Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds
  • C09D201/005—Dendritic macromolecules
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/65—Additives macromolecular

Definitions

• the present invention relates to a photocurable coating composition excellent in adhesion between a substrate and a hard coat layer, and further excellent in scratch resistance, a method for producing the same, and a plastic lens obtained using the coating composition And a manufacturing method thereof.
• the plastic lens is lighter and more impact resistant than glass, but its surface hardness is insufficient, so the surface is covered with various hard coat films to improve wear resistance.
• the coating liquid curing method for forming a hard coat film can be broadly divided into thermal curing and ultraviolet curing. Although thermal curing can provide a high effect of improving wear resistance, the curing process takes a long time and the pot There is a disadvantage that life is short.
• the plastic lens is a spectacle lens
• Patent Documents 1 to 3 are improved in the adhesion and surface hardness between the substrate and the hard coat film, but are not satisfactory in terms of both scratch resistance and adhesion, and are further free of radicals.
• the problem of oxygen inhibition during curing, the problem that the hardness of the hard coat film is inferior compared to thermal curing, and the problem that cationic curing requires a longer curing time than radical curing have not yet been solved.
• the curable resin composition of the above-mentioned Patent Document 4 does not correspond to conventional plastic substrates made of various types of materials, and is the main component, with respect to the adhesion of the coating film to the substrate. Since the dendrimer contains an aromatic ring, the hard coat film is yellowed when irradiated with ultraviolet rays, and the transparency is impaired, and the use of the curable resin composition is limited.
• the present invention has been made in view of the above circumstances, suppresses oxygen inhibition during ultraviolet irradiation, shortens the curing time, suppresses curing shrinkage, and is excellent for plastic substrates made of various conventional materials. It is an object of the present invention to provide a coating composition capable of achieving both adhesion and excellent scratch resistance and a method for producing the same. In addition, the present invention provides a plastic lens having both excellent adhesion of a hard coat layer to a plastic substrate made of various conventional materials and excellent scratch resistance, and a method for producing the same. Let it be an issue.
• this invention provides the following coating composition and its manufacturing method, and a plastic lens and its manufacturing method.
• a coating composition containing an acrylate component comprising 25 to 95% by mass of the following (A) component, 5 to 75% by mass of the following (B) component, and 0 to 40% by mass of the following (C) component.
• Component Two acrylates in one molecule 1.
• Bifunctional acrylate compound containing a group 2.
• Metal oxide 5 to 180 parts by mass of the component (D) is blended with respect to 100 parts by mass in total of the component (A) and the component (B), and the component (A) is 30 to 70% by mass and the component (B) 7.
• the manufacturing method of the coating composition of said 6 which is a process of mixing (D) component coat
• the plastic according to 11, wherein the coating composition is the coating composition according to any one of 1 to 5 or the coating composition obtained by the production method according to any one of 6 to 9. Lens manufacturing method.
• the coating composition of the present invention is capable of suppressing curing shrinkage at the time of ultraviolet irradiation to the maximum, suppressing oxygen inhibition, having high hardness not inferior to heat curing, and various types of conventional materials.
• Short hard coat film that has both excellent adhesion and excellent scratch resistance to plastic substrates made of, for example, each substrate exhibiting a refractive index of about 1.50 to a high refractive index of 1.67 or more.
• the film can be formed in time.
• the plastic lens of the present invention can form a hard coat layer on a base material while suppressing the curing shrinkage at the time of ultraviolet irradiation and suppressing oxygen inhibition.
• the plastic lens of the present invention has a high hardness that is not inferior to thermosetting, and is a conventional plastic substrate made of various types of materials, for example, a refractive index of about 1.50 to a high refractive index of 1.67 or more. It is a plastic lens having a hard coat layer that achieves both excellent adhesion to each substrate exhibiting a high rate and excellent scratch resistance. Furthermore, according to the method for producing a plastic lens of the present invention, since the hard coat layer can be formed in a short time, the plastic lens can be produced with high productivity.
• the coating composition of the present invention contains an acrylate component comprising 25 to 95% by mass of the following (A) component, 5 to 75% by mass of the following (B) component, and 0 to 40% by mass of the following (C) component.
• Component Dendritic aliphatic compound having an acrylate group at the terminal
• Component Two acrylates in one molecule Bifunctional acrylate compounds containing groups
• ⁇ (A) component polyfunctional acrylate compound containing 3 or more acrylate groups in the molecule>
• a polyfunctional acrylate compound containing three or more acrylate groups in one molecule is used as the component (A).
• the hard coat film can be made to have high hardness, and when used in combination with the component (B), the adhesion and scratch resistance can be further improved.
• the component (A) is preferably an aliphatic polyfunctional acrylate compound that does not contain an aromatic ring from the viewpoint of the weather resistance of the hard coat film.
• Examples of the component (A) include dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, and dipentaerythritol ethoxytetra.
• alkyl-modified (meth) acrylates of the above compounds caprolactone-modified (meth) acrylates, ethylene oxide-modified (meth) acrylates, propylene oxide-modified (meth) acrylates, (meth) acrylates of aliphatic polyols other than the above, etc. It is done.
• the said polyfunctional acrylate compound may be used independently and may use 2 or more types together.
• dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate, di Methylolpropane tri (meth) acrylate and tripentaerythritol (meth) acrylate are preferred.
• the component (A) includes a polyfunctional acrylate compound containing three or more acrylate groups and further a hydroxyl group in one molecule.
• the content ratio of the polyfunctional acrylate compound containing a hydroxyl group is preferably 30 to 80 mol%, more preferably 40 to 70 mol% in the component (A). If the content is 30 mol% or more, the hard coat film is not cloudy and good transparency can be obtained, and if it is 80 mol% or less, a high hardness film with a high crosslinking density can be formed.
• the polyfunctional acrylate compound containing the said hydroxyl group may be used independently, and the polyfunctional acrylate compound which does not contain a hydroxyl group, and the polyfunctional acrylate compound containing the said hydroxyl group may be used together.
• the polyfunctional acrylate compound which has a hydroxyl group and the polyfunctional acrylate compound which does not contain a hydroxyl group by which the hydroxyl group of this polyfunctional acrylate compound was substituted by the acrylate group is available.
• the molecular weight of the component (A) is preferably 200 to 1,500, more preferably 250 to 1,000.
• ⁇ (B) component dendritic aliphatic compound having an acrylate group at the end>
• a dendritic aliphatic compound having an acrylate group at the terminal is used as the component (B). If the dendritic aliphatic compound is used, the curing reaction proceeds in a short time, so that a hard coat film having a high hardness can be formed without being affected by oxygen inhibition during ultraviolet curing, and curing shrinkage can be prevented. It can suppress and can improve adhesiveness. Furthermore, since the component (B) does not contain an aromatic ring, the hard coat film can be made excellent in transparency and weather resistance without yellowing when irradiated with ultraviolet rays.
• the dendritic aliphatic compound having an acrylate group at the end of the component (B) is an aliphatic compound branched into a dendritic shape that does not contain an aromatic ring, and has many acrylate groups at the molecular end due to the dendritic shape. Therefore, it exhibits high reactivity.
• the component (B) is not particularly limited as long as it is a dendritic aliphatic compound having an acrylate group at the end, and one type may be used alone, or two or more types may be used in combination.
• dendritic aliphatic compounds as described above dendrimers or hyperbranched polymers are preferable.
• a dendrimer is a polymer branched with high regularity
• a hyperbranched polymer is a polymer branched with low regularity, and has a lower viscosity and better solvent solubility than a linear polymer.
• the component (B) As dendrimers that can be used as the component (B), Biscoat # 1000, Biscoat # 1020 (trade name) manufactured by Osaka Organic Chemical Industry Co., Ltd., and the like can be obtained.
• the biscoat # 1000 and biscoat # 1020 are mainly composed of a multi-branched (dendrimer type) polyester acrylate having an acrylate group at the terminal. Further, the viscoat # 1000 has a molecular weight of about 1,000 to 2,000, and the viscoat # 1020 has a molecular weight of about 1,000 to 3,000.
• STAR-501 SIRIUS-501, SUBARU-501 (trade name) manufactured by Osaka Organic Chemical Industry Co., Ltd. can be obtained.
• This STAR-501 has dipentaerythritol as a core and mainly contains a multi-branched (dipentaerythritol hexaacrylate (DPHA) -linked) polyacrylate having an acrylate group at the terminal.
• DPHA dipentaerythritol hexaacrylate
• STAR-501 has a molecular weight of about 16,000 to 24,000.
• the coating composition of the present invention includes (C) two acrylates per molecule in addition to the above components (A) and (B) as acrylate components.
• Bifunctional acrylate compounds containing groups can be included.
• bifunctional acrylate compound examples include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene.
• Glycol di (meth) acrylate tetraethylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, di (meth) acrylate of chrysidyl ether, caprolactone modified di (meth) ) Acrylate, ethylene oxide modified di (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, propylene oxide modified di (meth) acrylate, etc. It is.
• the said bifunctional acrylate compound may be used independently and may use 2 or more types together.
• a metal oxide may be contained from the viewpoint of further improving the scratch resistance.
• the component (D) is not particularly limited, and examples thereof include aluminum oxide, titanium oxide, antimony oxide, zirconium oxide, silicon oxide, cerium oxide, iron oxide, modified zirconium oxide-stannic oxide composite sol, and the like. Fine particles are mentioned.
• the said metal oxide may be used independently and may use 2 or more types together.
• the metal oxide is preferably in the form of a sol such as silica sol and zirconia sol.
• a metal oxide when (D) a metal oxide is contained, it is preferable to contain a metal oxide coated with a silane coupling agent.
• a metal oxide coated with a silane coupling agent By using a metal oxide coated with a silane coupling agent, the transparency and adhesion of the hard coat film are improved.
• the silane coupling agent a silane coupling agent having a functional group such as a (meth) acryloxy group is preferable.
• Specific examples of the silane coupling agent include methoxysilane, ⁇ -methacryloxypropylmethyldiethoxysilane, ⁇ -methacryloxypropyltriethoxysilane, and ⁇ -acryloxypropyltrimethoxysilane.
• the amount of the silane coupling agent to be used is preferably 1.5 to 10% by mass, more preferably 3 to 8% by mass, based on (D) the metal oxide. If it is 1.5 mass% or more, compatibility with (A) and (B) component is favorable, and if it is 10 mass% or less, film
• the content ratio of the (A) polyfunctional acrylate compound, (B) dendritic aliphatic compound, and (C) bifunctional acrylate compound used as the acrylate component is as follows depending on whether or not (D) a metal oxide is used. is there.
• the content ratio of the component (A), the component (B) and the component (C) is 25 to 95% by mass for the component (A), and 5 to 75 mass for the component (B).
• % And (C) component 0 to 40% by mass preferably (A) component 25 to 90% by mass, (B) component 5 to 70% by mass and (C) component 5 to 40% by mass, more preferably Are (A) component 40 to 80% by mass, (B) component 10 to 30% by mass, and (C) component 10 to 30% by mass. If (B) component is 5 mass% or more, the effect made to contain can be exhibited, and if (B) component is 75 mass% or less, adhesiveness is favorable. If the component (C) is 40% by mass or less, the film hardness is not impaired.
• the component (A) is preferably 30 to 95% by mass
• the component (B) is 5 to 70% by mass, more preferably the component (A) 40 to 70% by mass
• the component (B) 30 to 60% by mass. More preferably, the component (A) is 50 to 60% by mass and the component (B) is 40 to 50% by mass.
• the content ratio of the component (A), the component (B) and the component (C) is preferably 30 to 70% by mass of the component (A) and the component (B). 15 to 50% by mass and (C) component 0 to 35% by mass, more preferably (A) component 30 to 70% by mass, (B) component 15 to 35% by mass, and (C) component 15 to 35% by mass. More preferably, (A) component 35 to 65% by mass, (B) component 20 to 35% by mass, and (C) component 15 to 30% by mass.
• the contained effect can be exerted when the content ratio of the component (B) is 15% by mass or more, and when the component (B) is 50% by mass or less, the hard coat film is formed. Cloudiness does not occur and good transparency can be obtained. Further, when the component (C) is 35% by mass or less, the film hardness is not impaired. Further, in the case where the component (D) is contained, when the content ratio of the component (C) is 0% by mass, the content ratio of the component (A) and the component (B) depends on adhesion, scratch resistance, and film formability. In view of the above, (A) component is preferably 30 to 70% by mass, (B) 30 to 70% by mass, more preferably (A) component 50 to 60% by mass, and (B) 40 to 50% by mass. .
• the content ratio of the component (D) is preferably 5 to 180 parts by mass, more preferably 60 to 150 parts by mass with respect to 100 parts by mass of the acrylate component. If the content ratio of component (D) is 5 parts by mass or more, the contained effect can be exhibited, and if it is 180 parts by mass or less, the flexibility of the hard coat film is given and the heat resistance is impaired. There is no.
• a reaction initiator can be added to the coating composition of the present invention in order to cure the coating composition in a shorter time.
• various organic solvents and leveling agents can be added for the purpose of improving wettability during coating composition application and improving the smoothness of the cured film.
• ultraviolet absorbers, antioxidants, light stabilizers and the like can be added as long as they do not affect the physical properties of the cured film.
• the coating composition of this invention can be manufactured by mixing and stirring the said (A) component and (B) component and also (C) component, (D) component, and an additive as needed.
• an organic solvent may be used, and specifically, methyl ethyl ketone, 1-methoxy-2-propanol, propylene glycol monomethyl ether, or the like may be used.
• this invention uses the said (A) component, (B) component, and (D) component as a manufacturing method of a coating composition,
• the manufacturing method of the coating composition using the said (C) component is (D) component coat
• the component (C) may be mixed.
• the said coating process is performed by mixing and stirring (D) a metal oxide and a silane coupling agent, since the transparency of a hard-coat film
• membrane will be impaired when stirring is inadequate, it stirs until it becomes uniform.
• an organic solvent may be used when performing the coating step, and specifically, methyl ethyl ketone, 1-methoxy-2-propanol, propylene glycol monomethyl ether, or the like may be used. Furthermore, you may filter-filter the solution containing the coated metal oxide after performing a coating process.
• the said mixing process is performed by mixing and stirring (A) component, (B) component, and the coated (D) metal oxide, and there is no restriction
• the mixing step is performed by mixing and stirring the component (A), the component (B), the component (C), and the coated (D) metal oxide in the mixing step.
• the order of blending the components is not particularly limited.
• additives such as a leveling agent and a reaction initiator, may be added as needed, and it may stir and mix to make a coating composition.
• the coating composition of the present invention can minimize curing shrinkage during ultraviolet irradiation, suppress oxygen inhibition, and form a hard coat film with high hardness and adhesion to a substrate in a short time. be able to.
• the effects of the present invention are also exerted on plastic substrates made of various kinds of materials, for example, each substrate exhibiting a refractive index of about 1.50 to a high refractive index of 1.67 or more, and further when irradiated with ultraviolet rays. Since the hard coat film is excellent in transparency and weather resistance without yellowing, it is particularly suitable as a coating composition for forming a hard coat film for spectacle lenses.
• this invention provides the plastic lens which has a hard-coat layer on a base material, and the said hard-coat layer is formed by hardening the above-mentioned coating composition.
• the hard coat film and the hard coat layer in the description of the coating composition are synonymous.
• the method for producing a plastic lens of the present invention comprises a step of applying the above-mentioned coating composition to the surface of a substrate and irradiating with ultraviolet rays to cure the applied coating composition to form a hard coat layer. And a process comprising:
• a commonly performed method such as a dipping method, a spin coating method, or a spray method can be applied, but the spin coating method is particularly preferable in terms of surface accuracy and application speed. desirable.
• UV lamps such as a high-pressure mercury lamp, a metal hydride lamp, a xenon lamp, and a carbon arc lamp, laser light, and the like can be used.
• Ultraviolet irradiation amount varies depending on the type of light source, for example, preferably 100 ⁇ 3,000mJ / cm 2, further more preferably 100 ⁇ 2,000mJ / cm 2.
• the ultraviolet irradiation may be performed in an inert gas atmosphere such as nitrogen gas, but the coating composition of the present invention can be cured without being inhibited by oxygen even in an inert gas atmosphere. Can do.
• the thickness of the hard coat layer is usually about several ⁇ m, and preferably 0.1 to 10 ⁇ m from the viewpoint of improving the surface hardness of the plastic lens.
• the base material used for the plastic lens of the present invention can be a plastic base material made of various kinds of materials without particular limitation.
• the plastic base material include epoxy resin, epithio resin, acrylic resin, allyl resin, polycarbonate resin, urethane resin, thiourethane resin, and urethane urea resin.
• the substrate before applying the coating composition to the substrate, the substrate is subjected to chemical treatment with acid, alkali, various organic solvents, physical treatment with plasma, ultraviolet rays, etc., detergent treatment using various detergents, sandblast treatment, Furthermore, primer treatment using various resins may be performed. By performing these treatments, the adhesion between the substrate and the hard coat layer can be further improved.
• an inorganic oxide such as a vacuum vapor deposition method or a physical vapor deposition method such as sputtering, is formed on the hard coat layer.
• An antireflection film using an organic compound as a raw material can be provided.
• various functional films such as water repellency, antistatic property, antifogging property, etc. can be applied indirectly or directly or in combination on the antireflection film.
• Examples 1 to 32 [Comparative Examples 1 to 6] Using the materials described above, a coating composition solution was produced at a blending ratio shown in Table 1 or 2. The coating composition solution was produced by the following procedure depending on whether or not (D) a metal oxide was present.
• (D) When using metal oxide In a glass container, 1-methoxy-2-propanol as solvent, (D) metal oxide and silane coupling agent (trade name: KBM-503, ⁇ -methacryloxypropylmethyldiethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) ) And stirred at 55 ° C. and 450 rpm, and (D) the metal oxide was coated with the silane coupling agent. After the solution containing the coated metal oxide is filtered through a filter having a filtration diameter of 5 ⁇ m, (A) a polyfunctional acrylate compound and (B) a dendritic aliphatic compound are blended therein, and (C) a bifunctional acrylate.
• silane coupling agent trade name: KBM-503, ⁇ -methacryloxypropylmethyldiethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.
• the compound was blended and stirred at this stage when used. Thereafter, a leveling agent (trade name: Y-7006, polyoxyalkylene / dimethylpolysiloxane copolymer, manufactured by Toray Dow Corning Co., Ltd.) and a reaction initiator (trade name: IRGACURE 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) were added.
• the coating composition solution was prepared by stirring.
• the coating composition of the present invention is a plastic substrate made of various types of materials. Even so, it can be seen that it has excellent adhesion and scratch resistance effects. From the comparison of the plastic lenses obtained in Examples 1 to 32 and Comparative Example 4, the coating composition of the present invention has a high surface hardness not inferior to thermosetting, and from Comparative Examples 2 and 3 (B) When the component is not used, it can be seen that there is a difference in surface height depending on the presence or absence of nitrogen purge, but the coating composition of the present invention has excellent adhesion and scratch resistance regardless of whether or not nitrogen purge is present. It turns out that it is suppressing.
• Comparative Example 5 when the content ratio of the component (A) and the component (B) is outside the scope of the present invention, excellent adhesion and scratch resistance effects cannot be obtained, and all the substrates are used. In Comparative Example 6, cracks occurred upon irradiation with ultraviolet rays, and the coating layer could not be used.
• the coating composition of the present invention can suppress the cure shrinkage at the time of ultraviolet irradiation to the maximum and suppress oxygen inhibition, and is a plastic substrate made of various conventional materials, for example, a refractive index of about 1.50.
• the hard coat film having high hardness and adhesion can be formed in a short time for each group exhibiting a high refractive index of 1.67 or more from the refractive index of It is suitable as a coating composition for forming a film.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
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• Organic Chemistry (AREA)
• Paints Or Removers (AREA)
• Eyeglasses (AREA)
• Surface Treatment Of Optical Elements (AREA)
• Pigments, Carbon Blacks, Or Wood Stains (AREA)

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• 2013
  • 2013-02-27 WO PCT/JP2013/055252 patent/WO2013129531A1/fr not_active Ceased
  • 2013-02-27 JP JP2014502341A patent/JP6088484B2/ja active Active

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