JP2008081573A - Resin composition and laminated form using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a shock-absorbing resin composition for high-refractive index optical members, having impact resistance equivalent to those of conventional thermoset shock-absorbing primers by active energy ray irradiation alone with no need of any thermosetting step, and also giving a cured product of a high refractive index and excellent in adhesion to an optical base. <P>SOLUTION: The shock-absorbing resin composition for optical members comprises (A) a compound having a fluorene skeleton, (B) a rubber-modified resin, (C) a cationically curable compound other than the components (A) and (B), and (D) a photoacid generator. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an impact-absorbing resin composition for optical members, and particularly relates to a resin composition having good impact resistance with good adhesion to an optical substrate and a refractive index of a cured product of 1.55 or more.

  An optical member, for example, a plastic lens for eyeglasses has a merit that it is light and easy to process as compared with an inorganic glass lens, but has a disadvantage that its surface is soft and easily damaged. In order to solve this drawback, conventionally, a method has been used in which the surface of a plastic lens is covered with a hard coat to prevent damage. Further, in order to suppress the reflection of light, generally, an antireflection film is further formed on the surface of the hard coat. However, by forming a hard coat or an antireflection film on the surface of the plastic lens, the impact resistance of the spectacle lens is lowered. In order to solve this problem of reduced impact resistance, a technique of providing a primer layer for absorbing impact between the lens surface and the hard coat has been used in order to prevent damage to the lens.

As an impact resistant primer for eyeglass lenses, an impact resistant primer obtained by thermosetting acrylic polyol and organic isocyanate (Patent Document 1) and an aqueous solution comprising a copolymer of acrylic polyol and polyfunctional isocyanate compound- An aqueous impact resistant primer mainly composed of a urethane resin (Patent Document 2) has been used. These impact resistant primers needed to form a cured film by heating. Further, the obtained primer had a low refractive index, and it was necessary to increase the refractive index by adding a metal sol.
JP 61-114203 A Japanese Patent Laid-Open No. 2002-552022

  Therefore, the present inventors do not require a thermosetting step, and are excellent in adhesion to an optical substrate such as a spectacle lens substrate only by active energy ray irradiation, and have a refractive index of 1.55 or more. It is an object to provide a primer having excellent impact resistance.

  As a result of intensive studies to solve the above problems, the present inventor has reached the present invention.

  The present invention comprises a compound (A) having a fluorene skeleton, a rubber-modified resin (B), a cationic curable compound (C) other than the above (A) and (B), and a photoacid generator (D). The present invention relates to an impact-absorbing resin composition for optical members.

  Further, the present invention is based on the total amount of solid content, the compound (A) having a fluorene skeleton is 1 to 90 wt%, the rubber-modified resin (B) is 1 to 90 wt%, the (A) and (B) The present invention relates to the above-mentioned impact-absorbing resin composition for optical members, wherein the cation-curable compound (C) other than 1 to 90% by weight and the photoacid generator (D) is contained in an amount of 1 to 20% by weight.

The present invention also relates to the above-mentioned impact-absorbing resin composition for optical members, wherein the compound (A) having a fluorene skeleton is a compound represented by the following formula (1).
Formula (1)

(In the formula, R1 to R6 each independently represent a non-reactive group or a reactive group. However, any one of R1 to R4 is a reactive group. K1 and k2 are each independently 1 to 1) 5 represents an integer of 5, k3 and k4 each independently represents an integer of 0 or 1 to 5, and m1 and m2 each independently represents an integer of 0 or 1 to 4).
In the present invention, the reactive group is a group having at least one substituent selected from a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxyl group, and a glycidyl group. About.

  The present invention also relates to the above-mentioned impact-absorbing resin composition for optical members, wherein the reactive group has a glycidyl group.

  The present invention also relates to the impact-absorbing resin composition for optical members, wherein the rubber-modified resin (B) is a butadiene compound.

  The present invention also relates to the above-mentioned shock-absorbing resin composition for optical members, wherein the refractive index of the cured product of the resin composition is 1.55 or more.

  Moreover, this invention relates to the laminated body formed by forming the layer which consists of the said resin composition on the base material for optics.

Moreover, this invention relates to the manufacturing method of the laminated body characterized by performing active energy ray irradiation after forming the layer which consists of the said resin composition on the base material for optics.

  The impact-absorbing resin composition for an optical member of the present invention exhibits excellent effects with respect to adhesion to an optical substrate, high refractive index, and impact resistance. As another effect, since it is an active energy ray curable resin, the coating process time of the optical member can be shortened, and workability and economy can be improved.

  The optical member of the present invention refers to a member for transmitting or reflecting light, such as a lens, a polarizing plate, a prism, a filter, or a mirror.

  Hereinafter, although a spectacle lens will be described as a representative example, it is obvious that the present invention can be similarly applied to other lenses or optical members other than lenses.

  The impact-absorbing resin composition for spectacle lenses of the present invention is a resin composition that imparts impact resistance to spectacle lenses by covering part or the entire spectacle lens.

  The impact resistance refers to a property of preventing damage to the lens due to the impact of the spectacle lens molded article. By applying the resin composition of the present invention to an eyeglass lens, an eyeglass lens having excellent impact resistance can be obtained even when an antireflection layer comprising a hard coat or an inorganic vapor deposition film is applied.

  Furthermore, since the resin composition has a high refractive index, interference fringes hardly occur even when used for eyeglass lenses having a refractive index of 1.60 or more, and has excellent adhesion to a high refractive index eyeglass lens molded product. .

  Glasses lenses include correction lenses and sunglasses lenses. Examples of the correcting lens include a glass lens, an ultra-high refractive index plastic lens, a high refractive index plastic lens, and a low refractive index plastic lens. In the present invention, an ultrahigh refractive index plastic lens and a high refractive index plastic lens are preferable.

  The impact-absorbing resin composition for optical members of the present invention comprises a compound (A) having a fluorene skeleton, a rubber-modified resin (B), a cationic curable compound (C) other than the above (A) and (B), and a photoacid. It is characterized by containing a generator (D).

<About the compound (A) having a fluorene skeleton>
The compound (A) having a fluorene skeleton constituting the present invention is represented by the following formula (1).
Formula (1):

(Wherein R1 to R6 each independently represents a non-reactive group or a reactive group, provided that R1
Any of -R4 shall be a reactive group. k1 and k2 each independently represent an integer of 1 to 5, k3 and k4 each independently represent an integer of 0 or 1 to 5, and m1 and m2 each independently represents an integer of 0 or 1 to 4. )
Specific examples of the compound having a fluorene skeleton include fluorene, fluorenone, 2-acetamidofluorene, 2-acetylfluorene, 2-aminofluorene, 9-bromofluorene, 9-bromo-9-phenylfluorene, and 2,7-diaminofluorene. 2,7-di (acetamido) fluorene, 2,7-diacetylfluorene, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) ) Fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9bis [4- (2-hydroxyethoxy) phenyl] fluorene, 9,9-bis (4-hydro Shifeniru), and the like fluorene.

  Although it does not specifically limit as a non-reactive group of Formula (1), For example, carbon number, such as an alkyl group (Methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, s-butyl group, t-butyl group, etc. An alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and a cycloalkyl group (cyclopentyl group, cyclohexyl group, etc.) Cycloalkyl group, preferably a cycloalkyl group having 5 to 8 carbon atoms, more preferably a cycloalkyl group having 5 to 6 carbon atoms, an aryl group [phenyl group, alkylphenyl group (methylphenyl group (tolyl group), An aryl group having 6 to 10 carbon atoms such as a dimethylphenyl group (xylyl group, etc.), preferably an aryl group having 6 to 8 carbon atoms, especially a phenyl group], Hydrocarbon groups such as alkyl groups (eg, aryl-alkyl groups having 6 to 10 carbon atoms such as benzyl and phenethyl groups); alkoxy groups (such as alkoxy groups having 1 to 4 carbon atoms such as methoxy groups); acyl groups (acetyl) An acyl group having 1 to 6 carbon atoms such as a group); an alkoxycarbonyl group (an alkoxycarbonyl group having 1 to 4 carbon atoms such as a methoxycarbonyl group); an N, N-disubstituted amino group [for example, substituted with a hydrocarbon group] Amino groups (N, N-dialkylamino groups such as dimethylamino group (C1-6) and the like)]; halogen atoms (fluorine atoms, chlorine atoms and the like); nitro groups; cyano groups and the like.

  Examples of the reactive group of formula (1) include a group containing active hydrogen (an active hydrogen-containing group), a group not containing active hydrogen, and a group having both of these. Examples of the active hydrogen-containing group include a hydroxyl group, an amino group, and an N-monosubstituted amino group (for example, an amino group substituted with a hydrocarbon group [an N-monoalkylamino group such as a methylamino group (having 1 to 6 carbon atoms). ) Etc.]), carboxyl groups and the like, and a hydroxyl group, an amino group, or an N-monosubstituted amino group is preferable. In particular, a hydroxyl group or an amino group is preferable.

  Examples of groups that do not contain active hydrogen include glycidyl groups, oxetane groups, anhydride groups, and (meth) acryloyl groups. Examples of the group having at least one of these groups include groups obtained through active hydrogen of the active hydrogen-containing group (particularly, hydroxyl group or amino group). Such a group is not particularly limited. For example,-[X- (R13-O) nY] (wherein R13 is an alkylene group, and the group X is an oxygen atom (ether group) or An imino group, Y is a hydrogen atom, a glycidyl group or a (meth) acryloyl group, and n is 0 or an integer of 1 or more, provided that when n is 0, Y is not a hydrogen atom. It is done.

  The substitution number (or addition number) n of the alkyleneoxy unit is the same or different and can be selected from the range of 0 or about 1 to 15, for example, 0 or 1 to 12, preferably 0 or 1 to 8, more preferably It may be 0 or 1-6, especially 0 or about 1-4. In addition, when n is 2 or more, the polyalkoxy group (polyalkyleneoxy group) may be composed of the same alkylene group, and is composed of a mixture of different alkylene groups (for example, ethylene group and propylene group). Usually, it is often composed of the same alkylene group.

  In the compound having a fluorene skeleton represented by the formula (1), any of R1 to R4 is preferably a reactive group. In particular, one of R1 and R3 and one of R2 and R4 are often reactive groups. Moreover, it is preferable that either R1-R4 of Formula (1) has a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxyl group, and a glycidyl group. Of these, a glycidyl group is preferable.

  Specific fluorene compounds represented by the formula (1) include, for example, 9,9-bis (hydroxyphenyl) fluorenes or derivatives thereof, 9,9-bis (aminophenyl) fluorenes or derivatives thereof, and the like. .

  The 9,9-bis (hydroxyphenyl) fluorenes of the formula (1) include polyphenol fluorenes such as 9,9-bis (dihydroxyphenyl) fluorenes [particularly 9,9-bis (dihydroxyphenyl)]. Fluorene], 9,9-bis (trihydroxyphenyl) fluorenes [particularly 9,9-bis (trihydroxyphenyl) fluorene] and the like.

  As derivatives of 9,9-bis (hydroxyphenyl) fluorenes, alkylene oxide adducts of 9,9-bis (hydroxyphenyl) fluorenes, 9,9-bis (hydroxyphenyl) fluorenes or alkylene oxide adducts thereof Glycidyl ethers, 9,9-bis (hydroxyphenyl) fluorenes, or (meth) acrylates of alkylene oxide adducts thereof.

  9,9-bis (aminophenyl) fluorenes or derivatives thereof 9,9-bis (aminophenyl) fluorenes include compounds corresponding to the 9,9-bis (hydroxyphenyl) fluorenes, that is, 9,9 -Compounds in which the hydroxyl group of bis (hydroxyphenyl) fluorenes is an amino group or an N-substituted amino group.

  The 9,9-bis (aminophenyl) fluorene derivatives include alkylene oxide adducts of the 9,9-bis (aminophenyl) fluorenes, glycidyl ethers of the alkylene oxide adducts, and the alkylene oxide adducts. (Meth) acrylate and the like.

  The compound having a fluorene skeleton represented by the formula (1) is described in detail in JP-A-6-145087, JP-A-8-217713, and JP-A-2005-162785.

  Moreover, as a commercial item of the compound which has a fluorene skeleton shown by Formula (1), Osaka Gas Chemical Co., Ltd. BPEF-G, oncoat EX-1020, EX-1040 etc. can be mentioned, for example.

  Since the fluorene skeleton is composed mainly of an aromatic ring, it has a high refractive index, and even when used in a relatively small amount, it can provide a refractive index of 1.55 or higher. In particular, since the cardo structure has many aromatic rings, a high refractive index can be obtained relatively easily. In the present invention, an epoxy group can be introduced into these cardo structures to impart cationic polymerizability.

<About rubber-modified resin (B)>
The rubber-modified compound used in the present invention is not particularly limited as long as it has rubber-like elasticity near room temperature. For example, modified diene rubber (polyisoprene, polybutadiene, butadiene-styrene copolymer, carboxylated butadiene-styrene copolymer). , Butadiene-acrylonitrile copolymer, carboxylated butadiene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, hydrogenated butadiene-acrylonitrile copolymer, polychloroprene, isobutylene-isoprene copolymer, hydrogenated isobutylene-isoprene Copolymer, etc.), various synthetic rubbers such as modified acrylic rubber, modified polyurethane and modified polythiourethane.

Among the modified diene rubbers, those modified with functional groups at both ends of the main chain or in the middle of the main chain, particularly those modified with epoxy such as glycidyl group and cyclohexeneoxy group are desirable.
As the modified acrylic rubber, an acrylic rubber in which a glycidyl group or a cyclohexeneoxy group is pendant is desirable.

The modified polyurethane is obtained by reacting a diol and / or dithiol with a diisocyanate and further modifying it. Diols include alkylene glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, dipropylene glycol, diethylene glycol, and polypropylene glycol. , Polyalkylene glycols such as polyethylene glycol, polytetramethylene glycol, poly (ethylene adipate), poly (diethylene adipate), poly (tetramethylene adipate), poly (hexamethylene adipate), poly (neopentylene) Poly (alkylene adipates) such as adipate), polybutadienes such as poly-ε-caprolactan, poly (1,4-butadiene), poly (1,2-butadiene), poly (hexamethylene) Boneto) such as poly (alkylene carbonate), also include silicon polyol.
Examples of the dithiol include those obtained by replacing the hydroxyl group of the diol with a thiol group.

  Examples of the diisocyanate include aromatics such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 3,3′-dimethyl-4,4′-diphenyl isocyanate, 1,6-hexa Examples include aliphatic ones such as methylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, xylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, trimethylhexamethylene diisocyanate, and others. The diisocyanate can be used.

It is desirable to synthesize polyurethane and / or polythiourethane by reacting these diols and / or dithiols with diisocyanates and then epoxy-modifying both terminal functional groups.
These can be used alone or in admixture of two or more.

<Cation curable compounds (C) other than (A) and (B)>
(C) preferably has a cationically polymerizable group.

  Examples of such a cationically polymerizable compound (C) include a vinyl compound, an epoxy compound, and an oxetane compound.

  For example, as vinyl compounds, methyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, ethyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, ethylene glycol monovinyl ether, ethylene glycol divinyl ether, diethylene glycol monovinyl ether, diethylene glycol divinyl ether , Triethylene glycol monovinyl ether, triethylene glycol divinyl ether, tetraethylene glycol monovinyl ether, tetraethylene glycol divinyl ether, polyethylene glycol monovinyl ether, polyethylene glycol divinyl ether, propylene glycol monobi Ether, propylene glycol divinyl ether, dipropylene glycol monovinyl ether, dipropylene glycol divinyl ether, tripropylene glycol monovinyl ether, tripropylene glycol divinyl ether, tetrapropylene glycol monovinyl ether, tetrapropylene glycol divinyl ether, polypropylene glycol monovinyl ether, polypropylene glycol Divinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, butanediol-1,4-divinyl ether, hexanediol-1,6-divinyl ether, cyclohexanedimethanol monovinyl ether, cyclohexanedimethanol divinyl ether, vinylcarbazole, N-vinylpyrrolidone Vinyl caprolactone, diallyl phthalate, N-vinyl formamide, divinyl ethylene urea, vinyl imidazole, divinyl adipate, and the like.

  Specific examples of the compound having one oxetane ring include 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, Examples include 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, 3-cyclohexylmethyl-3-ethyl-oxetane, and the like.

  Specific examples of the compound having two oxetane rings include 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, bis {[(1-ethyl) 3-oxetanyl] methyl} ether. 1,4-bis [(3-ethyl-3-oxetanyl) methoxy] benzene, 1,3-bis [(3-ethyl-3-oxetanyl) methoxy] benzene, 3,7-bis (3-oxetanyl)- 5-oxa-nonane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,2- Bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopente Bis (3-ethyl-3-oxetanylmethyl) ether, and the like.

  Specific examples of the compound having three or more oxetane rings include trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3- And ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, and the like.

  Examples of epoxy compounds include glycidyl ether type epoxy resins, glycidyl ester type epoxy resins, alicyclic epoxy resins, glycidyl amine type epoxy resins, and aromatic epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins. Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, bisphenol fluorene type epoxy resin, hydrogenated bisphenol A type epoxy resin, and alicyclic type Examples thereof include glycidyl ether type epoxy resins such as epoxy resins, and glycidyl ester type epoxy resins such as glycidyl (meth) acrylate. These compounds can be used individually or in combination of 2 or more types.

  Moreover, in order to give adhesiveness with a base material and adhesiveness with the hard coat of an upper layer, it contained hydroxyl groups, such as monovinyl ether of glycols, 3-ethyl-3-hydroxymethyl oxetane, and hydroxybutyl vinyl ether, for example. A compound may be used.

<About photoacid generator (D)>
The photoacid generator refers to a compound that generates an acid and starts polymerization by irradiation with active energy rays.

  Photoacid generators used in the present invention include onium salt compounds, such as aromatic sulfonium salt derivatives, aromatic iodonium salt derivatives, diazonium salt derivatives, aromatic phosphonium salt derivatives, aromatic selenium salt derivatives, pyridinium salts. Derivatives and the like.

  Examples of the aromatic sulfonium salt derivative include UVI-6992 manufactured by Dow, Adeka optomer SP-150, SP-152 manufactured by Asahi Denka Kogyo, and the like. Examples of the aromatic iodonium salt derivative include RP-2074 manufactured by Rhodia and Irgacure 250 manufactured by Ciba.

  Of the photoacid generators, a compound having hexafluorophosphate as the anion moiety is preferable from the viewpoint of safety and versatility.

  The photoacid generator that constitutes the present invention is not limited to the above-mentioned compounds, and may have any ability to initiate polymerization by irradiation with active energy rays. These can be used alone or in combination.

  Although the usage-amount of a photoinitiator is not restrict | limited in particular, Preferably 1-20 weight part is good with respect to 100 weight part of solid content of to-be-cured material. When the concentration of the photoacid generator is small, the polymerization reaction cannot be sufficiently performed, and the performance of the cured film is deteriorated. In many cases, the photoacid generator acts as a plasticizer, and a sufficient cured film cannot be obtained. Further, a known sensitizer such as anthracene or anthracene derivative can be used in combination with the photoacid generator (D).

  In addition, various additions such as solvent dyes, antioxidants, polymerization inhibitors, leveling agents, moisturizers, viscosity modifiers, preservatives, antibacterial agents, antiblocking agents, ultraviolet absorbers, infrared absorbers, fillers as necessary An agent can be added.

  In addition, you may add a solvent to an impact-absorbing resin composition as needed. As the solvent used, various known organic solvents can be used. For example, ester systems such as ethyl acetate, butyl acetate and cellosolve acetate, ketone systems such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ether systems such as methoxybutanol and butyl cellosolve, alcohol systems such as ethanol, isopropyl alcohol and nbutyl alcohol, Aromatic hydrocarbons such as toluene and xylene, glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol diethyl ether, and propylene glycol monomethyl ether. These can be included alone or in combination.

  And when adding a solvent, it is preferable to volatilize a solvent in oven etc. before a hardening process.

  The ratio of the compound (A) having a fluorene skeleton, the rubber-modified resin (B), the cationic curable compound (C) other than the above (A) and (B), and the photoacid generator (D) is suitable depending on the required performance. The ratio is determined. In general, the compound (A) having a fluorene skeleton has a relatively high refractive index because it contains many aromatic rings. Moreover, since the fluorene structure is very rigid, it is excellent in the effect of relaxing the shrinkage of the cured film. However, the use of an excess amount makes the cured coating film brittle and reduces the flexibility of the coating. Therefore, the rubber-modified compound (B) imparts flexibility to the film and improves impact resistance. Furthermore, the cationic curable compound (C) other than (A) and (B) improves solution viscosity adjustment, solvent resistance, water resistance, etc. and imparts adhesion to the hard coat.

  Therefore, the impact-absorbing resin composition for an optical member of the present invention has 1 to 90 parts by weight of the compound (A) having a fluorene skeleton and the rubber-modified compound (B), where the total amount of solids is 100 parts. It is preferable to contain 1 to 90 parts by weight of the cationic curable compound (C) other than the above (A) and (B), and 1 to 20 parts by weight of the photoacid generator (D).

  The optimum amount of the photoacid generator to be used varies depending on the composition to be combined, the amount of ultraviolet irradiation, and the film thickness, but it is preferably used within the range of 1 to 20% by weight with respect to the solid content of the cured product. If it is less than 1% by weight, the curing reaction does not proceed, and if it exceeds 20% by weight, the residual unreacted material becomes a plasticizer, and in any case, the performance of the film may be lowered.

  The laminate of the present invention is formed by forming a layer comprising the resin composition of the present invention on an optical substrate.

  As the optical substrate, known materials such as glass, polycarbonate, acrylic resin, polyester such as PET, thiourethane, and polyacetate film can be used as long as light is transmitted. In addition, other known materials can be used as long as they are used for reflection. These may be physically and chemically treated. In particular, a thermoplastic resin such as polycarbonate is preferable in terms of economy and moldability. Further, since it is difficult to cope with an optical member having a refractive index exceeding 1.60 with a thermoplastic resin, a thermosetting type is preferably used.

  A known method may be used as a method for forming the optical substrate. For example, an optical base material having an arbitrary shape can be obtained by thermoforming and grinding the thermoplastic resin.

  Alternatively, a casting method in which a liquid raw material is poured into a mold and thermally cured is selected. As a result of the cross-linking reaction by thermosetting, the casting method can obtain an optical substrate excellent in physical and chemical strength. In addition, since the reaction and cooling are performed over a long period of time, the productivity is inferior, but there is also an advantage that an optical substrate with little polymerization distortion and less optical distortion can be obtained.

  The formation method of the layer which consists of the impact-absorbing resin composition with respect to the base material for optics is demonstrated. Examples of the forming method include coating and coating. As a coating / coating method, a method used in a known coating operation can be used. For example, there are a dip coating method, a flow coating method, a spin coating method and the like.

  Even when coating is performed by any of the above methods, it is necessary to control the film thickness of a layer made of a desirable resin composition. The preferred film thickness for the shock-absorbing layer is 1 to 10 μm. As a method for controlling the film thickness, for example, in the case of the spin coating method, it is determined in consideration of the rotation speed and rotation time of the spin coating, the viscosity of the resin composition, the type and solid content% of the diluent solvent, and the temperature. Must-have.

  When the impact-absorbing resin composition contains a solvent, hot air drying is performed after coating. In order to prevent thermal deformation of the optical substrate to be coated, it is important that the temperature of the hot air does not exceed the glass transition point due to the hot air, and is preferably 120 ° C. or lower. Therefore, it is preferable to prioritize drying by air volume over drying by temperature.

  After drying, the impact-absorbing resin composition is irradiated with active energy rays and cured.

  Examples of active energy rays include ultraviolet rays, visible rays, infrared rays, electron beams, α rays, and X rays. Ultraviolet rays are preferably used.

  Curing with an active energy ray has advantages such as curing in a short time and at a low temperature as compared with heat curing, and is particularly suitable for plastic optical substrates that are vulnerable to high temperatures.

The amount of ultraviolet light to be radiated is measured with a UV integrated light meter, and varies depending on the impact-absorbing resin composition, but the preferred light amount is 50 to 1000 mJ / cm ² . Excessive irradiation energy may cause yellowing of the coating film and lens. On the other hand, insufficient performance cannot provide sufficient performance.

  If there is a difference in the refractive index between the layer made of the shock-absorbing resin composition and the optical base material, light interference fringes are generated, the appearance of the optical member is impaired, and the commercial value is lowered. The closer the refractive index of an object is to the optical member, the better.

  In addition, the well-known various functional film | membrane may be further given to the laminated body of this invention for various physical property provision. Further, the range of covering the optical base material can be determined according to the application, and a part or the whole surface may be covered.

  Hereinafter, the present invention will be described specifically by way of examples. In the examples, “parts” represents “parts by weight” and “%” represents “% by weight”.

  According to the composition of Table 1, the resin compositions of Examples 1 to 5 and Comparative Example 1 were prepared and coated by the following methods, and refractive index measurement, adhesion to molded products, impact resistance, and elongation at break as flexibility. Rate was evaluated.

Next, a method for creating a cured film will be described.
"Coating method"
(Spin coating conditions)
2 cc of the primer solution for test was dropped near the center of a 2.0 mm thick acrylic plate and immediately rotated at 2000 rpm for 20 seconds to coat uniformly.
(Drying conditions)
The coated plate was then dried in an oven at 80 ° C. for 1 minute.
(UV curing conditions)
Next, the primer was cured by irradiating the dried plate with ultraviolet rays.

As the ultraviolet irradiation condition, a high-pressure mercury lamp was used, and the integrated light amount was 270 mJ / cm ² . The integrated light amount was measured using a light meter UV-350 (Oak Seisakusho).
Next, a physical property test of the cured film will be described.
"Physical property test"
For adhesion and impact resistance, physical properties were tested using the above primer-coated acrylic plate.
(Adhesion)
The coated surface was cut into a 10 × 10 grid pattern at 1 mm intervals with a cutter, and the portion was peeled off with a cellophane tape.
Evaluation was displayed by the number of peeling parts / 100.
(Impact resistance)
The above-mentioned primer-coated acrylic plate (thickness 2.0 mm) was placed flat on a cylinder having a diameter of 3 cm and a height of 3 cm, and a hard sphere was dropped from a position 127 cm higher than the acrylic plate. For the impact resistance, the weight of the hard sphere when the acrylic board was cracked or cracked was displayed.
(Refractive index measurement)
A PET coater is coated with a bar coater so as to have a film thickness of 5 to 7 μm as a primer, and a sample is prepared under the drying and curing conditions. The refractive index is measured with an Abbe refractometer in an environment of 25 ° C. and humidity of 40%.
(Elongation at break)
The solution was applied to the release PET so as to have a thickness of about 20 μm, dried in a solvent in an oven, and then irradiated with ultraviolet rays, and the cured coating film was taken out of the release PET and used as a measurement sample. The size of the measurement sample is 2.3 cm long x 0.5 cm wide, a tensile test is performed at a tensile speed of 5 mm / min, and a distance between grips (distance between marked lines) of 23 mm. The rate was expressed as the elongation at break.

  Table 2 shows the results of physical property tests of Examples 1 to 5 and Comparative Example 1.

  From Table 2, the impact resistance was improved by combining the rubber-modified resin (B) with the compound (A) having a fluorene skeleton.

  The impact-absorbing resin composition for optical members and the laminate thereof according to the present invention are not limited to eyeglass lenses, and can be widely used to prevent damage to members from impacts caused by the outside or the inside of the optical member.

Claims (9)

  It comprises a compound (A) having a fluorene skeleton, a rubber-modified resin (B), a cationic curable compound (C) other than the above (A) and (B), and a photoacid generator (D). An impact-absorbing resin composition for optical members.   1 to 90% by weight of the compound (A) having a fluorene skeleton, 1 to 90% by weight of the rubber-modified resin (B) based on the total amount of the solid content, and a cationic curable compound other than the above (A) and (B) The impact-absorbing resin composition for an optical member according to claim 1, wherein (C) is contained in an amount of 1 to 90% by weight and the photoacid generator (D) is contained in an amount of 1 to 20% by weight. 3. The impact-absorbing resin composition for an optical member according to claim 1, wherein the compound (A) having a fluorene skeleton is a compound represented by the following formula (1).
Formula (1)

(In the formula, R1 to R6 each independently represent a non-reactive group or a reactive group. However, any one of R1 to R4 is a reactive group. K1 and k2 are each independently 1 to 1) 5 represents an integer of 5, k3 and k4 each independently represents an integer of 0 or 1 to 5, and m1 and m2 each independently represents an integer of 0 or 1 to 4).   The impact-absorbing resin composition for an optical member according to claim 3, wherein the reactive group is a group having at least one substituent selected from a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxyl group, and a glycidyl group.   The reactive group has a glycidyl group, The impact-absorbing resin composition for optical members according to claim 4.   The shock-absorbing resin composition for optical members according to any one of claims 1 to 5, wherein the rubber-modified resin (B) is a butadiene compound.   The impact-absorbing resin composition for an optical member according to any one of claims 1 to 6, wherein the cured product of the resin composition has a refractive index of 1.55 or more.   The laminated body formed by forming the layer which consists of a resin composition in any one of Claims 1-7 on the base material for optics.   A method for producing a laminate, which comprises irradiating active energy rays after forming a layer comprising the resin composition according to any one of claims 1 to 7 on an optical substrate.