JPS5993708A - Polymerizable composition - Google Patents

Abstract

PURPOSE:To provide the titled composition giving a resin having high transparency, etc. suitable for lens, excellent surface hardness, etc. and high refractive index, by compounding a specific acrylic monomer containing biphenyl skeleton and a specific diacrylate monomer containing bisphenol skeleton. CONSTITUTION:The objective composition can be prepared by compounding (A) a biphenyl skeleton-containing acrylic monomer of formula I (R<1> is H or methyl; R<2> is 2-4C hydrocarbon group which may have substituent group such as methyl; R<3> is H, Cl, Br, methyl, etc.) [e.g. O-(2-acryloyloxyethoxy)biphenyl] or their mixture and (B) a bisphenol skeleton-containing diacrylate monomer of formula II (R<4> is bivalent hydrocarbon residue; Y and Y<1> are H, Cl or Br; n is 0-3) or their mixture, preferably at a ratio (A:B) of 40-60wt% to 10-60wt%. The composition is preferably polymerized by ultraviolet radiation to improve the productivity.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polymerizable composition, particularly a polymerizable composition that provides a high refractive index resin having a refractive index of 157 or more. The polymerizable composition of the present invention has a short curing time, enables high-speed coloring, and can provide a transparent resin having a high refractive index with little polymerization shrinkage during molding, so it can be used for eyeglass lenses, optical lenses, etc. It is also extremely useful as a transparent adhesive that can be used to bond various materials.

Traditionally, inorganic glass has been used for many purposes due to its excellent transparency, hardness, scratch resistance, weather resistance, etc. However, on the other hand, it is brittle. It has the disadvantages of being easy and heavy. On the other hand, 1. Organic glass has advantages over inorganic glass such as lightness, safety, processability, and dyeability, and polymers such as polymethyl methacrylate, polycarbonate, and diethylene glycol diallyl carbonate have been used. . In particular, organic glass polymers are used for applications such as eyeglass lenses due to their lightness, safety, and resistance to breakage.As the molding method is different from the casting method, it is not suitable for use in high-mix, low-volume production such as lenses. is unsuitable, and has poor heat resistance and solvent resistance, so there are limitations to its use at present. On the other hand, when manufacturing lenses using the cast molding method, they have the disadvantage that they must be thicker than inorganic glass lenses. In order to improve this drawback, several techniques for increasing the refractive index of the resin have been disclosed.

That is, for example, JP-A-55-1.3747 and JP-A-56-6.
No. 14.11, No. 56-61-4.12, No. 57-2
No. 311, No. 5 '7-23], No. 2, No. 57-2
No. 3611, No. 57-28], No. 1.5, No. 57-28
No. 28116, No. 57-28117 and No. 57-28
No. 118, etc. are disclosed.

However, in all of these prior art techniques, a desired cured product is obtained by injecting a homogeneous mixture of a monomer composition and a polymerization initiator into a casting jig and then polymerizing it over a long period of time. For this reason, the casting jig has various drawbacks, such as poor rotation of the casting jig, the need for a large number of casting jigs, a huge amount of thermal energy required for long polymerization, and extremely low productivity. have.

In view of the shortcomings of the prior art, as a result of intensive research, the present inventors have developed a polymerizable composition consisting of an acrylic monomer having a specific biphenyl skeleton and a diacrylate monomer having a specific bisphene/-exoskeleton, for example. By copolymerizing under irradiation with active energy rays such as ultraviolet rays or by heating, it has a high refractive index in an extremely short period of time with good productivity, and has surface hardness, solvent resistance, heat resistance, impact resistance, dyeability, etc. It has been discovered that a resin with a high refractive index that has excellent properties can be produced, and the present invention has been achieved.

That is, an object of the present invention is to provide a polymerizable composition that provides a high refractive index resin with a refractive index of 157 or higher.

Another object of the present invention is to provide a polymerizable composition that provides a high refractive index resin having transparency and non-coloring properties that are desirable for spectacle lenses and optical lenses.

Furthermore, the present invention has excellent surface hardness, solvent resistance, heat resistance,
An object of the present invention is to provide a polymerizable composition that provides a high refractive index resin with dyeability and processability.

The present invention is based on the general formula (I) (wherein R' represents hydrogen or a methyl group, and Bi represents a hydrocarbon group having 2 to 4 carbon atoms which may be substituted with a methyl group and/or a hydroxyl group). , X represents an oxygen atom, R3 is hydrogen, chlorine, bromine, methyl group, methoxy group,
represents a group selected from the group consisting of a phenyl group and a phenoxy group) and has a phenyl skeleton, or a mixture thereof; ), R represents a divalent hydrocarbon group, YlY may be the same or different, represents hydrogen, chlorine or bromine, and n represents 0 to 3. However, if R contains a hydroxyl group If not, h
= O. ) The present invention relates to a polymerizable composition comprising a diacrylate monomer having a bisphenol skeleton represented by the following formula or a mixture thereof.

The acrylic monomer represented by the general formula (I) used in the present invention includes 0-(2-acryloyloxyethoxy)biphenyl, 0-(2-(meth)acryloyloxyethoxy)biphenyl, 0-(3-(meth) )
Acryloyl-2-hydroxypropoxy)biphenyl, 0-(3-acryloyl-2-hydroxypropoxy)-0/-chlorbiphenyl, 0-(2-acryloyloxyethoxy), 0/-phenoxybiphenyl, 0-( 3-acryloyloxy-2-hydroxy-2-methyl-propoxy)biphenyl and the like are preferably used in an amount of 30 to 95% by weight, particularly preferably 40 to 90% by weight. If the amount of acrylic monomer used is less than 30% by weight↓, the table ji'i'
Although the hardness is significantly increased, the impact resistance and processability are unfavorable. On the other hand, if the amount of acrylic monomer used exceeds 95% by weight, the surface hardness
It is unfavorable due to insufficient solvent resistance and processability.

The amount of the diacrylate monomer represented by the general formula (II) used in the present invention cannot be uniquely determined because it varies depending on the type and amount of the acrylic monomer represented by the general formula (I) which is the copolymerization partner. No, but 5~
It is used in an amount of 70% by weight, preferably from 10 to 60% by weight.

In the present invention, it is possible to obtain a high refractive index resin by copolymerizing an acrylic monomer represented by general formula (I) or a mixture thereof with a diacrylic monomer represented by general formula (11) or a mixture thereof. Although this is easily possible, it is also possible to copolymerize other polymerizable monomers to further improve the impact resistance, dyeability, weather resistance, etc.

Polymerizable used for these [] targets? Examples of the body represented by b include methyl methacrylate, butylmethacrylate, diethylene glycol diacrylate, and diacrylate having a spiroa heptatal structure. The amount of these polymerized ゛゛〆l jit polymers to be used depends on the purpose of use, the general formula (I) and the general formula (II)
) is determined by taking into account the mixing ratio of the monomers represented by
at most 10% by weight, based on the mixture of TI).

Polymerization of the polymer composition of the present invention is carried out by radical polymerization, and methods include thermal polymerization, ultraviolet rays,
A polymerization method in which active energy rays such as γ rays are irradiated can also be used. In particular, 2111 polymerization using ultraviolet light is particularly suitable in the present invention because copolymerization can be carried out in a shorter time than thermal polymerization and has the advantage of significantly increasing productivity.

When carrying out thermal polymerization, common radical polymerization initiators such as benzoyl peroxide, diisopropylperoxydicarbonate-1-, and azohisinbutyronitrile can be used.

When carrying out ultraviolet polymerization, commonly known benzoin, benzoin methyl ether, benzine ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-benzoylpropane, azobisisobutyronitrile , benzyl, thioxanthone, and the like can be used. The amount of these radical polymerization initiators or photosensitizers used is at most 5% based on the copolymer composition.

Furthermore, when using radiation such as gamma rays, it is generally not necessary to add a polymerization accelerator.

The polymerizable composition of the present invention also contains an anti-yellowing agent (+
- Leveling agents (fluorosurfactants, etc.), ultraviolet absorbers (2-(2'-hydroxy-51-medylphenyl)-2H-benzotriazole, etc.) within a range that does not interfere with polymerization curing. It can be added within.

The refractive JJr index of the resin obtained from the polymerizable composition of the present invention varies depending on the blending ratio of the raw material monomers, but is 157 or more, and is 5% or more than a general transparent thermosetting resin (urea resin).
4. Melamine resin 155, Alkyd'J fat], 55
, diallyl phthalate 1-], , 56, diethylene glycol, cold diallyl carbonate resin 150).

As described above, the resin obtained from the polymerizable composition of the present invention is
Not only does it have a high refractive index, but it also has excellent surface hardness, so it is used not only for eyeglass lenses but also for camera lenses.
It can be used to seal light emitting diodes (I-materials, lens adhesives, luminous bead binders, etc.).

Hereinafter, the present invention will be further explained with reference to Examples.
explain.

The pipe properties of the molded products obtained in the Examples and Comparative Examples were measured by the following test method.

(]) The refractive index at 20'C was measured using the refractive index of Ii114 No. 1 index Ala. Bromonaphthalin was used as the contact liquid.

(2) Hardness It was measured using Barcol hardness 31.

(3) Surface condition: Visually observe the surface condition of the front and back surfaces of the molded product. ○ indicates that both the front and back surfaces are smooth; △ indicates that the surface is slightly rough; and △ indicates that the entire surface is rough. was marked as ×.

(4) Light transmittance was measured using a haze meter (manufactured by Ska Test Instruments (f/A)).

(5) Shock resistance test Based on FDA standards, the diameter is 59 mm from a height of 127 cm.
A steel ball weighing 162 g was dropped, and the ball (H+HrH) was considered good.

(6) Heat resistance After being placed in a hot air dryer at 120°C for several hours, no coloring or surface distortion can be observed by visual inspection.
And so.

(7) Dyeability The molded product was immersed in a 02% Tispers Brown 3 aqueous solution, soaked at 92°C for 10 minutes, pulled out, thoroughly washed with water, and dried. Among these dyed molded products, those with no uneven dyeing at all were marked as ○, and those with slight dyeing unevenness were marked as △.

Example 1 75 parts by weight of 0-biphenylogyethyl acrylate, bisphenol A and shrimp chloride.

The epoxy resin obtained by the condensation of 1 mole of epoxy resin and 2 moles of acrylic acid are
'25 parts by weight of epoxy acrylate obtained by heating reaction in the presence of a 11thium arsenic catalyst, 0.5 part by weight of 2-hydro-)-me-2-benzoyl-propane, W
Triphenylphosphine 0.
1 part by weight was mixed to form a uniform and transparent composition. This was injected into a mold made of a crow mold for lens molding with a diameter of 76 mm and a resin casket ratchet, and after sealing,
The front and back sides were irradiated for 4 seconds each at an irradiation distance of 10 cm using a W high-pressure mercury lamp with a lamp power of W/m.

Thereafter, the gasket and lens mold were removed, and heat treatment was performed in an oven at 100° C. for 1 hour to obtain a colorless and transparent lens. The physical properties of the spectacle lens thus obtained are shown in Table 1.

Example 2 In Example 1, 60 ffiffi parts of 0-biphenyloxyethyl acrylate, 1 part of epoxy acrylate
・Example] was repeated except that 40 parts by weight was used, and the front and back surfaces were each irradiated for 32 seconds and then heat treated to obtain a colorless and transparent lens. The physical properties of the spectacle lens thus obtained are shown in Table 1.

Example 3 0-biphenyloxyedyl acrylate-1/IO heavy f
fl@IL-2, Example 1 was repeated except that 60 parts by weight of 2-bis(β-acryloyloxyethoxyphenyl)propane was used, and the front and back sides were each irradiated for 4 seconds to obtain a colorless and transparent lens.

The physical properties of the spectacle lens thus obtained are shown in Table 1.

Comparative example 1 phenyl vinyl sulfoxy F4 Q jf4Q ls,
2.

2-bis(β-acryloyloxyethoxyphenyl)
Copolymerization was carried out using 1 part by weight of propane 60 fl (2-hydroxy-2-henzoyl-propane) using the irradiation apparatus of Actual KQ Example+, but it did not harden even after 72 seconds of irradiation.

Comparative Example 2 Instead of the monomer used in Example 1, CR-39, which is commonly used as a monomer for producing If' mirror lenses, was used.
(Diethylene glycol bisallyl carbonate) was used, but ultraviolet rays were irradiated under exactly the same conditions as in Example 1.
However, a cured product that could be used for lenses could not be obtained.

Margin below: 1 In the table, the numbers in parentheses ( ) represent parts for the monomer composition.

Note 2 In the table, the abbreviations for Moa 7-composition have the following meanings.

BPEA: 0-biphenyloxyethyl acrylate BPAPA: A reaction product obtained by adding acrylic acid to an epoxy resin produced by the condensation of bisphenol A and epichlorohydrin BPAEA: 2. 2-bis(β-acryloyl suboxyethoxyphenyl) ) Brongun I) VS + phenyl vinyl sulfogide CR-3
9 diethylene glycol diallyl carbonate From the above examples, the resin obtained using the polymerizable composition of the present invention is most suitable as a resin for high refractive index, and is excellent for use in various applications. It's obvious that there are.

Example 4 3~Methyl-37-ac 90yl-oxydiylbiphenyl (I) 50 ffi, ffl +s, epoxy acrylate-1-(fl) (epoxy purpose 2) 1 mol of epoxy resin and acrylic 0.2 parts by weight of hendyl peroxide as a thermal polymerization catalyst was mixed with 50 parts by weight of 2 moles of acid at 120°C in the presence of diethylamine-hydrochloric acid catalyst, and stirred well at /IO°C to form a homogeneous solution. And so. This was poured into a mold for making a test piece with dimensions of 2 mm; It was completely cured between 4+t and rp, and a transparent flat plate was obtained. The properties of this board were as follows.

Refractive index 1580 Color Colorless hardness BS 85, BH/1.0 Impact resistance Good surface condition ○ Light transmittance 90 Heat resistance ○ Dyeability ○ Note that this test piece did not have an optical rating of 1■≧.

Procedural amendment dated February 7, 1980, Mr. Kazuo Wakasugi, Commissioner of the Office of Time and Time1, Indication of the case, Patent Application No. 203732, filed in 1982,2, Title of the invention: Polymerizable composition:3. Relationship with the person making the amendment Patent applicant address 13-9 Shiba Daimon-chome, Minato-ku, Tokyo Name (20
0) Showa Denko Co., Ltd. (and 1 other person) Representative: Yasunobu Kishimoto 4 Agent: 1.05 Residence: 13-9 Shiba Daimon-chome, Minato-ku, Tokyo 6. No number of inventions to be increased due to amendment 7. Subject of amendment "o-(3-acryloyloxy-2-hydroxy-2-methyl-propoxy ) biphenylle[i'o-(3-acryloylkaquine-2-hydroxy7-2-methylpropoxy)biphenyl".

(3) "2,2-bis(β-acryloyloxyethoxyphenyl)" in lines 2 and 3 of page 14 of the same page is replaced with "2,2-bis(4-acryloyloxyethoxy phenyl)propane”.

Claims (1)

[Claims] (1) General formula (I) T? l (However, in the formula, R represents hydrogen or a methyl group, and E6i
;, 1 represents a hydrocarbon group having 2 to 71 carbon atoms which may be substituted with a methyl group and/or a hydroxyl group, R'
is hydrogen, chlorine, bromine, a methyl group, a methoxy group, a phenyl group, a fenogin group, a ranal monomer or a mixture thereof, and the general formula (1,1) (wherein R and R are as described above, and R4 is Represents a divalent hydrocarbon group, Y, Y'
may be the same or different and represent hydrogen, chlorine or bromine, and n does not represent 0 to 3. However, when R2 does not contain a hydroxyl group, n = O. ) A polymerizable composition comprising a diacrylate monomer having a bisphenol skeleton represented by: or a mixture thereof.