and dissolved.

The vinyl polymer (C) can be easily obtained by reacting polyvinyl alcohol with an aldehyde, for example.

The amount of the vinyl polymer (C) to be used is not particularly limited, and the amount required to develop the desired viscosity is usually applied to the synthetic resin composition comprising the component (A) and the component (B). Just add it. Specifically, the components (A) and (B)
0.01 to 50 parts by weight, preferably 1 to 5 parts by weight, is added per 100 parts by weight in total.

According to the knowledge of the present inventors, the thickening effect of the composition is that when polyvinyl butyral is used as the vinyl-based polymer, for example, only 3% by weight is added, and the initial viscosity is 10% of the initial viscosity when not added. It was found that the viscosity increased more than double.

The vinyl polymer (C) may be used alone, or may be used in combination with, for example, polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride.

The mixing ratio of the components (A), (B) and (C) in preparing the synthetic resin composition of the present invention is not particularly limited. The ratio of (A) and (B) varies depending on the types of the phenolic resin (A) and the divinylbenzenes (B) used, but usually the skeleton of the phenolic resin in the resin (A), that is, the bond of the phenolic skeleton. The total number of reaction bonds of the unsaturated double bonds of the methylene group in the phenol resin and the divinylbenzenes is made equal to or less than the equivalent number. It is preferably in the range of 1 equivalent to 0.8 equivalent.

Since the resin (A) is a phenolic substance that acts as a polymerization inhibitor, the resin (A) and the divinylbenzenes (B) can be blended at room temperature or under heating. However, considering safety, it is preferable to mix at a temperature as close to room temperature as possible.

The vinyl polymer (C) may be heated and melted in a mixture of the components (A) and (B), or the vinyl polymer (C) may be previously dissolved in the component (B). The mixture may be added to (A). Further, in the case where the final use method does not cause any problem even if the solvent is contained, the solvent may be added if necessary, and the thickener may be dissolved in the solvent and blended.

As the solvent in this case, any conventionally known solvent can be used. For example, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol and ethanol, hydrocarbons such as toluene and xylene, ethyl acetate and Esters such as butyl acetate can be used.

The synthetic resin composition of the present invention obtained as described above may further contain a curing accelerator if necessary,
It can be cured at room temperature or by heating.

Examples of the curing accelerator include metal chlorides such as aluminum chloride and stannous chloride, sulfuric acid, hydrochloric acid,
Inorganic acids such as phosphoric acid, organic sulfonic acids such as benzene sulfonic acid, paratoluene sulfonic acid, organic carboxylic acids such as acetic acid, oxalic acid, and maleic acid, as well as sulfo compounds derived from the resin (A), Latent catalysts represented by phosphites such as phosphorus monophenyl, esters derived from sulfuric acid and organic sulfonic acids, such as methyl p-toluene sulfonate, and salts such as ammonium chloride, that is, at a certain temperature It also includes those that decompose below to produce acidic components. These curing accelerators may be used alone or in combination of two or more.

In addition to the curing accelerators shown above, their halides, for example, aromatic rings such as aromatic sulfonic acids such as bromophenol sulfonic acid, fluorophenol sulfonic acid, trifluoromethylphenol sulfonic acid, etc. It is also possible to use a compound in which a hydrogen atom is replaced by a halogen atom or an atomic group having a halogen atom, or a compound in which a hydrogen atom of an alkyl group such as trifluoromethylcarboxylic acid and monobromoacetic acid is replaced by a halogen atom.

As the curing accelerator, organic sulfonic acid is preferable because a uniform solution can be easily obtained and the curing rate can be easily adjusted. The amount of the curing accelerator used is not limited, but is 0.1 per 100 parts by weight of the curing agent.
-5 parts by weight is preferred. It is also effective in some cases to use a mixture of the above-mentioned usual curing accelerator and the latent catalyst.

Further, as another curing means, active energy rays can be used, for example, curing with ultraviolet rays using a photocationic polymerization catalyst such as allyldiazonium salt, diallyliodonium salt, allylsulfonium salt and iron-allene complex. You can also

The curing time of the synthetic resin composition of the present invention depends on the types of resins (A), divinylbenzenes (B), thickeners (C) used, mixing ratio, curing means, types of curing accelerators and catalysts. It depends on the amount used and the amount used, so it is preferable to mix them appropriately and to try to cure them to select the optimum conditions.

When an organic sulfonic acid such as benzene sulfonic acid or paratoluene sulfonic acid is used as the above-mentioned curing accelerator, the organic sulfonic acid can be used, for example, in the production of the resin (A). It is preferable to use it in a diluted state by dissolving it in, because the composition can be cured uniformly without causing gel locally.

Since the synthetic resin composition of the present invention is excellent in the mixed solubility of the resin (A) and the divinylbenzenes (B), it can be handled as a stable solution and hardened as compared with the dispersion liquid. Since the reaction is a polyaddition of vinyl groups and ferils, there is no generation of gas at the time of curing unlike conventional phenolic resins, and moldability is good.

In the composition of the present invention, the desired viscosity can be adjusted as necessary by adding the vinyl polymer (C) to the conventional composition. And continuous molding such as fragment winding molding are possible, and it can be applied to a wider range of applications in the molding field.

Further, a vinyl polymer (C) is used as a thickener.
It can be said that the present composition is very effective, since the performance of the cured product is not deteriorated even if it is used and the tensile strength is rather improved.

The synthetic resin composition of the present invention can be used not only by curing the synthetic resin composition alone, but also by curing it together with known and commonly used reinforcing materials and fillers, which is useful for various purposes. It will be

The synthetic resin composition of the present invention may be cured by itself, but it may be cross-linked and cured by compounding with a reinforcing material and a filler to be molded. The molding method is not particularly limited, but for example, prepreg laminated compression molding, injection molding method, RIM method (reactive injection molding), SMC method, hand layup method, pultrusion molding method, filament winding molding method, etc. are adopted. can do.

The synthetic resin composition of the present invention solves the drawbacks of the conventional thermosetting novolak type phenolic resin composition such as workability and curability, and has the advantages of flame retardancy and low smoke generation. Since it also has heat resistance, strength, etc., for example, various molding materials, glass fiber sizing agents, binders for foundry sand, binders for grinding wheels, adhesives, binders for friction materials, bonds for fireproof materials, etc. Agents, binders for heat insulating materials, semiconductor encapsulation materials, electrical insulation laminates, foam materials, resin concrete, rubber reinforcing agents, paints for various applications, binders for filters, coating agents, etc. It can be used not only in the fields described above, but also in the fields where resol type phenolic resins, unsaturated polyester resins, etc. have been used, and it is expected that the performance will be improved.

[0044]

EXAMPLES The present invention will now be described in detail with reference to Examples.
Hereinafter, unless otherwise specified, “part” means “part by weight” and “%” means “% by weight”.

Reference Example [Synthesis Example of Resin (A)] In a four-necked 3 liter flask equipped with a stirrer, a condenser, a thermometer and a 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.

After that, the resin layer was heated to remove residual water, and the temperature was raised to 170.degree. After partially removing the free phenol at 170 ° C. under reduced pressure, the product was taken out from the reaction container to obtain a solid novolac type phenol resin. When this resin was washed 10 times with water, the content of zinc acetate was 0.003 ppm. This was heated again to remove residual water, and a solid novolac type phenol resin was obtained. This solid novolac type phenol resin is an ortho-
The para ratio was 3 or more.

Example 1 80 parts of a mixture of 64 parts of divinylbenzene and 16 parts of ethylstyrene and 5 parts of methanol were dissolved in 100 parts of the solid novolac-type phenol resin of Reference Example at 50 ° C. to obtain a viscosity of 60 cps (25 A homogeneous yellow-brown solution was obtained. This is referred to as Formulation Liquid 1. Further, 4 parts of S-REC BBL-1 [polyvinyl butyral manufactured by Sekisui Chemical Co., Ltd.] was added to the blended liquid 1, and the polyvinyl butyral was completely dissolved while stirring at 50 ° C. for 30 minutes. At this time, the viscosity was 800 cps.

Xylene sulfonic acid 0.82 was added to this composition.
Parts were added and mixed well. This compounded liquid was impregnated with glass fibers having polyvinyl acetate as a sizing agent, and the resin composition-impregnated glass fibers were taken out through a circular guide having a predetermined area to remove excess composition, and the adhesion rate was 30%. Adjusted so that 6 in the dryer
After preliminarily drying at 0 ° C. for 5 minutes, it was passed through a cylindrical drawing die having a diameter of 7 mm at 150 ° C., and pultrusion molding was carried out at a pulling time of 5 minutes. This was further post-cured at 180 ° C. for 1 hour to obtain a molded product.

The above composition was liquid and had good drawability, and no gas was generated during curing. Further, this molded product had more excellent tensile strength than that of Comparative Example 1. The flexural strength and flexural modulus of the molded product were measured. Table 1 shows the measurement results and moldability.
It was shown to.

Comparative Example 1 Formulation 1 was obtained in exactly the same manner as in Example 1. Viscosity is 60
It is cPs. Xylene sulfonic acid 0.8
Add 2 parts and mix well. A glass fiber having a polyvinyl acetate as a sizing agent was impregnated into the compounded liquid containing no S-REC BBL-1 and molding was carried out in the same manner as in Examples to obtain a molded product.

The flexural strength and flexural modulus of this cured product were measured. The measurement results and moldability are shown in Table-1.

Comparative Example 2 A mixed solution was prepared in the same manner as in Example 1 except that the same amount of carboxymethyl cellulose, which is well known as a thickener, was used in place of S-REC B BL-1. It did not dissolve in and was separated. The separated blended liquid was well stirred and subjected to pultrusion molding, but immediately separated, and only a molded product having inferior performance to the molded product of Comparative Example 1 using the composition without addition was obtained. I couldn't do it.

[0053]

[Table 1]

As can be seen from the above-mentioned Example 1 and Comparative Examples 1 and 2, the composition of the present invention has a higher viscosity and good impregnation / coating work. Therefore, even in the continuous molding method such as pultrusion molding, the resin composition is It can be seen that a molded product having a desired resin adhesion amount can be easily obtained without dropping off.

[0055]

According to the present invention, US Pat. No. 4,200,706 is used.
In a system of a curable resin composition comprising a novolac type phenolic resin, divinylbenzene and an acidic catalyst, as described in Japanese Patent No. 3,898,982, a vinyl polymer having a cyclic acetal bond as a thickener. In addition, in a continuous molding method such as pultrusion molding, a particularly remarkable effect that the moldability can be significantly improved is exhibited.

Claims (3)

[Claims] 1. A synthetic resin composition containing a phenolic resin (A), a divinylbenzenes (B) and a vinylic polymer (C) having a cyclic acetal bond as essential components. 2. The composition according to claim 1, wherein the vinyl polymer (C) is polyvinyl butyral. 3. The composition according to claim 1, wherein the phenolic resin (A) is a novolac type phenolic resin having an ortho-para ratio of 3 or more.