JPS6329701A - Resin lens having high refractive index - Google Patents

Abstract

PURPOSE:To obtain the titled lens having a high refractive index, while maintaining an excellent impact resistance of the lens by using a polyurethane resin contg. a urethane linkage and a N-(metha)acrylurea linkage as the titled lens. CONSTITUTION:The titled lens is composed of the polyurethane resin comprising a (meth)acrylic amide (A), an aromatic compd. (B) having >=2 isocyanate groups, an aromatic compd. having >=2 hydroxyl groups (C), and an aromatic monomer (D) capable of copolymerizing with the A component. And, the rate of the molar number (a) of the amid of component A, the molar number (b) of the isocyanate of component B and the molar member (c) of the hydroxyl of compo nent C is shown by the following formula (a+c)/(b)=0.5-2.0, (b/c)>1. The ratio of the component D is 0-70wt% to the total weight of said components (A)-(D). Thus, the titled lens having the high refractive index, while maintaining the excellent impact resistance of the lens is obtd. by using the resin contg. the urethane linkage and N-(meth)acryl urea linkage as the titled lens.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a high refractive index resin lens, and more particularly to a lens made of a high refractive index resin having urethane bonds and N-(meth)acrylic urea bonds. be.

[Prior art]

Traditionally, inorganic glass lenses have been widely used as eyeglass lenses for vision correction or lenses for optical equipment, but recently lenses made of resin have become more popular due to their light weight, impact resistance, workability, and stability. Due to its dyeability, mass productivity, and other advantageous features, it has begun to be widely used together with inorganic glass lenses.

On the other hand, there are various requirements regarding the physical properties of lenses, and among them, there is an extremely high demand for the material to have a high refractive index. This is because lenses with a high refractive index can be manufactured with a small thickness, and lens systems that play an important role in optical instruments such as microscopes, cameras, and telescopes can be made compact or entire. It can be made lightweight, and the eyeglass lens can be made lighter and the so-called edge thickness can be reduced, so it is a great practical advantage, especially when obtaining a high-number eyeglass lens. . As described above, it is of great significance to make lenses with a high refractive index, and therefore there is a strong desire to provide resin lenses made of materials with a high refractive index.

However, at present, a resin lens that has a high refractive index and is also satisfactory in terms of impact resistance has not yet been provided. To be more specific, the materials used for resin lenses for eyeglasses, which are currently in widespread use, are diethylene glycol bisallyl carbonate resin and polymethyl methacrylate, both of which have a low refractive index. is low at around 1.50.

On the other hand, polyurethane resins have begun to be studied in various fields as a material for resin lenses with a relatively high refractive index.
No. 313, U.S. Pat. No. 3,907,864,
Lenses made of polyurethane resin are disclosed in US Pat. No. 3,954,584 and others.

However, these polyurethane resin lenses do not have a sufficiently high refractive index, and are not necessarily satisfactory in this respect.

In addition, as a polyurethane resin having a higher refractive index, one containing a halogen atom was published in Japanese Patent Application Laid-Open No. 58-164.
No. 615, JP-A-59-133211, etc., and those containing a sulfur atom were proposed in JP-A-60-194401, and furthermore, a vinyl monomer containing a hydroxyl group and an isocyanate compound were proposed. A method in which a crosslinked structure is introduced into a polymer molecule by the reaction has been proposed in JP-A-58-168614 and others.

As described above, the current situation is that efforts are being made in various fields to find resin materials for lenses that have a high refractive index and excellent impact resistance.

[Purpose of the invention]

The present invention has been made based on the above circumstances.

That is, in general, a polymer having an amide bond +C-N+ has a high refractive index.For example, when compared with a polymer having an ester bond +C-0+, if other structures are the same, the refractive index will be higher than that of the polymer having an ester bond +C-0+. For example, ``Polymer Handbook J (Polymer Handbook J)'' is usually more expensive.
mer handbook (John Wiley
and Sons Inc., 1999), methyl methacrylate and N-methyl methacrylic acid amide having a similar structural formula, benzyl methacrylate and N-
Comparing polymers made of benzyl methacrylic amide, allyl methacrylate and N-allyl methacrylic amide, it has been revealed that the methacrylic amide polymer having an amide bond has a higher refractive index.

The present inventors focused on this fact, and in order to obtain a resin lens having a higher refractive index while obtaining the excellent impact resistance of polyurethane resins, we developed a polymer having both urethane bonds and namide bonds. or a copolymer would be effective, and as a result of intensive research, a specific JiL
Knowing that a copolymer obtained by combining polymers can provide a fully satisfactory high refractive index resin lens,
This completes the present invention.

The high refractive index resin lens of the present invention comprises the following components A, B, and C, the number of moles of acid amide groups in component A being a, the number of moles of isocyanate groups due to component B being b, and component C. When C is the number of moles of hydroxyl groups in It is characterized by being obtained by reaction and polymerization with the following components in a proportion of 0 to 70% by weight.

A component: Niacrylic acid amide or methacrylic acid amide C component: Aromatic compound having two or more isocyanate groups C component: Aromatic compound having two or more hydroxyl groups R component:
Aromatic monomer copolymerizable with component A [Effect] The high refractive index resin lens according to the present invention has excellent impact resistance characteristic of polyurethane resins, and has a refractive index of, for example, 1.58 or more. This is an extremely excellent lens with a sufficiently high price.

The high refractive index resin lens of the present invention contains the A component to the C component in a specific relative ratio, or the A component in a specific relative ratio.
By reacting and polymerizing the components or C components with the C component, polyurethane is produced, and the isocyanate groups generated at the terminals of the polyurethane are reacted with the acid amide groups contained in the A component, and the radicals caused by the A component are reacted. It can be obtained by polymerizing or copolymerizing using its polymerizability, and forming a lens from the resulting resin having both urethane bonds and N-(meth)acrylic urea bonds.

°Here, N-(meth)acrylurea bond means N-
Methacrylurea bond CH3 (-CH2-C- or N-acrylurea bond (-CH2-CH- 0°).

The present invention will be specifically explained below.

The copolymer constituting the high refractive index resin lens of the present invention includes the following specific copolymer components A component, C component and C
or from these components A to C and component C.

A component: Niacrylic acid amide or methacrylic acid amide C component: An aromatic compound having two or more isocyanate groups C component: An aromatic compound having two or more hydroxyl groups R component:
Aromatic monomer copolymerizable with component A The acrylamide or methacrylic acid amide as component A has a molecular weight of 71 or 85, respectively, which is a relatively high molecular weight for a monomer having a radically polymerizable vinyl group. It is an aliphatic compound with a small size and an amide group. By using such component A as a copolymerization component, it is possible to obtain a copolymer having a refractive index much higher than that of the same type of ester group-containing monomer, as described above.

The monomer of component A reacts with the isocyanate group of component C, but when component C forms a urethane bond with component C, it reacts with the isocyanate group at the end of the compound.

Component C and C component are polyfunctional isocyanates and polyfunctional alcohols that form urethane bonds, but in the present invention, the ratio b of the number of moles of isocyanate groups due to component C to the number of moles C of hydroxyl groups due to component C It is necessary that the value of /c is greater than 1, and by satisfying this condition, the isocyanate group that did not form a urethane bond at the end of the urethane compound due to the C component and the C component is removed. This isocyanate group reacts with component A, thereby forming a crosslinkable trifunctional urethane compound.

Here, the number of moles of isocyanate group is the number of moles of hydroxyl group C
If the amount is less, there will be no isocyanate group at the end of the urethane compound produced, so it will not be able to react with component A to form an N-(meth)acrylurea bond. Since the C components are both polyfunctional isocyanates and polyfunctional alcohols having aromatic groups, the copolymer finally obtained has a high refractive index.Both these C components are aromatic. If it is not a compound, a lens with a sufficiently high refractive index cannot be obtained.

Specific examples of aromatic compounds having two or more isocyanates (3) used as component C include, for example, tolylene diisocyanate, xylylene diisocyanate), (4)
．． Diisocyanate a such as 4'-diphenylmethane diisocyanate and naphthalene diisocyanate can be mentioned, and examples of aromatic isocyanate compounds having three or more isocyanate groups include, for example, the reaction between xylylene diisocyanate and a polyfunctional alcohol such as trimethylolpropane. Examples include, but are not limited to, adduct bodies and others.

Specific examples of aromatic compounds having two or more hydroxyl groups that can be used as component C include resorcinol, catechol, hydroquinone, bisphenol A1, tetrabromobisphenol A1, bisphenol S1, and suphenol A bis(2-hydroxyethyl) ether. , tetrabromobisphenol A bis(2-hydroxyethyl) ether, other polyhydric phenols, compounds obtained by adding monoepoxides (especially ethylene oxide, propylene oxide, etc.) to polyhydric phenols, phthalic acid, isophthalic acid, etc. Examples include aromatic polyester polyols which are condensates of polyhydric aromatic carboxylic acids and polyhydric alcohols, and others, but are not limited to these.

The relative proportions of component A, component B, and component C are the sum (a + c) of the number of moles of acid amide groups a due to component A and the number C of moles of hydroxyl groups due to component C, and the number of moles of isocyanate groups due to component B. The value of the ratio (a+c)/b to the number is 0.
The ratio b/c of the number of moles of the isocyanate group of the B component to the number of moles of the hydroxyl group of the C component, C, is required to be in the range of 5 to 2.0.
Needs to be bigger. That is, (a+c)/b-0,5~2.0 and b/c
> 1, and further, (a+c)/b=0.6~1.8 or 1.5>b
It is preferable that /c>1.

In the reaction of these three components, component B and component C react to produce a urethane compound having an isocyanate group at the end, and this terminal isocyanate group reacts with component A to form N-(meth)acrylic. Generates a urea bond.

In the present invention, since there are more isocyanate groups than hydroxyl groups in the monomer composition, a urethane compound having an isocyanate group at the end is produced, and this reacts with the amide group of component A, resulting in N-( A meth)acrylicurea bond will be formed. Of course, the reaction between component B and component C also proceeds.

In the relative proportions of the A component to C component, the ratio (
If the value of a+c)/b is less than 0.5, the proportion of non-crosslinked components in the reaction product will increase, making it difficult to obtain a polymer with high impact resistance, and the isocyanate group As a result, the final lens obtained becomes unstable. Also, the value of this ratio is 2.0
In these cases, a three-dimensional crosslinked structure is not formed and many non-bonding molecules are present, resulting in a lens with poor toughness.

In the present invention, in addition to the above-mentioned components A to C, a monomer copolymerizable with acrylic amide or methacrylic amide used as component A can be used as component D to copolymerize. By using the D component in this way, it is possible to improve the properties of the lens that is finally obtained, making it possible to obtain a resin lens with properties suitable for the purpose, or to favorably change the conditions for manufacturing the lens. For example, solvent resistance,
Various properties required for lenses, such as scratch resistance and stainability, can be improved, and the viscosity of the mixture can be lowered, making it easier to carry out cast polymerization.

The monomer for component D is preferably one that does not reduce the refractive index of the lens finally obtained, and for this reason, the monomer for component D is preferably an aromatic monomer. Examples of monomers that can be used as ) Aromatic allyl compounds such as diallyl phthalate, allyl phenol, allyl benzoate, (c) phenyl methacrylate, tribromophenyl methacrylate, acryloxy polyethoxy phenol,
2.2-bis(4-methacryloxyethoxyphenyl)
Examples include various acrylic esters or methacrylic esters such as propane, that is, esters of aromatic compounds having a -valent or polyvalent hydroxyl group and acrylic acid or methacrylic acid, and others. However, the invention is not limited to these examples.

In the present invention, the above-mentioned component monomers can be used alone or in combination depending on the purpose. Further, the amount of the i5D component may be generally within a range of 70% by weight or less based on the entire monomer composition including components A to C. That is, the A to C components are 30 or more in the entire monomer composition, which is
This is because if this proportion is less than 30% by weight, the final lens obtained will not have high strength and high refractive index.

The high refractive index resin lens of the present invention is produced by reacting and polymerizing an appropriate mixture or composition of the above-mentioned components A to C, or an appropriate mixture or composition of the above-mentioned components A to C. However, this reaction and polymerization can be carried out all at once in a casting container, for example, because the monomers related to each of the above components have sufficiently low viscosity and sufficiently high fluidity, and are therefore extremely easy. The high refractive index resin lens of the present invention has a great advantage in that it can be manufactured easily and at low cost.

As the casting polymerization method or the casting reaction method using a casting container, well-known techniques can be used as they are. As the casting container, plate-shaped, lens-shaped, cylindrical, prismatic, conical, spherical, or other molds or molds designed according to the purpose are used. The material may be any suitable material such as inorganic glass, plastic, or metal.

When obtaining the lens of the present invention by a cast polymerization method, components A to C or A are placed in an appropriate casting container.
The components may be added as a mixture or separately together with a polymerization initiator to carry out the reaction and polymerization.
The N-(meth)acrylurea reaction and the radical polymerization may be carried out simultaneously, or it is also possible to carry out one of the polymerization or reaction first and then carry out the other polymerization or reaction.

In the reaction and polymerization, the reaction rate of the acrylamide or methacrylic acid amide of the A component with the isocyanate group of the B component is slower than that of the hydroxyl group of the C component. As a result of the urethanization reaction between the and the hydroxyl group proceeding first, a relatively long-chain polyurethane is produced, and as a result of the poor compatibility of such polyurethane with other components, the transparency of the final lens is reduced. It may be low. In such a case, it is also useful to react component A with the isocyanate (M) of component B in advance, and then add component C to perform the urethane reaction.

The urethane reaction and N-(meth)acrylic urea reaction that occur between component A, component B, and component C can be performed without a catalyst under heating, but they can also be accelerated using a catalyst. It is.

As the catalyst, catalysts known in the field of polyurethane chemistry can be used.
There are amine catalysts and organometallic catalysts.

Specific examples of the former include triethylenediamine,
Triethylamine, N-methylmorpholine, etc., and specific examples of the latter include, for example, diptyltin dilaurate,
Stannath octoate and other organotin compounds can be mentioned.

Further, radical polymerization can be carried out at room temperature or in a heated state using a known radical polymerization initiator, thereby making it possible to obtain a polymer having a high molecular weight.

In the case of the cast polymerization method, each component may be put into a cast container all at once, or if necessary, a certain degree of polymerization or reaction may be carried out in advance using a separate container. Lenses can be obtained by method B, in which the obtained prepolymer or syrup is placed in a casting container to complete the reaction and polymerization. The mixture of each component may also contain colorants, ultraviolet absorbers, antioxidants, heat stabilizers, and other auxiliary agents depending on the intended use of the resulting lens.

The lens of the present invention is characterized in that the lens material is the above-mentioned cross-Wfl copolymer. Therefore, in addition to the method of directly obtaining the lens by casting polymerization, plate materials and other copolymers can be obtained. It can also be manufactured by cutting it out.

Furthermore, by performing surface polishing, antistatic treatment, and other post-treatments as necessary, the mechanical characteristics of the lens of the present invention can be further improved. In order to further increase the surface hardness, it is of course possible to coat the surface with an inorganic or organic hard coating agent by vapor deposition or dipping, or to apply a non-reflective coating.

Example 1 6.68 parts by weight (0,094 mol) of acrylamide and 17.71 parts by weight (0,094 mol) of metaxylylene diisocyanate
0,094 mol) in 50 parts by weight of styrene,
To this was added 0.02 parts by weight of di-n-butyltin dilaurate, and after the mixture was left to stand at a temperature of 80°C for 2 hours, 25.6 parts by weight (0,047 mol) of tetrabromobisphenol A was added and dissolved.

The sum (a
The value of the ratio (a+c)/b of +c) is 1. Q, ratio of the number of moles of isocyanate groups to the number of moles of hydroxyl groups C, b /
The value of c is 2.0.

0.8 parts by weight of lauroyl peroxide was added to this mixture, and the mixture was poured into a glass mold for lens production.
10 hours at 60℃, 2 hours at 80℃, 2 hours at 100℃
Reaction and polymerization were carried out by varying the time and reaction conditions to produce a colorless and transparent lens with a center thickness of 1.7 l1m.

The refractive index of this lens was measured using an Atsube refractometer.
It showed n'2-1.607. Furthermore, the resin of this lens was completely insoluble in organic solvents such as ethanol, acetone, methyl ethyl ketone, tetrahydrofuran, and toluene, and was thought to have a highly three-dimensional crosslinked structure. is strong and has AS
T? It had excellent impact resistance passing the falling ball test of IF659-80.

Comparative Example 1 Instead of acrylamide in Example 1, 6.68 parts by weight (0,051 parts by weight) of 2-hydroxyethyl methacrylate, which is an ester having a double bond with a hydroxyl group, was added.
A lens was produced in the same manner as in Example 1, except that the same procedure was used as in Example 1.

What is the refractive index of this lens? =1.593, and from this, it is clear that by using acrylamide as in Example 1, a lens with a high refractive index can be obtained.

Comparative Example 2, Since the molar ratio of acrylamide, metaxylylene diisocyanate, and tetrabromobisphenol A in Example 1 was set to 2/2/1, a double bond with a hydroxyl group was used instead of acrylamide. Using 2-hydroxyethyl methacrylate, which is an ester with 2-
The molar ratio of hydroxyethyl methacrylate, xylylene diisocyanate and te;・labromobisphenol A was 2/2/1 (11.01 parts by weight of 2-hydroxyethyl methacrylate, 15 parts by weight of xylylene diisocyanate).
．． 94 parts by weight and tetrabromobisphenol A
(23.04 parts by weight), and otherwise produced a lens in the same manner as in Example 1.

The refractive index of this lens is n = 1.591, and from this, even if it is made of a crosslinked copolymer as in Example 1, it is difficult to use acrylic acid amide as in Example 1. It is judged that this is advantageous for increasing the refractive index.

Example 2 A mixture having the same composition as in Example 1 except that 50 parts by weight of parachlorostyrene was used instead of styrene in Example 1, that is, 6.68 parts by weight of acrylamide and 17.71 parts by weight of metaxylylene diisocyanate. A colorless and transparent lens having a center thickness of 1.7 am was prepared in the same manner as in Example 1 using a mixture of 25.6 parts by weight of tetrabromobisphenol A and 50 parts by weight of chlorstyrene.

The refractive index of this lens was n 7 = 1.614.

Further, the resin of this lens is completely insoluble in organic solvents such as ethanol, acetone, methyl ethyl ketone, tetrahydrofuran, and toluene, and is considered to have a highly three-dimensional crosslinked structure. Furthermore, this lens was used in Example 1.
It was subjected to a similar drop test, but no damage was observed.

Comparative Example 3 A lens was produced in the same manner as in Example 2 except that 2-hydroxyethyl methacrylate was used instead of acrylamide in Example 2.

The refractive index of this lens was nV=1.600, and from this it is clear that using acrylic acid 7mide as in Example 2 is effective in increasing the refractive index.

Example 3 6.5 parts by weight of methacrylic acid amide and 20.0 parts by weight of tolylene diisocyanate were dissolved in 25 parts by weight of styrene, and 0.02 parts by weight of di-n-butyltin dilaurate was dissolved therein.
After adding parts by weight and standing at a temperature of 80°C for 2 hours, 48.5 parts by weight of tetrabromobisphenol A bis(2-hydroxyethyl) ether and 1.0 parts by weight of tert-butyl peroctoate) were added thereto. Then, the resulting mixture was poured into a glass mold for lens production, and the reaction conditions were changed to 60°C for 10 hours, 80°C for 4 hours, 100°C for 2 hours, and 120°C for 2 hours. Then, polymerization was carried out to obtain a pale yellow strong lens with a center thickness of 1.5 mm.

The value of the ratio (a+c)/b in the above mixture is 1.0, and the value of the ratio b/c is 1.5.

The refractive index of this lens was n''2 = 1.617.

Additionally, this lens is completely insoluble in ordinary organic solvents.
It was shown that the three-dimensional cross-linked structure is advanced.

Further, in the same falling ball test as in Example 1, no i-injury was observed at t2.

Comparative Example 4 A lens was obtained in the same manner as in Example 3 except that 6.5 parts by weight of 2-hydroxyethyl methacrylate was used instead of methacrylic acid amide in Example 3.

The refractive index of this lens is n' = 1.604, which is lower than that of Example 3, and it is clear that using methacrylic acid amide as in Example 3 is effective in increasing the refractive index. .

Comparative Example 5 4.0 parts by weight of methacrylic acid amide and 42.5 parts by weight of tolylene diisocyanate were dissolved in 25 parts by weight of styrene, and 0.02 parts by weight of di-n-butyltin dilaurate was dissolved therein.
After adding parts by weight and leaving at a temperature of 80°C for 2 hours, 28.5 parts by weight of tetrabromobisphenol A and 1.0 parts by weight of tert-butyl peroctoate were added,
Inject this mixture into a glass mold for lens production,
Reaction and polymerization were carried out using the same heating program as in Example 3 to produce a yellow lens.

The value of the ratio (a+c)/b in the above mixture is 0.31,
The straightness of the ratio b/c is 4.64.

The refractive index of this lens was n'2=1.607.

In addition, this lens failed the kneeling Li drop test similar to Example 1.

Example 4 6.12 parts by weight of acrylamide, 24.34 parts by weight of quinrylene diisocyanate, and 2 parts by weight of bisphenol A
9.54 parts by weight of di-n-butyltin dilaurate were mixed with 20 parts by weight of benzyl methacrylate and 20 parts by weight of 2,4.6-) lipcomophenyl methacrylate, and 0.02 parts by weight of di-n-butyltin dilaurate and tert. 1.0 parts by weight of butyl peroctoate was added and mixed, and this mixture was poured into a glass mold for making lenses, and the mixture was heated to 60°C for 10 minutes.
The reaction and polymerization were carried out by changing the reaction conditions for 4 hours at 80°C, 2 hours at 100°C, and 2 hours at 120°C to obtain a colorless and transparent lens.

The value of the ratio (a+c)/b in the above mixture is 0.153
, the value of the ratio b/c is 2.38.

The refractive index of this lens was as high as n1Z=1.594. Also, this lens contains ethanol, acetone, toluene, tetrahydrofuran, etc. It is insoluble in the a solvent, and it is clear that a crosslinked structure is formed. Further, in the same falling ball test as in Example 1, no damage was observed.

Comparative Example 6 14.5 parts by weight of acrylic acid amide and 13.0 parts by weight of xylylene diisocyanate were mixed with 25 parts by weight of benzyl methacrylate, and 0.02 parts by weight of di-n-butyltin dilaurate was mixed therewith. In addition, after standing at a temperature of 80°C for 2 hours, 47.51 parts of tetrabromobisphenol A bis(2-hydroxyethyl) ether and 1.0 parts by weight of tertiary-butyl peroctoate were added, and this mixture was used for lens production. The mixture was poured into a glass mold, and reaction and polymerization were carried out using the same heating program as in Example 4.

The value of the ratio (a+c)/b in the above mixture is 2.57,
The value of the ratio b/c is 0.92.

Although this lens was colorless and transparent, it was very brittle.Example 1
He was unable to pass a similar falling ball test.

Example 5 7.4 parts by weight of methacrylic acid amide and 32.7 parts by weight of 4,4-diphenylmethane diisocyanate are mixed and dissolved in 40 parts by weight of styrene under heating, and 0.5 parts by weight of di-n-butyltin dilaurate is added thereto. 02 parts by weight was added, and the temperature was 80°C.
After keeping it for 3 hours, add bisphenol A 19.9
Parts by weight are defined as parts by weight. This mixture was poured into a glass mold to make a lens, and heated at 60°C for 10 hours.
Reaction and polymerization were carried out by changing reaction conditions such as 80° C. for 4 hours, 100° C. for 2 hours, and 120° C. for 2 hours, and the polymerization was completed to obtain a pale yellow lens.

The value of the ratio (a+c)/b in the above mixture is 0.894
, the value of the ratio b/c is 1.78.

The refractive index of this lens was n7=1.58. It was also found that this lens was completely insoluble in ordinary ionic solvents and had a highly three-dimensional crosslinked structure. Further, in a falling ball test similar to Example 1, no damage (L2) was observed.

Claims (1)

[Scope of Claims] 1) The following components A, B, and C are defined as follows: a is the number of moles of acid amide groups in component A, b is the number of moles of isocyanate groups in component B, and hydroxyl groups in component C. When c is the number of moles of A high refractive index resin lens obtained by reaction and polymerization together with component D below in a proportion of ~70% by weight. A component: Acrylic acid amide or methacrylic acid amide B component: Aromatic compound having two or more isocyanate groups C component: Aromatic compound having two or more hydroxyl groups D component:
Aromatic monomer copolymerizable with component A