KR20040015309A - Plastic lens material, plastic lens composition, plastic lens obtained by curing the composition and process for producing the plastic lens - Google Patents

Abstract

A material for plastic lenses comprising at least one or more of the groups having the general formula (1) as a terminal group, and comprising a group having the general formula (2) as a repeating unit:

In formula, R <^1> represents an allyl group or a metaallyl group each independently, and A <^1> is derived from bivalent carboxylic acid or dicarboxylic anhydride which has an alicyclic structure and / or an aromatic ring structure as each independent organic residue. One or more organic residues;

Wherein A ² each represents an independent organic residue and represents one or more organic residues derived from a divalent carboxylic acid or dicarboxylic anhydride having an alicyclic structure and / or an aromatic ring structure, and each X represents an independent organic residue. A residue represents one or more organic residues derived from a polyhydric alcohol having an ether bond in its molecule, and X has a group represented by the general formula (1) as a terminal group and a group represented by the general formula (2) as a repeating unit. It is conditional to have branching structure further.

Description

PLASTIC LENS MATERIAL, PLASTIC LENS COMPOSITION, PLASTIC LENS OBTAINED BY CURING THE COMPOSITION AND PROCESS FOR PRODUCING THE PLASTIC LENS}

The organic glass is lighter in comparison with the inorganic glass, and so far contains organic polymers such as diethylene glycol bis (allyl carbonate) or methyl methacrylate represented by CR-39 (registered trademark) (trade name, manufactured by PPG). I have used glass. However, the refractive index of the organic glass is 1.49 to 1.50, which is relatively low compared to the inorganic glass (refractive index of the white crown glass: 1.523), and its thickness is thicker than that of the inorganic glass, which lowers the effect of weight reduction and is used when used as a vision correction lens. If it is high, there is a drawback that the appearance is poor.

To cope with this, various organic glasses using diallyl phthalate monomers have been proposed. However, they are fragile or problematic in transmittance. In order to improve these properties, when diluted with a monofunctional polymerizable monomer and used, the performance of heat resistance and solvent resistance is hindered, and the performance as an organic glass becomes insufficient.

Allyl esters of the following structural formulas are known which have allyl ester groups at their ends and are derived from polyhydric saturated carboxylic acids and polyhydric saturated alcohols therein.

CH ₂ = CHCH ₂ O {CORCOOB'O} _p CORCOOCH ₂ CH = CH ₂

Wherein R is an organic residue derived from a divalent carboxylic acid having 1 to 20 carbon atoms, B 'is a divalent organic residue derived from an alkanediol, and p is a number from 1 to 20.

The allyl ester provides a cured product having excellent impact resistance compared to an organic glass using a diallyl phthalate monomer. However, in this case, since an aliphatic hydrocarbon is used for the portion of B 'inside, when p in the formula is small, the impact resistance is weaker than that of CR-39 (registered trademark). When p in the formula is increased so that impact resistance comparable to CR-39 (registered trademark) can be expressed, there is a disadvantage that the viscosity becomes too high.

The present inventors proposed the following allyl ester oligomer in Japanese Patent Laid-Open No. 3-258821 (JP-A-3-258821).

CH ₂ = CHCH ₂ O {CORCOOC'O} _q CORCOOCH ₂ CH = CH ₂

Wherein R is an organic residue derived from aromatic dicarboxylic acid, C 'is a divalent organic residue derived from polyalkylene glycol, and q is a number from 1 to 20.

However, the use of allyl ester oligomers as a material for plastic lenses is not disclosed.

Materials generally used as materials for plastic lenses are described, for example, in Kino Zairyo (Functional Materials), July 1998 , Vol. 18, No. 7, 33 to 40, in addition to optical properties such as refractive index and Abbe number, as described in CMC Publications (June 5, 1998), cutting polishing, chemical resistance, heat resistance, impact resistance, weather resistance, It is necessary to have an excellent balance of various physical properties such as handling workability and specific gravity.

From the information disclosed in JP-A-3-258821, since it is a thermosetting resin, it is estimated that the cutting polishing property and the chemical resistance of the resin are excellent. However, since optical properties such as refractive index and Abbe's number, and physical properties such as heat resistance and impact resistance are not disclosed at all, it is not possible to determine whether or not the resin can be used as a material for plastic lenses, and thus the present invention is not taught. not.

The present invention relates to a plastic lens material, a plastic lens composition, a plastic lens obtained by curing the composition, and a method for producing the plastic lens.

More specifically, the present invention provides a plastic lens material, a plastic lens composition containing the material, having a viscosity suitable for the application of spectacle lenses and other optical lenses, having a high refractive index and low specific gravity, and curing the composition. It relates to a plastic lens obtained, and a method for producing the plastic lens.

The accompanying drawings are a 400 MHz ¹ H-NMR spectrum and an FT-IR spectrum of the material for a plastic lens described in the preparation example.

1 is a 400 MHz ¹ H-NMR spectrum of the allyl ester compound prepared in Preparation Example 1. FIG.

2 is an FT-IR spectrum of the allyl ester compound prepared in Preparation Example 1. FIG.

3 is a 400 MHz ¹ H-NMR spectrum of the allyl ester compound prepared in Preparation Example 2. FIG.

4 is an FT-IR spectrum of the allyl ester compound prepared in Preparation Example 2. FIG.

5 is a 400 MHz ¹ H-NMR spectrum of the allyl ester compound prepared in Preparation Example 3. FIG.

6 is an FT-IR spectrum of the allyl ester compound prepared in Preparation Example 3. FIG.

The beginning of a bill

An object of the present invention is to provide a plastic lens material having a good balance between heat resistance, impact resistance and refractive index, a plastic lens composition having a viscosity suitable for the application of spectacle lenses and other optical lenses, and having a high refractive index and a low specific gravity of the cured product. A plastic lens obtained by curing, and a method for producing a plastic lens.

The present inventors have made considerable efforts to solve the above problems, and as a result, the (meth) allyl ester compound having an organic moiety derived from a dicarboxylic acid having a specific structure and an organic moiety derived from a polyhydric alcohol having a specific structure has been modified. When used as a lens material, the composition containing the plastic lens material has a viscosity suitable for the application of spectacle lenses and other optical lenses, has a refractive index of at least medium (refractive index np> 1.54), low specific gravity, and impact resistance. The present invention has been completed by discovering that a composition for plastic lenses having a good balance of performance and heat resistance can be provided.

More specifically, the present invention (I) comprises a plastic lens material comprising at least one or more of the groups represented by the following general formula (1) as a terminal group, and comprising a group represented by the following general formula (2) as a repeating unit. to provide:

In formula, R <^1> represents an allyl group or a metaallyl group each independently, and A <^1> is derived from bivalent carboxylic acid or dicarboxylic anhydride which has an alicyclic structure and / or an aromatic ring structure as each independent organic residue. One or more organic residues;

Wherein A ² each represents an independent organic residue and represents one or more organic residues derived from a divalent carboxylic acid or dicarboxylic anhydride having an alicyclic structure and / or an aromatic ring structure, and each X represents an independent organic residue. A residue represents one or more organic residues derived from a polyhydric alcohol having an ether bond in its molecule, and X has a group represented by the general formula (1) as a terminal group and a group represented by the general formula (2) as a repeating unit. It is conditional to have branching structure further.

This invention (II) provides the composition for plastic lenses containing the material for plastic lenses which concerns on this invention (I), and the following component ((beta)):

Ingredient (β)

At least one compound selected from compounds represented by the following general formula (3):

In the formula, R ² and R ³ each independently represent an allyl group or a metaallyl group, and A ³ is an organic residue derived from a divalent carboxylic acid or dicarboxylic anhydride having an alicyclic structure and / or an aromatic ring structure. Indicates.

This invention (III) provides the composition for plastic lenses containing the material for plastic lenses which concerns on this invention (I), the following component ((beta)) and the following component ((gamma)):

Ingredient (β)

At least one compound selected from compounds represented by the general formula (3);

Component (γ)

At least one compound selected from compounds represented by the following general formula (4):

Wherein Y represents at least one organic moiety derived from a polyhydric alcohol having 2 to 20 carbon atoms and containing n hydroxyl groups, n is an integer from 2 to 6, and R ⁴ is each independently an allyl group or meta It represents an allyl group, s is an integer of 0-n-1, t is an integer of 1-n, provided s + t = n.

This invention (IV) provides the composition for plastic lenses containing the material for plastic lenses which concerns on this invention (I), following component ((beta)), and following component ((delta)):

Ingredient (β)

At least one compound selected from compounds represented by the general formula (3);

Component (δ)

At least one monofunctional compound.

This invention (V) provides the composition for plastic lenses containing the material for plastic lenses which concerns on this invention (I), the following component ((beta)), the following component ((gamma)), and the following component ((delta)):

Ingredient (β)

At least one compound selected from compounds represented by the general formula (3);

Component (γ)

At least one compound selected from compounds represented by the general formula (4);

Component (δ)

At least one monofunctional compound.

This invention (VI) contains 0.1-10 weight part of at least 1 or more radical polymerization initiator with respect to 100 weight part of all curable components in the composition for plastic lenses in any one of this invention (II)-this invention (V). Provided is a composition for plastic lenses according to any one of the present invention (II) to (V).

As used herein, the term "total curable component" means the total amount of radically polymerizable components contained in the composition for each plastic lens of the present invention (II) to (VI).

The present invention (VII) provides a plastic lens obtained by curing the composition for a plastic lens according to any one of the present invention (II) to (VI).

This invention (VIII) provides the manufacturing method of the plastic lens containing hardening the composition for plastic lenses which concerns on any one of this invention (II)-this invention (VI).

Embodiment of invention

Hereinafter, the present invention will be described in detail.

Hereinafter, the material for plastic lenses of the present invention (I) will be described.

This invention (I) is a plastic lens material which contains at least 1 or more of the group represented by the said General formula (1), and contains the group represented by the said General formula (2) by a repeating unit.

In General formula (1), R <^1> represents an allyl group or a metaallyl group each independently.

In general formula (1), A <^1> represents at least ¹ organic residue derived from the bivalent carboxylic acid or dicarboxylic anhydride which has an alicyclic structure and / or an aromatic ring structure as each independent organic residue.

In formula (2), A ² represents one or more organic residues derived from divalent carboxylic acid or dicarboxylic anhydrides each having an alicyclic structure and / or an aromatic ring structure as independent organic residues.

In addition, in general formula (2), each X represents an independent organic residue and represents one or more organic residues derived from a polyhydric alcohol having an ether bond in its molecule, and X represents a terminal group represented by the above general formula (1). It is condition that it has further the branched structure which has and has group represented by the said General formula (2) as a repeating unit.

In general formula (1), R <^1> represents an allyl group or a metaallyl group each independently. Moreover, in general formula (1), A <^1> is an independent organic residue, and each has an alicyclic structure and / or an aromatic ring structure. At least one organic moiety derived from a divalent carboxylic acid or dicarboxylic anhydride. In formula (2), A ² represents one or more organic residues derived from divalent carboxylic acid or dicarboxylic anhydrides each having an alicyclic structure and / or an aromatic ring structure as independent organic residues.

As used herein, the expression "R ¹ each independently represents an allyl group or a metaallyl group" indicates that all of the moieties represented by R ¹ in the terminal group represented by General Formula (1) in the plastic lens material of the present invention are allyl groups or It may be a metaallyl group or part may be an allyl group and the rest may be a metaallyl group.

As used herein, the expression "A ¹ is each independent organic residue" means that k A ¹ are each independently organic residues in the following general formula (5), which is an example of the material for a plastic lens of the present invention (I). do:

Wherein A ¹ represents one or more organic residues each derived from a divalent carboxylic acid or dicarboxylic anhydride having an alicyclic structure and / or an aromatic ring structure as an independent organic residue, and each X represents an independent organic residue. The residue represents one or more organic residues derived from alcohols having ether linkages in the molecule, and k represents an integer of 1 or more.

In general formula (5), for example, k A ¹ is an organic moiety derived from a divalent carboxylic acid or dicarboxylic anhydride having a different alicyclic structure and / or an aromatic ring structure (ie k kind) May be one organic residue derived from a separate divalent carboxylic acid or dicarboxylic anhydride having an alicyclic structure and / or an aromatic ring structure, or all of the same alicyclic structure and / or aromatic ring structure Organic moieties derived from divalent carboxylic acids or dicarboxylic anhydrides having (i.e. organics derived from divalent carboxylic acids or dicarboxylic anhydrides having one type of alicyclic structure and / or aromatic ring structure) K residues). Also, some of the k A ^1s are organic residues derived from divalent carboxylic or dicarboxylic anhydrides having the same alicyclic structure and / or aromatic ring structure, and others are separate kinds of alicyclic structure and / or Organic residues derived from divalent carboxylic acids or dicarboxylic anhydrides having an aromatic ring structure are also possible.

As used herein, the expression "In Formula (2), A ² is each an independent organic moiety" indicates that m A ² are each represented by Formula (6), which is an example of the material for plastic lenses of the present invention (I). It means an independent organic residue:

Wherein one A ¹ and m A ² each represents an independent organic residue and represents one or more organic residues derived from a divalent carboxylic acid or dicarboxylic anhydride having an alicyclic structure and / or an aromatic ring structure. , m each X is an independent organic residue and represents at least one organic residue derived from a polyhydric alcohol having an ether bond in its molecule, and m represents an integer of 1 or more.

In general formula (6), for example, m A ² are all organic residues derived from divalent carboxylic acid or dicarboxylic anhydrides having different alicyclic structures and / or aromatic ring structures (ie m type May be one organic residue derived from a separate divalent carboxylic acid or dicarboxylic anhydride having an alicyclic structure and / or an aromatic ring structure, or all of the same alicyclic structure and / or aromatic ring structure Organic moieties derived from divalent carboxylic acids or dicarboxylic anhydrides having (i.e. organics derived from divalent carboxylic acids or dicarboxylic anhydrides having one type of alicyclic structure and / or aromatic ring structure) M residues). In addition, some of the m A ² are organic residues derived from divalent carboxylic or dicarboxylic anhydrides having the same alicyclic structure and / or aromatic ring structure, and others are separate kinds of alicyclic structures and / or Organic residues derived from divalent carboxylic acids or dicarboxylic anhydrides having an aromatic ring structure are also possible. In addition, the mixed structure may be entirely random or partially repetitive.

As used herein, the expression “A ¹ represents at least one organic moiety derived from a divalent carboxylic acid or dicarboxylic anhydride having an alicyclic structure and / or an aromatic ring structure” is a plastic of the present invention (I) In Formula (5), an example of a lens material, some or all of the k A ^{1 's} include organic residues derived from divalent carboxylic or dicarboxylic anhydrides having an alicyclic structure and / or an aromatic ring structure. I mean.

In general formula (5), for example, k A ¹ is an organic moiety derived from a divalent carboxylic acid or dicarboxylic anhydride having an alicyclic structure and / or an aromatic ring structure (ie, an alicyclic structure) And / or k organic residues derived from a divalent carboxylic acid or dicarboxylic anhydride having an aromatic ring structure), or some of the k A ¹ 's may contain an alicyclic structure and / or an aromatic ring structure. It may have a mixed structure which is an organic moiety derived from a divalent carboxylic acid or dicarboxylic anhydride having the remaining portion and an organic moiety derived from a separate kind of compound.

As used herein, the expression "A ² represents at least one organic moiety derived from a divalent carboxylic acid or dicarboxylic anhydride having an alicyclic structure and / or an aromatic ring structure" is a plastic of the present invention (I) In Formula (6), an example of a lens material, some or all of m A ^{2 's} include organic residues derived from divalent carboxylic or dicarboxylic anhydrides having an alicyclic structure and / or an aromatic ring structure. I mean.

In general formula (6), for example, m A ² organic residues derived from a divalent carboxylic acid or dicarboxylic anhydride having an alicyclic structure and / or an aromatic ring structure (ie, an alicyclic structure) And / or m organic residues derived from a divalent carboxylic acid or dicarboxylic anhydride having an aromatic ring structure), or some of the m A ² 's may contain an alicyclic structure and / or an aromatic ring structure. It may have a mixed structure which is an organic moiety derived from a divalent carboxylic acid or dicarboxylic anhydride having the remaining portion and an organic moiety derived from a separate kind of compound. In addition, the mixed structure may be entirely random or partially repetitive.

Hereinafter, "A ¹ " and "A ² " are collectively represented by "A". Examples of the "organic moiety derived from a divalent carboxylic acid or dicarboxylic anhydride having an alicyclic structure and / or an aromatic ring structure" include organic residues represented by the following structural formulas (7) to (13). However, of course, organic residues are not limited to these embodiments.

Among the above, organic residues represented by Structural Formulas (7) to (9) are preferable in view of maintaining a high refractive index of the compound and ease of obtaining, and include 1,4-phenylene group, 1,3-phenylene group, and 1,2-phenyl. It is more preferable that the group is 1,4-phenylene and 1,3-phenylene.

In addition, organic residues derived from divalent carboxylic acids or dicarboxylic anhydrides other than organic residues derived from divalent carboxylic acids or dicarboxylic acid anhydrides having an alicyclic structure and / or an aromatic ring structure may be incorporated into the molecule. It may contain. This means that another divalent carboxylic acid or dicarboxylic acid anhydride can be used in combination with a divalent carboxylic acid or dicarboxylic anhydride having an alicyclic structure and / or an aromatic ring structure. Specific examples of another divalent carboxylic acid or dicarboxylic acid anhydride may include the following compounds.

Examples include aliphatic dicarboxylic acids and anhydrides thereof, such as succinic acid and its anhydrides, glutaric acid and its anhydrides, adipic acid, malonic acid and its anhydrides, 2-methylsuccinic acid and its anhydrides, maleic acid and their anhydrides And fumaric acid. Needless to say, however, another divalent carboxylic acid or dicarboxylic acid is not limited to these embodiments.

As used herein, the expression "X is each independent organic moiety" means that the v Xs contained in the repeating unit in the following general formula (14), which is one example of the material for the plastic lens of the present invention, are each independently organic moieties. do:

Wherein X represents at least one organic residue derived from a polyhydric alcohol having an ether bond as an independent organic residue each, v represents an integer of 0 or 1 or more, r represents an integer of 0 or 1 or more, and A is Each independently represents at least one organic moiety derived from a divalent carboxylic acid or dicarboxylic anhydride having an alicyclic structure and / or an aromatic ring structure.

In general formula (14), for example, v X are all organic residues derived from polyhydric alcohols having different kinds of ether bonds (i.e., organics derived from separate polyhydric alcohols having v kinds of ether bonds). May be one residue, or may be an organic residue derived from the same compound (ie, there are v organic residues derived from a polyhydric alcohol having one kind of ether bond), or a portion of v X May have a mixed structure wherein the organic moiety is derived from the same compound and the remainder is an organic moiety derived from a separate class of compounds. In addition, the mixed structure may be entirely random or partially repetitive.

As used herein, the expression "one or more organic moieties derived from a polyhydric alcohol having an ether bond" is a part of v X contained in the repeating unit in general formula (14), which is an example of the material for a plastic lens of the present invention or It is meant that all include organic moieties derived from polyhydric alcohols having ether bonds.

In general formula (14), for example, m A ² are all organic residues derived from divalent carboxylic or dicarboxylic anhydrides having an alicyclic structure and / or an aromatic ring structure (ie, an alicyclic structure). And / or m organic residues derived from a divalent carboxylic acid or dicarboxylic anhydride having an aromatic ring structure), or some of the m A ² 's may contain an alicyclic structure and / or an aromatic ring structure. It may have a mixed structure which is an organic moiety derived from a divalent carboxylic acid or dicarboxylic anhydride having the remaining portion and an organic moiety derived from a separate kind of compound. In addition, the mixed structure may be entirely random or partially repetitive.

In general formula (14), for example, v X may be all organic residues derived from a polyhydric alcohol having an ether bond (ie, v organic residues derived from a polyhydric alcohol having an ether bond) or Or, some of the v X's may have a mixed structure wherein the organic moiety is derived from a polyhydric alcohol having an ether bond and the other is an organic moiety derived from a separate class of compounds. In addition, the mixed structure may be entirely random or partially repetitive.

By the ester bond, X may have a branched structure containing general formula (1) as an end group and including general formula (2) as a repeating unit. More specifically, for example, when an organic moiety derived from 1,1,1-tris (2-hydroxyethoxymethyl) propane is present as an example of a trihydric alcohol having an X-Le bond, the present invention ( The material for plastic lenses of I) has a partial structure represented by the following general formula (15):

Of course, A each independently represents at least one organic moiety derived from a divalent carboxylic acid or dicarboxylic anhydride having an alicyclic structure and / or an aromatic ring structure.

In formula (2), X represents at least one organic residue derived from a polyhydric alcohol having an ether bond. Preferred examples of the "polyhydric alcohol having an ether bond" as used herein include the (heavy) condensates of the following alkane polyols. However, polyhydric alcohols having ether bonds are not limited to these embodiments.

Examples of dihydric alcohols include diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, ethylene glycol-propylene glycol (heavy) condensates, and alcohols having the following structural formula (16): Can be mentioned:

In formula, a represents the integer of 2 or more.

Examples of trihydric alcohols include alkylene oxide (mid) adducts of alkantriols, such as alkylene oxide (mid) adducts of trimethylolpropane (eg, ethylene oxide (mid) adducts of trimethylolpropane, trimethylolpropane Propylene oxide adducts of ethylene, ethylene oxide propylene oxide adducts of trimethylolpropane and alkylene oxide adducts of glycerin (e.g., ethylene oxide adducts of glycerin, propylene oxide of glycerin ) An adduct and ethylene oxide propylene oxide heavy adduct of glycerin).

Examples of tetravalent or higher polyhydric alcohols include alkylene oxide adducts of pentaerythritol, such as ethylene oxide (heavy) adducts of pentaerythritol, propylene oxide (heavy) adducts of pentaerythritol and ethylene oxide of pentaerythritol -Propylene oxide polyaddition, and alkylene oxide adduct of dipentaerythritol, such as ethylene oxide (heavy) adduct of dipentaerythritol, propylene oxide (heavy) adduct of dipentaerythritol and dipentaerythritol Ethylene oxide-propylene oxide heavy adducts.

Of these, preferred are polyethylene glycols such as diethylene glycol and triethylene glycol, polypropylene glycol such as dipropylene glycol and tripropylene glycol, ethylene glycol-propylene glycol (medium) condensates, and polyalkylene glycols such as general formula (16) And diethylene glycol and dipropylene glycol, and most preferably diethylene glycol.

Preferred of "organic residue derived from divalent carboxylic acid or dicarboxylic acid having alicyclic structure and / or aromatic ring structure" contained in one molecule and "organic residue derived from polyhydric alcohol having ether bond" The combination may include a combination of 1,3-phenylene and / or 1,4-phenylene and organic residues derived from diethylene glycol and / or dipropylene glycol, and a more preferable combination is 1,3-phenylene And / or combinations of organic residues derived from 1,4-phenylene and diethylene glycol, and most preferred combinations are 1,3-phenylene and combinations of organic residues derived from 1,4-phenylene and diethylene glycol to be.

Organic residues derived from polyhydric alcohols with ether bonds and organic residues derived from polyhydric alcohols without ether bonds can be included in the same molecule. That is, the polyhydric alcohol which does not have an ether bond can be used with the polyhydric alcohol which has an ether bond. As a specific example of the polyhydric alcohol which does not have an ether bond used in combination with the polyhydric alcohol which has an ether bond, the following chemicals etc. are mentioned.

Specific examples of the dihydric saturated alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, hexamethylene glycol, 1,4-cyclohexanedimethanol , p-xylene glycol, m-xylene glycol, o-xylene glycol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,1-cyclohexanedimethanol and 2-methyl- 1,1-cyclohexane dimethanol, etc. are mentioned. Specific examples of the trivalent or higher polyhydric saturated alcohol include glycerin, trimethylolpropane, trimethylol ethane, pentaerythritol, dipentaerythritol, sorbitol and the like. However, polyhydric alcohols having no ether bonds are not limited to these embodiments.

The number of repetitions of the group represented by the general formula (2), which is a repeating unit of the material of the present invention (I), is not particularly limited. You can mix materials with multiple repetitions. In addition, a material having a repetition number of 0 and a material having a positive repetition number of 1 or more may be used together, and such a combination is preferable to some extent. However, in order to achieve the object of the present invention, it is not preferable to use only a material having a repetition number of zero.

In the present invention, the material having a repetition frequency of 0 is defined not to be included in the plastic material of the present invention (I).

More specifically, when diallyl phthalate is used as a raw material for producing the plastic lens material of the present invention (I) and diallyl terephthalate remains, the remaining diallyl terephthalate is added to the plastic lens material of the present invention (I). It is not included but is included in component (β) of the present invention (II) to (VII).

As for the repetition number of the group represented by General formula (2) which is a repeating unit of the material of this invention (I), the integer of 1-50 is preferable normally. When a plastic lens material containing only a compound having a repetition number of more than 50 is used as the plastic lens composition, the concentration of the allyl group becomes low, which may cause an undesirable result of heat resistance deterioration. Preferably, the number of repetitions in the plastic lens material is an integer of 1 to 50, more preferably an integer of 1 to 30, even more preferably an integer of 1 to 10.

The plastic lens material of the present invention (I) may be used alone as a composition for a plastic lens, but when used as a composition for a plastic lens, it is used in combination with other curable compounds to reduce the viscosity or maintain a balance of other physical properties. A plastic lens material can be used and it is more preferred.

In the material of this invention (I), although the compound represented by General formula (3) may remain as a raw material according to the manufacturing conditions, the plastic lens material can be used even if it does.

The method for producing the plastic lens material of the present invention (I) is not limited, but in general, di (meth) allyl esters and ether bonds containing at least one compound represented by the general formula (3) in the presence of a catalyst The transesterification reaction of at least one or more polyhydric alcohols containing polyhydric alcohols can be carried out to obtain the plastic lens material of the invention (I). If necessary, steps such as purification may be provided.

The term "di (meth) allyl ester" as used herein means diallyl ester and / or dimethallyl ester and / or allylmethallyl ester.

The catalyst used in the transesterification process is generally not particularly limited as long as it can be used in the transesterification reaction. Particular preference is given to metal oxide compounds, specific examples of which are tetraisopropyl titanate, tetra-n-butyl titanate, di-n-butyltin oxide, di-n-octyltin oxide, hafnium acetylacetonate and zirconium acetyl Acetonate, and the like. However, the catalyst is not limited thereto. Of these, di-n-butyltin oxide and di-n-octyltin oxide are preferred.

Although the reaction temperature in the said process is not specifically limited, 100-230 degreeC is preferable and 120-200 degreeC is more preferable. In particular, when a solvent is used, the reaction temperature may be limited due to the boiling point of the solvent.

The solvent is not usually used in the above step, but a solvent may be used if necessary. The solvent that can be used is not particularly limited as long as it does not inhibit the transesterification reaction. Specific examples thereof include benzene, toluene, xylene, cyclohexane, and the like, but the solvent is not limited thereto. Among these, benzene and toluene are preferable. However, as described above, the process can be carried out without using a solvent.

Di (meth) containing at least one compound represented by the general formula (3) to at least one polyhydric alcohol containing a polyhydric alcohol having an ether bond in the preparation of the plastic lens material of the present invention (I) The ratio of allyl esters varies depending on the valence number of the polyhydric alcohol used.

However, the ratio of the total number of allyl groups and metaallyl groups contained in the total amount of di (meth) allyl esters used in the reaction to the total number of hydroxyl groups contained in the total amount of polyhydric alcohols used in the reaction is preferably 5 : 1 to 1.5: 1, more preferably 4: 1 to 1.8: 1, still more preferably 3.5: 1 to 2: 1.

Hereinafter, the composition for plastic lenses of this invention (II) is demonstrated.

This invention (II) is a composition for plastic lenses containing the material for plastic lenses concerning this invention (I), and the following component ((beta)).

Ingredient (β)

At least one compound selected from compounds represented by formula (3):

In the composition for plastic lenses of the present invention (II), the plastic lens material described in the present invention (1) is used for at least one purpose selected from among the maintenance and improvement of the refractive index, the maintenance and improvement of the impact resistance, and the improvement of the moldability of the composition. do.

Ingredient (β)

The component ((beta)) of the composition for plastic lenses of this invention (II) is demonstrated below.

In the composition for plastic lenses of the present invention (II), the component (β) is used for one or more purposes selected from among the improvement of heat resistance, the maintenance and improvement of the refractive index, and the decrease of the viscosity of the composition.

Component (β) of the composition for plastic lenses is at least one compound selected from compounds represented by the general formula (3):

In the general formula (3), R ² and R ³ each independently represent an allyl group or a metaallyl group.

More specifically, both R ² and R ³ may be an allyl group or both a metaallyl group, or one may be an allyl group and the other may be a metaallyl group. However, at least one of R ² and R ³ is preferably an allyl group.

A ³ represents an organic residue derived from a divalent carboxylic acid or dicarboxylic acid anhydride having an alicyclic structure and / or an aromatic ring structure.

Examples of “organic residues derived from divalent carboxylic acids or dicarboxylic acid anhydrides having an alicyclic structure and / or an aromatic ring structure” as used herein include organic residues represented by the formulas (7) to (13). Can:

However, needless to say, organic residues are not limited to these. Among these, organic residues represented by Structural Formulas (7) to (9) are preferable, 1,4-phenylene group, 1,3-phenylene group and 1,2-phenylene group are more preferable, and 1,4-phenylene group And 1,3-phenylene group are even more preferable.

Component (β) generally exists as a remaining raw material component in producing the plastic lens material of the present invention (I), but may be added after the production of the plastic lens material of the present invention (I).

The compounding quantity of the plastic lens material of this invention (I) in the composition for plastic lenses of this invention (II) becomes like this. Preferably it is 10-90 weight% with respect to the total curable component in the plastic lens composition of this invention (II), More preferably, it is 15 to 85 weight%, More preferably, it is 20 to 80 weight%.

When the compounding quantity of the plastic lens material of this invention (I) in the composition for plastic lenses of this invention (II) is less than 10 weight% with respect to the total curable component in the plastic lens composition of this invention (II), this invention (I The properties of the plastic lens material, i.e., properties such as improvement of impact resistance or easy moldability are not reflected in the properties of the cured product, which is not preferable. On the other hand, when the compounding quantity of the plastic lens material of this invention (I) in the composition for plastic lenses of this invention (II) exceeds 90 weight% with respect to the total curable component in the composition for plastic lenses of this invention (II), There is a possibility that the viscosity of the composition becomes very high and the heat resistance may deteriorate and be disadvantageous.

The compounding amount of the component (β) in the composition for plastic lenses of the present invention (II) is preferably 10 to 90% by weight, more preferably 15 to 15% based on the total curable components in the composition for plastic lenses of the present invention (II). 85% by weight, even more preferably 20 to 80% by weight.

When the compounding amount of the component (β) in the composition for plastic lenses of the present invention (II) is less than 10% by weight relative to the total curable components in the composition for plastic lenses of the present invention (II), the viscosity of the composition may be very high and heat resistance This may deteriorate and be disadvantaged. On the other hand, when the compounding quantity of the component ((beta)) in the composition for plastic lenses of this invention (II) exceeds 90 weight% with respect to the total curable component in the composition for plastic lenses of this invention (II), The properties of the material for the plastic lens, that is, the properties such as the improvement of impact resistance or the development of easy moldability are not reflected in the properties of the cured product, which is not preferable.

Curable components other than the plastic lens material of this invention (I) and component ((beta)) can be added to the composition for plastic lenses of this invention (II). As these specific examples, Component (γ) mentioned later; Component (δ) described later; Di (meth) allyl esters of aliphatic polyhydric carboxylic acids such as di (meth) allyl maleate, di (meth) allyl succinate, di (meth) allyl itaconate, di (meth) allyl malonate, di (meth) Allyl glutarate, di (meth) allyl 2-methyl succinate and di (meth) allyl adipate; Tri (meth) allyl esters such as tri (meth) allyl 1,2,4-benzenetricarboxylate, tri (meth) allyl 1,3,5-benzenetricarboxylate and tri (meth) allyl 1,2, 3-propanetricarboxylate; Tetra (meth) allyl esters such as tetra (meth) allyl 1,2,4,5-benzenetetracarboxylate and tetra (meth) allyl 1,2,3,4-butanetetracarboxylate; And allyl ester oligomers which do not belong to the category of the plastic lens material of the present invention (I). However, of course, the curable components that can be added are not limited to these embodiments.

Hereinafter, the composition for plastic lenses of this invention (III) is demonstrated.

The present invention (III) is a plastic lens composition comprising the material for a plastic lens according to the present invention (I), the following component (β) and the following component (γ):

Ingredient (β)

At least one compound selected from compounds represented by formula (3);

Component (γ)

One or more compounds selected from compounds represented by formula (4).

In the plastic lens composition of the present invention (III), at least one object selected from the case of the plastic lens composition of the present invention (II) is selected from among the maintenance and improvement of the refractive index, the maintenance and improvement of the impact resistance, and the improvement of the moldability of the composition. The plastic lens material described in the present invention (I) is used for this purpose.

In the composition for plastic lenses of the present invention (III), similar to the composition for the plastic lens of the present invention (II), component (β) is one selected from the following: improvement of heat resistance, maintenance and improvement of refractive index, and reduction of viscosity of the composition It is used for the above purpose.

Component (γ)

The component (γ) of the composition for plastic lenses of this invention (III) is demonstrated below.

In the composition for plastic lenses of the present invention (III), component (γ) is used for maintaining and improving impact resistance or for reducing the viscosity of the composition.

The component ((gamma)) of the composition for plastic lenses of this invention (III), ie, the compound represented by General formula (4), can be manufactured by a well-known method. Examples of the method include a method of performing a transesterification reaction between diallyl carbonate and a polyhydric alcohol in the presence of a catalyst (see Japanese Patent Publication No. 3-66327 (JP-B-3-66327)), allyl alcohol, A method of reacting phosgene and polyhydric alcohols with dehydrochloric acid (see US Pat. Nos. 2,370,565 and 2,592,058). However, the method is not limited to this.

In formula (4), Y has 2 to 6 hydroxyl groups and 2 to 20 carbon atoms, and represents an organic residue derived from alcohol. Examples of "a polyhydric alcohol having 2 to 6 hydroxyl groups and 2 to 20 carbon atoms" include the following compounds.

Specific examples of the dihydric alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-propanediol, 1,3-butanediol, neopentyl glycol, hexamethylene glycol, 1,3-cyclohexane dimethanol , Diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, ethylenel glycol-propylene glycol (heavy) condensate, and alcohol represented by the general formula (16).

Diols having carbonate bonds or ester bonds, such as di-2-hydroxyethyl carbonate and 2-hydroxyethyl β-hydroxypropionate, can also be used.

Specific examples of the trihydric alcohols include alkylene oxide adducts of alkantriols, such as alkylene oxide adducts of trimethylolpropane (eg, ethylene oxide adducts of trimethylolpropane, trimethylolpropane). Propylene oxide adducts, ethylene oxide propylene oxide adducts of trimethylolpropane and alkylene oxide adducts of glycerin (e.g., ethylene oxide adducts of glycerin, propylene oxide of glycerin) Addition product, ethylene oxide propylene oxide polyaddition product of glycerin) is mentioned.

Examples of tetravalent or higher polyhydric alcohols include alkylene oxide adducts of pentaerythritol, such as ethylene oxide (heavy) adducts of pentaerythritol, propylene oxide (heavy) adducts of pentaerythritol and ethylene oxide of pentaerythritol -Propylene oxide polyaddition, and alkylene oxide adduct of dipentaerythritol, such as ethylene oxide (heavy) adduct of dipentaerythritol, propylene oxide (heavy) adduct of dipentaerythritol and dipentaerythritol And ethylene oxide-propylene oxide polyaddition products. However, of course, polyhydric alcohols having 2 to 6 hydroxyl groups and 2 to 20 carbon atoms are not limited to these embodiments.

Among these polyhydric alcohols, preferred are divalent glycols. Preferred examples of divalent glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, di-2-hydroxyethyl carbonate, and the like. Among these, more preferable are di-2-hydroxyethyl carbonate and diethylene glycol, and diethylene glycol is most preferable. The poly (allyl carbonate) obtained when diethylene glycol is used as the polyhydric alcohol is diethylene glycol bis (allyl carbonate), and specific examples thereof include CR-39 (registered trademark) (trade name, manufactured by PPG).

In general formula (4), R <^4> represents an allyl group or a metaallyl group. Where R ⁴ is independent of each other. For example, when n = 3, the compound represented by general formula (3) is represented by a mixture of compounds represented by the following general formulas (17) to (19):

Here, for example, out of three R ⁴ of the general formula (17), three are allyl groups, three are allyl groups, two are allyl groups and one is metaallyl group, or one is allyl group Two may be a metaallyl group. In addition, two out of two R ⁴ in general formula (18) may be an allyl group, two may be a metaallyl group, or one may be an allyl group and one may be a metaallyl group. R ⁴ in general formula (19) may be an allyl group or a metaallyl group.

In formula (4), Y is an organic residue derived from a polyhydric alcohol having 2 to 6 hydroxyl groups and 2 to 20 carbon atoms. When a compound having an organic moiety derived from a polyhydric alcohol having more than six hydroxyl groups of Y is used in the composition for plastic lenses, the impact resistance of the plastic lens obtained by curing the composition is poor, which is undesirable. In addition, when a compound having an organic residue derived from an alcohol having less than two hydroxyl groups of Y (ie one) is used in a composition for plastic lenses, the heat resistance and solvent resistance of the plastic lens obtained by curing the composition are extremely It lowers and becomes disadvantageous.

Assuming that the number of hydroxyl groups of Y is n, s is an integer of 0 to n-1, t is an integer of 1 to n, and s + t = n. t is an integer greater than or equal to 1 is sufficient. However, in view of the physical properties of the final plastic lens, it is preferable to replace the carbonate group with as many hydroxyl groups as possible. Although t depends on the ratio of the compound which is less than n, it is preferable that the compound whose t = n in the compound represented by General formula (4) is 80 weight%, More preferably, it is 90 weight%. When the compound of t = n is less than 80% by weight, the releasability from the glass mold after molding may decrease.

The compounding quantity of the plastic lens material of this invention (I) becomes like this. Preferably it is 10-80 weight%, More preferably, it is 12-70 weight% with respect to the total curable component contained in the composition for plastic lenses of this invention (III). More preferably, it is 15 to 60 weight%. When the compounding quantity of the plastic lens material of this invention (I) is less than 10 weight% with respect to the total curable component contained in the composition for plastic lenses of this invention (III), the characteristic of the plastic lens material of this invention (I), That is, physical properties such as maintaining the refractive index, improving the impact resistance, or easily forming moldability are not reflected in the physical properties of the cured product, which is not preferable. On the other hand, when the compounding quantity of the plastic lens material of this invention (I) exceeds 80 weight% with respect to the total curable component in the composition for plastic lenses of this invention (III), there exists a possibility that the viscosity of a composition may become very high and heat resistance It may deteriorate and be disadvantaged.

The blending amount of the component (β) is preferably 10 to 80% by weight, more preferably 10 to 60% by weight, even more preferably based on the total curable component contained in the composition for plastic lenses of the present invention (III). 13 to 50% by weight. When the compounding amount of the component (β) is less than 10% by weight relative to the total curable component contained in the composition for plastic lenses of the present invention (III), the possibility of causing an increase in the viscosity of the composition, deterioration of heat resistance or a decrease in the refractive index of the cured product This is very high and this is not desirable. On the other hand, when the blending amount of the component (β) exceeds 80% by weight relative to the total curable component in the composition for plastic lenses of the present invention (III), the impact resistance is very likely to deteriorate, which is not preferable.

The compounding amount of component (γ) is preferably 10 to 80% by weight, more preferably 12 to 50% by weight, even more preferably 15 to the total curable component contained in the composition for plastic lenses of the present invention (III). To 40% by weight. When the amount of the component (γ) is less than 10% by weight relative to the total curable component contained in the composition for plastic lenses of the present invention (III), there is a possibility that it may cause an increase in the viscosity of the composition and a decrease in the impact resistance of the cured product. have. On the other hand, when the blending amount of the component (γ) exceeds 80% by weight relative to the total curable component in the composition for plastic lenses of the present invention (III), the refractive index of the cured product is decreased, which is undesirable.

The curable component which does not belong to the plastic lens material of this invention (I), a component ((beta)), and a component ((gamma)) can be added to the composition for plastic lenses of this invention (III). As these specific examples, Component (δ) mentioned later; Di (meth) allyl esters of aliphatic polyhydric carboxylic acids such as di (meth) allyl maleate, di (meth) allyl succinate, di (meth) allyl itaconate, di (meth) allyl malonate, di (meth) Allyl glutarate, di (meth) allyl 2-methylsuccinate and di (meth) allyl adipate; Tri (meth) allyl esters such as tri (meth) allyl 1,2,4-benzenetricarboxylate, tri (meth) allyl 1,3,5-benzenetricarboxylate and tri (meth) allyl 1,2, 3-propanetricarboxylate; Tetra (meth) allyl esters such as tetra (meth) allyl 1,2,4,5-benzenetetracarboxylate and tetra (meth) allyl 1,2,3,4-butanetetracarboxylate; And allyl ester oligomers which do not belong to the category of the plastic lens material of the present invention (I). However, of course, the curable components that can be added are not limited to these embodiments.

The present invention (IV) is a plastic lens composition comprising the material for a plastic lens according to the present invention (I), the following component (β) and the following component (δ):

Ingredient (β)

At least one compound selected from compounds represented by formula (3);

Component (δ)

At least one monofunctional compound.

The composition for plastic lenses of the present invention (IV) is selected from the maintenance and improvement of the refractive index, the maintenance and improvement of the impact resistance, and the improvement of the moldability of the composition, similarly to the case of the plastic lens composition of the present invention (II) or (III). The material for plastic lenses described in the present invention (I) is used for one or more purposes.

In the composition for plastic lenses of the present invention (IV), similar to the case of the composition for plastic lenses of the present invention (II) or (III), the component (β) exhibits improved heat resistance, maintenance and improvement of refractive index, and viscosity of the composition. Used for one or more purposes selected from among the reductions.

Component (δ)

The component (δ) of the composition for plastic lenses of this invention (IV) is demonstrated below.

Component (δ) of the composition for plastic lenses of the present invention (IV) is at least one monofunctional compound.

The term "monofunctional compound" as used herein means a compound having one radically polymerizable functional group in one molecule.

However, in the present invention, the monofunctional compound belonging to component (α) and component (γ) is defined as not included in component (δ). More specifically, the compound represented by the formula (19) is not included in component (δ) but in component (γ).

In the composition for plastic lenses of the present invention (IV), component (δ) is used for improving the impact resistance or for reducing the viscosity of the composition.

Specific examples of the component (δ) in the composition for plastic lenses of the present invention (IV) include the following compounds.

These examples include (meth) allyl benzoate, (meth) allyl p-phenylbenzoate, (meth) allyl m-phenylbenzoate, (meth) allyl o-phenylbenzoate, (meth) acryloyloxyethyl-4 -Phenylbenzoate, (meth) acryloyloxyethyl-3-phenylbenzoate, (meth) acryloyloxyethyl-2-phenylbenzoate, diphenyl maleate, dibenzyl maleate, dibutyl maleate, Dimethoxyethyl maleate, diphenyl fumarate, dibenzyl fumarate, (meth) allyl α-naphthoate, (meth) allyl β-naphthoate, (meth) acryloyloxyethyl-α-naphthalene carboxyl (Meth) acryloyloxyethyl-β-naphthalene carboxylate, (meth) allyl o-chlorobenzoate, (meth) allyl m-chlorobenzoate, (meth) allyl p-chlorobenzoate, (meth) ) Allyl 2,6-dichlorobenzoate, (meth) allyl 2,4-dichlorobenzoate, (meth) allyl 2,4,6-t Chlorobenzoate, (meth) allyl o-bromobenzoate, (meth) allyl m-bromobenzoate, (meth) allyl p-bromobenzoate, (meth) allyl 2,6-dibromobenzoate , (Meth) allyl 2,4-dibromobenzoate, (meth) allyl 2,4,6-tribromobenzoate, methyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth ) Acrylate, phenyl (meth) acrylate, vinyl acetate, vinyl benzoate, and the like. However, it goes without saying that component (δ) is not limited only to these embodiments.

The compounding quantity of the plastic lens material of this invention (I) becomes like this. Preferably it is 10-80 weight%, More preferably, it is 12-70 weight% with respect to the total curable component contained in the composition for plastic lenses of this invention (IV). More preferably, it is 15-65 weight%. When the compounding quantity of the plastic lens material of this invention (I) is less than 10 weight% with respect to the total curable component contained in the composition for plastic lenses of this invention (IV), the characteristic of the plastic lens material of this invention (I), That is, physical properties such as maintaining the refractive index, improving the impact resistance, or easily forming moldability are not reflected in the physical properties of the cured product, which is not preferable. On the other hand, when the compounding quantity of the plastic lens material of this invention (I) exceeds 80 weight% with respect to the total curable component in the composition for plastic lenses of this invention (IV), there exists a possibility that the viscosity of a composition may become very high and this is preferable. Not.

The blending amount of the component (β) is preferably 10 to 80% by weight, more preferably 10 to 65% by weight, even more preferably based on the total curable component contained in the composition for plastic lenses of the present invention (IV). 13 to 60% by weight. When the blending amount of the component (β) is less than 10% by weight relative to the total curable component contained in the composition for plastic lenses of the present invention (IV), the possibility of causing an increase in the viscosity of the composition, deterioration of heat resistance or a decrease in the refractive index of the cured product This is very high and this is not desirable. On the other hand, when the blending amount of the component (β) exceeds 80 wt% with respect to the total curable component in the composition for plastic lenses of the present invention (IV), it is very likely that the impact resistance is deteriorated, which is not preferable.

The blending amount of the component (δ) is preferably 1 to 20% by weight, more preferably 1 to 15% by weight, even more preferably 1 to the total curable component contained in the composition for plastic lenses of the present invention (IV). To 10% by weight. When the compounding quantity of component (δ) is less than 1 weight% with respect to the total curable component contained in the composition for plastic lenses of this invention (IV), the addition effect of component (δ) is hardly reflected in hardened | cured material. On the other hand, when the compounding quantity of component (δ) exceeds 20 weight% with respect to the total curable component in the composition for plastic lenses of this invention (IV), the heat resistance of hardened | cured material may deteriorate, which is undesirable.

The curable component which does not belong to the plastic lens material of this invention (I), a component ((beta)), and a component (delta) can be added to the composition for plastic lenses of this invention (IV). Specific examples thereof include component (γ); Di (meth) allyl esters of aliphatic polyhydric carboxylic acids such as di (meth) allyl maleate, di (meth) allyl succinate, di (meth) allyl itaconate, di (meth) allyl malonate, di (meth) Allyl glutarate, di (meth) allyl 2-methylsuccinate and di (meth) allyl adipate; Tri (meth) allyl esters such as tri (meth) allyl 1,2,4-benzenetricarboxylate, tri (meth) allyl 1,3,5-benzenetricarboxylate and tri (meth) allyl 1,2, 3-propanetricarboxylate; Tetra (meth) allyl esters such as tetra (meth) allyl 1,2,4,5-benzenetetracarboxylate and tetra (meth) allyl 1,2,3,4-butanetetracarboxylate; And allyl ester oligomers which do not belong to the category of the plastic lens material of the present invention (I). However, of course, the curable components that can be added are not limited to these embodiments.

This invention (V) is a composition for plastic lenses containing the material for plastic lenses which concerns on this invention (I), the following component ((beta)), the following component ((gamma)), and the following component ((delta)):

Ingredient (β)

At least one compound selected from compounds represented by formula (3);

Component (γ)

At least one compound selected from compounds represented by formula (4);

Component (δ)

At least one monofunctional compound.

In the composition for plastic lenses of the present invention (V), similar to the case of the composition for plastic lenses of the present invention (II) to (IV), the retention and improvement of the refractive index, the maintenance and improvement of the impact resistance, and the formability of the composition are improved. The plastic lens material described in the present invention (I) is used for at least one object selected from among them.

In the composition for plastic lenses of the present invention (V), similar to the case of the plastic lens compositions of the present invention (II) to (IV), the component (β) improves heat resistance, maintains and improves the refractive index, and It is used for one or more purposes selected from among the decreases in viscosity.

In the composition for plastic lenses of the present invention (V), similar to the case of the composition for plastic lenses of the present invention (III), component (γ) is used for maintaining and improving impact resistance or reducing the viscosity of the composition.

In the composition for plastic lenses of the present invention (V), similar to the case of the composition for plastic lenses of the present invention (IV), component (δ) is used for improving impact resistance or decreasing the viscosity of the composition.

The compounding quantity of the plastic lens material of this invention (I) becomes like this. Preferably it is 10-80 weight%, More preferably, it is 11-70 weight% with respect to the total curable component contained in the composition for plastic lenses of this invention (V). More preferably, it is 12 to 60 weight%. When the compounding quantity of the plastic lens material of this invention (I) is less than 10 weight% with respect to the total curable component contained in the composition for plastic lenses of this invention (V), the characteristic of the plastic lens material of this invention (I), That is, physical properties such as maintaining the refractive index, improving the impact resistance, or easily forming moldability are not reflected in the physical properties of the cured product, which is not preferable. On the other hand, when the compounding quantity of the plastic lens material of this invention (I) exceeds 80 weight% with respect to the total curable component in the composition for plastic lenses of this invention (V), there exists a possibility that the viscosity of a composition may become very high and this is preferable. Not.

The blending amount of the component (β) is preferably 8 to 80% by weight, more preferably 10 to 60% by weight, even more preferably based on the total curable component contained in the composition for plastic lenses of the present invention (V). 12 to 50 weight percent. When the amount of the component (β) is less than 10% by weight relative to the total curable components contained in the composition for plastic lenses of the present invention (V), the possibility of causing an increase in the viscosity of the composition, deterioration of heat resistance or a decrease in the refractive index of the cured product This is very high and this is not desirable. On the other hand, when the blending amount of the component (β) exceeds 80% by weight relative to the total curable component in the composition for plastic lenses of the present invention (V), there is a high possibility that the impact resistance is deteriorated, which is not preferable.

The compounding amount of component (γ) is preferably 8 to 80% by weight, more preferably 10 to 50% by weight, still more preferably 12 to the total curable component contained in the composition for plastic lenses of the present invention (V). To 40% by weight. When the amount of the component (γ) is less than 10% by weight relative to the total curable components contained in the composition for plastic lenses of the present invention (V), there is a possibility that it may cause an increase in the viscosity of the composition or a decrease in the impact resistance of the cured product, which may be disadvantageous. have. On the other hand, when the blending amount of the component (γ) exceeds 80% by weight relative to the total curable component in the composition for plastic lenses of the present invention (V), the refractive index of the cured product is decreased, which is undesirable.

The blending amount of the component (δ) is preferably 1 to 20% by weight, more preferably 1 to 15% by weight, even more preferably 1 to the total curable component contained in the composition for plastic lenses of the present invention (V). To 10% by weight. When the compounding quantity of component (δ) is less than 1 weight% with respect to the total curable component contained in the composition for plastic lenses of this invention (V), the addition effect of component (δ) is hardly reflected in hardened | cured material. On the other hand, when the compounding quantity of component (δ) exceeds 20 weight% with respect to the total curable component in the composition for plastic lenses of this invention (V), the heat resistance of hardened | cured material may deteriorate, which is undesirable.

In the composition for plastic lenses described in any one of the present invention (II) to (V), an ultraviolet absorber or a light stabilizer may be added to improve weather resistance of the plastic lens.

The ultraviolet absorbent or light stabilizer is not particularly limited as long as it can be blended in the composition, but specific examples thereof include the following compounds and the like. However, it is a matter of course that ultraviolet absorbers and light stabilizers are not limited to these specific examples.

As used herein, the term "ultraviolet absorber" refers to a material that absorbs light energy such as sunlight or fluorescent light and converts it into heat energy and the like. As used herein, the term "light stabilizer" means a substance that captures radicals generated due to photooxidation degradation.

Specific examples of the ultraviolet absorbent include compounds having a benzotriazole structural unit shown in the following structural formula.

Examples of the compound having a benzotriazole structural unit include compounds represented by the following structural formulas (20) to (35):

Examples of the benzophenone ultraviolet absorbers include the following structural formulas (36) to (40):

Further, a triazine ultraviolet absorber represented by the following structural formula (41), an oxanilide ultraviolet absorber represented by the following structural formula (42), a cyanoacrylate ultraviolet absorber represented by the following structural formulas (43) and (44), and the following structural formula ( The salicylate type ultraviolet absorber shown by 45) can also be used.

Specific examples of the light stabilizer include hindered amine light stabilizers represented by the following structural formulas (46) to (53), (55) and (57) to (60).

Wherein R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each -H or

Indicates. Except where R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are all hydrogen atoms.

In formula (53), R is an organic moiety represented by formula (54) and n is an integer.

In formula (55), R is an organic moiety represented by formula (56) and n is an integer.

Ultraviolet absorbers and light stabilizers can be used together. The amount of the ultraviolet absorber or light stabilizer to be used is preferably 0.001 to 3% by weight, more preferably 0.01 to 1.5% by weight based on the total curable component. When the added amount is less than 0.001% by weight, the deterioration prevention effect is not sufficiently expressed, and when it is used in excess of 3% by weight, it is not preferable from the viewpoint of coloring or economical at the time of curing.

To the composition for plastic lenses of the present invention (II) to (V), additives such as colorants (such as dyes and pigments), mold-releasing agents, and antioxidants are generally added to improve the performance of the plastic lens. Can be used.

Examples of colorants include organic pigments such as anthraquinones, azo-based, carbonium-based, quinoline-based, quinoneimine-based, indigoid-based and phthalocyanine-based; Organic dyes such as azo dyes and sulfur dyes; And inorganic pigments such as titanium yellow, iron oxide yellow, zinc sulfur, chrome orange, molybdem red, cobalt violet, cobalt blue, cobalt green, chromium oxide, titanium oxide, zinc sulfide and carbon black. Needless to say, however, the colorants are not limited to these embodiments.

Examples of the mold release agent include stearic acid, butyl stearate, zinc stearate, stearic acid amide, fluorine-containing compounds, silicone compounds and the like. However, of course, the mold release agent is not limited to these embodiments.

Examples of antioxidants that can be used generally include phenolic antioxidants, phosphite antioxidants and thioether antioxidants.

Specific examples of the phenolic antioxidant include compounds of the following structural formulas (61) to (70).

Specific examples of the phosphite-based antioxidant include compounds of the following structural formulas (71) to (82).

Specific examples of thioether antioxidants include compounds of the following structural formulas (83) to (88).

Antioxidants can be used with ultraviolet absorbers or light stabilizers.

The antioxidant is preferably 0.01 to 5% by weight, more preferably 0.1 to 3% by weight based on the total curable component. When the added amount is less than 0.01% by weight, the deterioration prevention effect is not sufficiently expressed, and when used in excess of 5% by weight, it is not preferable from an economical point of view.

To the composition for plastic lenses of the present invention, a fluorescent brightening agent such as 2,5-bis [5-tert-butylbenzooxazolyl (2)] thiophene (compound of formula (89)) can be added. Can be.

Hereinafter, the composition for plastic lenses of this invention (VI) is demonstrated.

This invention (VI) contains 0.1-10 weight part of at least 1 or more radical polymerization initiator with respect to 100 weight part of all curable components in the composition for plastic lenses described in any one of this invention (II)-this invention (V). It is a composition for plastic lenses as described in any one of this invention (II)-this invention (V).

A radical polymerization initiator can be added to the composition for plastic lenses according to any one of the present invention (II) to (V), as a curing agent, and is preferably added.

The radical polymerization initiator which can be added to the composition for plastic lenses concerning any one of this invention (II)-this invention (V) is not specifically limited. Known radical polymerization initiators can also be used as long as they do not adversely affect physical properties such as optical properties of the plastic lens obtained by curing the composition.

However, it is preferred that the radical polymerization initiator for use in the present invention be soluble in the other components present in the composition to be cured and simultaneously generate free radicals at 30 to 120 ° C. Specific examples of radical polymerization initiators that can be added include diisopropylperoxy dicarbonate, dicyclohexylperoxy dicarbonate, di-n-propylperoxy dicarbonate, di-sec-butylperoxy dicarbonate and tert- Butyl perbenzoate, including but not limited to. From the point of curability, the radical polymerization initiator which has a structure represented by following General formula (90) is preferable.

Wherein R ⁵ and R ⁶ each independently represent at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a substituted alkyl group, a phenyl group and a substituted phenyl group.

In general formula, R ⁵ and R ⁶ each independently represent at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a substituted alkyl group, a phenyl group and a substituted phenyl group.

Specific examples of the radical polymerization initiator represented by the general formula (90) include di-n-propylperoxy dicarbonate, diisopropylperoxy dicarbonate, bis (4-tert-butylcyclohexyl) peroxy dicarbonate, and di- 2-ethoxyethylperoxy dicarbonate, di-2-ethylhexylperoxy dicarbonate, di-3-methoxybutylperoxy dicarbonate, di-sec-butylperoxy dicarbonate and di (3-methyl-3 -Methoxybutyl) peroxy dicarbonate and the like. Among these, di-n-propylperoxy dicarbonate, diisopropylperoxy dicarbonate, di-2-ethoxyethylperoxy dicarbonate, di-2-ethylhexylperoxy dicarbonate and di (3-methyl- 3-methoxybutyl) peroxy dicarbonate is preferred, and diisopropylperoxy dicarbonate is more preferred.

The addition amount of a radical polymerization initiator is 0.1-10 weight part, Preferably it is 1-5 weight part with respect to 100 weight part of all curable components contained in the composition for plastic lenses of this invention (II)-this invention (V). If the amount is less than 0.1 part by weight, curing of the composition may proceed inadequately. Moreover, when it adds more than 10 weight part, it is not preferable from an economic viewpoint.

The viscosity of the composition for plastic lenses of the present invention (II) to (V) is generally 1000 mPa · s or less, preferably 500 mPa · s or less, in view of the filterability and mold workability of the composition. More preferably, it is 400 mPa * s or less.

As used herein, "viscosity" is a value measured with a rotational viscometer, details of the rotational viscometer are described in the Iwanami Physics Dictionary, 3rd Edition , 3rd Edition , 8th Printing, page 212, June 1, 1977 It is.

The following describes the present invention (VII) and the present invention (VIII).

The present invention (VII) is a plastic lens obtained by curing the composition for a plastic lens according to any one of the present invention (II) to (VI).

The present invention (VIII) is a method for producing a plastic lens by curing the composition for a plastic lens according to any one of the present invention (II) to (VI).

In this invention, it is suitable to perform cast molding as a shaping | molding process of the composition for plastic lenses. More specifically, a molding method may be used in which a radical polymerization initiator is added to the composition, the composition is injected through a line into a mold immobilized by an elastomeric gasket or spacer, and thermally cured in an oven. have.

Here, the material of the mold is metal or glass. In general, the mold of the plastic lens should be cleaned after the molding of the mold, and the cleaning is usually performed using a strong alkali solution or a strong acid. Unlike metal, the glass hardly deteriorates due to cleaning, and the glass is easily polished so that the surface roughness can be greatly reduced. For this reason, it is preferable to use glass.

The hardening temperature at the time of shape | molding the composition for plastic lenses described in any one of this invention (II)-this invention (VI) is about 30-120 degreeC, Preferably it is 40-100 degreeC. In consideration of shrinkage or strain during curing, it is preferable to manipulate the curing temperature by a method of gradually curing while raising the temperature. The curing time is generally from 0.5 to 100 hours, preferably from 3 to 50 hours, more preferably from 10 to 30 hours.

The plastic lens of the present invention can be dyed similarly to conventional plastic lenses.

The dyeing method of the plastic lens of the present invention is not particularly limited, and any method may be used as long as it is a known dyeing method of the plastic lens. Among these, the dip dyeing method known conventionally as a general method is preferable. As used herein, "immersion dyeing method" means a method of dyeing a plastic lens by dispersing the disperse dye in water together with a surfactant to prepare a dyeing solution, and immersing the plastic lens in the dyeing solution under heating.

The dyeing method of the plastic lens is not limited to the above immersion dyeing method, and other known methods such as a method of dyeing a plastic lens by sublimation of an organic pigment (see Japanese Patent Application Publication No. 35-1384 (JP-B-35-1384)). ) Or a method of dyeing a plastic lens by sublimation of a sublimable dye (see Japanese Patent Application Publication Nos. 56-159376 (JP-B-56-159376) and 1-277814 (JP-B-1-277814)). Can be used. Immersion dyeing method is most preferable at the point of simple operation.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

Various physical properties were measured as follows.

1. Refractive Index (n _D ) and Abbe Number

A 9 mm x 16 mm x 4 mm test piece was prepared and the refractive index n _D and Abbe number (ν _D ) were measured at 25 ° C using "Abe refractometer 1T" manufactured by Atago. As the contact solution, α-bromonaphthalene was used.

2. Viscosity

Measurement was carried out at a measurement temperature of 25 ° C. using a B-type viscometer (type B8U type) manufactured by Tokyo Keiki Co., Ltd ..

3. Bicol Hardness

It measured according to JISK6911 using the 934-1 type.

4. Charpy impact value

It measured according to JIS K 7111.

5. Measurement of glass transition point (Tg)

It measured using TMA / SS120 and DISC STATION SSC / 5200H (made by Seiko Instruments).

6. Measurement of specific gravity of cured product

The specific gravity of hardened | cured material after hardening was measured according to the up-and-down method (23 degreeC) of JISK7112.

Preparation Example 1

A 3-liter three-necked flask with a distillation unit was charged with 1,847.0 g (7.5 mol) of diallyl isophthalate, 265.3 g (2.5 mol) of diethylene glycol and 0.923 g of dibutyltin oxide, and heated at 155 ° C. under a nitrogen stream. The resulting allyl alcohol was distilled off. In the case of about 232 g of allyl alcohol, the inside of the reaction system was depressurized to 1.33 kPa to accelerate the rate of allyl alcohol. After the theoretical amount (290.4 g) of allyl alcohol was distilled off, it was heated for an additional 1 hour and then held at 160 ° C., 0.13 kPa for 1 hour. The reactor was then cooled to give 1,821.9 g of the allyl ester compound (hereinafter referred to as "sample A") The 270 MHz ¹ H-NMR spectrum (solvent: CDCl ₃ ) and FT-IR spectrum of Sample A obtained 1 and 2, respectively.

Gas chromatography (manufactured by Shimadzu Corporation, GC-14B, using a hydrogen salt ionization detector, column used: DB-23, film thickness of 0.25 µm, length 30 m, column temperature; 5 minutes after constant at 130 ℃, 5 ℃ / The temperature was raised to 200 ° C. in minutes, and then kept constant at 200 ° C.), and it was confirmed that Sample A contained 42% by weight of diallyl isophthalate.

Preparation Example 2

In a three liter three-necked flask with a distillation unit, 738.8 g (3.0 mol) of diallyl isophthalate, 738.8 g (3.0 mol) of diallyl terephthalate, 254.7 g (2.4 mol) of diethylene glycol and 0.739 g of dibutyltin oxide Allyl alcohol produced by heating at 160 DEG C under nitrogen stream was distilled off. When about 223 g of allyl alcohol was distilled off, the inside of the reaction system was decompressed to 1.33 kPa to accelerate the flow rate of allyl alcohol. After the theoretical amount (278.8 g) of allyl alcohol was distilled off, it was heated for an additional 1 hour and then held at 160 ° C., 0.13 kPa for 1 hour. The reactor was then cooled to give 1,453.5 g of an allyl ester compound (hereinafter referred to as "sample B") The 270 MHz ¹ H-NMR spectrum (solvent: CDCl ₃ ) and the FT-IR spectrum of Sample B obtained were obtained. 3 and 4, respectively.

Gas chromatography (manufactured by Shimadzu Corporation, GC-14B, using a hydrogen salt ionization detector, column used: DB-23, film thickness of 0.25 µm, length 30 m, column temperature; 5 minutes after constant at 130 ℃, 5 ℃ / The temperature was raised to 200 ° C. in minutes, and then kept constant at 200 ° C.), and it was confirmed that Sample B contained 18% by weight of diallyl terephthalate and 19% by weight of diallyl isophthalate.

Preparation Example 3

In a three liter three-necked flask with a distillation unit, 738.8 g (3.0 mol) of diallyl isophthalate, 738.8 g (3.0 mol) of diallyl terephthalate, 212.2 g (2.0 mol) of diethylene glycol and 0.739 g of dibutyltin oxide The allyl alcohol produced by filling and heating at 170 degreeC under nitrogen stream was distilled off. When about 223 g of allyl alcohol was distilled off, the inside of the reaction system was decompressed to 1.33 kPa to accelerate the flow rate of allyl alcohol. After the theoretical amount (278.8 g) of allyl alcohol was distilled off, it was heated for an additional 1 hour and then held at 170 ° C., 0.13 kPa for 1 hour. The reactor was then cooled to give 1,441.5 g of an allyl ester compound (hereinafter referred to as "sample C") The 270 MHz ¹ H-NMR spectrum (solvent: CDCl ₃ ) and FT-IR spectrum of Sample C obtained were obtained. 5 and 6, respectively.

Gas chromatography (manufactured by Shimadzu Corporation, GC-14B, using a hydrogen salt ionization detector, column used: DB-23, film thickness of 0.25 µm, length 30 m, column temperature; 5 minutes after constant at 130 ℃, 5 ℃ / The temperature was raised to 200 ° C. in minutes, and then maintained constant at 200 ° C.), and it was confirmed that Sample C contained 19% by weight of diallyl terephthalate and 20% by weight of diallyl isophthalate.

Preparation Example 4

In a 3-liter three-necked flask with a distillation unit, 1,231.3 g (5.0 mol) of diallyl isophthalate, 615.7 g (2.5 mol) of diallyl terephthalate, 265.3 g (2.5 mol) of diethylene glycol and 0.923 g of dibutyltin oxide The allyl alcohol produced by filling and heating at 170 degreeC under nitrogen stream was distilled off. In the case of about 232 g of allyl alcohol, the inside of the reaction system was depressurized to 1.33 kPa to accelerate the rate of allyl alcohol. After the theoretical amount (290.4 g) of allyl alcohol was distilled off, it was heated for an additional 1 hour and then held at 170 ° C., 0.13 kPa for 1 hour. The reactor was then cooled to give 1,821.9 g of an allyl ester compound (hereinafter referred to as "sample D") as a result.

Gas chromatography (manufactured by Shimadzu Corporation, GC-14B, using a hydrogen salt ionization detector, column used: DB-23, film thickness of 0.25 µm, length 30 m, column temperature; 5 minutes after constant at 130 ℃, 5 ℃ / The temperature was raised to 200 ° C. in minutes, and then kept constant at 200 ° C.), and it was confirmed that Sample D contained 28% by weight of diallyl isophthalate and 14% by weight of diallyl terephthalate.

Preparation Example 5

In a 3-liter three-necked flask with a distillation unit, 1,385.2 g (5.625 mol) of diallyl isophthalate, 461.7 g (1.875 mol) of diallyl terephthalate, 265.3 g (2.5 mol) of diethylene glycol and 0.923 g of dibutyltin oxide The allyl alcohol produced by filling and heating at 170 degreeC under nitrogen stream was distilled off. In the case of about 232 g of allyl alcohol, the inside of the reaction system was depressurized to 1.33 kPa to accelerate the flow rate of allyl alcohol. , It was kept at 0.13 kPa for 1 hour. The reactor was then cooled to give 1,821.9 g of allyl ester compound (hereinafter referred to as "sample E") as a result.

Gas chromatography (manufactured by Shimadzu Corporation, GC-14B, using a hydrogen salt ionization detector, column used: DB-23, film thickness of 0.25 µm, length 30 m, column temperature; 5 minutes after constant at 130 ℃, 5 ℃ / The temperature was raised to 200 ° C. in minutes, and then kept constant at 200 ° C.), and it was confirmed that Sample E contained 31.5% by weight of diallyl isophthalate and 10.5% by weight of diallyl terephthalate.

Preparation Example 6

In a 3-liter three-necked flask with a distillation unit, 1,108.2 g (4.5 mol) of diallyl terephthalate, 756.9 g (3.0 mol) of diallyl 1,4-cyclohexanedicarboxylate, 265.3 g (2.5 mol) of diethylene glycol And 0.923 g of dibutyltin oxide were charged and the allyl alcohol produced by heating at 170 ° C. under nitrogen stream was distilled off. When about 232 g of allyl alcohol was distilled off, the inside of the reaction system was decompressed to 1.33 kPa to accelerate the rate of allyl alcohol. After the theoretical amount (290.4 g) of allyl alcohol was distilled off, it was heated for an additional 1 hour and then held at 170 ° C., 0.13 kPa for 1 hour. The reactor was then cooled to give 1,821.9 g of an allyl ester compound (hereinafter referred to as "sample F") as a result.

Gas chromatography (manufactured by Shimadzu Corporation, GC-14B, using a hydrogen salt ionization detector, column used: DB-23, film thickness of 0.25 µm, length 30 m, column temperature; 5 minutes after constant at 130 ℃, 5 ℃ / Heated to 200 ° C. in minutes, and then kept constant at 200 ° C.), and sample F contained 26% by weight of diallyl terephthalate and 16% by weight of diallyl 1,4-cyclohexanedicarboxylate It was confirmed to contain.

Preparation Example 7

In a three liter three-necked flask with a distillation unit, 147.8 g (0.6 mol) of diallyl isophthalate, 1,329.8 g (5.4 mol) of diallyl terephthalate, 286.5 g (2.7 mol) of diethylene glycol and 0.739 g of dibutyltin oxide The allyl alcohol produced by filling and heating at 170 degreeC under nitrogen stream was distilled off. In the case of about 232 g of allyl alcohol, the inside of the reaction system was depressurized to 1.33 kPa to accelerate the rate of allyl alcohol. After the theoretical amount (313.6 g) of allyl alcohol was distilled off, it was heated for an additional 1 hour and then held at 170 ° C., 0.13 kPa for 1 hour. The reactor was then cooled to give 1,450.5 g of an allyl ester compound (hereinafter referred to as "sample G") as a result.

Gas chromatography (manufactured by Shimadzu Corporation, GC-14B, using a hydrogen salt ionization detector, column used: DB-23, film thickness of 0.25 µm, length 30 m, column temperature; 5 minutes after constant at 130 ℃, 5 ℃ / The temperature was raised to 200 ° C. in minutes, and then kept constant at 200 ° C.), and it was confirmed that Sample G contained 4% by weight of diallyl terephthalate and 28% by weight of diallyl isophthalate.

Preparation Example 8

In a three liter three-necked flask with a distillation unit, 295.5 g (1.2 mol) of diallyl isophthalate, 1,329.8 g (5.4 mol) of diallyl terephthalate, 286.5 g (2.7 mol) of diethylene glycol and 0.739 g of dibutyltin oxide Allyl alcohol produced by heating at 170 DEG C under nitrogen stream was distilled off. When about 250 g of allyl alcohol was distilled off, the inside of the reaction system was decompressed to 1.33 kPa to accelerate the flow rate of allyl alcohol. After the theoretical amount (313.6 g) of allyl alcohol was distilled off, it was heated for an additional 1 hour and then held at 170 ° C., 0.13 kPa for 1 hour. The reactor was then cooled to give 1,453.5 g of an allyl ester compound (hereinafter referred to as "sample H") as a result.

Gas chromatography (manufactured by Shimadzu Corporation, GC-14B, using a hydrogen salt ionization detector, column used: DB-23, film thickness of 0.25 µm, length 30 m, column temperature; 5 minutes after constant at 130 ℃, 5 ℃ / The temperature was raised to 200 ° C. in minutes, and then kept constant at 200 ° C.), and it was confirmed that Sample H contained 29% by weight of diallyl terephthalate and 8% by weight of diallyl isophthalate.

Preparation Example 9

A 1 liter three-necked flask with a distillation unit was charged with 738.8 g (3.0 mol) of diallyl isophthalate, 76.1 g (1.0 mol) of propylene glycol, and 0.739 g of dibutyltin oxide, and heated at 180 ° C. under a nitrogen stream. The resulting allyl alcohol was distilled off. When 81 g of allyl alcohol was distilled off, the inside of the reaction system was decompressed to 1.33 kPa to accelerate the flow rate of allyl alcohol. After the theoretical amount (116.2 g) of allyl alcohol was distilled off, it was heated for an additional 1 hour and then held at 180 ° C., 0.13 kPa for 1 hour. The reactor was then cooled to give 699.0 g of an allyl ester compound (hereinafter referred to as "sample I") as a result.

Gas chromatography (manufactured by Shimadzu Corporation, GC-14B, using a hydrogen salt ionization detector, column used: DB-23, film thickness of 0.25 µm, length 30 m, column temperature; 5 minutes after constant at 130 ℃, 5 ℃ / The temperature was raised to 200 ° C. in minutes, and then kept constant at 200 ° C.), and it was confirmed that Sample I contained 43% by weight of diallyl isophthalate.

Preparation Example 10

A 1 liter three-necked flask with a distillation unit was charged with 738.8 g (3.0 mol) of diallyl terephthalate, 76.1 g (1.0 mol) of propylene glycol and 0.739 g of dibutyltin oxide, which were produced by heating at 180 ° C. under a nitrogen stream. Allyl alcohol was distilled off. When 81 g of allyl alcohol was distilled off, the inside of the reaction system was decompressed to 1.33 kPa to accelerate the flow rate of allyl alcohol. After the theoretical amount (116.2 g) of allyl alcohol was distilled off, it was heated for an additional 1 hour and then held at 180 ° C., 0.13 kPa for 1 hour. The reactor was then cooled to give 699.0 g of an allyl ester compound (hereinafter referred to as "sample J") as a result.

Gas chromatography (manufactured by Shimadzu Corporation, GC-14B, using a hydrogen salt ionization detector, column used: DB-23, film thickness of 0.25 µm, length 30 m, column temperature; 5 minutes after constant at 130 ℃, 5 ℃ / The temperature was raised to 200 ° C. in minutes, and then kept constant at 200 ° C.), and it was confirmed that Sample J contained 43% by weight of diallyl terephthalate.

Example 1

As shown in Table 1, 100.0 parts by weight of Sample A and 3 parts by weight of diisopropylperoxy dicarbonate (IPP) were blended and mixed and stirred to measure the viscosity at that time as a completely uniform solution composition. Thereafter, a vessel containing the solution was placed in a depressurizable desiccator, and the vacuum pump was depressurized for about 15 minutes to degas the gas in the solution. The solution composition was carefully injected into a mold assembled from a glass-made mold for a spectacle plastic lens and a resin-made gasket by a syringe so that no gas was mixed therein, and then in an oven for 7 hours at 40 ° C., 40 to 40 ° C. It hardened by heating to 60 degreeC for 10 hours, 60 to 80 degreeC for 3 hours, 80 degreeC for 1 hour, and 85 degreeC for 2 hours.

Table 1 shows the refractive index, Abbe's number, Bicol hardness, glass transition point (Tg), Charpy impact value and specific gravity at 23 ° C of the obtained lens.

In formula, d represents the integer of 1 or more.

In the formula, each independently represents 1,4-phenylene or 1,3-phenylene, and e represents an integer of 1 or more.

In the formula, each independently represents 1,4-phenylene or 1,3-phenylene, and f represents an integer of 1 or more.

In the formula, one of R ¹¹ and R ¹² represents H, the other represents CH ₃ , and g represents an integer of 1 or more.

Examples 2 to 4 and Comparative Example 1

In the formulation shown in Table 1, the composition was lowered and the viscosity measurement was carried out in the same manner as in Example 1, followed by curing, and the refractive index, Abbe's number, bicol hardness, glass transition point (Tg), Charpy impact of the lens. Value and specific gravity measurement at 23 ° C. The results are shown in Table 1.

Example 5

As shown in Table 2, 70.0 parts by weight of sample A, 30.0 parts by weight of diethylene glycol bis (allyl carbonate) (trade name) CR-39 (registered trademark) of PPG, diisopropylperoxy dicarbonate (IPP) 3 The parts by weight were blended, mixed and stirred to measure the viscosity of the time as a completely uniform solution composition, after which a vessel containing the solution was placed in a pressure sensitive desiccator, and vacuum pumped for about 15 minutes to reduce the pressure. The gas in the solution was degassed, and the solution composition was carefully injected into a mold assembled from a glass-made mold for a spectacle plastic lens and a resin-made gasket by a syringe so that no gas was mixed therein, followed by an oven. At 40 ° C. for 7 hours, at 40 ° C. to 60 ° C. for 10 hours, at 60 ° C. to 80 ° C. for 3 hours, at 80 ° C. for 1 hour, and at 85 ° C. for 2 hours to heat the program.

Table 2 shows the refractive index, Abbe's number, Bicol hardness, glass transition point (Tg), Charpy impact value and specific gravity at 23 ° C of the obtained lens.

Wherein one of R ¹³ and R ¹⁴ represents H, the other represents CH ₃ , A each independently represents a 1,4-phenylene group or a 1,3-phenylene group, and h and i are each 0 Or an integer of 1 or more. However, (h + i) represents an integer of 1 or more.

In the formula, one of R ¹⁵ and R ¹⁶ represents H, the other represents CH ₃ , and w represents an integer of 1 or more.

Examples 6-9 and Comparative Example 2

In the formulation shown in Table 2, a composition was prepared and the viscosity measurement was performed in the same manner as in Example 1, followed by refractive index of the lens, Abbe number, Bicol hardness, glass transition point (Tg), Charpy impact value and 23 Specific gravity measurements at ° C were performed. The results are shown in Table 2.

Example 10

As shown in Table 3, 95.0 parts by weight of sample A, 5.0 parts by weight of allyl benzoate and 3 parts by weight of diisopropylperoxy dicarbonate (IPP) were combined and mixed and stirred to obtain a completely uniform solution composition at that time. The viscosity of was measured. Thereafter, a vessel containing the solution was placed in a depressurizable desiccator, and the vacuum pump was depressurized for about 15 minutes to degas the gas in the solution. The solution composition was carefully injected into a mold assembled from a glass-made mold for a spectacle plastic lens and a resin-made gasket by a syringe so that no gas was mixed therein, and then in an oven for 7 hours at 40 ° C., 40 to 40 ° C. It hardened by heating to 60 degreeC for 10 hours, 60 to 80 degreeC for 3 hours, 80 degreeC for 1 hour, and 85 degreeC for 2 hours.

Table 3 shows the refractive index, Abbe's number, Bicol hardness, glass transition point (Tg), Charpy impact value, and specific gravity measurement at 23 ° C of the obtained lens.

Examples 11-12 and Comparative Example 3

In the formulation shown in Table 3, a composition was prepared and the viscosity measurement was performed in the same manner as in Example 1, followed by refractive index of the lens, Abbe number, Bicol hardness, glass transition point (Tg), Charpy impact value and 23 Specific gravity measurements at ° C were performed. The results are shown in Table 3.

Example 13

As shown in Table 4, 65.0 parts by weight of Sample A, 30.0 parts by weight of diethylene glycol bis (allyl carbonate) (trade name; CR-39 (registered trademark)) of PPG, 5 parts by weight of allyl p-phenylbenzoate, and 3 parts by weight of diisopropylperoxy dicarbonate (IPP) was blended and mixed and stirred to measure the viscosity at that time as a completely uniform solution composition. Thereafter, a vessel containing the solution was placed in a depressurizable desiccator, and the vacuum pump was depressurized for about 15 minutes to degas the gas in the solution. The solution composition was carefully injected into a mold assembled from a glass-made mold for a spectacle plastic lens and a resin-made gasket by a syringe so that no gas was mixed therein, and then in an oven for 7 hours at 40 ° C., 40 to 40 ° C. It hardened by heating to 60 degreeC for 10 hours, 60 to 80 degreeC for 3 hours, 80 degreeC for 1 hour, and 85 degreeC for 2 hours.

Table 4 shows the refractive index, Abbe's number, Bicol hardness, glass transition point (Tg), Charpy impact value and specific gravity at 23 ° C of the obtained lens.

Examples 14-17 and Comparative Example 4

In the formulation shown in Table 4, a composition was prepared and the viscosity measurement was performed in the same manner as in Example 1, followed by refractive index of the lens, Abbe number, Bicol hardness, glass transition point (Tg), Charpy impact value and 23 Specific gravity measurements at ° C were performed. The results are shown in Table 4.

According to the present invention, there is provided a plastic lens material having an excellent balance of heat resistance, impact resistance and refractive index; A composition for plastic lenses having a viscosity suitable for application to spectacle lenses or other optical lenses and having a high refractive index and low specific gravity of the cured product; A plastic lens obtained by curing the composition; And it can provide a method for producing the plastic lens.

Claims (17)

A plastic lens material comprising at least one or more of the groups represented by the following general formula (1) as a terminal group, and comprising a group represented by the following general formula (2) as a repeating unit: In formula, R <^1> represents an allyl group or a metaallyl group each independently, and A <^1> is derived from bivalent carboxylic acid or dicarboxylic anhydride which has an alicyclic structure and / or an aromatic ring structure as each independent organic residue. One or more organic residues; Wherein A ² each represents an independent organic residue and represents one or more organic residues derived from a divalent carboxylic acid or dicarboxylic anhydride having an alicyclic structure and / or an aromatic ring structure, and each X represents an independent organic residue. A residue represents one or more organic residues derived from a polyhydric alcohol having an ether bond in its molecule, and X has a group represented by the general formula (1) as a terminal group and a group represented by the general formula (2) as a repeating unit. It is conditional to have branching structure further. The material for a plastic lens according to claim 1, wherein the polyhydric alcohol having an ether bond in the molecule is at least one selected from the group consisting of polyalkylene glycols. The organic moiety derived from the divalent carboxylic acid or dicarboxylic anhydride having the alicyclic structure and / or the aromatic ring structure comprises the following structural formulas (7) to (9). A material for plastic lenses, which is at least one selected from the group. A composition for plastic lenses, comprising the material for plastic lenses according to any one of claims 1 to 3 and the following component (β): Ingredient (β) At least one compound selected from compounds represented by the following general formula (3): In the formula, R ² and R ³ each independently represent an allyl group or a metaallyl group, and A ³ is an organic residue derived from a divalent carboxylic acid or dicarboxylic anhydride having an alicyclic structure and / or an aromatic ring structure. Indicates. The plastic according to claim 4, which contains 10 to 90% by weight of the plastic lens material according to any one of claims 1 to 3 and 10 to 90% by weight of the component (β) with respect to the total curable component. Lens composition. A composition for plastic lenses, comprising the material for plastic lenses according to any one of claims 1 to 3, the following component (β) and the following component (γ): Ingredient (β) At least one compound selected from compounds represented by the following general formula (3): In the formula, R ² and R ³ each independently represent an allyl group or a metaallyl group, and A ³ is an organic residue derived from a divalent carboxylic acid or dicarboxylic anhydride having an alicyclic structure and / or an aromatic ring structure. Indicates; Component (γ) At least one compound selected from compounds represented by the following general formula (4): Wherein Y represents at least one organic moiety derived from a polyhydric alcohol having 2 to 20 carbon atoms and containing n hydroxyl groups, n is an integer from 2 to 6, and R ⁴ is each independently an allyl group or meta It represents an allyl group, s is an integer of 0-n-1, t is an integer of 1-n, provided s + t = n. The plastic lens material according to any one of claims 1 to 3, 10 to 80% by weight of the component (β), and component (γ) according to claim 6 ) 10 to 80% by weight, a plastic lens composition. A composition for plastic lenses, comprising the material for plastic lenses according to any one of claims 1 to 3, the following component (β) and the following component (δ): Ingredient (β) At least one compound selected from compounds represented by the following general formula (3): In the formula, R ² and R ³ each independently represent an allyl group or a metaallyl group, and A ³ is an organic residue derived from a divalent carboxylic acid or dicarboxylic anhydride having an alicyclic structure and / or an aromatic ring structure. Indicates; Component (δ) At least one monofunctional compound. The plastic lens material according to any one of claims 1 to 3, 10 to 80% by weight of the component (β), and component (δ) according to claim 8 with respect to the total curable component. ) 1 to 20% by weight, a plastic lens composition. A composition for plastic lenses, comprising the material for plastic lenses according to any one of claims 1 to 3, the following component (β), the following component (γ) and the following component (δ): Ingredient (β) At least one compound selected from compounds represented by the following general formula (3): Wherein R ² and R ³ each independently represent an allyl group or a metaallyl group, and A ³ represents an organic residue derived from a divalent carboxylic acid or dicarboxylic anhydride having an alicyclic structure and / or an aromatic ring structure. Indicates; Component (γ) At least one compound selected from compounds represented by the following general formula (4): Wherein Y represents at least one organic moiety derived from a polyhydric alcohol having 2 to 20 carbon atoms and containing n hydroxyl groups, n is an integer from 2 to 6, and R ⁴ is each independently an allyl group or meta Represents an allyl group, s is an integer from 0 to n-1, t is an integer from 1 to n, provided that s + t = n; Component (δ) At least one monofunctional compound. The plastic lens material according to any one of claims 1 to 3, 8 to 80% by weight of component (β), component (γ) according to claim 10, ) 8 to 80% by weight, and 1 to 20% by weight of the component (δ). The composition for plastic lenses according to any one of claims 4 to 11, wherein the viscosity is at most 500 mPa · s at 25 ° C. The composition for plastic lenses according to any one of claims 4 to 12, which contains 0.1 to 10 parts by weight of at least one or more radical polymerization initiators based on 100 parts by weight of the total curable component in the composition for plastic lenses. The composition for plastic lenses according to claim 13, wherein the at least one radical polymerization initiator is a compound having a structure represented by the following General Formula (90): In the formula, R ⁵ and R ⁶ each independently represent at least one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a substituted alkyl group, a phenyl group and a substituted phenyl group. The plastic lens obtained by hardening the composition for plastic lenses of any one of Claims 4-14. A method for producing a plastic lens, comprising curing the composition for a plastic lens according to any one of claims 1 to 14. The manufacturing method of Claim 16 in which the said composition for plastic lenses is shape | molded at the curing temperature of 30-120 degreeC, and the hardening time of 0.5-100 hours.