JPH02281071A - Unsaturated polyester resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition, excellent in operating efficiency in curing, heat resistance and antistatic properties by blending an unsaturated polyester resin containing an unsaturated polyester and polymerizable vinyl monomer with a specific maleinimide compound. CONSTITUTION:A resin composition obtained by blending (a) 100 pts.wt. unsaturated polyester resin prepared by dissolving an unsaturated polyester in a polymerizable vinyl monomer with (B) 0.2 to 20 pts.wt. maleimide compound, prepared by reacting, e.g. maleic anhydride with a diamine composed of a tertiary and primary amines, such as diethylaminopropylamine, preparing a maleinimide compound containing the tertiary amino group and then adding an alkyl halide thereto and expressed by the formula (R1 and R2 are H, halogen or methyl; X is 1 to 6C alkyl, cyclohexylene group, etc.; R3 to R5 are 1 to 4C straight-chain or branched alkyl; Y is halogen).

Description

Detailed Description of the Invention <Industrial Application Field> The present invention provides an unsaturated material useful as a raw material for producing a cured product that has excellent workability during curing and has excellent heat resistance, antistatic properties, etc. The present invention relates to a polyester resin composition.

<Prior Art> It is generally known that various cured molded products can be obtained from unsaturated polyester resins by curing them with heat or light in the presence of a radical polymerization initiator together with, for example, glass fibers or inorganic fillers. There is. Specifically, automobile parts, electrical parts, etc. are manufactured using unsaturated polyester resin by heat-curing molding methods such as sheet molding compound (SMC) method and bulk molding compound (BMC) method, and hand lay-up. Fishing boats, septic tanks, pool walls, etc. are manufactured using room-temperature curing methods such as the method and the spray-up method.

In these applications, resins or curing systems that have as fast a curing speed as possible are required for cycle-up during curing operations, and cured products are required to have improved heat resistance and antistatic properties.

Conventionally, in order to increase the curing speed of unsaturated polyester resin, methods such as increasing the amount of radical polymerization initiator or raising the curing temperature are known, but with these methods, the resulting cured product This causes problems such as the material becoming brittle.

In order to increase the heat resistance of the cured product, methods have been proposed, such as adding arylmaleimides to unsaturated polyester resins or adding fillers with high heat resistance (Japanese Patent Publication No. 13058/1982). On the other hand, in order to prevent the cured product from being charged, it is generally known to add an antistatic agent. However, when the filler is added, although an improvement in heat resistance is observed, other properties are degraded, and when an arylmaleimide is added, although heat resistance is improved, a problem arises in antistatic properties.

Furthermore, when a low molecular weight antistatic agent is blended, there is a drawback that the antistatic agent bleeds out from the cured product over time.

<Problems to be Solved by the Invention> The objects of the present invention are to provide a material with excellent curing workability, a fast curing speed, and
Another object of the present invention is to provide an unsaturated polyester resin composition whose cured product has high heat resistance and semi-permanent antistatic properties.

<Means for Solving the Problems> According to the present invention, the following general formula (1) (wherein R1 and R2 are each represents a hydrogen atom, a halogen atom or a methyl group, and X represents an alkyl group having 1 to 6 carbon atoms, a cyclohexylene group, a phenylene group or -CH2-0-; and R1.R4 and R each have 1 to 6 carbon atoms. An unsaturated polyester resin composition containing a maleimide compound represented by 4 (representing a straight chain or branched alkyl group, and Y representing a halogen atom) in a proportion of 0.2 to 20 parts by weight is provided.

The present invention will be explained in more detail below.

The unsaturated polyester resin composition of the present invention is characterized by containing a specific unsaturated polyester resin and a specific maleimide compound.

The unsaturated polyester resin used in the present invention contains an unsaturated polyester and a polymerizable vinyl monomer,
The unsaturated polyester is, for example, an unsaturated dibasic acid such as maleic anhydride or fumaric acid, or the unsaturated dibasic acid and a saturated dibasic acid such as phthalic anhydride, isophthalic acid, adipic acid, or tetrachlorophthalic anhydride. and a polyhydric alcohol such as ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, bisphenol dioxyethyl ether, etc. by a conventional method. Preferably, it is blended in a ratio of 1:0.5 to 2 mol, for example, 150 to 250 mol in a nitrogen atmosphere.
The acid value of the reaction solution is preferably 20 to 80.
It can be obtained by terminating the reaction when the Examples of the vinyl monomer include styrene, 0-chlorostyrene, vinyltoluene, methyl methacrylate, diallyl phthalate, triallyl cyanurate, diallylbenzenephosphonate, etc., and these may be used alone or in combination. can.

In the present invention, the unsaturated polyester resin can be prepared by dissolving the unsaturated polyester in the polymerizable vinyl monomer. Although the blending ratio during dissolution is not particularly limited, it is preferable to blend the unsaturated polyester in a ratio of 70 to 40% by weight and the polymerizable vinyl monomer in a ratio of 30 to 60% by weight.

In the present invention, the maleimide compound has the following general formula (1
) can be expressed as

In the formula, R□ and R2 each represent a hydrogen atom, a halogen atom, or a methyl group, and X is an alkyl group having 1 to 6 carbon atoms, a cyclohexylene group, a phenylene group, or -CHI Oo-
represents. In addition, R, , R4 and R7 each have 1 carbon number
-4 represents a straight chain or branched alkyl group, and Y represents a halogen atom. In this case, X has 7 or more carbon atoms, R4 and R
When the number of carbon atoms in s is 5 or more, manufacturing becomes difficult. Examples of the maleimide compound represented by the general formula (1) include N-[2-(N'-diethyl-N'-methyl)ammonium ethylcomaleimide chloride, N-
(2-(N'-diethyl-N'-methyl)ammoniumethylcomaleimide iodide, N-(3-(N'-
Diethyl-N'-methyl)ammoniumpropylcomaleimide iodide, N-(3-(N'-diethyl-N
'-Methyl)ammoniumpropylcomaleimide chloride, N-(4-(N'-trimethyl)ammoniumcyclohexylcomaleimide bromide, N-(4-
Preferred examples include (N'-trimethyl)ammoniumcyclohexyl)maleimide iodide, N-(4-(N'trimethyl)ammoniumphenylcomaleimide chloride, etc.).The maleimide compound is 5, for example, with maleic anhydride.

A maleimide compound containing a tertiary amino group is prepared by reacting with a diamine consisting of tertiary and primary amines such as diethylaminopropylamine.

It can then be prepared by adding an alkyl halide to form a quaternary ammonium base.

The blending ratio of the unsaturated polyester resin and maleimide compound in the unsaturated polyester resin composition of the present invention is as follows:
The maleimide compound is added in a proportion of 0.2 to 20 parts by weight based on 100 parts by weight of the unsaturated polyester resin. If the blending ratio of the maleimide compound is less than 0.2 parts by weight, the effect of adding the maleimide compound, that is, the increase in curing rate and the antistatic effect of the cured product, will be insufficient, and the blending ratio of the maleimide compound will be 0 to 20 parts by weight. If it exceeds this, the cured product will become brittle, so it is necessary to maintain the above-mentioned mixing ratio.

The unsaturated polyester resin composition of the present invention can be prepared by, for example, dissolving an unsaturated polyester in a polymerizable vinyl monomer to obtain an unsaturated polyester resin, and then adding and dissolving the maleimide compound. I can do it. Further, as the unsaturated polyester resin,
It is also possible to use a commercially available product in which unsaturated polyester is dissolved in a polymerizable vinyl monomer in advance. Furthermore, in order to improve the stability over time during storage of the polyester resin composition, a polymerization inhibitor such as benzoquinone or hydroquinone may be added. You can also. It is also possible to form a compound by adding an inorganic filler paste, a reinforcing agent such as glass fiber, and the like.

<Effects of the Invention> Since the unsaturated polyester resin composition of the present invention has high curing workability, particularly fast curing speed, it can be cycled up. Furthermore, the cured product obtained by curing the unsaturated polyester resin composition of the present invention has high heat resistance and semi-permanent antistatic properties, so it can be used to eliminate dust when producing secondary processed products and molded products. It is also possible to prevent the adhesion of dust, etc.

<Example> The present invention will be described in more detail below with reference to Reference Examples, Examples, and Comparative Examples, but the present invention is not limited thereto. Note that parts in the examples represent parts by weight.

After dissolving 49 g of maleic anhydride in 100 mQ of dimethylformamide, 58 g of diethylaminoethylamine was added while cooling in an ice water bath so that the reaction temperature was 25°C or less.
was added dropwise over 30 minutes. As a result, brown crystals were obtained. Next, 0.0% of hydroquinone was added to the obtained brown crystals.
When 1g was added and vacuum distillation was performed, the bath temperature was 180℃.
℃, the distillation of dimethylformamide is also 0,
At 1 mFIg and 120°C, diethylaminoethylmaleimide distilled out, resulting in 56 g of a pale yellow solid with a melting point of about 30°C. Next, 20g of the pale yellow solid obtained was
A solution of 15 g of methyl iodide dissolved in 20 mQ of acetonitrile was added under stirring to react at 25°C for 10 hours, and then added to a large amount of ethanol to form a yellow solid, i.e., N- ((2-N'
-diethyl-N'-methyl)ammonium ethylcomaleimide iodide (hereinafter abbreviated as AEI) was obtained. The melting point of the obtained AEI was 146°C. Structure 1 names and abbreviations of the obtained compounds are shown in Table 1.

According to the method of Reference Example 1, maleimide compounds shown in Table 1 were prepared. Table 1 shows the structures, names and abbreviations of the obtained compounds.

(Left below) 78 parts of maleic anhydride, 178 parts of phthalic anhydride, and 167 parts of propylene glycol were added to a four-bottle flask equipped with a stirrer, thermometer, nitrogen gas blowing tube, and condenser, and nitrogen gas was added. The mixture was stirred and gradually heated under running water.

The mixture was heated to 150° C. over about 1 hour, and stirring was continued for 1 hour. Gradually raise the reaction temperature and keep it at 210 ° C.
After distillation of condensed water stopped, the acid value of one reaction solution was measured, and when the acid value reached 40, the reaction was terminated and cooled to obtain an unsaturated polyester reaction solution. Next, 200 parts of styrene monomer and 20 parts of AEI prepared in Reference Example 1 were added to the reaction solution and stirred uniformly. Then hydroquinone 0.05
A pale yellow unsaturated polyester resin composition was obtained.

To the commercially available unsaturated polyester resin (containing styrene as a polymerizable vinyl monomer) shown in Table 2.

The maleimide compounds obtained in Reference Examples 1 to 3 shown in Table 2 were added and dissolved to prepare unsaturated polyester resin compositions. Table 2 shows the unsaturated polyester resin and maleimide compound used, and their blending amounts.

Trial 1" 1-2i Using the unsaturated polyester resin compositions prepared in Examples 1 to 4, a curing reaction was carried out under the curing conditions shown in Table 3 to produce molded products. The Percoll hardness of the obtained molded product is determined by JIS
Measured according to K-6901. Also, similarly 120X
A 12×3 m cast mold was prepared, and the heat deformation temperature and frictional charging voltage were measured.

Table 3 shows the measurement results and curing conditions.

Except that a commercially available unsaturated polyester resin composition containing no maleimide compound shown in Table 3 was used.

Molded products and cast plates were produced under the curing conditions shown in Table 3, and measurements were performed in the same manner as in Test Examples 1 to 6. Table 3 shows the measurement results and curing conditions.

(Margin below)

Claims (1)

[Claims] For 100 parts by weight of an unsaturated polyester resin containing an unsaturated polyester and a polymerizable vinyl monomer, the following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) ( In the formula, R_1 and R_2 each represent a hydrogen atom, a halogen atom, or a methyl group, and X represents an alkyl group having 1 to 6 carbon atoms, a cyclohexylene group, a phenylene group, or ▲a mathematical formula, a chemical formula, a table, etc.▼. Also R_3, R_4
and R_5 each represent a linear or branched alkyl group having 1 to 4 carbon atoms, and Y represents a halogen atom). Resin composition.