JPH09136848A - Polyhydric alcohol mixture and its alpha, beta-unsaturated carboxylic acid ester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a monomer mixture for a light transparent resin, excellent in mechanical strength, useful as an optical material made of a synthetic resin, comprising a specific polyhydric alcohol and an ether and/or an ester compound of the polyhydric alcohol. SOLUTION: This polyhydric alcohol mixture comprises (A) 99-60wt.% of a mixture of (i) a dimer acid of a 11-22C higher unsaturated fatty acid (or its esterified substance)/(ii) a trimer acid of a 11-22C higher unsaturated fatty acid (or its esterified substance) in the weight ratio of 99/1 to 0/100 and (B) 1-40wt.% of an ether compound of an intermolecular dehydration reaction of the hydroxyl group of the component A and/or an ester compound of the component A with a corresponding carboxylic acid. The mixture is esterified with an α,β-unsaturated carboxylic acid of the formula R1 (R2 )C=C(R3 )COOR6 (R1 to R3 are each independently H or a 1-6C alkyl; R6 is H or a 1-8C alkyl) to give the objective polyfunctional α,β-unsaturated carboxylic acid ester.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyfunctional α, β which is a monomer for producing a polymer such as a synthetic resin optical material.
-Unsaturated carboxylic acid esters and intermediates thereof.

2. Description of the Related Art Higher diols having 20 or more carbon atoms are already known. Such a diol is usually produced by polymerizing a double bond part of a higher unsaturated fatty acid to form a dimer acid (hereinafter, also referred to as “dimer acid”) and subjecting this to a reduction treatment. The dimer diol thus obtained is then reacted with acrylic acid or methacrylic acid, and the resulting reaction product is used as a raw material for vinyl polymerization (JP-A-60-157106 and JP-A-3-236349). Issue).

However, a polymerization initiator is added to the esterified product of dimer diol with acrylic acid or methacrylic acid disclosed in these patents (hereinafter, also referred to as "difunctional α, β-unsaturated carboxylic acid ester"). In particular, the polymer obtained by polymerization does not have practical strength as mechanical strength as indicated by falling ball strength. Therefore, it is necessary to add a copolymerizable monomer capable of providing a crosslinked structure to the bifunctional α, β-unsaturated carboxylic acid ester to form a copolymer and improve the mechanical strength. Come on.
In this case, there is a problem that properties such as ultra-low specific gravity and low refractive index which the homopolymer of the bifunctional α, β-unsaturated carboxylic acid ester itself has are sacrificed by the addition of a large amount of monomer. Occurs.

DISCLOSURE OF THE INVENTION The present invention is a monomer for obtaining a transparent resin which is lightweight (low in specific gravity) and has excellent mechanical strength represented by falling ball strength and which is useful as an optical material made of synthetic resin. It is intended to provide a mixture and its raw material.

[0003]

The present invention relates to trimertriol alone or to a mixture with dimerdiol, an ether compound and / or the polyhydric alcohol obtained by intermolecular dehydration reaction of hydroxyl groups of these polyhydric alcohols. It was made based on the finding that the above-mentioned problems can be solved by using a monomer mixture obtained by esterifying a mixture in which a specific amount of an ester compound with carvone is used in combination with α, β-unsaturated carboxylic acids. That is, the present invention relates to (A) a higher unsaturated fatty acid having 11 to 22 carbon atoms of 2
99 / 1-0 / 1 with trimer acid (or its esterified product) which is a trimer of a dimer acid (or its esterified product) / a higher unsaturated fatty acid having 11 to 22 carbon atoms
99 to 60% by weight of a polyhydric alcohol obtainable by hydrogenating a mixture of 00 (weight ratio), and (B) an ether compound by an intermolecular dehydration reaction of a hydroxyl group of the polyhydric alcohol and / or the polyhydric alcohol A polyhydric alcohol mixture comprising 1 to 40% by weight of an ester compound with a corresponding carboxylic acid is provided.

The present invention also provides a mixture of polyhydric alcohols,
Provided is a polyfunctional α, β-unsaturated carboxylic acid ester which can be obtained by esterification with an α, β-unsaturated carboxylic acid represented by the general formula (I).

Embedded image R ₁ (R ₂ ) C═C (R ₃ ) COOR _6- (I) (In the formula, R ₁ , R ₂ and R ₃ are each independently hydrogen or C 1-6 Alkyl group, R ₆ is hydrogen or carbon number 1
Up to 8 alkyl groups are shown. )

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION A mixture of dimer acid and trimer acid (hereinafter, also referred to as "multimeric acid") for producing the polyhydric alcohol of the component (A) used in the present invention, or a lower alcohol of multimeric acid. The ester has 11 to 2 carbon atoms as a raw material.
2, preferably 14 to 20, more preferably 16 to 1
8 higher unsaturated fatty acid or an esterified product with a lower alcohol having 1 to 6 carbon atoms is used, and a Lewis acid or Bronsted acid type liquid or solid catalyst, preferably montmorillonite activated clay is used as a raw material for this raw material. To 1 to 20
%, Preferably 2 to 8%, and the dimerization reaction is carried out at 200 to 270 ° C., preferably 220 to 250 ° C. The pressure during the reaction is usually slightly increased, but it may be normal pressure. The reaction time varies depending on the amount of the catalyst and the reaction temperature, but is usually 5 to 7 hours. The reaction system thickens as the reaction progresses. After completion of the reaction, the catalyst can be filtered off and then distilled under reduced pressure to distill off unreacted raw materials, isomerized fatty acids and the like, and then dimer acid fraction can be distilled off. By further distilling, a trimer acid fraction can be obtained. The trimer acid thus obtained may be used alone, or may be used as a mixture with dimer acid. The mixing ratio is preferably dimer acid / trimer acid = 1/99 to 0/100, and more preferably 3/97 to 30/70.

The polymeric acid thus obtained is then hydrogenated. Multimeric acid (including its ester, the same applies hereinafter)
In order to make polyhydric alcohol, known methods such as reduction method using lithium aluminum hydride, lithium borohydride, metallic sodium / alcohol type hydrogenating agent or catalytic reduction method using hydrogen gas and catalyst are adopted. can do. That is, it is also possible to reduce in a solvent by using a hydrogenating agent such as lithium aluminum hydride, lithium borohydride, metallic sodium / alcohol system, etc., in an equimolar amount or more to the multimeric acid. Specifically, lithium aluminum hydride is used in an amount of twice the molar amount of the polymeric acid and dispersed in a diethyl ether or dioxane solvent, and the polymeric acid diluted with the same dispersed solvent is added dropwise. Reaction temperature is 0 ° C
~ Room temperature, reaction time is preferably 1-2 hours. After the completion of the reaction, the mixture is stirred at room temperature for about 30 minutes, and then the reaction is preferably terminated by gradually dropping about 4 times the amount of water with respect to lithium aluminum hydride. Next, the reaction solution is washed with water and the solvent layer is distilled off to obtain a polyhydric alcohol. As an example of the higher polyhydric alcohol used in the present invention produced by the above method, a reduction reaction product of dimer acid (dimer diol) derived from an unsaturated fatty acid having 18 carbon atoms (general formula (II) to ( V)] or the double bond part of the unsaturated aliphatic alcohol having 18 carbon atoms of the general formulas (VI) and (VII) and dimerization with the double bond part of the dimer diol of the general formulas (II) to (V). Examples thereof include a mixture of the reacted trimer acid with a reduction reaction product (trimer triol).

[0007]

Embedded image

[0008]

Embedded image

(In the formula, m, n, p and q are each an integer of 0 or 1 or more, and m + n + p + q = 28.
The composition ratio of the dimer diol represented by the general formulas (II) to (V) and the composition ratio of the unsaturated higher alcohol represented by the general formulas (VI) and (VII) are arbitrary. Next, a method for producing an ether compound by an intermolecular dehydration reaction of the hydroxyl group of the polyhydric alcohol of the component (B) used in the present invention will be described. First, in the obtained polyhydric alcohol, an acid catalyst such as paratoluenesulfonic acid, sulfuric acid, hydrogen fluoride, hydrogen trifluoride, methanesulfonic acid, activated clay, and synthetic zeolite is used as a catalyst for the raw polyhydric alcohol. 0.1 to 10%, preferably 0.5 to 5%, 150
The ether compound can be obtained by performing a dehydration reaction at a reaction temperature of 280 ° C. for 3 to 10 hours, preferably under reduced pressure.

On the other hand, the ester compound of the component (B) used in the present invention has a corresponding carboxylic acid, that is, a carbon number of 1
1 to 22 higher unsaturated fatty acid or dimer acid which is a dimer of lower alcohol ester thereof or dimer monocarboxylic acid monoalcohol obtained by partial hydrogenation of dimer acid ester, higher unsaturated fatty acid having 11 to 22 carbon atoms or Trimer acid, which is a trimer of the lower alcohol ester, or trimer carboxylic acid monoalcohol or trimer monocarboxylic acid dialcohol obtained by partially hydrogenating trimer acid ester, is added in an equimolar amount to the polyhydric alcohol,
As a catalyst, acid catalysts such as paratoluene sulfonic acid, sulfuric acid, hydrogen fluoride, hydrogen trifluoride and methane sulfonic acid,
Using a base catalyst such as sodium hydroxide, lithium hydroxide, sodium metal, etc., 0.1
-10%, preferably 0.5-5%, 50-150
An ester compound can be obtained by carrying out the reaction at a reaction temperature of C for 3 to 10 hours.

As a method for producing the component (B) from the multimeric acid other than the above-mentioned production method, when the multimeric acid is catalytically reduced under high pressure hydrogen, polyhydric alcohol and the component (B) are simultaneously produced. I found it. That is, Raney nickel, platinum-supported nickel diatomaceous earth, copper-chromium, copper-zinc, etc. are used as a catalyst in an amount of 0.1 to 7% with respect to the multimeric acid, and the reaction temperature is 100 to 300 ° C, preferably 250 to 280 ° C. The polyhydric alcohol can also be obtained by catalytic reduction under hydrogen pressure of atmospheric pressure to 300 kg / cm ² , preferably 150 to 250 kg / cm ² , and reaction time of 1 to 15 hours, preferably 4 to 8 hours. Although it is obtained, after the catalytic reduction, the product is analyzed by GPC (column manufactured by Tosoh Corporation, TSKgel G
1000 HXL + TSKgel G2500 HXL, tetrahydrofuran solvent), it was found that the component (B) is usually contained in an amount of 1 to 15%. Further, when an operation of removing water and lower alcohol by-produced during the catalytic reduction reaction is added to the outside of the system, the content of the component (B) further increases, and the content rate can reach 15 to 40%. . Further, the polyhydric alcohol obtained by this catalytic reduction reaction is separated and the above-mentioned etherification or esterification reaction is carried out to obtain the component (B). The composition ratio of the ether type and the ester type in the component (B) varies depending on the reaction conditions, but is usually ether type / ester type = 9/1 to 2/8
It exists in the range of (shooting ratio). Further, these composition ratios are optional because they do not affect the physical properties of the resin after polymerization even during the production of the α, β-unsaturated carboxylic acid ester of the present invention.

The amount of component (B) contained in the polyhydric alcohol is 1 to 40%, preferably 5 to 30%. Here, if the content of the component (B) is too large at 40% or more, the viscosity of the obtained polyfunctional α, β-unsaturated carboxylic acid ester becomes high and it becomes difficult to handle,
There are drawbacks such that the flexibility of the polymer is reduced. Next, the mixture of the component (A) and the component (B) produced by the above-mentioned method is esterified or transesterified with the α, β-unsaturated carboxylic acid represented by the general formula (I) to give polyfunctionality. A method for producing an α, β-unsaturated carboxylic acid ester will be described. Among the α, β-unsaturated carboxylic acids represented by the general formula (I), the α, β-unsaturated carboxylic acids having 3 to 6 carbon atoms and the alkyl esters having an alkyl group having 1 to 8 carbon atoms are preferable. Specifically, acrylic acid, methacrylic acid, crotonic acid or their methyl ester, ethyl ester, propyl ester, butyl ester, hexyl ester, octyl ester and the like can be mentioned. The amount of the α, β-unsaturated carboxylic acid used in the esterification or transesterification reaction is 1.0 to 5.0, preferably a carboxyl group amount, based on the —OH group of the polyhydric alcohol as a raw material. It is 1.05 to 2.0 equivalents.

The esterification reaction uses paratoluene sulfonic acid, sulfuric acid, hydrogen fluoride, hydrogen trifluoride, methane sulfonic acid, etc. as a catalyst, and is 0.1 to 10% with respect to the raw material polyhydric alcohol, preferably Using 0.5-5%, 50-
It is preferable to carry out at a reaction temperature of 150 ° C. for 3 to 10 hours. In the transesterification reaction, a metal alkoxide selected from titanium and aluminum as a metal atom is used as a catalyst in an amount of 0.01 to 10% with respect to the raw material alcohol, and 5
It is preferable to carry out the reaction at a reaction temperature of 0 to 150 ° C. for 3 to 10 hours.
In both reactions, 2,4-dimethyl-6-as a polymerization inhibitor
t-butylphenol, 2,4,6-trimethylphenol, 2,4-diethyl-6-t-butylphenol,
Hydroquinone, paramethoxyphenol and the like are 1 to 5000 ppm, preferably 10 to 1000, with respect to the final product polyfunctional α, β-unsaturated carboxylic acid ester.
It is better to add ppm. The resulting polyfunctional α, β-unsaturated carboxylic acid ester can be purified by distillation under reduced pressure or washing with an aqueous alkali solution, if necessary. The polyfunctional α, β-unsaturated carboxylic acid ester of the present invention can be polymerized alone as a monomer composition to form a crosslinked resin, but the ester is within a range not departing from the gist of the present invention. It can also be copolymerized with a copolymerizable monomer. This copolymerizable monomer is in the mixture,
It is preferably used in an amount of 50% or less, more preferably 10 to 40%.

As the copolymerizable monomer, various monomers having an acrylic group, a methacrylic group, a vinyl group and the like can be mentioned. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate,
Α, β having an aliphatic alkyl group such as butyl (meth) acrylate, isoburu (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate
-Has an aromatic group or an alicyclic group such as unsaturated carboxylic acid ester, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, naphthyl (meth) acrylate, 1,2,3-tribromophenyl (meth) acrylate (Meth) acrylates, and further ethylene glycol di (meth) acrylate, polyethylene glycol poly (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth)
Acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) ) Polyfunctional (meth) acrylates such as acrylate, 2,2-bis {4- (meth) acryloxyethoxyphenyl} propane, and 2,2-bis {4- (meth) acryloxypolyethoxyphenyl} propane. Yes, vinyl compounds such as styrene, divinylbenzene, α-methylstyrene, chloromethylstyrene, etc. are also used.

These monomers can be used alone or as a mixture of two or more kinds. Moreover, the copolymerizable monomer usable in the present invention is not limited to these monomers. In the present invention, the polyfunctional α, β-
A synthetic resin optical material can be obtained by polymerization of an unsaturated carboxylic acid ester or copolymerization thereof with another copolymerizable monomer. As the polymerization method, radical polymerization, ionic polymerization, photopolymerization or the like can be adopted, and a usual radical initiator or photopolymerization initiator can be used. For example, in the method of radical polymerization, the polymerization reaction is
Preference is given to using initiators which start at temperatures between 0 and 120 ° C. Further, in the photopolymerization, it is performed at a temperature of about room temperature,
A high pressure mercury lamp, a low pressure mercury lamp or the like is used as a light source. However, the above-mentioned resin is a polyfunctional α, β which is the main component.
Since the unsaturated carboxylic acid ester is a polyfunctional monomer, it is obtained as a crosslinked polymer. Therefore, when the obtained resin is used as a molding material with melting or melting,
Since it is practically impossible, as the polymerization method, it is preferable to use a casting polymerization method that directly obtains a molded product and is suitable for the shape of the target optical material.

The cast polymerization method is a well-known technique, and can be directly applied to the above-mentioned resin production method. As the casting container, plate-shaped, lens-shaped, cylindrical, prismatic, conical,
A spherical shape, a mold or a frame shape designed according to the intended use, and other containers are used. The material can be selected from inorganic glass, plastic, metal, and any other materials depending on the purpose. The actual polymerization reaction can be carried out by charging the monomer mixture and the polymerization initiator into a casting polymerization container and heating, but using a separate reaction container, the monomer components are preliminarily mixed to some extent. It is also possible to carry out the reaction by adding a prepolymer having an increased viscosity or a syrup to a casting polymerization container to complete the polymerization. In addition, the monomer component may include an antistatic agent, a coloring agent, a filler, depending on the intended use of the resulting copolymer.
An ultraviolet absorber, a heat stabilizer, an antioxidant, and other auxiliary agents can be contained. The synthetic resin optical material thus obtained is composed of the components (A) and (B) α, β.
-Since an unsaturated carboxylic acid ester is used as an essential monomer component, the optical material has a high crosslink density and a specific gravity of 1.03 or less, preferably 1.01 to 0.95. Further, those having a weight average molecular weight of 100,000 to 10,000,000 are preferable.

Industrial Applicability The resin obtained by polymerizing the polyfunctional α, β-unsaturated carboxylic acid ester of the present invention has a high cross-linking density and is excellent in transparency and heat resistance. As a high-performance acrylic resin,
It can be applied to various uses such as fields in which inorganic glass and ordinary acrylic resins are used. Next, the present invention will be described with reference to examples, but the present invention is not limited thereto. In addition,% shown below is% unless otherwise specified.

[0017]

【Example】

Example 1 A polyhydric alcohol mixture (mixture a) comprising the polyhydric alcohol of the component (A) and the ether compound and the ether compound of the component (B) was prepared as follows. First,
Higher unsaturated fatty acid methyl ester containing 72% methyl oleate, 18% methyl linoleate and 10% other higher saturated fatty acid methyl, as raw material, activated clay (7%)
Was used as a catalyst to carry out a dimerization reaction at 230 ° C. for 5 hours. Unreacted higher unsaturated fatty acid methyl ester fraction and isomerized higher unsaturated fatty acid methyl ester fraction were removed from the product obtained by vacuum distillation (230 ° C / 1 torr), and the residue was subjected to molecular distillation (280 ° C). /0.1 torr) to obtain dimethyl dimer acid and trimethyl trimerate as a distillation residue. Then, dimethyl dimerate / trimethyl trimerate = 7/3 was prepared, and these were subjected to high-pressure hydrogen condition (2
20 kg / cm ² ), adding 3% of copper-chromium catalyst, 270
Catalytic reduction was carried out at a temperature of 3 ° C. for 3 hours while flowing hydrogen for 10 minutes. The obtained product was analyzed by GPC (column: manufactured by Tosoh Corporation, TSKgel G1000 HXL + TSKgel G25).
00 HXL, tetrahydrofuran solvent)
It was found to be a polyhydric alcohol containing the component (B) as shown in. Subsequently, a part of the obtained mixture a was subjected to molecular distillation (280 ° C./0.01 torr) to prepare a polyhydric alcohol single product (mixture b), and then an ether compound obtained by dehydration reaction of the polyhydric alcohol and the polyhydric alcohol was performed. , Prepared as follows. 2 g of acidic activated clay was added to 100 g of polyhydric alcohol, and dehydration reaction was performed at 200 ° C. for 10 hours under a nitrogen stream. After removing the activated clay from the obtained product by filtration, molecular distillation was performed to remove unreacted polyhydric alcohol, and 25 g of an ether compound (mixture c, ¹ H-
Confirmation of characteristic peak by NMR: δ = 3.4 ppm, −
CH ₂ -O-CH ₂ -) was obtained. Table 1 shows the composition ratios of the mixture a to the mixture c and the hydroxyl value.

[0018]

[Table 1] Table-1 GPC analysis results of polyhydric alcohol and hydroxyl value Composition ratio (GPC,%) Dimer trimer Component (B) Diol Triol Hydroxyl value (KOH mg / g) Mixture a 59 25 16 16 ^{* 1} 179 Mixture b 70 30 197 Mixture c 100 ^{* 2} ) 141 ^{* 1 1 By} H-NMR Confirmation of characteristic peaks: δ = 3.4 ppm, —CH ₂ —O—CH ₂ — (ether type) δ = 4.1 ppm, 2.3 ppm, —CH ₂ —O—COCH ₂ — (ester) Type) From the above results, when calculated from the area ratio, the molar ratio of ether type / ester type in the polymer diol = 8/2 ^{* 2 1} H-NMR confirmed characteristic peaks: δ = 3.4 ppm, -CH ₂ -O-CH ₂ - (ether type) it can be seen that only the ether from this data exists.

Example 2 The methacrylic acid esterified product of the mixture a, b or c shown in Table 1 was synthesized as follows. 5 of contents 5l
A one-necked flask, a stirrer, a thermometer, a dropping funnel, a nitrogen introduction tube with an introduction tube extending into the liquid and an air introduction tube to the headspace, two condensers in one mouth (the first condenser is the reaction tank Direct connection, the second condenser was attached from the first condenser via a V-shaped tube, and the solution condensed by the second condenser was kept so as not to return directly to the reaction tank).

1000 g of the mixture a shown in Table 1, 342 g of methyl methacrylate, 2,4-dimethyl-6-t-
0.619 g of butylphenol was added to the above flask,
The temperature was raised to the reaction temperature while introducing nitrogen into the solution, and when the reaction temperature was reached, the pressure was reduced to 10 torr over 1 hour to remove water in the reaction solution. Then, after returning the pressure to normal pressure with nitrogen, nitrogen was passed through the liquid and air was passed through the head space, and a solution of titanium tetraisopropoxide 18.9 g dissolved in 200 g n-hexane (azeotropic solvent) was added dropwise to the dropping funnel. And added slowly over 2 hours. Methyl methacrylate is refluxed in the first condenser (set to an azeotropic temperature of n-hexane and methanol of 50 ° C), and n-hexane and methanol are captured in the second condenser (set to 0 ° C). Was returned to the reaction tank again. The reaction was continued until no more methanol distilled (4 hours after catalyst addition). After the transesterification, excess n-hexane and methyl methacrylate were removed under reduced pressure, activated carbon and water were added at 100 ° C, and the catalyst was hydrolyzed while stirring for 1 hour. After completion of the hydrolysis, excess water was removed at 80 ° C. under reduced pressure (10 torr). After adding 6.25 g of a filter aid (Hyflo Supercell (Celite)) to the obtained reaction product and stirring, 8
As a result of filtration at 0 ° C., 1060 g of a methacrylic esterified product of the mixture a (monomer aM) was obtained. ¹ H-MNR
Esterification rate is 98%, color tone (APHA) is 6
It was 0 (APHA of raw material mixture a: 60). In addition,
When a methacrylic ester compound other than the monomer aM was synthesized in the same manner, a color tone similar to that of the monomer aM and a color tone almost equal to that of the monomer aM was obtained.

Reference Example A methacrylic esterified product alone or a monomer copolymerizable therewith, wherein Monomer 1 or 2 shown in Table 2 was mixed in the composition shown in Table 3 and the mixture was mixed. A composition for polymerization was prepared by adding 1.0% perbutyl PB (manufactured by NOF CORPORATION) as a radical polymerization initiator.

[0022]

[Table 2] Table-2 Abbreviation of monomer for copolymerization Compound name Monomer 1 t-Butyl methacrylate monomer 2 Divinylbenzene Then , after passing nitrogen through this polymerization composition for 15 minutes, it was injected into a glass mold and heated to 50 ° C. For 15 hours, at 80 ° C. for 3 hours, and at 100 ° C. for 2 hours at different temperatures. This created a -2.00 diopter lens. The properties of the lens thus obtained were evaluated as follows. Specific gravity: Measured according to ASTM D792. Refractive index: The refractive index at 20 ° C. was measured with an Abbe refractometer. Total light transmittance: Performed according to JIS K7105. Falling ball strength: Various iron balls were dropped from a height of 127 cm (50 inches), and the maximum weight without breaking the lens was defined as the falling ball strength. If 400 g of iron balls did not crack, it was designated as NB. The results are also shown in Table-3.

[0023]

[Table 3] Table-3 No. 1 2 3 4 5 sets Monomer aM 100 85 70 Composition monomer bM 95 70 Ratio Monomer cM 5 30 Monomer 1 10 15 (%) Monomer 25 15 Specific gravity 0.971 0.971 0.965 0.983 0.998 Refractive index 1.498 1.498 1.498 1.501 1.512 Total light transmittance (%) 92 91 92 91 92 Falling ball strength (g) NB NB NB 250 120

[0024]

[Table 4] Table-3 (continued) No. 6 * 7 * 8 * 9 * group Monomer aM Monomer bM 100 70 30 85 Ratio monomer cM Monomer 1 15 35 10 (%) Monomer 2 15 35 5 Specific gravity 0.974 0.999 1.029 0.985 Refractive index 1.497 1.512 1.529 1.505 All rays Transmittance (%) 92 91 90 91 Falling ball strength (g) 120 50 10 120 In the table, 6 * to 9 * are comparative examples. As is clear from the results shown in Table 3, all of the lenses (Nos. 1 to 5) produced by using the composition for polymerization of the present invention have a specific gravity of 1.0 or less and a total light transmittance. Is good, the refractive index is high, and the mechanical strength shown in the falling ball strength is excellent.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location // C08F 20/20 MMV C08F 20/20 MMV

Claims (2)

[Claims] 1. (A) A dimer acid (or an esterified product thereof) which is a dimer of a higher unsaturated fatty acid having 11 to 22 carbon atoms / a trimer of a higher unsaturated fatty acid having 11 to 22 carbon atoms. 99 / with some trimer acid (or its esterified product)
99-60% by weight of a polyhydric alcohol obtainable by hydrogenating a mixture of 1 to 0/100 (weight ratio), and (B) an ether compound by an intermolecular dehydration reaction of a hydroxyl group of the polyhydric alcohol and / or A polyhydric alcohol mixture comprising 1 to 40% by weight of an ester compound of the polyhydric alcohol and the corresponding carboxylic acid. 2. A polyfunctional α, β-obtainable by esterifying the polyhydric alcohol mixture according to claim 1 with an α, β-unsaturated carboxylic acid represented by the general formula (I).
Unsaturated carboxylic acid ester. Embedded image R ₁ (R ₂ ) C═C (R ₃ ) COOR ₆ ─── (I) (wherein R ₁ , R ₂ and R ₃ are each independently hydrogen or C 1-6 Alkyl group, R ₆ is hydrogen or carbon number 1
Up to 8 alkyl groups are shown. )