JPH10110083A - Flame-retardant acrylic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant acrylic resin compsn. having a high flame retardance without using a halogenous flame retardant by compounding an acrylic resin with ammonium polyphosphate and red phosphorus in a specified molar ratio (in terms of phosphorus) of ammonium polyphosphate to red phosphorus or by compounding an acrylic resin with ammonium polyphosphate and aluminum hydroxide or magnesium hydroxide in a specified molar ratio of phosphorus to hydroxyl group. SOLUTION: This compsn. is prepd. by compounding 100 pts.wt. acrylic resin with 10-200 pts.wt. the sum of ammonium polyphosphate and red phosphorus in a molar ratio (in terms of phosphorus) of ammonium polyphosphate to red phosphorus of 0.85-8.5 or by compounding 100 pts.wt. acrylic resin with 10-200 pts.wt. the sum of ammonium polyphosphate and aluminum hydroxide or magnesium hydroxide in a molar ratio of phosphorus to hydroxyl group of 0.24-2.55. By the synergistic effects of the combination of ammonium polyphosphate with red phosphorus or with aluminum hydroxide or magnesium hydroxide, the compsn. has a high flame retardance even when these flame retardants are compounded in low amts.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant acrylic resin composition having excellent flame retardancy. For further details (A)
Based on the P element of ammonium polyphosphate,
Flame-retardant acrylic resin composition obtained by blending (B) P element of red phosphorus, (C) OH group of metal hydrate and (D) OH group of aliphatic polyhydric alcohol at a specific molar ratio. About.

[0002]

2. Description of the Related Art Acrylic resin has excellent optical properties,
It has excellent mechanical properties, water resistance, weather resistance, and electrical insulation, and it is easy to mold, so it can be used in a wide range of fields such as building materials, electrical equipment materials, automotive materials, paints, adhesives and adhesives. It is used. However, the acrylic resin has a disadvantage that it is easily combustible among synthetic resins. For this reason, various methods for adding a flame retardant for making the resin flame-retardant have been proposed as in the case of other flammable resins.

[0003] For example, flame retardation of polymers (Enhanced New Edition No. 2
Printing)-The chemistry and actual technology-, July 20, 1989,
Taiseisha Co., Ltd. issued an acrylic resin flame retardant
Organophosphorus compounds such as phosphate esters, tricresyl phosphate, and halogenated phosphate esters are described. However, orthophosphoric acid esters have the property of lowering the softening temperature in order to impart plasticity to the acrylic resin, and if they are added in large amounts for the purpose of imparting high flame retardancy, the orthophosphoric acid ester will cause the acrylic resin surface to have a positive effect. Since the phosphate ester bleeds, it was practically hardly used.

On the other hand, halogenated phosphate esters have been used as effective flame retardants for acrylic resins. For example, it is disclosed in JP-A-57-159087, JP-A-58-31756, JP-A-59-206454, and the like. However, various problems have been pointed out, such as environmental pollution due to halogen compounds and effects on the human body, and various restrictions have been imposed on their use. Further, since halogen-based flame retardants generate corrosive gas and black smoke during fire or incineration, it is desired to develop a safer flame retardant or flame retardant system in place of the flame retardant. Was.

D. A. Ballistreri,
et al); Journal of Polymer Science (J. Pol
ymer Sci), polymer -. chemistry - Ede _Lee and Deployment (P
olymer Chem. Ed.), 21 , 679 (1983) and A-.
C. Brown et al. (ECBrown et al.); ( ... J Polymer Sci Part A Polymer Chem) Ja - Naru of polymer - Science Pas - door A, polymer - - chemistry, 2
4 , 1297 (1986) and others, it is known that red phosphorus as a non-halogen flame retardant has a flame retardant effect on acrylic resins. However, when the red phosphorus is used alone, it is not practical because the flame retardant effect is small and a toxic acid gas is generated during combustion.

[0006] Studies have been made to use ammonium polyphosphates as flame retardants for acrylic resins. For example, JP-A-56-68106 discloses an acrylic orchid-like structure containing a phosphate compound in an acrylic copolymer. However, since the phosphate compound alone has a poor flame retarding effect on the acrylic resin, it needs to be added in a large amount to the resin, and as a result, it has a disadvantage that the original physical properties of the resin are lost. Was.
JP-A-8-193187 discloses a flame-retardant pressure-sensitive adhesive containing red phosphorus and a nitrogen-containing phosphorus-based compound, and a pressure-sensitive adhesive tape using the same. However, the flame retardancy of the pressure-sensitive adhesive was not yet sufficient.

[0007]

DISCLOSURE OF THE INVENTION The present inventors have proposed a flame retardant exhibiting high flame retardancy even with a small amount of compound due to the synergistic effect of ammonium polyphosphate and other flame retardants or flame retardant auxiliaries. Intensive study was conducted to obtain a hydrophilic acrylic resin composition. As a result, they have found that a composition in which a composite flame retardant obtained by mixing specific atoms or functional groups in the flame retardant in a specific molar ratio with an acrylic resin exhibits a remarkable flame retardant effect (synergistic effect). The present invention has been completed based on the findings. As is apparent from the above description, the object of the present invention is to
An object of the present invention is to provide a flame-retardant acrylic resin composition having high flame retardancy without using a halogen-based flame retardant.

[0008]

[Means for Solving the Problems]

(A) Ammonium polyphosphate and (B) red phosphorus are blended in a ratio of 10 to 200 parts by weight with respect to 100 parts by weight of an acrylic resin. The molar ratio of the element and the P element in (B) (hereinafter referred to as P _A
/ P that _B ratio) is flame-retardant acrylic resin composition, which is a 0.85 to 8.5. (2) Ammonium polyphosphate and (C) aluminum hydroxide and / or magnesium hydroxide in a total amount of 10 parts by weight of acrylic resin
(A) at this time.
Molar ratio of the P element and the OH group of (C) (hereinafter, P _A / OH _C
(Referred to as ratio) is 0.24 to 2.55. (3) The total amount of (A) ammonium polyphosphate, (B) red phosphorus and (C) aluminum hydroxide and / or magnesium hydroxide is 100 to 200 parts by weight with respect to 100 parts by weight of the acrylic resin. The PA / PB ratio at this time was 0.85 to 8.5, and the molar ratio of the P element of (A) and (B) to the OH group of (C) (hereinafter, (P _{A + B} ) / OH _C ) is from 0.26 to 4).

(4) To 100 parts by weight of the acrylic resin, at least one selected from (A) ammonium polyphosphate and (D) aliphatic polyhydric alcohols of the following (D1), (D2) and (D3) is used. , The total amount of which is 10-20
0 in proportions as a weight unit, the molar ratio of the OH groups of the P element (D) in (A) of this time (hereinafter, referred to as P _A / OH _D ratio) is 0.28 to 2 A flame-retardant acrylic resin composition. (D1) pentaerythritol, (D2) dipentaerythritol and (D2) polypentaerythritol. (5) With respect to 100 parts by weight of the acrylic resin, (A) ammonium polyphosphate, (B) red phosphorus and (D)
1) one or more selected from aliphatic polyhydric alcohols of (D2) and (D3), the total amount of which is 10 to 200;
Parts by weight, and the P _A / P _B ratio at this time is 0.85 to 8.5, and the P of (A) and (B)
The molar ratio of the OH groups of elements and (D) (hereinafter, P _A + B / OH _D hereinafter) ratio flame retardant acrylic resin composition, which is a 0.31 to 3. (D1) pentaerythritol, (D2) dipentaerythritol and (D2) polypentaerythritol. (6) Any of the above items 1 to 5, wherein the ammonium polyphosphate is ammonium polyphosphate, melamine-modified ammonium polyphosphate, ammonium carbamyl polyphosphate, or ammonium polyphosphate coated or microencapsulated with a thermosetting resin. The flame-retardant acrylic resin composition according to claim 1. (7) Any one of the above items 1, 3 or 5, wherein the red phosphorus is red phosphorus or coating (what kind of coating?) Red phosphorus
Item 10. The flame-retardant acrylic resin composition according to item 8.

The ammonium polyphosphate of the component (A) constituting the flame-retardant acrylic resin composition of the present invention includes ammonium polyphosphate, melamine-modified ammonium polyphosphate,
Ammonium carbamyl polyphosphate or coated ammonium polyphosphate can be used, and coated ammonium polyphosphate is particularly preferably used because it has water insolubility. Here, the coated ammonium polyphosphate is obtained by coating or microencapsulating ammonium polyphosphate with a thermosetting resin, and the water solubility of these ammonium polyphosphate is 0.5% by weight or less at 25 ° C. The resin that can be used for microencapsulation may be a thermosetting resin that forms a film that is hardly permeable to water and has excellent water resistance, such as alkyd resin, allyl resin, urea resin, melamine resin, epoxy resin, and phenol. Thermosetting resins such as resin, unsaturated polyester resin, silicone resin, urethane resin, xylene resin and furan resin, or modified types of them, specially modified such as those ion-modified to anions or cations or highly condensed types And at least one of those modified with others. Among these resins, melamine resin, urea resin, urea resin, urethane resin, and phenol resin are preferably used from the viewpoints of water resistance of the resin, strength of the film, and more precise coating.

When the ammonium polyphosphate is coated with a thermosetting resin, it is particularly preferable to select a resin which is close to the polarity (solubility parameter, SP value) of the epoxy resin. That is, by bringing the polarity of the ammonium polyphosphate surface closer to that of the acrylic resin, the dispersibility in the resin can be increased, and the synergistic effect with the combined flame retardant during combustion can be further enhanced. Commercially available products of the compound include:
Sumisafe P (trade name, manufactured by Sumitomo Chemical Co., Ltd.), Sumisafe PM (trade name, manufactured by Sumitomo Chemical Co., Ltd.), Nonenen W-3
(Trade name, manufactured by Marubishi Yuka Co., Ltd.), Hoscheck P / 30
(Trade name, manufactured by Monsanto), Hoscheck P / 40
(Trade name, manufactured by Monsanto Co.), Terage C60 (trade name, manufactured by Chisso Corporation), Terage C70 (trade name, manufactured by Chisso Corporation), Hostafram AP462 (trade name,
Hoechst) and the like.

The red phosphorus of the component (B) used in the present invention includes those untreated or containing black phosphorus due to aging (red phosphorus) and those surface-treated with an inorganic substance and / or an organic substance (hereinafter referred to as red phosphorus). Etc.). In particular, coated red phosphorus is preferably used in terms of safety and ease of handling. The coated red phosphorus is disclosed in JP-A-59-1701.
No. 76, surface-treated with a coating of an inorganic filler such as aluminum hydroxide, magnesium hydroxide, etc., as disclosed in JP-A-52-125489, Preferred are those whose surface is coated with a curable resin, and those further double-coated with a thermosetting resin on the coating of an inorganic filler.

The aluminum hydroxide or magnesium hydroxide used as the metal hydrate of the component (C) used in the present invention may be a conventional commercial product, but is of a fine particle type in that high flame retardancy is obtained. Those are preferred. Aluminum hydroxide is a hydrate that is suitably selected among various metal hydrates because decomposition starts at a relatively low temperature and the effect of controlling combustion expansion is remarkable. Furthermore, the mixed system of aluminum hydroxide and magnesium hydroxide,
It is preferably used because the temperature range in which water is decomposed by thermal decomposition is widened and high flame retardancy is exhibited. As a commercially available product (is it a mixed commercial product?), Heidilite H-42M
(Trade name, manufactured by Showa Denko KK), Kisuma 5B (trade name,
(Kyowa Chemical Industry Co., Ltd.).

The aliphatic polyhydric alcohol (D) used in the present invention includes pentaerythritol,
Dipentaerythritol and polypentaerythritol can be suitably used, but in addition, starch, polysaccharides such as cellulose, glucose, mannitol, oligosaccharides such as sorbitol, sugar alcohols and the like can also be used. Can be used.

The acrylic resin constituting the flame-retardant acrylic resin composition of the present invention includes a polymer of methyl methacrylate or a copolymer containing at least 80% by weight of a methyl methacrylate component, and a copolymer containing the polymer or the copolymer. Of acrylonitrile, a copolymer containing at least 80% of an acrylonitrile component, and a mixture of the polymer or the copolymer with another polymer. Examples of the monomer used for copolymerization include, for example, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, methacrylic acid, acrylamide, N-methylol acrylamide, Examples include styrene and vinyl acetate.

In order to obtain a flame-retardant acrylic resin composition having high flame-retardant performance by using (A) ammonium polyphosphate and (B) red phosphorus together, (A) molar ratio P _a of the moles P _B moles P _a and (B) P elements in red phosphorus P elements in ammonium polyphosphate
/ P _B ratio is 0.85 to 8.5 mixing flame retardant 10
200 parts by weight, preferably 100 to 150 parts by weight. If the compounding amount is less than 10 parts by weight, sufficient flame retardancy cannot be obtained, and even if the compounding amount exceeds 200 parts by weight, the decrease in resin physical properties becomes larger than the improvement in flame retardancy obtained.

In order to obtain a flame-retardant acrylic resin composition having high flame-retardant performance by using (A) ammonium polyphosphate and (C) metal hydrate together, an acrylic resin 10
With respect to 0 parts by weight, the ratio P _A / OH _C ratio of the number of moles of (A) ammonium polyphosphate and (C) gold axis hydrate was 0.24.
The mixed flame retardant of 2.5 to 2.55 is blended in an amount of 10 to 200 parts by weight, preferably 100 to 150 parts by weight.

Further, (A) ammonium polyphosphate,
In order to obtain a flame-retardant acrylic resin composition having high flame retardancy by using (B) red phosphorus and (C) a metal hydrate together,
The ratio of the number of moles of the P element of (A) ammonium polyphosphate to (B) red phosphorus relative to 100 parts by weight of the acrylic resin, P _A /
The P _B ratio is 0.85 to 8.5, and the molar number P _{A + B} of the P element in (A) and (B) and the O number of the metal hydrate (C)
10 to 200 parts by weight, preferably 100 to 1 part by weight of the mixed flame retardant having a ratio P _{A + B} / OH _{C to} the mole number of H of 0.26 to 4
It is blended in a proportion of 50 parts by weight.

On the other hand, in order to obtain a flame-retardant acrylic resin composition having high flame-retardant performance by using (A) ammonium polyphosphate and (D) an aliphatic polyhydric alcohol in combination, 100 parts by weight of the acrylic resin Te, (a) the molar ratio P _a / OH _D ratio of the moles OH _D moles P _a and (D) an aliphatic polyhydric alcohol OH of P elements of ammonium polyphosphate is from 0.28 to 2 10 to 200 parts by weight of the mixed flame retardant,
Preferably, it is blended at a ratio of 100 to 150 parts by weight.

Further, (A) ammonium polyphosphates,
In order to obtain a flame-retardant acrylic resin composition having high flame-retardant performance by using (B) red phosphorus and (D) an aliphatic polyhydric alcohol in combination, (A) Molar ratio P of ammonium polyphosphate and P element of (B) red phosphorus
_A / P _B ratio is 0.85 to 8.50, and the number of moles of P elements (A) and _(B) P _{A +} B and (D) moles OH _D aliphatic polyhydric alcohol OH molar ratio P _a + B / OH _D ratio 10 to 200 parts by weight of mixed flame retardant is 0.31 to 3 and, preferably in a proportion of 100 to 150 parts by weight.

In the acrylic resin composition of the present invention, ordinary plasticizers, stabilizers, additives and the like can be appropriately used in combination. The additives and the like are pigments, dyes, antibacterial agents and the like, and are not particularly limited, and can be added as needed. These additives and the like are generally added in a small amount, for example, 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight based on 100 parts by weight of the resin.

[0022]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, which by no means limit the scope of the present invention. The evaluation in Examples and Comparative Examples was performed by the following method.

(1) Flame retardancy: Oxygen index (O.I.) Conforms to Japanese Industrial Standard JIS K7201 (combustion test method for polymer materials by oxygen index method).

(2) Flame retardancy: Complies with the vertical flame test specified in "flame test of plastic materials for equipment parts" of UL94V UL Subject (Underwriter Laboratories, Inc.).
The thickness of the test piece: 0.5 mm.

(3) Measurement of Smoke Amount The concentration (%) of carbon dioxide and carbon monoxide 4 minutes after combustion in an NBS smoke chamber was measured with a gas detector tube. The reduction rate of the gas concentration calculated from the total concentration (%) of carbon dioxide and carbon monoxide generated when only the resin is burned, and the total concentration (%) of carbon dioxide and carbon monoxide after burning the test piece The smoke emission reduction rate (%) was evaluated as follows.

Examples 1 to 8 Acrydic 52-204 (trade name, nonvolatile content: 45% by weight, manufactured by Dainippon Ink and Chemicals, Inc.) as an acrylic resin
Terage C60 (trade name, P concentration: 28.5% by weight, manufactured by Chisso Corp.) as (A) ammonium polyphosphate prepared in the P _A / P _B ratio shown in Table 1 with respect to 100 parts by weight. And (B) Nova Excel 140 as red phosphorus
A mixed flame retardant (trade name, P concentration 95% by weight, manufactured by Rin Kagaku Kogyo Co., Ltd.) was blended in the amount shown in Table 1, mixed well and dispersed, and then coated on release paper with a bar coater, and then heated to 40 ° C. At 24
Dried for hours. Then, the test piece was cut out into a predetermined shape except for the release paper. UL-
An evaluation of 94 V, measurement of oxygen index and fuming test were performed. The results are shown in Table 1.

Examples 9 to 11 Sumisafe PM (trade name, P concentration: 20.5% by weight) as ammonium polyphosphate (A) prepared at a P _A / P _B ratio shown in Table 2 )) And (B) Nova Excel 140 as red phosphorus (trade name, P concentration 95)
56% by weight (Rin Kagaku Kogyo Co., Ltd.).
A predetermined test piece was prepared in accordance with Example 1 except that 25 parts by weight were blended, and UL-94V evaluation, measurement of oxygen index, and smoke emission test were performed using this. The results are shown in Table 2.

[0028] Teraju C60 (trade name of a (A) ammonium polyphosphate prepared in P _A / OH _C ratio shown in Example 12-19 Table 3,
P concentration 28.5% by weight, manufactured by Chisso Corporation) and (C) Hygilite H-42M as a metal hydrate (trade name, OH
A prescribed test piece was prepared in accordance with Example 1 except that a mixed flame retardant (concentration: 65.4% by weight, manufactured by Showa Denko KK) was blended at the blending ratio shown in Table 3. UL-9
Evaluation of 4V, measurement of oxygen index and smoke emission test were performed. Table 3 shows the results.

Example 20 Terage C60 (trade name, as (A) ammonium polyphosphate) prepared at the P _A / OH _C ratio shown in Table 3
P concentration 28.5% by weight, manufactured by Chisso Corporation) and (C) Kisuma 5B as a metal hydrate (trade name, OH concentration 58.3)
Weight percent, manufactured by Kyowa Chemical Industry Co., Ltd.)
A prescribed test piece was prepared in accordance with Example 1 except that it was added in parts by weight, and UL-94V evaluation, oxygen index measurement, and smoke emission test were performed using this. Table 3 shows the results.

Examples 21 to 23 Sumisafe PM (trade name, P) as (A) ammonium polyphosphate prepared to have a P _A / OH _C ratio shown in Table 4
(Concentration: 20.5% by weight, manufactured by Sumitomo Chemical Co., Ltd.) and (C)
Heidilite H-42M as a metal hydrate (trade name,
A prescribed test piece was prepared in accordance with Example 1 except that 56.25 parts by weight of a mixed flame retardant (OH concentration: 65.4% by weight, manufactured by Showa Denko KK) was blended and used to prepare UL. −94
Evaluation of V, measurement of oxygen index and fuming test were performed. Table 3 shows the results.

Examples 24 and 25 Terage C60 (trade name, P) as ammonium polyphosphate (A) prepared to have a P _A / OH _D ratio shown in Table 5
Concentration of 28.5% by weight, manufactured by Chisso Corporation) and (D) pentaerythritol as an aliphatic polyhydric alcohol (reagent,
A prescribed test piece was prepared in accordance with Example 1 except that a mixed flame retardant of 49.9% by weight of OH, Wako Pure Chemical Industries, Ltd.) was blended in a blending ratio shown in Table 5. UL using
An evaluation of -94 V, measurement of oxygen index and smoke emission test were performed. Table 5 shows the results.

[0032] Teraju C60 (tradename (A) ammonium polyphosphate prepared in P _A / OH _D ratio shown in the Examples 26-31 in Table 5, P
Flame retardant with a concentration of 28.5% by weight (manufactured by Chisso Corporation) and (D) dipentaerythritol as an aliphatic polyhydric alcohol (reagent, OH concentration 40.1% by weight, Wako Pure Chemical Industries, Ltd.) Was prepared in the same manner as in Example 1 except that the mixture was blended in the proportions shown in Table 5.
Evaluation of L-94V, measurement of oxygen index and smoke emission test were performed. Table 5 shows the results.

[0033] Sumi Safe PM (trade name of a (A) ammonium polyphosphate prepared in P _A / OH _D ratio shown in the Examples 32-34 Table 6, P
(Density: 20.5% by weight, manufactured by Sumitomo Chemical Co., Ltd.)
Dipentaerythritol as an aliphatic polyhydric alcohol (reagent, OH concentration 40.1% by weight, Wako Pure Chemical Industries, Ltd.)
A test piece was prepared in accordance with Example 1 except that the mixed flame retardant was mixed in the mixing ratio shown in Table 6, and the test piece was used for evaluation of UL-94V, measurement of oxygen index and smoke emission test. Was performed. Table 6 shows the results.

Examples 35 to 38 Terage C60 (trade name, P concentration: 28.5% by weight, Chisso Corporation) as (A) coated ammonium polyphosphate prepared to have a P _A / P _B ratio shown in Table 7 Made) and (B)
Nova Excel 140 as red phosphorus (trade name, P concentration 9
5% by weight, manufactured by Rin Kagaku Kogyo Co., Ltd.) and (C) Hygilite H-42M as a metal hydrate (trade name, O
H concentration 65.4 wt%, except that Showa Denko Co., Ltd.) was blended with P _{A + B} / OH _C ratio mixed flame retardant was prepared as shown in Table 7 at the mixing ratio shown in Table 7 described in Example 1 A predetermined test piece was prepared in accordance with, and UL-94V was evaluated, an oxygen index was measured, and a smoke test was performed using the test piece. Table 7 shows the results.

Examples 39 to 41 Terage C60 (trade name, P) as ammonium polyphosphate (A) prepared in the ratio P _A / P _B shown in Table 7
A mixture of 28.5% by weight (manufactured by Chisso Corporation) and (B) Nova Excel 140 as red phosphorus (trade name, P concentration 95% by weight, manufactured by Rin Kagaku Kogyo KK); (D) aliphatic Dipentaerythritol as polyhydric alcohol (reagent, O
H concentration 40.1Wt%, Wako Pure Chemical Industries, P _{A + B} / OH _D mixed flame retardant prepared in ratios shown in Table 7 Co.), except that the mixing at the mixing ratio set forth in Table 7 embodiment A predetermined test piece was prepared in accordance with Example 1 and used to evaluate UL-94V.
The measurement of the oxygen index and the fuming test were performed. Table 7 shows the results.

Comparative Examples 1 to 4 Terage C60 (trade name, P concentration: 28.5% by weight, manufactured by Chisso Corporation) as ammonium polyphosphate (A) prepared in the ratio P _A / P _B shown in Table 8 Example 1 except that a mixed flame retardant of NOVA EXCEL 140 (trade name, P concentration 95% by weight, manufactured by Rin Kagaku Kogyo KK) as red phosphorus was blended in the mixing ratio shown in Table 8. A predetermined test piece was prepared in accordance with, and UL-94V was evaluated, an oxygen index was measured, and a smoke test was performed using the test piece. Table 8 shows the results.

Comparative Examples 5 to 8 Terage C60 (trade name, P) as ammonium polyphosphate (A) prepared to have a P _A / OH _C ratio shown in Table 9
Concentration: 28.5% by weight, manufactured by Chisso Corporation) and (C) Heidilite H-42M as a metal hydrate (trade name, OH concentration: 65.4% by weight, manufactured by Showa Denko KK) A predetermined test piece was prepared in accordance with Example 1 except that the fuel was mixed in the mixing ratio shown in Table 9, and the test piece was used for evaluation of UL-94V, measurement of oxygen index, and smoke test. Table 9 shows the results.

Comparative Examples 9 to 12 Terage C60 (trade name, P concentration: 28.5% by weight, manufactured by Chisso Corporation) as ammonium polyphosphate (A) prepared at the P _A / OH _D ratio shown in Table 9 And (D) dipentaerythritol as an aliphatic polyhydric alcohol (reagent,
Example 1 except that an OH concentration of 40.1% by weight and a mixed flame retardant of Wako Pure Chemical Industries, Ltd. were blended in the blending ratio shown in Table 9.
A predetermined test piece is prepared in accordance with
An evaluation of 94 V, measurement of oxygen index and fuming test were performed. Table 9 shows the results.

[0039]

The flame-retardant acrylic resin composition of the present invention comprises:
Flame-retardant acrylic resin composition that exhibits high flame retardancy even with a small blending amount due to the synergistic effect of ammonium polyphosphate and other flame retardants or flame retardant aids without using halogen-based flame retardants And can be suitably used for the production of various molded products.

[0040]

[Table 1]

[0042]

[Table 2]

[0043]

[Table 3]

[0044]

[Table 4]

[0045]

[Table 5]

[0046]

[Table 6]

[0047]

[Table 7]

[0048]

[Table 8]

[0049]

[Table 9]

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 5/06 C08K 5/06

Claims (7)

[Claims] (1) 100 parts by weight of an acrylic resin,
(A) Ammonium polyphosphate and (B) red phosphorus are blended in such a ratio that the total amount thereof is 10 to 200 parts by weight. At this time, the mole number P _A of the P element in (A) and the P in (B) _A flame-retardant acrylic resin composition, wherein the molar ratio of the element to the number of moles P _B (hereinafter, referred to as P _A / P _B ratio) is 0.85 to 8.5. 2. An acrylic resin of 100 parts by weight,
(A) Ammonium polyphosphate and (C) aluminum hydroxide and / or magnesium hydroxide are blended at a ratio of a total amount of 10 to 200 parts by weight, and the number of moles P of the P element in (A) at this time is the molar ratio of the moles OH _C OH group _a and (C) (hereinafter, P _a / OH _C ratio of) flame-retardant acrylic resin composition characterized in that it is from 0.24 to 2.55 . 3. An acrylic resin of 100 parts by weight,
(A) Ammonium polyphosphate, (B) red phosphorus and (C) aluminum hydroxide and / or magnesium hydroxide are blended at a ratio of a total amount of 10 to 200 parts by weight, and a PA / PB ratio at this time is used. Is 0.85-8.5
And the molar number P _{A + B} of the P element in (A) and (B)
And the molar ratio of the number of moles of OH groups of (C) to OH _C (hereinafter, referred to as
_{(P A + B) / OH} C hereinafter) is flame-retardant acrylic resin composition, which is a 0.26 to 4. 4. An acrylic resin based on 100 parts by weight,
(A) ammonium polyphosphate and (D) the following (D
1) One or more selected from the aliphatic polyhydric alcohols of (D2) and (D3) are blended in such a proportion that the total amount thereof is 10 to 200 parts by weight. the molar ratio of the moles OH _D of OH groups and number of moles P _a (D) (hereinafter, referred to as P _a / OH _D ratio) flame retardant acrylic resin composition characterized in that it is from 0.28 to 2 Stuff. (D1) pentaerythritol, (D2) dipentaerythritol and (D2) polypentaerythritol. 5. An acrylic resin based on 100 parts by weight,
(A) ammonium polyphosphate, (B) red phosphorus and (D) at least one selected from the following aliphatic polyhydric alcohols (D1), (D2) and (D3), in a total amount of 10 to 200 Parts by weight, the P _A / P _B ratio at this time is 0.85 to 8.5, and the number of moles P _{A + B} of the P element in (A) and (B) and (D moles OH _D ratio of OH groups) (hereinafter, P _a + B / OH _D hereinafter) ratio 0.3
A flame-retardant acrylic resin composition, which is 1 to 3. (D1) pentaerythritol, (D2) dipentaerythritol and (D2) polypentaerythritol. 6. An ammonium polyphosphate, wherein the ammonium polyphosphate is an ammonium polyphosphate, a melamine-modified ammonium polyphosphate,
The flame-retardant acrylic resin composition according to any one of claims 1 to 5, which is ammonium carbamyl polyphosphate or ammonium polyphosphate coated or microencapsulated with a thermosetting resin. 7. The red phosphorus according to claim 1, wherein the red phosphorus is red phosphorus or coated red phosphorus surface-treated with an inorganic substance and / or an organic substance.
Alternatively, the flame-retardant acrylic resin composition according to claim 5.