JP2000313785A - Resin composition for flame retardant molding material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition for flame retardant molding materials having sufficient flame retardancy and workability. SOLUTION: This resin composition for flame retardant molding materials comprises a radically polymerizable resin containing a phosphoric acid ester (meth)acrylate and aluminum hydroxide. The phosphorous atom content in the radically polymerizable resin is 0.7-10 wt.% based on the whole amount of the radically polymerizable resin. The phosphoric acid ester (meth)acrylate is at least one species selected from a group comprising phosphoric acid monoester (meth)acrylate, phosphoric acid diester (meth)acrylate and phosphoric acid triester (meth)acrylate and the relation among the molar ratio (M1) of phosphoric acid monoester (meth)acrylate, the molar ratio (M2) of phosphoric acid diester (meth)acrylate and the molar ratio (M3) of phosphoric acid triester (meth)acrylate is expressed by the following equations, 1.5<=[(M1)×1+(M2)×2+(M3)×3]<=3 and (M1)+(M2)+(M3)=1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a vehicle / machine component,
The present invention relates to a resin composition for a flame-retardant molding material suitably used as a material for molded articles such as building materials, containers, electronic / electric parts, OA equipment, precision machines, films, sheets, pipes and the like.

[0002]

2. Description of the Related Art Unsaturated polyester, epoxy (meth)
In recent years, radical polymerizable oligomers such as acrylate, urethane (meth) acrylate, and polyester (meth) acrylate can impart various excellent physical properties after curing when used as a radical-curable resin composition. And in the field of molded articles. Molded articles obtained by curing the resin composition containing these radically polymerizable oligomers have inherently flammable properties as organic substances. It is necessary to provide the flame retardancy required to meet the standards.

It is known to use aluminum hydroxide as a technique for imparting flame retardancy to a molded article. This is because the hydrated aluminum hydroxide releases water of crystallization during combustion to absorb heat.
However, in order to impart sufficient flame retardancy to a molded product simply by adding aluminum hydroxide to the resin composition,
It is necessary to mix a very large amount of aluminum hydroxide, and as a resin composition, there are various problems in workability, physical properties of molded articles, and the like.

Accordingly, a technique has been proposed in which aluminum hydroxide and a phosphate ester as a flame retardant are used in combination in a resin composition for a molding material. The phosphoric acid ester as the flame retardant is generally esterified with a phosphoric acid compound such as phosphoric anhydride or phosphorus oxychloride and an alcohol. The phosphoric acid ester is capable of forming a film of phosphorus oxide on the surface by a thermal decomposition step at the time of combustion and exhibiting flame retardancy to a molded article by an effect of shielding oxygen by the film. Therefore, a molded article made of a resin composition for a molding material in which aluminum hydroxide and a phosphoric acid ester are blended is more effective due to a synergistic effect of an action of absorbing heat during combustion and an action of shielding oxygen on the surface of the molded article. It is considered that the flame retardancy of the molded article can be improved.

[0005] However, since such a phosphate ester is generally simply added to a resin composition,
During the molding or over time, the phosphate ester may bleed on the surface of the molded product, and it may not be possible to obtain uniform flame retardancy as a molded product. Further, the molded product has heat resistance, water resistance, electric characteristics, and the like. Properties may be reduced. In addition, when aluminum hydroxide and a certain phosphate ester are simultaneously added to the resin composition, the interaction between the two causes a significant increase in the viscosity of the resin composition, resulting in markedly inferior workability during molding. There is also a problem that it is difficult to produce a molded article in the above application. Therefore, by blending aluminum hydroxide and a phosphate ester, while imparting sufficient flame retardancy to the molded product, heat resistance and water resistance, various physical properties required for the molded product such as electrical characteristics do not decrease, Further, a resin composition for a flame-retardant molding material having sufficient workability has been demanded.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition for a flame-retardant molding material having sufficient flame retardancy and workability in view of the above situation.

[0007]

The present invention relates to a resin composition for a flame-retardant molding material, comprising a radically polymerizable resin containing a phosphate (meth) acrylate and aluminum hydroxide. The content of phosphorus atoms in the radically polymerizable resin is 0.7 to 10% by weight based on the total amount of the radically polymerizable resin, and the phosphoric ester (meth) acrylate is a phosphoric monoester (meth)
It is composed of at least one selected from the group consisting of acrylate, phosphoric diester (meth) acrylate, and phosphoric triester (meth) acrylate, and has a molar ratio of the phosphoric acid monoester (meth) acrylate (M1 ), The molar ratio of the phosphoric diester (meth) acrylate (M2), and the molar ratio of the phosphoric triester (meth) acrylate (M3) are: 1.5 ≦ [(M1) × 1 + (M2) × 2+ (M3) ×
3] ≦ 3 (provided that (M1) + (M2) + (M3) = 1).

The present invention is also a molded article obtained by molding the resin composition for a flame-retardant molding material. Hereinafter, the present invention will be described in detail.

The resin composition for a flame-retardant molding material of the present invention comprises:
It comprises a radically polymerizable resin and aluminum hydroxide. The radical polymerizable resin is a component that is cured by a radical polymerization reaction in the resin composition for a flame-retardant molding material of the present invention. The radical polymerizable resin contains a phosphate (meth) acrylate. The radical polymerizable resin contains a phosphorus atom. The content of the phosphorus atom in the radical polymerizable resin is 0.7 to 10% by weight based on the total amount of the radical polymerizable resin. 0.7
If the amount is less than 10% by weight, sufficient flame retardancy cannot be imparted to the molded article. If the amount exceeds 10% by weight, the cost of the resin composition increases. More preferably, 1.5 to 10% by weight
It is.

In this specification, (meth) acrylate means acrylate or methacrylate,
(Meth) acryloyl represents acryloyl or methacryloyl.

The phosphoric acid ester (meth) acrylate of the present invention forms a film of phosphorus oxide on the surface by a thermal decomposition step during burning of the molded article, and the molded article has a flame-retardant property due to its action of shielding oxygen. The resin composition is incorporated into the resin skeleton by a polymerization reaction during curing of the resin composition, so that there is little risk of bleeding on the surface of the molded product, and uniform flame retardancy is imparted to the molded product. And the action can be exerted over time in the molded article. The phosphate (meth) acrylate is at least one selected from the group consisting of phosphate monoester (meth) acrylate, phosphate diester (meth) acrylate, and phosphate triester (meth) acrylate. It is.

The phosphoric acid monoester (meth) acrylate, the phosphoric diester (meth) acrylate, and the phosphoric acid triester (meth) acrylate include one, two, and three phosphoric acid esters, respectively. The monomer is not particularly limited as long as it has a bond and a (meth) acryloyl group, and examples thereof include the following. These may be used alone or in combination of two or more.

Examples of the above-mentioned phosphoric acid monoester (meth) acrylate include mono (2- (meth) acryloyloxyethyl) acid phosphate and mono (2- (meth) acryloyloxyethyl) acid phosphate.
(Meth) acryloyloxypropyl) acid phosphate, mono (3- (meth) acryloyloxypropyl) acid phosphate, mono (3- (meth) acryloyl-2-hydroxyloxypropyl) acid phosphate, mono (2- (meth) acryloyl) (Oxyethyl) methyl acid phosphate, mono (2- (meth) acryloyloxyethyl) ethyl acid phosphate, and the like.

Examples of the phosphoric diester (meth) acrylate include di (2- (meth) acryloyloxyethyl) acid phosphate and di (2- (meth) acrylate).
Acryloyloxypropyl) acid phosphate,
Di (3- (meth) acryloyloxypropyl) acid phosphate, di (3- (meth) acryloyl-2-
(Hydroxyloxypropyl) acid phosphate,
(3- (meth) acryloyloxypropyl) (2-
(Meth) acryloyloxyethyl) acid phosphate and the like.

Examples of the phosphoric acid triester (meth) acrylate include tri (2- (meth) acryloyloxyethyl) phosphate, tri (2- (meth) acryloyloxypropyl) phosphate, tri (3-
(Meth) acryloyloxypropyl) phosphate,
Tri (3- (meth) acryloyl-2-hydroxyloxypropyl) phosphate, di (3- (meth) acryloyl-2-hydroxyloxypropyl) (2- (meth) acryloyloxyethyl) phosphate, (3-
(Meth) acryloyl-2-hydroxyloxypropyl) di (2- (meth) acryloyloxyethyl) phosphate and the like.

Further, compounds having a monoester, diester or triester structure in the same molecule can also be used. Among these, the following general formulas are given because the possibility of generating a combustible substance during combustion of the molded article is low, and the content of phosphorus atoms in the radically polymerizable resin is appropriate.

[0017]

Embedded image

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents a divalent hydrocarbon chain having 1 to 10 carbon atoms and / or a —CH ₂ CH (OH) CH ₂ — chain. Where n is
Represents an integer of 1 to 3. ) Are preferred.

The molar ratio (M1) of the phosphoric acid monoester (meth) acrylate and the phosphoric acid diester (meth)
The molar ratio of the acrylate (M2) and the molar ratio of the phosphate triester (meth) acrylate (M3) are: 1.5 ≦ [(M1) × 1 + (M2) × 2 + (M3) ×
3] ≦ 3 (where (M1) + (M2) + (M3) = 1). When the above value is less than 1.5, the mixing ratio of the phosphoric acid monoester (meth) acrylate increases, and the interaction between the phosphoric acid monoester (meth) acrylate and aluminum hydroxide is strong. The workability during molding is inferior because the viscosity of the product is too high. More preferably, 1.6 ≦ [(M1) × 1 + (M2) × 2 + (M3) ×
3] ≦ 3.0, particularly preferably 1.7 ≦ [(M1) × 1 + (M2) × 2 + (M3) ×
3] ≦ 3.0, and when a high level of flame retardancy is required for the molded article and the blending amount of aluminum hydroxide is extremely large, 1.8 ≦ [(M1) × 1 + ( M2) × 2 + (M3) ×
3] ≦ 3.0 is preferred.

Thus, the phosphate ester (meth)
In the acrylate, by reducing the proportion of the phosphate monoester (meth) acrylate,
Since the interaction between the phosphate (meth) acrylate and the aluminum hydroxide is moderate, the viscosity of the resin composition becomes appropriate, and the resin composition becomes excellent in workability at the time of molding. In the above phosphate ester (meth) acrylate, M1 + M2 + M3 is 1.

JP-A-51-125182 discloses a resin composition comprising an epoxy acrylate and a reactive monomer, a ketone resin and an acid phosphate compound having at least one unsaturated monobasic ester group in the molecule. However, since the curable resin composition is mainly intended for a paint or an ink suitable for coating a metal surface, the curable resin composition is difficult to use. It does not disclose the use of a relatively large amount of aluminum hydroxide in combination to impart flammability. Further, in the acid phosphate compound having one or more unsaturated monobasic acid ester groups to be applied, it is not disclosed that the ratio of the monoester is relatively small, and sufficient flame retardancy as a molded article is imparted. Therefore, when aluminum hydroxide is blended in a relatively large amount, the viscosity of the resin composition becomes extremely high due to the interaction between the monoester and aluminum hydroxide, and the workability may be reduced. The flame-retardant molding material resin composition of the present invention is used in combination with aluminum hydroxide because the content of phosphorus atoms in the radically polymerizable resin is an amount necessary to make the molded article sufficiently flame-retardant. Thereby, sufficient flame retardancy can be imparted to the molded article. In addition, since the phosphoric acid ester (meth) acrylate contains a relatively low ratio of the phosphoric acid monoester (meth) acrylate, the interaction with aluminum hydroxide is moderate, so that the resin composition And the resin composition for flame-retardant molding materials is excellent in workability during molding.

Usually, the phosphoric acid ester (meth) acrylate is obtained by esterifying a phosphoric acid compound such as phosphoric anhydride or phosphorus oxychloride with hydroxyalkyl (meth) acrylate, glycidyl (meth) acrylate or the like, Each can be easily obtained as a mixture of monosubstituted, disubstituted, and trisubstituted ones. Therefore, as the phosphoric acid ester (meth) acrylate, the proportions of the phosphoric acid monoester (meth) acrylate, the phosphoric diester (meth) acrylate, and the phosphoric acid triester (meth) acrylate should be adjusted as described above. Thereby, sufficient flame retardancy can be imparted to the molded product, and the resin composition becomes excellent in workability at the time of molding.

In the radically polymerizable resin of the present invention, the other radically polymerizable compound other than the phosphoric acid ester (meth) acrylate has a radically polymerizable group in the molecule, and is polymerized with the phosphoric acid ester (meth) acrylate. It is not particularly limited as long as it is made of a reactable substance, but in order to make the molded article have sufficient basic performance, it must be a mixture of a radical polymerizable oligomer and a radical polymerizable monomer. Is preferred.

The radical polymerizable oligomer is not particularly limited, but preferably has two or more radical polymerizable groups in the molecule and has a number average molecular weight (Mn) of 500 or more. 1 radical polymerizable group in the molecule
If the number is individual or the number average molecular weight (Mn) is less than 500, the molded article may be inferior in basic performance such as strength. The number average molecular weight (Mn) is more preferably 8,000 or less, since the viscosity of the resin composition becomes appropriate and the resin composition becomes excellent in workability during molding. It is not particularly limited as long as it has two or more radically polymerizable groups in the molecule and has a number average molecular weight (Mn) of 500 or more. For example, unsaturated polyester, epoxy (meth) acrylate, urethane (meth) acrylate , Polyester (meth) acrylate and the like. These may be used alone or in combination of two or more.

The radical polymerizable monomer is not particularly limited as long as it is a monomer capable of undergoing a polymerization reaction with a radical polymerizable oligomer or a phosphate (meth) acrylate. Methyl styrene, vinyl toluene, divinyl benzene, diallyl phthalate, N-vinyl pyrrolidone, diethylene glycol divinyl ether, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate,
Methoxyethylene glycol (meth) acrylate, 2
-Phenoxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropanetri (Meth) acrylate and the like. These may be used alone or in combination of two or more.

The ratio of the radical polymerizable oligomer to the radical polymerizable monomer is not particularly limited, but is preferably 2/8 to 9/1. When the ratio of the radical polymerizable oligomer is higher than 9/1, the viscosity of the resin composition increases and the workability decreases, and
If the curability is reduced and the ratio of the radical polymerizable oligomer is smaller than 2/8, the basic performance such as the strength of the molded article may be reduced. More preferably, 4/6 to 8 /
2.

In the case where the radically polymerizable resin contains the other radically polymerizable compound, the proportion of the phosphate (meth) acrylate and the other radically polymerizable compound is not particularly limited. The phosphoric acid ester (meth) acrylate is preferably 5 to 80% by weight and the other radically polymerizable compound is preferably 20 to 95% by weight based on the total amount of the polymerizable resin. If the content of the phosphoric acid ester (meth) acrylate is less than 5% by weight or the content of other radically polymerizable compounds exceeds 95% by weight, the flame retardancy of the molded article may decrease, and the phosphoric acid ester (meth) If the acrylate content exceeds 80% by weight or the content of other radically polymerizable compounds is less than 20% by weight, the basic performance such as the strength of the molded article may be reduced. More preferably, the content of the phosphate (meth) acrylate is 10 to 60% by weight, and the content of the other radical polymerizable compound is 40 to 90% by weight.

The aluminum hydroxide used in the present invention has a function of absorbing heat during combustion of the molded article, and synergistically imparts flame retardancy to the molded article together with the phosphate (meth) acrylate. . The content of the aluminum hydroxide is preferably 100 to 300 parts by weight based on 100 parts by weight of the radical polymerizable resin. If the amount is less than 100 parts by weight, it may not be possible to impart sufficient flame retardancy to the molded article, and if it exceeds 300 parts by weight, the basic properties such as flexibility of the molded article may be reduced.

The resin composition for a flame-retardant molding material of the present invention may contain an inorganic filler other than aluminum hydroxide and reinforcing fibers in order to improve the basic properties such as the strength of the molded article. The inorganic filler is not particularly limited and includes, for example, calcium carbonate, barium sulfate, alumina, metal powder, kaolin clay, talc, milled fiber, silica sand, diatomaceous earth, crystalline silica, fused silica, glass powder and the like. These may be used alone,
More than one species may be used in combination. The reinforcing fibers are not particularly limited, and include, for example, inorganic fibers such as glass fibers and carbon fibers; and organic fibers such as vinylon, phenol, Teflon, aramid, and polyester. These may be used alone or in combination of two or more. The shape of the reinforcing fibers is not particularly limited, and examples thereof include cloth; mat shapes such as chop strand mats, preformable mats, continuous strand mats, and surfacing mats; chop shapes; roving shapes; .

The resin composition for a flame-retardant molding material of the present invention may further contain a flame retardant in order to further improve the flame retardancy of the molded article. The flame retardant is not particularly limited, and includes, for example, those commonly used in resin compositions for flame-retardant molding materials. These may be used alone or in combination of two or more. Among these, a flame retardant having no halogen atom in the molecule is preferable in order that the molded article does not cause environmental pollution by dioxin during combustion. The flame retardant having no halogen atom in the molecule is not particularly limited, and examples thereof include phosphate esters such as triphenyl phosphate, cresyl diphenyl phosphate, resorcin diphenyl phosphate; phosphorus compounds such as ammonium polyphosphate; melamine, benzoguanamine And amino compounds such as guanidine; phosphorus-amino complex compounds such as melamine phosphate and guanidine phosphate;
Boric acid compounds such as zinc borate and aluminum borate;

The resin composition for a flame-retardant molding material of the present invention contains other resins, additives for the molding material, etc. in order to improve the dispersibility and moldability of the resin composition and the basic performance of the molded article. Can be blended. It is preferable to add a curing agent to the resin composition for a flame-retardant molding material of the present invention in order to increase the curing speed during molding and improve production efficiency. In addition, a curing accelerator can be added to adjust the curability. The curing agent and the curing accelerator may be added to the flame-retardant molding material resin composition in advance, or may be added at the time of curing, but in consideration of the pot life of the resin composition. It is preferable to set the timing of addition.

The curing agent is not particularly limited, and examples thereof include organic peroxides such as benzoyl peroxide, t-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide and the like. Oxides; azo compounds and the like. These may be used alone or in combination of two or more. The amount of the curing agent is not particularly limited, but is preferably 0.05 to 10% by weight based on 100 parts by weight of the resin composition for a flame-retardant molding material. If the amount is less than 0.05% by weight, the curing rate of the resin composition may be low, resulting in inferior production efficiency. If the amount exceeds 10% by weight, the curing rate of the resin composition may be too high, resulting in poor workability. There is.

The phosphate (meth) acrylate in the resin composition for a flame-retardant molding material of the present invention does not bleed on the surface of the molded product during molding or over time, and imparts uniform flame retardancy to the molded product. be able to. In addition, the resin composition for a flame-retardant molding material of the present invention has a function of absorbing water by crystallization water being released by aluminum hydroxide when a molded article is burnt, and a resin having a function of absorbing phosphoric acid ester (meth) acrylate. In the thermal decomposition stage, a film of phosphorus oxide is formed on the surface, and has a function of shielding oxygen. In addition, since the interaction between the aluminum hydroxide and the phosphate ester is moderate, the viscosity of the resin composition is appropriate, and the workability during molding is excellent. Therefore, the resin composition for a flame-retardant molding material of the present invention can impart sufficient flame retardancy to a molded article by effectively utilizing the action of aluminum hydroxide and phosphate (meth) acrylate. In addition to being able to do so, workability during molding is excellent.

The resin composition for a flame-retardant molding material of the present invention comprises:
Vehicle / mechanical parts, building materials, containers, electronic / electric parts,
It can be suitably used as a material for molded articles for applications requiring flame retardancy, such as OA equipment, precision machines, films, sheets, pipes and the like.

The molded article of the present invention is obtained by molding the resin composition for a flame-retardant molding material of the present invention. The above-mentioned molding can be performed by curing the resin composition by a usual molding method and molding conditions. The molded article has sufficient flame retardancy, and is easy to mold because the flame-retardant molding material resin composition has excellent workability during molding, and is used for various applications. Is what you can do. The above-mentioned molded article is also one of the present invention.

[0036]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Preparation Example 1 Araldide GY was prepared by using a four-necked flask equipped with a thermometer, a stirrer, a gas injection pipe, and a reflux condenser as a reaction vessel.
370 parts by weight of -250 (trade name, bisphenol type epoxy compound having an average epoxy equivalent of 185, manufactured by Ciba Specialty Chemicals), 172 parts by weight of methacrylic acid, 0.10 part by weight of hydroquinone, and 2.3 parts of triethylamine were charged. It is. Then, the mixture was reacted at 115 ° C. for 6.5 hours with stirring in an air stream,
An epoxy methacrylate having an acid value of 4.5 mgKOH / g and a number average molecular weight (Mn) of 940 was obtained. Further, 232 parts by weight of styrene, 48 parts by weight of mono (2-methacryloyloxyethyl) acid phosphate, and 124 parts by weight of di (2-methacryloyloxyethyl) acid phosphate were blended to obtain a radical polymerizable resin (1). I got Table 1 shows the phosphorus atom content of the obtained radically polymerizable resin.

Preparation Example 2 An epoxy methacrylate was obtained in the same manner as in Preparation Example 1. Further, 232 parts by weight of styrene and di (2
-Methacryloyloxyethyl) (3-methacryloyl-2-hydroxyloxypropyl) phosphate 38
By mixing 0 parts by weight, a radical polymerizable resin (2) was obtained. Table 1 shows the phosphorus atom content of the obtained radically polymerizable resin.

Preparation Example 3 Araldide GY-25 was placed in the same reaction vessel as in Preparation Example 1.
0 (trade name) 370 parts by weight, hiker CTBN1300
× 8 (trade name, carboxyl group-containing acrylonitrile butadiene, BF Goodrich (BF Goodrid)
ch), 90 parts by weight, 168 parts by weight of methacrylic acid,
0.10 parts by weight of hydroquinone and 2.3 parts by weight of triethylamine were charged. Then, the mixture was reacted at 115 ° C. for 7.5 hours while stirring in an air stream,
An epoxy methacrylate having an acid value of 6.0 mgKOH / g and a number average molecular weight (Mn) of 1560 was obtained. Further, 269 parts by weight of styrene, 56 parts by weight of mono (2-methacryloyloxyethyl) acid phosphate, and 143 parts by weight of di (2-methacryloyloxyethyl) acid phosphate are further blended to form a radical polymerizable resin (3). I got Table 1 shows the phosphorus atom content of the obtained radically polymerizable resin.

Comparative Preparation Example 1 An epoxy methacrylate was obtained in the same manner as in Preparation Example 1. Further, 232 parts by weight of styrene, mono (2-methacryloyloxyethyl) acid phosphate 11
2 parts by weight and 17 parts by weight of di (2-methacryloyloxyethyl) acid phosphate were blended to obtain a comparative radical polymerizable resin (1). Table 2 shows the phosphorus atom content of the obtained comparative radical polymerizable resin.

Comparative Preparation Example 2 An epoxy methacrylate was obtained in the same manner as in Preparation Example 1. In addition, 232 parts by weight of styrene and mono (2-methacryloyloxyethyl) acid phosphate are added.
2 parts by weight, and 20.8 parts by weight of di (2-methacryloyloxyethyl) acid phosphate,
A comparative radical polymerizable resin (2) was obtained. Table 2 shows the phosphorus atom content of the obtained comparative radical polymerizable resin.

Examples The radically polymerizable resins (1) obtained in Preparation Examples 1 to 3
(3) Hydilite H-32I (trade name, manufactured by Showa Denko KK) as aluminum hydroxide in 100 parts by weight of each.
By adding 150 parts by weight and stirring uniformly, resin compositions (1) to (3) for flame-retardant molding materials were obtained, respectively.
The amount of the radically polymerizable resin and aluminum hydroxide in the obtained resin composition for a flame-retardant molding material, and [(M1) × 1 +
(M2) × 2 + (M3) × 3] are shown in Table 1. To 250 parts by weight of each of the obtained resin compositions (1) to (3) for a flame-retardant molding material, 1.0 part by weight of Perbutyl Z (trade name, manufactured by NOF CORPORATION) as a curing agent was added and mixed uniformly. As a result, resin compositions (1) to (3) for a flame-retardant molding material to which a curing agent was added were obtained. Then 3mm
Each of the resin compositions for a flame-retardant molding material to which a curing agent was added was poured into a glass plate case sandwiched with the spacers, and cured at 100 ° C. for 30 minutes in a hot-air circulation drying oven. Cured at 175 ° C. for 30 minutes. After curing, it is cooled to room temperature, the glass plate is removed and the molded product (1)-
(3) was obtained respectively. The obtained resin compositions for flame-retardant molding materials and molded articles were evaluated by the following evaluation methods. The results are shown in Table 1.

[0043]Evaluation method  (1) Viscosity of resin composition The obtained resin composition for a flame-retardant molding material was subjected to BROOKF
IELD (HELIPATH SPINDLE type) viscosity
The viscosity (mPa · s) was measured at a constant temperature of 30 ° C using a meter.
Specified. (2) Flame retardancy of molded article The obtained molded article is 70 mm long and 6.5 ± 0.5 m wide.
m, which were cut into strips having flame retardancy. Flame retardant
The evaluation method is based on JIS K 7201 (1995)
Acid method in accordance with the index test method for combustion test of polymer materials "
We performed with prime index. The oxygen index is an index that indicates flame retardancy.
And the material sustains combustion under the given test conditions
Of the minimum oxygen concentration expressed in% by volume of
Numerical values, those with large numbers have high self-extinguishing properties and are
And high flame retardancy.

[0044]

[Table 1]

Comparative Example A resin composition for a comparative molding material to which a curing agent was added in the same manner as in the Examples using the comparative radically polymerizable resins (1) and (2) obtained in Comparative Preparation Examples 1 and 2, respectively. (1)
And (2) were obtained, respectively. In addition, the radical polymerizable resin (1) obtained in Preparation Example 1 was prepared without adding aluminum hydroxide as a comparative molding material resin composition (3).
To 100 parts by weight of the resin composition for comparative molding material (3), 1.0 part by weight of Perbutyl Z (trade name) as a curing agent was added and uniformly mixed, so that a resin composition for comparative molding material to which a curing agent was added was added. The product (3) was obtained. The amount of the radical polymerizable resin and aluminum hydroxide in the obtained resin composition for comparative molding material, and [(M1) × 1 + (M2) × 2 + (M3) × of phosphate ester (meth) acrylate
3] are shown in Table 2. Next, in the same manner as in the examples, comparative molded articles (1) to (3) were obtained, and the resin composition for comparative molding material and the comparative molded article were evaluated. The results are shown in Table 2.

[0046]

[Table 2]

As is clear from Table 1, in Examples, the resin compositions (1) to (3) for flame-retardant molding materials have appropriate viscosities and have sufficient workability during molding. Was. On the other hand, as is clear from Table 2, in the comparative example, in the resin composition for comparative molding material (1),
Since the value of [(M1) × 1 + (M2) × 2 + (M3) × 3] was 1.1, the viscosity was extremely high, and the workability during molding was poor. In the resin composition for comparative molding material (2), since the content of phosphorus atoms in the comparative radical polymerizable resin was as low as 0.4% by weight, the oxygen index was low and the flame retardancy was inferior. In the resin composition for comparative molding material (3), since there was no synergistic effect between aluminum hydroxide and the phosphate ester, the oxygen index was low and the flame retardancy was poor.

[0048]

The resin composition for a flame-retardant molding material of the present invention has a sufficient flame retardancy because it has the above-mentioned constitution, and furthermore has an appropriate viscosity and excellent workability during molding. It is a thing. The molded article of the present invention has sufficient flame retardancy and can be used for various applications because of easy molding.

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Claims (2)

[Claims] 1. A resin composition for a flame-retardant molding material, comprising a radical polymerizable resin containing a phosphoric acid ester (meth) acrylate, and aluminum hydroxide, wherein a phosphorus atom in the radical polymerizable resin is The content is 0.7 to 10% by weight based on the total amount of the radical polymerizable resin, and the phosphate (meth) acrylate is a phosphate monoester (meth) acrylate, a phosphate diester (meth) acrylate, And at least one selected from the group consisting of phosphoric acid triester (meth) acrylates, the molar ratio of the phosphoric acid monoester (meth) acrylate (M1), the phosphoric acid diester (meth) acrylate And the molar ratio of the phosphoric triester (meth) acrylate (M2)
3) is 1.5 ≦ [(M1) × 1 + (M2) × 2 + (M3) ×
3] ≦ 3 (where (M1) + (M2) + (M3) = 1). A resin composition for a flame-retardant molding material, characterized by satisfying the following relationship: 2. A molded article obtained by molding the resin composition for a flame-retardant molding material according to claim 1.