JP2003221417A - Curable composition having excellent optical property - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for optical applications from which optical materials having well-balanced and excellent optical, mechanical and thermal properties are prepared. <P>SOLUTION: The curable composition comprises (a) an aromatic diallyl compound, (b) an aromatic dimethallyl compound, and (c) a (meth)allyl carbonate compound and is expressed by formula (1). (wherein R<SP>1</SP>and R<SP>2</SP>are each a hydrogen atom or a methyl group, R<SP>3</SP>is a divalent organic group optionally containing an oxygen atom, n is the number of repeating units, and is an integer of 1-10). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical component such as a plastic lens and a camera lens, which has good optical characteristics with respect to a refractive index, Abbe number, transparency and the like and is excellent in various mechanical characteristics. The present invention relates to a curable resin composition for optical materials, which can provide optical-related products such as adhesives and coating agents.

[0002]

2. Description of the Related Art Organic glass is lighter than inorganic glass and is therefore attracting attention as an optical material, especially as a lens material.
Currently diethylene glycol bis (allyl carbonate)
Organic glasses made of polymers such as the above are often used.
Organic glass made of diethylene glycol bis (allyl carbonate) is lightweight and has impact resistance,
It has excellent dimensional stability, machinability, dyeability, and hard coat properties, and is often used as a material for spectacle lenses in place of inorganic glass. However, diethylene glycol bis (allyl carbonate) has an Abbe number of 5
The refractive index was as high as 8, and the dispersion was small, but the refractive index was as low as about 1.50. Therefore, practically, the lens thickness had to be increased, the merit of weight reduction was lost, and the appearance was poor. .

Various organic glasses using a diallyl phthalate monomer have been proposed in order to improve such a defect, but there is a problem in coloring. As a known technique for solving the problem, a pigment or a dye is often added for the purpose of masking coloring. However, in that method, the dispersibility of pigments and dyes and the uniformity of color are not sufficient, there is a problem in the stability of quality, and a fundamental solution to prevent coloring has been desired.

On the other hand, an organic glass using a dimethallyl phthalate-based monomer has been proposed (JP-A-60-
158208 etc.). A relatively colorless cured product was obtained from this product, but it did not dye well with a general-purpose dyeing agent, and there was a problem in dyeability. In general, when a radical polymerizable monomer typified by diethylene glycol bisallyl carbonate is polymerized and molded, an organic peroxide (diisopropyl peroxydicarbonate, etc.) having a 10-hour half-life of 80 ° C. or less is generally used for polymerization. Where it is used as an agent, in the case of polymerization molding of a dimethallyl phthalate-based monomer, when such an organic peroxide is used as a polymerization initiator, the methallyl group has a slow polymerization rate and a sufficient hardness at the end of the polymerization. Since it could not be produced, it was difficult to use it as an optical material, especially as a lens material.

[0005]

The object of the present invention is to apply the conventional lens molding conditions as they are, and to obtain a well-balanced and good optical property (low coloring property, high refractive index, high Abbe number, etc.), The present invention provides an optical resin composition capable of preparing an optical material (plastic lens) having mechanical properties (impact resistance etc.) and thermal properties (heat resistance etc.).

[0006]

The present invention provides (a) at least one aromatic diallyl compound, (b) at least one aromatic dimethallyl compound (c) general formula (1):

[Chemical 2] [In the formula, R ¹ and R ² may be the same or different and each is a hydrogen atom or a methyl group. R ³ is a divalent organic group which may have an oxygen atom. The number of repeating units n is 1 to 10. ] The curable composition which comprises at least 1 type of (meth) allyl carbonate compound shown by these.

The aromatic diallyl compound (a) used in the present invention may be a polybasic acid ester of allyl alcohol having an aromatic ring. The aromatic ring is a ring having 4n + 2 (n is a positive integer) π electrons as shown by Huckel's rule. Examples of aromatic rings include benzene-based aromatic rings (benzene ring, and condensed rings (naphthalene ring, pyrene ring, etc.)),
Non-benzene aromatic ring (tropylium ring, cycloproperium ring, etc.), heteroaromatic ring (pyridine ring, pyrrole ring, etc.)
Is.

As an example of the aromatic diallyl compound (a),
Diallyl orthophthalate, diallyl isophthalate,
Examples include diallyl terephthalate. The aromatic diallyl compound (a) is used alone or in combination of two or more. The amount of the aromatic diallyl compound (a) to be compounded is 10 to 100 parts by weight of the total amount of the components (a) to (c).
90 parts by weight is preferable, and 20 to 50 parts by weight is more preferable.

The aromatic dimethallyl compound (b) used in the present invention may be a polybasic acid ester of methallyl alcohol having an aromatic ring. The aromatic ring is a ring having 4n + 2 (n is a positive integer) π electrons as shown by Huckel's rule. Examples of aromatic rings include benzene-based aromatic rings (benzene ring, and condensed rings (naphthalene ring, pyrene ring, etc.)), non-benzene-based aromatic rings (tropylium ring, cycloproperium ring, etc.), heteroaromatic rings (pyridine ring, Pyrrole ring). The aromatic dimethallyl compound (b) has a methallyl group at both ends and a plurality of (for example, 2 to 10) aromatic rings between the methallyl group and the methallyl group, and between the aromatic ring and the aromatic ring. May be a compound in which an alkylene glycol (eg, propylene glycol) monomer or oligomer is present. Examples of such compounds are:
It is a compound represented by the formula (2). CH ₂ = C (R ¹¹ ) CH ₂ -OC (= O) -Ph-C (= O) O- (CH ₂ C (R ¹² ) H) -OC (= O) -Ph-C (= O) O- (CH ₂ C (R ¹³ ) H) -OC (= O) -Ph-C (= O) O- (CH ₂ C (R ¹⁴ ) H) -OC (= O) -Ph-C (= O) O-CH ₂ C (R ¹⁵ ) = CH ₂ (2) [in the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵
Is hydrogen or a methyl group, and Ph is a phenylene group. ]

Examples of compound (2) are as follows. (I) CH ₂ = CHCH ₂ -OC (= O) -Ph-C (= O) O- (CH ₂ CH ₂ ) -OC (= O) -Ph-C (= O) O- (CH ₂ CH ₂ ) -O C (= O) -Ph-C (= O) O- (CH ₂ CH ₂ ) -OC (= O) -Ph-C (= O) O-CH ₂ CH = CH ₂ (ii) CH ₂ = C (CH ₃ ) CH ₂ -OC (= O) -Ph-C (= O) O- (CH ₂ C (CH ₃ ) H) -OC (= O) -Ph-C (= O) O -(CH ₂ C (CH ₃ ) H) -OC (= O) -Ph-C (= O) O- (CH ₂ C (CH ₃ ) H) -OC (= O) -Ph-C (= O ) O-CH ₂ C (CH ₃ ) = CH ₂

Examples of the aromatic dimethallyl compound (b) include dimethallyl orthophthalate, dimethallyl isophthalate and dimethallyl terephthalate. The aromatic dimethallyl compound (b) is used alone or in combination of two or more. The blending amount of the aromatic dimethallyl compound (b) is preferably 5 to 60 parts by weight, more preferably 20 to 40 parts by weight, based on 100 parts by weight of the total amount of the components (a) to (c).

(Meth) allyl carbonate compound (c)
In, it is preferable that both R ¹ and R ² are hydrogen atoms.

R ³ is a divalent organic group which may have an oxygen atom, for example, -A ¹ -A ² -O-A ^3- [wherein A ¹ , A ² and A ³ are: It is a linear or branched alkylene group having 1 to 6 carbon atoms. ] The organic group shown by these may be sufficient.

Specific examples of A ¹ , A ² and A ³ include ethylene group, 1-methylethylene group, trimethylene group, 1-
Examples thereof include a methylpropylene group and a 2,2-dimethylpropylene group. The number of n is 1 to 10, for example 1 to 5.

(Meth) allyl carbonate compound (c)
Specific examples of ethylene glycol bis (allyl carbonate), propylene glycol bis (allyl carbonate), 1,3-propanediol bis (allyl carbonate), 1,4-butanediol bis (allyl carbonate), 1,3- Examples include butanediol bis (allyl carbonate), neopentyl glycol bis (allyl carbonate), diethylene glycol bis (allyl carbonate), and dipropylene glycol bis (allyl carbonate).

(Meth) allyl carbonate compound (c)
May be in the form of a monomer, or may be in the form of a dimer or trimer.

(Meth) allyl carbonate compound (c)
Examples of the dimer or trimer include diethylene glycol bis (allyl carbonate), diethylene glycol bis (allyl carbonate) dimer, and diethylene glycol bis (allyl carbonate) trimer.

(Meth) allyl carbonate compound (c)
The total amount of components (a) to (c) is 100
5 to 50 parts by weight is preferable, and 10 to 4 parts by weight.
0 weight part is more preferable.

The other compound (d) used in the present invention is
It may or may not be used. The compound (d) can improve physical properties and mechanical properties such as impact resistance, shrinkability and dyeability, and can improve or adjust optical properties such as refractive index. The compound (d) is a polymerizable compound having polymerizability. The compound (d) may be any one as long as the polymer obtained by using the compound (d) does not impair the transparency. Specific examples of the compound (d) include acrylic acid or methacrylic acid esters such as methyl methacrylate and phenyl methacrylate, styrene, p-
Chlorostyrene, bromostyrene, divinylbenzene,
Examples thereof include aromatic vinyl compounds such as vinylnaphthalene, and cyanuric acid derivatives such as triallyl cyanurate and triallyl isocyanurate. The amount of compound (d) is the same as that of component (a)
0 to 40 parts by weight is preferable, and 0 to 20 parts by weight is more preferable, based on 100 parts by weight of the total of (c).

By curing the curable composition of the present invention, an organic glass (particularly a plastic lens) can be obtained. Organic glass is a monomer in the presence of a polymerization initiator,
It can be obtained by heat copolymerization by a known molding method such as cast polymerization. After the polymerization initiator is added, the curable composition may be slightly polymerized in advance at a predetermined temperature, and then the curable composition may be charged into a mold and cured by heating to polymerize. Alternatively, it is possible to polymerize using ionizing radiation such as X-rays and α-rays, or so-called light such as ultraviolet rays, visible rays and infrared rays.

A cured product is obtained by polymerizing the monomers. The polymerization is generally radical polymerization, but may be ionic polymerization. A polymerization initiator to initiate the polymerization,
For example, a radical polymerization initiator or an ionic polymerization initiator can be used.

Examples of radical polymerization initiators are organic peroxides and azo compounds. For example, benzoyl peroxide,
Diisopropyl peroxydicarbonate, tert-butyl peroxypiperate, t-butyl butyl peroxy neodecanoate, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, benzophenone, azobis Examples thereof include isobutyronitrile and azobisisobutyrovaleronitrile.

An ionic polymerization initiator may be used for the polymerization.
Yes. H as a cationic polymerization initiator _TwoSO_Four, HClO
_FourHydrogen acid such as BeCl_Two, BF_ThreeLewis acids such as
And as an anionic polymerization initiator, Li, Na
Alkali metals such as C and_TwoH₅Na, C_TwoH₅Li etc.
Examples include ruffin catalysts.

The amount of the polymerization initiator used is preferably 10 parts by weight or less, for example, 0.05 to 5.0 parts by weight, based on 100 parts by weight of the total weight of the raw material monomers.

If desired, the polymerizable composition may further contain colorants such as dyes and pigments, ultraviolet absorbers, antioxidants, polymerization regulators, various stabilizers, antistatic agents and photochromic compounds. it can.

The plastic lens can be manufactured as follows. A polymerization initiator and an additive are mixed with the compounds (a) to (c) and optionally the compound (d),
Degas after stirring. The resulting composition is then cast under nitrogen or air pressure into a mold assembled from the mold and gasket. Polymerization is 1 to 4 at 20 to 120 ° C.
After heating for 8 hours and releasing, the lens is obtained.
In the case of photopolymerization, a known light source such as a chemical lamp, a xenon lamp, a low or high pressure mercury lamp is used, and an active energy ray, preferably, a wavelength of 200 to 600 nm is used for each type for 1 to 10 minutes. A lens is obtained by irradiating to some extent. Furthermore, the outer circumference of the lens is shaved,
A product is obtained by performing a finish for cleaning dirt.

The stirring may be performed by shaking using a shaker or the like. The stirring time varies depending on the raw material, but the viscosity of the system
If it is 100 cps or less, it takes about 3 to 30 minutes. Defoaming is
Shake occasionally under reduced pressure to expel dissolved air. If defoaming is neglected, many minute bubbles may be generated in the molded product, which may cause product defects. In a 500 ml cube, 1
A system of 00 cps takes about 3 to 30 minutes.

The mold to be poured has glass molds having different curves arranged in parallel, and is supported by a ring-shaped gasket made of a suitable resin. The gasket has a suitable injectable portion and the composition is injected using an injector with an injection needle.

Polymerization is carried out by gradually increasing the temperature from room temperature to a maximum of about 100 ° C. However, in consideration of the half-life of the polymerization initiator, it is preferable that the rate of temperature rise be increased with the polymerization time. In the mold release step, after the completion of polymerization, 6
Disassemble and remove the glass mold and gasket that have been cooled to approximately 0 ° C. In the case of photopolymerization, after irradiating with active energy rays, the glass mold and the gasket of the cured lens are disassembled and removed, and if necessary, 30 minutes to 2 minutes.
It is also possible to carry out thermal polymerization for about an hour. For finishing, the outer circumference of the product lens is scraped off to adjust the size, and surface dirt is removed.

The present invention will be described below with reference to examples.
The present invention is not limited to the examples.

[Examples] Evaluation of physical properties in Examples and Comparative Examples is as follows.
It went as follows. Coloring degree Using a color difference meter (Nippon Denshoku Industries Co., Ltd.), the degree of yellowness is b *
The values were measured, and those having a value of 2.0 or less were regarded as having less coloration and passed (indicated by a circle).

Abbe number An Abbe refractometer (manufactured by Atago) was used at 25 ° C. using alpha bromonaphthalene as an intermediate solution. Impact resistance A 1.6 mm center thickness minus 5 diopter lens obtained by cast polymerization, US FDA standard drop ball test, ie a diameter of 5/8 inch 16.2
A test was conducted in which a steel ball of g was dropped from a height of 50 inches (about 127 cm) above the lens. If the cured product did not crack, it was passed (indicated by a circle).

[0032] The dyeing Sumikaron -E-FBL (manufactured by Sumitomo Chemical Engineering) 1g, 1L
The solution dispersed in water was heated to 90 ° C., and the lens was immersed in this for 10 minutes to visually confirm whether it could be dyed uniformly without color unevenness. Those that could be dyed uniformly were passed (indicated by a circle).

Example 1 Two glasses of a mixture of 45 parts by weight of diallyl isophthalate, 30 parts by weight of dimethallyl orthophthalate, 25 parts by weight of diethylene glycol bisallyl carbonate and 3.0 parts by weight of diisopropyl peroxydicarbonate as a polymerization initiator. And EVA (P-1407 manufactured by DuPont Mitsui Polychemicals) were poured into a mold and placed in a constant temperature bath and gradually heated from 30 ° C to 85 ° C over 20 hours. After the obtained cured resin was released from the mold, it was further heated at 110 ° C. for 2 hours to carry out post-polymerization. This cured resin had a coloring degree (b *) of 1.00, a refractive index of 1.55, an Abbe number of 38, and a heat distortion temperature of 70 ° C. Minus 5 with a center thickness of 1.6 mm obtained by cast polymerization
With the Diopter lens, the US FDA standard drop ball test, that is, the method of dropping a 16.2 g steel ball having a diameter of 5/8 inch from a height of 50 inches (127 cm) above the lens, and the lens is not broken confirmed.

Examples 2 to 4 The mixture having the composition (unit: parts by weight) shown in Table 1 was cast-polymerized in the same manner as in Example 1 to measure the physical properties of the cured product. The results are shown in Table 2.

Comparative Example 1 A mixture of 100 parts by weight of dimethallyl orthophthalate and 3.0 parts by weight of diisopropyl peroxy as a polymerization initiator was cast-polymerized in the same manner as in Example 1, but the curing was not sufficient and the physical properties could be measured. No sample was obtained.

Comparative Examples 2-3 A mixture having the composition (unit: parts by weight) shown in Table 1 was cast-polymerized in the same manner as in Example 1 to measure the physical properties of the cured product. The results are shown in Table 2.

[0037]

[Table 1]

[0038]

[Table 2]

Continued front page    (72) Inventor Toru Kitamura             1-10-8 Edobori, Nishi-ku, Osaka City, Osaka Prefecture             Within Daiso Corporation F term (reference) 4J026 HA45 HB07 HB35 HE02                 4J027 AB17 AB28 BA18 BA22 CB03                       CB09 CC02 CC08 CD04                 4J100 AB15P AB15Q CA05 DA52                       DA62 DA63 JA01 JA03 JA33

Claims (7)

[Claims] 1. (a) at least one aromatic diallyl compound, (b) at least one aromatic dimethallyl compound (c) general formula (1): [In the formula, R ¹ and R ² may be the same or different and each is a hydrogen atom or a methyl group. R ³ is a divalent organic group which may have an oxygen atom. n is 1-10. ] The curable resin composition which consists of at least 1 type of (meth) allyl carbonate compound shown by these. 2. A polymerizable compound (d) other than the compounds (a) to (c) in addition to the aromatic diallyl compound (a), the aromatic dimethallyl compound (b) and the (meth) allyl carbonate compound (c). The curable composition according to claim 1, further comprising: 3. The amount of the aromatic diallyl compound (a) is 10 to 100 parts by weight of the total amount of the components (a) to (c).
90 parts by weight, the amount of the aromatic dimethallyl compound (b) is 5 to
60 parts by weight, (meth) allyl carbonate compound (c)
The amount of 5 to 50 parts by weight, and the amount of the other polymerizable compound (d) to 0 to 40 parts by weight, The curable resin composition according to claim 1 or 2. 4. The curable resin composition according to claim 1, wherein the aromatic diallyl compound (a) is at least one compound selected from diallyl orthophthalate, diallyl isophthalate and diallyl terephthalate. 5. The aromatic dimethallyl compound (b) is dimethallyl orthophthalate, dimethallyl isophthalate,
The curable resin composition according to any one of claims 1 to 4, which is at least one compound selected from dimethallyl terephthalate. 6. The (meth) allyl carbonate compound (c) is at least one compound selected from diethylene glycol bisallyl carbonate, diethylene glycol bisallyl carbonate dimer, and diethylene glycol bisallyl carbonate trimer. The curable resin composition according to claim 1. 7. A plastic lens obtained by curing the curable resin composition according to claim 1.