JPS62225551A - Phenolic resin composition - Google Patents

Abstract

PURPOSE:A phenolic rein composition useful as a molding material or varnish, having improved solvent resistance and impact resistance, readily producible, comprising a radically polymerizable monomer and oligomer, a phenolic resin and a polymerization catalyst as essential components. CONSTITUTION:5-75wt% of a monomer (divinylbenzene, styrene, etc.) and an oligomer (polyethylene glycol, polybutadiene, etc., having 200-5,000, preferably 400-2,000 number-average mol.wt.) containing a carbon-carbon unsaturated double bond in the molecule wherein either the monomer or the oligomer is bi- or more functional is blended with (B) a novolak or resol phenolic resin and further (C) 0.05-15wt% based on the mixture of the component A and B of a radical polymerization catalyst, preferably azo type radical polymerization catalyst such as 2,2'-azobisisobutyronitrile, etc. The blend is further mixed with a curing agent in the case where the component B is novolak phenolic resin.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a phenolic resin composition used as a molding material or a face.

Conventional technology> Phenolic resin has excellent heat resistance, chemical resistance, and solvent resistance.
It has excellent electrical and mechanical properties and is used in a wide range of fields. However, phenolic resins have nine drawbacks, such as being brittle and having low impact resistance because of their rigid molecular structure.

As a method to improve these drawbacks, there is a method of simply blending the rubber components (Br, Polym, J 15゜7
6 (1983)), rubber component? A method of chemically bonding phenol with sesame oil (Japanese Patent Publication No. 43-27492) or a method of modifying a phenol resin with a drying oil (Japanese Patent Publication No. 45-20507) is known.

<Intermediate point solved by the invention and achieved as Work 5> However, in the method of blending a rubber component with a phenolic resin, only certain rubbers such as nitrile rubber can be used due to the problem of compatibility between the rubber component and the phenolic resin. . Easily phase separated during heat curing.

The disadvantage is that the rubber component is easily extracted by solvents, resulting in poor solvent resistance.

Furthermore, the method of chemically bonding the rubber component to phenol-A fat or the method of modifying it with drying oil has the problem of high cost due to its complexity.

The present invention was developed as a result of intensive studies in view of the above circumstances, and the present invention was developed as a result of intensive studies. It is an object of the present invention to provide a phenol resin composition that has 4I@ agent properties, impact resistance, and is easily formed into an iL shape.

So many problems! Means for Solving> When the present inventors heated a mixture of a rubber component having a carbon-carbon unsaturated double bond Z in a molecule and a phenol resin with a radically weighted catalyst, the rubber component was a phenol resin. and IPN (Interpetrating Poly
Forming a mer network (interpenetrating network) structure is a perfect companion to the present invention.

V That is, the present invention is a monomer-based oligomer having lacquer 4Ii synthesis property, a phenol position (fat, a radical polymerization catalyst, and
The gist is a phenolic resin composition containing as an essential component and having a temperature of .degree.

The monomer or oligomer having the radical
Methacrylic acid ester, styrene, acrylonitrile,
It has one or more radically reactive type 2 bonds in its molecule, such as olefins or dienes such as acetylated vinyl, butadiene, and inoprene, edelene glycol di(meth)acrylate, divinylbenzene, and diallyl phthalate. These γ-polymerizable monomers may be used alone or in combination of two or more.

Next, as an oligomer having radical polymerizability, a number average molecular weight of 200 to 5,000.
The liquid polymer, which preferably has a molecular weight of 400 to 2,000, is a solid oligomer, specifically polyethylene glycol,
Polypropylene gellicol, 1,6-hexanediol, polybutadiene, polyurethane and its derivatives diacrylate, dimethacrylate, sialylate,
Triacrylate: unsaturated polyester, 1.2 polybutadiene, etc., and these oligomers may be used alone or in combination of b or more.

Here, the combination of radically polymerizable oligomers and monomers must be small (both must have two or more functionalities).The polyfunctional compound serves as a crosslinking point for the polymerization component, and is essential for making IPN@. It is an ingredient.

Next, the phenolic resin used in the present invention is a novolac type or resol type phenolic resin derived from various phenols and formaldehyde. These phenolic resins may be modified with drying oil, xylene resin, melamine resin, etc.

In the case of novolak type phenolic resin, polyamines such as hequinamine, epoxy resins, isocyanate compounds,
A curing agent such as polyformaldehyde or a resol type phenol resin is often used in combination.The amount of free 11-phenol in the phenol resin is not a particular problem in the present invention.

Next, as a radical X combination catalyst, 'C' is not particularly limited, but an azo-based superposed catalyst is preferable, and specifically, 2,2'-azobisisobutyronitrile (AIBN).

Dimethyl-2,2'-azobisbutyrate, 1,1'-
Azobis(1-cyclohexine carbonitrile), 2,2'-azobis(2,4,4-trimethylpentane), etc. are used. These M-8 catalysts can also be used alone or in combination of two or more.

The ratio of the above-mentioned monomer/oligomer to phenolic resin is such that the ratio of the rubber component is 5 to 75%. If the monomer/oligomer ratio is less than 5*fi%, there is no modification effect, and 75
If it exceeds % by weight, the curing of the phenolic resin will be slow, which is not preferable.

Although the ratio of the oligomer to the monomer is not particularly limited, the ratio of the bifunctional or higher functional compound is preferably α5 to 80% by weight, and more preferably 1 to 50% by weight.

When the phenolic resin is wrapped in a novolac type, an amount of curing agent normally used for curing the resin is added.

Next, the radical polymerization catalyst is applied to the above mixture with α05-15
] 1%, preferably 5% by weight. If the catalyst # degree is less than 105%, the crosslinking reaction will proceed and W
<S If it exceeds 1S%, the reaction proceeds rapidly, making it impossible to obtain a homogeneous cured product.

There is no restriction in any way in blending components other than the above-mentioned components in the composition according to the present invention (various fillers,
Anti-singing agents, curing accelerators, plasticizers, flame retardants, mold release agents, coloring agents, etc. may be used freely.

Is there a stirrer as a device for mixing each of the above ingredients? A mixer or a conventional kneader can be used.

By heating the mixture M obtained at °C as described above, the monomer/oligomer component having carbon-carbon unsaturated double bonds undergoes crosslinking polymerization with the radical polymerization catalyst Kj, and becomes entangled with the chains of phenolic resin molecules. The so-called interpenetrating network (In
terperjetrating Polymer N
(hereinafter abbreviated as fPN) 411) structure.

For example, Shibayama (Kobunshi Kagaku, pp. 23.24-29, 1966) et al. reported on the temperature of a polymer blend system with an IPN structure, but unlike conventional polymer blends and graft polymers, two types of Polymer meshes intertwine and form an intertwined structure.

In the polymer mixture system of iL that forms the IPN structure, there is crosslinking at least inside the polymer 1a, but there is substantially no crosslinking between different types of polymers.

Therefore, even if the component polymers are incompatible, a polymer blend yarn having an IPN structure will not undergo phase separation and will have a homogeneous structure because the networks of the two types of polymers are intertwined with each other as described above. A cured product having the following properties is obtained.

MA can be recognized by combining observation with an electron microscope, determination of viscoelasticity/mechanical properties, and measurements other than solvent extraction as a method for IPN structures, but in the present invention, light transmittance, solvent extraction, etc. Observations were made by determining the presence or absence of extracts and the tensile strength of the cured product.

<Example> The present invention will be explained below based on an example lacking the invention.

Examples 1 to 2 175 g of a resol type phenol resin (obtained by reaction under an ammonia catalyst with a formaldehyde/phenol molar ratio of 1.2 and a gel time of 2.5 minutes at 160°C) was added to 175 g of polyethylene with a molecular weight of about 1000. 30 g of glycol dimethacrylate and 45 g of 2-ethylhexyl acrylate (Example 1).
g and 30 g of ethylene glycol diacrylate (Example 2) in a 7 L AlBN 2.5 ga' flask.
The mixture was stirred and mixed at room temperature until it became homogeneous to obtain a pale yellow transparent liquid. This hostile composition was filled into a mold and heated at 170° C. for 90 minutes to obtain a cured product, which was used for testing.

On the other hand, Comparative Example 1 was prepared by omitting the AIBN produced in Example 1 and blending at °C. Further, reference example 1 was prepared by curing only the above-mentioned phenol 41!4 fat under 'a'l river conditions.

Properties 7 of the cured product are shown in Table 1.

Examples 3-4 30 g of polyethylene glycol dimethacrylate having a molecular weight of about 1000 was added to 175 g of a novolac type phenol resin (synthesized using a salt IM medium with a formaldehyde/phenol molar ratio of y11'0.8 and a softening point of 80°C). , 2-ethylhexyl acrylate) (Example 9133) 1 or 45 g of polyethylene glycol ethoxylate acrylate with a molecular weight of about 1000 1 30 g of ethylene glycol diacrylate (% flow side 4) and 2.5 g of AlBN A cured product was obtained in the same manner as in Examples 1 and 2 using 25 g of the phenol resin.
Reference Example 2 was obtained by adding hexamine equivalent to i% and curing under the same conditions.

Table 1 shows the properties of the cured product.

Table 1 (Note 1) Measurement of uniform winding was performed by visually observing the lightness of the temple with a thickness of 1.6 + n + n.

2. The solvent extractable amount was determined from the amount of weight loss of the polymer after 20 hours of extraction at THF reflux temperature from Soxhlet extraction mVc.

5. Tensile strength and elongation rate were measured using a Tensilon type tensile tester using a test piece according to JIS K71131 type test piece.

As is clear from the results shown in Table 1, the cured product obtained from the phenolic resin composition according to the present invention has a homogeneous structure and is excellent in solvent resistance and impact resistance.

〈Effect of invention〉

Claims (1)

[Scope of Claims] 1. A phenol resin composition comprising a monomer or oligomer having radical polymerizability, a phenol resin, and a radical polymerization catalyst as essential components. 2. The phenol resin composition according to claim 1, wherein either the radically polymerizable monomer or oligomer contains two or more carbon-carbon unsaturated double bonds in the molecule. 3. The phenol resin composition according to claim 1, wherein the phenol resin is a resol type phenol resin. 4. The phenolic resin composition according to claim 1, wherein the phenolic resin is a novolac type phenolic resin.