WO1992005206A1

WO1992005206A1 - Flame-retardant thermosetting resin composition

Info

Publication number: WO1992005206A1
Application number: PCT/JP1991/001214
Authority: WO
Inventors: Hiromi Kochi; Kiyoshi Mishima; Atsushi Sakabayashi
Original assignee: Manac Inc.
Priority date: 1990-09-13
Filing date: 1991-09-12
Publication date: 1992-04-02
Also published as: JPH04122776A; JP2854948B2

Abstract

A flame-retardant thermosetting resin composition comprising a thermosetting resin and a brominated polystyrene, as the flame retardant, having a weight-average molecular weight of 600 to 10,000 and a bromine content of 30 to 80 wt%. It is excellent in shelf stability and can give, when cured, a product excellent in flame retardance, thermal resistance and mechanical properties.

Description

Specification

Flame retardant thermosetting resin composition

"Technical field"

The present invention relates to a flame-retardant thermosetting resin composition containing brominated polystyrene having a specific molecular weight range.

"Background technology"

Thermosetting resins have excellent heat resistance, high mechanical strength, good dimensional accuracy, and high cost performance, so they can be used as molding materials for electric and electronic parts, civil engineering and construction materials, and automotive parts. It is widely used in household goods. In addition, a laminate obtained by impregnating a thermosetting resin into a laminate base material, drying and heating and pressing is used as a material for a printed wiring board used in industrial and consumer electric and electronic equipment. I have high expectations.

However, thermosetting resins have the drawback of being easily flammable. Therefore, when they are used for electric and electronic parts, flame retardancy is strongly demanded from the viewpoint of disaster prevention.

A commonly used method for imparting flame retardancy is to use a compound containing a halogen such as chlorine or bromine or a phosphorus-containing compound such as a phosphoric acid ester alone or in combination. Halogen-containing compounds have excellent flame retardant effects. These flame retardants include reactive flame retardants and additive flame retardants. The reactive flame retardant reacts to become a component of the polymer, but the reactive flame retardant has poor storage stability of the resin varnish and pre-bleder, making it difficult to adjust the curing reaction. However, there is a disadvantage that the resin tends to change with time. Additive type flame retardant The higher the halogen content, the greater the flame-retardant effect, but the higher the melting point, the higher the melting point of the crystals and the lower the solubility in solvents, resulting in poor compatibility with other resins. The disadvantage is that the properties of the processed product are degraded because of the pan.

As described above, various methods for making a thermosetting resin flame-retardant have been proposed, but there are very few that are practically satisfactory.

"Disclosure of the invention"

The present inventors have conducted intensive studies to completely solve the above-mentioned unsolved problems regarding flame retardancy of thermosetting resins, and as a result, have found that brominated polystyrene having a specific molecular weight has been obtained. Was found to be easily soluble in solvents, had low viscosity when dissolved, and had excellent compatibility with thermosetting resins. In addition, thermosetting resins containing the brominated polystyrene The processed product obtained by curing the resin composition was found to be excellent in flame retardancy and other properties, and reached the present invention.

That is, the present invention relates to a brominated polyolefin having a weight average molecular weight of 600 to 100,000 as a flame retardant and a bromine content of 30 to 80% by weight as a flame retardant. It is a flame-retardant thermosetting resin composition containing styrene.

In the present invention, examples of the thermosetting resin include a fuanol resin, a urethane resin, a melamine resin, an epoxy resin, an unsaturated polyester resin, a diaryl phthalate resin, and a polyurethane resin. Resin that is cured by heating. In addition, the flame-retardant thermosetting resin composition of the present invention may contain a flame retardant such as an antimony compound and / or a phosphoric acid ester, a flame retardant auxiliary, a plasticizer, a curing agent, and a curing accelerator, if necessary. Additives such as agents, surface treatment agents, surfactants, protective colloids, heat stabilizers, light stabilizers, coloring agents, fillers, lubricants, solvents, and water can be added.

The flame retardant of the present invention has a weight average molecular weight of 600 to 100,000 as measured by gel permeation chromatography, and a bromine content of 30 to 80% by weight. is necessary. When the weight-average molecular weight is less than 600, the heat resistance of brominated pristine is inferior, so that it is not practical as a flame retardant. If the weight-average molecular weight is more than 10.0, the solubility of the brominated polystyrene in the solvent will be reduced, and the compatibility with the luster will be poor, resulting in low mechanical and other physical properties of the resin. Let it down. A preferred range of the weight average molecular weight is 700 to 8,000, a more preferred range is 800 to 6,000, and a most preferred range is 850 to 4.500. When the bromine content of the flame retardant is less than 30% by weight, it is necessary to increase the blending amount of the flame retardant, thereby deteriorating physical properties such as mechanical properties of the resin. Further, brominated polystyrene having a bromine content of more than 80% by weight cannot be practically synthesized.

The method for synthesizing the brominated polystyrene of the present invention is not particularly limited. It can be obtained by a method of brominating polystyrene and a method of polymerizing a promostylene monomer. In the method for brominating polystyrene, a solvent such as methylene chloride, ethylene dichloride, carbon tetrachloride, and methylene bromide can be used as a solvent for the bromination reaction. As a reaction catalyst, a catalyst such as anhydrous aluminum chloride, anhydrous ferric chloride, or antimony trichloride is used. Succinic acid and metal powders such as aluminum, iron and antimony can be used. As the brominating agent, bromine, bromine chloride or the like can be used.

The amount of the flame retardant in the flame-retardant thermosetting resin composition of the present invention is determined by considering the effective flame retardancy, various physical properties such as mechanical properties of the resin, and the economical efficiency. A preferred range is 3 to 40 parts by weight based on parts by weight.

With the flame-retardant thermosetting resin composition of the present invention, molded articles such as various molded articles, films, synthetic resin-impregnated paper, laminated articles, paints, adhesives and the like can be obtained. Further, a laminated board can be obtained by impregnating the flame-retardant thermosetting resin composition of the present invention into a laminated board substrate, followed by drying and heating and pressing. Examples of the base material for a laminated board include paper and cloth made of various cellulosic fibers, synthetic fiber, cloth sheet made of glass fiber and mineral fiber, mat and nonwoven fabric. In particular, as a combination of a base material and a resin, a paper phenol or glass epoxy base material is preferable. In addition, a copper-clad laminate obtained by laminating a copper foil on a brig reg impregnated and dried with the flame-retardant thermosetting resin composition of the present invention, and subjecting the copper-clad laminate to heat-press molding is subjected to an etching treatment on the copper foil portion, and a circuit It can be used as a printed wiring board for manufacturing the formed wiring board.

"Best mode for carrying out the invention"

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In the following, “%” means “% by weight” and “parts” means “parts by weight”.

In this example, the weight average molecular weight, bromine content, solubility, viscosity The storage stability of the toluene solution was measured by the method described below. Weight average molecular weight

It was measured by gel permeation chromatography. In advance, a calibration curve with a molecular weight of up to about 120,000 will be created using Tosoh standard polystyrene. Next, 0.1 g of the sample was dissolved in 100 mL of tetrahydrofuran, and the 10 was injected into a CCPM system manufactured by Tosoh Corporation. Calculate the weight average molecular weight of the styrene conversion. The analysis conditions are as follows. Column (Tosoh TSK-Gel G4000Hxl x 1, G3000xl X 1, 2000 Hxl 2 4 connected), mobile phase (tetrahydrofuran), flow rate (1.0 m £ / mm), Column temperature (40 ° C), detection wavelength (UV254 nm).

Bromine content

It was determined by the flask combustion method (JISK-729).

solubility

1 g of sample was added and dissolved in 100 g of toluene at 20 ° C, the weight of the sample before the sample was no longer dissolved was determined, and the concentration of the solution at that time was calculated. . "Viscosity

A 70% toluene solution was prepared for each of the brominated polystyrenes obtained in Examples 1 to 3, and a 50% toluene solution was prepared for the brominated polystyrene obtained in Comparative Example 1. Then, the viscosity at 25 ° C was measured with a B-type viscometer (Type BM, manufactured by Tokyo Keiki Co., Ltd.). Storage stability ''

The method of leaving the saturated flame retardant solution of the flame retardant at room temperature for 12 hours and at 0 ° C for 12 hours was repeated for 5 days, and the state of the solution was observed.

Example 1

In a £ 1 glass reactor (with stirrer, capacitor, thermometer, dripping funnel and gas absorber), add 755 g of ethylene dichloride and a port of 730 weight average molecular weight. After completely dissolving 150 g of styrene (softening point 780 ° C) and 11 g of antimony trichloride, the previously prepared chloride was maintained while maintaining the reaction temperature at 10 to 25 ° C. 72 g of a bromine solution (70% by weight of ethylene chloride solution) was added dropwise from a dropping funnel over 2 hours. After completion of the dropwise addition, the internal temperature was maintained at 20 to 30 and aged for 1 hour. After the completion of the aging, the reaction product was washed with water, and the organic layer was dropped and crystallized in 3,000 g of methanol. After the crystals were overdried, 410 g of brominated polystyrene was obtained. The weight average molecular weight of this brominated polystyrene was 1,190, and the bromine content was 70.5%. The solubility in toluene (20 ° C.) was 78.1%. The storage stability of the toluene solution was good.

Example 2

A brominated polystyrene having a weight-average molecular weight of 2,300 (softening point: 93 ° C) was used in place of polystyrene in Example 1 in the same manner. There was obtained 418 g of polystyrene. The weight average molecular weight was 3.450, and the bromine content was 65.6%. The solubility (20.C) was 77.8%. 1 1

7 Example 3

408 g of brominated polystyrene was obtained in the same manner as in Example 1, except that polystyrene having a weight average molecular weight of 530 was used instead of polystyrene. The weight average molecular weight was 860, and the bromine content was 69.4%. The solubility (20 ° C.) was 81.5%.

Comparative Example 1 '

Bromine was produced in the same manner except that polystyrene having a weight average molecular weight of 8,150 (softening point: 120 ° C) was used in place of polystyrene in Example 1. 421 g of polystyrene was obtained. The weight average molecular weight was 12,600, and the bromine content was 64.0%. The solubility (20 ° C.) was 57.3%.

Comparative Example 2

A brominated polystyrene was produced in the same manner except that polystyrene having a weight average molecular weight of 24,000 (softening point: 145 ° C) was used instead of the polystyrene in Example 1. 4 24 g were obtained. The weight average molecular weight was 64.000, and the bromine content was 68.2%. The solubility (20 ° C) was 10% or less. Table 1 summarizes the analysis results of Examples 1, 2 and 3 and Comparative Examples 1 and 2. Table 1 Weight average molecular weight Bromine content (%) Solubility (%) Viscosity (cps) Storage stability Example 1 1, 190 70.5 78.1 254 No precipitation

2 3, 450 65.6 78.8 1.150 Nono 3 860 63.8 81.5 130

Comparative Example 12, 600 64.0 57.3 70

2 64, 700 68.2 10 or less

Examples 4, 5 and Comparative Example 3

The flame retardants of Examples 1 and 2 and Comparative Example 1 were each dissolved in toluene, and the solutions adjusted to a flame retardant solid content of 70% were added to 100 parts of tung oil-modified phenol resin for a laminate, respectively. 30 parts were added, and 20 parts of cresyldiphenylphosphine were further added to prepare a resin varnish for impregnation. In addition, each of the impregnating resin varnishes was left at room temperature to observe a change in state. The varnish was impregnated with craft paper to adjust the resin content to 50% by weight. The prepreg was further dried to obtain a prepreg. A predetermined number of the prepregs were stacked, and the prepreg was breathed at 170 ° C. for 70 minutes under a pressure of 100 kg cm ² to obtain a laminate. The appearance and flammability (UL-94) of the obtained laminate were evaluated. Table 2 shows the results.

Table 21 Cresyl diphenyl-phenolic resin of laminated board Flame retardant Storage stability of phosphine varnish Flammability Example 4 100 parts A30 part 20 parts Good V-0

5 100 parts B30 parts 20 parts Good V-0 Comparative Example 3 100 parts C30 parts 20 parts Good V-1 Flame retardant A: 70% solution of brominated polystyrene of Example 1 in toluene solution B: Bromination of Example 2 70% toluene solution of polystyrene C: 55% solution of brominated polystyrene of Comparative Example 1 in toluene

(Examples 6 and 7 and Comparative Example 4)

Unsaturated polyester oligomer (composition: 1 mol of maleic anhydride, 1 mol of tetrahydrophthalic anhydride and 2.1 mol of ethylene glycol) 100 parts of Examples 1, 2 and Comparative Example 2 Each of the flame retardants was dissolved in styrene, and 16 parts, 22 parts of styrene, and 2 parts of tris (2-chloroethyl) phosphine were adjusted to a flame retardant solid content of 50%. Two parts were mixed and dissolved to obtain a resin composition liquid. This resin solution was left at room temperature to observe a change in state. After mixing 1 part of benzoyl peroxide, 0.5 part of methyl ethyl ketone peroxide and 0.5 part of cobalt naphthenate in each resin solution, sprinkle a small amount of resin on the glass mat. And soaked. Another glass mat was stacked on top of this, and the same operation was performed. After laminating three sheets, they were left at room temperature, and further heated by a dryer at 60 for 2 hours to obtain a laminated board. The appearance and flammability (UL-94) of each laminate were evaluated. Table 3 shows the results.

Table 3 Unsaturated Polyester Tris (2-Chlorethyl) Varnish Molded Polystyrene Flame Retardant Styrene

Phosphate Storage stability Flame retardant Example 6 100 parts D: 16 parts 22 parts 2 parts Good V-0

7 100 parts E: 16 parts 22 parts 2 parts Good V-0 Comparative Example 4 100 parts F: 16 parts 22 parts 2 parts Phase separation V-2 Flame retardant A 50% styrene solution of brominated polystyrene of Example 1

B 50% styrene solution of brominated polystyrene of Example 2

C 50% styrene solution of brominated polystyrene of Comparative Example 2

(Examples 8, 9 and Comparative Example 5)

The flame retardants of Examples 1, 2 and Comparative Example 1 were dissolved in 100 parts of a bisphenol A-type epoxy resin having an epoxy equivalent of 18.6 in molysyl glycidyl ether of Jib mouth, and the flame retardant solid content was reduced to 50%. 25 parts of the prepared solution, 3 parts of antimony trioxide, 2 parts of dicyandiamide and 0.5 part of 2-ethyl-4-methylimidazole were added to prepare a resin composition varnish. Each varnish was impregnated into epoxy silane-treated plain woven glass cloth so that the resin content was 35%, and dried to obtain a prepreg. A predetermined number of the obtained pre-bledas were stacked and hot-pressed with a press at 160 ° C. and 70 kgZcm ² for 1 hour to obtain a laminate. The flammability (UL-94) of the obtained laminate was measured and evaluated. The results are shown in Table 4.

Table 4

2 — Ethiloo 4

Epoxy resin Flame retardant antimony trioxide dicyandiamide

Methyli midazo

Example 8 100 parts G: 25 parts 3 parts 2 parts 0.5 part V-0.

9 100 parts H: 25 parts 3 parts 2 parts 0.5 parts V-0 Comparative Example 5 100 parts 1:25 parts 3 parts 2 parts 0.5 parts V-2 Flame retardant G: 50% dibromo of the brominated polystyrene of Example 1 Cresyl glycidyl ether solution

H: 50% dibromocresyl glycidyl ether solution of brominated polystyrene of Example 2 I: 50% mocresyl glycidyl ether solution of brominated polystyrene of Comparative Example 2

(Examples 10 and 11 and Comparative Example 6)

The flame retardants of Examples 1, 2 and Comparative Example 1 were dissolved in 100 parts of a polypropylene triol having a hydroxyl value of 56 in moclesyl glycidyl ether of Jib mouth, and the solid content was adjusted to 50%. Each 15 parts of the solution was dissolved. This solution was stored at room temperature and the condition was observed. 0.1 parts of triethylenediamine, 1.2 parts of a silicone foam stabilizer (Toray Silicone SH190), 0.4 parts of tin octylate and 4 parts of water are added to the mixture, and the mixture is added. After stirring for 10 minutes, add 50 parts of TDI-8 (a mixture of 2,4—trirange isocyanate and 2,6—trirange isocyanate 80/20) and add vigorously. After thorough stirring, it was cured in a dryer at 80 for 1 hour. The flammability (JISD-121) of the obtained polyurethane was measured and evaluated. Table 5 shows the results.

Table 5

(Polyurethane resin)

Polypropylene T D I — 8 0

Triol Flame retardant Storage stability Flame retardant Example 10 100 parts 50 parts G: 15 parts Good Self-extinguishing

11 100 parts 50 parts H: 15 parts Good Self-extinguishing

Comparative Example 6 100 parts 50 parts 1:15 parts Phase separation Slow flame 2nd grade Flame retardant G: 50% solution of brominated polystyrene of Example 1 in moclesyl glycidyl ether solution at 50% jib mouth

B: 50% molysyl glycidyl ether solution of brominated polystyrene of Example 2 in dibut mouth C: 50% molysyl glycidyl ether solution of brominated polystyrene in Comparative Example 2

"Industrial applicability"

As described above in detail, the flame retardant of the present invention has extremely good solubility in a solvent and compatibility with a resin varnish, and has a low viscosity when dissolved in a solvent. The resin composition has good storage stability. Further, molded articles obtained by curing the composition have good flame retardancy, and their physical properties such as heat resistance and mechanical properties are satisfactory, so that processed articles with excellent commercial value can be obtained. .

Claims

The scope of the claims

1. Blended polystyrene with a weight average molecular weight of 600 to 100,000 and a bromine content of 30 to 80% by weight as a flame retardant is blended with the thermosetting resin. A flame-retardant thermosetting resin composition characterized by the following.

2. The thermosetting resin is a fluorinated resin, a urine resin, a melamine resin, an epoxy resin, an unsaturated polyester resin, a diaryl phthalate resin or a polyurethane resin. 2. The flame-retardant thermosetting resin composition according to claim 1.

3. The flame-retardant thermosetting resin composition according to claim 2, wherein the thermosetting resin is a fuanol resin.

4. The flame-retardant thermosetting resin composition according to claim 2, wherein the thermosetting resin is an unsaturated polyester oligomer.

5. The flame-retardant thermosetting resin composition according to claim 2, wherein the thermosetting resin is an epoxy resin.

6. The flame-retardant thermosetting resin composition according to claim 2, wherein the thermosetting resin is a polyurethane resin.

7. The flame-retardant thermosetting resin composition according to claim 1, wherein the brominated polystyrene has a weight average molecular weight of 700 to 8,000.

8. The flame-retardant thermosetting resin composition according to claim 1, wherein the brominated polystyrene has a weight average molecular weight of 800 to 6.0000.

9. The flame-retardant thermosetting resin composition according to claim 1, wherein the brominated polystyrene has a weight average molecular weight of 850 to 4.50.

10. The flame-retardant thermosetting resin according to claim 1, wherein the amount of the brominated polystyrene is 3 to 40 parts by weight based on 100 parts by weight of the thermosetting resin. Resin composition.

11. The flame-retardant thermosetting resin composition according to claim 1, wherein an antimony compound and Z or phosphate ester are used in combination as another flame retardant.

12. A molded article obtained by processing with the flame-retardant thermosetting resin composition according to any one of claims 1 to 11.

13. The molded article according to claim 12, wherein the molded article is various molded articles, films, synthetic resin-impregnated paper, laminated articles, paints or adhesives.

D o

14. A bribleg obtained by impregnating a substrate for a laminate with the flame-retardant thermosetting resin composition according to any one of claims 1 to 11, and drying the resultant.

15. A copper-clad laminate obtained by laminating copper foil on the prepreg according to claim 14 and subjecting the prepreg to heating and pressure molding.

16. The copper-clad laminate according to claim 15, wherein the base material for the laminate of the pre-bredder is a paper phenol base material.

17. The copper-clad laminate according to claim 15, wherein the laminate substrate of the Brig reg is a glass epoxy substrate.

18. The copper according to claim 15, which is a printed wiring board. Upholstered laminate.

1 9. Brominated polystyrene having a weight average molecular weight of 600 to 100,000 as a flame retardant and a bromine content of 30 to 80% by weight as a flame retardant A method for making a thermosetting resin flame-retardant, characterized by adding a compound.