JPS5941349A - Flame-retardant acrylic resin composition and its preparation - Google Patents

Abstract

PURPOSE:To prepare a highly flame-retardant composition without lowering the heat resistance of the base resin, by compounding a halogen-containing condensed phosphoric acid ester to a copolymer of methyl methacrylate, alpha-methylstyrene, styrene, maleic anhydride, and methacrylic acid. CONSTITUTION:The objective resin composition is prepared by adding 3-40wt% of a halogen-containing condensed phosphoric acid ester, preferably a chlorinated polyphosphate having a phosphorus-content of 10-20wt% and chlorine-content of 20-40wt% as a flame-retardant, to a mixture of 40-88wt% of methyl methacrlate or its oligomer, 1-15wt% of alpha-methylstyrene, 5-15wt% of styrene, 5- 15wt% of maleic anhydride, and 1-15wt% of methacrylic acid, or the prepolymer of the mixture, and polymerizing the monomers by heating in the presence of a polymerization initiator. The molar ratio (alpha-methylstyrene+styrene)/(maleic anhydride) is preferably 1.1-1.5 to obtain a polymer having balanced heat resistance, flame retardance and optical properties, etc. USE:Building material, material for electric device, illumination material, etc.

Description

[Detailed Description of the Invention] The green invention is a flame-retardant acrylic resin set that has a high degree of flame retardancy, flame resistance, and excellent physical properties! This invention relates to an i15 product and a method for producing the same. More specifically, the present invention is as follows.

Methyl methacrylate, α-methylstyrene, styrene,
Anhydrous Malein MAN Yopi Methacrylic [, J': Rinaru 5
A flame-retardant acrylic resin composition having excellent physical properties comprising a copolymer and a rogen-condensed phosphoric acid ester, and a method for producing the same.

Acrylic resin is a thermoplastic resin whose main component is methyl methacrylate, and its outstanding transparency, excellent weather resistance, good mechanical properties, and heat resistance make it suitable for lighting materials, signboards, displays, and building materials. Although it is widely used in electrical equipment, equipment, etc., its field of use is limited because it is flammable.

It is already known that flame retardancy can be imparted to acrylic resins by adding certain organic phosphate esters; (In addition to significantly lowering the heat distortion temperature of the fat molded product, the λ strength is also thicker and lower.
V: It had some drawbacks such as: Also, due to the added flame retardant, the water absorption of the final set f'Jy increases greatly, so when this brochure board is used outdoors, the sheet may absorb water and become deformed or craze may occur. This often led to product complaints.

Therefore, there is a need to minimize the amount of flame retardant added in order to achieve flame retardant effects.

Although many studies have been conducted regarding this issue, no satisfactory results have yet been obtained.

The present inventors have conducted intensive studies to improve the above-mentioned drawbacks of conventional flame-retardant acrylic (tI) resins, and as a result, we have found that only conventional methyl methacrylate, f, or methyl methacrylate and methacrylate can be used as a paste polymer. Methyl methacrylate with a specific composition in place of the acrylic resin made of aluminum.

A 5-element copolymer consisting of α-methylstyrene, styrene, maleic anhydride and methacrylic acid is used, and a rogen condensed phosphoric acid ester is added as a flame retardant.
The present invention was achieved based on the discovery that by doing so, superior flame retardancy compared to conventional flame retardant acrylic resins can be obtained.

That is, 1 the gist of the present invention is that 40 to 88ti% of methyl methacrylate, 1 to 88ti% of α-methylstyrene
15tRt%, methyl ref 5-15 weight part, maleic anhydride [5-15 weight part], and methacrylic acid 1-15M (1
A flame-retardant acrylic resin composition consisting of a 1% copolymer and a halogen-containing condensed phosphoric acid ester, and a methyl methacrylate monomer or a partial polymer thereof 40 to 88 it
%, α-methylstyrene 1-15% by weight.

A monomer mixture or a partial polymer thereof consisting of 5 to 15 percent by weight of methacrylic acid, 5 to 15 percent by weight of maleic anhydride, and 1 to 15 percent by weight of methacrylic acid.

A method for producing a flame-retardant acrylic resin composition, characterized in that a halogen-containing condensed phosphoric acid ester is added and polymerized in the presence of a polymerization initiator.

As mentioned above, the copolymers constituting the composition of the present invention include 40 to 5% methyl methacrylate, 1 to 15% α-menalstyrene, and 5 to 15% styrene.
, Maleic anhydride 5E15 It is obtained from polymerized Kotoriko.

The methacrylic acid ester component that makes up the copolymer has optical properties inherent to methacrylic resin. It is a necessary component to maintain weather resistance or mechanical properties, and its content is used in the range of 40 to 88]j㎖φ in the copolymer, and the amount used is 40 to 88㎖.
If it is less than Chongqi Man, the upper ml will lose its l) property, and 8
If the amount exceeds 8 times [jt%], the effect of improving heat resistance 1 (I:) and flammability becomes small, which is not preferable.

Further, the α-methylstyrene component constituting the copolymer is one of the components that improves the heat resistance of the obtained copolymer, and is contained in the range of 1 to 15% by weight in the copolymer. Preferably 3~
It is conveniently used in a range of 10% by weight. If it is less than It-t & %, the heat resistance will not be sufficient, and if it exceeds 15 M, the mechanical properties will deteriorate and at the same time the green Pr properties will decrease, making it undesirable (
The styrene component constituting the copolymer is not a component that directly improves the heat resistance and flame retardance of the copolymer, but it is a component that directly improves the heat resistance and flame retardance of the copolymer, but it does not directly improve the heat resistance and flame retardancy of the copolymer, but it does contain α-methylstyrene and maleic anhydride, which are heat-resistant clay components. It indirectly improves heat resistance by increasing the copolymerization reactivity of acids, and at the same time has a significant effect on improving productivity, and improves the mechanical properties, colorability, and moldability of the resulting copolymer. It also has an extremely favorable effect on improving workability. Especially mechanical properties. A completely unexpected effect was observed in improving coloration. The proportion of styrene used in the copolymer is 5 to 15 times. If the 5TLIM is less than 1%, the productivity is poor, and if it exceeds 15%, the heat resistance and optical properties tend to deteriorate, which is not preferable.

In addition, the maleic anhydride component constituting the copolymer has the effect of increasing the copolymerization reactivity of α-methylstyrene and its interaction with styrene, and has the effect of improving the heat resistance of the copolymer. A range of 5 to 15% by weight is required, preferably 10 to 15% by weight. [If the historical ratio is less than 5% fjk, productivity and heat resistance will be poor.

If the content exceeds 15% by weight, the mechanical properties and heat resistance will deteriorate, which is not preferable.

Furthermore, the methacrylic acid component constituting the copolymer has a great effect on improving the flame retardancy and heat resistance of the flame-retardant resin composition of the present invention, and its usage ratio is 1-15 IJt%,
It is preferably 3-10% by weight, more preferably 5-7% by weight. If the usage ratio is less than one ridge φ, the effect of improving flame retardancy and heat resistance will be small, and if it exceeds 15 weight ratio, the haze value of the flame retardant resin composition will increase, and the water absorption rate will increase, etc. This is undesirable because it has a negative impact on the environment.

The above are the essential components of the copolymer constituting the composition of the present invention and their usage ratios, but what about productivity?
Heat resistance and flame retardance of the final copolymer 1 Considering the overall resin properties such as mechanical properties, optical properties, or processability, how many moles of α-methylstyrene, α, and how many moles of snalene? When the number of moles of α-methylstyrene/, styrene and maleic anhydride in the copolymer is γ, the blending ratio of α-methylstyrene/, styrene and maleic anhydride (α + β)/r is 1
．． It is most desirable that the relationship be between 1 and 1.5. When the blending ratio was less than 1.1, it was observed that mechanical properties, 1III' aqueous properties, and optical properties tended to be low.71. , in a range larger than 1.5, there is a tendency for heat resistance to decrease.

In the present invention, the copolymer constituting the composition may be acrylic acid, methinoacrylic acid, or acrylic acid within the scope of the present invention, depending on the purpose of use.

(meth)ethyl acrylate, (meth)acrylic v fuy
Polyfunctional polymers such as divinylbenzene, triallyl cyanurate, triallyl in cyanurate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, etc. -C- within the range of 20% by weight or less in the crosslinkable single M body age/copolymer
One or more of them may be further blended and copolymerized.

Further, in the present invention, part or all of methacrylic acid, which is one component of the copolymer, may be substituted with other compounds 1 & 2, if necessary.
f? It is also possible to replace IJ with unsaturated organic acids such as acrylic powder, maleic acid, itaconic acid, and saturated organic acids;
When used at night, the flame retardant and heat resistant effects are more pronounced.

As the halogen-containing condensed phosphoric acid ester of the flame retardant used to form the composition of the present invention, chlorinated polyphosphate is preferable. It is preferable to use 10 to 20 double stitches and a chlorine containing TLT of 20 to 40 tJf clay because it has a strong flame retardant effect.

Examples of chlorinated polyphosphates include CR-505 and CR-50 produced by Daihe Chemical Industry Co., Ltd.
9, CR-511 and CR-513, Kashima Industries Co., Ltd.
Vyroll 77.1lfl Glass Co., Ltd., which is produced by
Examples include APR-THIOl, which is produced in

Among these, cR-5o9 is effective when used in the resin composition of the present invention. Regarding CR-5 (19), the exact number of parts is unknown.

A chlorine-containing condensed phosphoric acid ester having a phosphorus-carbon bond,
Its base content h1. is 26.0% and phosphorus content is 14.
It is 0%.

The acid of the halogen-containing condensed phosphorus ester used in the present invention cannot be determined unconditionally depending on the degree required for the product, but usually 3 to 40 polymers per resin composition, more preferably 10 to 30 polymers. I am in charge. If the total amount of flame retardant is less than 3M@3, it will not be sufficient in terms of imparting flame retardancy, and if it exceeds 40% by weight, the heat resistance of the resin composition will decrease and the water absorption rate will increase, resulting in poor physical properties. It is not desirable because it is large.

The resin composition of the present invention may be used as long as it does not impede the object of the present invention.V) There are no particular restrictions on the manufacturing method. 1311 minutes M compound + C** is added to a flaming cup and subjected to bulk polymerization or bath iv * polymerization in the presence of a polymerization initiator, and the above-mentioned 4L
) A method such as blending a copolymer consisting of an it-form with a retardant and a retardant may be mentioned.

A preferred example of the case where a monomer mixture or a partial polymer thereof is added to the monomer mixture or a partial polymer thereof is added to the monomer mixture or a partial polymer thereof, and the polymerization is carried out in the presence of a polymerization initiator. , (50 to 150°C with addition of a polymerization initiator of 1.01 to 1.0 Jyusha).

Preferably, the partially polymerized product obtained by heating at a temperature of 65 to 100°C is decomposed by adding a &l combustion agent and a polymerization initiator, and then heated to a template made of glass, stainless steel, or aluminum, etc. It is injected into a cell composed of a gas quart made of vinyl chloride and polymerized at a temperature of 50 to 90°C, resulting in a secondary polymerization of 100 to 16 liters (10 to 1 liter at a temperature of 1°C).
Cast polymerization, which is a bulk polymerization method in which polymerization is carried out for 80 minutes, begins at t''L. The method for preparing a partial polymer when performing cast polymerization is not particularly limited, and in addition to the above-mentioned method, 1.
A method of mixing and dissolving the above-mentioned other monomer components and flame retardant, in which the methyl methacrylate 1F polymer or its copolymer and the flame retardant are dissolved in a mixture of methyl methacrylate and other monomers. For example, the composition of the polymer part in the one-part polymer and the composition of the monomer mixture i'ilj may be different.

As the polymerization initiator used in cast polymerization, known radical polymerization initiators can be used.9 For example, azobisisobutyronitrile, 2゜2'-azobis-2,4-
azobis-based catalysts such as dimethylvaleronitrile, lauro(/l/peroxide, penzoyl baroxide,
Examples include diacyl peroxide-based catalysts such as bis(3,5°5-trimethylhexanoyl)peroxide, and barcarbonate-based catalysts.

On the other hand, as a method for producing a composition by a blending method, there is a method in which V) still or bog melt of a copolymer obtained by bulk or solution polymerization is blended with an M11 retardant and then extruded.

The resin composition of the present invention may also be used in combination with known flame retardant additives, if desired. Ultraviolet absorber according to the necessary expenses, release! (Rehearsal 1 [.

Heat stable firmness, plasticizer, lubricant, antistatic IF agent 1 foaming agent.

Additives such as a dispersant, a nucleating agent, and a coloring agent may be added. Furthermore, inorganic materials such as aluminum hydroxide, magnesium hydroxide, glass fiber, glass powder, powdered metals, carbon black, etc. can also be added.

Instead of using a conventional methyl methacrylate polymer or a copolymer of methyl methacrylate and methacrylic acid as a base polymer, the acrylic resin composition of the present invention has nine monomers of the above-mentioned specific composition of the present invention, Are you looking for a resin composition of a copolymer obtained from a mixture or a partial polymer thereof, and a halogen-containing condensed phosphoric acid ester? Nashinohiji and [
~Using - "by the same &+l#: Combustion reduction m
When using tY, the flame retardance of No. 7 is significantly improved compared to conventional flame retardant acrylic resins.

4. The acrylic thread and fat silk composition according to the present invention has excellent flame retardancy and physical properties. For building materials.

Electrical equipment materials, signboards, gusseting materials: T6 and lighting materials, etc., which are useful once a month.

Examples (C1r) A concrete explanation of the present invention will be given below. However, these are merely illustrative examples of the present invention and are not intended to limit the present invention in any way.

Implementation 1] 1 Methyl methacrylate 76 (1/, α-methylstyrene 407', styrene 1 (1 (I P and
J((water maleic acid 1 (10/'(!'cooling tube, 7
^A After putting it into a separable flask set with a temperature meter, 1.q stirring, and heating it while stirring, the internal temperature was 70℃ and the temperature was 2.2
'-azobis-(2,4-dimethylvaleronitrile) 1
．． After adding OJ'Y and maintaining the internal temperature at 95° C. for 10 minutes, the mixture was cooled to room temperature to obtain a silubular partial polymer.

For this partially polymerized product 730P, methacrylic acid 70/
, CR-509 (j, i-polyphosphate, Co., Ltd.)
200 Table 2 Compare the results of Table 1 and pAz table. It is clear that the ρMp flame 1/t is extremely superior to the conventional flame-retardant acrylic (νI fat composition VC), which is a co-tlr combination of former methyl and methacrylic acid -Svory 7-1. 〇：Spear, Ru.

Example 2 Methacrylic 1 methyl 10001' (+- cooling tube, temperature i+, stir bar placed in a separable flask with stirring bar, then heated with stirring to give 2.2'-azobis-(2, 4-dimethylvaleronitrile) 650
After adding RLL and holding at an internal temperature of 100'C for 7 minutes, the mixture was cooled to room temperature to obtain a slag-like partial polymer.

For this partially polymerized product 558.4/, α-methylstyrene 25.67', styrene/73/, anhydrous malemono 73/, methacrylic h Schiff 0/, CR-50920 (
JJ', Aerosolol 0TIJ', and 2,
2'-azobis-(2,4-dimethylvaleronitrile)
After adding and dissolving the composition in 6401n9', the composition was injected into a cell formed by two sheets of tempered glass facing each other at a distance of 3 through a polyvinyl chloride gasket.
It was immersed in warm water at ℃ for 16 hours to polymerize and harden. then 1
The mixture was treated in an air heating oven at 35°C for 2 hours. After cooling, the frame was removed to obtain a 4Ii (fat board) with a thickness of 3 mm.About this resin board, U
A vertical in combustion test was conducted in accordance with L standard 5 object 94. For a set of five samples, the combustion duration after the first and second IO injection flames was determined to be rt? Flammability was good.

Comparative Example 2 In Example 2, α-methylstyrene and sutisine. The procedure was exactly the same as in Example 2 except that only a partial polymer of methacrylic acid was used without using maleic anhydride.℃ 3 consisting of a copolymer of methyl methacrylate and methacrylic acid
I got my friend's resin board.

When the same combustion test as in Example 2 was carried out on this (α The duration of combustion after second flame contact was longer than 3 () seconds.

Example 3 α-methylstyrene 28,
Styrene 79 F, anhydrous maleic acid 79/, methacrylic acid 60/, CR-509150/, Aerosolol 0TI)j4 and 2,2'-azobis-(2,4-
After addition of dimethylvaleronitrile (dimethylvaleronitrile) 672 No. 9, the same procedure as in Example 2 was carried out to obtain a 4[f] thick plate with a thickness of 3 fins.

Regarding this resin plate, the same UL standard 5ubj as in Example 1 is applied.
A vertical combustion test was conducted in accordance with ECT 94. The first and second 1O second contact coal bale combustion durations were measured for a set of five samples. The results are shown in Table WJ3.

Table 3 The optical properties of this plate were measured according to ASTM D 1003, and the total light transmittance was 92.4 cm, and the haze value was 1.0, which was good. Also, the heat distortion temperature is ASTM
I) When measured in accordance with 648 V, it was found to be 96.0, which was good.

Comparative Example 3 For comparison, a partial polymer of methyl methacrylate was prepared for 7901 without using alpha-methyl styrene/l styrene/maleic anhydride 1112 in Example 3. y) σ) I read the grain board once a month.

Examples: 3 and 1 conducted various combustion tests on this resin plate.
1 The results are shown in Table 4.

Table 4 'A Comparison of 3rd coat and 4th coat, Marimotoza 6 light σ, > mI
It is clear that the flammability of the acrylic resin composition shows an immediate effect on fJ+.

Claims (2)

[Claims] (1) Methyl methacrylate 40-88 ht%,
α-Methylstyrene 1-153[1%], methacrylic acid 5-15%, maleic anhydride 5-15% and methacrylic acid 1-15%, and halogen-containing condensed phosphoric acid ester A flame-retardant acrylic resin composition consisting of. (2) Methyl methacrylate monomer or partial polymer thereof 40-88% by weight, α-methylstyrene 1-15t
lt person, styrene 5~15iLlf. 5-15% by weight of maleic anhydride and 1-1% of methacrylic acid
A flame-retardant acrylic resin composition characterized in that a halogen-containing condensed phosphoric acid ester is added to a monomer mixture consisting of 15 monomers or a partial polymer thereof and polymerized in the presence of a polymerization initiator. Production method.