JPH0255301A - Organic glass - Google Patents

Abstract

PURPOSE:To obtain excellent transparency, hardness, weatherability, and dyeability by copolymerizing a vinyl monomer having a specific compsn. and a radically polymerizable monomer having a specific value or above of the refractive index of the homopolymer. CONSTITUTION:Org. glass is obtd. by copolymerizing the vinyl monomer expressed by the formula and the radically polymerizable monomer which is the other monomer copolymerizable with this vinyl monomer and has >=1.560 refractive index of the homopolymer. In the formula, R is an alkylene group; X1-X4 and Z1-Z4 are respectively the same or different and are a hydrogen atom, halogen atom or vinyl group. The org. glass obtd. in such a manner is the copolymer obtd. by the copolymn. of the monomer and the monomer. This copolymer has 1.590 refractive index, is colorless and transparent and has the excellent surface hardness, dyeability, weatherability, etc. The resulted org. glass is, therefore, optimum for optical lenses such as, for example, spectacle lenses and optical apparatus lenses.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an organic glass having high refractive index, excellent weather resistance, transparency, hardness, dyeability, etc.

[Prior art]

Conventionally, various studies have been conducted on organic glasses to replace inorganic glasses, but they have many drawbacks and have not yet achieved fully satisfactory properties. For example, methyl methacrylate and diethylene glycol carbonate.
Polymers made from monomers whose main component is , are used as optical materials and lenses, but their refractive index is approximately 1.
It's as low as 50.

Various high refractive index resins have been proposed to improve this drawback. For example, high refractive index resins such as polycarbonate and polysulfone have been proposed. Although these resins have a high refractive index of about 1.60, they have problems such as low light transmittance, lack of optical homogeneity, and coloring.

For this reason, various crosslinkable high refractive index resins have been proposed. For example, resins containing a large number of halogen atoms, such as phenyl methacrylate, in which phenyl groups are substituted with halogen atoms, have been proposed in JP-A-61-28901.

However, these resins have large specific gravity and poor weather resistance. In addition, α-
A composition for a high refractive index resin containing naphthyl methacrylate as a main component has been proposed. Although the resin obtained from this has a high refractive index, it has poor weather resistance because it contains naphthyl groups.

[Problem to be solved by the invention]

Based on the above-mentioned prior art, organic glasses that can be suitably used for optical applications, that is, high refractive index, good transparency,
Organic glasses with well-balanced properties such as hardness, weather resistance, and dyeability are strongly desired.

Therefore, the problem to be solved by the present invention is that the refractive index is 1.
．． 590 or higher and has excellent transparency, hardness, weather resistance, dyeability, etc.

[Means to solve the problem]

As a result of extensive research to solve the above problems, the present inventors have discovered that a polymer obtained by polymerizing a vinyl monomer having a specific structure is an excellent organic material with the above properties. They discovered that it could be made into glass and completed the present invention.

That is, the present invention (8) General formula CI below) The vinyl monomer shown below is also referred to as monomer (A).

) and (B) other monomers that can be copolymerized with the above vinyl monomer, and whose homopolymer has a refractive index of 1.560 or more (hereinafter referred to as monomers) It is an organic glass made by copolymerizing the following:

In the general formula (1), R may be an alkylene group,
The number of carbon atoms is not particularly limited, but generally has 1 to 1 carbon atoms.
Preference is given to 10 straight-chain or branched alkylene groups. In particular, from the viewpoint of the refractive index of the organic glass obtained by polymerization, a linear or branched alkylene group having 1 to 4 carbon atoms is preferred. Also, X+, Xz, Xl, X4, Zl, Z2, Z3 and Z
4 is the same or different hydrogen atom, halogen atom, or vinyl group, and as the halogen atom, a chlorine atom or a bromine atom is particularly preferably used from the viewpoint of weather resistance of the resulting organic glass. Furthermore, as the number of halogen atoms in the vinyl monomer represented by general formula (1) increases, the refractive index of the resulting resin increases, but at the same time, the specific gravity increases and weather resistance deteriorates. The number of halogen atoms in the vinyl monomer molecule represented by ) is preferably selected from 0 to 4. Further, the number of vinyl groups in the vinyl heavy molecule represented by the general formula [1] is preferably selected to be 1 to 3 from the viewpoint of weather resistance of the resulting resin.

Specific examples of vinyl monomers represented by general 2N) that are preferably used in the present invention are as follows.

N-(0-vinylphenylmethyl)phthalimide, N
-(m-vinylphenylmethyl)phthalimide, N-(
p-vinylphenylmethyl)phthalimide, N-(o-
vinylphenylethyl)phthalimide, N-(m-vinylphenylpropyl)phthalimide, N-(p-vinylphenyl-4s).

propyl)phthalimide, N-(m-vinylphenylbutyl)phthalimide, N-(2-chloro-4-vinylphenylmethyl)phthalimide, N-(3-chloro-4-
Vinylphenylmethyl)phthalimide, N-(2-bromo-4-vinylphenylmethyl)phthalimide, N-(
2-promo3-vinylphenylmethyl)phthalimide,
N-(5-bromo-3-vinylphenylmethyl)phthalimide, N-(2,6-dichloro-4-vinylphenylmethyl)phthalimide, N-(3,5-dibromo-4-
vinylphenylmethyl)phthalimide, N-(4-chloro-2-vinylphenylethyl)phthalimide, 3-chloro-N-(p-vinylphenylmethyl)phthalimide, 4-chloroN-(m-vinylphenylethyl)phthalimide, 4,5-dichloro-N-(m-vinylphenylmethyl)phthalimide, 4-bromo-N-(m-vinylphenylmethyl)phthalimide, 3.6-dibromo-N-(p-vinylphenylmethyl)phthalimide, 2
．． 3.4-Trichloro-N-(0-vinylphenylmethyl)phthalimide, 2゜3.4.5-tetrachloro-N
-(m-vinylphenylmethyl)phthalimide, 3-chloro-N(1'-chloro-4'-vinylphenylmethyl)phthalimide, 4,5-dichloro-N-(2'bromo-5'-vinylphenylmethyl) Phthalimide, N-(
3,5-divinylphenylmethyl)phthalimide, 3-
Bromo-N-(3',5'divinylphenylmethyl)phthalimide, 3-vinyl-N-(4'-vinylphenylmethyl)phthalimide, 4,5-divinyl-N-(3'
-vinylphenylmethyl)phthalimide and the like.

The other component of the organic glass of the present invention is another monomer capable of co-electrifying with the vinyl monomer represented by the general formula (+), and the refractive index of the homopolymer is 1. It is a radically polymerizable monomer with a molecular weight of .560 or higher. Examples of such monomers include benzyl methacrylate, phenyl nacrylate, bromophenyl methacrylate, bisphenol A dimethacrylate, 2.2',6.6'-tetrabromobisphenol A diacrylate, and bisphenol S dimethacrylate. Methacrylic acid esters and acrylic esters such as styrene, chlorostyrene, bromostyrene, dipromostyrene, tribromostyrene, divinylbenzene, vinylnaphthalene, etc. Allyls such as diallyl phthalate, diallyl isophthalate, diallyl chlorendate, etc. Compounds, etc. and mixtures thereof.

In the present invention, the composition ratio of monomer (A) and monomer (B) cannot be generally limited because there is a suitable ratio depending on the type of each monomer, but generally, the composition ratio of monomer (A) and monomer (B)
The monomer (A) represented by is preferably used in a range of 20 to 70% by weight, more preferably 30 to 60% by weight.
used within the range.

In addition, when the organic glass of the present invention is used for applications requiring beading or cutting, the monomer (A
) or (B) is preferably crosslinkable. That is, when the monomer (A) is a -functional monomer, it is preferable that a part or all of the monomer (B) is a bifunctional or higher crosslinkable monomer.

The method of copolymerizing monomer (A) and monomer (B) is not particularly limited, and any known cast polymerization method can be employed.

Polymerization initiation means can be carried out by using radical polymerization initiators such as various peroxides and azo compounds, by irradiation with ultraviolet rays, α-rays, β-rays, T-rays, etc., or by using a combination of both.

To illustrate a typical polymerization method, the above monomer mixture containing a radical polymerization initiator is injected between molds held by an elastomer gasket or spacer,
It can be cured in an air oven and then taken out.

The radical polymerization initiator is not particularly limited and any known one can be used, but representative examples include benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, and acetyl peroxide. Diacyl peroxides such as oxide; peroxy esters such as t-butylperoxy-2-ethylhexanate, -butylperoxyneodecanate, cumylperoxyneodecanate, t-butylperoxybenzoate; diisopropylperoxybenzoate; carbonates, percarbonates such as di-2-ethylhexyl peroxydicarbonate and di-Sec 7 butyl peroxydicarbonate; and azo compounds such as azobisisobutyronitrile. The amount of the radical polymerization initiator used varies depending on the polymerization conditions, the type of initiator, and the composition of the monomer mixture, and cannot be generally limited.
Generally, 0.01 to 10 parts by weight per 100 parts by weight of total monomers.
It is suitable to use it in parts by weight, preferably in the range of o, oi to 5 parts by weight.

Among polymerization conditions, temperature particularly affects the properties of the resulting organic glass. This temperature condition is affected by the type and amount of initiator and the type of monomer, so - although it cannot be generalized - 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 under high temperature at the end of polymerization.

Like temperature, polymerization time also varies depending on various factors, so it is preferable to determine the optimal time according to these conditions in advance, but in general, conditions should be selected so that polymerization is completed in 2 to 40 hours. is preferred.

Of course, during the polymerization, various stabilizers and additives such as release agents, ultraviolet absorbers, antioxidants, color inhibitors, antistatic agents, fluorescent dyes, dyes, and pigments may be selected and used as necessary. You can.

Furthermore, the organic glass obtained by the above method can also be subjected to the following treatments depending on its use. That is,
Dyeing using dyes such as disperse dyes, hard coating agents mainly composed of silane coupling agents, sol of oxides such as silicon, zirconium, antimony, aluminum, etc., and hard coating agents mainly composed of organic polymers. Processing and secondary treatments such as hard coating treatment, anti-reflection treatment by vapor deposition of thin films of metal oxides such as SiO□, TiO□, and ZrO, and coating of thin films of organic polymers, antistatic treatment, etc. can also be performed. It is possible.

〔effect〕

The organic glass obtained by the present invention is a copolymer obtained by copolymerizing monomer (8) and monomer (B).

This copolymer has a refractive index of 1.590 or more, is colorless and transparent, and has excellent surface hardness, dyeability, weather resistance, etc. Therefore, the organic glass obtained by the present invention is suitable for optical lenses such as eyeglass lenses and optical equipment lenses, and can also be suitably used for other applications such as prisms, optical disk substrates, and optical fibers.

〔Example〕

EXAMPLES Hereinafter, in order to specifically explain the present invention, Examples will be given and explained, but the present invention is not limited to these Examples.

In addition, various physical properties of the organic glasses obtained in the examples were measured by the following test methods.

(The refractive index at 20° C. was measured using an Atsube refractometer with a refractive index of 11. Bromonaphthalene was used as the contact liquid.

(2) Hardness Using a Rockwell hardness meter, the L-scale value was measured for a test piece with a thickness of 2 cranes.

(3) Appearance Judgment was made visually.

(4) Dyeable disperse dye (product name Vista Brown from Eye Seiko)! 2g was dispersed in water and heated to 90° C., and those that could be dyed were evaluated as ○, and those that could not be dyed were evaluated as ×.

(5) Place the sample in a long-life xenon fade meter (FAC-25AX-1 (C type)) manufactured by Suga Test A side,
After being exposed to xenon light for 00 hours, the surface condition of the sample was visually observed and evaluated as ○ if the degree of coloring was lower than that of polystyrene, △ if it was the same, and × if it was high.

In addition, the monomers used in the following examples are represented by the following symbols. However, the number in [ ] is the refractive index of the homopolymer.

p-MP: N-(p-vinylphenylmethyl)phthalimide m-MP: N-(m-vinylphenylmethyl)phthalimide BP: N-(m-vinylphenylethyl)phthalimide BrMP: 4-bromo N-(m- Vinyl 7k Br
BP (1'!M P C1', MP MP αSt VB 2MA DMA Nylmethyl)phthalimide: N-(2-bromo-5-vinylphenylbutyl)phthalimide: N-(2,6-dichloro-4-vinylphenylmethyl) Phthalimide: 3,4,5,6-titrachloro N -(p-vinylphenylmethyl) phthalimide: N-(2,4-divinylphenylmethyl) phthalimide: Styrene (1,590): Chlorostyrene (0 form, m form mixture) (1,610) Nidivinylbenzene (1,615): Benzyl methacrylate (1,568): 2.2', 6.6'-tetrabromobisphenol A dimethacrylate) (1,6043 Example 1 1st To 100 parts by weight of a mixture of 50 parts by weight of monomer (A) shown in the table and 50 parts by weight of styrene as monomer (B), 1 part by weight of benzoyl peroxide as a radical polymerization initiator was added and mixed well. This mixed solution was injected into a mold consisting of a gasket made of a glass plate and an ethylene-vinyl acetate copolymer, and cast polymerization was performed.Polymerization was performed at 80 to 30 °C using an air furnace. The temperature was gradually raised over 18 hours and maintained at 1.30°C for 2 hours.

After the polymerization was completed, the mold was taken out from the air oven, and after cooling, the polymer was removed from the glass mold. Various physical properties of the obtained organic glass were measured and shown in Table 1.

Example 2 The same procedure as in Example 1 was carried out except that a composition consisting of monomer (8) and monomer (II) shown in Table 2 was used.

The physical properties of the obtained organic glass were measured and shown in Table 2.

Example 3 The same procedure as in Example 1 was carried out except that a mixture of three monomers shown in Table 3 was used. The physical properties of the obtained organic glass are shown in Table 3.

Claims (1)

[Claims] (1) (A) General formula below ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ However, R is an alkylene group, X_1, X_2, X_
3, X_4, Z_1, Z_2, Z_3 and Z_4 are the same or different hydrogen atoms, halogen atoms or vinyl groups, respectively. Vinyl monomers represented by (B) other monomers copolymerizable with the above vinyl monomers, which are radically polymerizable monomers with a homopolymer refractive index of 1.560 or more Organic glass made by copolymerizing bodies.