JPH07238119A - Polymerizable composition - Google Patents

Abstract

PURPOSE:To provide a transparent resin suitable for a glass lens by compounding a specific di(meth)acrylate, an alkyl (meth)acrylate, a urethane (meth)acrylate, and a phosphite. CONSTITUTION:A polymerizable compsn. comprises 100 pts.wt. di(meth)acrylate of formula I (wherein R<1> and R<2> are each Hor methyl; m and n are each 0-2; X is a halogen other than F; and(a)is 0-4), 5-200 pts.wt. alkyl (meth)acrylate, 1-30 pts.wt. urethane (meth)acrylate of formula II [wherein R<3> is H or methyl; R<4> is an alkylene group optionally substd. by a (meth)acryloyloxymethyl group; s is 2-4; and A is an org. group], and 0.01-5 pts.wt. phosphite. A too low amt. of the alkyl (meth)acrylate increases the viscosity; a too high amt. decreases the refractive index, A too low amt. of the urethane (meth)acrylate gives a yellowed lens; a too high amt. decreases the refractive index and increases the viscosity. The phosphite contributes to releasability and resistances to yellowing and light. The compsn. is cast and polymerized to give lenses for glasses and optical instruments.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymerizable composition suitable as a raw material for producing transparent resins, particularly spectacle lenses. More specifically, it is suitable for producing a transparent resin that has low water absorption, excellent dyeability, and is not colored and has sufficient physical properties as an eyeglass lens, for example, dispersion characteristics, hardness, light resistance, heat resistance, and the like. A polymerizable composition is provided.

[0002]

2. Description of the Related Art Conventionally, various researches have been made on organic glass which replaces inorganic glass, but many drawbacks have not been obtained yet and those having sufficiently satisfactory properties have not yet been obtained. For example, a polymer obtained by polymerizing a monomer containing methyl methacrylate or diethylene glycol bis (allyl carbonate) as a main component is used as an optical material or a lens, but its refractive index is as low as about 1.50.

Various high-refractive-index resins that have improved this drawback have been proposed. For example, polycarbonate and polysulfone-based high refractive index resins have been proposed. Although these resins have a high refractive index of about 1.60, they have a low light transmittance, suffer from optical homogeneity, and are colored.

Therefore, various crosslinkable high refractive index resins have been proposed. For example, JP-A-4-227617 proposes a resin containing dimethacrylate of a bisphenol compound and polyoxyalkylene glycol dimethacrylate. However, since this resin contains polyoxyalkylene glycol dimethacrylate, it has a high water absorbency, and is likely to cause deviation of the lens and cracks in the coating film when an antireflection coating of an inorganic compound is applied to the lens substrate surface. Further, Japanese Patent Application Laid-Open No. 55-13747 proposes a composition for a high refractive index resin, which comprises a bisphenol compound such as dimethacrylate and phenylmethacrylate. However, these resins have poor impact resistance.

Further, WO92 / 05209 discloses improvement of impact resistance by adding alkyl acrylate or methacrylate such as butyl acrylate or methacrylate to a polymerizable composition having dimethacrylate of bisphenol compound. However, there is a drawback that the lens is colored yellow. In addition, JP-A-1
No. 209401 discloses a polymer molded product obtained from a polymerizable composition comprising urethane poly (meth) acrylate, a di (meth) acrylate of a bisphenol compound and a radical-polymerizable vinyl monomer having a boiling point of 100 ° C. or more. The heat yellowing resistance is improved. However, since the compounding ratio of the urethane poly (meth) acrylate as the main component is as high as 30 to 90 parts by weight of the total amount of monomers, the viscosity becomes high and casting workability becomes poor, and when the compounding ratio is further increased, the refractive index decreases. , Has the drawback of leading to high prices.

[0006]

The object of the present invention is to provide a polymer which has low water absorption, excellent dyeability, excellent impact resistance, is not colored, and has excellent physical properties as a lens for spectacles. The present invention is to provide a polymerizable composition.

[0007]

Means for Solving the Problems As a result of intensive studies aimed at achieving the above object, the present inventors have found that (A) a diacrylate compound or dimethacrylate compound having a specific structure, and (B) an alkyl acrylate or an alkyl group. It has been found that the above object can be achieved by a polymerizable composition containing a methacrylate, (C) a specific urethane acrylate compound or urethane methacrylate compound and (D) a phosphite ester, and the present invention has been completed.

That is, the present invention provides (A) general formula (1)

[0009]

[Chemical 3]

(Wherein R ¹ and R ² are hydrogen atoms or a methyl group, m and n are each an integer of 0 to 2, X is a halogen atom other than fluorine, and a is 0 to 0).
It is an integer of 4. ) 100 parts by weight of a diacrylate compound or dimethacrylate compound, and (B) an alkyl acrylate or an alkyl methacrylate.
~ 200 parts by weight, (C) general formula (2)

[0011]

[Chemical 4]

[Wherein R ³ is a hydrogen atom or a methyl group, R ⁴ is an alkylene group which may be substituted with an acryloyloxymethyl group or a methacryloyloxymethyl group, and s is an integer of 2 to 4] And A is an s-valent organic group. ] 1-30 weight part of the urethane acrylate compound or urethane methacrylate compound shown by these, and 0.01-5 weight part of (D) phosphite ester are a polymeric composition containing.

In the following description, acrylates and methacrylates are generically called (meth) acrylates.

In the general formula (1), m and n are each independently an integer of 0 to 2, and a is an integer of 0 to 4. m and n are preferably 0 or 1 in consideration of the refractive index of the resin obtained by polymerizing the polymerizable composition of the present invention, and a is preferably 0-2. X is a halogen atom excluding fluorine. As a halogen atom, chlorine,
Although each atom of bromine and iodine is adopted, a chlorine atom or a bromine atom is particularly preferable from the viewpoint of light resistance.

Examples of the di (meth) acrylate compound represented by the general formula (1) used in the present invention are as follows. 2,2-bis (4-methacryloyloxyphenyl) propane, 2,2-bis (4-methacryloyloxy-3-chlorophenyl) propane, 2,2-bis (4-methacryloyloxy-3,5-dichlorophenyl) propane, 2,2-bis (4-methacryloyloxy-3-bromophenyl) propane, 2,2-bis (4
-Methacryloyloxy-3,5-dibromophenyl)
Propane, 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxyethoxy-3-chlorophenyl) propane, 2,2-bis (4-methacryloyloxyethoxy-3,5 -Dichlorophenyl) propane, 2,2-bis (4-methacryloyloxyethoxy-3-bromophenyl) propane, 2,2-bis (4-methacryloyloxyethoxy-3,5-dibromophenyl) propane,
2,2-bis (4-methacryloyloxyethoxyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxyethoxyethoxy-3-chlorophenyl)
Propane, 2,2-bis (4-methacryloyloxyethoxyethoxy-3,5-dichlorophenyl) propane, 2,2-bis (4-methacryloyloxyethoxyethoxy-3-bromophenyl) propane, 2,2-bis (4 -Methacryloyloxyethoxyethoxy-3,
5-dibromophenyl) propane etc. can be mentioned. These di (meth) acrylate compounds may be used alone or in combination of two or more.

Next, the alkyl (meth) acrylate used as the component (B) of the polymerizable composition of the present invention is an esterification reaction product of a corresponding alcohol and acrylic acid or methacrylic acid, and is known. The compound can be used without any limitation. The alkyl (meth) acrylate preferably used in the present invention is represented by the general formula as follows. The following general formula (10)

[0017]

[Chemical 5]

(Wherein R ²¹ is a hydrogen atom or a methyl group, and R ²² is an alkyl group).

The alkyl group represented by R ²² in the above general formula (10) is not limited in any way such as linear, branched or cyclic, and is not particularly limited in carbon number, but is obtained by polymerization. Considering the impact resistance and heat resistance of the resin used, R ²²
Is preferably an alkyl group having 3 to 15 carbon atoms. Specific examples of the alkyl (meth) acrylates preferably used in the present invention include n-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-.
Butyl (meth) acrylate, iso-amyl (meth)
Acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth)
Acrylate, isobornyl (meth) acrylate, etc. can be mentioned. These alkyl (meth) acrylates may be used alone or in combination of two or more.

As the urethane (meth) acrylate compound which is the component (C) of the polymerizable composition of the present invention, known compounds can be used without any limitation as long as they are represented by the general formula (2). In the present invention, a compound having 2 to 6 acryloyl groups or methacryloyl groups in one molecule is particularly preferable.

Further, specific examples of the organic group represented by A in the general formula (2), the following equation when ^{s = 2 - (R 23 NHCOOR} 24 OCONH) v R 25 - a and, s = 3 or 4, the following formula {-(R ²³ NHCOOR ²⁴ ) _v } _w R ²⁶ {wherein R ²³ , R ²⁴ and R ²⁵ are the same or different alkylene groups, respectively,

[0022]

[Chemical 6]

(Wherein R ²⁷ and R ²⁸ are the same or different alkylene groups or arylene groups, respectively,
x and y are each 0 or 1, and z is 1 to 1.
0 is an integer, and u is an integer of 1 to 8. ) Or the following formula

[0024]

[Chemical 7]

[0025] or

[0026]

[Chemical 8]

(Wherein R ²⁹ is a hydrogen atom, a halogen atom or an alkyl group, R ³⁰ is a hydrogen atom or a methyl group, t is an integer of 0 to 8 and p and q are each independently 0 or Is an integer of 2), R ²⁶ is a trivalent or tetravalent hydrocarbon residue, and
Is an integer of 0 to 10, w is the number of groups bonded to R ²⁶ , and is an integer of 3 or 4. } Is an organic group. In the above formula, the number of carbon atoms of the alkyl group and the alkylene group is preferably in the range of 1 to 6, and the ethylene group or trimethylene group is generally used as the alkylene group. The arylene group preferably has 6 to 10 carbon atoms, and a phenylene group is particularly common. Further, as the hydrocarbon residue, a trivalent or tetravalent group derived from an alkane having 2 to 6 carbon atoms is preferable.

The urethane (meth) acrylate compound used in the present invention is produced by reacting a polyfunctional isocyanate compound, a compound having a hydroxyl group and a polymerizable double bond, and / or a polyol compound by a known method. To be done. Specific examples of the polyfunctional isocyanate compound include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, tolylene diisocyanate, polyisocyanate prepolymer, and the like, and a hydroxyl group and a polymerizable double bond. Examples of the compound having and include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, and glycerin diacrylate. As the polyol compound, polyethylene glycol, polypropylene glycol, bisphenol A, an ethylene oxide adduct of bisphenol A, polyester,
Polyurethane polyol, pentaerythritol, 2,
2-bis (hydroxymethyl) butanol and the like can be mentioned.

As the phosphite ester which is the component (D) of the polymerizable composition of the present invention, known compounds can be used without any limitation. By using a phosphite ester, not only the coloration of the polymer, heat-resistant yellowing, and light resistance can be improved, but also the releasability of the polymer molded product from the mold can be improved, and the transparency can be improved. An excellent molded product can be obtained. Particularly in the present invention, phosphite esters represented by the following formulas (3) to (9) can be preferably used.

[0030]

[Chemical 9]

[0031]

[Chemical 10]

[0032]

[Chemical 11]

[0033]

[Chemical 12]

[0034]

[Chemical 13]

[0035]

[Chemical 14]

[0036]

[Chemical 15]

[However, the above formulas (3) (4) (5) (6)
(7) In (8) and (9), R ⁵ , R ⁶ , R ⁷ , R ⁸ ,
R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are the same or different hydrogen atoms, alkyl groups or aryl groups, and each may be substituted. R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R
¹⁷ is an alkylene group of each same or different, R ^18,
R ¹⁹ is an alkylene group or

[0038]

[Chemical 16]

[0039]

[Chemical 17]

R ²⁰ is a phenyl group or an alkyl group, and d is a positive integer. In the general formulas (3) to (9), the alkyl group is not particularly limited in carbon number, but from the viewpoint of hydrolyzability and odor, a linear, branched or cyclic group having 2 to 50 carbon atoms. An alkyl group of, for example, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group,
Pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group and the like can be preferably adopted. The aryl group is not particularly limited in carbon number, but from the viewpoint of hydrolyzability and odor, an aryl group having 6 to 40 carbon atoms, for example, phenyl group, tolyl group, xylyl group, t-butylphenyl group, 2,6 A -di-t-butyl-4-methylphenyl group or the like can be preferably adopted. Further, the above general formulas (3) to (9)
The alkylene group therein is preferably a methylene group. Furthermore, the number of d in the general formulas (7) and (9) is not particularly limited, but is preferably 2 to 30.

[0041] To exemplify Particularly preferred as these phosphorous esters, such as 4,4'-isopropylidene - diphenyl alkyl (C ₁₂ ~C ₁₅₎ phosphite, triphenyl phosphite, tridecyl phosphite, tri Lauryltrithiophosphite, tris (nonylphenyl) phosphite, triethylphosphite, tris (2-ethylhexyl) phosphite, tris (tridecyl) phosphite, diphenylmono (2-ethylhexyl) phosphite, diphenylmonodecylphosphite, diphenyl Mono (tridecyl) phosphite, dilauryl hydrogen phosphite, diphenyl hydrogen phosphite, tetraphenyl dipropylene glycol diphosphite, tetraphenyl tetra (tridecyl) pentaeryth Litol tetraphosphite, tetra (tridecyl) -4,4'-isopropylidene diphenyl diphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, tristearyl phosphite, di Stearyl pentaerythritol diphosphite, tris (2,4-di-t-butylphenyl) phosphite, hydrogenated bisphenol A.pentaerythritol phosphite polymer, hydrogenated bisphenol A.phosphite polymer and the like can be mentioned.

In the present invention, the above-mentioned (A),
The blending amounts of the components (B), (C) and (D) are 5 to 200 parts by weight of the component (B) and 1 to 30 parts by weight of the component (C) with respect to 100 parts by weight of the component (A). And (D)
The component must be in the range of 0.01 to 5 parts by weight, more preferably 10 to 150 parts by weight of the component (B) and 4 to 10 parts by weight of the component (C) with respect to 100 parts by weight of the component (A). It is preferable that the amount of the component (D) is 25 parts by weight, and the amount of the component (D) is 0.05 to 3 parts by weight. When the three components excluding the component (C), that is, the composition of only the three components of the component (A), the component (B) and the component (D) are polymerized, the resulting polymer is colored yellow and is no longer a lens. It cannot be used for purposes. Further, when three components excluding the component (D), that is, a composition containing only three components of the component (A), the component (B) and the component (C) are polymerized, the polymer is released from the glass mold. It becomes extremely difficult, and the coloring, heat yellowing and light resistance of the polymer cannot be improved. The viscosity of the composition remarkably increases only with the components (A), (C) and (D),
Practically, injection polymerization becomes difficult. Furthermore, a sufficient refractive index cannot be obtained only with the components (B), (C) and (D).

When the blending amounts of the component (B), the component (C) and the component (D) do not fall within the above ranges per 100 parts by weight of the component (A), various physical properties of the polymer obtained, That is, heat resistance, dyeability, light resistance, etc. are deteriorated, which is not preferable. Specifically, when the amount of the component (B) is less than 5 parts by weight relative to 100 parts by weight of the component (A), the viscosity of the composition remarkably increases and the operability is poor, and when it exceeds 200 parts by weight. The refractive index decreases. In addition, (A) component 10
When the amount of the component (C) is less than 1 part by weight with respect to 0 parts by weight, the lens is colored or heat-resistant yellowing occurs, and when it exceeds 30 parts by weight, the refractive index decreases. Further, the viscosity is remarkably increased, which makes casting polymerization difficult. When the amount of the component (D) is less than 0.01 parts by weight relative to 100 parts by weight of the component (A), the releasability of the resulting polymer cannot be sufficiently improved, and the polymer is Is not preferable because the coloring, heat-resistant yellowing, and light resistance cannot be improved, and if the amount exceeds 5 parts by weight, the hardness of the resulting polymer decreases.

In the present invention, when the polymerizable composition is polymerized, the polymerization is often performed to facilitate the polymerization, control the viscosity of the polymerizable composition, control the refractive index, or control other physical properties. It is also possible to mix the polymerizable composition and another radically copolymerizable monomer to perform copolymerization. Examples of these other monomers include unsaturated carboxylic acids such as methacrylic acid, maleic anhydride, and fumaric acid; and suitable functional groups such as 2-hydroxyethyl (meth) acrylate and glycidyl (meth) acrylate ( (Meth) acrylic acid ester compound; alkylene glycol (meth) acrylate compound such as methoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate; methylthio ( Thio (meth) acrylate compounds such as (meth) acrylate and benzylthio (meth) acrylate; Fumarate compounds such as monomethyl fumarate, diethyl fumarate, diphenyl fumarate; Styrene Styrene or α-methylstyrene derivative such as divinylbenzene, α-methylstyrene, α-methylstyrene dimer, bis (vinylbenzyl) ether; diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl tartrate, diallyl epoxysuccinate, diallyl styrene Examples thereof include allyl compounds such as rate, allyl cinnamate, diallyl carbonate and allyl diglycol carbonate; epoxy (meth) acrylate and the like. These other monomers may be used alone or in combination of two or more.

The blending amount of these other monomers may be selected according to the purpose, but it is preferably used in the range of 0 to 200 parts by weight with respect to 100 parts by weight of the component (A).

Particularly in the present invention, in consideration of the physical properties such as the refractive index, the hard coat property, the heat yellowing property and the dyeing property of the polymer obtained, the polymer has a phenyl group per 100 parts by weight of the component (A) ( It is preferable to use (meth) acrylate, (meth) acrylate having a hydroxyl group, glycidyl methacrylate, epoxy acrylate, and alkylene glycol (meth) acrylate in combination in the range of 1 to 50 parts by weight. Examples of the (meth) acrylate having a phenyl group include phenyl methacrylate, benzyl methacrylate, diphenyl methacrylate and the like. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,2-dihydroxyethyl methacrylate and 2-hydroxypropyl methacrylate. Examples of the alkylene glycol (meth) acrylate include methoxy (tetraethylene glycol) methacrylate, methoxy (nonaethylene glycol) methacrylate, tetraethylene glycol dimethacrylate, nonaethylene glycol dimethacrylate and the like.

The polymerizable composition of the present invention can be polymerized by a known cast polymerization method. The polymerization initiation method is
It can be carried out by thermal polymerization using various radical polymerization initiators such as peroxides and azo compounds. To exemplify a typical polymerization method, it is possible to exemplify a cast polymerization in which the polymerizable composition of the present invention is injected between molds held by an elastomer gasket or a spacer, cured in an air oven, and then taken out. it can.

The radical polymerization initiator is not particularly limited and known ones can be used. Typical examples thereof include benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, Diacyl peroxides such as acetyl peroxide; tert-butylperoxy-2
-Ethyl hexanoate, tert-butyl peroxydicarbonate, cumyl peroxyneodecanate, t
ert-butyl peroxyneodecanate, tert-
Peroxyesters such as butylperoxybenzoate; diisopropyl peroxydicarbonate, di-2
-Ethylhexyl peroxydicarbonate, di-se
Percarbonates such as c-butyl peroxydicarbonate; azo compounds such as azobisisobutyronitrile.

The amount of the radical polymerization initiator used varies depending on the polymerization conditions, the type of the initiator, and the type and composition of the above-mentioned monomers and cannot be unconditionally limited, but generally, the total amount of all the monomers is 100.
It is preferably used in the range of 0.01 to 10 parts by weight with respect to parts by weight.

Among the polymerization conditions, the temperature particularly affects the properties of the obtained resin. Since this temperature condition is affected by the type and amount of radical polymerization initiator and the type of monomer, it cannot be unconditionally limited, but generally the polymerization is initiated at a relatively low temperature and the temperature is slowly raised. It is preferable to carry out so-called taper type two-stage polymerization in which the composition is cured at a high temperature at the end of the polymerization.

Since the polymerization time also depends on various factors like the temperature, it is preferable to determine the optimum time according to these conditions in advance, but generally, the conditions are set so that the polymerization is completed within 2 to 40 hours. Is preferred.

Further, the polymerizable composition of the present invention can be similarly cast-polymerized by known photo-polymerization using ultraviolet rays or visible rays, in addition to the above-mentioned cast-polymerization method by thermal polymerization. In this case, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzophenol, acetophenone, 4, as a photopolymerization initiator,
4'-dichlorobenzophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzylmethylketal, 1- (4-
Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-isopropylthioxanthone, 2,
4,6-trimethylbenzoyldiphenylphosphine oxide and the like can be mentioned. These photopolymerization initiators are
In order to prevent coloring and deterioration of the obtained polymer, it is generally used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of all the monomers.

Further, the light source used in the photopolymerization is
Those that emit ultraviolet rays are preferable, for example, a mercury lamp,
A sterilization lamp, a xenon lamp, a metal halide lamp, etc. can be used conveniently. In addition, visible light such as sunlight can also be used. The irradiation time is
Since it depends on the wavelength and intensity of the light source and the shape and material of the polymer, it may be determined in advance by preliminary experiments.

When photopolymerization is carried out, it is necessary that at least the light-irradiated surface of the mold is transparent, and generally glass or the like is used for this portion. In particular, a material such as quartz glass that easily transmits ultraviolet rays is preferable, but the material is not particularly limited as long as it is transparent. Further, there is no problem in polymerizing while applying pressure from outside during molding.

In the above-mentioned polymerization, a polymerization accelerator, a polymerization regulator, a release agent, an ultraviolet absorber, an antioxidant, a coloring inhibitor,
Various additives such as antistatic agents, fluorescent dyes, dyes, pigments and fragrances can be selected and used according to need.

The polymer obtained by the above-mentioned method can be coated with a known coating agent to improve the scratch resistance of the surface depending on the application, to form a cured film. At this time, the coating agent forming the cured film reacts with heat, a catalyst, a curing agent, light, radiation, etc., and particularly forms a three-dimensional network structure to form a cured film.
So-called crosslinkable substances can be used without limitation. For example, a melamine-based coating agent made of melamine and other reactive substances such as formaldehyde, an acrylic coating agent made of acrylic acid esters and acrylic acid amides, and other reactive substances such as epoxies and bisphenol A. Etc., an epoxy-based coating agent, a urethane-based coating agent made of other reactive substances such as polyfunctional isocyanates and polyfunctional alcohols, a silicon-based coating agent made of organosilicon compounds such as methyltrimethoxysilane, etc., Alternatively, a known coating agent that combines these is used.

An example of the coating agent preferably used in the present invention is as follows. The following general formula (11)

[0058]

[Chemical 18]

(Wherein A ′ is a divalent functional group, R ³¹ and R ³² are the same or different alkyl groups or alkoxyalkyl groups, and R ³³ and R ³⁴ are the same or different alkyl groups, respectively. Group or an alkoxy group) as a constituent. The general formula (1
In 1), A'is, for example, an alkylene group such as butylene group, isobutylene group, hexamethylene group, or -C.
_{H 2 CH 2 OCH 2 CH 2} -, - CH 2 CH 2 CH 2 OCH 2 C
An alkylene group having an ether bond such as H ₂ CH ₂ —,
_{CH 2 CH 2 CH 2 OCOOCH 2} CH 2 CH 2 -, - CH 2
CH ₂ CH ₂ OCOOCH ₂ CH ₂ OCOOCH ₂ CH ₂ CH
₂ - an alkylene group having a carbonate group such as, -CH _{2
CH 2 COOCH 2 CH 2 OCOCH 2} CH 2 -, - CH 2 C
H (CH ₃ ) COOCH ₂ CH ₂ OCOCH (CH ₃ ) CH
Examples of suitable groups include alkylene groups having an ester group such as _2- . R ³¹ and R ³² have 1 to 6 carbon atoms
And an alkyl group having 2 to 6 carbon atoms are exemplified. Further, R ³³ and R ³⁴ have 1 carbon atoms.
An alkyl group having 4 to 4 or an alkoxy group having 1 to 4 carbon atoms is preferable.

Further, in order to further strengthen the adhesion between the polymer and the cured film, it is often a preferred embodiment to pretreat the polymer before coating. For example, a known alkali treatment can be used as the pretreatment method, and the stronger the alkalinity, the stronger the adhesion. However, if the alkalinity is too strong, the polymer itself may deteriorate.
It is preferable that the alkaline treatment conditions are milder than the treatment conditions of 80 ° C. for 1 hour with the above NaOH aqueous solution.

If desired, a film of an inorganic hard material as an antireflection agent can be formed on the polymer molded product obtained by curing the polymerizable composition. As a method for coating the inorganic hard material, a known method can be used without particular limitation. For example, a vacuum plating method, an ion plating method, a dry plating method such as a sputtering method can be preferably used. The thickness of the coating film of the inorganic hard material is not particularly limited because it varies depending on the purpose, but 0.1 to 10 μm is generally preferable.

As the above-mentioned inorganic hard material, an inorganic compound or a metal capable of forming a film on the surface of the polymer molding by the dry plating method as described above can be used without limitation, and can be appropriately selected according to the purpose. do it. For example, in order to impart scratch resistance, silicon oxide (SiOx, x = 1 to 2), aluminum oxide and the like are generally used. In order to impart antireflection property, for example, metal oxides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, magnesium oxide, cerium oxide, indium oxide, tantalum oxide, hafnium oxide; magnesium fluoride, fluorine. Examples thereof include metal fluorides such as cerium chloride, lithium fluoride and neodymium fluoride; metal sulfides such as zinc sulfide; and metals such as aluminum, gold, silver and chromium. Of such inorganic hard materials, a low refractive index material can be coated with a single layer, and a low refractive index material and a high refractive index material can be alternately laminated to have an optical thickness. Further, in order to impart both reflectivity and scratch resistance at the same time, it is possible to coat amorphous carbon with diamond-like carbon in which diamond microcrystals are scattered.

[0063]

The polymer molded product obtained by polymerizing the polymerizable composition of the present invention is excellent in releasability, has a high refractive index, is non-colored, has low water absorption, and has dyeability and impact resistance. It is also excellent in
Further, it has excellent physical properties as a lens for eyeglasses, for example, dispersion characteristics, hardness, transparency, light resistance, heat yellowing resistance, and odorlessness during cutting.

Therefore, the polymer molded product obtained by polymerizing the polymerizable composition of the present invention is useful as an organic glass, and is most suitable as an optical lens such as a lens for spectacles or a lens for optical equipment. It can be suitably used for applications such as optical disc substrates, optical fibers and the like.

[0065]

EXAMPLES The present invention will now be described with reference to examples, but the present invention is not limited to these examples.

Various properties of the resins obtained in the examples were measured by the following test methods.

(1) Refractive Index and Abbe Number The refractive index at 20 ° C. was measured using an Abbe refractometer manufactured by Atago Co. Bromonaphthalene was used as the contact liquid.

(2) Hardness The Rockwell hardness meter was used to measure the value on the L-scale of a test piece having a thickness of 2 mm.

(3) Yellowness (YI) YI of a sample was measured with a color difference meter (SM-4 type) manufactured by Suga Test Instruments Co., Ltd.
Was measured.

(4) Specific gravity Electronic specific gravity meter (ED-120T, manufactured by Mirage Trading Co., Ltd.)
Type).

(5) Dyeing property 2 g of a disperse dye (trade name: Vista Brown, manufactured by Hattori Seiko Co., Ltd.) was dispersed in 1 liter of water and heated, and the sample piece was dyed at 90 ° C. for 10 minutes. The dyeing density at that time was expressed as a decrease rate (percentage) of the light transmittance of 550 nm using a double beam spectrophotometer 220A manufactured by Hitachi Ltd.

(6) Light resistance After placing the sample in a long life xenon fade meter (FAC-25AX-HC type) manufactured by Suga Test Instruments Co., Ltd. and exposing it to xenon light for 100 hours, Suga Test Instruments Co., Ltd. The color difference meter (SM-4 type) was used to measure the YI of the sample, which was indicated by the increment ΔYI with respect to the initial YI.

(7) Impact resistance 16 g, 32 g, 48 g, 64 g, 80 g, 96 from a height of 127 cm on a test plate having a thickness of 2 mm and a diameter of 65 mm.
Steel balls of g, 112 g and 131 g were naturally dropped, and the weight of the heaviest steel ball that did not damage the test plate was evaluated.

(8) Hard coat property A silicon type hard coat agent (trade name: TS-56T, manufactured by Tokuyama Soda Co., Ltd.) was used, and after preparation, the hard coat agent was applied for 1 week and 1 month. A hard coating agent having a good adhesion of 1 month after preparation was evaluated as ⊚, a hard coating agent having a good adhesion of 1 week after preparation was evaluated as ◯, and a bad adhesion was evaluated as x.

(9) Heat-resistant yellowing After heating a sample having a thickness of 2 mm at 130 ° C. for 2 hours, the YI of the sample was measured with a color difference meter (SM-4 type) manufactured by Suga Test Instruments Co., Ltd. Is shown by ΔYI.

(10) Water Absorption Rate A sample piece dried at 120 ° C. for 1 hour was allowed to stand in water at 25 ° C. for 3 days, and the rate of increase in weight (percentage) was measured.

(11) Releasability When 10 lenses were polymerized and released from the mold, the number without cracks was shown.

The compounds used in the following Examples and Comparative Examples are as follows.

Component (A): di (meth) acrylate compound BPM: 2,2-bis (4-methacryloyloxyphenyl) propane

[0080]

[Chemical 19]

BPEM: 2,2-bis (4-methacryloyloxyethoxyphenyl) propane

[0082]

[Chemical 20]

TBEM: 2,2-bis (4-methacryloyloxyethoxy-3,5-dibromophenyl) propane

[0084]

[Chemical 21]

Component (B): Alkyl Methacrylate BuMA: n-Butyl Methacrylate i-BuMA: iso-Butyl Methacrylate i-AMMA: iso-Amyl Methacrylate CHMA: Cyclohexyl Methacrylate IBMA: Isobornyl Methacrylate (C) Component: Urethane (meta) ) Acrylate compound UA-HTP1: urethane methacrylate of the following formula

[0086]

[Chemical formula 22]

UA-HTP2: Urethane acrylate of the following formula

[0088]

[Chemical formula 23]

UA-GXE: urethane methacrylate of the following formula

[0090]

[Chemical formula 24]

UA-HTP3: urethane methacrylate of the following formula

[0092]

[Chemical 25]

UA-HTP4: Urethane acrylate of the following formula

[0094]

[Chemical formula 26]

Component (D): phosphite ester PRE-1: phosphite ester of the following formula

[0096]

[Chemical 27]

(However, R ³⁵ is an alkyl group having 9 to 18 carbon atoms.) PRE-2: phosphite ester represented by the following formula

[0098]

[Chemical 28]

PRE-3: Phosphite ester represented by the following formula

[0100]

[Chemical 29]

PRE-4: phosphite ester represented by the following formula

[0102]

[Chemical 30]

PRE-5: phosphite ester of the following formula

[0104]

[Chemical 31]

PRE-6: phosphite ester represented by the following formula

[0106]

[Chemical 32]

PRE-7: phosphite ester represented by the following formula

[0108]

[Chemical 33]

PRE-8: phosphite of the following formula

[0110]

[Chemical 34]

PRE-9: phosphite ester represented by the following formula

[0112]

[Chemical 35]

PRE-10: phosphite ester represented by the following formula

[0114]

[Chemical 36]

Component (E): other monomer HEMA: 2-hydroxyethyl methacrylate GMA: glycidyl methacrylate PhMA: phenyl methacrylate BzMA: benzyl methacrylate 40G: methoxypolyethylene glycol # 230 methacrylate 90G: methoxypolyethylene glycol # 400 methacrylate Example 1 With respect to 100 parts by weight of the polymerizable composition containing the components (A), (B), (C), (D) and (E) shown in Table 1, t-butylperoxide was used as a radical polymerization initiator. 1 part by weight of oxyneodecanate was added and mixed well. This mixed solution was poured into a mold composed of a gasket made of a glass plate and an ethylene-vinyl acetate copolymer, and cast polymerization was performed. Polymerization is carried out in an air oven at 30 ° C to 90 ° C
The temperature was gradually raised over 15 hours and maintained at 90 ° C. for 2 hours. After completion of the polymerization, the mold was taken out of the air furnace, allowed to cool, and then the polymer was removed from the glass of the mold. The physical properties of the obtained polymer are shown in Table 1.

Comparative Example The same procedure as in Example 1 was carried out except that the ingredients shown in Table 1 were used. The physical properties of the obtained polymer are shown in Table 1.

[0117]

[Table 1]

[0118]

[Table 2]

[0119]

[Table 3]

Example 2 100 parts by weight of a polymerizable composition containing the components (A), (B), (C), (D) and (E) shown in Table 2 was used as a photopolymerization initiator. 0.1 parts by weight of 1-hydroxycyclohexyl phenyl ketone and 0.1 parts by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide were added and mixed well. This mixed solution was poured into a mold composed of a gasket made of a glass plate and an ethylene-vinyl acetate copolymer, and was irradiated with ultraviolet rays for 15 seconds using a metal halide lamp with an output of 120 W / cm. After the polymerization was completed, the polymer was removed from the mold glass. The physical properties of the obtained polymer are shown in Table 2.

[0121]

[Table 4]

[0122]

[Table 5]

[0123]

[Table 6]

Claims (2)

[Claims] 1. (A) General formula (1): (However, R ¹ and R ² are a hydrogen atom or a methyl group, m and n are each an integer of 0 to 2, X is a halogen atom other than fluorine, and a is an integer of 0 to 4. ) 100 parts by weight of a diacrylate compound or dimethacrylate compound represented by the formula (B), alkyl acrylate or alkyl methacrylate (B) 5 to 200 parts by weight, (C) general formula (2) [Wherein R ³ is a hydrogen atom or a methyl group, and R 3
⁴ is an alkylene group which may be substituted with an acryloyloxymethyl group or a methacryloyloxymethyl group, s is an integer of 2 to 4, and A is an s-valent organic group. ] The polymerizable composition which comprises 1 to 30 parts by weight of the urethane acrylate compound or urethane methacrylate compound represented by the above, and 0.01 to 5 parts by weight of (D) phosphite. 2. An organic glass comprising a polymer of the polymerizable composition according to claim 1.