JPH0782324A - Flame-retardant transparent resin - Google Patents

Abstract

PURPOSE:To impart flame retardancy while maintaining material properties including surface hardness, rigidity, impact, heat and chemical resistances, and weatherability by copolymerizing a monomeric phosphorus compound having a polymerizable double bond with monomers which give a transparent resin. CONSTITUTION:At least either of a monomer having the functional group represented by formula (1) [e.g. an N-(3-isopropenyl-alpha,alpha-dimethylbenzyl)-2- acryloyloxyethylcarbamate] and a monomer having the functional group represented by formula (2) [e.g. a compound represented by formula (3) (wherein n is 1-2)] is mixed with a monomer having one or more functional groups selected from acrylic, methacrylic, and styryl groups (e.g. methyl acrylate) and a monomeric phosphorus compound having a polymerizable double bond (e.g. beta-styrylethylphosphine). This mixture is poured into a mold for cast polymerization and heated to copolymerize the monomers, thereby giving the objective resin. The proportion of the monomers is regulated according to the contents of the respective functional groups.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a flame-retardant transparent resin. Molded products of this resin are used for windows of cars, railway vehicles, aircraft, etc. for which visibility, protection and safety are required,
Alternatively, it can be used as various glazing materials such as windows for opening / closing doors in these vehicles, windows for other various buildings, and members for obtaining wide lighting from a part of the roof, ceiling or wall of these buildings.

[0002]

2. Description of the Related Art The inventors of the present invention have previously described surface hardness, rigidity,
We have disclosed a high-hardness transparent resin that has excellent chemical resistance and heat resistance, as well as impact resistance and weather resistance, and proposed its use as a glazing material. However, since these resins have insufficient flame retardancy, improvement in this respect has been demanded.

Generally, flame retardation of a resin is achieved by blending a flame retardant. In other words, a compound or element that has the effect of suppressing and stopping the combustion of resin is chemically bound in the molecule (reactive flame retardant) or physically added (addition flame retardant) It is endowed with sex. Additive flame retardants are classified into organic flame retardants such as phosphorus, nitrogen and halogen, and inorganic flame retardants such as boron compounds, antimony trioxide, and aluminum hydroxide, both of which are mainly thermoplastic resins. Widely used. However, in order to enhance the flame retarding effect, it is necessary to increase the amount of the flame retardant added, which causes a problem that molding processability and mechanical properties of the molded product are significantly reduced. Also, when a halogen-based compound is added to the resin as a flame retardant, the effect of flame retardancy is relatively large, but a toxic, harmful, or corrosive substance is generated during a fire or incineration process. Therefore, it has been pointed out that problems such as rescue and rescue activities, fire extinguishing activities, and treatment work become difficult or cause environmental pollution.

On the other hand, as the reactive flame retardant, a bromine compound having a reactive group such as a hydroxyl group, a double bond, a carboxyl group, an epoxy group and an imide group can be used in almost all resins. It is used for thermosetting resin. However, these flame retardants are applied to individual resins,
If the amount used in that case is not strictly selected, not only will flame retardancy not be fully exhibited, but the physical properties of the resin will also be reduced. In addition, the resinification conditions at that time are not necessarily the same as the resinification conditions when the flame retardant is not included,
Therefore, there is a problem that it is necessary to study new resinification conditions according to the type of flame retardant. Further, although a broadly defined reactive flame retardant, oligomeric and polymeric flame retardants with a high bromine content are also commonly used, these flame retardants are mainly used for engineering plastics and resins that require transparency. Is not applicable.

To solve these problems, low-halogen flame retardants, halogen-free flame retardants, and smoke suppression technology at the time of combustion have been developed, but there is still a risk that the physical properties of the resin will deteriorate. There is. Moreover, the current situation is that the development of flame-retardant resins that are non-flame retardants has not been sufficiently answered.

[0006]

The object of the present invention is to provide various physical properties such as surface hardness, rigidity, chemical resistance, heat resistance, impact resistance, weather resistance, and the like. It is to provide a flammable transparent resin.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a monomer having a polymerizable unsaturated double bond containing phosphorus, The inventors of the present invention have found that the copolymer resin with the transparent resin monomer previously proposed solves the above-mentioned problems, and completed the present invention. That is, the present invention is a monomer (A) having a functional group represented by the following general formula (1) (Chemical Formula 2) in one molecule.
And / or a monomer having at least one functional group selected from the group consisting of a monomer (B) having a functional group represented by the following general formula (2) (Chemical formula 2), an acryl group, a methacryl group, and a styryl group. The flame-retardant transparent resin obtained by copolymerizing the body (C) and the monomer (D) having a polymerizable unsaturated double bond containing phosphorus, and the monomer (D) is a (meth) acrylic resin. The present invention relates to the above flame-retardant transparent resin which is a phosphoric acid ester.

[0008]

[Chemical 2] Further, a mixture of the monomer (A) and / or the monomer (B), the monomer (C), and the monomer (D) is poured into a casting polymerization mold and heated. And a glazing material using the resin-molded product.

First, each monomer of the resin of the present invention will be described in detail. Specific compounds of the monomer (A) include
N- (3-isopropenyl-α, α-dimethylbenzyl) -2-acryloyloxyethyl carbamate, N
-(3-isopropenyl-α, α-dimethylbenzyl)
-2-methacryloyloxyethyl carbamate, N-
(4-isopropenyl-α, α-dimethylbenzyl)-
2-acryloyloxyethyl carbamate, N- (4
-Isopropenyl-α, α-dimethylbenzyl) -2-
Methacryloyloxyethyl carbamate, N- (3-
Isopropenyl-α, α-dimethylbenzyl) -1-acryloyloxypropan-2-ylcarbamate, N
-(3-isopropenyl-α, α-dimethylbenzyl)
-1-methacryloyloxypropan-2-ylcarbamate, N- (4-isopropenyl-α, α-dimethylbenzyl) -1-acryloyloxypropan-2-ylcarbamate, N- (3-isopropenyl-α, α −
Dimethylbenzyl) -1,3-diacryloyloxypropan-2-ylcarbamate, N- (3-isopropenyl-α, α-dimethylbenzyl) -1,3-dimethacryloyloxypropan-2-ylcarbamate, N-
(3-isopropenyl-α, α-dimethylbenzyl)-
1-acryloyloxy-3-methacryloyloxy-
2-ylcarbamate, N- (4-isopropenyl-
α, α-Dimethylbenzyl) -1,3-diacryloyloxypropan-2-ylcarbamate, N- (3-isopropenyl-α, α-dimethylbenzyl) -2,2-
Diacryloyloxymethyl-3-acryloyloxypropyl carbamate, N- (4-isopropenyl-
α, α-dimethylbenzyl) -2,2-dimethacryloyloxymethyl-3-methacryloyloxypropyl carbamate and the like. These are disclosed in, for example, Japanese Patent Laid-Open No. 2-8
4406 and the like. Examples of the monomer (B) include the following general formula (3) (Chemical Formula 3),
(4) (Chemical formula 4), (5) (Chemical formula 5), and (6) (Chemical formula 6)
Are compounds represented by. These can be produced, for example, by the method described in JP-A-3-14804.

[0010]

[Chemical 3] (In the formula, n represents a positive number of 1 or 2, and when n = 1,
The position of the isopropenyl group is m-position, and when n = 2, the position of the isopropenyl group is p-position)

[0011]

[Chemical 4] (In the formula, R ¹ represents a hydrogen atom or a methyl group, when R ¹ is a hydrogen atom, the position of the isopropenyl group is the m-position, and when R ¹ is a methyl group, the isopropenyl group is The position is p-)

[0012]

[Chemical 5] (In the formula, R ² is the same or different and represents a hydrogen atom or a methyl group, and the position of the isopropenyl group is m-position or p-position.)

[0013]

[Chemical 6] (In the formula, R ³ represents a hydrogen atom or a methyl group, and the position of the isopropenyl group is m-position or p-position)

Specific compounds of the monomer (C) include
Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, benzyl acrylate, benzyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxyethyl acrylate, ethoxyethyl Methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate,
1,4-butylene glycol monoacrylate, 1,4
-Butylene glycol monomethacrylate, glycidyl acrylate, glycidyl methacrylate, styrene,
Chlorostyrene, bromostyrene, chloromethylstyrene, methoxystyrene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, dipropylene glycol diacrylate, dipropylene glycol Dimethacrylate,

2,2-bis (4-acryloyloxyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, 2,2-
Bis (4-acryloyloxydiethoxyphenyl) propane, 2,2-bis (4-acryloyloxypropyroyloxyphenyl) propane, 2,2-bis (4-
Methacryloyloxypropyroyloxyphenyl) propane, 1,3-butanediol diacrylate, 1,
3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, neo Pentyl glycol dimethacrylate, hydroxybivalic acid neopentyl glycol ester diacrylate,

Spiroglycol diacrylate, spiroglycol dimethacrylate, epoxy acrylate,
Epoxy methacrylate, 2-propenoic acid {2- [1,1-dimethyl-2- (1-oxo-2-propenyl) oxy] ethyl-5-ethyl-1,3-dioxan-5-yl} methyl ester , Trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, bis (acryloyloxyethyl) hydroxyethyl isocyanurate, bis (methacryloyloxyethyl) hydroxyethyl isocyanurate, tris (acryloyloxyethyl) ) Isocyanurate, tris (methacryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, Dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, methyl tri (acryloyl) silane, glycerol diacrylate, glycerol dimethacrylate, dibromoneopentyl glycol diacrylate,
Examples include dibromoneopentyl glycol dimethacrylate, divinylbenzene, urethane acrylates and urethane methacrylates. Note that some of these are commercially available.

Specific examples of the compound (D) having a polymerizable unsaturated double bond containing phosphorus include phosphine derivatives such as β-styryl-ethylphosphine and β-styryl-propylphosphine. β-styryl-isopropylphosphine, β-styryl-butylphosphine, phenyl-allylphosphine, p-vinylphenyl-ethyl-phosphine, p-vinyl-butylphosphine, p-vinyl-propylphosphine, p-vinyl-isopropylphosphine, p -Vinylbenzyl-
Ethylphosphine, p-vinylbenzyl-diethylphosphine, phenyl-2-vinyloxyethylphosphine, allylphosphonoasdichloride, allylphosphonoasdibromide, vinylphosphonoasdichloride,
Vinylphosphonoasdibromide, diallylphosphinoasbromide, diallylphosphinoasbromide,
Divinylphosphinoasbromide, divinylphosphinoasbromide,

Phosphinic acid derivatives such as allylphosphonoasacid, vinylphosphonoasacid, p
-Vinylphenylphosphonoasacid, p-vinylbenzylphosphonoasacid, allyl-ethylphosphinoasacid, diallylphosphinoasacid, vinyl-ethylphosphinoasacid, β-styryl-
Ethylphosphinoasacid, ethyl-diallylphosphonite, phenyl-diallylphosphonite, ethyl-
Divinylphosphonite, phenyl-divinylphosphonite, diethyl-allylphosphinite, diethyl-vinylphosphinite, diphenyl-allylphosphinite, diphenyl-vinylphosphinite,

A phosphonic acid derivative having a valence of 3, for example,
Vinyl phosphite, allyl phosphite, p-vinyl phenyl phosphite, p-vinyl benzyl phosphite, divinyl phosphite, diallyl phosphite, 2
-Acryloyloxyethyl phosphite, 2-methacryloyloxyethyl phosphite, 2-acryloyloxypropyl phosphite, 2-methacryloyloxypropyl phosphite, divinyl phosphite, diallyl phosphite, butyl-2-acryloyloxyethyl phosphite, butyl 2-methacryloyloxyethyl phosphite, di (2-acryloyloxyethyl) phosphite, di (2-methacryloyloxyethyl) phosphite, di (2-acryloyloxypropyl) phosphite, di (2-methacryloyloxypropyl) Phosphite, tri (2-acryloyloxyethyl) phosphite, tri (2-methacryloyloxyethyl) phosphite, tri (2-acryloyloxypropyl) phosphite Ito, tri (2-methacryloyloxy propyl) phosphite, allyl - dichloro phosphite, allyl - dibromo phosphite,

Phosphonic acid derivatives having a valence of 5, such as vinylphosphonic acid, p-vinylphenylphosphonic acid, β-styrylphosphonic acid,
Isopropenylphosphonic acid, allylphosphonic acid, divinylphosphinic acid, di (p-vinylphenyl) phosphinic acid, diallylphosphinic acid, diphenyl-vinylphosphine oxide, diphenyl-isopropenylphosphine oxide, diallyl- Phenylphosphine oxide, vinyl-diphenylphosphine oxide, isopropenyl-diphenylphosphine oxide, phenyl-diallylphosphonate, di (2-chloroethyl) -vinylphosphonate, 1-cyanovinyl-dimethylphosphonate, 1-cyanovinyl-diethylphosphonate, 1-cyano- 2-phenylvinyl-diethylphosphonate, phenyl-2,2-dichlorovinyl-methylphosphinate, divinylphosphine Rukuroraido, divinyl phosphinyl bromide, vinyl phosphonyl distearate chloride, vinyl phosphonyl distearate bromide, p- vinylbenzyl phosphonyl distearate chloride, p- vinylbenzyl phosphonyl distearate bromide, divinyl phosphinyl chloride, divinyl phosphinyl bromide,

Phosphoric acid derivatives such as 2-acryloyloxyethyl phosphate, 2-methacryloyloxyethyl phosphate, 2-acryloyloxypropyl phosphate, 2-methacryloyloxypropyl phosphate, di (2-acryloyloxyethyl) phosphate, di (2) -Methacryloyloxyethyl) phosphate, di (2-acryloyloxypropyl) phosphate, di (2-methacryloyloxypropyl) phosphate, methyl-2-acryloyloxyethyl phosphate, methyl-2-methacryloyloxyethyl phosphate, methyl-2-acryloyl Oxypropyl phosphate, methyl-2-methacryloyloxypropyl phosphate, ethyl-2-acryloyloxyethyl phosphate Ethyl-2-methacryloyloxyethyl phosphate, ethyl-2-acryloyloxypropyl phosphate, ethyl-2-methacryloyloxypropyl phosphate, propyl-2-acryloyloxyethyl phosphate, propyl-2-methacryloyloxyethyl phosphate, propyl-2-acryloyl Oxypropyl phosphate, propyl-2
-Methacryloyloxypropyl phosphate,

Butyl-2-acryloyloxyethyl phosphate, butyl-2-methacryloyloxyethyl phosphate, butyl-2-acryloyloxypropyl phosphate, butyl-2-methacryloyloxypropyl phosphate, pentyl-2-acryloyloxyethyl phosphate, pentyl- 2-methacryloyloxyethyl phosphate, pentyl-2-acryloyloxypropyl phosphate, pentyl-methacryloyloxypropyl phosphate, hexyl-2-acryloyloxyethyl phosphate, hexyl-2-methacryloyloxyethyl phosphate, hexyl-2
-Acryloyloxypropyl phosphate, hexyl-2-methacryloyloxypropyl phosphate, heptyl-2-acryloyloxyethyl phosphate,
Heptyl-2-methacryloyloxyethyl phosphate, heptyl-2-acryloyloxypropyl phosphate, heptyl-2-methacryloyloxypropyl phosphate, octyl-2-acryloyloxyethyl phosphate, octyl-2-methacryloyloxyethyl phosphate, octyl-2-acryloyl Oxypropyl phosphate, octyl-2-methacryloyloxypropyl phosphate, phenyl-2-acryloyloxyethyl phosphate, phenyl-2-methacryloyloxyethyl phosphate,

Phenyl-2-acryloyloxypropyl phosphate, phenyl-2-methacryloyloxypropyl phosphate, tri (2-acryloyloxyethyl) phosphate, tri (2-methacryloyloxyethyl) phosphate, tri (2-acryloyloxypropyl) phosphate , Tri (2-methacryloyloxypropyl) phosphate, dimethyl-2-acryloyloxyethyl phosphate, dimethyl-2-methacryloyloxyethyl phosphate, dimethyl-2-
Acryloyloxypropyl phosphate, dimethyl-
2-methacryloyloxypropyl phosphate, diethyl-2-acryloyloxyethyl phosphate, diethyl-2-methacryloyloxyethyl phosphate, diethyl-2-acryloyloxypropyl phosphate, diethyl-2-methacryloyloxypropyl phosphate, dipropyl-2-acryloyloxyethyl Phosphate, dipropyl-2-methacryloyloxyethyl phosphate, dipropyl-2-acryloyloxypropyl phosphate, dipropyl-2-methacryloyloxypropyl phosphate, dibutyl-2
-Acryloyloxyethyl phosphate, dibutyl-
2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyloxypropyl phosphate,

Dibutyl-2-methacryloyloxypropyl phosphate, dipentyl-2-acryloyloxyethyl phosphate, dipentyl-2-methacryloyloxyethyl phosphate, dipentyl-2-acryloyloxypropyl phosphate, dipentyl-2-
Methacryloyloxypropyl phosphate, dihexyl-2-acryloyloxyethyl phosphate, dihexyl-2-methacryloyloxyethyl phosphate, dihexyl-2-acryloyloxypropyl phosphate, dihexyl-2-methacryloyloxypropyl phosphate, diheptyl-2-acryloyloxyethyl phosphate, Diheptyl-2-methacryloyloxyethyl phosphate, diheptyl-2-acryloyloxypropyl phosphate, diheptyl-2-
Methacryloyloxypropyl phosphate, dioctyl-2-acryloyloxyethyl phosphate, dioctyl-2-methacryloyloxyethyl phosphate, dioctyl-2-acryloyloxypropyl phosphate, dioctyl-2-methacryloyloxypropyl phosphate, diphenyl-2-acryloyloxyethyl phosphate, Diphenyl-2-methacryloyloxyethyl phosphate, diphenyl-2-acryloyloxypropyl phosphate, diphenyl-2-
Methacryloyloxypropyl phosphate, chloro-
Diallyl phosphate,

Phospholane derivatives such as allyl-ethyl-butyl-benzylphosphorus bromide, vinyl-ethyl-butyl-benzylphosphorus bromide, phosphonium salt derivatives such as tributyl-vinylphosphonium chloride, tributyl-vinylphosphonum bromide. , Tributyl-2-acryloyloxymethylphosphonium chloride, tributyl-
2-acryloyloxymethylphosphonium bromide, phosphazene derivatives such as 1,1,3,3,5,
5-hexa (acryloyloxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (methacryloyloxy) cyclotriphosphazene, 1,1,3,3,3
5,5-hexa (acryloylethylenedioxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (methacryloylethylenedioxy) cyclotriphosphazene, and the like. Phosphoric acid derivatives are preferable, and (meth) acrylic phosphoric acid esters are more preferable. The monomer (D) may be used alone or in combination of two or more kinds. Some of these are commercially available.

The flame-retardant transparent resin of the present invention is obtained by copolymerizing the above-mentioned monomer (A) and / or monomer (B), monomer (C), and monomer (D). Obtainable. Here, the composition ratio of each monomer at the time of copolymerization cannot be unconditionally determined depending on the type of functional group possessed by each monomer, the structure and molecular weight of the monomer, etc., but the phosphorus content in the mixture If the amount is small, sufficient flame retardancy cannot be obtained, and if it is too large, the polymerization is difficult to proceed, or conversely, it may be difficult to control the polymerization depending on the composition of the monomer. The physical properties of the resin tend to be significantly reduced. The proportion of each monomer used is such that the monomer (A) and / or the monomer (A) and / or the monomer (B) is equivalent to 1 equivalent of the isopropenylphenyl group in the monomer (B).
Alternatively, the monomer (B) and the acrylic group in the monomer (C),
The total sum of methacrylic groups or styryl groups is preferably in the range of 0.3 to 10 equivalents. On the other hand, monomer (D)
Is the acrylic content in the monomer (A) and / or the monomer (B), and the monomer (C) in the range of 0.5 to 9.0% in the monomer mixture. It is preferable that the total amount of the functional groups in the monomer (D) is in the range of 0.1 to 10 times the equivalent of the total amount of the groups, the methacrylic group or the styryl group.

The flame-retardant transparent resin molding of the present invention can be obtained by injecting a mixture of monomers prepared within the above-mentioned limited range into a casting polymerization mold and polymerizing. Here, the casting polymerization mold used in the present invention will be briefly described. After arranging two glass plates with smooth surfaces (mold material) and one of them with sheet silicon rubber (gasket), these two are integrated with a stopper, and the gasket thickness The above-mentioned mixture can be injected into a considerable space. The mold material is not limited to glass, but may be metal or C (or G) FRP, and may have any shape. Any gasket may be used as long as it has appropriate heat resistance, chemical resistance, and flexibility. However, in any case, the mold material and the gasket must not be made of a material that reacts with the injected monomer mixture or causes corrosion by the monomer mixture.

The main polymerization is radical polymerization, and the polymerization method may be not only thermal polymerization but also a method using ultraviolet rays, γ rays or the like. However, the thermal polymerization method is particularly preferable because it is simple. The radical polymerization initiator at the time of performing thermal polymerization is not particularly limited, and known benzoyl peroxide, p-chlorobenzoyl peroxide,
Organic peroxides such as diisopropyl peroxide, di (2-ethylhexyl) peroxycarbonate and t-butylperoxyvibarate, azo compounds such as azobisisobutyronitrile and the like can be used. The usage is
The proportion is 0.01 to 5% by weight with respect to the mixture of monomers. In the thermal polymerization, the heating temperature is 50 to 200 ° C. and the time is 1 to
It may be carried out under the optimum polymerization conditions depending on the resin composition within the range of 10 hours.

On the other hand, in the case of the curing method using ultraviolet rays, the photosensitizer is not particularly limited, and known benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, 2-hydroxy-2- Benzoin propane, azobisisobutyronitrile, benzyl, thioxanthone, diphenyl disulfide and the like can be used. The amount used is 0.01 to 5% by weight with respect to the mixture of monomers. or,
When curing is performed using radiation such as γ rays, a polymerization initiator or the like is generally not always necessary.

The mixture of monomers before the polymerization may be added in advance with an additive such as an ultraviolet absorber, a near infrared absorber, an antioxidant, a coloring inhibitor, a fluorescent dye, or another monomer. Etc. may be added as appropriate. The mixture of monomers thus prepared is subjected to defoaming treatment under reduced pressure, if necessary, and then polymerized.

[0031]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In addition, the part in an Example represents a weight part. Also,
The evaluation method of the resin obtained by the polymerization shown in the examples is shown below. -Evaluation method (1) Appearance: The resin plate was visually observed. Those with no cracks or surface roughness were marked with (◯), and those with cracks were marked with (x). (2) Flammability: Tested according to the flammability test method for railway vehicles established by the Ministry of Transport, and nonflammable according to the flammability standard.
Extreme flame retardancy, flame retardancy, flammability, etc. were evaluated. (3) Surface hardness: Pencil hardness: Measured using a JIS-K-5401 pencil scratch tester for coating film. Vickers hardness: Measured using a Terazawa microhardness meter (manufactured by Toyo Seiki Seisakusho Co., Ltd.). Rockwell M scale hardness: Measured according to ASTM-D-786. (4) Impact resistance: Tested without notches by the Charpy impact test method for hard plastics according to JIS-K-7111. (5) Flexural modulus: Measured according to JIS-K-7203 method. (6) Heat resistance: The resin plate was allowed to stand in a hot air drying oven at 120 ° C. for 4 hours, then taken out and visually judged. Those with no coloring or surface distortion (○), those with (x)
And (7) Chemical resistance: Immersed in each of isopropanol and toluene at room temperature for 24 hours, taken out, and then taken out with a pencil having a hardness of HB (○). In some cases, the mark that left a mark was marked with (x). (8) Workability: The one that can be ground by a ball-shaving machine for processing spectacle lenses is marked (◯), and the one that cannot be ground is marked (×).

EXAMPLE 1 115.5 parts of ethylene glycol-bis [N- (3-isopropenyl-α, α-dimethylbenzyl)] carbamate and N- (3-isopropenyl-) were added to a heating mixer equipped with a pressure reducing device. Charge 82.3 parts of α, α-dimethylbenzyl) -2-methacryloyloxyethyl carbamate,
The internal temperature was kept at 45 ° C. Then, 131.3 parts of pentaerythritol-tetraacrylate was added thereto and mixed well, then 48.7 parts of 2-acryloyloxyethyl phosphate was added and mixed well again, and then under reduced pressure while maintaining the same temperature. Defoaming was performed. Then, 0.8 part of t-butylperoxy-2-ethylhexanoate was added to this mixture as a radical polymerization initiator, and then defoaming was performed again. Then, this mixture was poured into a casting polymerization mold (internal dimensions: 4 mm × 300 mm × 300 mm), and this mold was placed in a polymerization hot air oven and heated from 60 ° C to 170 ° C over 3 hours. Raise the temperature, then 180 ℃
Polymerization was carried out by heating for 30 minutes. As a result, a transparent, pale yellow resin plate was obtained.

Example 2 235.9 parts of N- (3-isopropenyl-α, α-dimethylbenzyl) -2-acryloyloxyethylcarbamate was charged into a heating mixer equipped with a pressure reducing device, and the internal temperature was adjusted to 45 ° C. I kept it. Then, 84.1 parts of trimethylolpropane triacrylate was added thereto and mixed well, and then 53.1 parts of 1,1,3,3,5,5-hexa (acryloyloxy) cyclotriphosphazene was added,
After mixing well again, defoaming was performed under reduced pressure while maintaining the same temperature. Then, 4.4 parts of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was added to this mixture, and then defoaming was performed again. afterwards,
This mixture is cast polymerization mold (internal size: 4 mm x 300 mm x
(300 mm), the mold was placed in a hot-air oven for polymerization, and heated from 60 ° C. to 170 ° C. for 3 hours to raise the temperature to carry out polymerization. As a result, a transparent, pale yellow resin plate was obtained.

Example 3 N- (3-isopropenyl-α, α-dimethylbenzyl) -1,3-diacryloyloxypropan-2-ylcarbamate was added to 200.
8 parts were charged and the internal temperature was kept at 45 ° C. And to this,
Di (2-acryloyloxyethyl) phosphate was added to 7
After adding 3.6 parts and mixing well, degassing was performed under reduced pressure while maintaining the same temperature. Then, to this mixture, 0.3% lauroyl peroxide was used as a radical polymerization initiator.
And 1.5 parts of benzoyl peroxide were added, and then defoaming was performed again. Then, after pouring this mixture into a casting polymerization mold (internal dimensions: 4 mm × 250 mm × 250 mm), this mold is placed in a polymerization hot air oven and heated from 60 ° C to 170 ° C over 3 hours. The temperature was raised to carry out polymerization. As a result, a transparent, pale yellow resin plate was obtained.

Example 4 A heating mixer equipped with a pressure reducing device was charged with 113.8 parts of neopentyl glycol diacrylate, and the internal temperature was kept at 45 ° C. Then, [N- (3-isopropenyl-
121.9 parts of α, α-dimethylbenzyl] (4-isopropenylphenyl) carbamate were added and mixed well,
Then, p-vinylbenzyl-ethylphosphine was added to 2
After adding 7.6 parts and thoroughly mixing again, defoaming was performed under reduced pressure while maintaining the same temperature. Then, benzoyl peroxide was added to this mixture as a radical polymerization initiator in an amount of 1.
After adding 2 parts, defoaming was performed again. Then, this mixture was cast into a casting mold (internal dimensions: 4 mm × 250 mm × 250
mm) and then the mold was placed in a hot air oven for polymerization, and the temperature was raised from 70 ° C. to 170 ° C. over 2 hours to carry out polymerization. As a result, a transparent, pale yellow resin plate was obtained.

Example 5 In a heating mixer equipped with a pressure reducing device, diethylene glycol-
1 bis (4-isopropenylphenyl) carbonate
98.0 parts were charged and the internal temperature was kept at 45 ° C. Then, add pentaerythritol-tetraacrylate to this 4
0.9 part was added and mixed well, then, 26.0 parts of 4-acryloyloxybutyl phosphate was added, mixed well again, and then degassed under reduced pressure while maintaining the same temperature. Then, as a radical polymerization initiator, t
-Butylperoxy-2-ethylhexanoate was added to 0.
After adding 8 parts, defoaming was performed again. Then, this mixture was cast into a casting mold (internal dimensions: 4 mm × 250 mm × 250
mm), the mold was placed in a hot air oven for polymerization, and heated from 50 ° C. to 100 ° C. for 3 hours to raise the temperature,
Then, it was heated at 130 ° C. for 1 hour to carry out polymerization. As a result, a colorless and transparent resin plate was obtained.

Example 6 100.0 parts of N- (3-isopropenyl-α, α-dimethylbenzyl) -methylcarbamate was charged into a heating mixer equipped with a pressure reducing device, and the internal temperature was kept at 45 ° C. Then, 70.0 parts of N- (3-isopropenyl-α, α-dimethylbenzyl) -2-methacryloyloxyethyl carbamate was added thereto and mixed well, and then tri (2-acryloyloxyethyl) phosphate was added. 16
After adding 7.4 parts and thoroughly mixing again, degassing was performed under reduced pressure while maintaining the same temperature. Then, t-butylperoxy-2- was added to this mixture as a radical polymerization initiator.
After 0.7 part of ethylhexanoate was added, defoaming was performed again. Then, this mixture was poured into a casting polymerization mold (internal dimensions: 4 mm x 250 mm x 250 mm), and this mold was placed in a polymerization hot air oven and heated from 60 ° C to 180 ° C for 2 hours. The temperature was raised and polymerization was performed. as a result,
A pale yellow and transparent resin plate was obtained. The evaluation results of the resins obtained by the polymerization described in Examples 1 to 6 are shown in Table-1 (Table 1).

[0038]

[Table 1]

Comparative Example 1 Polymerization in the monomer composition shown in Example 1 without addition of 2-acryloyloxyethyl phosphate was carried out under the same conditions as shown in Example 1 to give a transparent resin. A yellow resin plate was obtained. Comparative Example 2 In the monomer composition shown in Example 2, 1,1,3
Polymerization with a composition containing no 3,5,5-hexa (acryloyloxy) cyclotriphosphazene was carried out under the same conditions as shown in Example 2 to obtain a transparent pale yellow resin plate. Comparative Example 3 The monomer composition shown in Example 3 was polymerized in a composition containing no di (2-acryloyloxyethyl) phosphate under the same conditions as in Example 3 to give a transparent resin. A yellow resin plate was obtained.

Comparative Example 4 In the monomer composition shown in Example 4, polymerization was carried out using a composition containing no p-vinylbenzylphosphine under the same conditions as shown in Example 4 to give a transparent pale yellow. A resin plate of Comparative Example 5 In the monomer composition shown in Example 5, polymerization with a composition containing no 4-acryloyloxybutyl phosphate was carried out under the same conditions as shown in Example 5 to give a colorless transparent resin plate. Obtained. Comparative Example 6 In the monomer composition shown in Example 6, polymerization was performed in a composition containing no tri (2-acryloyloxyethyl) phosphate under the same conditions as shown in Example 6,
A pale yellow and transparent resin plate was obtained. The evaluation results of the resins obtained by the polymerization described in Comparative Examples 1 to 6 are shown in Table 2 (Table 2).

[0041]

[Table 2]

[0042]

EFFECT OF THE INVENTION Since the monomer having a polymerizable unsaturated double bond containing phosphorus has both the flame retardant function of phosphorus and the crosslinking function of the polymerizable unsaturated double bond, the present inventors have The resin of the present invention obtained by copolymerizing with the monomer of the transparent resin proposed above has surface hardness, rigidity, which the transparent resin essentially has,
It is possible to have flame retardancy while maintaining various physical properties such as impact resistance, heat resistance, chemical resistance, and weather resistance. In addition, the resin molded product of the present invention can be expected to be widely used as a glazing material for vehicles and the like.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kenichi Fujii 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (4)

[Claims] 1. A compound represented by the following general formula (1)
A monomer (A) having a functional group represented by and / or a monomer (B) having a functional group represented by the following general formula (2) (chemical formula 1), A monomer (C) having at least one functional group selected from the group consisting of an acrylic group, a methacrylic group, and a styryl group,
In addition, a flame-retardant transparent resin obtained by copolymerizing a monomer (D) having a polymerizable unsaturated double bond containing phosphorus. 2. The flame-retardant transparent resin according to claim 1, wherein the monomer (D) is a (meth) acrylic phosphate ester. 3. A monomer (A) and / or a monomer (B),
The flame-retardant transparent resin according to claim 1 or 2, wherein the monomer (C) and a mixture of the monomer (D) are injected into a casting polymerization mold and heated to copolymerize. Molded body. 4. A glazing material using the flame-retardant transparent resin molding according to claim 3.