JPH06166800A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition capable of freely regulating the objective physical properties due to a wide range of an added modifier, good in operating efficiency and capable of performing the hybridization and providing a solventless state by blending an epoxy resin with a specific liquid resin as the modifier. CONSTITUTION:The objective composition is obtained by including a liquid resin prepared by copolymerizing (A) phenols with (B) a fraction, obtained by thermally cracking petroleums and consisting essentially of hydrocarbons having 140-280 deg.C boiling point using an acidic catalyst (preferably a solid acid catalyst such as silica/alumina or an ion exchange resin) in an amount of preferably 5-100 pts.wt. based on 100 pts.wt. epoxy resin. The component (A) is usually obtained as a thermal cracking by product oil in thermally cracking naphtha, LPG, etc., for producing ethylene, propylene, etc. The liquid resin preferably has 100-30000cP viscosity and 40-280KOHmmg/g hydroxyl value.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an epoxy resin composition. More specifically, it relates to an epoxy resin composition prepared by blending a specific liquid resin as a modifier.

[0002]

2. Description of the Related Art Epoxy resins are used in a wide range of fields such as civil engineering, construction, paints, adhesives, etc., but when applied to these applications, workability is always a problem and low viscosity is required from this point of view. Has been done. As is well known, bisphenol A type epoxy resin, which is a general-purpose epoxy resin, has a viscosity of about 80 to 150 poise at room temperature, and it is used in a solventless system for applications such as impregnation, casting and coating. In that case, the viscosity decreases from the point where the viscosity is high, so it is always necessary to use a diluent together. In addition, studies have been made to reduce the viscosity of the epoxy resin itself, but this is not yet sufficient.

Conventionally known viscosity reducing agents include reactive diluents and non-reactive diluents. Typical examples of the reactive diluents are phenyl glycidyl ether, butyl glycidyl ether and cresyl glycidyl. Ethers, allylglycidyl ethers, styrene oxides, butanediol-diglycidyl ethers, hexanediol-diglycidyl ethers, polyoxyalkylene glycol-glycidyl ethers, low viscosity mono- or di-olefins such as olefin oxides Non-reactive diluents include organic solvents such as benzene, toluene, xylene, pine oil, benzyl alcohol, furfuryl alcohol, biphenyls, propylene glycol, phthalic acid esters, and co-solvents. Examples include tar and white tars, all of which are practical It has been put.

However, these diluents have the following drawbacks. For example, a reactive diluent generally has relatively good performance as a cured product, but is expensive. Since it has an epoxy group in the molecule, it can be premixed on the epoxy side but cannot be mixed on the curing agent side, and it has toxicity. There is a drawback in terms of workability.

On the other hand, many non-reactive diluents have difficulty in compatibility with epoxy resins and curing agents, and addition of these non-reactive diluents having poor compatibility remarkably improves the physical properties of the obtained cured product. In addition to being limited to a small amount to reduce,
When the cured product is exposed to the outdoors for a long period of time, an undesirable phenomenon such as bleeding of the diluent or evaporation of the diluent from the cured product and deterioration of performance is often observed. In addition, the use of volatile organic solvents causes environmental pollution such as poisoning.

Further, in the field of epoxy resin paints and the like, solid resins such as xylene resins and petroleum resins are used as modifiers in order to improve adhesion and weather resistance. However, since these resins are solid, it is necessary to use an organic solvent and the like, which causes a phenomenon such as drying properties and thinning of the cured product, which causes a drawback that thick coating cannot be performed. In recent years, liquid modifiers have been proposed in order to solve these drawbacks, and are aimed at achieving high solids and solvent-free properties. However, no satisfactory liquid modifier has been proposed yet.

[0007]

The object of the present invention is to solve these problems and improve the compatibility with epoxy resins.
Even if added in a large amount, there is no deterioration in the physical properties of the cured product or bleeding,
It is an object of the present invention to provide a modifier made of a liquid resin containing phenols which enables high solidification and solvent-free, and an epoxy resin composition containing the same.

[0008]

The present inventors have completed the present invention as a result of intensive studies to improve the drawbacks of conventional plasticizers, diluents and modifiers and to achieve the above object. It is a thing.

That is, as a means for solving the above problems, the first aspect of the present invention mainly comprises phenols and hydrocarbons having a boiling point of 140 to 280 ° C. obtained by thermal decomposition of petroleum. The present invention relates to an epoxy resin composition comprising a liquid resin obtained by copolymerizing a fraction in the presence of an acid catalyst.

In the second aspect of the present invention, a fraction mainly containing hydrocarbons having a boiling point of 140 to 280 ° C. obtained by thermal decomposition of petroleum is copolymerized with phenols in the presence of an acid catalyst. It relates to a modifier for an epoxy resin, which is composed of a liquid resin obtained as described above.

The present invention will be described in detail below. In the present invention, any conventionally known epoxy resin can be used. Usually, epoxy resin is epoxy,
It is a resin containing two or more three-membered ring ether groups called 1,2-epoxide or oxirane in its molecule, and is a monomer or prepolymer that gives a thermosetting plastic by reaction with a curing agent.

Generally, a condensation reaction product of a polyfunctional halohydrin and a polyvalent phenol is commercially available as an epoxy resin. Typical polyvalent phenols used in the production of epoxy resins include, for example, various bisphenols which are condensation products of resorcin or phenol with aldehydes or ketones such as formaldehyde, acetaldehyde, acetone and methyl ethyl ketone, There are low molecular weight phenol-aldehyde condensation products, that is, novolak resins.

One of the raw materials of the liquid resin used in the present invention is obtained during the thermal decomposition of petroleum such as naphtha, LPG or butane which is widely used industrially for producing ethylene, propylene and the like. It is a pyrolysis byproduct oil and is a fraction mainly containing hydrocarbons having a boiling point in the range of 140 to 280 ° C. Usually, the fraction mainly contains various aromatic hydrocarbons having 9 carbon atoms such as vinyltoluene and indene, and the content of the unsaturated hydrocarbon component which can be copolymerized is 30 to 70% by weight.

The phenols to be copolymerized in the present invention are
Phenol; naphthol; cresol, xylenol or ethylphenol, isopropylphenol, t
alkylphenols such as ert-butylphenol, tert-octylphenol, nonylphenol; aralkyl or arylphenols such as phenylphenol, benzylphenol, etc., which may be used alone or in combination. Can be used.

The catalyst used in the present invention is an acid catalyst,
For example, Bronsted acid type acid catalysts such as sulfuric acid and Nafion (trade name), aluminum chloride, boron trifluoride,
Examples thereof include Lewis acid type acid catalysts such as silica / alumina, and any acid catalyst can be used.

It is preferable to use a solid acid catalyst such as silica / alumina, activated clay or an ion exchange resin from the viewpoint of easy removal of the catalyst after polymerization.

In the present invention, phenol is used in an amount of 0.5 to 5 mol, preferably 0.5 to 2.5 mol, per 1 mol of the above-mentioned polymerizable unsaturated hydrocarbon. Pheno
If the amount of the resin is less than 0.5 mol, the viscosity of the liquid resin obtained by the polymerization at room temperature will be high and the compatibility with the epoxy resin will be poor. On the other hand, if the amount is more than 5 mol, there is a disadvantage that the resin yield is deteriorated, which is not preferable.

The method for polymerizing the phenols and the liquid unsaturated hydrocarbon may be either a fixed bed flow type or a batch type. For example, when using a silica-alumina catalyst as the acid catalyst in a batch-wise polymerization, the polymerization conditions are: a polymerization temperature of 80 to 200 ° C., a polymerization time of 0.5 to 6 hours,
The amount of the catalyst is 5 to 50% by weight with respect to the polymerizable unsaturated hydrocarbon, but is not limited to this range.

After completion of the polymerization, the catalyst is removed by an appropriate method,
The liquid resin of the present invention is obtained by removing the unreacted components by a method such as conventional distillation.

The liquid resin of the present invention is a resin which is liquid at room temperature and which is polymerized by the above-mentioned method, and has a viscosity of 100 to 100,000 c.
P (25 ° C.), preferably 100 to 30,000 cP, and when the viscosity is higher than 100,000 cP, high solidification and solvent-free are difficult.

The hydroxyl value is 10 to 280 KOH.
mmg / g, preferably 40-280 KOH mmg / g
However, if it is lower than 10 KOH mmg / g, the compatibility with the epoxy resin becomes poor.

The liquid resin of the present invention generally varies from 5 to 200 parts by weight to 100 parts by weight of the epoxy resin, though it varies depending on the physical properties required for the intended compound or cured product, such as viscosity and mechanical properties. Parts, preferably 5-10
Used in the range of 0 parts by weight. When the amount of the liquid resin is less than 5 parts by weight, the effects of dilution, plasticization and modification are not remarkable, while when it is more than 200 parts by weight, the performance of the epoxy resin cured product is extremely deteriorated. There is no phenomenon. The liquid resin may be used after being mixed with the epoxy resin at the beginning of mixing, or may be used after being mixed with the curing agent.

As the curing agent, those generally used as curing agents for epoxy resins are used. For example, amines having two or more active hydrogens in the molecule, such as ethylenediamine, diethylenetriamine, triethylenetetramine, benzyldimethylamine, dimethylaminomethylphenol, trimethylaminomethylphenol, piperidine, pyridine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, dimer acid polyamide, adipic acid dihydrazide, etc .; linoleic acid dimer, etc. were reacted with ethylenediamine, etc. Polyamide resin: Organic acid anhydrides such as oxalic acid, furanic acid anhydride, maleic acid anhydride, hexahydrophthalic acid anhydride, dodecylsuccinic acid anhydride and the like can be mentioned, but not limited thereto.

In the epoxy resin composition of the present invention, other known plasticizers, organic solvents, reactive or non-reactive diluents, extenders, fillers, reinforcing agents, etc. may be added, if necessary.
Various additives such as pigments, flame retardants, thickeners, accelerators and flexibility-imparting agents can be added.

[0025]

EXAMPLES The present invention will be specifically described below based on Examples and the like.

Production Example 1 (Preparation of Liquid Resin 1) A flask equipped with a thermometer and a stirrer was charged with phenol and a silica / alumina catalyst (manufactured by Nippon Shokubai Kasei Co., Ltd., alumina content 28%) while stirring. Heated to 130 ° C, boiling point 1 which is a pyrolysis by-product oil from naphtha crackers
Pyrolysis by-product oil mainly containing hydrocarbons in the range of 40 to 280 ° C. (hereinafter referred to as cracked oil A. The unsaturated hydrocarbon content was 67% by weight) was required for 1 hour. Dripping,
Then, the temperature was kept at 130 ° C. for 3 hours for copolymerization. The unsaturated hydrocarbon component of cracked oil A and the molar ratio of phenol were 1: 2, and the catalytic amount corresponded to 20% by weight of the unsaturated hydrocarbon component of cracked oil A. After the polymerization, the catalyst was filtered and unreacted substances were removed by distillation to obtain liquid resin 1.

Production Example 2 (Preparation of Liquid Resin 2) Liquid Resin 2 was obtained in the same manner as Liquid Resin 1 except that the ratio of cracked oil A to phenol was 1: 0.8.

Production Example 3 (Preparation of Liquid Resin 3) Except that the catalyst was changed to activated clay (manufactured by Mizusawa Chemical Co., Ltd., trade name Galeonace NSR) and the polymerization temperature was 150 ° C.,
Liquid resin 3 was obtained in the same manner as liquid resin 1.

Production Example 4 (Preparation of Liquid Resin 4) The cracked oil A is further distilled to give a boiling point of 140 to 17
Liquid resin 4 was obtained by polymerizing in the same manner as liquid resin 1 except that a fraction mainly containing hydrocarbons in the range of 5 ° C. was obtained and used as cracked oil A. Table 1 shows the properties (appearance, viscosity, OH value, hue) of these liquid resins 1 to 4.

[0030]

[Table 1]

Examples 1 to 5 and Comparative Examples 1 to 2 Liquid resins 1 to 4 were mixed at the blending ratios shown in Table 2 with a bisphenol A type epoxy resin (manufactured by Shell Chemical Co., trade name Epicort 828, epoxy equivalent 184). ~ 194, molecular weight about 3
80, viscosity 12000 to 15000 cP @ 25 ° C) and cured with TEPA (tetraethylenepentamine) (100 ° C x 1 hour), and the resulting cured product has an appearance (○; good appearance, Δ; poor appearance). ), The condition of the surface bleeding after 24 hours of curing (bleeding from the cured product), cracking of the cured product due to reaction shrinkage, etc. were observed.

For comparison, DOP (Comparative Example 1) and alkylbenzene (dodecylbenzene) (Comparative Example 2) were also mixed with the epoxy resin in the same manner as the liquid resins 1 to 4 and cured in the same manner. The results are shown in Table 2.

[0033]

[Table 2]

[0034]

From the above description, the epoxy resin composition of the present invention can be used in a wide range of fields such as paints, flooring agents and adhesives, and is different from conventionally used modifiers for epoxy resins. Since the liquid resin having excellent compatibility with the epoxy resin is used, the range of addition is wide, and the desired physical properties can be freely adjusted, so that it can be used in a wide range of fields. Further, since the modifier is liquid, an organic solvent is unnecessary, and there is no fear of environmental pollution. Therefore, the liquid resin of the present invention can be used not only as a modifier but also as a diluent or a plasticizer. Further, the epoxy resin composition of the present invention has improved industrial workability and has high industrial value because it can be made high solid and solvent-free.

Claims (2)

[Claims] 1. A liquid resin obtained by copolymerizing phenols and a fraction mainly containing hydrocarbons having a boiling point of 140 to 280 ° C. obtained by thermal decomposition of petroleum with an acid catalyst. An epoxy resin composition comprising: 2. A liquid resin obtained by copolymerizing phenols and a fraction mainly containing hydrocarbons having a boiling point of 140 to 280 ° C. obtained by thermal decomposition of petroleum with an acid catalyst. A modifier for an epoxy resin, characterized in that