JPH09165426A - Sulfur-containing urethane/vinyl compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a transparent sulfur-containing urethane/vinyl compound excellent in impact resistance by reacting an aromatic vinyl compound containing a hydroxyl group and a sulfur atom and represented by a specified formula with an isocyanate compound. SOLUTION: An isocyanate compound (e.g. m-xylylene diisocyanate) is added dropwise to an aromatic vinyl compound containing a hydroxyl group and a sulfur atom (e.g. p-hydroxyethylthiomethylstyrene) and represented by the formula (wherein R is a 1-4C hydrocarbon group) in the presence of a di-m- butyltin dilaurate, and the mixture is reacted by heating to about 50-100 deg.C to obtain a sulfur-containing urethane/vinyl compound. One hundred (100) pts.wt. curing composition containing this compound is mixed with about 0.01-5 pts.wt. actinic-radiation-sensitive radical polymerization initiator (e.g. 2,4,6- trimethylbenzoyldiphenylphosphine oxide), the resultant mixture is poured into a specified mold and cured by irradiation with an actinic radiation having a wavelength of 100-600nm using e.g. a halogen lamp to obtain the transparent molding.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel sulfur-containing urethane-vinyl compound useful as an oligomer for various transparent resins.

[0002]

2. Description of the Related Art In recent years, plastic lenses are lighter in weight, harder to break than inorganic lenses, can be dyed, and are easy to perform precision molding. In recent years, eyeglass lenses, camera lenses, Fresnel lenses, lenticular lenses and prisms It has rapidly spread to optical lens products such as. Especially in eyeglass lenses and camera lenses, heat resistance and chemical resistance are required.
A thermosetting resin obtained by radical polymerization of polydiethylene glycol bisallyl carbonate or the like is currently used instead of a thermoplastic resin obtained by radical polymerization of polystyrene or the like. This resin has various characteristics such as excellent impact resistance, light weight, excellent dyeability, and good workability such as machinability and abrasiveness. However, a glass lens having a general refractive index (n _D =
Compared with 1.52), n _D = 1.50 is small, and in order to obtain the optical characteristics equivalent to those of glass lenses, it is necessary to increase the center thickness, edge thickness, and curvature of the lens, and the overall thickness is And it was not possible to obtain a thin lens. In addition, since this resin has an allyl group having a low radical polymerizability as a functional group, it takes 20 to 30 hours for the template thermal polymerization, and there is a problem in the productivity of the lens.

[0003]

Therefore, as a resin for a lens having a high refractive index, a material obtained by radical polymerization of an aromatic (meth) acrylate into which a bromine atom is introduced (JP-A-57-28117). Or a material obtained by reacting a polyol compound containing a sulfur atom with a polyisocyanate (JP-A-60-217229), or a material obtained by reacting a vinyl compound containing a sulfur atom with a polyisocyanate (JP-A-1-217). 1975
No. 14) is known.

However, although the lenses obtained from these materials have a certain degree of improvement in the refractive index as compared with the lenses using CR39, they are still insufficient in the required refractive index and various requirements such as impact resistance. Since the balance of performance is insufficient and the allyl group having low radical polymerizability is a functional group, a lens is obtained by molding by thermal polymerization of the template, and there is a problem in productivity.

[0005]

In view of such circumstances, the inventors of the present invention have made earnest studies on the materials for optical lens products, and as a result, have determined that a vinyl monomer containing a specific sulfur atom is bonded via a urethane bond. It was found that the use of a polyfunctional urethane-vinyl compound makes it possible to obtain a resin having a high refractive index and impact resistance required for optical lens products, and has completed the present invention.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION That is, a feature of the present invention is to provide a sulfur-containing urethane-vinyl compound obtained by reacting an aromatic vinyl compound having a hydroxy group and a sulfur atom represented by the general formula (I) with an isocyanate compound. is there.

[0007]

Embedded image (In the formula, R represents a hydrocarbon group having 1 to 4 carbon atoms.)

Hereinafter, the present invention will be described in detail.

The sulfur-containing urethane-vinyl compound of the present invention comprises an aromatic vinyl compound containing a hydroxyl group and a sulfur atom represented by the above-mentioned general formula (I) and 1 in the molecule.
It is obtained by a urethanization reaction with an isocyanate compound having at least one isocyanate group. Specific examples of the aromatic vinyl compound having a hydroxyl group and a sulfur atom represented by the general formula (I) include:

Embedded image Examples of the compound include meta-isomers of the above compounds, mixtures thereof, and the like, and p-hydroxyethylthiomethylstyrene is more preferable from the viewpoint of obtaining a compound having a higher refractive index.

The isocyanate compound used for producing the sulfur-containing urethane-vinyl compound of the present invention includes, for example, isocyanatoethyl methacrylate, isocyanatoethyl acrylate, methacryloyl isocyanate, acryloyl isocyanate, 1,6-hexamethylene diisocyanate, Tris (isocyanatohexyl) isocyanurate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, cyclohexane diisocyanate,
Isophorone diisocyanate, bis (4,4'-isocyanatocyclohexyl) methane, bis (4,4'-isocyanatocyclohexyl) propane, 1,3-bis (isocyanatomethyl) cyclohexane, metaxylylene diisocyanate, paraxylylene diisocyanate , Meta-trimethylxylylene diisocyanate, meta-tetramethylxylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, (4,4′-isocyanatophenyl) methane, naphthalene diisocyanate and the like. . Among these, isocyanatoethyl methacrylate, tris (isocyanatohexyl) isocyanurate, isophorone diisocyanate, bis (4,4′-isocyanatocyclohexyl) methane, 1,3-bis (isocyanatomethyl) cyclohexane, metaxylylene diisocyanate , Meta-tetramethylxylylene diisocyanate is particularly preferred.

In the present invention, when a polyisocyanate having two or more isocyanate groups in the molecule is used, the polyisocyanate is reacted with a polyol, polyester, or polyamide diol to synthesize an adduct, and then the It can also be synthesized by reacting the remaining isocyanate group with the hydroxyl group of the aromatic vinyl compound represented by the general formula (I).

The polyol, polyester, or polyamide diol used in the synthesis of the adduct reacted with the polyisocyanate compound may be a generally known compound and is not particularly limited. Specific examples of the polyol used in the synthesis of this adduct include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, ethylene oxide adduct of bisphenol A, ethylene oxide adduct of bisphenol S, and ethylene oxide addition of diphenyl disulfide. Things etc. are mentioned.

The sulfur-containing urethane-vinyl compound of the present invention is synthesized by mixing the aromatic vinyl compound represented by the general formula (I) with an isocyanate compound in the presence of a tin catalyst such as n-butyltin dilaurate. 50 to 100 ° C., so that the group and the hydroxyl group of the aromatic vinyl compound represented by the general formula (I) are in almost equimolar amounts.
At 5 to 20 hours, particularly preferably at 60 to 70 ° C. for 10
It can be performed by heating for 20 hours. Since this reaction product generally has a high viscosity, it is preferable to appropriately dilute with a low-viscosity methacrylate compound or acrylate compound during or after the reaction.

The sulfur-containing urethane-vinyl compound of the present invention can provide a transparent resin molding having a high refractive index and excellent impact resistance, such as an optical lens product, by the following method. First, an active energy ray-sensitive radical polymerization initiator such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and / or a heat-sensitive radical polymerization initiator such as t-butylperoxyisobutyrate is included in the present invention. 0.01 to 5 parts by weight, more preferably 0.1 to 2 parts by weight, is added to 100 parts by weight of the curable composition containing the sulfur urethane-vinyl compound. Next, the inner surface is made of mirror-polished glass, plastic,
Alternatively, it is poured into a mother mold composed of two molds made of metal or the like and a gasket made of an adhesive tape made of a thermoplastic resin such as ethylene-vinyl acetate copolymer or polyester. Then, in an atmosphere such as air or an inert gas such as argon, a high pressure mercury lamp, a metal halide lamp, a halogen lamp, or the like is used to generate an active energy ray having a wavelength of 100 to 600 nm from one side or both sides of the mold. Irradiate and cure in the range of ˜50 J / cm ² .

In addition, the irradiation amount of the active energy ray is set to 0.
5 to 3 J / cm ^2, and after making the injectate (the resin composition) gel and immobilize, the hot air oven at 80 to 150 ° C or the hot water at 70 to 100 ° C for 1 to 5 hours. Leave it alone
2 by active energy rays and heat to complete the polymerization
It is also possible to use a hardening method such as step hardening or heat hardening using only heat.

When molding the curable resin composition containing the above-mentioned sulfur-containing urethane-vinyl compound, an antioxidant and an anti-yellowing agent may be added together with various polymerizable vinyl compounds. , UV absorber, bluing agent,
You may add various additives, such as a pigment, an anti-settling agent, a defoaming agent, an antistatic agent, and an antifogging agent.

The obtained transparent resin molded product may be provided with antireflection, high hardness, abrasion resistance, chemical resistance, antifogging property, surface polishing, antistatic treatment, hard coating, if necessary. Physical or chemical treatment such as coating treatment, antireflection coating treatment, dyeing treatment, and light control treatment can be performed.

The transparent resin molding obtained from the cured product containing the sulfur-containing urethane-vinyl compound of the present invention thus obtained has an extremely high refractive index and excellent impact resistance, and is lightweight, colorless and transparent. Because of this, eyeglass lenses, Fresnel lenses, rod lenses, lenticular lenses,
It is suitable for various optical lens products such as fθ lenses, prisms such as triangular prisms and triangular prism sheets, and optical products such as optical fibers. Further, the sulfur-containing urethane-vinyl compound of the present invention can be suitably used not only as a transparent resin molded product but also as a material for paints, adhesives and the like.

[0019]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples.

Example 1 Synthesis of Sulfur-Containing Urethane-Vinyl Compound (SUV) In a 1-liter, 4-neck round bottom flask equipped with a stirrer and a cooling tube, p-hydroxyethylthiomethylstyrene 398 was added.
g, 0.30 g of di-n-butyltin dilaurate, and 0.06 g of hydroquinone monomethyl ether were added, and m-xylylene diisocyanate (manufactured by Takeda Yakuhin Kagaku Co., trade name: Takenate 500) while maintaining the internal temperature at 60 ° C. )
188 g was added dropwise over 3 hours. Then, set the internal temperature to 80
The temperature was raised to ℃, and reacted at 80 ℃ for 5 hours to synthesize a sulfur-containing urethane-vinyl compound (hereinafter referred to as SUV). This reaction was traced by IR spectrum, and it was confirmed that the absorption of isocyanate (2200 cm ^-1 ) disappeared (see Fig. 1).

[0021]

[Table 1]

The obtained SUV was a colorless transparent viscous liquid, and had a refractive index of 20 ° C. and a D-line of 1.610. The ¹ H-NMR analysis result is shown in FIG.

[0023]

[Table 2]

[0024]

Embedded image

Example 2 SUV6 synthesized in Example 1
5 g, phenoxyethyl acrylate 35 g, 2,4
After mixing 0.05 g of 6-trimethylbenzoyldiphenylphosphine oxide and stirring well at room temperature, 5
The pressure was reduced to 0 mmHg and degassing was performed for 10 minutes. Two flat glass sheets of 70 mm in diameter, which were mirror-finished, were surrounded by a polyester tape, and had an internal thickness of 2 m.
m and 5 mm of two types of molds were injected. Next, ultraviolet rays of 30 J / cm ² were irradiated from both sides of the mother die with a high pressure mercury lamp of 2 kW to complete the curing. Then, the hardened plastic flat plate was released from the mother die, heated at 130 ° C. for 1 hour, and annealed. The thus obtained flat plate has a refractive index of 1.596 at 20 ° C., is colorless and transparent, and has Rockwell hardness indicating surface hardness (L scale, JIS.
(Measured according to K 7202) was also as high as 105.

Comparative Example 1 Diethylene glycol bisallyl carbonate (PPG, trade name: CR-39)
100 g, diisopropyl peroxypercarbonate (Nippon Yushi Co., Ltd., trade name: perloyl IPP) 3 g
Were mixed and well stirred, and then the mixture was poured into the same mother mold as that used in Example 2, 10 minutes at 45 ° C., 3 hours at 60 ° C., and 8 hours.
Molding was carried out by holding at 0 ° C for 3 hours and at 95 ° C for 6 hours. Then, after molding, the plastic flat plate is released from the mother die,
It was annealed at 0 ° C. for 1 hour. This flat plate was colorless and transparent and had a Rockwell hardness of 90 but a refractive index of 20.
It was as low as 1.499 at ℃.

[0027]

INDUSTRIAL APPLICABILITY The sulfur-containing urethane-vinyl compound of the present invention can provide a transparent resin which is colorless and transparent, has a high refractive index and is excellent in impact resistance, and is particularly preferably used as an optical lens material. be able to.

[Brief description of the drawings]

1 is a sulfur-containing urethane-obtained in Example 1;
It is an IR spectrum of a vinyl compound.

FIG. 2 is a sulfur-containing urethane-obtained in Example 2;
It is a < ¹ > H-NMR spectrum of a vinyl compound.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshio Nagasaka 4-60, Sunadabashi, Higashi-ku, Nagoya-shi, Aichi Mitsubishi Rayon Co., Ltd. Product Development Laboratory

Claims (2)

[Claims] 1. A sulfur-containing urethane-vinyl compound obtained by reacting an aromatic vinyl compound represented by the general formula (I) containing a hydroxy group and a sulfur atom with an isocyanate compound. Embedded image (In the formula, R represents a hydrocarbon group having 1 to 4 carbon atoms.) 2. The isocyanate compound is any one of meta-xylylene diisocyanate, meta-tetramethyl xylylene diisocyanate, isocyanatoethyl (meth) acrylate, and isophorone diisocyanate. Sulfur-containing urethane-vinyl compound.