JPH03121108A - Resin composition for optical material - Google Patents

Abstract

PURPOSE:To provide the title composition having a low specific gravity and excellent transparency, heat resistance, impact resistance, etc., by mixing a specified N-substituted phenylmaleimide with a diphenic acid derivative and a bisphenol A derivative in a specified weight ratio. CONSTITUTION:A resin composition for optical materials is produced by mixing 1-50wt.% N-substituted phenylmaleimide of formula I wherein X is H, a 1-5C aliphatic group, an aromatic group or a halogen atom; and a is 1-5 with 5-50wt.% diphenic acid derivative of formula II wherein X is H or a methyl and 1-30wt.% bisphenol A derivative of formula III wherein X and Y are each H or a methyl; and a+b=2-50, as the essential components. The refractive index, crosslinking density, etc., of the resin composition can be controlled by further adding a monomer having a radical-polymerizable functional group containing a C-C double bond in the molecule (e.g. styrene or phenyl acrylate) to the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel transparent resin for optical materials that has low specific gravity, excellent transparency, heat resistance, and processability, and is easy to mold.

[Conventional technology]

Conventionally, various synthetic resins to replace inorganic glass have been studied, proposed, and put into practical use. For example, diethylene glycol bisallyl carbonate can be mentioned. However, since diethylene glycol bisallyl carbonate has a low refractive index of 1.50, various resins have recently been used to increase the refractive index. For example, compounds containing aromatic rings, halogens, and sulfur atoms in their molecules have been proposed and some have been put into practical use. Furthermore, resins containing urethane or thiourethane bonds obtained by reacting incyanate compounds with polyols or polythiols have also been proposed and put into practical use.

[Problem to be solved by the invention]

However, conventional resins do not necessarily satisfy all required physical properties. In other words, in order to increase the refractive index, resins containing halogen have a specific gravity of 1.45 or more, making them heavy.On the other hand, (meth)acrylic resins are easy to mold, but often have poor impact resistance. Furthermore, although some urethane resins have good impact resistance, they suffer from poor moldability during cast polymerization.

[Means to solve the problem]

The present inventors have completed the present invention as a result of intensive research to improve the problems of conventional resins.

That is, the present invention provides (A) general formula [1] (wherein, X represents a hydrogen atom, an aliphatic group having 1 to 5 carbon atoms, an aromatic group, or a halogen atom, and a is an integer of 1 to 5) N-substituted phenylmaleimide (first monomer) represented by
; 1-50% polymerization (B) Diphenic acid derivative (second monomer) represented by general formula [2] O x (wherein, X represents a hydrogen atom or a methyl group); 5- 50% by weight and (C) general formula [3] (wherein, X and Y each independently represent a hydrogen atom or a methyl group, a and b both represent a positive integer, and a + b is 2 to 50 This is a resin composition for optical materials obtained by three-dimensionally crosslinking a liquid mixture containing 1 to 30% by weight of a bisphenol A derivative (third monomer) represented by (3) by a radical polymerization reaction.

N- which is the first monomer represented by general formula [1] of the present invention
Specific examples of substituted phenylmaleimide include N-phenylmaleimide, N-(2-chlorophenylmaleimide)
, N-diethylphenylmaleimide, N-dimethylphenylmaleimide, N-()ribromophenylmaleimide), and N-(4-phenylphenylmaleimide).

Specific examples of the second monomer and diphenic acid derivative of the present invention and general formula [2] include biphenyl-2,2'-diallyl ester and biphenyl-2,2'-diallyl ester.

Specific examples of the third monomer bisphenol A derivative represented by the general formula [3] of the present invention include 2.2'-bis(4-acryloxyethoxyphenyl)propane, 2.
2'-bis(4-methacryloxyethoxyphenyl)propane, 2.2'-bis(4-acryloxyjethoxyphenyl)propane, 2.2'-bis(4-methacryloxyjethoxyphenyl)propane, a + b is 10
dimethacrylic acid ester (for example, Shin Nakamura Chemical 11
NK ester BPE-500), a + b is 30
Examples include dimethacrylic acid esters (for example, NK ester BPE-1300 from Shin Nakamura Kagaku a).

In the present invention, (A) at least one type of first monomer represented by general formula (1); and (B) general formula [2
] at least one type of second monomer represented by (C
) A monomer mixture containing at least one type of third monomer represented by general formula [3] in a specific ratio is polymerized in the presence of a radical polymerization initiator.

In the present invention, the content of the above (A) is preferably 1 to 50% by weight, preferably 5 to 30% by weight. Ingredients (A
), the heat resistance of the polymer obtained by polymerization is improved, but if the content of component (A) is less than 1% by weight, the improvement in heat resistance is insufficient and the present invention can't achieve their goals. On the other hand, if component (A) exceeds 50 folds, the coloring of the monomer mixture remains unresolved even after polymerization, resulting in undesirable coloring of the product.

The content of the above (B) is preferably 5 to 50% by weight, preferably 10 to 45% by weight. The higher the content of component (B), the higher the refractive index and lower specific gravity of the polymer obtained by polymerization. However, if the content of component (B) is less than 5% by weight, the above physical properties Not enough to improve it. On the other hand, if component (B) exceeds 50% by weight, the moldability of the monomer mixture decreases, or the dispersion value of the copolymer decreases, resulting in an Abbé number of 30 or less, resulting in poor performance as an optical lens. It will be inferior. Furthermore, the impact resistance to the falling ball test deteriorates significantly, making it difficult to handle the lens.

The content of (C) above is 1 to 30% by weight, preferably 2% by weight.
~20% by weight is preferred. The higher the content of component (C), the better the transferability of the glass mold, and the better the moldability of the polymer obtained by polymerization.

When the content of component (C) is less than 1% by weight, mold release etc. tend to occur and the quality of the mold deteriorates. On the other hand, if the content of component (C) exceeds 30% by weight, the viscosity of the monomer mixture becomes extremely high, productivity decreases, and peeling from the glass mold becomes apt to occur.

In addition, a+b in the above (C) is 2 to 50, preferably 20
-50 is suitable. Regardless of the value of a+b, the moldability of the lens can be improved by adding the above content. Furthermore, when the value of a+b is 20 to 50, the impact resistance of the lens in a falling ball test can be significantly improved. On the other hand, if the value of a + b exceeds 50, the properties of the bisphenol A portion of component (C) will be relatively small compared to that of the polyethylene chain or polypropylene chain portion, which is outside the scope of the present invention. It is.

Furthermore, the present invention provides (D) a fourth monomer consisting of a compound having at least one radically polymerizable functional group containing a carbon-carbon double bond in the molecule, regardless of its type; 1 to 50;
% by weight. The fourth monomer is the above (A
), (B), and (C) without reducing the physical properties of the monomer mixture, such as adjusting the refractive index of the resin, adjusting the viscosity of the monomer mixture, and adding the desired properties to the resin obtained by polymerization. It is suitably used for adjusting crosslink density. The carbon-carbon double bond mentioned above is preferably a vinyl group, an acrylic group, or an allyl group.

Specific examples of the fourth monomer are listed below. Compounds having 1 gJ of a radically polymerizable functional group containing a carbon-carbon double bond in the molecule, regardless of its type, include styrene, 4-chlorostyrene, bromostyrene, dipromostyrene, phenyl acrylate, Examples include phenyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, benzyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, and allyl benzoate.

Next, among the fourth monomers, compounds that have two or more radically polymerizable functional groups containing a carbon-carbon double bond in the molecule, regardless of the type, are those that have vinyl groups such as divinylbenzene. Monomer; 2.2'-bis(4-acryloxy-3,5-dibromophenyl)propane, 2.2
'-bis(4-methacryloxy-3,5-')bromophenyl)propane, 2.2'-bis(4-acryloxyethoxy-3,5-dibromophenyl)propane, 2.
Bisphenol A derivatives such as 2'-bis(4-methacryloxyethoxy-3,5-dibromophenyl)propane, 2,2'-bis(4-acryloxyphenyl)sulfone, 2,2'-bis(4-acryloxyphenyl), bisphenol S derivatives such as oxyethoxyphenyl) sulfone, 2,2”-bis(4-acryloxyethoxy-3,5-dibromophenyl) sulfone, bis(4-acryloxyphenyl) sulfide, bis(4-methacryloxyphenyl) )
Sulfide, bis(4-acryloxyethoxyphenyl) sulfide, bis(4-methacryloxyethoxy-3
, 5-dibromophenyl) sulfide, ethylene glycol diacrylate, tetraethylene glycol diacrylate, nano ethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, nano ethylene glycol dimethacrylate, 1.
Monomers having methacrylic groups as aliphatic alcohol derivatives such as B-hexanediol diacrylate, l,3-nonanediol diacrylate, neopentylambacteryl dimethacrylate, trimethylolpropane trimethacrylate; bisallyl terephthalate Examples include monomers having an allyl group such as ester, bisallyl isophthalate, and triallyl trimellitate.

The method of polymerizing the resin composition of the present invention is not particularly limited, and any known polymerization method can be employed. For example, the mixed solution is cured by heating in the presence of a polymerization initiator between molds held by gaskets or spacers, but resin molded products can also be produced by photopolymerization or radiation polymerization. The polymerization initiator used here is not particularly limited, and known ones can be used. As the polymerization initiator used for thermosetting, for example, 2.2
°-Azobis(2-cyclopropylpropionitrile)
, 2,2'-azobis(2,4-dimethylvaleronitrile), 2-phenylazo4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4,4
-trimethylpentane), dimethyl 2,2'-azobis(2-methylpropionate), or azo compounds such as t-butylperoxyisobutyrate, t-butylbaroxybiparate, t-butylperoxy (2-
ethylhexanoate), peroxyesters such as t-butylperoxyisopropyl carbonate, peroxydicarbonates such as diisopropylperoxydicarbonate, benzoyl peroxide, 3,3,5
- Diacyl peroxides such as triethylhexanoyl peroxide, dialkyl peroxides such as dicumyl peroxide, hydroperoxides such as t-butyl hydroperoxide, 1,1. −Bis(
Examples include peroxyketals such as t-butylperoxycyclohexane, ketone peroxides such as cyclohexanone peroxide, and other peroxides. In addition, when curing with ultraviolet rays,
Examples of the initiator include, but are not limited to, benzoin isopropyl ether, benzophenone, benzoin isobutyl ether, acetophenone, and the like. The poison of the polymerization initiator is usually 0.001 to 10% by weight, preferably 0.01 to 10% by weight based on the monomer.
It is 5% by weight. The type and concentration of the polymerization initiator used are determined in consideration of the composition of the seven-mer mixture, reactivity, reaction rate control, etc.

In addition, the resin composition of the present invention may contain an ultraviolet absorber of 0.03 to improve its light resistance and weather resistance, if necessary.
It is desirable to contain up to 3.0% by weight. When the concentration of ultraviolet absorber is 0.01% by weight, the light resistance is extremely high.
It has almost no effect on improving weather resistance, and if the polymerization percentage exceeds 3.0%, yellow coloring becomes noticeable and the commercial value tends to decrease.

The UV absorbers used in the present invention include a wide range of UV absorbers such as benzotriazole, benzophenone, salicylic acid, and cyanoacrylate, as well as hindered amine, Ni complex, and benzoate UV stabilizers.

Furthermore, during polymerization, mold release agents, antioxidants,
Additives such as antistatic agents and various stabilizers, and bluing agents may be contained. Further, the resin molded body of the present invention includes:
A coating can also be applied to the surface of the molded body to improve optical and mechanical stability.

[Function and effect]

The resin composition of the present invention has excellent transparency, surface properties, surface hardness, heat resistance, processability, and impact resistance, has a low specific gravity of 1.39 or less, and furthermore has diethylene glycol bisallyl carbonate resin (CR-39 ) has a higher refractive index than 1
．． 570 or higher, making it extremely excellent as a material for optical materials. Furthermore, the polymerization method is simple and moldability is good.

The resin composition of the present invention is suitably used for optical materials such as eyeglass materials, so-called lenses such as camera lenses, prisms, disks such as video disks, mirrors such as concave mirrors and polygons, and optical fibers.

〔Example〕

Next, the present invention will be explained in detail, but the present invention is not limited thereto. In addition, the test method for each characteristic was performed as follows.

Moldability: Good (
O), those with slight peeling etc. are rated as slightly good (△),
Those with severe peeling etc. were rated poor (×).

Heat resistance: Lenses left in a hot air dryer at 120°C for 1 hour are taken out. Those with no visible distortion of the reflected image reflected on the surface are marked as (O), and those with slight distortion are marked as (O).
Δ), and those in which considerable distortion could be observed were marked (×).

Workability: Good (O) for those with a good polished surface after grinding with a beading machine for eyeglass lens processing, and Fair for those with a good polished surface (
△), and bad ones were rated poor (×).

Appearance: Colorless and transparent (O), slightly yellow (△), quite yellow (×)
And so.

Refractive index and Atsube number: Measured using an Atsube refractometer.

Example I 30 parts by weight of N-(2-10 lophenylmaleimide), 45 parts by weight of diphenic acid bisallyl ester, general formula [3]
A mixed solution consisting of 25 parts by weight of a monomer in which X is a methyl group, Y is a hydrogen atom, and a + b = 30, and 2 parts by weight of t-butyl peroxy (2-ethylhexanoate) as a radical polymerization initiator is prepared. The mixture was poured into a mold assembled with a glass mold and an ethylene-vinyl acetate copolymer gasket, and heated from 40°C to 120°C over 20 hours. As shown in Table 1, the lens thus obtained was colorless and transparent, and exhibited excellent moldability, heat resistance, workability, refractive index, Abbe's number, and specific gravity.

Examples 2 to 12 Polymerization was carried out in exactly the same manner as in Example 1 to obtain colorless and transparent lenses of various volatile compositions. The results are shown in Table 1.

Comparative Example 1 70 parts by weight of diphenic acid bisallyl ester, general formula [3]
A mixed solution consisting of 30 parts by weight of a monomer where X is a methyl group, Y is a hydrogen atom, and a + b = 30, and 2 parts by weight of diisopropyl peroxydicarbonate as a radical polymerization initiator was treated in the same manner as in Example 1. When polymerization was carried out using
The resulting lens was soft (polymerization was insufficient).

Comparative Example 2 Diphenic acid bisallyl ester 70 heavy iM, general formula [3]
A mixed solution consisting of 30 parts by weight of a monomer in which X and Y are hydrogen atoms and a = 4, and 2 parts by weight of t-butyl peroxy (2-ethylhexanoate) as a radical polymerization initiator was carried out. Polymerization was carried out using the same method as in Example 1 to obtain a colorless and transparent lens. The lenses thus obtained had insufficient heat resistance as shown in Table 1, and reflected image distortion occurred when annealing was performed.

Comparative Example 3 Mixture consisting of 30 parts by weight of N-(2-chlorophenylmaleimide), 70 parts by weight of diphenic acid bisallyl ester, and 2 parts by weight of t-butylperoxy(2-ethylhexanoate) as a radical polymerization initiator. The liquid was polymerized using the same method as in Example 1 to obtain a colorless and transparent lens. The lenses thus obtained were brittle and peeled from the glass mold as shown in Table 1.

Comparative Example 4 A liquid mixture consisting of 100 parts by weight of diphenic acid bisallyl ester and 2 parts by weight of diisopropyl peroxydicarbonate as a radical polymerization initiator was polymerized in the same manner as in Example 1 to produce a colorless and transparent lens. I got it.

Comparative Example 5 A mixed solution consisting of 70 parts by weight of diphenic acid bisallyl ester, 30 parts by weight of diallyl isophthalate, and 2 parts by weight of diisopropyl peroxydicarbonate as a radical polymerization initiator was polymerized using the same method as in Example 1. conduct,
A colorless and transparent lens was obtained.

Example 13 The impact resistance of the lenses molded in Examples 1 to 18 and Comparative Examples 3 to 5 was evaluated by a falling ball test using a steel ball having a diameter of 5/8 inch and a weight of 0° and 56 ounces. The tests included -4,00 power lenses with center thicknesses ranging from 1.3 to 4II11 and 0.0 power lenses with center thicknesses ranging from 1.8 to 91cm, respectively.
0 lenses were used.

The evaluation method was to continue the test while increasing the drop position successively from a height of 0 to 100 inches until the lens broke, and the impact resistance was expressed by the steel ball drop position before the lens cracked. The results are shown in Table 2, and the lenses of Examples, especially Examples 1 and 2,
The lens obtained showed excellent impact resistance.

Abbreviations in Table 1; CPMI: N-(2-OU phenylmaleimide).

EPMI: N-(2,G-diXf phenylmaleimide).

DPA Nidiphenic acid bisallyl ester.

BPE1300 general formula [3] A monomer in which x is a methyl group, Y is a hydrogen atom, and a+b:30.

BPE500 Monomer of the general formula [3], where X is a methyl group, Y is a hydrogen atom, and a+b=10.

In BAGII general formula [3], X and Y are hydrogen atoms, a
+b=4 monomer.

In BAEO2 general formula [3], X and Y are hydrogen atoms, a
+b=2 monomer, (2,2'-bis(4-acryloxyethoxyphenyl)propane BzMA: vinyl methacrylate.

PhEtOA: phenoxyethyl acrylate.

TBP:2,4. G,-Triphyllomophenyl methacrylate.

TBA: 2,2'-bis(2,6-bis(2,6-)'romo,4-methacryloxyethoxyphenyl)propane DAIP diallylisophthalate.

TMTA:) Limeliftic acid triallyl ester table 2 table (continuation)

Claims (4)

[Claims] (1) (A) General formula [1] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, X represents a hydrogen atom, an aliphatic group having 1 to 5 carbon atoms, an aromatic group, or a halogen atom, a represents an integer from 1 to 5.) N-substituted phenylmaleimide; 1 to 50% by weight (B) General formula [2] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X is 5 to 50% by weight and (C) general formula [3] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ (In the formula, X and Y are Each independently represents a hydrogen atom or a methyl group, a and b both represent a positive integer, and a+b is 2 to 50.) An optical material containing 1 to 30% by weight of a bisphenol A derivative; Resin composition for use. (2) a+b of the monomer represented by the above general formula [3] is 2
The resin composition for optical materials according to claim 1, which has a molecular weight of 0 to 50. (3) The resin composition for optical materials further includes (D) a fourth monomer consisting of a compound having at least one radically polymerizable functional group containing a carbon-carbon double bond in the molecule regardless of its type. The resin composition for optical materials according to claim 1, containing 1 to 50% by weight. (4) The functional group of the fourth monomer is a vinyl group, (meth)
Claim 3 which is an acrylic group or an allyl group
The resin composition for optical materials as described in 2.