JPS5912690B2 - resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a flame-retardant unsaturated polyester resin composition.

Conventionally, in order to make unsaturated polyester resin flame retardant, a method of blending hydrated alumina has been adopted. power,
When hydrated alumina was added to unsaturated polyester resin, the resin viscosity increased, making it impossible to use it for manufacturing sheet molding materials (SMC) or prepregs for laminates. For this reason, a method has been devised in which the styrene monomer content is increased to lower the overall viscosity, but increasing the styrene monomer content is not preferable because the performance deteriorates. On the other hand, it is possible to reduce the viscosity of the resin by reducing its molecular weight, but in this case, the viscosity increasing effect cannot be obtained, and furthermore, with the conventional manufacturing method, the thickness accuracy is poor when molding a laminate (resin board). However, it was not possible to obtain the desired shape, so it was molded using a spacer or the like. The present invention provides an unsaturated polyester resin composition made flame retardant with hydrated alumina, which improves the above-mentioned drawbacks.

Therefore, in the present invention, when synthesizing an unsaturated polyester, the molar ratio of glycol/15 dibasic acid is 1.06 or less,
Preferably, the reaction temperature is 1.04 or less, and the viscosity of the obtained liquid crosslinking agent solution of unsaturated polyester is 1 at 25°C.
Hydrated alumina, a divalent metal compound, and a hardening agent are mixed with a resin liquid whose temperature is 00 centipoise or less and the liquid crosslinking agent content of this solution is 50% by weight or less, and if necessary, other fillers and pigments are added. It is characterized in that it is made by mixing a mold release agent and the like to form a slurry composition, which is integrated with a glass fiber base material and then heated and aged. 25 The unsaturated polyester used in the present invention is prepared by using in combination an unsaturated dibasic acid such as maleic anhydride or fumaric acid and, if necessary, a saturated acid such as phthalic anhydride or isophthalic acid, together with ethylene glycol, propylene glycol, or propylene. glycol, neopliers 3
The reaction is carried out using a known method using glycols such as hydrogenated bisphenol glycol, hydrogenated bisphenol A) and bisphenol A propylene acid adduct.

In this case, the usage ratio is determined so that the molar ratio of glycol/dibasic acid is 1.06 or less, preferably 1.04 or less.
5 counts. If the molar ratio exceeds the above value, the thickening property will become worse. The unsaturated polyester obtained as described above is dissolved in a liquid crosslinking material such as styrene.

In this case, the content of the crosslinking agent is 50% by weight or less, preferably 45% by weight or less. If these limits are exceeded, the water resistance and other performance of the product will deteriorate. As the filler, inorganic powder such as alumina, calcium carbonate, silica, etc. is used. As the 211ifi metal compound, oxides and hydroxides of magnesium, calcium, zinc, etc. are used.

These may be used in combination. The mixing ratio of the above ingredients is 1 part of hydrated alumina to 100 parts of resin liquid (same parts below by weight).
Preferably, the amount is 50 parts or more, the divalent metal compound is preferably 0.4 to 2.0 parts, and the curing agent is 0.5 to 4 parts. Note that the amount of fillers, pigments, mold release agents, and other additives to be mixed is arbitrary. This slurry-like resin composition is impregnated into a glass fiber base material such as glass mat or glass chipped strand mat to integrate it.
It is sandwiched between two pieces of plastic film (polyethylene, polypropylene, etc.) and heated and aged to form a sheet-shaped molding material (SMC). This operation is usually carried out by applying a slurry composition onto a plastic film using an SMC manufacturing machine, and then sandwiching the glass fiber base material from above and below and using rolls to degas and impregnate it. Or, conversely, feed a slurry composition onto a glass fiber base material,
Apply two plastic films from the outside and roll to defoam and impregnate. The resultant is aged for 24-48 hours at a temperature of 40-50°C. The SMC thus obtained is dry to the touch even without the plastic film and has no adhesive properties. S obtained as above
MC has flame retardancy and is excellent in resin impregnation and moldability.

However, the thickness accuracy of the molded product obtained from this method is also excellent. Example 1 First, the first stage reaction was carried out using a mixture of 332 parts of isophthalic acid, 296 parts of phthalic anhydride, and 797 parts of propene glycol, and then 696 parts of fumaric acid and 20 parts of the total amount of reactants.
A second stage reaction was carried out by adding 0 ppm of hydroquinone to obtain an unsaturated polyester having an acid value of 32.

This was dissolved in styrene monomer so that the unsaturated polyester concentration was 55% by weight, and the viscosity was 90 centipoise (2
5° C.) was obtained. Glycol in this case/
The molar ratio of dibasic acid was 1.05. Next, the resin liquid [
An unsaturated polyester with an acid value of 32 was obtained in almost the same manner except that propylene glycol was changed to 814 parts with respect to the formulation of [A], and it was dissolved in the same amount of styrene to obtain a resin liquid [B] with a viscosity of 73 centipoise. .

The glycol/diacid molar ratio in this case was 1.07. Apart from the above, there is a resin liquid [C] which has the same composition as the resin liquid [A], has an acid value of 20, and has a viscosity of 320 centipoise.
] was obtained.

Using the resin liquids [A], [B], and [C] obtained above, 150 parts of hydrated alumina and t-
After mixing 1.2 parts of butyl perbenzoate, 1.5 parts of magnesium oxide was further added to obtain a slurry composition.

These were used to impregnate a glass fiber mat so that the glass fiber content was 3801), and both sides were sandwiched between polypropylene films and heated at 45° C. for 48 hours to age.
At this stage, the resin liquid [C] used had an excessively high viscosity due to thickening, and could not be impregnated into the glass fiber mat. Those using resin liquids [A] and [B] were able to be sufficiently impregnated. However, the resin solution [B] did not increase in viscosity even after impregnation and did not become dry to the touch.
Glass fiber mat impregnated with resin liquid [A] resulted in SMC that was dry to the touch. Pressure is 35kf when these two SMCs are stacked! Molding was carried out under the conditions of /d1 temperature of 140° C. and time of 30 minutes, and a resin liquid having the performance as shown in Table 1 was obtained. Note that the thickness accuracy was good even without using a spacer. Example 2 A two-stage reaction was carried out in the same manner as in Example 1 using a blend of 539 parts of maleic anhydride, 8301 isophthalic acid, 208 parts of neopentyl glycol, and 608 parts of propylene glycol to obtain an unsaturated polyester with an acid value of 81.

Using this, it was dissolved in styrene monomer so that the unsaturated polyester concentration was 58%, and the viscosity was 23 centipoise (
A resin liquid [D] was obtained at a temperature of 25°C. The glycol/diacid molar ratio of this product was 0.95. In addition, resin liquid [
Resin liquid [E] with the same concentration and viscosity of 123 centipoise (25°C) was reacted with the same formulation as [D] until the oxidation level reached 63.
I got it. Using this resin liquid [DLCE], resin liquid 10
0 parts, 170 parts of hydrated alumina, 1.2 parts of t-butyl perbenzoate, and 0.8 parts of magnesium oxide were mixed to form a slurry composition, and the slurry was mixed with glass fiber mat bonded with a thermosetting resin binder. , glass fiber content is 4
It was impregnated to a concentration of 0%. The resin liquid [D] composition had a viscosity of 7000 centipoise and was well impregnated into the glass fiber mat. However, the resin liquid [E] composition had a viscosity of 70,000 centipoise and could not be impregnated into glass fiber mat. A glass fiber mat impregnated product of the composition using the resin liquid [D] was heated and aged in the same manner as in Example 1 to obtain SMC. Stack two of these, 401
<g/C7lll The resin plate molded at 38° C. for 30 minutes had a good surface condition and had the performance shown in Table 2. Note that the thickness accuracy of the resin plate was good even without using a spacer.

Example 3 664 parts of isophthalic acid, 310 parts of ethylene glycol,
The first stage reaction was carried out by adding 380 parts of propylene glycol, and then the second stage reaction was carried out by adding 812 parts of fumaric acid to obtain an unsaturated polyester having an acid value of 92.

In this case the glycol/diacid molar ratio was 0.91. This unsaturated polyester was divided into two parts, one was dissolved in styrene so that the unsaturated polyester content was 50% by weight, and the resin liquid [F] had a viscosity of 15 centiboise (25 C). 45% by weight
Dissolve the styrene so that the viscosity is 8 centipoise (
Resin liquid [G] was prepared at a temperature of 25°C). Using the above resin liquid, 100 parts of the resin liquid and 200 parts of hydrated alumina were mixed, and 1.0 part of t-butyl perbenzoate and 1.5 parts of magnesium oxide were added and mixed. Example 2 The SMC was impregnated into a glass fiber mat similar to the above, and then sandwiched between two polypropylene films and heated and aged at 48° C. for 45 hours to obtain SMC that was dry to the touch. The glass fiber content of each was 30% by weight. For each of the above SMCs, two sheets of each are stacked, and then copper foil (manufactured by Fukuda Kinzoku Co., Ltd., product name CF-TS) is layered on top of that.14
A copper-clad board was obtained by molding at 0° C. and 40 kg/CTIIl for 25 minutes.

Claims (1)

[Claims] 1 Unsaturated polyester obtained by reacting at a glycol/dibasic acid molar ratio of 1.06 or less as a liquid crosslinking agent,
150 parts by weight or more of hydrated alumina and 0.0 parts by weight of a divalent metal compound are added to 100 parts by weight of a resin solution dissolved so that the viscosity at 25° C. is 100 centipoise or less and the concentration of the liquid crosslinking agent is 50% by weight or less. Impregnating a glass fiber base material with a composition comprising 4 to 2.0 parts by weight, 0.5 to 4 parts by weight of a curing agent, and other additives such as fillers, pigments, and mold release agents if necessary, A resin composition obtained by aging.