KR810000139B1 - Unsaturated Polyester Resin Composition - Google Patents

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Description

Unsaturated Polyester Resin Composition

FIG. 1 shows a test piece of copper green side used in the copper green side test of the Examples.

2 is a perspective view of a test piece used to test the shear adhesion of the example.

3 is a side view thereof.

The present invention reduces the bronze generated on the contact surface with copper by adding at least one compound selected from the group of 1,2,4-triazole and its derivatives and organic acid manganese salt. It is related with providing the unsaturated polyester resin composition which improved adhesive force and improved air drying property on it.

Unsaturated polyester resin compositions are used in various fields such as molding materials, FRP, and electrical insulation because of their excellent economy and workability.

However, conventional unsaturated polyester resin compositions generate bronze on the contact surface with copper at the time of curing, and have a problem especially in the case of electrical insulation. The copper bronze is known to have an effect such as hydroxyl and malonic acid. For example, cobalt is generally used as a curing accelerator (hereinafter, accelerator) of an unsaturated polyester resin composition. In order to form a complex easily with metals, such as manganese, nickel, iron, lead, and a lithium, and to produce precipitation in a short time at room temperature, the use was limited.

However, it was found that the use of at least one compound selected from the group of 1,2,4-triazole and its derivatives in place of fisheries could solve their precipitation problem by using copper anti-rust agent.

In addition, when the unsaturated nolyester resin composition is used for electrical insulation, for example, a rotating machine such as a motor may be subjected to stress such as vibration and centrifugal force, and in the case of a power transformer or the like, the coil may be loaded at load. The electromagnetic force acts between the wires and the cores, which causes wear and tear of enameled copper wires when used over a long period of time, and also causes short circuits. It is preferable.

However, when at least one compound selected from the group of 1,2,4-triazoles and derivatives thereof is used, the stability of the varnish is improved, but metal salts such as cobalt, lithium, lead, nickel, iron, etc. which are commonly used in curing ( There was a problem in that air-drying was badly worsened when i) was used as an accelerator.

The inventors of the present invention have conducted various studies. As a result of the addition of organic acid manganese salt as an accelerator to a composition with a resin using at least one compound selected from 1,2,4-triazole and derivatives thereof as an anti-corrosive agent, it is very air-drying. It was found that this was excellent, the stability of the varnish was excellent, and effectively prevented the hearing.

The present invention uses at least one compound selected from 1,2,4-triazole and derivatives thereof in a composition containing an unsaturated polyester, a crosslinkable monomer and a curing agent, and adds an organic manganese salt as a curing accelerator. The present invention relates to an unsaturated polyester resin composition, and is particularly suitable for molding, impregnation, and dripping impregnation as a varnish for electric insulation, but also to FRP and laminated sheet molding materials used in contact with other copper.

The unsaturated polyester resin composition according to the present invention

(a) 80-30% by weight of unsaturated polyester, preferably 70-50% by weight.

(b) with respect to 100 g of the composition of 20-70% by weight of crosslinkable monomer, preferably 30-50% by weight.

(c) 0.000012-0.036 mol of at least one compound selected from 1,2,4-triazole and derivatives thereof. Preferably 0.00012-0.024 mol.

(d) 0.5-3.0 g of hardener preferably 1.0-2.0 g and

(e) The organic acid manganese salt is formulated so as to be 0.001-1.5 g, preferably 0.005-0.05 g, as the metal powder.

As the above unsaturated polyester, generally used resins are used. For example, an unsaturated polyester is obtained by polycondensing the polyalcohol component containing 20-80 mol% of a polyalcohol component and unsaturated polycarboxylic acid. At the time of a polycondensation reaction, you may contain monocarboxylic acid, such as a fatty acid, and a modified component as a reaction component. The molecular weight of the unsaturated polyester is preferably about 500-3,000.

As the polyalcohol component, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, derivatives thereof, compounds thereof and the like are used. Examples of the polycarboxylic acid components include saturated polycarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, entomethylene tetrahydrophthalic anhydride, methylenedomethylene tetrahydrophthalic anhydride, isophthalic acid, telephthalic acid and adipic acid. There are carboxylic acids, and as monocarboxylic acids, fatty acids obtained from vegetable oils such as linseed oil, soybean oil, soil oil, palm oil and castor oil are used.

As the poor component, dicyclopentadiene, dicropentadiene and the like are used.

As the crosslinkable monomer, styrene, vinyltoluene, α-methyl styrene, tertiary butyl styrene, crorostyrene, divinylbenzene diaryl phthalate, diaryl isophthalate, various acrylic esters, various methacrylic acid esters and the like are used.

General formula (1)

In the general formula (1), R and R ¹ are

R 'is an aryl group such as an alkyl group such as a butyl group, a phenyl group, a halogen-substituted phenyl group, a cresol group, a halogen-substituted cresol group, R ² is an alkyl group having 8 to 10 carbon atoms, and R ³ is

As a curing agent added at the time of curing, acyl peroxides such as benzoyl peroxide and acetyl peroxide, tertiary butyl peroxide, cumene hydroperoxide, ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, dicumyl per Oxide, such as alkyl peroxide, tertiary butyl per benzoate, oxy peroxide, such as tertiary butyl peroxy acetate, etc. are used.

Manganese naphthenate, manganese octenate, etc. are used as organic acid manganese salt.

As a polymerization inhibitor used as needed, the quinones, such as hydrokinone, a butyl catechol, pyrocarol, and other general use are used.

Next, Examples and Comparative Examples of the present invention will be described. Part is a weight part.

Comparative Example 1

15 parts of soybean oil fatty acid, 45 parts of maleic anhydride, 40 parts of isophthalic acid, 52 parts of propylene glycol, 52 parts of dipropyrene glycol were condensed at 200-220 ° C. for 5-8 hours to synthesize a resin having an acid value of 20.5. 40 parts of styrene are melt | dissolved about 60 parts, and unsaturated polyester resin composition (1) is created. Varnish A was obtained by adding and stirring 0.5 part of cobalt octenate (6% of metal content) and 1.0 part of benzoyl peroxide to 100 parts of the composition (1).

Comparative Example 2

Varnish B was obtained by adding and mixing 100 parts of the composition (1) prepared in Comparative Example (1), 0.2 part of 1,2,4-triazole, 0.5 part of cobalt octate (6% of metal content) and 1.0 part of benzoyl peroxide. .

Comparative Example 3

100 parts of compositions (1), 0.2 parts of 3-amino-1,2,4-triazole, 0.2 parts of cobalt octate (6% of metal content) were mixed and stirred and 1.0 parts of benzoyl peroxide were obtained to obtain varnish C.

[Comparative Example 4]

100 parts of compositions (1), 0.2 parts of 1,2,4-triazole 0.2 parts of lead naphthenate (metal content 24%) and 1.0 part of benzoyl peroxide were mixed and stirred to obtain varnish D.

[Comparative Example 5]

Varnish E was obtained by mixing and stirring 100 parts of composition (1), 1.0 part of 3-amino-1,2,4-triazole 1.0 part octenate (24% of metal), and 1.0 part of benzoyl peroxide.

Comparative Example 6

Varnish F was obtained by mixing and stirring 100 parts of compositions (1), 0.2 part of oxalic acid, 0.2 part of cobalt octate (6% of metal content), and 1.0 part of benzoyl peroxide.

Comparative Example 7

Varnish F was obtained by mixing and stirring 100 parts of compositions (1) and manganese naphthenic acid salt (8% of metal content) and 1.0 parts of benzoyl peroxide.

Example 1

Varnish H was obtained by mixing and stirring 100 parts of compositions (1), 0.2 parts of 1,2,4-triazole, 0.2 parts of 8% manganese naphthenic acid, and 1.0 part of benzoyl peroxide.

Example 2

Varnish I was obtained by mixing and stirring 100 parts of composition (1), 0.2 parts of 3-amino-1,2,4-triazole, 0.2 parts of manganese naphthenate (8% of metal content) and 1.0 part of benzoyl peroxide.

Example 3

Varnish J was obtained by mixing and stirring 100 parts of compositions (1), 0.2 parts of 1,2,4-triazole, 0.2 parts of manganese octenate (8% of metal content) and 1.0 part of benzoyl peroxide.

Example 4

100 parts of compositions (1), 0.2 parts of 3-amino-1,2,4-triazole, 0.2 parts of manganese octenate (8% of metal content), and 1.0 part of benzoyl peroxide were mixed and stirred to obtain a varnish K.

Comparison of characteristics of varnish A-K obtained in the above example is shown in Table 1.

[Table 1 Comparison of Varnish Characteristics]

The test method of the characteristic shown in Table 1 is as follows.

1. Stability of varnish

The varnish is placed in a test tube of 18 mm in diameter up to a length of 7 cm, and left at room temperature for 7 days to determine the presence or absence of a precipitate.

(Decision criteria, × ………… precipitate, ○ ………… no precipitate)

2. Appearance of Hardened Varnish

The varnish was applied to a tin plate (100 mm × 40 mm × 0.25 mmt) and cured at 110 ° C. for 1.5 hours to determine the appearance of the coating film.

(Judgement criteria, ○ ………… The coating film is smooth and uniform, x ... ……… granular hardened | cured material and wrinkles generate | occur | produce).

3. Green greenery (cheongcheong)

A test piece wound loosely with the filter paper 2 and a copper plate having a thickness of 0.25 mm inward on a glass 1 having a diameter of 8 mm shown in FIG. 1 was impregnated with a varnish, and subjected to a condition of 1.5 hours at 110 ° C. After curing, the copper plate and the filter paper are spread out to determine whether the filter paper turns blue.

(Judgement criteria, ○ …… blue rust does not occur, filter paper is not rusted. △ …… filter paper is slightly rusted. × …… The entire filter paper is rusted.).

4. Varnish Airlessness

The varnish was apply | coated to a tin plate (100 mm x 40 mm x 0.25 mmt), and air-drying property after 110 degreeC and 1.0 hour was determined.

(Judgement criteria, ○ …… touched not sticky, × …… touched sticky).

5. As shown in Fig. 2, make a bare copper wire 4 with a diameter of 2 mm and a length of 80 mm and make contact with the edge of the contact part with a bare copper wire 5 with a diameter of 2 mm and a length of 40 mm. This was lightly fixed with enameled copper wire 6, and hardened by impregnation of the varnish. Then, pull the bare copper wire 1 to both sides, and measure the shear adhesive force at that time.

Example 5

84 g (1.0 mole) of 3-amino-1,2,4-triazole and 186 g (1.0 mole) of methylene anhydride methylene tetrahydrophthalic acid were placed in a 300 ml four-neck flask, and 120-130 ° C., 60 The reaction was carried out in minutes to obtain a solid adduct (I).

0.4 parts of adducts (I) dissolved in 1 part of methyl alcohol were dissolved in 100 parts of varnish G to obtain varnish L.

Example 6

84 g (1.0 mole) of 3-amino-1,2,4-triazole and 166 g (1.0 mole) of methyltetrahydrophthalic anhydride were added to a 300 ml four-necked flask and allowed to react at 120-130 ° C. for 60 minutes, Adduct (II) was obtained. Varnish M was obtained by dissolving 0.5 part of adduct (II) dissolved in 1 part of methyl alcohol in 100 parts of varnish G.

Example 7

500g of 84g (0.1 mol) of 3-amino-1,2,4-triazole and 266 g (1.0 mol) of anhydrous dodecenyl succinic acid were placed in a four-necked flask and reacted at 120-130 ° C. for 60 minutes to give a solid -Solid adduct (III) was obtained. 0.8 parts of adducts (III) were stirred and mixed in 100 parts of varnish G to obtain varnish N.

Table 2 shows a comparison of the properties of varnish K-N obtained in the above examples.

In addition, the adduct (I)

Adjunct (II)

And adduct (III)

And

Is a mixture of.

Table 2 Test Results

Curing condition 120 ℃, 5h

Example 8

84 g (1.0 mole) of 3-amino-1,2,4-triazole and 228 g (1.0 mole) of Kadler E (manufactured by Cell Chemicals) were placed in a 500 ml four-necked flask and reacted at 150 ° C-160 ° C for 60 minutes. To obtain a viscous adduct (IV).

0.7 parts of adducts (IV) were added to 100 parts of varnish G, followed by mixing and stirring to obtain varnish O.

Example 9

Adduct viscous by adding 48 g (1.0 mole) of 3-amino-1,2,4-triazole and 150 g (1.0 mole) of phenylglycell ether to a 300 ml four-necked flask and reacting at 120-130 ° C. for 60 minutes. V) was obtained. 0.5 part of adducts (V) were added to 100 parts of varnish G, mixed and stirred to obtain varnish P.

Example 10

84 g (1.0 mole) 3-amino-1,2,4-triazole and 130 g (1.0 mole) butyl glycol ether were reacted at 120-130 ° C. for 60 minutes to obtain a viscous adduct (VI).

0.5 part of adduct (VI) was added to 100 parts of varnish G, and mixed and stirred to obtain varnish Q.

Table 3 shows a comparison of the properties of varnishes O to Q obtained in the examples for the above comparison.

The adduct (IV) is of the general formula

A mixture of compounds represented by (wherein R ² is a C8-10 tertiary alkyl group),

Adjunct (Ⅴ)

And adduct (VI)

to be.

Table 3 Test Results

Curing condition 120 ℃, 5h

In Table 1-3, varnish A and varnish G did not add 1,2,4-triazole and its derivatives, resulting in copper greening (blue and blue) and poor adhesion to copper. Varnish B-E uses a metal salt (cobalt, lead) other than organic acid manganese salt as an accelerator and thus has poor air-drying properties. In varnishes F and G to which oxalic acid is added, the stability of the varnish and the appearance of the hardened material of the varnish are poor.

However, in varnishes H to Q of the examples, the stability of the varnish, the appearance of the cured product of the varnish, the greening of the copper, and the air-drying property of the varnish are all good. In particular, varnish H-K has excellent adhesion. The same applies to other varnishes L to Q. From the above results, organic acid manganese salt is used as at least one compound and promoter selected from 1,2,4-triazole and derivatives thereof. The unsaturated polyester resin composition of the present invention has been shown to be excellent in copper rust, air drying, varnish stability, and adhesion to copper.

Claims (1)

0.000012-0.036 mol of at least one compound selected from 1,2,4-triazole and its derivatives relative to 100 g of a composition having 80-30% by weight of unsaturated polyester and 20-70% by weight of crosslinkable monomer. The unsaturated polyester resin composition mix | blended so that 0.5-3.0g of hardening | curing agents and 0.001-1.5g of organic acid manganese salt may be used.

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