JP2006265499A - Curable composition for optical part - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a curable composition for a (meth)acrylic optical part, which has excellent transparency, hardly causes discoloration, change of properties and deterioration and has excellent moldability, dimensional stability and water resistance. <P>SOLUTION: The curable composition for an optical part has no aromatic hydrocarbon structure and comprises a (meth)acrylic acid esterified product of a compound containing two or more hydroxy groups in one molecule in which at least a part of the esterified product contains an ether structure represented by chemical formula 1, the content of the ether structure is ≥5% by mass based on the total of the composition, the content of sulfonic acid, sulfonate and/or a sulfonic acid ester is ≤100 ppm based on the total of the composition and the glass transition temperature of a cured product is -10 to 50°C. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a curable composition for optical components. In detail, this invention relates to the improvement for improving the weather resistance of the curable composition for optical components.

  Transparent plastics are preferably used in various applications such as optical members, lighting members, and automobile members because they have better moldability than transparent inorganic materials such as glass.

  A curable (meth) acrylic composition is conventionally known as a material for obtaining a transparent plastic excellent in mechanical strength and molding processability. Specifically, formed by a curable (meth) acrylic composition comprising bisphenol A dimethacrylate modified with ethylene oxide, diacrylate of an ester of hydroxypivalic acid and neopentyl glycol, and phenoxy (ethoxy) ethyl acrylate An optical component is disclosed (see, for example, Patent Document 1).

  However, the transparent plastic obtained by curing the composition disclosed in Document 1 does not have a sufficient level of light resistance to light from a light source having an emission wavelength distribution from the short wavelength region to the ultraviolet region of visible light. It was. This is considered to be because the composition has an aromatic hydrocarbon structure.

  The light resistance level of a transparent plastic obtained by curing such a composition is still insufficient in terms of discoloration over time as compared with a transparent inorganic material such as glass. Thus, for example, an optical component that can be directly exposed to sunlight during use, such as a solar cell or an outdoor electronic bulletin board, or a light emitting diode that uses a light source having a light emission wavelength distribution from the short wavelength region to the ultraviolet region of visible light, When they are used for optical parts such as optical cables and display devices, there remains a big problem in terms of discoloration and deterioration over time.

  On the other hand, a photocurable composition containing an alkylene (oxy) di (meth) acrylate, a predetermined photopolymerization initiator, and a predetermined ultraviolet absorber in a predetermined ratio is disclosed (for example, see Patent Document 2). ).

The transparent plastic obtained by curing the composition disclosed in Document 2 has relatively good transparency and light resistance. However, if the polyoxyalkylene chain is too short, there is a risk that molding defects and dimensional stability may be insufficient due to shrinkage during curing. On the other hand, if the polyoxyalkylene chain is too long, the water resistance may be insufficient.
JP-A-6-263831 Japanese Patent No. 3055068

  Thus, the conventional curable composition does not always provide a cured product that is sufficiently excellent in transparency and light resistance, and also excellent in dimensional stability, moldability, and water resistance. At present, development of a curable composition that can provide a product is strongly desired.

  Therefore, the present invention is excellent in transparency and is less likely to be colored, altered, or deteriorated even with respect to light from a light source having a light emission wavelength distribution from the short wavelength region to the ultraviolet region of visible light. It aims at providing the curable composition for (meth) acrylic-type optical components which is excellent also in stability and water resistance.

  The present inventors have intensively studied to solve the above problems.

  First, in a conventional composition containing a (meth) acrylic ester of a compound having two or more hydroxyl groups in one molecule, the emission wavelength distribution of the obtained cured product from the short wavelength region of visible light to the ultraviolet region In order to search for the cause of coloring, alteration, and deterioration of the light from the light source having the above, the types, contents, production conditions, and the like of the constituent components of the composition were examined.

  As a result, the present inventors (1) described above when using a compound having no aromatic hydrocarbon structure as a (meth) acrylic ester of a compound having two or more hydroxyl groups in one molecule. That coloring, alteration, and deterioration by light in the short wavelength region can be suppressed, and (2) the sulfonic acid derivative contained in a trace amount in the conventional composition is one of the above-mentioned factors of coloring, alteration, and degradation. (3) When an esterified product having a predetermined ether structure is used, the above-mentioned coloring, alteration, and deterioration can be remarkably suppressed, and (4) the glass transition temperature of the cured product is a value within a predetermined range. When it exists, it discovered that said coloring, a quality change, and deterioration could be suppressed.

  Based on the above findings, the present inventors have completed the present invention.

That is, this invention is a curable composition for optical components which does not have an aromatic hydrocarbon structure but contains the (meth) acrylic ester (A) of the compound which has a 2 or more hydroxyl group in 1 molecule. There,
The esterified product (A) has the following chemical formula 1:

The content of the ether structure represented by is 5% by mass or more based on the total amount of the composition, and the content of the sulfonic acid, sulfonic acid salt and / or sulfonic acid ester is sulfur based on the total amount of the composition It is 100 ppm or less in terms of atoms, and the glass transition temperature of a cured product obtained by curing the composition is -10 to 50 ° C.

  According to the present invention, it is excellent in transparency and is less likely to be colored, altered, or deteriorated even with respect to light from a light source having a light emission wavelength distribution from the short wavelength region to the ultraviolet region of visible light. A curable composition for (meth) acrylic optical parts that is also excellent in dimensional stability and water resistance can be provided.

  Hereinafter, embodiments of the present invention will be described in detail. However, the technical scope of the present invention is not limited to only the following forms, and can be appropriately modified within a range not impairing the gist of the present invention.

The present invention is a curable composition for optical components, which contains a (meth) acrylic ester (A) of a compound having no aromatic hydrocarbon structure and having two or more hydroxyl groups in one molecule. ,
The esterified product (A) has the following chemical formula 1:

The content of the ether structure represented by is 5% by mass or more based on the total amount of the composition, and the content of the sulfonic acid, sulfonic acid salt and / or sulfonic acid ester is sulfur based on the total amount of the composition It is 100 ppm or less in terms of atoms, and the glass transition temperature of a cured product obtained by curing the composition is -10 to 50 ° C.

  First, the curable composition for optical components of the present invention (hereinafter also simply referred to as “the composition of the present invention”) contains a predetermined esterified product (A). The esterified product (A) does not have an aromatic hydrocarbon structure and has a compound having two or more hydroxyl groups in one molecule (also simply referred to as “polyol compound” in this specification), (meth) acrylic An esterified product (A) that can be produced from an acid.

  Examples of the “polyol compound” include ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanediol, 1,16-hexadecanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,2-cyclohexane Diol, 1,3-cyclohexanediol, 1,4-cyclohexanediol Alkane diols such as tricyclodecane dimethanol, cyclohexane dimethanol, hydrogenated bisphenol A, neopentyl glycol, butyl ethyl propane diol, and esterified products of neopentyl glycol with hydroxypivalic acid, β, β, β ′, β ′ -Tetramethyl-2,4,8,10-tetraoxaspiro [5,5] undecane-3,9-dienol and the like. However, other compounds may be used. For example, trimethylolethane, trimethylolpropane, trimethylolbutane, trimethylolhexane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, glycerin, polyglycerin, and the like may be used. In addition, as for these polyol compounds, only 1 type may be used independently and 2 or more types may be used together.

  From the viewpoint of improving the resistance to deterioration or discoloration of the cured product obtained by curing the curable composition, the polyol compound is preferably a compound that does not have β hydrogen with respect to the hydroxyl group that it has. . Examples of such a compound include neopentyl glycol, butyl ethyl propane diol, esterified product of neopentyl glycol with hydroxypivalic acid, β, β, β ′, β′-tetramethyl-2,4,8,10. -Tetraoxaspiro [5,5] undecane-3,9-dienol, trimethylolethane, trimethylolpropane, trimethylolbutane, trimethylolhexane, ditrimethylolpropane, pentaerythritol, dipentaerythritol and the like. Especially, as a polyol compound excellent in said effect, neopentyl glycol, butyl ethyl propanediol, or trimethylol propane is mentioned.

  As said esterified substance (A), when goods are marketed, the said goods may be purchased and used, and you may prepare and use them.

  Examples of methods for preparing the esterified product (A) by themselves include a transesterification method and a dehydration condensation method. Hereinafter, each method will be briefly described.

  First, the transesterification method will be described. In the transesterification method, the polyol compound and the (meth) acrylic acid ester undergo a dealcoholization reaction (transesterification reaction) in the presence of a predetermined catalyst, whereby a predetermined esterified product (A) is generated.

  In the transesterification method, the charged molar ratio of the polyol compound to the (meth) acrylic acid ester (hydroxyl group in the polyol compound: (meth) acrylic acid ester) is preferably 1: 1 to 1:20, more preferably. It is 1: 1.5-1: 10, More preferably, it is 1: 2-1: 5.

  Examples of the catalyst include alkali metal alcoholates, magnesium alcoholates, aluminum alcoholates, titanium alcoholates, dibutyltin oxide, anion exchange resins, and the like. The amount of the catalyst used is not particularly limited, but is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and still more preferably, with respect to 100 parts by mass of the total amount of reaction. 0.1 to 3 parts by mass. In addition, it is preferable to remove a catalyst after reaction.

  Examples of the solvent include pentane, cyclopentane, hexane, cyclohexane, methylcyclohexane, heptane, cycloheptane, octane, isooctane, benzene, toluene, and cymene. Although the usage-amount of a solvent is not restrict | limited in particular, Preferably it is 1-70 mass parts with respect to 100 mass parts of total preparations of reaction, More preferably, it is 5-50 mass parts, More preferably, it is 10-30 masses. Part.

  In addition, it is preferable to add a polymerization inhibitor to the reaction system for the purpose of preventing the polymerization of the (meth) acrylic acid ester during the transesterification reaction. Examples of the polymerization inhibitor include 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl (4H-TEMPO) and its derivatives (TEMPO derivatives); phenols such as hydroquinone and hydroquinone monomethyl ether; Examples include quinones such as benzoquinone and diphenylbenzoquinone; phenothiazines; copper salts and the like. The addition amount of the polymerization inhibitor is not particularly limited, but is preferably 0.0001 to 2 parts by mass, more preferably 0.005 to 0.5 parts by mass with respect to 100 parts by mass of the total charge of the reaction. .

  Although there is no restriction | limiting in particular also about reaction temperature, Preferably it is 50-150 degreeC, More preferably, it is 70-140 degreeC, More preferably, it is 90-130 degreeC.

  Subsequently, the dehydration condensation method will be described. In the dehydration condensation method, a predetermined esterified product (A) is generated by causing a dehydration reaction between a polyol compound and (meth) acrylic acid in the presence of a predetermined catalyst.

  In the dehydration condensation method, the charged molar ratio of the polyol compound and (meth) acrylic acid (hydroxyl group in the polyol compound: (meth) acrylic acid) is preferably 1: 1 to 1: 5, more preferably 1: 1.01 to 1: 2, more preferably 1: 1.05 to 1: 1.5.

  Examples of the catalyst include acid catalysts such as sulfuric acid, hydrochloric acid, phosphoric acid, p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, and cation exchange resin. The amount of the catalyst used is not particularly limited, but is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and still more preferably, with respect to 100 parts by mass of the total amount of reaction. 0.1 to 3 parts by mass. In addition, it is preferable to remove a catalyst after reaction.

  Among the above catalysts, a cation exchange resin is preferably used as the catalyst from the viewpoint that the content of the sulfonic acid derivative (sulfur component) in the resulting curable composition can be reduced. Examples of the cation exchange resin include Amberlist (registered trademark) and Amberlite (registered trademark) manufactured by Rohm and Haas, Diaion (registered trademark) manufactured by Mitsubishi Chemical Corporation, and the like. In addition, when using a cation exchange resin as a catalyst, it is preferable to thoroughly wash with an organic solvent such as toluene or methanol or water before use to prevent elution of the sulfonic acid derivative (sulfur component). .

  The kind and amount of the solvent used, and the reaction temperature are not particularly limited. As these preferable forms, the form mentioned above about the solvent and reaction temperature of a transesterification method may be employ | adopted similarly.

  In addition, it is preferable to add a polymerization inhibitor to the reaction system for the purpose of preventing polymerization of the (meth) acrylic acid ester during the dehydration condensation reaction. As a preferable form of the polymerization inhibitor and its addition amount, the form described in the above-mentioned column of the transesterification method can be similarly employed.

  In the composition of the present invention, at least a part of the esterified product (A) is represented by the following chemical formula 1:

The ether structure represented by these is contained. When such an ether structure is present in the esterified product (A), a decrease in water resistance and an increase in water absorption of the obtained cured product can be suppressed.

  When the esterified product (A) contains the ether structure of the above chemical formula 1, the ether structure has a form inserted in the ester structure portion of the esterified product (A). If the esterified product (A) used in the examples described later is described as an example, dimethacrylate (M-1) of an ethylene oxide 8-mol adduct to neopentyl glycol prepared in Synthesis Example 1 is neopentyl. An average of eight ethylene oxide units are added to the two hydroxyl groups of glycol, and methacrylic acid has an ester bond with each terminal ethylene oxide group. In the present application, not only a compound in which a hydroxyl group of the above polyol compound and (meth) acrylic acid directly form an ester bond, but also an ether structure represented by the above chemical formula 1 as in M-1. The compound inserted in the ester structure portion is also included in the “esterified product (A)”.

  In the composition of the present invention, the content of the ether structure represented by Chemical Formula 1 is 5% by mass or more based on the total amount of the composition. If the content of the ether structure is less than 5% by mass, the above-described effect exhibited by the presence of the ether structure may not be sufficiently obtained. A viewpoint that the cured product improves performance (that is, light resistance) that hardly causes discoloration, alteration, and deterioration of the cured product with respect to light from a light source having an emission wavelength distribution in a short wavelength region to an ultraviolet region of visible light. The content of the ether structure is preferably as large as possible, and the content of the ether structure represented by Chemical Formula 1 is preferably 10% by mass or more, more preferably 20% by mass with respect to the total amount of the composition. Or more, more preferably 30% by mass or more, and particularly preferably 40% by mass or more. The upper limit of the content of the ether structure is not particularly limited, but from the viewpoint of improving the water resistance of the cured product, the content of the ether structure is preferably 65% by mass or less based on the total amount of the composition. Preferably it is 60 mass% or less, More preferably, it is 55 mass% or less. The value of the ether structure content is controlled, for example, by adjusting the amount of the ether structure precursor (eg, ethylene oxide) used in the production of the esterified product (A) having such an ether structure. sell. In addition, as a value of content of an ether structure, the value measured by the method explained in full detail in the below-mentioned Example shall be employ | adopted.

  Subsequently, the ether structure of the above Chemical Formula 1 will be described in detail.

  The ether structure of Chemical Formula 1 has alkylene oxide units as repeating units. The alkylene oxide unit may have a side chain depending on the case. However, this side chain must satisfy the above conditions. In order to produce an ether structure satisfying such conditions, ethylene oxide, propylene oxide, and butylene oxide (1,2-butylene oxide, 2,3-butylene oxide, One or more alkylene oxides selected from the group consisting of (isobutylene oxide) may be used.

  In the ether structure of Chemical Formula 1, the number of repeating alkylene oxide units (n in Chemical Formula 1) is 1 to 100, preferably 2 to 15, more preferably 4 to 10, and still more preferably 6 -10. If n is too small, sufficient light resistance may not be obtained. On the other hand, if n is too large, the water resistance and the resilience may be reduced. However, in some cases, an esterified product (A) to which a number of alkylene oxide units outside the above preferred range is added may be used.

  As the esterified product (A) having an ether structure represented by Chemical Formula 1, when the product is commercially available, the product may be purchased and used, or may be prepared by itself.

  As an example of a method for preparing the esterified product (A) having an ether structure by itself, first, a desired number of alkylene oxide units are added to a hydroxyl group of a polyol compound by a conventionally known method. Thereafter, the obtained compound and (meth) acrylic acid (or (meth) acrylic acid ester) are esterified by the above-described transesterification method or dehydration condensation method, whereby an esterified product (A) can be generated. In addition, when the polyol compound to which a desired number of alkylene oxide units are added is commercially available, the product may be purchased and only the esterification reaction performed.

  The curable composition of the present invention may contain other components in addition to the esterified product (A) described above. Examples of the component that the composition of the present invention may contain in addition to the esterified product (A) include, for example, a polymerizable monomer other than the esterified product (A); a polymer and / or copolymer of (meth) acrylate ester (B ); Polymerizable oligomers; Other polymers other than these; Polymerization initiators; Other additives other than these. Details will be described below.

When a polymerizable monomer other than the esterified product (A) is added to the composition, effects such as reduction of the viscosity of the composition and improvement of the curing rate can be obtained. Examples of such polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-nonyl (meth) acrylate. , Lauryl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, (meth) acrylic acid, adamantyl (meth) acrylate, norbornyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, monofunctional (meth) acrylates such as α-hydroxymethyl butyl acrylate;
Monofunctional (meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide;
Monofunctional vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, chloroethyl vinyl ether;
Monofunctional N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, N-vinyl-N-methylformamide, N-vinylimidazole, N-vinylformamide, N-vinylacetamide;
Monofunctional vinyl compounds such as styrene, α-methylstyrene, vinyl toluene, allyl acetate, vinyl acetate, vinyl propionate, vinyl benzoate;
Maleic anhydride, maleic acid, dimethyl maleate, diethyl maleate, monomethyl maleate, monoethyl maleate, fumaric acid, dimethyl fumarate, diethyl fumarate, monomethyl fumarate, monoethyl fumarate, itaconic anhydride, itaconic acid, itacone Dimethyl acid, Diethyl itaconate, Monomethyl itaconate, Monoethyl itaconate, Methylenemalonic acid, Dimethyl methylenemalonate, Monomethyl methylenemalonate, Cinnamic acid, Methyl cinnamate, Ethyl cinnamate, Crotonic acid, Methyl crotonate, Ethyl crotonate Monofunctional α, β-unsaturated compounds such as
Polyfunctional vinyl ethers such as hexanediol divinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether;
Polyfunctional vinyl compounds such as divinylbenzene;
Etc. As for these polymerizable monomers, only 1 type may be used independently and 2 or more types may be used together.

  The (meth) acrylic acid ester polymer and / or copolymer (B) is obtained by polymerization of a monomer component containing 50 mol% or more of (meth) acrylic acid ester and / or (meth) acrylic acid. It may be anything, and its specific form is not particularly limited. Moreover, as said polymer and / or copolymer (B), only 1 type may be used independently and 2 or more types may be used together.

  Examples of the monomer component (polymerizable monomer) used for the preparation of such a polymer and / or copolymer (B) include the compounds exemplified above as polymerizable monomers that can be included in the composition of the present invention. It can be used as well.

  In a preferred embodiment of the present invention, the polymer and / or copolymer (B) that can be contained in the composition of the present invention can be polymerized with the esterified product (A) that is the main component of the composition of the present invention. Has a functional group. According to such a form, the optical characteristics of the obtained cured product can be improved. Specifically, the toughness and water resistance of the cured product can be improved.

When the polymer and / or copolymer (B) having a functional group polymerizable with the esterified product (A) is prepared by itself, for example, the following five methods:
(1) A method of reacting a polymerizable monomer containing a carboxyl group and a copolymer of (meth) acrylic acid ester with a polymerizable monomer containing a glycidyl group, or a polymerizable monomer containing a glycidyl group and ( A method of reacting a copolymer of a (meth) acrylic ester and a polymerizable monomer containing a carboxyl group;
(2) A method of reacting a polymerizable monomer containing a hydroxyl group and a (meth) acrylic acid ester copolymer with a polymerizable monomer containing an isocyanate group, or a polymerizable monomer containing an isocyanate group and (meta ) A method of reacting a copolymer of acrylic ester with a polymerizable monomer containing a hydroxyl group;
(3) A method of reacting a polymerizable monomer containing a hydroxyl group and / or a carboxyl group and a copolymer of (meth) acrylic acid ester with a polymerizable monomer containing a vinyl ether group and another polymerizable group, or A method of reacting a polymerizable monomer containing a vinyl ether group and another polymerizable group and a copolymer of (meth) acrylic acid ester with a polymerizable monomer containing a hydroxyl group and / or a carboxyl group;
(4) A method of reacting a polymerizable monomer containing a hydroxyl group and a copolymer of (meth) acrylic acid ester with a polymerizable monomer containing an acid anhydride group, or a polymerizable monomer containing an acid anhydride group And a method of reacting a copolymer of (meth) acrylic acid ester with a polymerizable monomer containing a hydroxyl group;
(5) A method in which a polymerizable monomer composition containing a polyfunctional monomer is partially polymerized to leave part of the double bond in the side chain of the polymer,
Either of these can be adopted. However, it is needless to say that other methods may be used.

When the polymerizable oligomer is added to the composition of the present invention, an effect of improving the toughness of the cured product is obtained. Examples of such polymerizable oligomers include saturated or unsaturated polybasic acids or anhydride acids thereof (eg, maleic acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, etc.) A saturated or unsaturated polyhydric alcohol (for example, ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, polyethylene glycol) , Polypropylene glycol, 1,4-dimethylolbenzene, trimethylolpropane, pentaerythritol and the like) and (meth) acrylic acid to obtain a polyester (meth) acrylate;
Polyfunctional epoxy compounds (for example, bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexenyl-3 ', 4'-epoxycyclohexene carboxylate, hexahydrophthalic acid diglycidyl ether, triglycidyl Epoxy (meth) acrylate obtained by reaction of isocyanurate and the like with (meth) acrylic acid;
Polyfunctional oxetane compounds (eg, 4,4′-bis [(3-ethynyl-3-oxetanyl) methoxymethyl] biphenyl, bis [(3-ethynyl-3-oxetanyl) methyl] ester of 1,4-benzenedicarboxylic acid 9,9-bis [2-methyl-4- {2- (3-oxetanyl)} butoxyphenyl] fluorene, 9,9-bis [4 [2- {2- (3-oxetanyl)} butoxy] ethoxyphenyl ] Oxetane (meth) acrylate obtained by reaction of fluorene and the like with (meth) acrylic acid;
Saturated or unsaturated polyhydric alcohol (for example, ethylene glycol, neopentyl glycol, polytetramethylene glycol, polyester polyol, polycaprolactone polyol, etc.) and organic polyisocyanate (for example, tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, etc.) ) And a hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, etc.)) (Meth) acrylate;
Polysiloxane poly (meth) acrylate obtained by reaction of polysiloxane with (meth) acrylic acid;
Polyamide poly (meth) acrylate obtained by reaction of polyamide with (meth) acrylic acid;
Etc. These polymerizable oligomers may be used alone or in combination of two or more.

  Polymers other than the above-described polymers may be added to the composition of the present invention. For example, polymers such as polycarbonate, polystyrene, silicon resin, polyimide, polyamide, saturated polyester, polyvinyl acetate, polyvinyl chloride, polyvinyl alcohol, polyvinyl acetal, AS resin, EVA resin can be added to the composition of the present invention. . When such a polymer is added to the composition, effects such as improvement of optical properties and mechanical properties of the cured product can be obtained. In addition, only 1 type may be used individually for these polymers, and 2 or more types may be used together.

  The curable composition of the present invention may contain a polymerization initiator. When a polymerization initiator is contained in the composition, polymerization (curing) of the composition is started according to a predetermined polymerization initiation factor. Although the form in particular of a polymerization initiator is not restrict | limited, A photoinitiator (C1) and a thermal polymerization initiator (C2) are illustrated. Preferably, a photopolymerization initiator (C1) is added. According to such a form, the manufacturing efficiency of the optical component using the curable composition of the present invention can be improved. More preferably, both the photopolymerization initiator (C1) and the thermal polymerization initiator (C2) are included in the composition of the present invention. According to such a form, the fall of the light resistance of the composition accompanying the addition of a photoinitiator can be suppressed. As a result, the manufacturing efficiency of the optical component can be further improved.

As an example of the polymerization initiator, examples of the photopolymerization initiator (C1) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2 -Hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2- Acetophenones such as dimethylamino-1- (4-morpholinophenyl) butanone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomers;
Benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether;
Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 2,4 , 6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium chloride, etc. Benzophenones;
2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3,4- Thioxanthones such as dimethyl-9H-thioxanthone-9-one mesochloride;
2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenyl Acylphosphine oxides such as phosphine oxide;
Etc. Among these, those not containing an aromatic hydrocarbon structure can be preferably used. In addition, as for these photoinitiators (C1), only 1 type may be used independently and 2 or more types may be used together.

On the other hand, examples of the thermal polymerization initiator (C2) include methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, acetyl acetate peroxide, 1,1-bis (t-hexylperoxy). −3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) -cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1 -Bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) -cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 1,1-bis (T-Butylperoxy) butane, 2,2-bis (4,4- -T-butylperoxycyclohexyl) propane, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t- Butyl cumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide Oxide, octanoyl peroxide Id, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, m-toluoyl benzoyl peroxide, benzoyl peroxide, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-t-butyl) (Cyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethoxyhexyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-s-butyl peroxydicarbonate, Di (3-methyl-3-methoxybutyl) peroxydicarbonate, α, α′-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethyl Rubutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypi Valate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) ) Hexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-hexyl Peroxyisopropyl monocarbonate, t-butyl peroxyisobutyrate, t-butyl Tilperoxymalate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxyisopropylmonocarbonate, t-butylperoxy-2-ethylhexyl Monocarbonate, t-butylperoxyacetate, t-butylperoxy-m-toluylbenzoate, t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate, 2,5-dimethyl-2,5-bis (M-toluylperoxy) hexane, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyallyl monocarbonate, t-butyltrimethylsilyl peroxide, 3,3 ′, 4,4′-tetra (t-bu Tilperoxycarbonyl) benzophenone, organic peroxide initiators such as 2,3-dimethyl-2,3-diphenylbutane;
2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1-[(1-cyano-1-methylethyl) azo] formamide, 1,1′-azobis (cyclohexane-1-carbonitrile), 2, 2'-azobis (2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2- Methylpropionamidine) dihydrochloride, 2,2′-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2′-azobis [N- (4-chlorophenyl) -2-methylpropionamidine] dihydride Chloride, 2,2'-azobis [N- (4-hydrophenyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azo [2-Methyl-N- (phenylmethyl) propionamidine] dihydrochloride, 2,2′-azobis [2-methyl-N- (2-propenyl) propionamidine] dihydrochloride, 2,2′-azobis [N -(2-hydroxyethyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl) propane ] Dihydrochloride, 2,2'-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2 ' Azobis [2- (5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- [1- (2-hydroxyethyl) -2- Imidazolin-2-yl] propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis [2-methyl-N- [1,1- Bis (hydroxymethyl) -2-hydroxyethyl] propionamide], 2,2′-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide], 2,2′-azobis [2-Methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis (2-methylpropionamide), 2,2′-azobis (2,4,4-trimethylbenzene) Tan), 2,2'-azobis (2-methylpropane), dimethyl-2,2-azobis (2-methylpropionate), 4,4'-azobis (4-cyanopentanoic acid), 2,2 ' -Azo initiators such as azobis [2- (hydroxymethyl) propionitrile];
Etc. In addition, only 1 type may be used individually for these thermal polymerization initiators (C2), and 2 or more types may be used together.

  When the above thermal polymerization initiator (C2) is added to the composition of the present invention, a thermal polymerization accelerator may be further added to the composition of the present invention. Examples of the thermal polymerization accelerator include metal soaps such as cobalt, copper, tin, zinc, manganese, iron, zirconium, chromium, vanadium, calcium, and potassium; primary, secondary, or tertiary amine compounds; quaternary Examples include ammonium salts; thiourea compounds; ketone compounds and the like. Of these, acetylacetone and methyl acetoacetate can be preferably used. In addition, only 1 type may be used individually for these thermal polymerization accelerators, and 2 or more types may be used together.

  As mentioned above, although the specific example of the additive which can be added to the composition of this invention was demonstrated, additives other than the above may be added in the composition of this invention. Examples of such additives include plasticizers, ultraviolet absorbers, antioxidants, inorganic fillers, antifoaming agents, thickeners, thixotropic agents, leveling agents, mold release agents, and the like. There is no restriction | limiting in particular about the specific form of these additives, A conventionally well-known knowledge can be referred suitably.

If it is desired to produce a more precise optical component using the composition of the present invention, the choice of release agent should be made with caution. Here, as the release agent, for example, metal soap such as zinc stearate, calcium stearate, magnesium stearate, lithium stearate, barium stearate, sodium stearate;
Caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, myristoleic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, 12-hydroxystearic acid Fatty acids such as acids, ricinoleic acid;
Higher alcohols such as lauryl alcohol, stearyl alcohol, behenyl alcohol;
Fatty acid esters such as methyl stearate, stearyl stearate, behenyl behenate, sorbitan monostearate;
Silicone mold release agents such as KF96, KF965, KF410, KF412, KF4701, KF54, KS61, KM244F, KS702, KF725, KS707, KS800P, which are products of Shin-Etsu Chemical Co., Ltd .;
Product names of Polynova PF-136A, PF-156A, PF-151N, PF-636, PF-6320, PF-656, PF-6520, PF-651, PF-652, PF-3320 Fluorosurfactants such as
Etc. As for these mold release agents, only 1 type may be used independently and 2 or more types may be used together. Among these, fatty acids, higher alcohols, fatty acid esters, and fluorosurfactants can be preferably used from the viewpoint that they can exhibit releasability while maintaining transparency.

  The compounding ratio of each component contained in the curable composition of the present invention is not particularly limited, and can be appropriately adjusted by referring to conventionally known knowledge about the curable composition. If an example of a compounding ratio is given, in the composition of this invention, the compounding quantity of said esterified substance (A) becomes like this. Preferably it is 10-95 mass% with respect to the whole quantity of a composition, More preferably, it is 20-90 mass. %, More preferably 30 to 85% by mass. When the blended amount of the esterified product (A) is within such a range, the balance of heat resistance, dimensional stability, and moldability of the resulting cured product can be improved. In the composition of the present invention, the blending amount of the polymer and / or copolymer (B) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass with respect to the total amount of the composition. %, More preferably 15 to 30% by mass. When the blending amount of the polymer and / or copolymer (B) is within such a range, the shrinkage at the time of curing of the composition is effectively suppressed, and the moldability of the cured product is improved. sell. Furthermore, in the composition of the present invention, the blending amount of the polymerization initiator (the total amount of the photopolymerization initiator (C1) and the thermal polymerization initiator (C2)) is preferably relative to the total amount of the composition. 0.001 to 10% by mass, more preferably 0.001 to 5% by mass, further preferably 0.001 to 3% by mass, particularly preferably 0.001 to 2% by mass, and most preferably 0.01 to 2% by mass. %. If the amount of the polymerization initiator is too small, the polymerizability may be lowered. On the other hand, when there are too many compounding quantities of a polymerization initiator, there exists a possibility that the light resistance of hardened | cured material may fall. Moreover, when the composition of this invention contains both a photoinitiator (C1) and a thermal-polymerization initiator (C2), mass ratio (thermal-polymerization initiator (C2) / photoinitiator of these compounding quantities ( C1)) is preferably 1 to 100, more preferably 2 to 100, still more preferably 2 to 50, still more preferably 2 to 30, particularly preferably 3 to 20, Preferably it is 5-20. When this mass ratio is too small, there is a possibility that the effect for improving the weather resistance cannot be sufficiently obtained. On the other hand, if this mass ratio is too large, the curability by active energy rays may be reduced.

  As mentioned above, although the preferable form of the compounding quantity in the composition of this invention was demonstrated, these are only a preferable form to the last, and the technical scope of this invention is not necessarily restrict | limited to these ranges. Therefore, depending on the case, a blending amount outside the above range may be employed.

  In the composition of the present invention, the upper limit of the content of specific impurities is also defined. That is, in the composition of the present invention, the content of sulfonic acid, sulfonic acid salt and / or sulfonic acid ester (hereinafter also simply referred to as “sulfonic acid derivative”) is 100 ppm in terms of sulfur atom with respect to the total amount of the composition. Hereinafter, it is preferably 50 ppm or less, more preferably 30 ppm or less, still more preferably 20 ppm or less, and particularly preferably 10 ppm or less. When the content of the sulfonic acid derivative in the composition is in such a range, a decrease in light resistance of the cured product due to the presence of the sulfonic acid derivative and a color change with time can be suppressed. In addition, as a value of content of a sulfonic acid derivative, the value measured by the method explained in full detail in the below-mentioned Example shall be employ | adopted.

  As a method for setting the content of the sulfonic acid derivative in the composition within the above range, (1) the sulfonic acid derivative is not used in the production process of the composition; or (2) in the production process of the composition, When a sulfonic acid derivative is used, there are two methods of further performing a removal step of removing the sulfonic acid derivative.

  When the above method (1) is adopted, a compound (for example, cation exchange resin) other than the most commonly used sulfonic acid derivative (particularly p-toluenesulfonic acid) is used as a catalyst. The esterified product (A) may be produced using a conventional dehydration condensation method or a transesterification method using a metal alcoholate or the like as a catalyst. According to such a method, the content of the sulfonic acid derivative is theoretically zero, and it is not necessary to add a removal step, which is preferable from the viewpoint of manufacturing cost.

  When the above method (2) is employed, means for removing the sulfonic acid derivative in the removal step include, for example, washing with water or an alkaline aqueous solution, basic inorganic salt (for example, MgO) or anion exchange. Examples include adsorption filtration using a resin.

  The curable composition of the present invention is further characterized in that the glass transition temperature of the cured product exhibits a value within a predetermined range. Here, "glass transition" refers to a phenomenon in which when a glassy substance such as an amorphous polymer compound is heated, the temperature dependency of the substance such as the heat capacity and the coefficient of thermal expansion changes rapidly. The temperature at which “glass transition” occurs is referred to as “glass transition temperature”. In addition, in this application, the value measured by the method (dynamic viscoelasticity measuring method) explained in full detail in the below-mentioned Example as a value of a glass transition temperature shall be employ | adopted.

  The glass transition temperature of the hardened | cured material obtained by hardening of the curable composition of this invention is -10-50 degreeC, Preferably it is 0-45 degreeC, More preferably, it is 0-35 degreeC, More preferably, it is 0. ~ 30 ° C. If the glass transition temperature of the cured product is too low, the water resistance and restoration properties of the cured product may be reduced. On the other hand, if the glass transition temperature of the cured product is too high, cracks may occur during mold release when an optical component such as a lens sheet is manufactured using a mold. The value of the glass transition temperature of the cured product is, for example, the number of repeating ether oxide alkylene oxide units (n in Formula 1) of the esterified product (A) contained in the composition or the esterified product (A). It can be controlled by adjusting the type of polyol compound to be prepared, the type of monomer constituting the polymer and / or copolymer (B), and the like.

  As described above, the cured product obtained by curing the curable composition of the present invention is excellent in light resistance. As an index representing such characteristics, for example, there is a yellow index change rate (hereinafter also referred to as “ΔYI”) indicating the degree of discoloration before and after the weather resistance test. The specific value of ΔYI of the cured product obtained by curing the curable composition of the present invention is not particularly limited, but ΔYI of the cured product is preferably 1.5 or less, more preferably 1.4 or less. More preferably, it is 1.3 or less, More preferably, it is 1.2 or less, More preferably, it is 1.1 or less, Especially preferably, it is 1.0 or less, Most preferably, it is 0.5 or less It is. However, the technical scope of the present composition is not limited only to the form in which the cured product exhibits ΔYI within such a range. In addition, as the value of ΔYI, a value measured by a method described in detail in Examples described later is adopted.

  The curable composition for optical components of the present invention includes, for example, the esterified product (A) controlled to have a desired structure, a polymer and / or copolymer (B) of (meth) acrylic acid ester, and It can be produced by preparing other additive components and mixing them by a conventionally known method in the field of composition production.

  In some cases, the (meth) acrylic ester polymer and / or copolymer (B) may be partially polymerized to partially polymerize the (meth) acrylic polymer and / or copolymer and the (meth) acrylic monomer. It can also be produced by preparing a mixture of monomers and adding the above esterified product (A) and other additive components to this mixture.

  Furthermore, by preparing a polymer and / or copolymer of a (meth) acrylic acid ester having a functional group by partial polymerization, and mixing and reacting with a methacrylate having another functional group capable of reacting with the functional group. A mixture of the above esterified product (A), a polymer and / or copolymer (B) of (meth) acrylic acid ester, and other additive components may be produced.

  The curable composition for optical components of the present invention becomes a cured product by curing. By utilizing this property, for example, it can be used for the production of optical components (for example, lens sheets). The means for curing the composition to obtain a cured product is not particularly limited, and conventionally known knowledge about curing of the curable composition can be appropriately referred to. If an example is given, as a hardening means in case the composition of this invention contains a photoinitiator, irradiation of an active energy ray is mentioned, for example. In this case, examples of the active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, electron beams, and gamma rays.

  In the case of curing by ultraviolet rays, it is preferable to use a light source including light within a wavelength range of 150 to 450 nm. As such a light source, a solar ray, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like is preferable. Along with these light sources, it is possible to use heat by infrared rays, far infrared rays, hot air, high frequency heating or the like.

  For curing by electron beam irradiation, an electron beam having an acceleration voltage of preferably 10 to 500 kV, more preferably 20 to 300 kV, and still more preferably 30 to 200 kV can be used. Under the present circumstances, the irradiation amount of an electron beam becomes like this. Preferably it is 2-500 kGy, More preferably, it is 3-300 kGy, More preferably, it is 5-200 kGy. Along with the electron beam, it is possible to use heat by infrared rays, far infrared rays, hot air, high-frequency heating or the like.

  On the other hand, heating is mentioned as a hardening means in case the composition of this invention contains a thermal-polymerization initiator (and thermal-polymerization accelerator as needed).

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example and a comparative example, the technical scope of this invention is not necessarily restrict | limited only to the following form.

[Synthesis Example 1]
A flask equipped with a stirrer, a thermometer, a condenser, and a mixed gas introduction tube of air and nitrogen was added to an ethylene oxide 8-mol adduct of neopentyl glycol (hereinafter also referred to as “NPG-8EO”) (456 g), methyl methacrylate. (Hereinafter also referred to as “MMA”) (400 g), dibutyltin oxide as a catalyst (hereinafter also referred to as “DBTO”) (9.12 g), and 4-hydroxy-2,2,6,6 as a polymerization inhibitor -Tetramethylpiperidine-N-oxyl (hereinafter also referred to as “4H-TEMPO”) (45.6 mg) was added and stirred, and the temperature was raised to 110 ° C. After raising the temperature, the esterification reaction was carried out by transesterification over 6 hours while distilling off the methanol produced by the reaction.

  Unreacted MMA was distilled off from the resulting reaction solution to obtain NPG-8EO dimethacrylate as the esterified product (A). This is referred to as “compound (M-1)”.

  When the content rate of the sulfur atom contained in the obtained compound (M-1) was measured by the inductively coupled plasma (ICP) analysis method, the sulfur atom was not detected.

  In addition, a compound (M-1) is used as a manufacturing raw material of a curable composition in Examples 1-4 and 8 mentioned later.

[Synthesis Example 2]
A flask equipped with a stirrer, a thermometer, a condenser, and a mixed gas introduction tube of air and nitrogen was added to an ethylene oxide 6-mol adduct of neopentyl glycol (hereinafter also referred to as “NPG-6EO”) (368 g), MMA (400 g). ), DBTO (7.36 g), and 4H-TEMPO (36.8 mg) were added and stirred, and the temperature was raised to 110 ° C. After raising the temperature, the esterification reaction was carried out by transesterification over 6 hours while distilling off the methanol produced by the reaction.

  Unreacted MMA was distilled off from the resulting reaction solution to obtain NPG-6EO dimethacrylate as the esterified product (A). This is referred to as “compound (M-2)”.

  When the content rate of the sulfur atom contained in the obtained compound (M-2) was measured by the inductively coupled plasma (ICP) analysis method, the sulfur atom was not detected.

  In addition, a compound (M-2) is used as a manufacturing raw material of a curable composition in Example 5 mentioned later.

[Synthesis Example 3]
NPG-8EO (456 g), MMA (400 g), potassium t-butoxide (hereinafter also referred to as “t-BuOK”) in a flask equipped with a stirrer, thermometer, condenser, and mixed gas introduction tube of air and nitrogen (4.56 g) and 4H-TEMPO (45.6 mg) were added and stirred, and the temperature was raised to 110 ° C. After raising the temperature, the esterification reaction was carried out by transesterification over 4 hours while distilling off the methanol produced by the reaction.

  Unreacted MMA was distilled off from the resulting reaction solution to obtain NPG-8EO dimethacrylate as the esterified product (A). This is referred to as “compound (M-3)”.

  When the content rate of the sulfur atom contained in the obtained compound (M-3) was measured by the inductively coupled plasma (ICP) analysis method, the sulfur atom was not detected.

  In addition, a compound (M-3) is used as a manufacturing raw material of a curable composition in Example 6 mentioned later.

[Synthesis Example 4]
In a flask equipped with a stirrer, thermometer, condenser, and mixed gas introduction tube of air and nitrogen, NPG-8EO (456 g), methacrylic acid (hereinafter also referred to as “MAA”) (189 g), cation exchange resin Amberlist 15D (manufactured by Organo Corporation; washed with toluene and water three times and dried) (25 g), toluene (50 g), and 4H-TEMPO (45.6 mg) were added and stirred at 110 ° C. The temperature was raised to. After raising the temperature, an esterification reaction was carried out by a dehydration condensation method over 6 hours while distilling off water produced by the reaction.

  After completion of the reaction, the cation exchange resin was removed by filtration, and toluene and unreacted MAA were distilled off by heating under reduced pressure to obtain NPG-8EO dimethacrylate as the esterified product (A). This is referred to as “compound (M-4)”.

  When the content rate of the sulfur atom contained in the obtained compound (M-4) was measured by the inductively coupled plasma (ICP) analysis method, the sulfur atom content rate was 6 ppm.

  In addition, a compound (M-4) is used as a manufacturing raw material of a curable composition in Example 7 mentioned later.

[Synthesis Example 5]
NPG-8EO (456 g), MAA (189 g), p-toluenesulfonic acid (hereinafter also referred to as “PTS”) in a flask equipped with a stirrer, a thermometer, a condenser, and a mixed gas introduction tube of air and nitrogen. 10 g), toluene (50 g), and 4H-TEMPO (45.6 mg) were added and stirred, and the temperature was raised to 110 ° C. After raising the temperature, an esterification reaction was carried out by a dehydration condensation method over 6 hours while distilling off water produced by the reaction.

  After completion of the reaction, washing with water and allowing to stand, and repeating the operation of separating the aqueous layer portion three times, further, toluene and unreacted MAA were distilled off by heating under reduced pressure, and NPG-8EO dimethacrylate was obtained as the esterified product (A). Got. This is referred to as “compound (M-5)”.

  When the content rate of the sulfur atom contained in the obtained compound (M-5) was measured by the inductively coupled plasma (ICP) analysis method, the sulfur atom content rate was 310 ppm.

  In addition, a compound (M-5) is used as a manufacturing raw material of a curable composition in Example 8 and the comparative example 1 which are mentioned later.

[Synthesis Example 6]
To a flask equipped with a stirrer, a thermometer, a condenser, and a mixed gas introduction tube of air and nitrogen, NPG-6EO (368 g), ethyl acrylate (400 g), DBTO (7.36 g), and 4H-TEMPO (36 .8 mg) was added and stirred, and the temperature was raised to 110 ° C. After raising the temperature, the esterification reaction was carried out by transesterification over 6 hours while distilling off the methanol produced by the reaction.

  Unreacted ethyl acrylate was distilled off from the resulting reaction solution to obtain NPG-6EO diacrylate as the esterified product (A). This is referred to as “compound (M-6)”.

  When the content rate of the sulfur atom contained in the obtained compound (M-6) was measured by the inductively coupled plasma (ICP) analysis method, the sulfur atom was not detected.

  In addition, a compound (M-6) is used as a manufacturing raw material of a curable composition in Example 9 mentioned later.

[Synthesis Example 7]
In a flask equipped with a stirrer, a thermometer, a condenser, and a mixed gas introduction tube of air and nitrogen, 4 mol of ethylene oxide and 4 mol of propylene oxide (hereinafter referred to as “NPG-4EO-4PO”) (512 g) ), MMA (400 g), DBTO (10.24 g), and 4H-TEMPO (51.2 mg) were added and stirred, and the temperature was raised to 110 ° C. After raising the temperature, the esterification reaction was carried out by transesterification over 6 hours while distilling off the methanol produced by the reaction.

  Unreacted MMA was distilled off from the resulting reaction solution to obtain NPG-4EO-4PO dimethacrylate as the esterified product (A). This is referred to as “compound (M-7)”.

  When the content rate of the sulfur atom contained in the obtained compound (M-7) was measured by the inductively coupled plasma (ICP) analysis method, the sulfur atom was not detected.

  In addition, a compound (M-7) is used as a manufacturing raw material of a curable composition in Example 10 mentioned later.

[Synthesis Example 8]
A flask equipped with a stirrer, a thermometer, a condenser, and a mixed gas introduction tube of air and nitrogen was added to an ethylene oxide 4 mol adduct of butylethylpropanediol (hereinafter also referred to as “BEPD-4EO”) (336 g), MMA ( 400 g), DBTO (6.72 g), and 4H-TEMPO (33.6 mg) were added and stirred, and the temperature was raised to 110 ° C. After raising the temperature, the esterification reaction was carried out by transesterification over 6 hours while distilling off the methanol produced by the reaction.

  Unreacted MMA was distilled off from the resulting reaction solution, and BEPD-4EO dimethacrylate was obtained as an esterified product (A). This is referred to as “compound (M-8)”.

  When the content rate of the sulfur atom contained in the obtained compound (M-8) was measured by the inductively coupled plasma (ICP) analysis method, the sulfur atom was not detected.

  In addition, a compound (M-8) is used as a manufacturing raw material of a curable composition in Example 11 mentioned later.

[Synthesis Example 9]
A flask equipped with a stirrer, a thermometer, a condenser, and a mixed gas introduction tube of air and nitrogen was added to a 12-methyl trimethylolpropane ethylene oxide adduct (hereinafter also referred to as “TMP-12EO”) (662 g), MMA (600 g). ), DBTO (13.24 g), and 4H-TEMPO (66.2 mg) were added and stirred, and the temperature was raised to 110 ° C. After raising the temperature, the esterification reaction was carried out by transesterification over 6 hours while distilling off the methanol produced by the reaction.

  Unreacted MMA was distilled off from the obtained reaction liquid, and TMP-12EO trimethacrylate was obtained as an esterified product (A). This is referred to as “compound (M-9)”.

  When the content rate of the sulfur atom contained in the obtained compound (M-9) was measured by the inductively coupled plasma (ICP) analysis method, the sulfur atom was not detected.

  In addition, a compound (M-9) is used as a manufacturing raw material of a curable composition in Example 12 mentioned later.

[Synthesis Example 10]
A flask equipped with a stirrer, a thermometer, a condenser, and a mixed gas introduction tube of air and nitrogen was added to neopentyl glycol (135 g), MMA (400 g), t-BuOK (1.35 g), and 4H-TEMPO (13 0.5 mg), and the mixture was stirred and heated to 110 ° C. After raising the temperature, the esterification reaction was carried out by transesterification over 4 hours while distilling off the methanol produced by the reaction.

  Unreacted MMA is distilled off from the obtained reaction solution, and then unreacted neopentyl glycol, neopentyl glycol monomethacrylate, and t-BuOK are removed by washing with water, and neopentyl glycol dicarboxylate having no ether structure is removed. Methacrylate was obtained. This is referred to as “compound (M-10)”.

  When the content rate of the sulfur atom contained in the obtained compound (M-10) was measured by the inductively coupled plasma (ICP) analysis method, the sulfur atom was not detected.

  In addition, a compound (M-10) is used as a manufacturing raw material of a curable composition in the comparative example 2 mentioned later.

[Synthesis Example 11]
A flask equipped with a stirrer, a thermometer, a condenser, and a mixed gas introduction tube of air and nitrogen was added to a 25-mole ethylene oxide adduct of neopentyl glycol (hereinafter also referred to as “NPG-25EO”) (1204 g), MMA (400 g). ), DBTO (24.08 g), and 4H-TEMPO (120.4 mg) were added and stirred, and the temperature was raised to 110 ° C. After raising the temperature, the esterification reaction was carried out by transesterification over 8 hours while distilling off the methanol produced by the reaction.

  Unreacted MMA was distilled off from the resulting reaction solution to obtain NPG-25EO dimethacrylate. This is referred to as “compound (M-11)”.

  When the content rate of the sulfur atom contained in the obtained compound (M-11) was measured by the inductively coupled plasma (ICP) analysis method, the sulfur atom was not detected.

  In addition, a compound (M-11) is used as a manufacturing raw material of a curable composition in the comparative example 3 mentioned later.

[Synthesis Example 12]
A flask equipped with a stirrer, a thermometer, a condenser, and a mixed gas introducing tube of air and nitrogen was added to ethylene oxide 2-mol adduct of bisphenol A (hereinafter also referred to as “BPA-2EO”) (228 g), MMA (400 g). , DBTO (4.56 g), and 4H-TEMPO (22.8 mg) were added and stirred, and the temperature was raised to 110 ° C. After raising the temperature, the esterification reaction was carried out by transesterification over 6 hours while distilling off the methanol produced by the reaction.

  Unreacted MMA was distilled off from the resulting reaction solution to obtain BPA-2EO dimethacrylate. This is referred to as “compound (M-12)”.

  When the content rate of the sulfur atom contained in the obtained compound (M-12) was measured by the inductively coupled plasma (ICP) analysis method, the sulfur atom was not detected.

  In addition, a compound (M-12) is used as a manufacturing raw material of a curable composition in the comparative example 4 mentioned later.

[Synthesis Example 13]
MMA (190 g), MAA (8.6 g), and toluene (463 g) were placed in a flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube, stirred, and heated to 70 ° C. after nitrogen substitution. . After the temperature increase, 2,2′-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries, Ltd .; V-65) (0.99 g) as a thermal polymerization initiator was diluted with toluene (50 g). The solution was slowly added dropwise, taking care of the exotherm. After reacting at 70 ° C. for 3 hours, the temperature was raised to 90 ° C. and reacted at 90 ° C. for 2 hours to complete radical polymerization of MMA and MAA.

  Subsequently, methoquinone (0.68 g), glycidyl methacrylate (156 g), and tetraphenylphosphonium bromide (2.71 g) were added, and the temperature was raised to 100 ° C. while introducing a mixed gas of air and nitrogen. The reaction was continued until the acid value was 5 or less. The obtained polymer solution was reprecipitated with n-hexane, and then n-hexane was removed under reduced pressure to obtain a copolymer of MMA and MAA. This is referred to as “compound (P-1)”.

  When the molecular weight of the obtained compound (P-1) was measured by gel permeation chromatography (GPC), the number average molecular weight (Mn) was 35000 and the weight average molecular weight (Mw) was 78000.

  Furthermore, when the content rate of the sulfur atom contained in the obtained compound (P-1) was measured by the inductively coupled plasma (ICP) analysis method, the sulfur atom was not detected.

  In addition, a compound (P-1) is used as a manufacturing raw material of a curable composition in Example 2 mentioned later.

[Synthesis Example 14]
MMA (85 g), polyethylene glycol monomethyl ether methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .; NK ester M-90G; hereinafter simply referred to as “M-90G” (Also referred to as “)” (15 g) and toluene (100 g) were added and stirred, and the temperature was raised to 70 ° C. after nitrogen substitution. After the temperature increase, 2,2′-azobis (2,4-dimethylvaleronitrile) (made by Wako Pure Chemical Industries, Ltd .; V-65) (1.5 g) as a thermal polymerization initiator was diluted with toluene (50 g). The solution was slowly added dropwise, taking care of the exotherm. After reacting at 70 ° C. for 4 hours, the temperature was raised to 90 ° C. and reacted at 90 ° C. for 1 hour to complete radical polymerization of MMA and M-90G.

  The obtained polymer solution was reprecipitated with n-hexane, and then n-hexane was removed under reduced pressure to obtain a copolymer of MMA and M-90G. This is referred to as “compound (P-2)”.

  When the molecular weight of the obtained compound (P-2) was measured by gel permeation chromatography (GPC), the number average molecular weight (Mn) was 14,000 and the weight average molecular weight (Mw) was 25000.

  Furthermore, when the content rate of the sulfur atom contained in the obtained compound (P-2) was measured by the inductively coupled plasma (ICP) analysis method, the sulfur atom was not detected.

  In addition, a compound (P-2) is used as a manufacturing raw material of a curable composition in Example 3 and 5 mentioned later.

[Examples 1 to 12 and Comparative Examples 1 to 4]
The curable compositions for optical components of Examples 1 to 12 and Comparative Examples 1 to 4 were prepared according to the formulation shown in Table 1 below. When preparing the composition, first, the components of the composition were mixed thoroughly to obtain a uniform solution. Thereafter, the solvent was removed by heating under reduced pressure to prepare a composition in which each component was well dispersed. The following components were used as additive components other than the respective compounds prepared in the above synthesis examples. The numbers in the table indicate “parts by mass”.

D-1173: Photopolymerization initiator; 2-hydroxy-2-methyl-1-phenylpropan-1-one (manufactured by Ciba Specialty Chemicals; Darocur 1173)
PBO: thermal polymerization initiator; t-butyl peroxy-2-ethylhexanoate (manufactured by NOF Corporation; perbutyl O)
PMMA: Polymethyl methacrylate (manufactured by Sumitomo Chemical Co., Ltd .; Sumipex LG-6A)
PF-656: mold release agent; fluorosurfactant (Omnova Solutions)

[Characteristic evaluation of composition]
About the curable composition obtained by said Example and comparative example, content of the ether structure and sulfonic acid derivative in a composition was measured with the following methods. The values obtained by measurement are shown in Table 2 below.

<Method for measuring ether structure content>
Composition (15 mg) and 48% hydrobromic acid (200 mg) were placed in a 5 mL aluminum sealed vial, sealed through a Teflon silicone septum and heated in an oven at 150 ° C. for 2 hours to decompose bromate The ether structure in the composition was brominated. After completion of the reaction, the content of bromide (for example, 1,2-dibromopropane, 1,2-dibromobutane, 1,4-dibromobutane, etc.) in the reaction solution is measured by gas chromatography, and compared with a calibration curve. Quantified. The content of the ether structure in the composition was calculated from the quantified bromide content value.

<Measurement method of sulfonic acid derivative content>
The composition was dissolved in toluene, water was added, and sulfonic acid and sulfonate were extracted into the aqueous layer with a separatory funnel. The aqueous layer was separated, concentrated using an evaporator, and water was removed using a hot air dryer. Then, it was dissolved again in acetone, the sulfonic acid content was measured by gas chromatography, and quantified by comparison with a calibration curve.

  On the other hand, water was added again to the toluene layer of the above separatory funnel, and the mixture was heated at 100 ° C. for 10 hours with stirring to decompose the sulfonate ester into sulfonic acid. Subsequently, the aqueous layer was separated from the reaction solution using a separatory funnel, concentrated using an evaporator, and water was removed using a hot air dryer. Then, it was dissolved again in acetone, the sulfonic acid content was measured by gas chromatography, and quantified by comparison with a calibration curve.

  The contents of the sulfonic acid obtained by both the above determinations were summed to obtain the content of the sulfonic acid derivative in the composition. Table 2 below shows values converted to the sulfur atom content.

[Production of sheet-like molded product and evaluation of its properties]
About the curable composition obtained by said Example and comparative example, the sheet-like molded object which has a thickness of 0.2 mm or 1 mm was produced with the following methods, and glass was obtained using the obtained molded object. The transition temperature and water absorption were measured, and the weather resistance was evaluated. The obtained results are shown in Table 2 below. As for the curing means of the composition, thermal curing was used only in Example 4, and ultraviolet (UV) curing was used in the other Examples and Comparative Examples.

<Method for producing sheet-like molded body>
Ultraviolet (UV) curing: A silicon rubber spacer (thickness: 0.2 mm or 1 mm) was placed on a glass plate, and a curable composition was injected into a region surrounded by the spacer. A PET film (thickness: 250 μm) was placed on the film, and ultraviolet rays (main wavelength: 365 nm, irradiation intensity: 43 mJ / cm ² · second) were irradiated for 93.2 seconds using a 250 mW ultra-high pressure mercury lamp. Cured. After natural cooling to room temperature, the glass plate was removed to obtain a sheet-like molded body.

  Thermosetting: The curable composition was poured into a case in which a silicon rubber spacer (thickness: 0.2 mm or 1 mm) was sandwiched between two glass plates. Then, it heated in 60 degreeC warm water for 1 hour, and was hardened slowly. After curing, it was post-cured in a dryer at 110 ° C. for 2 hours. After natural cooling to room temperature, the glass plate was removed to obtain a sheet-like molded body.

<Measuring method of glass transition temperature>
The sheet-like molded body having a thickness of 0.2 mm produced as described above was cut into a strip having a width of 5 mm to obtain a test piece, and a viscoelasticity measuring device (manufactured by TA Instruments Japan Co., Ltd .; RSA-II) Was used to measure the dynamic viscoelasticity, and the glass transition temperature (° C.) was measured. Specific measurement conditions were set to tensile mode, frequency: 1 Hz, distance between clamps: 25 mm, amplitude: 0.1%, and rate of temperature increase: 5 ° C./min. The temperature at which the loss tangent (tan δ) peaked when the temperature was raised from −40 ° C. to 100 ° C. was defined as the glass transition temperature (° C.).

<Measurement method of water absorption>
Except that the 1 mm-thick sheet-shaped molded body produced above was cut into a size of 40 mm × 40 mm to obtain a test piece, the mass (W1) of the test piece before water absorption and water absorption were obtained in accordance with JIS K 6911. The mass (W2) of the later test piece was measured, and the water absorption was calculated according to the following formula 1.

<Evaluation method of weather resistance>
An accelerated weather resistance test was performed using the sheet-like molded body having a thickness of 1 mm produced above. Specifically, using a super energy irradiation tester (manufactured by Suga Test Instruments Co., Ltd.), light irradiation for 6 hours (irradiation intensity: 100 mW / cm ² , wavelength: 295 to 450 nm, humidity: 70% Rh, temperature: 60 ) And 6 hours of condensation (humidity: 90% Rh or more, temperature: 30 ° C.) as one cycle, a weather resistance test of 10 cycles (total of 120 hours) was conducted. In addition, the discoloration by 10 cycles of this accelerated weathering test was almost equivalent to the discoloration in the outdoor exposure test for 2.5 years.

  The discoloration of the sheet-like molded body before and after the weather resistance test was measured in a transmission mode using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd .; Sigma 90 system). In Table 2, the measurement results are shown as yellow index change rate (ΔYI) values.

  Furthermore, the discoloration and water resistance deterioration (whitening) of the sheet-like molded body before and after the weather resistance test were visually observed. In the table, “◯” indicates that discoloration and whitening were not observed, “△” indicates that discoloration and whitening were slightly observed, and “×” indicates that significant discoloration and whitening were observed. Show.

[Production of lens sheet and evaluation of its characteristics]
About the curable composition obtained by said Example and comparative example, the lens sheet was produced with the following methods, and crack resistance and restoring property were evaluated about the obtained lens sheet. The obtained results are shown in Table 2 below. As for the curing means of the composition, thermal curing was used only in Example 4, and ultraviolet (UV) curing was used in the other Examples and Comparative Examples.

<Lens sheet manufacturing method>
Ultraviolet (UV) curing: A curable composition was injected between a lens sheet mold and an acrylic resin plate (thickness: 0.2 mm). Thereafter, using a 250 mW ultra-high pressure mercury lamp, ultraviolet rays (main wavelength: 365 nm, irradiation intensity: 43 mJ / cm ² · second) were irradiated for 93.2 seconds from the acrylic resin plate side to cure the composition. After natural cooling to room temperature, the mold was removed to obtain a lens sheet.

  Thermosetting: A curable composition was injected between a lens sheet mold and an acrylic resin plate (thickness: 0.2 mm). Then, it heated in 60 degreeC oven for 1 hour, and was hardened slowly. After curing, it was post-cured in a dryer at 110 ° C. for 2 hours. After natural cooling to room temperature, the mold was removed to obtain a lens sheet.

<Crack resistance evaluation method>
When producing a lens sheet by said method, it was observed using the optical microscope whether the lens sheet cracked when removing a type | mold. In the table, “◯” indicates that no crack was observed, and “x” indicates that a crack was observed.

<Restorability evaluation method>
The nail | claw was pressed with respect to the lens sheet produced by said method, and the mark was made. After 30 minutes, it was visually observed whether or not the nail pressing trace remained. In the table, “◯” indicates that the pressing trace was not observed, and “X” indicates that the pressing trace was observed.

  From the results shown in Table 2, in the curable composition containing the predetermined esterified product (A), the content of the ether structure of the esterified product (A), the content of the sulfonic acid derivative in the composition, and curing When the glass transition temperature of the product is a value within a predetermined range, it is indicated that the various properties such as water resistance, weather resistance, crack resistance, and resilience are excellent.

  The curable composition for optical parts of the present invention can be suitably used for the production of optical parts that require a high degree of colorless transparency and light resistance. Examples of such optical components include optical components that can be directly exposed to sunlight at the time of use, such as solar cells and outdoor electric bulletin boards, and light sources having a light wavelength distribution from the short wavelength region to the ultraviolet region of visible light. And optical components such as light emitting diodes, optical cables, and display devices.

Claims (7)

A curable composition for optical parts, which contains (meth) acrylic acid ester (A) of a compound having no aromatic hydrocarbon structure and having two or more hydroxyl groups in one molecule,
At least a part of the esterified product (A) is represented by the following chemical formula 1:

Containing an ether structure represented by
The content of the ether structure is 5% by mass or more based on the total amount of the composition,
The content of the sulfonic acid, sulfonate and / or sulfonic acid ester is 100 ppm or less in terms of sulfur atom with respect to the total amount of the composition, and
The glass transition temperature of the cured product obtained by curing the composition is −10 to 50 ° C.,
The curable composition for optical components characterized by the above-mentioned.   The curable composition for optical components according to claim 1, wherein the content of the ether structure is 5 to 65% by mass with respect to the total amount of the composition.   In the esterified product (A), one or more alkylene oxides selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide are added to a compound having two or more hydroxyl groups in one molecule. The curable composition for optical components according to claim 1, which is a (meth) acrylic acid ester of a compound to be obtained.   The curable composition for optical components according to any one of claims 1 to 3, wherein the compound having two or more hydroxyl groups in one molecule is a compound having no β hydrogen relative to the hydroxyl group.   5. The compound according to claim 4, wherein the compound having no β hydrogen with respect to the hydroxyl group is one or more compounds selected from the group consisting of neopentyl glycol, butyl ethyl propane diol, or trimethylol propane. Curable composition for optical parts.   The curable composition for optical components according to any one of claims 1 to 5, further comprising a polymer and / or copolymer (B) of (meth) acrylic acid ester.   The curable composition for optical components according to any one of claims 1 to 6, further comprising a photopolymerization initiator (C1) and / or a thermal polymerization initiator (C2).