JPS58179801A - Organic optical glass - Google Patents

Abstract

PURPOSE:To obtain org. optical glass made of a polymer of a divinyl compound or the compound with a monomer whose homopolymer has a specified refractive index and having superior optical characteristics and workability. CONSTITUTION:This org. glass is made of a polymer of 10-100wt% divinyl compound represented by formula I (where A is alkylene or a bivalent group having -O-; X is halogen; and each of (a) and (b) is 1-4) with 0-90wt% monomer whose homopolymer has >=1.5 refractive index. In the formula I , the especially preferred alkylene group is methylene, ethylene or butylene, and the preferred bivalent group having -O- is a group represented by formula II-IV (where R is 0-8C alkylene, and each of (k), (l), (m) and (n) is 0-3). The org. glass is suitable for use as the material of an optical lens, a fiber scope and an optical communication element for spectacles, a microscope, a camera, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an organic optical glass with excellent optical properties and processability. ] Organic optical glass made of transparent synthetic resin is lightweight and has excellent safety against breakage, and is attracting attention as a new material to replace inorganic optical glass.For example, the uses of organic optical glass include: It is expected to be used in fields such as optical lenses for microscopes, cameras, glasses, etc., and prisms. On the other hand, in such applications, the properties required of organic glasses include processability such as cuttability and polishability, and optical properties such as transparency and light refraction. However, almost no organic optical glass has been proposed that satisfies both of the above properties. Although it has properties that are practically satisfactory to some extent, it has the drawback that its refractive index is as small as /, +9 degrees. Furthermore, although I-restyrene, polycarbonate, and the like have an excellent refractive index of 1.5 or more and excellent transparency, they have problems in processability such as cutting and polishing properties.

Therefore, the development of an organic optical glass that has excellent optical properties and processability has been a major challenge.

The inventors of the present invention have conducted extensive research in order to achieve the above S*. As a result, a divinyl compound with a specific structure or
The present invention was completed by discovering that a polymer of an iron compound and a monomer whose homopolymer has a specific refractive index has very excellent properties as an organic optical glass.

The present invention relates to a divalent group of the general formula. X is halogen, and a%b is an integer from 1 to t. )
It is an organic optical glass consisting of a divinyl compound lθ~100% by weight and a homopolymer and a monopolymer having a refractive index of 5 or more and a polymer of O~90% by weight.

The organic optical glass of the present invention has a unique crosslinked structure derived from the above general formula +11, and therefore has an extremely excellent refractive index and transparency. In addition, machinability, such as the absence of cracks during cutting and ease of cutting,
It also has excellent workability such as polishing properties. Furthermore, as will be described later, when the proportion of the divinyl compound is high, excellent flame retardance is exhibited. However, it also has excellent mechanical properties such as impact resistance, and other properties such as dimensional stability. Therefore, the organic optical glass of the present invention can be used for the same purposes as inorganic optical glass, and can be made lighter. In particular, since the organic optical glass of the present invention has the above-mentioned properties, it can be suitably used as optical lenses for glasses, eyeglasses, cameras, etc., 7-eye perspective coordinates, and optical communication elements.

The structure of the present invention will be explained in detail below. In the present invention, the divinyl compound represented by the general formula Not restricted.

In the present invention, an alkylene group is a generic term including a methylene group. For example, an alkylene group has a carbon number of l.
-g, particularly methylene group, ethylene group, globylene group, butylene group, trimethylene group, tetramethylene group, etc. are preferred. Further, as the divalent group having a →-year unit, a group of the general formula /II is suitable. The above general formula (2
1 to (41, RFi alkylene with carbon number Og, k,!, m%n is θ to 3 (however, if R is θ, n is also 0
~t (in the formula, each R can independently take any number) is preferred. Specifically, as the divalent group of general formula (2),
-0-, -CH-0-CH-CH20CH, CH20C
H2-12- Hs -CH20CHCH20CH2-1-CH20CH2C
H20C) 12CH20CH2-2-oCH, CH20
-, etc., but also a divalent group of the general formula (3ν and a general formula (lI
In the divinyl compound, the position of each vinyl group may be any of the ortho, meta, and para positions up to the A group. In addition, the positions of each vinyl group may be different, but especially when the above-mentioned vinyl groups are lowered, they liquefy at room temperature. For example, a mixture of the above-mentioned divinyl compounds having each vinyl group at the meta and para positions is preferred because it is easy to use and is suitable for practical use. A cough divinyl compound can be used in combination with a divinyl compound each having a vinyl group at the same position to lower the melting point.

Generally, it may be used in a ratio of about 20-/θθ weight-.

In the general formula (11), X is a halogen atom, and Ct or Filr is particularly preferred.

Further, in the present invention, monomers whose homopolymers have a refractive index of 1.5 or more are those having one or more functional groups capable of radical copolymerization with the divinyl compound, and are used without particular limitation.

Typical monomers that are generally suitably used include:
L-functional monomers include styrene, vinyltoluene,
Methoxystyrene, chlorstyrene, bromstyrene,
4-dostyrene, dichlorostyrene, diprostyrene
, trichlorstyrene, tribromustyrene, P-styryltrimethylsilane, P-styryltrimethylsilane and other styrene derivatives, phenyl methacrylate, phenyl acrylate, chlorphenylacrylate, dichlorophenyl methacrylate, fc1 muphenylacrylate, dichlorophenyl methacrylate, Pentabromphenyl methacrylate, methoxyphenyl acrylate, benzyl methacrylate, chromium benzyl acrylate, brombenzikll acrylate, diprombenzyl methacrylate),) IJ prombenzylmethac IJ
Acrylates, methacrylates such as interbromobenzyl methacrylate, l-vinylnaphthalene, covinylnaphthalene, α-s7tyl methacrylate, β-s7tyl methacrylate, α-naphthyl acrylate, vinyl-α- Naphthalene derivatives such as naphthylphenylsilane, polyfunctional monomers include /, 4(-dimethacryloxybenzene, l, dimethacrylogine ethoxybenzene, di(comethacryloxethyl) phthalate), 2, covis (termethacryloxyphenyl)
7#rot47% j z , 2his(4-acryloxyphenyl)sol/4in, cocobis(termethacryloxyethoxyphenyl)pronogun, cocobis(termethacryloxyethoxy-3,s-dibromphenyl) Pronodan, 22 is (termethacryloxethoxy-3,
! -dichlorophenyl)propane, CH-2+'+ CH.

Dimethacrylates, cyacrylates, diallyl compounds such as diallyl phthalate, diallyl isophthalate, etc., and mixtures thereof.

In the present invention, the amount of the divinyl compound represented by the general formula (1) to be used relative to the monomer may be determined within the range of 70 to 700% by weight, preferably within the range of 100% by weight. If the amount used is less than the above range, it is difficult to fully exhibit the effects derived from the divinyl compound trap, that is, excellent optical properties and processability.In addition, if the amount of the divinyl compound used is more than SO0 weight, especially Those with a weight of 0 or more have excellent flame retardancy.

The method for producing the polymer which is the organic optical glass of the present invention involves adding a divinyl compound represented by the general formula Ill or a monomer having a homopolymer having a refractive index of i, s or more to a radical polymerization initiator. A common method is to carry out radical polymerization in the presence of a compound.

The above-mentioned radical polymerization initiator is not particularly limited and any known one can be used, but representative examples include penzoyl oxide, p-chlorobenzoyl oxide, p-chlorobenzoyl oxide, decanoyl oxide, and launoyl peroxide. Ogicide, diacyl-oxide such as acetyl-4-oxide, diisozolopyr-oxydicarbonate, disecanyl-lipyl peroxydicarbonate, di-n-propyl peroxydicarbonate, dicoethylhexyl-oxydicarbonate, and di-oxydicarbonate. /4'-Cardenates such as styryl peroxydicardenate, alkyl peresters such as tertiary butyloxyneodecanate, tertiary butyloxycoethylhexanate, tertiary dityl/4'-oxybivalate, etc. Alternatively, it is an azo compound such as azoin butyronitrile.

The amount of the radical polymerization initiator used depends on the polymerization type, polymerization conditions,
Although it varies depending on the type of monomer aim of the copolymer component and cannot be definitively defined, generally o, o for all monomers.
It is most suitable to use in the range of ooi to io (heavy t)no.

In the present invention, the radical polymerization method #'i is not particularly limited, and any known polymerization method can be used. As a representative example, a cast polymerization method is preferred. For example, the polymerization component monomer containing a radical polymerization initiator is injected between the molds held by a gasket or a gasket made of Nidistomer, polymerized and cured in a heating furnace, and then taken out. Of course, it is also possible to preliminarily polymerize the monomers to be polymerized in the presence of a polymerization initiator to increase the viscosity and then perform cast polymerization.

Among polymerization conditions, temperature particularly affects the properties of the obtained polymer. Generally, it is preferable to carry out so-called teno polymerization or monopolymerization, which is carried out at a relatively low temperature.

For example, it is preferable to start the polymerization slowly at room temperature to about 1IO°C, gradually raise the temperature, and terminate the polymerization at a high temperature of about go~/20''C.

In particular, when the objective is to obtain a thick polymer, it is preferable to lengthen the polymerization time at a low temperature or to perform the preliminary polymerization described above. However, if the polymerization time is too long, the resulting polymer may be colored, for example yellowish, unless the polymerization time is particularly long at high temperatures, so it is not preferable to select a polymerization time longer than necessary. generally 5
It is preferable to select conditions such that the polymerization is completed in ~30 hours. Since the polymerization time varies depending on various conditions, it is preferable to determine the optimum time according to these conditions in advance.

Of course, during the polymerization, additives such as a release agent, ultraviolet absorber, antioxidant, anti-coloring agent, antistatic agent, fluorescent dye, and various stabilizers may be selected and used as necessary. I can do it.

In addition, in the above-mentioned production method, the polymer of the present invention can be obtained by copolymerizing a monomer that does not adversely affect the obtained polymer as an additional component, if necessary. Examples of monomers for the above-mentioned additional components include those that improve mechanical properties, such as methyl methacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, trimethylol glonotrimethacrylate, aliphatic acrylates and methacrylates, molding Books that further improve properties include allyl compounds such as diallyl phthalate, diallyl inphthalate, diethylene glycol bis(allyl carbonate), sialyl tartrate, diallyl epoxysuccinate, allyl methacrylate, allyl cinnamate, co-hydroxyethyl methacrylate, and glycidyl. 10H of methacrylate, tetramethylolzolopane-up methacrylate, etc.
These include acrylates and methacrylates having groups such as acrylonitrile, vinyl acetate, methyl α-trimethylsilyl acrylate, and mixtures thereof.

The amount of the monomer added as an additional component is preferably about θ~/S weight tS relative to the total amount of other components.

In order to explain the present invention more specifically, Examples are shown below. From these results, it is easy to understand that the organic optical glass made of the specific polymer of the present invention has excellent optical properties and processability.Of course, the present invention is not limited to these examples. It is not something that will be done.

In addition, various physical properties of the polymers obtained in the examples were measured using a manure test method.

B: Refractive index (no. 20) The refractive index at 20° C. was measured using an Atsube refractometer. Monobromonaphthalin was used as a contact liquid.

(21 Transmittance (Tt%) Measured using a fade meter.

(31 Machinability: When cut with a grinder, it can be cut cleanly without cracking, ○, when there is no cracking, but the cutting powder is slightly fused, Δ, when the cracks or powder is strongly fused, it is X) It was shown in

Examples -/~6 Styrene (hereinafter abbreviated as st) was added in the composition shown in Table 1, and Si 2 was used as a radical polymerization initiator. 1
．． 2゜-oya/tsuka1-□7. o. Added part by weight and mixed well.

＼ Ethylene polymerization of this mixed solution was carried out using a glass plate with a diameter of 73 mm using an air furnace. Polymerization was initially started at 30°C, and the temperature was gradually raised to 50°C after /g hours. Furthermore, 0℃
After polymerization for several hours, the polymer was taken out from the gasket and mortold.

The polymer was further postpolymerized at 100° C. for 1 hour. Various physical properties of the polymer thus obtained were measured and are shown in Table 1.

Examples 7-q B Polymers were obtained in the same manner as in Examples/-6, except that a CV mixture (20Tos of pp-form, 5ots of m-p-form) was used in the ratio shown in Table 2. Various physical properties of the obtained polymer were measured and the optical results are shown in Table 2.

Examples 1 to 1 In Examples 7 to 9, various radically polymerizable monomers shown in Table 3 were used in place of 5trc. Others are from Example 7
It was carried out in the same manner as in 9. The results are shown in Table 3.

Example/,! Polymerization with Kst was carried out in the same manner as in Example 9, except that divinyl compounds were used in place of t-,211 (CH2=CH)-CH2)2 and various groups. The results are shown in the table below.

Example S~ Polymerization was carried out in the same manner as in Example 1, except that various divinyl compounds and various initiators shown in Table 6 were used. The results are shown in Table J.

In Table 5, Cbust=chlorstyrene TB,: 2,2-bis(q-methacryloyloxyethoxy-3,S-dibromphenyl)glopane DAT: diallyl tartrate HEM^: 2-hydroxyethyl methacrylate llO
EM: CH2=C-C00CH2CH-Cl-12-
OCI-12CH20CH2CHC) 42Hs 00C-C= CH2 DAP Nidiallyl phthalate BAC Nidiethylene glycol bis(allyl car &
Net) ND: Tertiary butyrno? -Oxyneodecanate MSP: myristyrylno-9-oxycarbonate
: Raunoyl peroxide Ipp : Diisoglobyl-oxydicarbonate Comparative Example 11 Styrene and diethylene glycol bis÷
A polymer was obtained in the same manner as in Example 1, except that each (allyl carbonate) was used alone. Various physical properties of the obtained polymer were measured and the results are shown in Table 6.

Table 6 Patent applicant: Tokuyama Soda Co., Ltd.

Claims (1)

[Claims] General formula (where ^ is an alkylene group or a divalent group having one → unit, and X is /Sa +' :/, an integer from -1bFi/ to da) An organic optical glass comprising a polymer of ~100% by weight of a divinyl compound represented by the following formula and 0 to 90% by weight of a monomer whose homopolymer has a refractive index of 1.5 or more. (2) A divalent group having units of -〇- years has the general formula % formula % Jj alkylene with carbon number O-g, k% 1. m. The organic optical glass according to claim 1'11, wherein 1 is one type of group selected from θ to 3). (3) The organic optical glass according to claim 11, which is a lens.