JPS5813565B2 - Koukakanounajiyusoshibutsu - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a curable resin composition suitable for various uses such as glass fiber reinforced plastics, paints, linings, castings, adhesives, and the like.

Currently, unsaturated polyesters are widely used in the above-mentioned applications such as glass fiber reinforced plastics (hereinafter referred to as FRP).

Although unsaturated polyesters certainly have excellent properties, they are not completely free from improvements.

What is particularly sought after for improvement is to change the property of anaerobic properties, that is, non-curing properties when in contact with air, to curable properties, as is well known.

The method currently employed for this purpose is to add small amounts of wax to the resin.

That is, the added wax precipitates when the resin hardens, forms a thin film on the resin surface, blocks contact between the resin and air, and enables the resin to harden.

Another method for the same purpose is to use polyhydric alcohol esters containing an allyl ether group (10-CH2-CH=CH2) as a component of the resin to make the resin surface dry. Are known.

However, the above methods have certain drawbacks.

For example, waxes used in conjunction with FRP molding have the disadvantage that they prevent resin from impregnating between glass fibers and tend to entrain air bubbles.

Remaining air bubbles not only impair the physical properties of FRP, but also cause chemical leaching in tanks, linings, etc. that require chemical resistance, so improvements are needed.

Further, resins obtained by using allyl ethers in combination are hard but relatively brittle, have insufficient adhesion properties, and have the drawbacks of being high in cost.

In view of the above-mentioned situation, the present inventors investigated various methods for solving the problem, and as a result, the present inventors discovered a polymerizable cyclo represented by the following formula described in Japanese Patent Publication No. 16992/1987, which the present inventors had previously invented. The acetal compound [A] itself is air-curable, and not only does it completely cure in the presence of air, but it can also be used in combination with conventional unsaturated polyesters. The present inventors have discovered that the anaerobic effects can be completely eliminated, and have completed the present invention.

However, R is -H or -CH3. The resin composition of the present invention is composed of a polymerizable cycloacetal compound and an unsaturated alkyd, and not only the curing performance is greatly improved by compensating for each other's defects, but also the base material,
The adhesion to the reinforcing material is also significantly improved compared to the case of using unsaturated polyester alone, which has very effective advantages such as improving the physical properties of FRP.

As mentioned above, the present invention comprises (a) a polymerizable cycloacetal compound obtained by reacting an unsaturated cycloacetal compound and an unsaturated alcohol, and (b) an α-β unsaturated polybasic acid as one component. It consists of an unsaturated alkyd obtained by esterification with a polyhydric alcohol, with or without modification with any saturated polybasic acid, and with or without the addition of a polymerizable monomer. The present invention relates to the resulting curable resin composition.

The resin composition according to the present invention can be used in coatings, casting, lamination, adhesion,
It can be used in various fields such as, but the ratio of the combination is determined depending on the application and does not need to be particularly limited.

The polymerizable cycloacetal compound (A) used in the present invention is obtained by the reaction of, for example, sialilitenpentaerythritol, which is obtained by condensation of a polyhydric alcohol and an unsaturated aldehyde, with hydroxyethyl methacrylate according to the following formula.

Incidentally, as the unsaturated cycloacetal compound, polyvalent crotonaldehyde acetal, polyvalent acrolein acetal, etc. can be used, and these are all obtained by reacting a polyhydric alcohol with an unsaturated aldehyde under an acid catalyst.

One example is Angewante He-. - (Angew
, Chem. ) Vol. 62, No. 5, pp. 105-118 (1950).

However, in order to obtain a product that is preferable in terms of hue, curing properties, and physical properties after curing, acrolein acetals, which are reaction products of acrolein and polyhydric alcohols, are desirable, but from a practical standpoint, this is not sufficient. be.

Further, the unsaturated alkyd used in the present invention is α
- Contains β-unsaturated polybasic acids, is usually obtained by modifying with saturated polybasic acids and esterifying with polyhydric alcohols, and is generally commercially available in the form dissolved in monomers, especially No limitations are necessary for the invention.

In the present invention, even if a monomer is not used in combination, for certain applications such as baking paints, the purpose may be achieved by using an unsaturated alkyd and a polymerizable cycloacetal compound in combination.

The unsaturated alcohols used in the present invention include hydroxyethyl methacrylate, hydroxypyrmethacrylate, hydroxyethyl acrylate, trimethylolpropane dimethacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, trimethylolethane diacrylate, Examples include glycerin dimethacrylate, allyl alcohol, etc.
In addition to these, a reaction product of an unsaturated epoxy compound such as glycidyl methacrylate and a monocarboxylic acid such as acrylic acid and having a free hydroxyl group can also be used.

Among them, hydroxyalkyl (meth)acrylates are most preferably used.

Of course, the above methods can also be used together. It goes without saying that fillers, pigments, reinforcing materials, etc. can be optionally used in the composition according to the present invention depending on the intended use.

Next, examples will be shown below to help understand the present invention.

Example 1 Synthesis of polymerizable cycloacetal compound CA) A 1-liter four-tube flask was equipped with a stirrer, a thermometer, a gas inlet tube, and a condenser, and diarylidenepentaerythritol 212
S', 2-hydroxyethyl methacryly}21OS'
, balatoluenesulfonic acid 1.5y, hydroquinone 0.
4? When the composition is reacted for 8 to 10 hours in an inert gas stream at 80 to 100°C, more than 80% of the hydroxyl groups react and disappear.

The product is the radically polymerizable polymerizable cycloacetal compound CA) of the following formula described above.

Composition CB was prepared by adding 0.2 parts of dimedone and 30 parts of styrene to 100 parts of this polymerizable cycloacetal compound [A].
) was manufactured.

Synthesis of unsaturated polyester [C] In a 3-liter four-sol flask equipped with a stirrer, thermometer, gas introduction tube, and fractionation condenser, propylene glycol 80
7. Phthalic anhydride 740g, maleic anhydride 490g,
and the reaction temperature was 180-210℃ in an inert gas stream.
Esterification proceeded at ℃, and when the acid value reached 40 or less, the reaction was stopped and hydroquinone was added to 0.45? was added, dissolved in styrene 1 1 50r, unsaturated polyester [C
] was synthesized.

Coating test 100 parts of each resin shown in Table 1 was mixed with 1.5 parts of methyl ethyl ketone peroxide and cobalt naphthenate (6%
Add 0.5 part of Co) to a polished steel plate for painting at 25℃.
．． It was coated using a knife coater to a thickness of 2 vans.

The results are shown in Table 1.

As is clear from Table 1, the combined use of a polymerizable cycloacetal compound is extremely effective in improving the surface drying properties of unsaturated polyesters.

Example 2 Radically polymerizable polymerizable cycloacetal compound CD
350 g of triarylidene sorbitol synthesized from sorbitol and acrolein, 420 g of 2-hydroxyethyl methacrylate, and 2 g of p-toluenesulfonic acid were mixed at 80 to 100°C in the same apparatus as in Example 1. After reacting for a long time, the free hydroxyl groups almost disappear according to infrared analysis.

The obtained radically polymerizable polymerizable cycloacetal compound CD) is a viscous pale yellowish brown liquid that is presumed to have the following structural formula.

0.3 parts of dimedone was added to 100 parts of this compound to prepare composition CE).

Synthesis of unsaturated polyester CF) [Polymerizable cycloacetal compound [D]] Neopentyl glycol 1190f and isophthalic acid 8301 were charged into the same apparatus as in Example 1, and the mixture was heated to
Esterification proceeds at 210°C, and when the acid value drops below 40, maleic anhydride 490'? was added, esterification was continued, the reaction was stopped at a final acid value of 39.4, 0.35P of hydroquinone was added, and further dissolved in 1300P styrene to synthesize unsaturated polyester [F].

Physical Properties of Laminated Product To 100 parts of the resin composition shown in Table 2, 1.5 parts of methyl ethyl ketone peroxide and cobalt naphthenate (6% Co) were added.
F with a glass content of 26.4 to 29.1 (%) with a thickness of 3 mm using a #450 glass mat.
RP board molded at room temperature.

The test results for FRP are shown in Table 2.

Example 3 Synthesis of unsaturated polyester [G] Hydrogenated bisphenol 250 was placed in a 1 liter four-eye flask equipped with a stirrer, a fractional distillation condenser, a thermometer, and a waste inlet tube.
116 g, neopentyl glycol, 1 isophthalic acid
66g and heated to 210-220℃ in an inert gas stream.
Esterification is proceeded with, and when the oxidation value reaches 35 or less, 98 g of maleic anhydride is added, and the reaction is further advanced to bring the acid value to 30 or less.

After the reaction is completed, 0.1 of hydroquinone! 1 was added and then dissolved in 450 g of styrene to synthesize an unsaturated polyester (CG).

Manufacture and testing of gel coat; The formulation of the colored gel coat is 100 parts of resin, 5 parts of styrene, 3 parts of phthalocyanine green, 3 parts of Erosil,
Knead 0.8 part of cobalt naphthenate (6% Co) using three rolls.

300% x 300% x 5 A wax-based mold release agent was applied on a glass plate, and then a polyvinyl alcohol-based mold release agent was applied and dried, followed by a blended gel coat 100.
1.5 parts of methyl ethyl ketone peroxide is added to each part and applied by spraying.

After curing, 1 ply of surface mat (#30 type), 3 plies of #450 mat and unsaturated polyester [G]
Lamination was carried out using

Curing conditions were the same as in Example 2.

After curing is complete, cut out a test piece into a 6% x 6% square.
When a boiling test was conducted, the results shown in Table 3 were obtained.

The combined use of Example 10 polymerizable cycloacetal composition CB) was extremely effective in improving workability during gel coating and lining, boiling resistance of the cured resin, and the like.

Example 4 Synthesis of polymerizable cycloacetal compound [H) Diarylidenepentaerythritol 31 was added to the same apparatus as in Example 1.
M', 2-hydroxyethyl acrylate}365S',
Paratoluenesulfonic acid 2.5g, hydroquinone 0.3
1 in an inert gas stream at 90 to 100°C.
After 0 hours of reaction, more than 80% of the free hydroxyl groups disappear.

The obtained polymerizable cycloacetal compound [H] was a pale yellow liquid having the following structure and a viscosity of 1.6 poise (25° C.).

Synthesis of unsaturated polyester CI) Diethylene glycol 12 was added to a 1 liter four-eye flask equipped with a stirrer, a fractionating condenser, a gas inlet tube, and a thermometer.
0P, 7” Ropylene glycol 82g, Itaconic acid 11
6g, adipic acid 146'? , and carried out an esterification reaction at 180 to 200°C in an inert gas stream, and when the acid value reached 43.4, hydroquinone was 0.04? was added to obtain an unsaturated polyester CI) exhibiting a viscous syrup-like appearance.

Baking paint test: 100 parts of resin of each composition shown in Table 4, 10 parts of titanium white,
20 parts of talc, 1 part of Erosil, cobalt octylate (
8%Co) 0. Knead 3 parts well with 3 rolls.

If the viscosity during kneading is too high, dilute with toluene.

Add 1 part of tertiary butyl perbenzoate to 100 parts of the above blended resin, apply a putty coat to a thickness of 1 mm on a polished steel plate for a paint test, and then bake at 120°C for 1 hour to harden and obtain a tough hardened film. It was done.

The performance of the coating film was as shown in Table 4. That is, it was not possible to make a baking paint using the unsaturated polyester [■] alone, and a practical paint composition could only be obtained by using the polymerizable cycloacetal compound [H] in combination.

Example 5 Synthesis of polymerizable cycloacetal compound CJ) Diarylidenepeitaerythritol 21 was added to the same apparatus as in Example 1.
2S', 1147 ml of allyl alcohol, 1 ml of p-toluenesulfonic acid, and 0.11 ml of hydroquinone were charged, and the mixture was reacted for 35 hours at 90 to 95°C in an inert gas stream.

Next, a solution of 3 grams of bicarbonate of soda dissolved in 200 grams of water was added for washing, the water was separated by decanting, and after washing twice with IOOCC water, a small amount of benzene was added and an azeotropic distillation device was attached. Benzene was refluxed to remove water.

Benzene was then removed under reduced pressure of about 100 miHg to obtain a pale yellowish brown liquid with a viscosity of 2.1 poise, with almost no free hydroxyl groups observed in the infrared absorption spectrum.

The obtained polymerizable cycloacetal compound [J] had the following structural formula.

Synthesis of unsaturated polyester (K) Ethylene glycol 2.0
0 I? , 333 g of diethylene glycol, 4561 g of tetrahydrophthalic anhydride, and 348 g of fumaric acid were charged, and esterification was carried out at a temperature of 190 to 210°C for 8 hours in an inert gas stream. When the acid value reached 29.4, the reaction was carried out. After stopping the reaction, 0.21% of hydroquinone and 685z of styrene were added at 140°C to synthesize unsaturated polyester CK).

The obtained unsaturated polyester CK) had a viscosity of 4.7 poise and a Hazen color number of 400.

300iiX 300mmX6mm lauan plywood was sealed, and 100 parts of a mixture of polymerizable cycloacetal compound [J] and unsaturated polyester [K], 1.5 parts of methyl ethyl ketone peroxide, and cobal naphthenate were added to it. 0.7 part of the composition was added to a thickness of 0.7 parts. 2y
It was painted so that it became 100 nm.

The results are shown in Table 5, and the combined use of polymerizable cycloacetal compound [J] was extremely effective in imparting air curability.

Example 6 Synthesis of polymerizable cycloacetal compound [L] Diarylidenepentaerythritol 21 was added to the same apparatus as in Example 1.
2g, trimethylolpropane dimethacrylate (dimethacrylate component 87%, trimethacrylate component 4%)
, a mixture of 8% monomethacrylate component and about 1% others) 5602, para-toluenesulfonic acid 2.1fI1 hytroquinone 0.2? ;r: When the mixture was charged and reacted at 90 to 95°C for 4 hours, it was estimated that about 84% of the hydroxyl groups had reacted as a result of infrared analysis.

Next, it was washed with 200 cc of water containing 3 g of sodium bicarbonate, and then twice with IOOCC water, and then dehydrated using benzene in the same manner as in Example 5.

After distilling off the benzene, add 0.21 of hydroquinone,
A polymerizable cycloacetal compound CL) was synthesized.

The obtained polymerizable cycloacetal compound (L) was yellowish brown and had a viscosity of about 500 poise.

Synthesis of unsaturated polyester (M) Propylene glycol 82
0 g, 830 g of isophthalic acid, 180-200
After esterification was carried out at °C to give an acid value of 34, 490 g of maleic anhydride was added to proceed with esterification in an inert gas stream, and when the acid value reached 37, the reaction was stopped.

After adding 0.31 g of hydroquinone, the mixture was poured into a stainless steel container and solidified to obtain a yellow-brown unsaturated polyester [M] with a melting point of about 70°C.

Manufacture and physical properties of molding material: After kneading the mixture in a heated seconder at 80 to 85°C, it was passed through an extrusion type pelletizer to form pellets with a particle size of about 5 square meters.

JIS test piece mold 17 with thermosetting injection molding machine
It was heated to 0 to 175°C and injection molded.

The physical property values of the obtained test piece are as shown in Table 6, and it was found to be extremely promising as an insulating material.

Claims (1)

[Scope of Claims] 1(a) a polymerizable cycloacetal compound obtained by reacting an unsaturated cycloacetal compound obtained by condensation of a polyhydric alcohol and an unsaturated aldehyde with an unsaturated alcohol, and (b) α - An unsaturated alkyd obtained by esterifying a β-unsaturated polybasic acid with a polyhydric alcohol with or without modifying it with any saturated polybasic acid, with or without addition of a polymerizable monomer. A curable tree composition characterized in that it can be obtained without any process.