JPS63159466A - Unsaturated polyester resin composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. which does not cause interference in curing by the addition of a nitrite and gives good laminates and cast products, by incorporating a specified amount of an N,N-dialkylaniline (derivative) in an unsaturated polyester and a polymerizable monomer. CONSTITUTION:An unsaturated polyester resin compsn. contains an unsaturated polyester (A), a polymerizable monomer (B) (e.g., styrene) and 0.7-2.0wt% (based on the total amount of the components A and B) N,N-dialkylaniline or derivative (C) (e.g., N,N-dimethylaniline). It is known that an unsaturated polyester resin composed of the compds. A and B can be cured in the presence of diacyl peroxide and the compd. C at room temp. However, the curing reactivity is so high that the amount of the compd. C may be as low as 0.01-0.2wt% based on that of the resin. However, interference in curing with a nitrite cannot be prevented. When 0.7-2.0wt% compd. C is incorporated, the curing is hardly affected by the nitrite and no interference in curing occurs.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an unsaturated polyester resin composition that can be used to produce unsaturated polyester resin laminates and cast products without causing curing inhibition.

(Prior Art) Unsaturated polyester resin laminates are used for bathtubs, septic tanks, ships, automobile parts, tanks, etc., and cast products are also used for many purposes such as building materials, artificial marble, and electrical parts. These products are obtained by curing an unsaturated polyester resin composition mixed with a filler, but when nitrite is mixed in, curing by diacyl peroxide and N,N-dialkylaniline or its derivatives is significantly inhibited. It turned out that. It was subsequently discovered that even in unsaturated polyester resin compositions that do not contain fillers, curing is inhibited if nitrites are mixed in.

However, there is no conventional technology for preventing curing inhibition of unsaturated polyester resin compositions caused by nitrites, and a method for preventing curing inhibition of unsaturated polyester resin compositions caused by hydroxide steel is disclosed in JP-A-59-77396. Showa 59-58
This method is only disclosed in Japanese Patent Application Laid-open No. 394, Japanese Patent Application Laid-Open No. 59-58395, and the like.

(Problems to be Solved by the Invention) Sodium, which is disclosed in JP-A-59-77396, is added to an unsaturated polyester resin composition to which nitrite is added.
After adding and mixing an aqueous solution of magnesium or calcium hydroxide, curing with diacyl peroxide and N,N-dialkylaniline or its derivatives did not prevent curing inhibition, but only molded products with low hardness and low mechanical strength were obtained. could not. Furthermore, when powders of sodium, magnesium, or calcium hydroxides or oxides were added and mixed, hardly any effect of preventing curing inhibition was observed. Moreover, these powders do not dissolve in the unsaturated polyester resin composition but precipitate.

It cannot be used for products where appearance is important, such as transparent cast products.

The present invention provides an unsaturated polyester resin composition that can be used to produce good unsaturated polyester resin laminates and cast products without causing curing inhibition due to nitrites.

(Means for Solving the Problems) The present invention provides an unsaturated polyester, a polymerizable monomer, and an unsaturated polyester and a polymerizable monomer of 0.7
The present invention relates to an unsaturated polyester resin composition containing ~2.0% by weight of N,N-dialkylaniline or a derivative thereof.

Curing of an unsaturated polyester resin consisting of an unsaturated polyester and a polymerizable monomer is performed using diacyl peroxide and N.
, N-dimethylaniline and its derivatives are often cured at room temperature. However, N,N-dialkylaniline or its derivatives have very good curing reactivity of unsaturated polyester resins with diacyl peroxide, so the amount used is 0.000% compared to conventional unsaturated polyester resins. A range of 0.01 to 0.2 weight was considered to be good. In particular, when adding and mixing to unsaturated polyester resin using equipment such as an injection pump before molding, the amount used is small.

Usually, N,N-dialkylaniline or its derivatives are used in a solvent such as toluene, xylene, or styrene.

Dissolved in polymerizable monomers such as methyl methacrylate.

A method was adopted in which injection errors due to nine devices were reduced by using the solution as a 5-20% by weight solution. N, N-
It has not been conventional to use dialkylaniline or a derivative thereof in an amount of 0.7 to 2% by weight based on the unsaturated polyester and the polymerizable monomer.

By using the amount within this range, curing inhibition caused by nitrite can be prevented and good molded products can be produced.

(Function) Nitrite as used in the present invention means an alkali metal or alkaline earth metal salt of nitrous acid, and when it absorbs moisture or is heat treated together with a filler, its hardening inhibiting effect becomes greater. The greater the amount of nitrite added, the greater the curing inhibiting effect, but if it is added at 0.07% by weight or more to the unsaturated polyester resin, the gelation time at room temperature will be approximately twice as long as when no nitrite is added. This results in a molded product with low hardness.

Next is the unsaturated polyester used in the present invention.

There are no particular limitations, and acid components include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, mesaconic acid; α, β-unsaturated dibasic acids such as chlorinated maleic acid, and phthalic anhydride as necessary. acid.

Saturated polybasic acids such as isophthalic acid, terephthalic acid, monochlorophthalic acid, het acid, endomethylenetetrahydrophthalic anhydride, tetrahydrophthalic anhydride, adipic acid, succinic acid, trimellitic anhydride, and ethylene glycol and propylene as alcohol components. Glycol, diethylene glycol 1 di/'robylene glycol, triethylene glycol, 1,3-butylene glycol, 1
．． 4-butylene glycol, neopentyl glycol,
Dioxyethyl ether adduct of hexamethylene glycol, hydrogenated bisphenol, and bisphenol A.

It is a condensate of bisphenol A with glycol, such as a dioxypropyl ether adduct. It is also possible to add desired amounts of alcohol components such as glycerin, trimethylolpropane, and pentalit.

The ratio of the acid component to the alcohol component is preferably such that the alcohol component is in excess of 3 to 90 moles relative to the acid component,
More preferably, the amount is in excess of 8 to 45%. If the alcohol component excess ratio is small, it takes a long time to reach a predetermined acid value, and it tends to gel easily, and even as an unsaturated polyester resin, it tends to have poor storage stability. If the alcohol component excess ratio is too large, the mechanical strength, water resistance, and chemical resistance of the molded article tend to decrease.

As the polymerizable monomer, all polymerizable monomers that can be copolymerized with unsaturated polyester can be used.

Typical examples include styrene, α-methylstyrene, vinyltoluene, chlorostyrene, cyhinylbenzene, alkyl esters of acrylic acid or methacrylic acid,
Vinyl acetate, acrylonitrile, trimethylolpropane diallyl ether.

Examples include diallyl phthalate. The amount of the polymerizable monomer to be used is preferably in the range of 20 to 80'i, based on the total amount of the unsaturated polyester, due to problems in one operation, curing shrinkage, and the like.

The unsaturated polyester resin composition of the present invention is as follows.

It is cured with diacyl peroxide, but as diacyl peroxide, benzoyl peroxide? Do-parachlorobenzoyl peroxide.

There are inbutyryl peroxide, 2,4-dichlorobenzoyl peroxide, acetyl peroxide, decanoyl peroxide, lauroyl peroxide, succinic acid peroxide, etc., and the amount used is 0 relative to the unsaturated polyester resin composition. A range of .5 to 2% by weight is preferred.

As N,N-dialkylaniline or its derivative,
N,N-dimethylaniline, N,N-diethylaniline, methylethylphenylamine.

N, N-jetanolaniline, N, N-dimethyl metatoluidine, N, N-diethyl metatoluidine, N
, N-dimethyl para-toluidine, N, N-diethyl para-toluidine, dimethyl-4-chlorophenylamine, etc., and the amount used is 0.7 to 2.0% by weight based on the unsaturated polyester and polymerizable monomer. The range of If the amount of N,N-dialkylaniline or its derivative used is less than 0.7% by weight, inhibition of curing by nitrite cannot be prevented.

If the amount used is more than 20% by weight, cracks and the like are likely to occur due to rapid curing heat generation.

In the unsaturated polyester resin composition of the present invention.

Polymerization inhibitors such as hydroquinone, benzoquinone, and t-butylcatechol may be added as necessary, and further calcium carbonate, clay, and gypsum.

Fillers such as aluminum hydroxide and sodium sulfate.

Plasticizers such as dibutyl phthalate, dibutyl maleate, dioctyl phthalate, tributyl phosphate, trischloroethyl phosphate, flame retardants such as paraffin monochloride, amine trioxide, decabromophenyl ether, organic or inorganic pigments, heat A low shrinkage imparting agent such as a plastic resin may also be added. Of course, glass roving is used in the production of unsaturated polyester resin laminates.

The unsaturated polyester resin composition may be laminated and cured using reinforcing materials such as glass roving cloth, glass strand mat, surface mat, glass nonwoven fabric, linter pulp paper, carbon fiber, and nylon cloth.

(Example) Next, the present invention will be explained by examples.

Example 1 3929 maleic anhydride, 888 g of phthalic anhydride, propylene glycol 6089, and ethylene glycol 2309 were charged into a flask equipped with a stirrer, a thermometer, an inert gas inlet, a partial condenser, and a total condenser, and the mixture was placed in an inert gas atmosphere. The temperature was raised at a lower temperature to advance polymerization. After 2 hours, the temperature reached 200°C, and then the temperature was kept until the acid value reached 37. This unsaturated polyester was rapidly cooled to 130°C, and 0.0% of hydroquinone was added.
Dissolved in styrene containing 022% by weight, non-volatile content 55%
% by weight of unsaturated polyester resin A was obtained. This unsaturated polyester resin A999 has N,N-dimethylanily7
1 g was added and dissolved to obtain an unsaturated polyester resin composition A. Add nitrous acid to this unsaturated polyester resin composition A309) IJum (water absorption rate 15%, same hereinafter) o, s
After adding sg, the liquid temperature was adjusted to 25° C., 1.59 g of benzoyl peroxide (50 thi paste, the same applies hereinafter) was added, and the gelation time at room temperature was measured according to JIS K 6901.

Moreover, the surface hardness of the obtained cured product after one day was measured using a Shore D hardness meter. The results are shown in Table 1.

Example 2 0.589% of sodium nitrite and 509% of sodium sulfate were mixed and dried at 200°C for 2 hours, then placed in a desiccator and cooled to room temperature. Add this mixture 259 to unsaturated polyester resin composition A259.

The same measurements as in Example 1 were carried out by adding 7 sg of silver peroxide o. The results are shown in Table 1.

Example 3 0.359% of sodium nitrite was added to unsaturated polyester resin composition A309. After adding and mixing calcium carbonate 209,
Further, 0.99% of benzoyl peroxide was added and the same measurements as in Example 1 were carried out. The results are shown in Table 1.

Example 4 N,N-dimethylaniline 19 of Example 1 was converted to N,N-
The same measurements as in Example 1 were carried out using the same additive formulation as in Example 1 except that diethylaniline 19 was used. The results are shown in Table IK.

Example 5 The same measurements as in Example 1 were carried out using the same additive formulation as in Example 1, except that 1 g of N,N-dimethylaniline in Example 1 was changed to 1 g of N,N-dimethyl paratoluidine. The results are shown in Table 1.

Comparative Example 1 0.1 g of N,N-dimethylaniline was added and dissolved in 99.9 g of unsaturated polyester resin A to obtain unsaturated polyester resin composition B. Using this unsaturated polyester resin composition B, the same measurements as in Example 1 were carried out with the same additives as in Example 1.

The results are shown in Table 1.

Comparative Example 2 Using unsaturated polyester resin composition B, the same measurements as in Example 1 were carried out with the same additives as in Example 3.

The results are shown in Table 1.

Reference Example 1 The same measurements as in Example 1 were carried out except that only nitrous acid and IJium were added from the formulation of Example 1. The results are shown in Table 1.

Table 1 Example 6 In the same synthesis apparatus as in Example 1, 5809° of 7-maric acid and 7409° of phthalic anhydride were added. Diethylene glycol 3189.1.
3-Butylene glycol 4509° and hexamethylene glycol 4139 were charged, and polymerization was proceeded in the same manner as in Example 1 to obtain an unsaturated polyester having an acid value of 18. This unsaturated polyester was dissolved in styrene containing 0.05% by weight of hydroquinone to obtain an unsaturated polyester resin B having a nonvolatile content of 55%. This unsaturated polyester resin B9
99 and 1 g of N,N-dimethylaniline was added and dissolved therein to obtain an unsaturated polyester resin composition C.

After adding nitrous acid and ssg to this unsaturated polyester resin composition C509, the liquid temperature was adjusted to 25°C.
Add 1 g of benzoyl peroxide.

The same measurements as in Example 1 were made. The results are shown in Table 2.

Example 7 Example 6 except that 1 g of N,N-dimethylaniline in Example 6 was changed to 71 g of N,N-dimethyl metatoluidi.
The same measurements as in Example 1 were carried out using the same additive formulation. The results are shown in Table 2.

Example 8 The 0.58 g of sodium nitrite used in Example 6 was changed to 19 g of potassium nitrite (water content: 10%).

The same measurements as in Example 6 were made. The results are shown in Table 2.

Comparative Example 3 0.19% of N,N-dimethylaniline was added and dissolved in 99.99% of unsaturated polyester resin B to obtain an unsaturated polyester resin composition. Using this unsaturated polyester resin composition, the same measurements as in Example 1 were carried out with the same additives as in Example 6. The results are shown in Table 2.

Comparative Example 4 0.1 g of N,N-dimethyl metatoluidine was added and dissolved in unsaturated polyester resin B99.9G to obtain unsaturated polyester resin composition E. Using this unsaturated polyester resin composition E, the same measurements as in Example 1 were carried out using the same additives as in Example 7. The results are shown in Table 2.

Comparative Example 5 After adding 1 g of potassium nitrite to unsaturated polyester resin composition D509, the liquid temperature was adjusted to 25°C.

1 g of benzoyl peroxide was added and the same measurements as in Example 1 were carried out. The results are shown in Table 2.

Reference Example 2 The same measurements as in Example 1 were made except that only nitrous acid and IJium were added from the formulation of Example 6. The results are shown in Table 2.

Table 2 (Effects of the invention) As is clear from Examples 9, the unsaturated polyester resin composition of the present invention is hardly affected by room temperature gelling time or surface hardness due to the addition of nitrite, and curing is not inhibited. . On the other hand, in conventional unsaturated polyester resin compositions containing a small amount of N,N-dimethylaniline, when nitrite is added, the gelation time at room temperature becomes about 10 times longer, and the surface of the cured product after 1 day is Hardness was also unmeasurable.

Agent Patent Attorney Kunihiko Wakabayashi = 22,,’,! .

Claims (1)

[Claims] 1, unsaturated polyester, polymerizable monomer, and 0.7 to 2 for unsaturated polyester and polymerizable monomer.
An unsaturated polyester resin composition containing 0% by weight of N,N-dialkylaniline or a derivative thereof.