JP2003226806A - Transparent molded product and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent molded product having excellent transparency, scarcely causing yellowing with heat or ultraviolet rays and suitable for optical uses. <P>SOLUTION: The transparent molded product comprises a polymer of the following components (A) and (B) and the polymer further contains the following component (C). The component (A): an isocyanate-terminated prepolymer which is a reactional product of an aliphatic diisocyanate having a cyclic structure in the molecule with a diol having 300-2,500 average molecular weight, the component (B): one or more kinds of aromatic diamines represented by formula (I) (wherein, R<SB>1</SB>, R<SB>2</SB>and R<SB>3</SB>are each independently any of methyl group, ethyl group and thiomethyl group) and the component (C): one or more kinds of phosphorus-based peroxide decomposing agents. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent molded product such as a lens and a method for manufacturing them. In particular, the present invention relates to a transparent molded article which is excellent in transparency and is less likely to yellow due to light or heat, and which is made of polyurea having a urethane bond in its molecule and is suitable for optical use, and a method for producing the same.

[0002]

2. Description of the Related Art Compared with glass, plastic is lighter in weight, harder to break, and easier to dye, so that it is used for optical applications such as spectacle lenses and various other lenses.
Typical examples thereof include polydiethylene glycol bisallyl carbonate and polymethyl methacrylate. However, these have a low refractive index of about 1.50 and a specific gravity of about 1.2 or more. Therefore, for example, when used in a spectacle lens, the thickness and edge thickness near the center of the lens must be increased as the power increases,
There was a risk that the superiority of lightweight plastic would be impaired. Although they are more difficult to break than glass, there is a growing demand for more resistance to breakage. In order to take full advantage of the characteristics of light weight and hard-to-crack plastics, polycarbonates obtained by injection molding and polythiourethanes obtained by cast polymerization have begun to be used for optical applications. Although this polycarbonate has very high strength, it has low solvent resistance, which is a drawback common to injection molding materials. On the other hand, although polythiourethane does not show the above-mentioned defects common to injection molding materials, it is the current situation that it is inferior to polycarbonate in terms of strength.

Therefore, in order to avoid the drawbacks common to injection molding materials, a material obtained by cast polymerization and having a strength comparable to that of polycarbonate has been desired. As a material having such characteristics, a material obtained by casting polymerization of an isocyanate-terminated prepolymer having a urethane bond in the molecule and an aromatic diamine (US Pat.
62617 and US Pat. No. 6,127,505) are known. However, US Pat. No. 5,962,617
The material disclosed in the publication has a problem in that the aromatic diamine used is a solid at room temperature and the polymerization reaction is fast, so that undissolved residue occurs and the resulting molded body has low transparency. . On the other hand, US Pat. No. 6,127,505
The material disclosed in Japanese Patent Publication has sufficient transparency as an optical material by devising an aromatic diamine as a raw material, but the material is not transparent when polymerized due to oxidation of the aromatic diamine. Yellowing due to heat and light (especially ultraviolet rays) was a major drawback.

[0004]

Problems to be Solved by the Invention US Pat. No. 6,127,500
In order to make up for this point, JP-A No. 5 discloses the use of ultraviolet absorbers, light stabilizers and antioxidants, but only lists general-purpose products and also mentions detailed prescription amounts and the like. Absent. As a result, it was not a practically sufficient countermeasure, and yellowing due to heat or light during polymerization remained a major problem.
Therefore, an object of the present invention is a material obtained by casting polymerization of an isocyanate-terminated prepolymer having a urethane bond in the molecule and an aromatic diamine, which is excellent in transparency and hardly causes yellowing due to heat or light. Another object of the present invention is to provide a transparent molded article suitable for optical use and a method for producing the same.

[0005]

The inventors of the present invention cast-polymerize an isocyanate-terminated prepolymer having a urethane bond in the molecule and an aromatic diamine as disclosed in US Pat. No. 6,127,505. With respect to the material obtained by the above method, the inventors have earnestly studied to develop a material suitable for optical use by imparting good oxidation resistance (yellowing resistance) without impairing its transparency. As a result, an optical material obtained by casting and curing a composition containing a component containing a specific isocyanate-terminated prepolymer, a component containing a specific aromatic diamine and a component containing a phosphorus-based peroxide decomposing agent, is obtained. The inventors have found that they are suitable for the above purpose, and have completed the present invention.

The present invention which achieves the above object is as follows. (1) A transparent molded article comprising a polymer of the following component (A) and component (B), wherein the polymer further contains the following component (C). Component (A): Isocyanate-terminated prepolymer which is a reaction product of an aliphatic diisocyanate having a cyclic structure in the molecule and a diol having an average molecular weight of 300 to 2500 Component (B): represented by the general formula (I) One or more aromatic diamines

[Chemical 3] (In the general formula (I), R ₁ , R ₂ and R ₃ are each independently any one of a methyl group, an ethyl group and a thiomethyl group) Component (C): 1 type or 2 or more types of phosphorus type The weight of the peroxide decomposer (2) component (C) is in the range of 0.02 to 5.0% of the total weight of the component (A), the component (B) and the component (C), and the transparent molded article according to (1). . (3) The transparent molded article according to any one of (1) and (2), wherein the phosphorus-based peroxide decomposing agent as the component (C) contains a structure represented by the following general formula (II). .

[Chemical 4] (In the general formula (II), R ₄ and R ₅ are each independently a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 16 carbon atoms, R ₆ and R ₇ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.) (4) R ₄ and R ₅ in the general formula (II) have 12 to 12 carbon atoms.
The transparent molded article according to any one of (1) to (3), which is 14 alkyl groups. (5) The transparent molded article according to any one of (1) to (4), wherein the aliphatic diisocyanate having a cyclic structure in the molecule, which is a raw material of the component (A), is an alicyclic diisocyanate. (6) Alicyclic diisocyanate is 4,4'-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, 1,3-bis (isocyanatomethyl)
The transparent molded article according to (5), which is at least one selected from the group consisting of cyclohexane and norbornene diisocyanate. (7) The transparent molded article according to any one of (1) to (6), wherein the diol having a mean molecular weight of 300 to 2500, which is a raw material of the component (A), is a polyether diol or a polyester diol. (8) The transparent molded article according to any one of (1) to (7), wherein the isocyanate group content of the component (A) is in the range of 10 to 20% by weight. (9) R ₁ in the general formula (I) is a methyl group, and R ₂
And the transparent molded product according to any one of (1) to (8), wherein R ₃ is either an ethyl group or a thiomethyl group. (10) The transparent molded article according to any one of (1) to (9), wherein the molar ratio of the isocyanate group of the component (A) to the amino group of the component (B) is in the range of 1.00 to 1.15. (11) The transparent molded body according to any one of (1) to (10), wherein the transparent molded body is a lens. (12) The transparent molded article according to (11), wherein the lens is a spectacle lens. (13) The transparent molded body according to any one of (1) to (12), wherein the transparent molded body has a cured film on its surface. (14) The cured film is obtained from a coating composition containing the component (D) and the component (E) (1
The transparent molded article according to 3). Component (D): an organosilicon compound represented by the general formula (III) or a hydrolyzate thereof (R ₈ ) _a (R ₁₀ ) _b Si (OR ₉ ) _{4- (a + b)} ... (III) (In the general formula (III), R ₈ is an organic group having an epoxy group, a methacryloxy group, a mercapto group, an amino group, or a phenyl group, and R ₉ is an alkyl group having 1 to 4 carbon atoms or 1 carbon atom. Is an acyl group of 4 to 4, and R ₁₀ has 1 to 1 carbon atoms.
It is an alkyl group of 6, and a and b are integers of 0 or 1. Component (E): Metal oxide colloidal particles (15) Antireflection film on the surface of which the transparent molding is formed or on the cured film. The transparent molded article according to any one of (1) to (14), having (16) The transparent molding according to (15), wherein the antireflection film is a multilayer antireflection film, and at least one layer of the multilayer antireflection film is a high refractive index layer containing niobium oxide. body. (17) A mixture of the component (A), the component (B), and the component (C) described in any one of (1) to (10) is poured into a mold, and then the component (A) and the component (B). ) Is polymerized to obtain a molded product. (18) The method for producing a transparent molded article according to (17), wherein the mixture is prepared by further mixing the component (B) with the mixture of the component (A) and the component (C).

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The transparent molded article of the present invention comprises a polymer of component (A) and component (B). Component (A) Component (A) is an isocyanate-terminated prepolymer which is the reaction product of an aliphatic diisocyanate having a cyclic structure in the molecule and a diol having an average molecular weight of 300 to 2500. Diisocyanate, which is one of the starting materials for the isocyanate-terminated prepolymer, is an aliphatic diisocyanate having a cyclic structure in the molecule, which facilitates reaction control during prepolymer production or polymerization, and finally obtains Appropriate elasticity can be imparted to the formed body. Furthermore, it is possible to impart high heat resistance and good mechanical properties to the obtained molded product.

The aliphatic diisocyanate having a cyclic structure in the molecule is an aliphatic diisocyanate having a cyclic structure in the main chain or side chain, and the cyclic structure includes an alicyclic ring, an aromatic ring,
Alternatively, it may be a heterocycle. However, the aliphatic diisocyanate having a cyclic structure in the molecule is preferably an alicyclic diisocyanate from the viewpoint of preventing yellowing and maintaining sufficient elasticity and hardness. Compared with alicyclic diisocyanates, the yellowing of the obtained molded product tends to proceed with isocyanate having an aromatic ring, and the molded product obtained with aliphatic chain isocyanate tends to be soft, and the shape retention tends to decrease. .

Further, alicyclic diisocyanates include, for example, 4,4'-methylenebis (cyclohexylisocyanate), isophorone diisocyanate, 1,2-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane. , 1,4-bis (isocyanatomethyl) cyclohexane, 1,2-diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane,
1,4-diisocyanatocyclohexane, norbornene diisocyanate and the like can be mentioned. Examples of the diisocyanate having an aromatic ring include m-xylylene diisocyanate, o-xylylene diisocyanate, p-xylylene diisocyanate, m-tetramethylxylylene diisocyanate, and the like. In particular, 4,4'-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, 1,3
It is preferably at least one selected from the group consisting of bis (isocyanatomethyl) cyclohexane and norbornene diisocyanate.

The average molecular weight of the diol, which is the other raw material of the isocyanate-terminated prepolymer of the above component A, is 3
It is 00 to 2500. The average molecular weight of the diol is 300
If it is smaller, toughness cannot be imparted to the obtained molded product, and if it is larger than 2500, the molded product obtained becomes soft and cannot retain its shape. The average molecular weight of the diol is preferably 400 to 1000. 300-2
The diol having an average molecular weight of 500 can be, for example, a polyether diol or a polyester diol. These diols are preferable because they have good compatibility with other components. In the case of a diol having poor compatibility, it may be necessary to add another component such as a compatibilizing agent in order to maintain the transparency of the obtained molded product, or the transparency may be impaired.

Examples of such diols include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyester diol composed of ethylene glycol and adipic acid, polyester diol composed of propylene glycol and adipic acid, and diethylene glycol. Polyester diol consisting of adipic acid, polyester diol consisting of 1,4-butanediol and adipic acid, polyester diol consisting of neopentyl glycol and adipic acid, polyester diol consisting of 1,6-hexanediol and adipic acid, 1,10- Polyester diol consisting of decanediol and adipic acid, polyester diol consisting of 1,4-butanediol and sebacic acid, ethylene glycol and ε-caprolact Polycaprolactone diol consisting of, Polycaprolactone diol consisting of propylene glycol and ε-caprolactone, Polycaprolactone diol consisting of diethylene glycol and ε-caprolactone, Polycaprolactone diol consisting of 1,4-butanediol and ε-caprolactone, Neopentyl glycol and ε -Polycaprolactone diol consisting of caprolactone, polycaprolactone diol consisting of 1,6-hexanediol and ε-caprolactone, polycaprolactone diol consisting of 1,10-decanediol and ε-caprolactone, polycarbonate glycol, etc. Oxypropylene glycol,
Polyoxytetramethylene glycol, polyester diol composed of 1,4-butanediol and adipic acid, polyester diol composed of neopentyl glycol and adipic acid, polyester diol composed of 1,6-hexanediol and adipic acid, 1,10-decane Examples thereof include polyester diols composed of diol and adipic acid.

The isocyanate group content of the component (A) isocyanate terminated prepolymer is preferably in the range of 10 to 20% by weight. If the isocyanate group content is smaller than the above range, the hardness of the obtained molded article tends to be low, and if it is higher than the above range, the toughness (sufficient strength) of the obtained molded article tends to be difficult to obtain. Further, the isocyanate group content is more preferably in the range of 11 to 15% by weight.

Component (B) Component (B) is one or two of the above general formula (I).
One or more aromatic diamines. R ₁ , R ₂ and R _{3 in the} general formula (I) are each independently a methyl group, an ethyl group or a thiomethyl group. R ₁ , R ₂ and R ₃
By being the above group, the crystallinity can be suppressed and the compatibility with other components can be enhanced. Further, if these groups are absent or the number is small, the crystallinity is high and handling becomes difficult, and if other groups are used, the compatibility with other components may be deteriorated and the transparency of the obtained material may be lowered.

More specifically, the aromatic diamine is
For example, the following compounds. 1,3,5-trimethyl-2,4-
Diaminobenzene, 1,3,5-trimethyl-2,6-diaminobenzene, 1,3,5-triethyl-2,4-diaminobenzene, 1,
3,5-triethyl-2,6-diaminobenzene, 1,3,5-trithiomethyl-2,4-diaminobenzene, 1,3,5-trithiomethyl-2,6-diaminobenzene, 3,5-diethyl-2 , 4-Diaminotoluene, 3,5-diethyl-2,6-diaminotoluene, 3,5-
Dithiomethyl-2,4-diaminotoluene, 3,5-dithiomethyl-2,6-diaminotoluene, 1-ethyl-3,5-dimethyl-2,4
-Diaminobenzene, 1-ethyl-3,5-dimethyl-2,6-diaminobenzene, 1-ethyl-3,5-dithiomethyl-2,4-diaminobenzene, 1-ethyl-3,5-dithiomethyl-2, 6-diaminobenzene, 1-thiomethyl-3,5-dimethyl-2,4-diaminotoluene, 1-thiomethyl-3,5-dimethyl-2,6-diaminotoluene, 1-thiomethyl-3,5-diethyl-2 , 4-Diaminotoluene, 1-thiomethyl-3,5-diethyl-2,6-diaminotoluene, 3-ethyl-5-thiomethyl-2,4-diaminotoluene, 3-
Ethyl-5-thiomethyl-2,6-diaminotoluene, 3-thiomethyl-5-ethyl-2,4-diaminotoluene and the like.

In the above aromatic diamine, when R ₁ is a methyl group and R ₂ and R ₃ are each an ethyl group or a thiomethyl group, the resulting molded article is less likely to become cloudy and the resulting molded article is It is particularly preferable from the viewpoint that sufficient toughness can be imparted to the body.

Specific examples of such aromatic diamine include, for example, 3,5-diethyl-2,4-diaminotoluene, 3,5-diethyl-2,6-diaminotoluene and 3,5- Dithiomethyl-2,4-diaminotoluene, 3,5-dithiomethyl-2,
6-diaminotoluene and the like can be mentioned.

The sufficient ratio of the component (A) and the component (B) is that the molar ratio of the isocyanate group of the component (A) to the amino group of the component (B) is in the range of 1.00 to 1.15. It is preferable from the viewpoint that (strength) can be obtained. The above molar ratio is more preferably in the range of 1.02 to 1.12. The molded product of the present invention is the above-mentioned polymer and further contains the following component (C).

Ingredient (C) Ingredient (C) is one or more phosphorus-based peroxide decomposing agents, and it decomposes the peroxide generated by heat or light during the oxidation process to give a yellow color. It has the effect of suppressing the change.
Sulfur-based peroxide decomposers are known to exhibit the same effect, but they react with the amine compounds contained in the above-mentioned component (B) and other stabilizers to reduce the activity or cause coloring. It is inappropriate because it causes the cause, and it is important that it is phosphorus-based. Among them, in particular, the structure represented by the general formula (II) is included, and R ₄ and R ₅ are each independently a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms or 1 to 16 carbon atoms. R ₆ and R ₇ are each independently a hydrogen atom or a carbon number of 1 to 10
From the viewpoint of excellent compatibility with other components, one of the general formula (II)
It is more preferable that R ₄ and R ₅ are each independently an alkyl group having 12 to 14 carbon atoms from the viewpoint of high solubility in the component (A) and the component (B).

Examples of the phosphorus-based peroxide decomposing agent include the following.

[Chemical 5]

Examples of particularly preferable phosphorus-based peroxide decomposing agents include the following.

[Chemical 6]

More preferable phosphorus-based peroxide decomposing agents include the following.

[Chemical 7]

The weight of the component (C) is preferably 0.02 to 5.0% of the total weight of the components (A) to (C). When the weight of the component (C) is less than the above range, the effect of suppressing yellowing becomes difficult to obtain, and when it is more than the above range, transparency may be deteriorated. The weight of component (C) is more preferably in the range of 0.1 to 2.0% of the total weight of components (A) to (C).

Production Method For the transparent molded article of the present invention, for example, a mixture of the above-mentioned components (A) to (C) is poured into a molding die, and then the component (A).
And a component (B) are polymerized to obtain a molded product. However, since the components (A) and (B) have high polymerizability (reactivity) and the reaction proceeds even at room temperature, the mixture (a mixture of components (A) to (C)) is Add component (C) to A),
The component (B) is mixed with the homogeneously dissolved product (mixture).
It is preferable to inject it into the mold immediately after the preparation. The polymerization reaction conditions, etc.
For example, the conditions and the like described in column 5 of US Pat. No. 6,127,505 can be appropriately adopted, and will also be described in detail in Examples described later.

In addition to the component (C), the molded product of the present invention may optionally contain additional components such as an ultraviolet absorber, an antioxidant, a light stabilizer, a release agent and an achromatizer. It can be added to such an extent that the transparency and mechanical properties of the molded product are not impaired. Examples of the additive component as the release agent include, for example, one or more phosphoric acid monoesters represented by the general formula (IV) (in the general formula (IV), R ₁₁ has 1 carbon atom). ~
10 alkyl groups, n ₁ is 1 or 2) and one or more phosphodiesters represented by the general formula (V) (in the general formula (V), R ₁₂ and R ₁₃ are Each independently represents an alkyl group having 1 to 10 carbon atoms, n ₂ and n ₃
Is 1 or 2) and the like.

[Chemical 8]

With the mixture of the above-mentioned phosphoric acid monoester and phosphoric acid diester, the obtained molded product does not become cloudy, and it is possible to obtain a molded product excellent in transparency and releasability. . Preferably, R ₁₁ in the general formula (IV) and R ₁₂ and R ₁₃ in the general formula (V) each independently have a carbon number of 2 to 6 from the viewpoint of having the best compatibility with other components. They are phosphoric acid monoesters and phosphoric acid diesters that are alkyl groups.

Examples of the phosphoric acid monoester represented by the general formula (IV) include methoxyethyl acid phosphate, ethoxyethyl acid phosphate, propoxyethyl acid phosphate, butoxyethyl acid phosphate, pentyloxyethyl acid phosphate, hexyloxyethyl. Acid phosphate,
Heptyloxyethyl acid phosphate, octyloxyethyl acid phosphate, nonyloxyethyl acid phosphate, decyloxyethyl acid phosphate and the like can be mentioned. Particularly preferred phosphoric acid monoesters include, for example, ethoxyethyl acid phosphate, propoxyethyl acid phosphate, butoxyethyl acid phosphate, pentyloxyethyl acid phosphate, hexyloxyethyl acid phosphate and the like.

Examples of the phosphoric acid diester represented by the general formula (V) include methoxyethyl-ethoxyethyl acid phosphate, methoxyethyl-propoxyethyl acid phosphate, ethoxyethyl-propoxyethyl acid phosphate, ethoxyethyl-butoxyethyl acid. Phosphate, propoxyethyl-butoxyethyl acid phosphate, di (methoxyethyl) acid phosphate, di (ethoxyethyl) acid phosphate, di (propoxyethyl) acid phosphate, di (butoxyethyl) acid phosphate, di (pentyloxyethyl) acid phosphate , Di (hexyloxyethyl) acid phosphate, di (heptyloxyethyl) acid phosphate, di (octyloxyethyl) Chill) acid phosphate, di (nonyloxyethyl) acid phosphate,
Di (decyloxyethyl) acid phosphate, and the like. As the phosphoric acid diester, preferably,
Examples thereof include di (ethoxyethyl) acid phosphate, di (propoxyethyl) acid phosphate, di (butoxyethyl) acid phosphate, di (pentyloxyethyl) acid phosphate, di (hexyloxyethyl) acid phosphate.

The transparent molded article of the present invention includes, for example, lenses such as eyeglass lenses and optical lenses, prisms, optical fibers,
It can be used for optical applications such as recording medium substrates and filters used for optical disks and magnetic disks. Preferably, the transparent molded article of the present invention can be used for lenses, particularly preferably for spectacle lenses.

Further, the transparent molded article of the present invention may have a cured film on its surface. Especially in the case of lenses,
It is preferable to have a cured film on the optically functional surface. Examples of the cured film include a film obtained by curing a coating composition containing the component (D) and the component (E). Component (D): an organosilicon compound represented by the general formula (III) or a hydrolyzate thereof (R ₈ ) _a (R ₁₀ ) _b Si (OR ₉ ) _{4- (a + b)} ... (III) (In the general formula (III), R ₈ is an organic group having an epoxy group, a methacryloxy group, a mercapto group, an amino group, or a phenyl group, and R ₉ is an alkyl group having 1 to 4 carbon atoms or 1 carbon atom. Is an acyl group of 4 to 4, and R ₁₀ has 1 to 1 carbon atoms.
6 is an alkyl group, and a and b represent an integer of 0 or 1) Component (E): Metal oxide colloidal particles

Specific examples of the organosilicon compound represented by the general formula (III) include the following compounds. Methyl silicate, ethyl silicate, n-propyl silicate, i-propyl silicate, n-butyl silicate, sec-butyl silicate, t-butyl silicate,
Tetraacetoxysilane, methyltrimethoxysilane,
Methyltriethoxysilane, methyltripropoxysilane, methyltriacetoxysilane, methyltributoxysilane, methyltriamyloxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methyltriphenethyloxysilane, glycidoxymethyltrimethoxysilane , Glycidoxymethyltriethoxysilane, α-glycidoxyethyltriethoxysilane, β
-Glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β -Glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ
-Glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β -Glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-
Glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyl Triethoxysilane, β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,3
4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-
Epoxycyclohexyl) propyltriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, δ- (3,4-epoxycyclohexyl) butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethyl Methyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane,
α-glycidoxypropylmethyldimethoxysilane, α
-Glycidoxypropylmethyldiethoxysilane, β-
Glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane , Γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropyl Vinyldimethoxysilane, γ-glycidoxypropyl vinyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane Emissions, vinyltrimethoxysilane, vinyltriacetoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyl triacetoxy silane, .gamma.
Chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane Silane, γ-mercaptopropyltriethoxysilane, β-
Cyanoethyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, N-
(Β-aminoethyl) γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) γ-aminopropyl Triethoxysilane, N- (β-aminoethyl) γ-aminopropylmethyldiethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ -Chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ- Le mercaptopropyl methyl diethoxy silane, methyl vinyl dimethoxy silane,
Methyl vinyl diethoxysilane.

Examples of the metal oxide colloidal particles as the component (E) include tungsten oxide (WO ₃ ), zinc oxide (ZnO), silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), titanium oxide. (TiO ₂ ), zirconium oxide (ZrO ₂ ), tin oxide (SnO ₂ ), beryllium oxide (BeO), antimony oxide (Sb ₂ O ₅ ).
Etc. can be used alone or in combination of two or more.

The amount of the above coating composition used is (D).
It is desirable to add 1 to 500 parts by weight of the metal oxide colloidal particles as the component (E) to 100 parts by weight of the organosilicon compound as the component. If the amount of the (E) component metal oxide colloidal particles is less than 1 part by weight, the scratch resistance of the cured film will not be improved, and conversely, if it is 500 parts by weight or more, cracks and the like tend to occur between the cured film and the substrate, and the transparency is further improved. Sex tends to decrease.

The above coating composition contains (1) a curing agent for accelerating the reaction, or (2) various surfactants for improving the wettability at the time of application and enhancing the smoothness of the cured film. Can be appropriately contained. Further, an ultraviolet absorber, an antioxidant and the like can be added as long as they do not affect the physical properties of the cured film.

Examples of the curing agent include amines such as allylamine and ethylamine, and various acids and bases including Lewis acid and Lewis base such as organic carboxylic acid, chromic acid, hypochlorous acid, boric acid, perchloric acid, Salts or metal salts containing bromic acid, selenious acid, thiosulfuric acid, orthosilicic acid, thiocyanic acid, nitrous acid, aluminate, carbonic acid, etc., and metal alkoxides containing aluminum, zirconium, titanium, or metal chelate compounds thereof, etc. Is mentioned.

The above coating composition is applied to the surface of the transparent molded article of the present invention and cured to form a cured film. Curing of the coating composition is performed by hot air drying or activation energy.
It is performed by irradiation with a ray, and the curing condition is 70 to 200.
It is good to carry out in hot air at ℃, preferably 90 ~ 150 ℃
Is desirable. Far infrared rays and the like are used as the active energy rays, and damage due to heat can be suppressed to a low level.

A dipping method, a spin method, a spray method or the like is generally used as a method for forming a cured film made of the above-mentioned coating composition on a substrate. Method and spin method are particularly preferable. Furthermore, before coating the above-mentioned coating composition on a substrate, acid, alkali, chemical treatment with various organic solvents, physical treatment with plasma, ultraviolet rays, ozone, etc.,
By performing a detergent treatment using various detergents and a primer treatment using various resins, the adhesion between the base material and the cured film can be improved.

The transparent molded product of the present invention is directly applied onto the molded product.
Alternatively, an antireflection film may be provided on the cured film. The type of the antireflection film is not particularly limited, and conventionally known inorganic oxides, MgF _{2 and the} like can be used in a single layer or a multilayer. Examples of the antireflection film include those disclosed in JP-A-2-262104 and JP-A-56-11.
The antireflection film disclosed in Japanese Patent No. 6003 can be used. Furthermore, the above-mentioned cured film can be used as a multi-functional film by adding functional components such as antifogging, photochromic and antifouling. Further, the antireflection film is a multilayer antireflection film, and at least one of the multilayer antireflection films is used.
The layer can also be a high refractive index layer containing niobium oxide. Further, the high refractive index layer containing niobium oxide can also contain zirconium oxide and / or yttrium oxide.

[0038]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The physical properties of the plastic lenses obtained in the examples and comparative examples were evaluated using the evaluation methods described below.

(1) Transparency The obtained lens was visually observed in a dark place under a fluorescent lamp, and a lens having no cloudiness or deposition of an opaque substance was designated as A. On the other hand, the case where slight cloudiness was observed was designated as B, and the case where the degree of cloudiness was severe or where the precipitation of opaque material was clearly observed was designated as C. C is obviously unsuitable as a lens.

(2) Resistance to yellowing [yellowing resistance during polymerization] The yellowing resistance to heat during polymerization is measured by measuring the 380-780 nm spectral spectrum of the lens immediately after polymerization and calculating the YI value from the result. Was evaluated.
When the YI value is less than 2.5, it is A;
A value of 3.5 or more was set as C. [Yellow Resistance to Light] The obtained lens was measured for a spectral spectrum at 380 to 780 nm before and after irradiation for 200 hours with a xenon lamp, and the YI value of each was calculated from the results. The value obtained by subtracting the YI value before irradiation from the YI value after irradiation was designated as ΔYI and used as an index of yellowing resistance to light.
When ΔYI was less than 1, A was designated as 1, 1 or more and less than 2 was designated as B, and 2 or more was designated as C. C for either heat-resistant or light-resistant yellowing
What was either or both were B are unsuitable as a lens.

(3) Impact resistance A steel ball weighing 16 g was naturally dropped from the height of 1.27 m, which is also the FDA standard, to the center of the S-4.00 lens having a center thickness of 1.3 mm, and all the test samples were produced. A is not destroyed,
B was the one in which breakage such as cracking or penetrating occurred in less than 30% (at least one sheet) of the test sample was B, and C in which more than 30% was broken. In addition, the weight of the steel ball is 1
A test in which the dose was increased to kg was also performed and the same evaluation was performed.

(Example 1) Isocyanate-terminated prepolymer having an average content of 400% of polytetramethylene glycol and 4,4'-methylenebis (cyclohexyl isocyanate) having an isocyanate group content of 13% (ITP-1 in Table 1) 100 parts by weight of 4,4'-butylidene-bis (3-methyl-6-t-butylphenyl-di-tridecyl) phosphite (PO- in Table 1).
0.5 parts by weight, 2- (2'-hydroxy-5 ')
1.5 parts by weight of -t-octylphenyl) benzotriazole, bis (1,2,2,6,6-pentamethyl-4-
Piperidinyl) sebacate 1.25 parts by weight, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.25
Parts by weight were added to each to uniformly dissolve and defoam.
Next, 3,5-diethyl-2,4-toluenediamine and 3,5
25.5 parts by weight of a mixture of -diethyl-2,6-toluenediamine (denoted as DETDA in Table 1) were uniformly mixed at 60 to 70 ° C, and stirred at high speed for a short time. Furthermore, the mixture immediately after stirring is poured into a glass mold for lens molding, and 120
Polymerization was performed at 15 ° C. for 15 hours to obtain a plastic lens (transparent molding). Table 1 shows the physical properties of the obtained plastic lens. From Table 1, the obtained plastic lenses are excellent in yellowing resistance to heat and light, and have excellent transparency without cloudiness caused by white turbidity or scattering by fine crystals. It was Further, it was not broken by the falling ball test of 1 kg as well as the FDA standard of 16 g, and was excellent in impact resistance.

(Examples 2 to 9) A plastic lens (transparent molded article) was obtained in the same manner as in Example 1 except that the components shown in Table 1 were used. Table 1 shows the physical properties of these plastic lenses. From Table 1, the obtained plastic lenses were excellent in yellowing resistance to heat and light, and were also excellent in transparency without clouding due to white turbidity or scattering by fine crystals. Also, not only the FDA standard of 16 g, but also the 1 kg falling ball test is not destroyed,
It was also excellent in impact resistance.

Comparative Example 1 The same operation as in Example 1 was carried out except that PO-1 was not used. Table 1 shows the physical properties of the obtained plastic lens. From Table 1, the obtained plastic lens has excellent transparency without clouding caused by white turbidity or scattering by fine crystals, which is FDA standard 1.
Not only 6 g but also 1 kg was not destroyed in the falling ball test, but it was inferior in yellowing resistance to heat and light.

COMPARATIVE EXAMPLE 2 Except that PO-1 was replaced by sulfur-based peroxide decomposer ditridecyl-3,3'-thiodipropionate (indicated as SO-1 in Table 1). The same operation as in Example 1 was performed. Table 1 shows the physical properties of the obtained plastic lens. From Table 1, the obtained plastic lens was inferior in transparency due to slight clouding, and inferior in yellowing resistance to heat and light, resulting in a colored lens. Also, it was not destroyed by the FDA standard 16g drop ball test, but 1kg
Then, it was also inferior in impact resistance so that about 20% of the test samples were cracked.

[0046]

[Table 1]

Description of component names in the table ITP-1; Polyisocyanate having an average molecular weight of 400 and 4,4'-methylenebis (cyclohexyl isocyanate) having an isocyanate content of 1
3% isocyanate-terminated prepolymer ITP-2; polyoxypropylene glycol having an average molecular weight of 500 and 4,4′-methylenebis (cyclohexyl isocyanate) having an isocyanate content of 11%
Isocyanate-terminated prepolymer DETDA; a mixture of 3,5-diethyl-2,4-toluenediamine and 3,5-diethyl-2,6-toluenediamine PO-1; 4,4'-butylidene-bis (3- Methyl-
6-t-butylphenyl-di-tridecyl) phosphite PO-2; hexatridecyl-1,1,3-tris (2
-Methyl-4-hydroxy-5-t-butylphenylbutane) triphosphite PO-3; 4,4'-isopropylidene diphenol alkyl phosphite [alkyl is a mixture of 12 to 15 carbon atoms]

(Examples of Molded Article Having Cured Film) The plastic lenses (transparent molded article) having a cured film obtained in this Example and Comparative Example were measured for various physical properties by the following measuring methods. (4) -1 Scratch resistance test The lens surface was rubbed with a steel wheel # 0000 to visually determine the scratch resistance. The criteria for judgment are as follows. A. Almost no scratches even when rubbed hard B. If it is rubbed strongly, it will be considerably damaged. The same scratch as the lens board is attached. (4) -2 Adhesion test Cross-cut at 100 mm intervals at 1 mm intervals, strongly adhere an adhesive tape (product name "Sero Tape" manufactured by Nichiban Co., Ltd.), rapidly peel it off, and see if the cured film peels off. I checked. (4) -3 Appearance Inside the room, the transparency and the surface condition were visually examined. (4) -4 Impact resistance test A steel drop test was conducted. Specifically, a 16 g or 1 kg steel ball was naturally dropped from the height of 1.27 m to the center of the lens, and one that did not crack was passed. A: Pass, B: Fail

(Example 10-1) (Preparation of coating liquid) Water-dispersed colloidal silica (solid content: 40%, average particle size: 15 millimicrons) in a glass container equipped with a magnetic stirrer; E)) 1
While adding 41 parts by weight and stirring, add 30 parts by weight of acetic acid,
The mixture was thoroughly mixed and stirred. Thereafter, 74 parts by weight of γ-glycidoxypropyltrimethoxysilane (component (D)) was added dropwise, and the mixture was stirred at 5 ° C for 24 hours. Next, 100 parts by weight of propylene glycol monomethyl ether, 150 parts by weight of isopropyl alcohol, and 0.2 of a silicone-based surfactant.
Parts by weight, aluminum acetylacetone as a curing agent
(7.5 parts by weight) was added, and the mixture was sufficiently stirred and then filtered to prepare a coating composition liquid.

(Formation of Hardened Film) The plastic lens (transparent molding) prepared in Example 1 was used at 55 ° C. and 10%.
After thoroughly immersing in the aqueous solution of sodium hydroxide for 5 minutes to perform sufficient washing, the coating liquid prepared by the above method was used to coat the surface by a dipping method (pulling speed: 20 cm / min).
Coating, heating at 120 ° C. for 2 hours to form a cured film, and various evaluations were performed. The plastic lens (transparent molded article) having the obtained cured film was excellent in scratch resistance, adhesion, appearance and impact resistance as shown in Table 2.

(Example 10-2) Magnetic star
Isopropyl alcohol-dispersed colloidal silica (manufactured by Nissan Chemical Industries: solid content 30
%, Average particle size 15 millimicrons; 189 parts by weight of component (E) was added and, with stirring, 74 parts by weight of γ-glycidoxypropyltrimethoxysilane (component (D)) was added.
19 parts by weight of 10 ^-2N hydrochloric acid was added dropwise with stirring, and the ^{mixture was} stirred at 5 ° C for 24
Stir for hours. Next, 100 parts by weight of propylene glycol monomethyl ether, 100 parts by weight of isopropyl alcohol, 0.2 parts by weight of a silicone-based surfactant, and 7.5 parts by weight of aluminum acetylacetonate as a curing agent were added, and the mixture was sufficiently stirred. Filtration was performed to prepare a coating composition liquid. Other than that was performed like Example 10-1. The plastic lens (transparent molded article) having the obtained cured film was excellent in scratch resistance, adhesion, appearance, and impact resistance as in Example 10-1, as shown in Table 2.

(Example 10-3) A composite sol containing tin oxide / tungsten oxide / zirconia oxide / silicon oxide as a main component in a glass container equipped with a magnetic stirrer (manufactured by Nissan Chemical Industries, Ltd .: trade name HIS-40MH). : Methanol dispersion: Solid content 30%; 94 parts by weight of component (E), n-propyl cellosolve dispersed colloidal silica (manufactured by Nissan Chemical Industries:
Product name NPC-ST30: Solid content 30%; While thoroughly mixing and stirring 94 parts by weight of component (E), while stirring 67.0 parts by weight of γ-glycidoxypropyltrimethoxysilane (component (D)) Dropped. After the dropping, 16 parts by weight of 10 ^-2 normal hydrochloric acid,
Propylene glycol monomethyl ether 23 as a solvent
0 parts by weight, 0.2 parts by weight of a silicone surfactant, and 3 parts by weight of aluminum acetylacetonate as a curing accelerator were added, and the mixture was sufficiently stirred and filtered to obtain a coating composition. Other than that was performed like Example 10-1. As shown in Table 2, the obtained plastic lens (transparent molded article) having a cured film was used in Example 10-1.
Similar to the above, it was excellent in scratch resistance, adhesiveness, appearance and impact resistance.

(Comparative Examples 3-1 to 3-3) Example 10-1
Plastic lens used in 10-3 (transparent molding)
Example 10-, except that a lens made of a diethylene glycol bisallyl carbonate polymer was used in place of
It carried out similarly to 1-3. As shown in Table 2, the impact resistance was inferior as compared with the plastic lens (transparent molding) of the present invention.

[0054]

[Table 2]

[0055]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide a molded article suitable for optical use which is less likely to yellow due to light and heat, and a method for producing the same. In particular, said US Pat.
Yellowing resistance to light and heat without impairing the transparency of the material obtained by casting polymerization of an isocyanate-terminated prepolymer having a urethane bond in the molecule and an aromatic diamine as disclosed in JP-A No. Is given,
It is possible to provide a molded article suitable for optical use and a method for producing the same.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/49 C08K 5/49 (72) Inventor Masanori Kadota 2-7-5 Nakaochiai, Shinjuku-ku, Tokyo Hoya Co., Ltd. (72) Inventor Takeshi Mitsuishi 2-7-5 Nakaochiai, Shinjuku-ku, Tokyo Hoya Co., Ltd. (72) Inventor Kenichi Shinde 2-7-5 Nakaochiai, Shinjuku-ku, Tokyo Ho Ya Co., Ltd. (72) Inventor Hitoshi Kamura 2-7-5 Nakaochiai, Shinjuku-ku, Tokyo Hoya Co., Ltd. F term (reference) 4F071 AA53 AC15 AE22 AF22 AF23 AF31 AH19 BB01 BC07 4F100 AA17B AA17C AH03A AH03J AK51A AK51J AK51K AK52B AK52K AL01A AR00B AR00C BA02 BA03 BA07 BA10C CA30A CA30H DE01B GB90 JB12B JK10 JK12 JN01A JN18C JN28 YY00A 4F204 AA38 AA42 AH74 EA03 EA04 EB01 EK13 EK17 4J002 CK02 CK02 6 FD196 GP01 4J034 BA08 CA15 CB02 CB03 CC12 JA41 JA42 MA16 QA03 QA05 QB08 QC03 QD03 RA13

Claims (18)

[Claims] 1. A transparent molded article comprising a polymer of the following component (A) and component (B), wherein the polymer further contains the following component (C). Component (A): Isocyanate-terminated prepolymer component (B) which is a reaction product of an aliphatic diisocyanate having a cyclic structure in the molecule and a diol having an average molecular weight of 300 to 2500: represented by the following general formula (I) Type 1 or 2
One or more aromatic diamines (In the general formula (I), R ₁ , R ₂ and R ₃ are each independently any one of a methyl group, an ethyl group and a thiomethyl group) Component (C): 1 type or 2 or more types of phosphorus type Peroxide decomposer 2. The transparent molded article according to claim 1, wherein the weight of the component (C) is in the range of 0.02 to 5.0% of the total weight of the component (A), the component (B) and the component (C). 3. The transparent molded article according to claim 1, wherein the phosphorus peroxide decomposer as the component (C) has a structure represented by the following general formula (II). . [Chemical 2] (In the general formula (II), R ₄ and R ₅ are each independently a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 16 carbon atoms, R ₆ and R ₇ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.) 4. The transparent molded article according to claim 1, wherein R ₄ and R ₅ in the general formula (II) are each independently an alkyl group having 12 to 14 carbon atoms. 5. The transparent molded article according to claim 1, wherein the aliphatic diisocyanate having a cyclic structure in the molecule, which is a raw material of the component (A), is an alicyclic diisocyanate. 6. The alicyclic diisocyanate is at least one selected from the group consisting of 4,4′-methylenebis (cyclohexylisocyanate), isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane and norbornene diisocyanate. Item 5. A transparent molded article according to item 5. 7. The transparent molding according to claim 1, wherein the diol having a mean molecular weight of 300 to 2500, which is a raw material of the component (A), is a polyether diol or a polyester diol. body. 8. The isocyanate group content of component (A) is
The transparent molded product according to any one of claims 1 to 7, which is in a range of 10 to 20% by weight. 9. The transparent according to claim 1, wherein R ₁ in the general formula (I) is a methyl group, and R ₂ and R ₃ are each an ethyl group or a thiomethyl group. Molded body. 10. The transparent molded article according to claim 1, wherein the molar ratio of the isocyanate group of the component (A) to the amino group of the component (B) is in the range of 1.00 to 1.15. 11. The transparent molded article is a lens.
10. The transparent molded article according to any one of 10. 12. The lens is an eyeglass lens.
The transparent molded article according to. 13. The transparent molded body according to claim 1, wherein the transparent molded body has a cured film on the surface thereof. 14. The transparent molded article according to claim 13, wherein the cured film is obtained from a coating composition containing the component (D) and the component (E). Component (D): an organosilicon compound represented by the general formula (III) or a hydrolyzate thereof (R ₈ ) _a (R ₁₀ ) _b Si (OR ₉ ) _{4- (a + b)} ... (III) (In the general formula (III), R ₈ is an organic group having an epoxy group, a methacryloxy group, a mercapto group, an amino group, or a phenyl group, and R ₉ is an alkyl group having 1 to 4 carbon atoms or 1 carbon atom. Is an acyl group of 4 to 4, and R ₁₀ has 1 to 1 carbon atoms.
6 is an alkyl group, and a and b represent an integer of 0 or 1) Component (E): Metal oxide colloidal particles 15. The transparent molded article according to claim 1, which has an antireflection film on its surface or on the cured film. 16. The antireflection film is a multilayer antireflection film, and at least one layer of the multilayer antireflection film is a high refractive index layer containing niobium oxide. Transparent molded body. 17. A mixture of the component (A), the component (B), and the component (C) according to any one of claims 1 to 10 is poured into a mold, and then the component (A) and the component. A method for producing a transparent molded article, which comprises polymerizing (B) into a molded article. 18. The method for producing a transparent molded article according to claim 17, wherein the mixture is prepared by further mixing the component (B) with the mixture of the component (A) and the component (C).