JPS5962610A - Manufacture of flame retardant acrylic resin molded article - Google Patents

Abstract

PURPOSE:To obtain the titled molded article having high flame retardance, by supplying methyl methacrylate, a styrene derivative, and an unsaturated acid together with a flame retardant, an alkyl acid phosphate, etc. into the space formed by the gaskets running between a pair of endless belts. CONSTITUTION:A pair of running endless belts 1, 1' are placed opposite to each other interposing a gap therebetween. A forming space is formed by the opposite faces of the belts 1, 1' and the gaskets 7, 7' running in accordance with the movement of the belts and sandwiched between the belts. A monomer mixture composed of 40-88wt% of methyl methacrylate or its prepolymer, 1-15wt% of alpha-methylstyrene, 5-15wt% of styrene, 5-15wt% of maleic anhydride, 1-15wt% of methacrylic acid, and proper amounts of a halogen-containing flame retardant, an alkyl acid phosphate, and a polymerization initiator, is supplied to the front end of the forming space by the feeder 6, and polymerized continuously in the space. A polymer plate 12 is obtained from the outlet end of the belts.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a flame-retardant acrylic resin molded product having a high degree of flame retardancy and excellent physical properties. More specifically, the present invention relates to methyl methacrylate, α-methylstyrene, and styrene.

A resin material made of maleic anhydride and methacrylic acid,
From halogen-containing flame retardants, alkyl acid phosphates and polymerization initiators; <7. ) This invention relates to a method for producing a flame-retardant acrylic resin molded product having excellent physical properties, which involves continuous casting of a polymerization raw material.

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

It is already known that flame retardancy can be imparted to acrylic resin by adding certain organic phosphate esters, but these organic phosphate esters generally have a plasticizing effect, and the resulting acrylic resin moldings It had the disadvantage that the heat distortion temperature was significantly lowered and the mechanical strength was also significantly lowered.In addition, due to the added flame retardant, the water absorption of the final composition was greatly increased. For,
When this flame retardant board was used outdoors, the sheet would absorb water and become deformed, causing crazes, which often caused product complaints.

However, it is also required to reduce the amount of flame retardant added to achieve the flame retardant effect.

Many studies have been conducted in this regard, but no satisfactory results have been obtained so far.

The present inventors have conducted intensive studies to improve the above-mentioned drawbacks of conventional flame-retardant acrylic resins, and as a result, we have found that the base polymer is either conventional methyl methacrylate alone or acrylic resin consisting of methyl methacrylate and methacrylic acid. Methyl methacrylate with a specific composition in place of resin.

Conventionally, molded products are obtained by continuously polymerizing a resin material consisting of α-methylstyrene, styrene, maleic anhydride, and methacrylic acid, a halogen-containing flame retardant, and an alkyl acid phosphate in the presence of a polymerization initiator. The present invention was developed based on the discovery that flame retardancy can be imparted superior to that of flame-retardant acrylic resins, and that the production method is economically advantageous.

In other words, the gist of the present invention is to form a gasket formed by the opposing surfaces of two endless belts that run opposite each other with a certain gap, and a gasket that follows the running of the belts while being sandwiched between the two belts. From the upstream end, methyl methacrylate monomer or its part B is added to the molding space where it is applied.
15% by weight, styrene 5-15M 1%.

Maleic anhydride 5-15% by weight and methacrylic acid 1-15% by weight
Resin material consisting of 15 heavy weight materials, halogen-containing flame retardant,
A polymerization raw material consisting of an alkyl acid phosphate and a polymerization initiator is supplied.

This allows nucleic acids to be continuously polymerized within the space.

The present invention provides a method for producing a flame-retardant acrylic resin molded article, characterized in that a plate-shaped polymer is taken out from the downstream end.

The methacrylic acid ester component constituting the molded product of the present invention has the C-chemical properties inherent to methacrylic resin.

It is a necessary component to maintain weather resistance or mechanical properties, and its li: is used in the range of 40 to 88% by weight in the resin material, and the amount used is less than 40M%. Properties are lost, and if the weight exceeds the 88-weight range, the effect of improving heat resistance and *ii combustion efficiency decreases.

Further, the α-methylstyrene component constituting the molded product is one of the components that improves the heat resistance of the molded product obtained, and is in the range of 1 to 151% by weight, preferably 3 to 1% by weight in the resin material.
Used in the 0 weight range. 1! If it is less than t%, the heat resistance will not be sufficient, and if it exceeds 15% by weight, the mechanical properties will deteriorate and at the same time productivity will decrease.

In addition, the styrene component that makes up the molded product is not a component that directly improves the heat resistance and flame retardance of the molded product, but it is a copolymer of α-methylstyrene and maleic anhydride, which are heat resistance improving components. Increasing reactivity indirectly improves heat resistance. At the same time, it has a significant effect on improving productivity, and improves the mechanical properties, colorability, and molding processability of the resulting molded product. It also has extremely favorable effects. In particular, an unexpected effect was observed in the improvement of mechanical properties and coloration properties.The ratio of styrene used is 5 to 15% by weight in the resin strip, which is less than 8% by weight. and inferior in terms of productivity.

If it exceeds 15% by weight, there is a tendency for heat resistance and optical properties to deteriorate.

In addition, the maleic anhydride component that constitutes the molded product has the effect of increasing the copolymerization reactivity of α-methylstyrene and the effect of improving the heat resistance of the molded product through interaction with styrene.
The proportion used must range from 5 to 15 M of the resin material, preferably 10 to 15 M by weight. If the usage ratio is less than 5N, it will be inferior in terms of productivity and heat resistance.
If the amount exceeds 5N, the mechanical properties and heat resistance will deteriorate.

Furthermore, the methacrylic acid component constituting the molded product has a great effect on improving flame retardancy and surface heat resistance, and its usage ratio is 1 to 15% by weight of the resin material.

Preferably it is 3 to 10% by weight, more preferably 5 to 7% by weight. If the proportion used is less than 1% by weight, the effect of improving flame retardancy and heat resistance will be small.

If it exceeds 15% by weight, the haze value of the molded product will become thicker, and the water absorption rate will increase, resulting in adverse effects on physical properties.

The above are the two essential components that make up the molded product of the present invention and their usage ratios, but they also affect productivity, heat resistance, and flame retardance of the final molded product.

Considering the overall balance of resin properties such as mechanical properties, optical properties, and processability, the number of moles of α-methylstyrene is α, and the number of moles of styrene is β.

and when the number of moles of maleic anhydride is γ.

4N α-methylstyrene in fat material F), styrene 7 j
6 and maleic anhydride blending ratio (α+β)/γ is 1.1
The most desirable relationship is between 1.5 and 1.5. When the blending ratio is less than 1.1 (13), there is a tendency for the mechanical properties, water resistance and optical properties to decrease,
In a range larger than 1.5, there is a tendency for heat resistance to decrease.

In the present invention, acrylic acid, methyl acrylate, and ethyl (meth)acrylate are used within the scope of the present invention depending on the purpose of use.

Other copolymerizable monomers such as butyl (meth)acrylate, vinyl acetate, or divinyl p/zey.

Triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate.

Polyfunctional crosslinking monomer such as trimethylolpropane trimethacrylate is added to the resin material in an amount of 20% by weight or less.
More than one species may be further blended and copolymerized.

In the present invention, a part or all of methacrylic acid, which is one component of the copolymerization, may be added to other organic acids such as acrylic acid or maleic acid.

Although it is possible to replace it with an unsaturated organic acid such as itaconic acid or a saturated organic acid, the use of methacrylic acid as in the present invention is more flame retardant.

The effect of improving heat resistance is remarkable.

The flame retardant used to construct the molded article of the present invention is a halogen-containing flame retardant such as a halogen-containing condensed phosphoric acid ester or a halogenated polyphosphonate. As the halogen-containing condensed phosphoric acid ester, chlorinated polyphosphate is desirable, and among the chlorinated polyphosphates, phosphorus-containing, i
It is preferable that the chlorine content be 5 to 30% by weight, preferably 10 to 20% by weight, and the chlorine content be 20 to 40% by weight because the flame retardant effect is large.

Examples of chlorinated polyphosphates include CR-505゜CR-509 produced by Taihe Chemical Industry Co., Ltd.
, CR-511 and CR-513, Pyro Lure 7 produced by Kashima Kogyo Co., Ltd., and APR-TH101 produced by Asahi Glass Co., Ltd., etc. Among these, CR-509 is effective when used in the present invention. Although the exact structure of CR-509 is unknown, it is a chlorine-containing condensed phosphoric acid ester with a phosphorus-carbon bond, and its chlorine content is 26.0% and phosphorus content is 14.0 yen. It is.

In addition, the chlorinated polyphosphonate used in the present invention is preferably a chlorinated polyphosphonate, and among these, a compound of the following formula called Phosgard C-22-TI produced by Monsando Corporation in the United States is particularly preferred. Effective.

0 0 CH, 0 11 II I II Argyl acid phosphate, which is used in combination with the above-mentioned rogen-containing oxidizing agent as an auxiliary combustion agent, is usually a monoalkyl acid phosphate (HO)2. - P -OR and sialgyl acid 1 phosphate HO-P-(OR)2 is an equimolar mixture, and the presence or absence is not limited to an equimolar mixture only. R is 2 to 6 carbon atoms; Of these, ethyl acid bosphate and butyl acid phosphate have excellent flame retardant synergistic effects,
Butyl acid bosphate is particularly desirable.

The amount of flame retardant used in the present invention cannot be determined unconditionally depending on the degree of flame retardance required for the product, but the amount of the main flame retardant, a compound containing Monochu 3~
40 weight ratio, more preferably 10 to 307 T yen weight ratio. The amount of alkyl acid phosphate used in combination with the nitrogen-containing flame retardant to provide a synergistic effect is 0.1 to 8N in the molded product, preferably 0.5 to 8N.
6 N, fit %, more preferably in the range of 1.0 to 4 degrees I. If the amount of the V116 retardant containing NOx is less than 3M in the molded product, it will not be sufficient to impart flame retardancy. : If it exceeds 40% by weight, the heat resistance of the molded product will decrease, and the physical properties will be significantly lowered, such as increased water absorption, so it is not preferable. Furthermore, if the alkyl acid phosphate content is too high, the synergistic effect will tend to be greater than 7;

The production method of the present invention uses the above-mentioned methyl methacrylate monomer.
a resin material comprising α-methylstyrene, styrene, maleic anhydride and methacrylic acid, and the above-mentioned ψ11 combustion agent.

After preparing polymerization group 1 by adding the alkyl acid phosphate I and the required polymerization initiator of 11.

The polymerization raw material. The upstream end of the molding space is formed by the opposing surfaces of two endless belts running opposite each other with a certain gap between them, and the gasket that follows the running of the belts while being sandwiched between the two belts. This is a method in which the polymer is supplied from the molding space, continuously polymerized inside the molding space, and a plate-shaped polymer is taken out from the downstream end.

The polymerization raw material in the method of the present invention is prepared by the 3-filtration method, or, without particular limitation, for example, adding a flame retardant and an alkyl acid phosphate to the monomer mixture described above,
Alternatively, after dissolving the flame retardant and the alkyl acid phosphate in the monomer mixture, 0.01 to 1% by weight of a radical polymerization initiator is added to the monomer mixture to produce 50 to 150T.
; Preferably, by heating at 65 to 100°C for a certain period of time, or by mixing and dissolving the above-mentioned other monomer components, flame retardant, and alkyl acid phosphate in the methacrylate-strengthened methyl partial polymer; A liquid or syrup-like resin material is prepared by, for example, dissolving a polymer flame retardant and an alkyl acid phosphate in a mixture of brown methyl methacrylate and other monomers. ′? ' A polymerization initiator is added to the resin material in an amount of 0.01 to 1.0%, preferably 0.0%. 0
Examples include a method of adding 2 to 0.5 weights. In addition,
In the method of the present invention or in the resin material, the component composition of the polymer portion and the component composition of the monomer mixed portion may be different.

The viscosity of the polymerization raw material is not particularly limited, but it is preferably about 300 to 10,000 cp (2o°'c) since it is injected onto the belt surface from an injection device. If the viscosity of Sillag is too low, there is a risk that the polymerization raw material may leak through the gasket or the injection end of the belt, and if the viscosity of Sillag is too high, it may be difficult to inject onto the belt or there is a risk of polymerization inside the piping. There are two difficulties in handling.

The polymerization raw material containing the flame retardant prepared as described above is then injected from an injection device located at one end of the endless belt into a molding space surrounded by both the upper and lower belts and the gasket. The polymerization raw material injected into the belt advances as the endless belt runs, and in the first polymerization zone, the polymerization raw material is
The polymer was heated to ~95°C and then polymerized and cured, and heat treated in a second polymerization zone at 1100~160°C to reduce residual monomers.Then, it was cooled and separated from the endless belt from the other end of the endless belt. It is extracted as a plate-like product with a size of about 5 to 30 nm. The polymerization time is 10 to 90 minutes in total in the first polymerization zone and the second polymerization zone. Further, the running speed of the endless bell i is preferably 0.5 to 4.0 fn/min.

According to the method of the present invention, it is necessary that the polymerization raw material injected into the opposing endless belts is mostly polymerized in the first polymerization zone and enters the second polymerization zone in a cured state.1. (Therefore, the selection of the polymerization initiator used is very important.

In the production method of the present invention, 't is an appropriate known radical M
(Although metering starters can be used, examples are
Azobis catalysts such as 4-dimethylvaleronitrile, lauroyl peroxide, benzoyl peroxide,
Bis(3,5゜5-trimethylhexanoyl)peroxide 7F Which diacyl oxide catalyst, bis(
Examples include bar carboner-1 type catalysts such as 4-t-butylcyclohexyl) haoxydite 7-bonate. Particularly suitable polymerization initiators in the present invention have a decomposition temperature of 30 to 90°C, preferably 40 to 90°C, with a half-life of 10 hours.
It is at 80°C. Among them, 2,2'-azobis-
2,4-dimethylvaleronitrile, azobisinbutyronitrile, bis(3,5,5-trimethylhexanoyl) haoxide, bis(4-t-butylcyclohexyl)peroxycabo t-+- are preferred in %.

If desired, other known flame retardants may be used in combination with the method of the present invention.

In addition, additives such as ultraviolet absorbers, male molding agents, heat stabilizers, plasticizers, lubricants, antistatic agents, 2 blowing agents, 2 dispersants, 9 coloring agents may be added as required. Additionally, aluminum hydroxide and magnesium hydroxide.

Inorganic fillers such as glass fiber and glass powder, powdered metals, carbon black, etc. can also be added.

Next, a continuous plate-making apparatus used in the method of manufacturing the sheet 4, which is a flammable acrylic resin molded product of the present invention, will be explained based on the drawings. FIG. 1 shows an example for implementing the present invention. However, the continuous plate making apparatus used in the present invention is not limited to the apparatus shown in the drawings.

In FIG. 1, C (11, (1')) is an endless belt, and the material of the belt is generally metal or stainless steel.

These metal belts are carefully polished to obtain a seat plate with excellent surface appearance. .

In some cases, plating is applied. The thickness of the metal belt is preferably 0.1 to 3 mm, particularly 0.5 to 2 mm.

Belt (main pulley (2), (3) and (2')
, (3') are given a predetermined tension. In the example shown in Fig. 1, a hydraulic cylinder is installed in Wang Bu IJ (21, (z')), and the tension of the belt is changed by changing the oil pressure.There is also a method of adjusting the belt tension using a spring or other mechanical method. It is publicly known.

The belt tension is preferably as high as possible in order to improve the belt configuration and improve the sheet thickness accuracy, but it is generally operated at 3 to 15 kl/myw2.

The belt is made to run again by oscillating the main pulley (3'). The belt is the main pulley (2) and (3).

The meandering can be adjusted by adjusting the angles of (2') and (3'). The meandering adjustment of the belt can be achieved by using the rolls (4), (4') in contact with the back side of the belt, or by the angle of the rolls (4), (4') provided on the return side of the belt (as shown).
: Be adjusted by changing things.

(5) shows the process of supplying polymerization raw materials.

The warmed monomers or partial mixtures of catalysts and other auxiliaries are generally fed at a constant flow rate using a constant flow pump. (6) is an injection device for supplying this liquid polymerization raw material to the space of the opposing belt. (7)
, (7') are gaskets which run following the running of the belts while being sandwiched between the opposing belts to prevent the leakage of the single polymerization raw material to the outside of the belts. The gasket used is one manufactured using soft polyvinyl chloride, polyethylene, ethylene-vinyl acetate copolymer, polyurethane, or other materials.

(4) and (4') indicate roll groups that support opposing belts from the back side. The rolls must be arranged in front of the polymerization zone and in the polymerization zone to such an extent that one polymerization raw material does not leak outside from the space formed by the opposing belts and gaskets.

The belt flexes between adjacent rolls due to the liquid pressure of the polymerization raw material, the repulsive force of the gasket, etc., but when the amount of flexure increases, the sheet thickness accuracy deteriorates and the belt becomes distorted.

Furthermore, if a gap occurs between the belt and the gasket, the polymerization raw material will leak.

In some cases, outside air can enter through the rinsing gap and form bubbles in the sheet. A way to solve these problems is to keep the deflection of the belt to a minimum, but it is desirable to narrow the roll spacing and increase the belt tension. For this purpose, it is desirable that the roll arrangement interval, that is, the estimated distance between adjacent rolls, be approximately 20 to 100 crrL.

The rolls are set so that even when the polymerization raw material polymerizes and shrinks, it moves with the polymerization raw material and does not move away from the back surface of the belt.

(8) and (8') indicate a spray device for heating a belt provided in the polymerization zone by applying water leakage to the belt. Any temperature below iO O'C can be used as the hot water temperature, but in order to avoid increasing the size of the continuous polymerization apparatus and to reduce productivity, it is preferable to carry out the polymerization as quickly as possible. Temperatures on the order of 50-95°C are used. (9).

(9') indicates a far-infrared heater provided in the second polymerization zone that heats the sheet to 100°C or higher, usually 100 to 160'''C, in order to remove residual monomers.

A far-infrared heater is an effective heating means for raising the temperature of the sheet. The heater is generally covered with a belt by a heat insulating duct in order to effectively utilize its heat quantity. The heated sheet passes through a heat insulating duct so as to be maintained at a required temperature for a required period of time. To achieve an appropriate temperature profile, multiple far-infrared heaters can be installed as appropriate, or air can be blown into heat-insulating ducts.

Another method 2 is also possible, for example by providing a hot air stove.

(lO) and (11) indicate cooling or insulating zones for cooling the notes that have passed through the second polymerization zone under appropriate neutrality.

(12) shows a sheet manufactured through the above process.

The method of the present invention makes it possible to produce highly flame-retardant acrylic resin molded articles continuously and with high productivity, and furthermore, it is possible to produce flame-retardant acrylic resin molded articles continuously and with high productivity, and furthermore, it is impossible to produce them using the conventional cell-casting method using glass. This makes it possible to produce long sheets and wide sheets, which is extremely advantageous industrially.

The flame-retardant acrylic resin molded article produced by the method of the present invention uses the above-mentioned specific copolymer as a base polymer in combination with two kinds of flame retardants: a halogen-containing flame retardant and an alkyl acid bosphate. Therefore, the mutual synergistic effect imparts excellent flame retardancy and physical properties, resulting in U
Even when achieving flame retardancy that passes the L standard V-O standard, it is possible to reduce the amount of the main flame retardant added to about 20 inches, and the physical properties decrease due to the addition of a flame retardant. In particular, it has a unique effect of significantly improving the decrease in heat resistance.

By the method of the present invention? % leakage resin moldings.

Due to its excellent flame retardancy and physical properties, it is used as a building material,
It is useful for applications such as electrical equipment materials, signboards, glazing materials, and lighting materials.

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

In addition, the physical property evaluation fi[Ii in the examples is I- measured based on the method below.

1) Combustion test Using the vertical method in accordance with the U.S. UL standard 5ubject 94, a set of 5 samples was tested (1) Maximum combustion duration (seconds) after the first 10 seconds of flame contact (2) Maximum value of combustion duration (seconds) after the second 1.0 second flame contact and (3) 11 dazzers/pull (5 pieces) measured in the first and second combustion tests above. Coordination of combustion duration (
seconds) was measured.

2) Heat distortion temperature (1-I, D, T) After annealing and drying at 80°C for 16 hours.

Measured in accordance with ASTM D-648.

3) Water absorption: 80"C: The sample was annealed and dried for 16 hours in tap water. After immersing the sample for 24 hours, the adhering water was wiped off with gauze, and the increase in Mt was measured.

Example 1 76.5 parts of methyl methacrylate, 35% of α-methylstyrene, 10 parts of styrene, and maleic anhydride were placed in a 3,000 p cylindrical vertical reactor equipped with a heating jacket, a cooling jacket, a condenser, and a vertical stirrer. acid 10%
A monomer mixture of 1.000-6 was charged and heated. When the temperature of the monomer mixture was raised to 80°C, 2,2'-azobis-2,4-dimethylvaleronitrile was added as a polymerization initiator in an amount of 0.25% based on the monomer mixture and stirred. The monomer mixture started the polymerization reaction and reached a saturation temperature due to the heat of combination, and after 15 minutes had passed from the time when reflux started from the condenser and one polymerization initiator was added, it was rapidly cooled and heated to 20°C. A silubular partial polymer having a viscosity of 2,610 cp and a polymerization conversion of 31 was obtained.

To 72 parts of the siliculate partial polymer prepared as above, 6 parts of methacrylic acid, 20 parts of CR-509 (chlorinated polyphosphate, manufactured by Ohana Kagaku Kogyo Co., Ltd.), JP
2 parts of -504 (butylated bosphate, manufactured by Johoku Kagaku Kogyo Co., Ltd.), 1000 ppm of aerosolol OT (dioctyl sulfosuccinate), additional polymerization initiator Dojimata Tribonox 36 (binu (3,5,5- trimethylhexanoyl) peroxide, manufactured by Kayaku Nouri Co., Ltd.)
was added at a ratio of 0.14% to the resin component and dissolved by stirring. Next, the obtained polymerization raw material was degassed under reduced pressure to form a mirror-finished product with a thickness of 2 mm and a width of 1 mm.
．． It was poured into a continuous polymerization reactor V equipped with a 200 mm stainless steel bell 14' and set at a belt clearance of 3 mm as shown in Figure 1, and then heated at 8 (+'C) for 30 minutes at 136°C.
The material was heated and polymerized for 3 minutes to obtain a 9-plate thickness of 3 mx.

The physical properties of this plate were evaluated and the results are shown in Table 1. The resulting resin plate had good transparency and haze value (ASTM
]-, )1.003) was 1.3%.

Comparative example 1 Methyl methacrylate, α-methylstyrene/.

The same cylindrical vertical reaction vessel as in the case where only methyl methacrylate monomer was used in place of the monomer mixture of glutinous acid and maleic anhydride was heated at 1000 A. After the temperature of the monomer was raised to 80 DEG C., 0.065 ml of 2,2'-azobis-2,4-dimethylvaleronitrile as a polymerization initiator was added to the monomer and stirred. The monomer starts the polymerization reaction, reaches saturation temperature due to polymerization heat, begins to reflux from the condenser, and after 8 minutes have passed from the time when 1 polymerization initiator is added, it is rapidly cooled, and the viscosity at 20°C is 1800c
A silubular partial polymer with a conversion ratio of 22 was obtained.

Methacrylic H6? fL CIl-5092
0 parts, Aerosolol OT 1.000 ppm Additional 2,2'-azobis-2,4-dimethylvaleronitrile was added as a polymerization initiator at a ratio of 0.083% to the resin component, stirred, and dissolved. I let it happen. Next, the obtained polymerization raw material was degassed under reduced pressure "F-", and then poured into the same continuous plate making apparatus as in Example 1 with a belt clearance of 3 mm, and heated at 74°C for 33 minutes. 136℃
The resin plate was heated and polymerized for 3.5 minutes to obtain a resin plate having a thickness of 3πm.

The physical properties of this resin plate were evaluated and the results are shown in Table 1.

Table 1 As is clear from Table 1, the resin molded product of the present invention (Example 1)
) has significantly improved flame retardancy and heat distortion temperature compared to the conventional flame-retardant acrylic resin composition (Comparative Example 1), and
It can be seen that it passed the L94V-0 standard, and the water absorption rate was also reduced, indicating that the physical properties were improved.

Example 2 The viscosity at 20'C8C was 357 in the same manner as Comparative Example 1.
A siliculate partial polymer of 0 cp of methyl methacrylate was prepared, and the siliculate partial polymerization 'II 502.
6 parts, 25.6 parts of α-methylstyrene, 73 parts of styrene, 73 parts of maleic anhydride, 70 parts of methacrylic acid, 200 parts of CR-509, JP-5042
-0 parts, Aerosolol OT 1 part, Tribonox 36
3.2 parts and 55.8 parts of Acrybet VH (polymethyl methacrylate powder manufactured by Mitsubishi Rayon Co., Ltd.) were added and dissolved. Next, the obtained polymerization raw material was placed under reduced pressure and degassed, and the belt clearance was set to 3 mm K.
It was injected into the continuous polymerization apparatus of Example 1 which was heated at 82"C for 3
The resin plate was then heated at 136° C. for 3.5 minutes to obtain a resin plate with a thickness of 3. The transparency C of this plate was good.

The physical properties of this plate were evaluated and shown in Table 2.

Comparative Example 2 The methacrylic acid j of Example 2 with a viscosity of 3540 cp
Methyl methacrylate monomer was added to the silt-like partial polymer of H/L/, and the viscosity was adjusted to 7.100 cp Vr.
- To 710 parts of the prepared product and 70 parts of methacrylic acid, 200 parts of cR-509, 420 parts of JP-50, 1 part of Aerosolol OT and 0.664 parts of 2,2'-azobis-2,4-dimethylvaleronitrile were added. Stir again to dissolve. The resulting polymerization raw material was then degassed under reduced pressure, poured into the continuous polymerization apparatus of Example 1 with a belt clearance of 3 mm, and heated and polymerized at 74°C for 33 minutes and then at 136°C for 3.5 minutes. A resin plate with a thickness of 3 mm was obtained.

The physical properties of this plate were measured and shown in Table 2.

Table 2 Example 3 Silk-like portion prepared in Example 1 (methacrylic [70 parts, CR-509200
parts, JP-50431) parts, bis(4-t-butylcyclohegycyl)baroxydicarbonate 3.5 parts
After dissolving and adding part of the resin, a resin plate having a thickness of 3 mm was obtained in the same manner as in Example 1. When a combustion test was conducted on this resin plate, the maximum value of the first combustion duration was 0. /[
seconds, the maximum value of the second combustion duration is 0.8 seconds.

The total burn duration was 4.0 seconds. Further, the heat deformation temperature of the resin plate was measured and found to be 75.8°C.

In addition, in the above example, methacrylic acid was not used, except that 770 parts of the siliculate partial polymer was used (in the same manner, a flammable acrylic resin board of 30 cm was manufactured. Regarding the board (when we conducted a combustion test, the maximum value of the first combustion duration was 1.2 seconds, but the maximum value of the second combustion duration was 28.3 seconds, The total time was 49.7 seconds.The heat deformation temperature of the resin plate was 62.4°C.

Example 4 30 parts of methacrylic, 200 parts of CR-509,
JP-504], part O, and 3.4 parts of 2.2'-azobis=(2,4-dimethylvaleronitrile) were dissolved and added, and the same procedure as in Example 1 was carried out to obtain a 3 mm resin plate. . When we conducted a combustion test on this resin plate, the maximum value of the first combustion time was 0.9 seconds, the maximum value of the second combustion time was 5.8 seconds, and the total combustion duration. is 1
It was 2.9 seconds.

In addition, in this example, JP-504 was not used and 770 parts of the syllabary partial polymer was used.
A resin plate of mm was obtained. When this resin plate was subjected to a combustion test at °C, the maximum value of the first combustion duration was 2.
5 seconds, the maximum value of the second combustion duration is 34.2 seconds,
The total burn duration was 65.8 seconds.

Example 5 The cylindrical column of Example 1 was used as a reaction tank, and 76% of methyl methyl, 4% of α-methylstyrene, and 10% of sulfuric acid were added.
Monomer mixture 10 consisting of and 10% maleic anhydride
00. , e were prepared and heated.

When the monomer mixture was externally heated to 80°C, polymerization started at 1[
Then, 625% of the monomer mixture was added with -C2,2'-isobis-2,4-dimethyl)chloronitrile and stirred. The mixture of monomers starts a monomer reaction, reaches a saturation temperature due to the heat of polymerization, begins to reflux from the condenser, and after 15 minutes have elapsed since the addition of the nitrogen initiator, it is rapidly cooled to a temperature of 20'C. A 7-lap partial polymer having a viscosity of 2,530 cp and a polymerization conversion of 30.5 was obtained.

6 parts of methacrylic fermentation, 20 parts of Phosgard C-22-R (chlorinated polyphosphonate 1, manufactured by Monza/To Co., Ltd.), and JP-504 for 72 parts of the slag-like partial polymer prepared as above. (butyl acid bosphate, manufactured by Johoku Kagakujo Co., Ltd.) 2 parts, additional polymerization initiator and tribonox 36 (bis(3,5,5-trimethylhexanoyl)noxide), Kayaku Nouri ( Co., Ltd.) was added at a ratio of 10.4 parts to the resin component and dissolved by stirring. Next, the resulting polymerization raw material was degassed under reduced pressure, poured into the continuous polymerization apparatus in which the belt clearance of Example 1 was set to 3, and was heated at 80°C for 30 minutes.
The resin plate was then heated and polymerized at 136°C for 3 minutes to obtain a resin plate with a thickness of 3 mm.

The physical properties of this plate were evaluated and shown in Table 3 (Zamburu 1).

For comparison, only methyl methacrylate was used and the viscosity at 20°C was 1830 in the same manner as in Comparative Example 1.
cp, a silubular partial polymer with a polymerization conversion of 22.1% was prepared. Using this silubular partial polymer, the method of this example was repeated to obtain a resin plate having a thickness of 3πm.

The physical properties of this plate were evaluated and the results are shown in Table 3 (Zangle %2).

Table 3

[Brief explanation of drawings]

FIG. 1 is a side view of the entire apparatus showing an example for implementing the present invention, (11, (1') is a work/dress belt, (2), (2'), (3), (3 ') represents the main pulley, (5) represents the injection device, (7) and (7') represent the gasket, and (12) represents the sheet-like molded product.

Claims (1)

[Claims] (]) Opposing surfaces of two endless belts running opposite each other with a certain gap, and a running gap gasket that follows the running of the belt while being sandwiched between the two belts. From the upstream end, methyl methacrylate monokuma 8 or its partial polymer 40 to H polymer is introduced into the molding space. α-methylstyrene 1-15tt%, methylef 5-1
A polymerization raw material consisting of a resin material consisting of a 5-fold f# group, a 5-15 weight group of maleic anhydride, and a 1-15 weight group of methacrylic acid, a non-rogen-containing flame retardant, an alkyl acid phosphate, and a monopolymerization initiator. 1. A method for producing a flame-retardant acrylic resin molded article, which comprises supplying the polymer, continuously polymerizing it inside the molding space, and taking out a plate-shaped polymer from the downstream end. (2) Flame retardancy as described in item (1) of the patent tram request, characterized in that the halogen-containing flame retardant is at least one selected from halogen-containing condensed phosphoric acid esters or halogenated polyphosphonates. A method for producing an acrylic resin molded product. (3) A method for producing a flame-retardant acrylic resin molded product according to claim (1), wherein the polymerization initiator is 2,2'-azobis-2,4-dimethylvaleronitrile. . (4) T4j that the polymerization initiator is bis(3,5,5-)IJ methylhexanoyl)barogizide.
A method for producing a flame-retardant acrylic resin molded article according to claim (1). (5) Production of a flame-retardant acrylic resin molded product according to claim (1), wherein the M initiator is bis(4-t-butylcyclohexyl)baroxydicarbonate. Method. (6) The method for producing a flame-retardant acrylic resin molded product according to claim (1), wherein the viscosity of the polymerization raw material is 300 to 10,000 centimeters/cm (20°C).