JPS5949253A - Flame-retardant acrylic resin composition and manufacture of the same - Google Patents

Abstract

PURPOSE:To obtain titled composition retaining flame-retardancy comparable to or higher than that of conventional flame-retardant acrylic resins, also having high heat resistance and low water absorptivity, by blending a specific five- component copolymer consisting mainly of methyl methacrylate with specific two sorts of organophosphorus-based flame-retardant. CONSTITUTION:The objective composition can be obtained by blending (A) a coplymer prepared from (1) 40-88wt% of methyl methacrylate or its partial polymer, (2) 1-15wt% of alpha-methylstyrene, (3) 5-15wt% of styrene, (4) 5- 15wt% of maleic anhydride, and (5) 1-15wt% of methacrylic acid with (B) 3- 40wt% based on the whole composition, of a halogenated polyphosphonate (esp. chlorinated polyphosphonate of formula) and (C) 0.1-8wt% based on the whole composition, of an alkyl acid phosphate (esp. butyl acid phosphate). Alternatively, the mixture of the above five components (1)-(5) is incorporated with the above two flame-retardants followed by carrying out a copolymerization to obtain the objective compostion. The molar ratio [(2)+(3)]/(4) of 1.1-1.5 is most preferable in the context of total resin balance.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention 0 relates to a flame-retardant acrylic resin composition having high flame-retardant properties and excellent physical properties, and a method for producing the same.

More specifically, the present invention combines a five-component copolymer of poly(methyl methacrylate/styrene/maleic anhydride/α-methylstyrene/methacrylic acid) with two specific organophosphorus flame retardants. Used flame-retardant acrylic 4R41 resin composition with excellent physical properties and Part 8! ! It is related to the method of sending.

Acrylic resin is an outstanding thermoplastic resin whose main component is methyl methacrylate. transparency.

Excellent weather resistance, good mechanical properties and thermal properties make it suitable for lighting materials, heavy boards, displays, and festival materials.

Although it is widely used as a material for electrical equipment, its field of application is limited because it is flammable.

By adding a certain type of organic phosphate ester to acrylic resin! D) Il=Although it is already known that flammability can be imparted, these organic phosphoric acid esters generally have a plasticizing effect. It has the disadvantage that it significantly lowers the heat distortion temperature of the resulting acrylic resin molded product and also lowers its mechanical strength. Furthermore.

Due to the added flame retardant, the water absorption of the 4ff+ fat composition increases, and when used outdoors, the molded product absorbs water and deforms or crazes, which often results in product complaints.

The present inventors conducted extensive research to improve the above-mentioned drawbacks of conventional flame-retardant acrylic resins.

As a base polymer, a 5-component copolymer of poly (methyl methacrylate/styrene/maleic anhydride/α-methylstyrene/methacrylic acid) with a specific composition was used instead of the conventional acrylic resin made of methyl methacrylate. By using this in combination with two specific types of organic phosphorus flame retardants, it is possible to maintain flame retardancy equivalent to or higher than conventional flame retardant acrylic resins, while achieving even better heat resistance and lower water absorption. This has led to the completion of the invention of a novel female flammable resin composition having the following physical properties.

The present invention particularly provides (A) methyl methacrylate or a partial polymer thereof 40
-88 Jugeki% (]3) α-Methylsgoolene 1-15% by weight
(c) A copolymer prepared from 5-15% by weight of styrene, 5-15% by weight of maleic anhydride, and (g) 9g of methacrylic acid, 1-15% by weight, a 10-genated polyphosphonate, and an alkyl acid phosphate. It is a flame-retardant acrylic resin composition that is characterized by:

Furthermore, the present invention provides methyl methacrylate monomer or partial polymer thereof, 40-8-8% polyphase, α-methyl/L styrene 1-
15% by weight, 5-15% by weight of styrene.

A mixture consisting of maleic anhydride 5-15% and methacrylic acid 1-1%, or a partial polymer thereof, to which a no-loginated polyphosphonate and an alkyl acid pos-7ate are added, :tli combination Di
This is a method for producing a flame-retardant acrylic resin composition, which is characterized by copolymerizing in the presence of an initiator.

In the present invention, 40-88% by weight of the methyl methacrylate monomer or partial polymer (A) is unnecessary in order to maintain the original optical properties, weather resistance, or mechanical properties of the methacrylic resin. If the ingredients are less than 40 weight and 9 C, these properties will be lost; on the other hand, if the weight exceeds 88 weight, the effect of improving heat resistance and 77. .

■) The component α-methylstyrene is 4 of the resulting copolymer.
It is one of the ingredients that improves thermal properties, and the ready-to-prepare ratio is required to be in the range of -15 to 9.

Preferably it is 3-10% by weight. If the amount is less than 1%, the thermal properties are sufficient, and if it exceeds 15%, the mechanical property Jj1 decreases and at the same time the productivity decreases.
Component 3 and C), which is undesirable, does not directly improve heat resistance or combustibility. By increasing heat resistance, it indirectly improves heat resistance, and at the same time has a remarkable effect on improving productivity, and also improves the mechanical properties, colorability, and moldability of the resulting copolymer. It also has extremely favorable effects on styrene.In particular, completely unexpected effects were observed in improving mechanical properties and coloration.The blending ratio of styrene is required to be 5-15% by weight. If it is less than 5% by weight, the productivity is poor, and 15% by weight.
Exceeding this is not preferable because there is a tendency for heat resistance and optical properties to deteriorate.

Maleic anhydride (component 0) is α-methylstyrene (component)
It has the effect of increasing the copolymerization reactivity of /N and the interaction with the styrene of component G), and has the effect of improving the heat resistance of the copolymer, and a range of 5-15% is required. , preferably l (1-15 weight t9g).

If it is less than 5% by weight, the productivity and heat resistance will be poor, and if it exceeds 15% by weight, the mechanical properties and heat resistance will deteriorate and the building will not be good.

Component (c) methacrylic acid has a great effect on improving the flame retardancy and heat resistance of the flame-retardant resin composition of the present invention, and its composition ratio is required to be 1-15% by weight. preferably 3-10% by weight, more preferably L (Id 5 7
Heavy, F': Teal at 19. tff! When it is less than t-1ii"X, the effect of improving flame retardancy and iJ thermal properties is small,
If it exceeds 5% by weight, the haze value of the flame-retardant resin composition becomes large and the water absorption rate increases, resulting in undesirable physical effects.

The above are the 9 components essential for the synthesis of the base polymer required for the present invention: - Non-polymer (for methyl methacrylate, it also includes its partial polymer) components and their blending ratios. ↓Finally (the heat resistance of the copolymer,
Flame retardancy 1 Resin (mechanical properties, optical properties, processability, etc.)
Considering the overall balance of t and 44 properties, the blending ratio of each component is (
The most desirable quantitative relationship is that α+β)/r is 1.1 to 1.5.
When the ratio is too small, mechanical properties, i=I aqueous properties, and optical properties tend to deteriorate; 1. FIJ: In a larger range, there is a tendency for surface j thermal properties to decrease.

Depending on the purpose of use, other copolymerizable monomers such as acrylic acid, methyl acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, vinyl acetate, or divinylbenzene, Contains polyfunctional crosslinkable monomers such as triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate-1, and trimethylolpropane trimethacrylate within a range of 20% or less. Above the weight 6th. 7th. ...It may be blended as a component.

This invention'! A part or all of the methacrylic acid is a monomer component of the base polymer that makes up 1 g of methacrylic acid. Although it is possible to replace it with a saturated organic acid, when methacrylic acid is used as in the present invention, the effect of improving flammability and heat resistance is more remarkable.

As the chlorinated polyphosphonate (used in the present invention), chlorinated polyphosphonates are preferable, and among them, Posgard C, which is well produced by Komeshi Monosanto Co., Ltd.
A compound of the following formula called -22-R failed [I];
It is particularly effective when used together with a resin composition.

In the present invention, as an auxiliary fuel, an alkyl acid phosphate used together with the halogenated polyphosphonate (01) is usually present as a monoalkyl compound, but is limited to a 1-equimolar mixture. Long life. 10h (: In the formula, R is an alkyl group having 2 to 6 carbon atoms, among which ethyl acid phosphate and phthyl azide phosphate are non-flammable synergistic 'I'
Excellent JJ effect + 'H' has the desired amount of phthyl azide phosphate.

As the alkyl acid phosphate used for foil cutting, either a non-halogenated alkyl acid phosphate or a halogenated alkyl acid phosphate can be used, but it is necessary to use an alkyl acid phosphate that is halogenated with lf or Ir. "Na(,!1ijA
In terms of synergistic combustion effect and peeling effect of the molded product from the mold, non-halogenated alkyl acid phosphates give more favorable results.

``A--The length of the sash 1 used in the invention can vary considerably depending on the specifics of the sash 1''1 required for the product.

The usage date of the halogenated polyphosphonate at the main combustion time 1 is usually 9, and the final quick combustion composition is formed! 3-4 against the snout
0i'Lj 4;) '? X + 4d, I
O-30゛ser4% TAl. Its use is less than 3 times and 1 time, and it is not sufficient in terms of combustible force. If the weight ratio of 40 is increased, the properties of the resin composition decrease to 1 of 1, and the water absorption rate increases by 1. The use of an alkyl acid phosphate used in combination with the non-rogenated polyphosphonate is usually 1,1 to 8 times the alkyl Acid phosphate has a strong plasticizing effect and tends to increase the water absorption ratio of resin molded products, so it is not desirable to use more than 8 times (0, 5-6, It is preferably within the range of 0% by weight.

It is particularly preferable to use it within the range of 1.0-4.0% by weight. If it is less than 0.1% by weight, a sufficient phase separation effect cannot be obtained.

As long as the resin composition of the present invention achieves the object of the present invention, there are no particular limitations on the manufacturing method thereof.

For example, a method in which a flame retardant is added to the above monomer mixture or a partial polymer thereof and bulk polymerization or solution polymerization is carried out in the presence of a polymerization initiator, and a method in which a flame retardant is added to the above monomer mixture or a partial polymer thereof, and a method in which a flame retardant is added to the above monomer mixture or a partial polymer thereof and subjected to bulk polymerization or solution polymerization in the presence of a polymerization initiator; Examples of methods include blending with a curing agent.

A preferred example of adding a flame retardant to a monomer mixture or a partial polymer thereof and carrying out polymerization in the presence of a polymerization initiator is to add 0 to the monomer mixture or a partial polymer thereof. .01 T 1. A flame retardant and a polymerization initiator were added and dissolved in a partially polymerized product obtained by adding OM Kage% of a polymerization initiator and heating at a temperature of 50 to 150 °C, preferably 65 to 100 °C. After that, it is injected into a cell composed of a template made of glass, stainless steel, or aluminum, etc. and a gasket made of polyvinyl chloride, and the
Cast polymerization is a bulk polymerization method in which polymerization is carried out at a temperature of 0° C. for 10 to 180 minutes, followed by polymerization at a temperature of 100 to 160° C. for 10 to 180 minutes. The method for preparing a partial polymer when performing cast polymerization is not particularly limited, and in addition to the above-mentioned method, for example, a partial polymer of methacrylic G (methyl), the other base metal components described above, and a llj retardant may be added to the partial polymer. How to mix and dissolve.

Examples include a method of dissolving a methyl methacrylate polymer or a copolymer thereof and a flame retardant in a mixture of methyl methacrylate and other monomers, and the component composition of the polymer portion in a one-part polymer. The component compositions of the monomer mixing portion and the monomer mixing portion may be different.

As the polymerization initiator used during cast polymerization, known radical polymerization initiators can be used.

For example, azobis-based melts such as azobisisobutyronitrile, j,2'-azobis-2,4-dimethylvaleronitrile, lauroyl peroxide, benzoyl peroxide, bis(3,,5,5-trimethylhexane), etc. Examples include diacyl peroxide-based catalysts such as (noyl) peroxide, and percarbonate-based catalysts.

On the other hand, as a method for producing a composition using a blending method.

Examples include a method of blending a pulverized or melted copolymer obtained by bulk or solution polymerization with a flame retardant and extruding the mixture.

If desired, other known flame retardant agents can be used in combination with the resin composition of the present invention.

Also, if necessary, UV absorber + LT + F type agent, heat stabilizer, plasticizer, lubricant, antistatic agent, 9 foaming agent, 1 dispersant.

Nucleating agent 2 Additives such as coloring agents may be added. Furthermore, inorganic fillers such as aluminum hydroxide, magnesium hydroxide, glass fiber and glass powder, powdered metals, carbon black, etc. can also be added.

The flame-retardant acrylic resin composition according to the present invention uses the above-mentioned specific copolymer as a base polymer together with two types of flame retardants: a halogen-containing condensed horn-↑ acid ester and an alkyl acid phosphate. The additive effect of each other gives excellent flame retardancy and physical properties, and as a result, the addition of main 46 flame retardants can provide flame retardancy that passes the standards of UL standard V-O. It is possible to reduce the amount to about 20%, and has the unique effect of significantly improving the deterioration of physical properties, especially the deterioration of heat resistance, caused by the addition of a refractory agent.

The acrylic resin composition according to the present invention has excellent flame retardancy and physical properties, so it is useful for applications such as building materials, electric spacing materials, signboards, glazing materials, and lighting. .

The content of the present invention will be specifically explained below with reference to Examples.
The present invention is not limited to these.

In addition, physical property evaluation in Examples was measured based on the following method.

(1) Combustion test...US UL standard 5 object 9
For one set of 5' samples using the vertical method according to 4.

1. The maximum value of the combustion duration after the first 10-second indirect flame (seconds) 2. The maximum f residue value of the combustion duration after the second 10-second indirect flame (seconds); and 3. dl of the samples (5 pieces) traced 15'+-" in the first and second combustion tests described in Jl.
The total baking duration (in seconds) was measured.

(2) Heat distortion temperature: Annealing at 80°C for 16 hours.

After INK'l/Xl, measured in accordance with ASTM D-648.

(3) Water absorption: Annealing at 8()°C between l G +r: ;

j;2: 24 orb of the sample in tap water
After soaking for 62 minutes, the adhering water was wiped off with gauze and the weight increase was measured. (To) 11 cases 1 Methyl methacrylate 760 f, α-methylstyrene 402. Styrene 1 (+ (1?) and maleic anhydride 1002 were placed in a separable flask equipped with a cooling tube, a thermometer, and a stirring bar, and then heated with stirring to form 2,2'-azobis at an internal temperature of 70°C. -(2,4-dimethylvaleronitrile) 1°Of was added.

After maintaining the internal temperature at 95° C. for 10 minutes, the mixture was cooled to room temperature 1 to obtain a silubular partial polymer.

For this partially polymerized product 7202, methacrylic acid 602,
Phosgard C-22-R (chlorinated polyphosphonate, U.S. Monosanto ■5) 200f, JP504 (butyl acid phosphate, made by Johoku Kagaku 2°14@) 20
After adding and dissolving 624 μl of 2 and 2,2′-azobis-(2,47 dimegylvaleronitrile), it is formed with two sheets of tempered glass facing each other at a distance of 3ffI+ with a polyvinyl chloride gasket interposed between them. The composition was injected into the prepared cell and immersed in warm water at 65° C. for 16 hours to polymerize and harden.

Then, it was heat treated in an air heating furnace at 135°C for 2 hours. After cooling, the cell was removed to obtain a resin plate with a thickness of approximately 3 m. The physical properties of this plate were evaluated by TT' and the values shown in Table 1 were obtained.

Ratio Example 1 Instead of a monomer mixture consisting of methyl methacrylate, α-methylstyrene, styrene and maleic anhydride, 1
A resin plate of Comparative Example 1 was obtained in exactly the same manner as in Example 1, except that a syllabary partial polymer was prepared using only 00(l) of methyl methacrylate monomer.The physical properties of the resin plate were evaluated. The values shown in Table 1 were obtained.

As shown in Table 1, when the physical properties of the resin plates of Example 1 and Comparative Example 1 are compared, it is clear that the effects of the present invention are excellent.

Table 1 As is clear from Table 1, the flame-retardant acrylic resin composition of the present invention (Example 1) using the resin composition of the present invention as a pace polymer was obtained from methyl methacrylate and methacrylic acid. Compared to the conventional flame-retardant acrylic resin composition (Comparative Example 1) using a copolymer as a base polymer, the flame retardance and heat distortion temperature are significantly improved, and the UL94V-
It can be seen that it passes the standard of 0. It can also be seen that the water absorption rate has also been improved.

Example 2 Methacrylic acid 302% was added to 7601% of the siliculate partial polymer prepared in Example 1. Phosgard C-22-R2
00f, JP504 10 f, 2.2'-azobis-
(2,4-dimethylvaleronitrile) 6401”?
After adding and dissolving 1 ton of Hyaazolol OT (dioctyl sulfosuccinate), 311! ! ! The composition was injected into a cell formed by two sheets of tempered glass facing each other at a distance of 65
It was immersed in warm water at ℃ for 16 hours to polymerize and harden. then 1
Heat treatment was performed for 2 hours in an air heating oven at 35°C. After cooling, the cells were removed to obtain a resin plate with a thickness of approximately 3 mm. Combustion tests were conducted on this board, and for a set of five samples, the maximum combustion duration after the first 10 seconds of indirect flame was 0.
3 seconds, the maximum combustion duration after the second 10 second indirect flame was 5.4 seconds, and the total combustion duration was 11.6 seconds.

Sample Example 2 A comparative resin plate f was obtained in exactly the same manner as in Example 2, except that JP504 was not used in Example 2. A combustion test was conducted on this resin plate in the same manner as in Example 2.
The maximum combustion duration after second indirect flame was 2.8 seconds, but the combustion duration after second 10 second indirect flame tel:
There were times when the time exceeded 3 seconds and 6 seconds. A comparison between Example 2 and Comparative Example 2 reveals the excellent flame retardant effect achieved by the combination of the two sister flame agents of the present invention.

Example 3 Methacrylic acid 702. Phosgard C-22-R
After starving and dissolving 200r, JP 504 30f and 2,2'-azohysu(2,4-dimethylvaleronitrile) 616■, two reinforced sheets facing a 3-ga gap formed by a polyvinyl chloride gasket were added. The composition is injected into a cell formed of glass.

It was immersed in warm water at 65° C. for 16 hours to polymerize and harden.

Then, it was heat treated in an air heating furnace at 135°C for 2 hours. After cooling, one cell was removed to obtain a resin plate with a thickness of about 3'+++m. This plate was subjected to a combustion test in the same manner as in Example 2, and the heat distortion temperature was measured. 1. As a result, the combustion duration after the first flame contact was about 0.3 seconds for the f-triple, and the combustion duration after the second flame contact was 1.3 seconds for each sample. () seconds or less 3, heat distortion temperature) 6
9 was 76.1°C.

Comparative Example 3 A resin board was obtained in exactly the same manner as in Example 3, except that methacrylic acid was not used and the siliculate partial polymer 7702 used in Example 1 was used. A combustion test was conducted on this resin plate in the same manner as in Example 3; the deformation temperature was measured. As a result, in the combustion test, the combustion duration after the first flame contact was less than 1.0 seconds for each sample, but the maximum combustion duration after the second flame contact was 24 to 35 seconds. The combustion duration was 160 seconds.

Moreover, the heat distortion temperature decreased to 62.5°C.

Example 4 After putting 1,000 g of methyl methacrylate into a separable flask equipped with a cooling tube, a thermometer, and a stirring pot, it was heated with stirring to produce 2.2'-azobis-(2.2'-azobis-() at an internal temperature of 85°C.
2,4-dimethylvaleronitrile) was added,
After maintaining the internal temperature at 100° C. for 7 minutes, the mixture was cooled to room temperature to obtain a silubular partial polymer.

For this partial polymer 558.41F, α-methylstyrene 25.6f, styrene "t3t, m water maleic acid 73F, methacrylic acid 602. Phosgard C-22-
R180r, JP 504 301F, -1-
Azolol o'rlr, and 2,2'-azobis-(2
, 4-dimethylvaleroni) IJ Le) 632■ was added and dissolved.

The composition was injected into a cell formed of two sheets of reinforced glass facing each other at a three-fur interval with a polyvinyl chloride gasket interposed therebetween, and was immersed in warm water at 65° C. for 16 hours to polymerize and harden. It was then treated in an air heating bath at 135°C for 2 hours.

After cooling, the cells were removed to obtain resin plates with three different thicknesses. A combustion test was conducted on this resin plate. For each set of 5 samples, the combustion duration after the first 10 second indirect flame was measured, and the combustion duration after the second 10 second indirect flame was measured.
The results shown in Table 2 were obtained.

Table 2 shows the optical properties of this resin plate according to ASTM D1003.
When measured based on 1-t, the total light permittivity was 91.8%.

The haze value is also 1. ' 39 (, and the transparency was good.

The heat distortion temperature was 75.4°C.

Example 5 For 527.'l of the siliculate partial polymer of methyl methacrylate prepared in Example 1, 24.1? of α-methylstyrene, 69? of styrene, and maleic anhydride (
1469f, methacrylic acid 602. Hosgard C knee 22-R220f, JP504 30? , aerosol 0Txf, and 2,2′-azobis=(
After adding and dissolving 600 μm of 2,4-dimethylvaleronitrile, a flame-retardant acrylic resin composition of the present invention was obtained in the same manner as in Example 4.

A combustion test similar to that in Example 4 was conducted on this plate.

As a result, the combustion duration after the first flame contact was almost zero seconds for each sample, and the combustion duration after the second flame contact was 1 second or less for each sample. Furthermore, the combustion duration was 3 seconds. The total light transmittance of this plate was 92.09g, the haze value was good at 2.1%, and the heat distortion temperature was 72.0°C.

Claims (1)

[Claims] J, Methyl methacrylate or partial polymer thereof 4088
M amount %, α-methylstyrene 1-15i'B, 9
, 5-15% by weight of styrene, 95-15% by weight of maleic anhydride and 1-15% by weight of methacrylic acid, and a halogenated polyphosphonate and an alkyl acid phosphate. Acrylic resin composition. 2. The flame-retardant acrylic resin composition according to claim 1, wherein the halogenated polyphosphonate is a chlorinated polyphosphonate. 3. 40-88% by weight of methyl methacrylate single fI deca or its partial polymer, 1-15% by weight of α-methylstyrene, 5-15% by weight of styrene, 5-15% by weight of maleic anhydride
% by weight and methacrylic #1-15% by weight, or a partial polymer thereof, after adding thereto the halogenated polyphosphonate and the alkyl acid phosphate. A method for producing a flame retardant acrylic resin composition, which comprises copolymerizing in the presence of a polymerization initiator.