JPS6354291B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention particularly relates to a method for producing a high refractive index resin having excellent impact resistance. Conventionally, various studies have been conducted on synthetic resins to replace inorganic glass, but for example, the refractive index of diethylene glycol bisallyl carbonate polymer is
It is low at 1.49. In recent years, proposals have been made to improve the refractive index of synthetic resins and to produce high refractive index resins. In order to obtain such a high refractive index resin, it is necessary to use a monomer with a high refractive index, and generally bifunctional and monofunctional monomers having an aromatic ring and furthermore an aromatic ring having a nuclear halogen substituent are used. A quantity has been proposed. However, in the case of the above-mentioned high refractive index resin, the refractive index is improved to 1.54 to 1.61, but because the raw material monomer has an aromatic ring and/or has an aromatic ring having a nuclear halogen substituent, , polymers tend to be hard and brittle. In this way, a high refractive index resin with low impact resistance loses one of the characteristics of a plastic lens compared to a glass lens. That is, one of the characteristics of plastic lenses, which is higher impact resistance and safety than glass, is lost. In view of the above, the present inventors have proceeded with the development of high refractive index resins with excellent impact resistance. The present invention was completed based on the knowledge that a high refractive index resin obtained by copolymerizing with carbonate exhibits particularly high impact resistance. The high refractive index of the present invention is due to the fact that the raw material monomer used is a bifunctional monomer having an allyl group, which makes it easy to control polymerization and has excellent polymerization moldability, and because it has a crosslinked structure. It has excellent mechanical properties, dimensional stability, machinability, and particularly good impact resistance, and other practical properties.
In addition, there is no initial coloration of the polymer, which is extremely important in terms of commercial value, and as will be described later, the high refractive index of the present invention and the manufacturing method of the resin do not impair transparency.
Polymerized molds can be made into various thicknesses and shapes. Therefore, the high refractive index resin of the present invention can be used for almost the same purposes as inorganic glass, and is particularly suitable for use in lenses such as microscopes, cameras, lenses, prisms, dustproof glass, windshield glass, and the like. The present invention will be explained in detail below. The present invention comprises (a) bis(oxyalkylene phenyl) diallyl carbonate or a derivative thereof, (b) diallyl ester having an aromatic ring, and (c) monoallyl carbonate having an aromatic ring,
In the presence of a radical polymerization initiator and the above (c) is combined with (a)
(b) Present in an amount of 0.5 to 20% by weight based on the total amount of
This is a method for producing a high refractive index resin characterized by polymerization. The present invention also provides (a) bis(oxyalkylene phenyl) diallyl carbonate or a derivative thereof, (b) diallyl ester having an aromatic ring, (c) monoallyl carbonate having an aromatic ring, and (d) polyoxyalkylene polyol polyol. Allyl carbonate in the presence of a radical polymerization initiator and the above (c)
The present invention also provides a method for producing a high refractive index resin, characterized in that it is present in an amount of 0.5 to 20% by weight based on the total amount of (a), (b), and (d) and is polymerized. The raw material shown in (a) above used in the present invention, that is, bis-(oxyalkylene phenyl) diallyl carbonate or derivatives thereof, generally has the following general formula: (In the above formula, R ₁ is H, CH ₃ , R ₂ is -CH ₂ CH ₂ O-,

【formula】

X is Cl, Br Y is -, -O-, -CO-, -SO ₂ -, -CH ₂
-, -CH=CH-,

[Formula] m and n are integers of 1, 2, 3, or 4, a is an integer of 0, 1, 2, 3, or 4, and l is an integer of 1 or 2). used for. According to the above formula, specific examples of typically used bis(oxyalkylene phenyl) diallyl carbonates or derivatives thereof include: and mixtures thereof. Particularly, in order to obtain a high refractive index resin, a derivative obtained by nuclear halogenation of the above-mentioned bis(oxyalkylene phenyl) diallyl carbonate is suitable. In addition, in the present invention, by copolymerizing the above-mentioned bis(oxyalkylene phenyl) diallyl carbonate or a derivative thereof as a main component with a monoallyl carbonate having an aromatic ring,
In order to easily obtain a high refractive index resin with excellent impact resistance, it is necessary to coexist a diallyl ester having an aromatic ring. That is, a mixed composition of bis(oxyalkylene phenyl) diallyl carbonate or a derivative thereof and monoallyl carbonate having an aromatic ring does not undergo high polymerization under normal polymerization conditions, or can be polymerized using a large amount of a polymerization initiator. However, the desired high refractive index resin cannot be obtained because the polymer is colored. For example, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, triallyl isocyanurate, etc. are suitable as the raw material shown in (b) above, that is, diallyl ester having an aromatic ring, used in the present invention, and the raw material bis(oxyalkylene phenyl) 1 to 99% by weight, especially 5 to 80% by weight, based on diallyl carbonate or derivatives thereof
Used within the range of That is, the amount of the above diallyl ester having an aromatic ring to be used may be determined in consideration of the ease of polymerization operation, since increasing the amount will reduce the refractive index and hardness of the resulting high refractive index resin. The present invention combines the above-mentioned (a) bis(oxyalkylene phenyl) diallyl carbonate or a derivative thereof and (b) diallyl ester having an aromatic ring.
(c) The coexistence of monoallyl carbonate in the aromatic ring is essential in order to obtain a high refractive index resin with excellent impact resistance. Examples of the monoallyl carbonate having an aromatic ring include penzyl allyl carbonate, phenoxyethyl allyl carbonate, metabromobenzyl allyl carbonate,
Para-cyanobenzyl allyl carbonate, phenyl allyl carbonate, and the like are preferably used.
In the present invention, the amount of monoallyl carbonate having an aromatic ring to be used is based on a mixed composition consisting of bis(oxyalkylene phenyl) diallyl carbonate or a derivative thereof, diallyl ester having an aromatic ring, and polyoxyalkylene polyol polyallyl carbonate. generally 0.5
It is preferable to select it in the range of 1 to 20% by weight, especially 1 to 15% by weight. That is, the amount of monoallyl carbonate having the above aromatic ring used is 0.5% by weight.
If the amount is less than 20% by weight, the impact resistance of the target high refractive index resin will not be sufficiently improved, and if it is more than 20% by weight, the impact resistance will be improved but the refractive index and hardness will decrease, so this is not preferred. do not have. In addition, in the present invention, in order to obtain the desired high refractive index resin with excellent impact resistance, it is effective to further use polyoxyalkylene polyol polyallyl carbonate in combination. Examples of such polyoxyalkylene polyol polyallyl carbonate include diethylene glycol bis(allyl carbonate), and particularly those having a molecular weight of 150 or more,
It is very effective to use polyallyl carbonate of polyoxyalkylene polyol, preferably 200 to 1200. Specific examples of polyoxyalkylene polyol polyallyl carbonates with specified molecular weights include polyethylene glycols with molecular weights of 200, 300, 400, and 600.
Polyethylene glycol bisallyl carbonate (hereinafter referred to as PEG200-BAC,
PEG300―BAC, PEG400―BAC, PEG600―
BAC), similarly polypropylene glycol bisallyl carbonate whose molecular weight is 200, 400, 950, 1000 (hereinafter referred to as PPG200-BAC, PPG400- respectively)
BAC, PPG950-BAC, PPG1000-BAC), polyoxypropylated glycerin trisallyl carbonate with a molecular weight of 400 and 600 (hereinafter, respectively)
GP400-TAC, GA400-TAC), the molecular weight of polyoxypropylated sorbitol is 750.
polyoxypropylated sorbitol polyallyl carbonate (hereinafter abbreviated as SP750-PAC), and polyoxyethylenated glycerin trisallyl carbonate whose molecular weight is 400 and 600 (hereinafter referred to as SP750-PAC, respectively).
GE400-TAC, GE600-TAC), the molecular weight of polyoxyethylated sorbitol is 600.
polyoxyethylenated sorbitol polyallyl carbonate (hereinafter abbreviated as SE600-PAC), polyoxytetramethylene glycol bisallyl carbonate (hereinafter referred to as
PTMG1000-BAC) etc. are preferably used. In the present invention, when the above polyoxyalkylene polyol polyallyl carbonate is used in combination, the monomer composition of bis(oxyalkylene phenyl) diallyl carbonate or a derivative thereof and diallyl ester having an aromatic ring is used. , generally 0.5-25% by weight, especially 1
It is preferable to use it in a range of 20% by weight. That is, if the amount of polyoxyalkylene polyol polyallyl carbonate used is less than 0.5% by weight, the impact resistance of the high refractive index resin will not be sufficiently improved, and if it is more than 25% by weight, the impact resistance will be However, this results in a decrease in the refractive index. In order to produce a high refractive index resin with excellent impact resistance, which is the object of the present invention, bis(oxyalkylene phenyl) diallyl carbonate or derivatives thereof, diallyl ester having an aromatic ring, monoallyl having an aromatic ring, etc. It can be obtained by adding polyoxyalkylene polyol polyallyl carbonate to carbonate or the above monomer, and using a known radical polymerization method such as in the presence of a radical polymerization initiator and irradiation with ultraviolet rays or radiation. The above-mentioned radical polymerization initiator is not particularly limited, and known ones can be used. Typical examples include benzoyl peroxide, P-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, decanoyl Peroxide, diacyl peroxide such as launoyl peroxide and acetyl peroxide, percarbonate such as diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, t-butyl peroxide These are alkyl peresters such as oxy 2-ethylhexanate and t-butylperoxypivalate, or azo compounds such as azobisisobutyronitrile. The amount of the radical polymerization initiator used varies depending on the polymerization type, polymerization conditions, type of second monomer, etc., and cannot be absolutely limited, but it is generally 0.05 to 10% by weight based on the total monomers, preferably
Most preferably, it is used in a range of 0.1 to 8% by weight. The polymerization method in the present invention is not particularly limited,
Known polymerization methods can be employed. An example of a typical polymerization method is a cast polymerization method. For example, the monomer containing a radical polymerization initiator may be injected between molds held by elastomer gaskets or spacers, cured in an air oven, and then taken out. Alternatively, the monomer can be preliminarily polymerized in the presence of a polymerization initiator to increase the viscosity of the monomer, and then cast polymerization can be carried out. Among the polymerization conditions, temperature particularly affects the properties of the high refractive index resin obtained. These temperature conditions are based on the bis(oxyalkylene phenyl) diallyl carbonate or its derivatives used, other copolymerizable monomers used as necessary, and the type, amount, and type of monoallyl carbonate having an aromatic ring. Although it cannot be definitively defined as it is affected by the type of polymerization initiator, generally polymerization is started at a relatively low temperature and the temperature is slowly raised.
It is preferable to carry out so-called tapered two-stage polymerization in which the polymer is cured at high temperature upon completion of polymerization. In addition, since the polymerization time varies depending on various conditions, it is preferable to determine the optimal time according to these conditions in advance, but it is generally recommended to select conditions so that polymerization is completed in 2 to 40 hours. preferable. Of course, during the polymerization, various stabilizers and additives such as mold release agents, ultraviolet absorbers, antioxidants, color inhibitors, antistatic agents, and fluorescent dyes can be selected and used as necessary. I can do it. EXAMPLES In order to explain the present invention more specifically, Examples will be given below, but the present invention is not limited to these Examples. The physical properties of the high refractive index resins obtained in the examples were measured using the following test methods. (1) Refractive index (abbreviated as η ₀ ) The refractive index at 20° C. was measured using an Atsube refractometer. Monobromnaphthalene was used as a contact liquid. (2) Hardness (abbreviated as H _L ) Using a Rockwell hardness tester, the value on the L scale was measured for a 2 mm thick test piece. (3) Impact resistance Steel balls of various weights were dropped from a height of 127 cm onto the center of a plano lens manufactured to a thickness of 2 mm, and the weight of the steel ball was measured at the point where the lens was destroyed. Examples 1 to 7 2,2bis(4-allyl carbonate ethoxy-3,5-dibromphenyl)propane (hereinafter referred to as
70 parts by weight of diallyl isophthalate (hereinafter abbreviated as DAIP), and 30 parts by weight of diallyl isophthalate (hereinafter abbreviated as DAIP) and diethylene glycol bisallyl carbonate (hereinafter abbreviated as DEG-BAC) shown in Table 1,
A predetermined amount of PEG200-BAC or PEG300-BAC was added, and benzyl allyl carbonate (hereinafter abbreviated as BzAc) was added to each mixed composition in a predetermined amount shown in Table 1, and diisopropyl was added as a radical polymerization initiator. 1.5 to 2.0 parts by weight of peroxydicarbonate was added and thoroughly mixed.
Next, this mixed solution was poured into a mold consisting of a glass plate with a diameter of 73 mm and a gasket made of ethylene-vinyl acetate copolymer, and cast polymerization was performed. For polymerization, the temperature was gradually raised from 40°C using an air oven, and after reaching 90°C in 18 hours, the polymerization was further carried out at 90°C for 2 hours. After the polymerization was completed, the mold was taken out from the air furnace, the gasket was removed, and the polymer was removed from the glass mold after being allowed to cool. Various physical properties of the polymer were measured and the results are shown in Table 1. Comparative Examples 1 to 6 Examples 1 to 7 except that the polyoxyalkylene polyol polyallyl carbonate and BzAc were changed as shown in Table 1 Comparative Examples 1 to 6.
It was carried out in exactly the same way. The results are shown in Table 1.

【table】

[Table] Examples 8 to 13 60 parts by weight of 2,2 bis(4-allyl carbonate ethoxy-3,5-dibromophenyl)propane was added to 40 parts by weight of diallyl terephthalate, and polyethylene glycol was further added as another weight substance.
Using a specified amount of 200 bis (allyl carbonate),
A predetermined amount of monoallyl carbonate having various aromatic rings shown in Table 2 was added, and 3.5 parts by weight of di-2-ethylhexyl peroxydicarbonate as a radical polymerization initiator was added and thoroughly mixed. Next, it was carried out in exactly the same manner as in Examples 1 to 9. The results are also listed in Table 2. Comparative Examples 7 and 8 Examples 8 to 13 were carried out in the same manner except that the monoallyl carbonate having an aromatic ring was not used. The results are shown in Table 2.

[Table] Examples 14 to 21 In Examples 1 to 7, predetermined amounts of various bis(oxyalkylene phenyl) diallyl carbonates and diallyl esters having an aromatic ring were added, and monomers having an aromatic ring as shown in Table 3 were added. The same procedure as Examples 1 to 7 was carried out except that a predetermined amount of allyl carbonate was added.

[Table] The abbreviations (A) to (F) shown in Table 3 indicate the following bis(oxyalkylene phenyl) diallyl carbonate. In addition, other abbreviations in Table 3 indicate the following compounds. DAIP = diallyl isophthalate DAP = diallyl phthalate DATP = diallyl terephthalate.

Claims (1)

[Scope of Claims] 1 (a) bis(oxyalkylene phenyl) diallyl carbonate or a derivative thereof, (b) diallyl ester having an aromatic ring, and (c) monoallyl carbonate having an aromatic ring,
In the presence of a radical polymerization initiator and the above (c) is combined with (a)
(b) Present in an amount of 0.5 to 20% by weight based on the total amount of
A method for producing a high refractive index resin characterized by polymerization. 2 (a) bis(oxyalkylene phenyl) diallyl carbonate or a derivative thereof, (b) diallyl ester having an aromatic ring, (c) monoallyl carbonate having an aromatic ring, and (d) polyoxyalkylene polyol polyallyl carbonate. , in the presence of a radical polymerization initiator and the above (c)
A method for producing a high refractive index resin, which comprises polymerizing in the presence of 0.5 to 20% by weight based on the total amount of (a), (b), and (d).