CN115066329A - Active energy ray-curable resin composition, cured product, laminate, and lens - Google Patents
Active energy ray-curable resin composition, cured product, laminate, and lens Download PDFInfo
- Publication number
- CN115066329A CN115066329A CN202180012833.8A CN202180012833A CN115066329A CN 115066329 A CN115066329 A CN 115066329A CN 202180012833 A CN202180012833 A CN 202180012833A CN 115066329 A CN115066329 A CN 115066329A
- Authority
- CN
- China
- Prior art keywords
- energy ray
- active energy
- resin composition
- curable resin
- ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/005—Dendritic macromolecules
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F9/00—Registration or positioning of originals, masks, frames, photographic sheets or textured or patterned surfaces, e.g. automatically
- G03F9/70—Registration or positioning of originals, masks, frames, photographic sheets or textured or patterned surfaces, e.g. automatically for microlithography
- G03F9/7003—Alignment type or strategy, e.g. leveling, global alignment
- G03F9/7042—Alignment for lithographic apparatus using patterning methods other than those involving the exposure to radiation, e.g. by stamping or imprinting
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Optics & Photonics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention addresses the problem of providing an active energy ray-curable resin composition having excellent crack resistance that can prevent the inorganic layer from cracking in a laminate comprising a resin layer and an inorganic layer, a cured product of the active energy ray-curable resin composition, a laminate, and a lens comprising the laminate. The present inventors have solved the above-mentioned problems by using an active energy ray-curable resin composition for forming a resin layer, which comprises a laminate of a resin layer and an inorganic layer, wherein the active energy ray-curable resin composition contains a multi-branched polymer compound (a) having a (meth) acryloyl group.
Description
Technical Field
The present invention relates to an active energy ray-curable resin composition, a cured product, a laminate, and a lens.
Background
In recent years, curable resin compositions such as active energy ray-curable resin compositions that can be cured by active energy rays such as ultraviolet rays and thermosetting resin compositions that can be cured by heat have been widely used in the fields of inks, paints, coating agents, adhesives, optical members, and the like. Among them, in the field of the optical member, it can be preferably used as a resin for a lens used in a smart phone or an in-vehicle camera. As a method for molding the resin for a lens, a manufacturing process using photo-embossing has been actively studied in association with the reduction in thickness of the lens module and the improvement in production efficiency. The photo-imprint is a method in which after an uncured resin is applied to a base material such as a wafer, shape transfer is performed by sandwiching the resin between lens molds, and photo-curing is performed, whereby hundreds of wafer level lenses can be molded at a time.
As a resin used for the above-described photo-imprint, a curable resin composition containing a urethane (meth) acrylate is known (for example, see patent document 1), but when the resin is used after a lens is molded and an upper layer of the lens is covered with an antireflection film, there is a problem that cracks are generated at the time of heat treatment such as reflow.
Therefore, there is a need for a material for forming a resin layer having excellent crack resistance that can suppress the generation of cracks in an inorganic layer when reflow processing is performed after the inorganic layer such as an antireflection film is formed.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2008/149766
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide an active energy ray-curable resin composition for forming a resin layer, which has excellent crack resistance and can suppress the generation of cracks in an inorganic layer, a cured product of the active energy ray-curable resin composition, a laminate, and a lens including the laminate, in a laminate including the resin layer and the inorganic layer.
Means for solving the problems
The present inventors have made extensive studies to solve the above problems, and as a result, have found that the above problems can be solved by using an active energy ray-curable resin composition containing a multibranched polymer compound having a (meth) acryloyl group, and have completed the present invention.
That is, the present invention relates to an active energy ray-curable resin composition for forming a resin layer, which is a resin composition for forming a resin layer comprising a laminate of a resin layer and an inorganic layer, and which contains a multi-branched polymer compound (a) having a (meth) acryloyl group, a cured product of the active energy ray-curable resin composition, a laminate, and a lens comprising the laminate.
ADVANTAGEOUS EFFECTS OF INVENTION
The active energy ray-curable resin composition of the present invention can suppress the generation of cracks in the inorganic layer in the laminate comprising the resin layer and the inorganic layer, and therefore can be preferably used for the production of a lens by photoimprinting.
Detailed Description
The active energy ray-curable resin composition of the present invention is characterized by containing a multi-branched polymer compound (A) having a (meth) acryloyl group.
In the present invention, "(meth) acryloyl" means acryloyl and/or methacryloyl. Further, "(meth) acrylate" means acrylate and/or methacrylate. Further, "(meth) acrylic acid" means acrylic acid and/or methacrylic acid.
Examples of the multibranched polymer compound (a) having a (meth) acryloyl group include: a compound having a dendrimer (dendrimer) structure (dendritic structure) (hereinafter, sometimes referred to as "dendrimer"), a compound having a hyperbranched structure (hyperbranched structure) (hereinafter, sometimes referred to as "hyperbranched" or "hyperbranched polymer"), a compound having a star-shaped structure, and the like.
Examples of commercially available products of the compound having a dendrimer structure include "bosch (Viscoat) #1000 LT" manufactured by osaka organic chemical industry co., ltd and "miramo (Miramer) SP 1106" manufactured by Meiyuan (MIWON). These compounds having a dendrimer structure may be used alone, or two or more of them may be used in combination.
Examples of commercially available products of the compound having a hyperbranched structure include "CN 2302", "CN 2303" and "CN 2304" manufactured by Arkema, inc; "Buddha tourbillon (Photomer) 5500" manufactured by IGM corporation, and the like. These compounds having a hyperbranched structure may be used alone or in combination of two or more.
The average number of (meth) acryloyl groups per molecule of the multi-branched polymer compound (a) is more preferably in the range of 6 to 64, and particularly preferably in the range of 10 to 32, in order to obtain an active energy ray-curable resin composition having excellent crack resistance capable of suppressing the generation of cracks in the inorganic layer.
The weight average molecular weight (Mw) of the multi-branched polymer compound (A) is preferably in the range of 500 to 30,000, more preferably in the range of 1,000 to 10,000, in order to obtain an actinic energy ray-curable resin composition having excellent crack resistance capable of suppressing the generation of cracks in the inorganic layer. In the present invention, the weight average molecular weight (Mw) represents a value measured by a Gel Permeation Chromatography (GPC) method.
The viscosity of the multi-branched polymer compound (A) at 25 ℃ is preferably in the range of 10 to 1,500 mPas, more preferably in the range of 100 to 1,000 mPas. In the present invention, the viscosity represents a value measured by an E-type viscometer.
The method for producing the multibranched polymer compound (a) is not particularly limited, and can be produced by an appropriate conventional method. Examples thereof include: a divergent (divergent) method in which a molecule is bonded to a central nuclear molecule one by one to form a branch, a convergent (convergent) method in which a branch portion synthesized in advance is bonded to a nuclear molecule, a method in which a monomer ABx including a branch portion having two or more reaction points B and a linking portion having another reaction point a in one molecule is synthesized in one stage, and the like. Among these, the dispersion method is preferred, and for example, the production is preferably carried out by a method in which a polyol is subjected to an esterification reaction with a compound having one or more carboxyl groups and two or more hydroxyl groups to obtain a multi-branched polyester polyol, and then the terminal hydroxyl groups are reacted with (meth) acrylic acid.
The content of the multi-branched polymer compound (a) in the resin layer-forming active energy ray-curable resin composition of the present invention is preferably 1 to 80 parts by mass, more preferably 5 to 45 parts by mass, in terms of improvement in crack resistance, and particularly preferably 10 to 35 parts by mass, because crack resistance is further improved when the entire resin layer-forming active energy ray-curable resin composition is 100 parts by mass.
Examples of the polyol include: glycerin, trimethylolpropane, ditrimethylolpropane, trimethylolethane, ditrimethylolethane, tris (2-hydroxyethyl) isocyanurate, 1, 2, 4-butanetriol, pentaerythritol, dipentaerythritol, sorbitol, mannitol, and alkylene oxide adducts or caprolactone adducts thereof. These polyhydric alcohols may be used alone or in combination of two or more.
Examples of the compound having one or more carboxyl groups and two or more hydroxyl groups include: 2, 3-dihydroxypropionic acid, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid, tartaric acid, 2, 3-dihydroxybenzoic acid, 2, 4-dihydroxybenzoic acid, 2, 5-dihydroxybenzoic acid, 2, 6-dihydroxybenzoic acid, 3, 4-dihydroxybenzoic acid, 3, 5-bis (2-hydroxyethoxy) benzoic acid, 2, 6-dihydroxy-4-methylbenzoic acid, 3, 5-dihydroxy-4-methylbenzoic acid, citrazinic acid, 2, 3-dihydroxyphenylacetic acid, 2, 4-dihydroxyphenylacetic acid, 2, 5-dihydroxyphenylacetic acid, 2, 6-dihydroxyphenylacetic acid, 3, 4-dihydroxyphenylacetic acid, 3, 5-dihydroxyphenylacetic acid, derivatives thereof, and the like. These compounds may be used alone or in combination of two or more.
As the multi-branched polyester polyol, a commercially available product can be used in addition to the one obtained by subjecting a polyol and a compound having one or more carboxyl groups and two or more hydroxyl groups to esterification reaction as described above.
Examples of commercially available products of the multibranched polyester polyol include: botton (BOLTORN) H20, Botton (BOLTORN) H30, Botton (BOLTORN) H40, Botton (BOLTORN) H311, Botton (BOLTORN) H2003, Botton (BOLTORN) H2004, Botton (BOLTORN) P500, Botton (BOLTORN) P501, Botton (BOLTORN) P1000, and the like, manufactured by Perstorp (Perstorp).
The active energy ray-curable resin composition of the present invention may contain a photopolymerization initiator as needed.
Examples of the photopolymerization initiator include: 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [ 4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2' -dimethoxy-1, 2-diphenylethan-1-one, diphenyl (2, 4, 6-trimethoxybenzoyl) phosphine oxide, 2, 4, 6-trimethylbenzoyldiphenyl phosphine oxide, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, and mixtures thereof, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, and the like.
Examples of commercially available products of the other photopolymerization initiators include: "ornitade (Omnirad) -1173", "ornitade (Omnirad) -184", "ornitade (Omnirad) -127", "ornitade (Omnirad) -2959", "ornitade (Omnirad) -369", "ornitade (Omnirad) -379", "ornitade (Omnirad) -907", "ornitade (Omnirad) -4265", "ornitade (Omnirad) -1000", "ornitade (Omnirad) -651", "ornitade (Omnirad) -TPO", "ornitade (Omnirad) -819", "ornitade (Omnirad) -2022", "ornitade (Omnirad) -2100", "ornitade (Omnirad) -754", "ornitade (Omnirad) -784", "ornitade (Omnirad) -500", "ornitade (Omnirad) -81" (manufactured by IGM corporation); "Kayacure (Kayacure) -DETX", "Kayacure (Kayacure) -MBP", "Kayacure (Kayacure) -DMBI", "Kayacure (Kayacure) -EPA", "Kayacure (Kayacure) -OA" (manufactured by Nippon chemical Co., Ltd.); "Baigu (Vicure) -10" and "Baigu (Vicure) -55" (manufactured by Stauffer Chemical Co., Ltd.); "Tiger sodium (Trigonal) P1" (manufactured by Aksu (Akzo)); "Sandoride (Sandoray) 1000" (manufactured by Sandebo (Sandoz) Co.); "Dupu (DEAP)" (manufactured by appjohn corporation); "quantacu (Quantacure) -PDO", "quantacu (Quantacure) -ITX", "quantacu (Quantacure) -EPD" (manufactured by Ward blendsup (Ward Blenkinsop)); "Huatiguo (Runtecure) -1104" (manufactured by Huati (Runtec) Co., Ltd.), and the like. These photopolymerization initiators may be used alone or in combination of two or more.
The content of the photopolymerization initiator in the total amount of components other than the solvent in the active energy ray-curable resin composition is, for example, preferably in the range of 0.05 to 10% by mass, and more preferably in the range of 0.1 to 5% by mass.
The photopolymerization initiator may be used in combination with a photosensitizer.
Examples of the photo sensitizer include amine compounds, urea compounds, sulfur compounds, phosphorus compounds, chlorine compounds, and nitrile compounds.
The active energy ray-curable resin composition of the present invention may contain, if necessary, a (meth) acrylic compound having a carbonate structure, a (meth) acrylic compound having a cyclic structure, a compound having one or two (meth) acryloyl groups in one molecule, and a compound having an alkanediol structure in one molecule.
Examples of the (meth) acrylic compound having a carbonate structure include those obtained by reacting a polycarbonate polyol with (meth) acrylic acid and/or a (meth) acrylate.
Examples of the polycarbonate polyol include a reaction product of a compound having two or more hydroxyl groups and a carbonate ester.
As the compound having two or more hydroxyl groups, for example, there can be used: ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 3-butanediol, 1, 2-butanediol, 2-methyl-1, 3-propanediol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, 1, 5-hexanediol, 3-methyl-1, 5-pentanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 8-nonanediol, 2-ethyl-2-butyl-1, 3-propanediol, 1, 10-decanediol, 1, 12-dodecanediol, 1, 4-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, trimethylolpropane, trimethylolethane, glycerol and the like. These compounds may be used alone or in combination of two or more.
Examples of the carbonate include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate. These compounds may be used alone or in combination of two or more.
As the (meth) acrylate, for example, there can be used: methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, octyloxypolyethylene glycol-polypropylene glycol mono (meth) acrylate, lauroxypolyethylene glycol mono (meth) acrylate, stearoxypolyethylene glycol mono (meth) acrylate, phenoxypolyethylene glycol-polypropylene glycol mono (meth) acrylate, phenoxypolyethylene glycol-polypropylene glycol mono (meth) acrylate, and mixtures thereof, Nonylphenoxypolypropylene glycol mono (meth) acrylate, nonylphenoxypoly (ethylene glycol-propylene glycol) mono (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, and the like. These (meth) acrylates may be used alone or in combination of two or more.
Further, commercially available products of the (meth) acrylic compound having a carbonate structure include, for example: "UH-100 DA", "UM-90 (1/3) DA", "UM-90 (1/1) DA", "UM-90 (3/1) DA", "UH-100 DM", "UM-90 (1/3) DM", "UM-90 (1/1) DM", "UM-90 (3/1) DM", and the like, manufactured by Yongcheng products, Ltd, of Yu department.
As the (meth) acrylic compound having a cyclic structure, for example, a (meth) acrylic compound having a monocycloparaffin structure, a benzene ring, a tricyclodecane structure, a dicyclopentenyl structure, an isobornyl structure, a heterocyclic structure in which an oxygen atom is a hetero atom, or the like can be used. These compounds may be used alone or in combination of two or more.
Examples of the (meth) acrylic compound having a monocycloparaffin structure include cyclohexyl (meth) acrylate, 1, 4-cyclohexanedimethanol monoacrylate, and the like. These compounds may be used alone or in combination of two or more.
Examples of the (meth) acrylic compound having a benzene ring include benzyl (meth) acrylate, phenoxy ester (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, and the like. These compounds may be used alone or in combination of two or more.
Examples of the (meth) acrylic compound having a tricyclodecane (dicyclopentyl) structure include dicyclopentyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, tricyclodecane diol di (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate. These compounds may be used alone or in combination of two or more.
Examples of the (meth) acrylic compound having a dicyclopentenyl structure include dicyclopentenyl (meth) acrylate and dicyclopentenyloxyethyl (meth) acrylate. These compounds may be used alone or in combination of two or more.
Examples of the (meth) acrylic compound having an isobornyl structure include isobornyl (meth) acrylate and isobornyl di (meth) acrylate. These compounds may be used alone or in combination of two or more.
Examples of the (meth) acrylic compound having a heterocyclic structure or the like in which an oxygen atom is a hetero atom include: cyclic trimethylolpropane formal acrylate, (2-methyl-2-ethyl-1, 3-dioxolan-4-yl) methyl (meth) acrylate, (3-ethyloxetan-3-yl) methyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, neopentyl glycol-modified trimethylolpropane di (meth) acrylate, and the like. These compounds may be used alone or in combination of two or more.
The compound having one or two (meth) acryloyl groups and an alkanediol structure in one molecule is a compound which must have one or two (meth) acryloyl groups and an alkanediol structure in one molecule.
Examples of the alkanediol structure include: 1, 2-ethanediol (ethanediol), 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 2-propanediol (propanediol), 1, 2-butanediol, 1, 3-butanediol, 2-methyl-1, 3-propanediol, 1, 2-pentanediol, 1, 3-pentanediol, 1, 4-pentanediol, 2-dimethyl-1, 3-propanediol (neopentyl glycol), 3-methyl-1, 3-butanediol, 2-methyl-1, 3-butanediol, 1, 2-hexanediol, 1, 5-hexanediol, 2, 5-hexanediol, 3-methyl-1, 5-pentanediol, 2, 3-dimethyl-2, 3-butanediol, 2-ethyl-2-methyl-1, 3-propanediol, 1, 2-heptanediol, 2-methyl-2-propyl-1, 3-propanediol, 2, 4-dimethyl-2, 4-pentanediol, 3, 6-octanediol, 2, 4-trimethyl-1, 3-pentanediol, 2, 5-dimethyl-2, 5-hexanediol, 2-ethyl-1, 3-hexanediol, 1, 2-nonanediol, 1, 8-nonanediol, 1, 5-nonanediol, 2, 8-nonanediol, 2-butyl-2-ethyl-1, 3-propanediol, 2, 4-diethyl-1, 5-pentanediol, 1, 2-decanediol, 2-diisobutyl-1, 3-propanediol, and the like. These alkylene glycol structures may have only one kind of structure in one molecule, or may have two or more kinds of structures.
Further, commercially available products of the compound having one or two (meth) acryloyl groups in one molecule and an alkanediol structure in one molecule include, for example: "Milamor (Miramer) M170", "Milamor (Miramer) M202", "Milamor (Miramer) M210", "Milamor (Miramer) M216", "Milamor (Miramer) M220", "Milamor (Miramer) M222", "Milamor (Miramer) M232", "Milamor (Miramer) M280", "Milamor (Miramer) M282", "Milamor (Miramer) M284", "Milamor (Miramer) M286", "Milamor (Miramer) M2040", "Milamor (Miramer) M231", "Milamor (Miramer) M233", "Milamor (Miramer) M235", "Milamor (Miramer) M281", "Milamor (Miramer) M283"; "NK Ester (NK Ester) A-30G", "NK Ester (NK Ester) A-90G", "NK Ester (NK Ester) A-130G", "NK Ester (NK Ester) AM-30 PG", "NK Ester (NK Ester) A-200", "NK Ester (NK Ester) A-400", "NK Ester (NK Ester) A-600", "NK Ester (NK Ester) APG-100", "NK Ester (NK Ester) APG-200", "NK Ester (NK Ester) APG-400", "NK Ester (NK Ester) APG-700", "NK Ester (NK Ester) A-PTMG-65", "NK Ester (NK Ester) M-20G", "NK Ester (NK Ester) M-30G", "NK Ester (NK Ester) M-40G", "NK Ester (NK Ester) M-90G "NK Ester (NK Ester) M-130G", "NK Ester (NK Ester) M-30 PG", "NK Ester (NK Ester) EH-4E", "NK Ester (NK Ester) B-20G", "NK Ester (NK Ester) S-12E", "NK Ester (NK Ester) 2G", "NK Ester (NK Ester) 3G", "NK Ester (NK Ester) 4G", "NK Ester (NK Ester) 9G", "NK Ester (NK Ester) 14G", "NK Ester (NK Ester)3 PG", "NK Ester (NK Ester)9 PG"; "Light Ester (Light Ester) BC", "Light Ester (Light Ester)130 MA", "Light Ester (Light Ester) BC", "Light Ester (Light Ester)2 EG", "Light Ester (Light Ester)3 EG", "Light Ester (Light Ester)4 EG", "Light Ester (Light Ester)9 EG", "Light Ester (Light Ester)14 EG", "Light Acrylate (Light Acrylate) EC-A", "Light Acrylate (Light Acrylate) MTG-A", "Light Acrylate (Light Acrylate) EHDG-AT", "Light Acrylate (Light Acrylate) 130A", "Light Acrylate (Light Acrylate) DPM-A", "Light Acrylate (Light Acrylate) P2H-A", "Light Acrylate (Light Acrylate) P200-A", manufactured by Co., Ltd, "Light Acrylate (Light Acrylate)4 EG-A", "Light Acrylate (Light Acrylate)9 EG-A", "Light Acrylate (Light Acrylate)14 EG-A", "Light Acrylate (Light Acrylate) PTMG-250"; fancryl (Fancryl) FA-240A, Fancryl (Fancryl) FA-P240A, Fancryl (Fancryl) FA-P270A, Fancryl (Fancryl) FA-PTG9A, Fancryl (Fancryl) FA-400M (100), Fancryl (Fancryl) FA-240M and Fancryl (Fancryl) FA-PTG9M manufactured by Hitachi chemical Co., Ltd; "New Frontier (New Frontier) ME-3", "New Frontier (New Frontier) ME-4S", "New Frontier (New Frontier) MPE-600", "New Frontier (New Frontier) PE-200", "New Frontier (New Frontier) PE-300", "New Frontier (New Frontier) PE-400", "New Frontier (New Frontier) PE-600", "New Frontier (New Frontier) MPEM-400", "New Frontier (New Frontier) TEGDMA", manufactured by first Industrial pharmaceutical products, Inc.; "Kayarad (KAYARAD) PEG400 DA" and "Kayarad (KAYARAD) PEG400 DA" manufactured by Nippon chemical Co., Ltd; "costock (Viscoat) # 190", "costock (Viscoat) # MTG", "MPE 400A", "MPE 550A", "costock (Viscoat) #310 HP", and the like, manufactured by osaka organic chemical industries, ltd.
The active energy ray-curable resin composition of the present invention may further contain urethane (meth) acrylate, epoxy (meth) acrylate, acrylic (meth) acrylate, and the like, as necessary.
The cured product of the present invention can be obtained, for example, by irradiating the active energy ray-curable resin composition with an active energy ray. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. In the case of using ultraviolet rays as the active energy rays, the curing reaction by ultraviolet rays can be efficiently performed, and in addition, the irradiation can be performed in an atmosphere of an inert gas such as nitrogen gas or in an atmosphere of air.
As the ultraviolet light generating source, an ultraviolet lamp is generally used from the viewpoint of practicality and economy. Specifically, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a gallium lamp, a metal halide lamp, sunlight, a Light-Emitting Diode (LED), and the like can be cited.
The cumulative amount of the active energy rays is not particularly limited, but is preferably 100mJ/cm 2 ～10,000mJ/cm 2 More preferably 300mJ/cm 2 ～8,000mJ/cm 2 . By setting the integrated light amount within the above range, curing failure due to insufficient light amount and deterioration of the cured product due to excessive light amount can be suppressed.
The irradiation with the active energy ray may be performed in one stage, or may be performed in two or more stages.
In view of suppressing chromatic aberration, the abbe number vD of the cured product is preferably 53 or more, and more preferably in the range of 55 to 60.
The refractive index nD of the cured product at a wavelength of 589nm is preferably 1.48 or more, and more preferably in the range of 1.49 to 1.55.
The laminate of the present invention has a resin layer containing the cured product and an inorganic layer. Further, a substrate may be provided as required.
The inorganic layer is a layer containing an inorganic compound, and generally has functions such as antireflection and scratch resistance.
Examples of the inorganic compound include a metal oxide, a complex oxide, a metal nitride, a metal fluoride, a complex fluoride, a silicon oxide, a silicon nitride, and a mixture thereof.
Examples of the metal include lithium, sodium, magnesium, aluminum, titanium, yttrium, indium, tin, zirconium, niobium, cerium, hafnium, tantalum, and the like.
In the case where the inorganic layer is used as an antireflection film layer, the antireflection film layer may be a single layer, but may have a low refractive index layer and a high refractive index layer. In addition, the low refractive index layer and the high refractive index layer may be one layer or a plurality of layers, respectively. The order of stacking the low refractive index layer and the high refractive index layer is not particularly limited.
As the inorganic compound used in the high refractive index layer, for example, lanthanum titanate (LaTiO) can be mentioned 3 ) Zirconium oxide (ZrO) 2 ) Titanium oxide (TiO) 2 ) Tantalum oxide (Ta) 2 O 5 ) Niobium oxide (Nb) 2 O 5 ) Hafnium oxide (HfO) 2 ) Cerium oxide (CeO) 2 ) Yttrium oxide (Y) 2 O 3 ) And mixtures of these, and the like.
Examples of the inorganic compound used for the low refractive index layer include magnesium fluoride (MgF) 2 ) Silicon dioxide (SiO) 2 ) Aluminum fluoride (AlF) 3 ) And mixtures of these, and the like.
The inorganic layer is obtained by forming a film on the surface of the resin layer. The method for forming the inorganic layer is not particularly limited, and a conventional film forming method can be appropriately used, but it is preferable to form the inorganic layer by Physical Vapor Deposition (PVD) or Chemical Vapor Deposition (CVD).
From the viewpoint of consistency and simplification of the film formation step, the Physical Vapor Deposition (PVD) is more preferably used as the film formation method, and examples thereof include vacuum vapor deposition, ion plating, sputtering, and the like.
As the vacuum evaporation, for example, a resistance heating method, a high-frequency induction heating method, an electron beam heating method, or the like can be used.
The sputtering may be Direct Current (DC) sputtering or Radio Frequency (RF) sputtering, and may also be magnetron sputtering or ion beam sputtering. Further, the system may be a parallel plate target system or an opposed target system. Examples of the gas introduced into the vacuum chamber include argon, krypton, oxygen, and nitrogen, and these gases may be used alone or in combination.
The film thickness of the inorganic layer may be appropriately adjusted depending on the intended function, and in the case where the antireflection function is intended, the range of 10nm to 5,000nm is preferable, and from the viewpoint of the film strength and productivity of the inorganic layer, the range of 100nm to 2,000nm is more preferable, and the range of 250nm to 1,000nm is particularly preferable.
As the substrate, for example, there can be used: polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefin resins such as polypropylene, polyethylene, and polymethylpentene; cellulose resins such as cellulose acetate (e.g., diacetylcellulose and triacetylcellulose), cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, cellulose acetate phthalate, and cellulose nitrate; acrylic resins such as polymethyl methacrylate; vinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride; polyvinyl alcohol; ethylene-vinyl acetate copolymer; polystyrene; a polyamide; a polycarbonate; polysulfones; polyether sulfone; polyether ether ketone; polyimide resins such as polyimide and polyetherimide; resin films such as norbornene-based resins (for example, "carnot (Zeonor)" manufactured by nippon (Zeon) corporation), modified norbornene-based resins (for example, "alton (Arton)" manufactured by JSR corporation), and cyclic olefin copolymers (for example, "APEL (APEL)" manufactured by mitsui chemical corporation); semiconductor wafers of silicon, silicon carbide, silicon nitride, sapphire, aluminum nitride, gallium phosphide, gallium arsenide, indium phosphide, gallium nitride and the like; quartz glass, borosilicate glass, soda lime glass, silicate glass, optical glass (crown glass, flint glass), and the like.
Examples of the method for applying the active energy ray-curable composition of the present invention to the film substrate include die coating, microgravure coating, gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, dip coating, spin coating, brush coating, full-surface coating with a screen, wire bar coating, flow coating, dispenser, inkjet printing, screen printing, and offset printing.
The lens of the present invention comprises the laminate.
Examples of the method for producing the lens include: a method of coating an active energy ray-curable resin composition on a wafer or a sensor substrate, irradiating an active energy ray using a die or the like so as to form a desired shape, thereby curing the active energy ray-curable resin composition, then washing an uncured portion with an organic solvent, and cutting a laminate obtained by forming an inorganic layer on the surface of the cured product of the active energy ray-curable resin composition by physical vapor deposition or the like into a desired shape.
Examples of the organic solvent include: ketone solvents such as methyl ethyl ketone, acetone, isobutyl ketone, cyclopentanone, and cyclohexanone; cyclic ether solvents such as tetrahydrofuran, dioxolane, and dioxane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylglycol monoalkyl ether, and dialkylglycol monoalkyl ether acetate. These organic solvents may be used alone or in combination of two or more.
Examples
The present invention will be specifically described below with reference to examples and comparative examples.
In the present example, the weight average molecular weight (Mw) is a value measured by Gel Permeation Chromatography (GPC) under the following conditions.
A measuring device: HLC-8220 manufactured by Tosoh corporation
Pipe column: protection pipe column H manufactured by Tosoh corporation XL -H
+ TSKgel G5000HXL manufactured by Tosoh corporation
+ TSKgel G4000HXL manufactured by Tosoh corporation
+ TSKgel G3000HXL manufactured by Tosoh corporation
+ TSKgel G2000HXL manufactured by Tosoh corporation
A detector: RI (differential refractometer)
Data processing: SC-8010 manufactured by Tosoh corporation
The measurement conditions were as follows: the temperature of the column is 40 DEG C
Solvent tetrahydrofuran
Flow rate 1.0 ml/min
The standard is as follows: polystyrene
Sample preparation: obtained by filtering a tetrahydrofuran solution (0.4 mass% in terms of solid content of resin) with a microfilter (100. mu.l)
Synthesis example 1 production of hyperbranched Polymer Compound (A-1) having an acryloyl group
134 parts by mass of trimethylolpropane, 2,500 parts by mass of dimethylolpropionic acid and 15 parts by mass of p-toluenesulfonic acid were charged into a reaction vessel equipped with a partial condenser (partial condenser), a thermometer and a stirring rod, and stirred at 100 ℃ to prepare a uniform liquid mixed melt. Then, 100 parts by mass of toluene was injected, and the temperature was raised to 140 ℃ to remove water produced by azeotropic distillation out of the system while refluxing the toluene. Then, after the reaction was continued at 140 ℃ for 3 hours, toluene was distilled off from the system to obtain a multibranched polyester polyol (a). The weight average molecular weight of the multi-branched polyester polyol (a) was 1,800.
Then, 100 parts by mass of the multibranched polyester polyol (a), 80 parts by mass of acrylic acid, 0.26 part by mass of methoxyphenol, 1.70 parts by mass of p-toluenesulfonic acid, and 120 parts by mass of toluene were charged into a reaction vessel equipped with a partial condenser, a thermometer, and a stirring rod, and water was removed by azeotropic distillation from the reaction vessel while refluxing toluene at a reaction temperature of 110 ℃. After the reaction was continued at 110 ℃ for 5 hours, the reaction mixture was neutralized with a 20 mass% aqueous solution of sodium hydroxide and washed three times with brine. Finally, toluene was distilled under reduced pressure out of the system to obtain a multibranched polymer compound (A-1) having an acryloyl group. The weight average molecular weight of the multibranched polymer compound having an acryloyl group (A-1) was 2,600.
Example 1 preparation of an active energy ray-curable resin composition (1)
A multibranched polymer compound having an acryloyl group (A-1) obtained in example 1, polycarbonate diacrylate ("UM-90 (1/3) DA") 85 parts by mass, tricyclodecane dimethanol dimethacrylate ("NK Ester (NK Ester) DCP") 10 parts by mass, and a photopolymerization initiator ("Hua TiGu (Runtecure) 1104" manufactured by Hua Titanic chemistry (Runtech Chemical) 1 parts by mass were blended in a 200mL brown bottle and heated at 60 ℃ for 30 minutes to be uniformly dissolved and defoamed, thereby obtaining an active energy ray-curable composition (1).
Example 2 preparation of resin composition curable with active energy ray (2)
A multibranched polymer compound having an acryloyl group (A-1) obtained in example 1, polycarbonate diacrylate ("UM-90 (1/3) DA") 80 parts by mass, tricyclodecane dimethanol dimethacrylate ("NK Ester (NK Ester) DCP") 15 parts by mass, and a photopolymerization initiator ("Hua TiGu (Runtecure) 1104" manufactured by Hua Titanic chemistry (Runtech Chemical) Co., Ltd.) were blended in a 200mL brown bottle and heated at 60 ℃ for 30 minutes to be uniformly dissolved and defoamed, thereby obtaining an active energy ray-curable composition (2).
Example 3 preparation of active energy ray-curable resin composition (3)
A multibranched polymer compound having an acryloyl group (A-1) obtained in example 1, polycarbonate diacrylate ("UM-90 (1/3) DA") 75 parts by mass, tricyclodecane dimethanol dimethacrylate ("NK Ester (NK Ester) DCP") 15 parts by mass, and a photopolymerization initiator ("Hua TiGu (Runtecure) 1104" manufactured by Hua Titanic chemistry (Runtech Chemical) 1 parts by mass were blended in a 200mL brown bottle and heated at 60 ℃ for 30 minutes to be uniformly dissolved and defoamed, thereby obtaining an active energy ray-curable composition (1).
Example 4 preparation of an active energy ray-curable resin composition (4)
A multibranched polymer compound having an acryloyl group (A-1) obtained in example 1, 55 parts by mass of polycarbonate diacrylate ("UM-90 (1/3) DA" manufactured by Yongji Product Co., Ltd., Yu division) and 1 part by mass of a photopolymerization initiator ("Hua Tio (Runtecure) 1104" manufactured by Hua Tio Chemical Co., Ltd., were blended in a 200mL brown bottle and heated at 60 ℃ for 30 minutes to be uniformly dissolved and defoamed, thereby obtaining an active energy ray-curable composition (4).
Example 5 preparation of resin composition curable with active energy ray (5)
The multibranched polymer compound having an acryloyl group (A-1) obtained in example 1, 30 parts by mass of polycarbonate diacrylate ("UM-90 (1/3) DA" manufactured by Yongji Product Co., Ltd., Yu division), and 1 part by mass of a photopolymerization initiator ("Hua Tio (Runtecure) 1104" manufactured by Hua Tio Chemical Co., Ltd., were blended in a 200mL brown bottle and heated at 60 ℃ for 30 minutes to be uniformly dissolved and defoamed, thereby obtaining an active energy ray-curable composition (5).
Example 6 preparation of resin composition curable with active energy ray (6)
A200 mL brown bottle was charged with 60 parts by mass of the multi-branched polymer compound (A-1) having an acryloyl group obtained in example 1, 40 parts by mass of polycarbonate diacrylate ("UM-90 (1/3) DA" manufactured by Utsubishi corporation, Ltd.), and 1 part by mass of a photopolymerization initiator ("Huatiou solid (Runtecure) 1104" manufactured by Huatiou Chemical company, and the mixture was heated at 60 ℃ for 30 minutes to be uniformly dissolved and defoamed, thereby obtaining an active energy ray-curable composition (6).
Example 7 preparation of an active energy ray-curable resin composition (7)
A multibranched polymer compound (A-1) having an acryloyl group obtained in example 1,50 parts by mass of polycarbonate diacrylate ("UM-90 (1/3) DA" manufactured by Yongji Product Co., Ltd., Yu division) and 50 parts by mass of a photopolymerization initiator ("Hua Tio (Runtecure) 1104" manufactured by Hua Tio Chemical Co., Ltd., 1 part by mass were blended in a 200mL brown bottle and heated at 60 ℃ for 30 minutes to be uniformly dissolved and defoamed, thereby obtaining an active energy ray-curable composition (7).
Example 8 preparation of an active energy ray-curable resin composition (8)
A multibranched polymer compound having an acryloyl group (A-1) obtained in example 1, polycarbonate diacrylate ("UM-90 (1/3) DA" manufactured by Yongji Product Co., Ltd., Yu., 35 parts by mass, and a photopolymerization initiator ("Hua Tigu (Runtecure) 1104" manufactured by Hua Titanic Chemical Co., Ltd., 1 part by mass were blended in a 200mL brown bottle and heated at 60 ℃ for 30 minutes to be uniformly dissolved and defoamed, thereby obtaining an active energy ray-curable composition (8).
Example 9 preparation of an active energy ray-curable resin composition (9)
A multibranched polymer compound having an acryloyl group (A-1) obtained in example 1, 35 parts by mass of polycarbonate diacrylate ("UM-90 (1/3) DA") manufactured by Yongkun Co., Ltd., Yu, 45 parts by mass of polyethylene glycol diacrylate ("NK Ester (NK Ester) A-400") manufactured by Ningwa Chemical industries, Ltd., 20 parts by mass of a photopolymerization initiator ("Hua Tiguo (Runtecure) 1104" manufactured by Hua Titan Chemical industries, Ltd., 1 part by mass were blended in a 200mL brown bottle, and heated at 60 ℃ for 30 minutes to be uniformly dissolved and defoamed, thereby obtaining an active energy ray-curable composition (9).
Example 10 preparation of an active energy ray-curable resin composition (10)
A dendrimer-type polymer compound having an acryloyl group (manufactured by Osaka organic Chemical industries, Ltd. "visco (Viscoat) #1000 LT") 35 parts by mass, polycarbonate diacrylate (manufactured by Yuchang products, Ltd. "UM-90 (1/3) DA") 45 parts by mass, polyethylene glycol diacrylate (manufactured by Xinzhou Chemical industries, Ltd. "NK Ester (NK Ester) A-400") 20 parts by mass, and a photopolymerization initiator (manufactured by Huati Chemical (Runtech Chemical) 1104) 1 part by mass were blended in a 200mL brown bottle, and heated at 60 ℃ for 30 minutes to be uniformly dissolved and defoamed, thereby obtaining an active energy ray-curable composition (10).
Example 11 preparation of an active energy ray-curable resin composition (11)
A200 mL brown bottle was charged with 35 parts by mass of a hyperbranched polymer compound having an acryloyl group ("CN 2302" manufactured by Arkema corporation), 45 parts by mass of polycarbonate diacrylate ("UM-90 (1/3) DA" manufactured by UK.K., 20 parts by mass of polyethylene glycol diacrylate ("NK Ester (NK Ester) A-400") manufactured by Xinzhongcun Chemical industry Co., Ltd., and 1 part by mass of a photopolymerization initiator ("Hua Ti solid (Runtecure) 1104" manufactured by Hua Ti Chemical company, and the mixture was uniformly dissolved and defoamed by heating at 60 ℃ for 30 minutes to obtain an active energy ray-curable composition (11).
Example 12 preparation of an active energy ray-curable resin composition (12)
A200 mL brown bottle was charged with 35 parts by mass of a hyperbranched polymer compound having an acryloyl group ("CN 2303" manufactured by Arkema corporation), 45 parts by mass of a polycarbonate diacrylate ("UM-90 (1/3) DA" manufactured by UK.K.; product Ltd.), 20 parts by mass of a polyethylene glycol diacrylate ("NK Ester (NK Ester) A-400" manufactured by Xinzhou Chemical industries Ltd.), and 1 part by mass of a photopolymerization initiator ("Hua Tiguo (Runtecure) 1104" manufactured by Hua Tio Chemical corporation, and the mixture was uniformly dissolved and defoamed by heating at 60 ℃ for 30 minutes to obtain an active energy ray-curable composition (12).
Example 13 preparation of an active energy ray-curable resin composition (13)
A hyperbranched polymer compound having an acryloyl group ("CN 2304" manufactured by Arkema corporation), polycarbonate diacrylate ("UM-90 (1/3) DA" manufactured by UK.K.), 45 parts by mass of polyethylene glycol diacrylate ("NK Ester (NK Ester) A-400" manufactured by Xinzhou Chemical industries, Ltd.), and 1 part by mass of a photopolymerization initiator ("Hua TitanGu (Runtecure) 1104" manufactured by Hua Titanic Chemical industries, Ltd.) were mixed in a 200mL brown bottle, and uniformly dissolved and defoamed at 60 ℃ for 30 minutes to obtain an active energy ray-curable composition (13).
Comparative example 1 preparation of resin composition curable with actinic energy ray (R1)
A200 mL brown bottle was charged with 81 parts by mass of polycarbonate diacrylate ("UM-90 (1/3) DA" manufactured by Utsu Kagaku K.K., Ltd.), 19 parts by mass of tricyclodecane dimethanol dimethacrylate ("NK Ester (NK Ester) DCP" manufactured by Xinzhongcun Chemical Co., Ltd.), and 1 part by mass of a photopolymerization initiator ("Hua Tigu (Runtecure) 1104" manufactured by Huati Chemical (Runtech Chemical Co., Ltd.), and heated at 60 ℃ for 30 minutes to be uniformly dissolved and defoamed, thereby obtaining an active energy ray-curable resin composition (R1).
Comparative example 2 preparation of resin composition curable with active energy ray (R2)
In a 200mL brown bottle, 35 parts by mass of dipentaerythritol hexaacrylate ("A-DPH 6A" manufactured by Kyowa Kagaku K.K., "" UM-90(1/3) DA "") 45 parts by mass, polyethylene glycol diacrylate ("NK Ester (NK Ester) A-400" manufactured by Xinzhou Kagaku K.K., K.K.), and 1 part by mass of photopolymerization initiator ("Hua Tiguo (Runtecure) 1104") were mixed, and the mixture was heated at 60 ℃ for 30 minutes to be uniformly dissolved and defoamed, thereby obtaining an active energy ray-curable resin composition (R2).
Comparative example 3 preparation of active energy ray-curable resin composition (R3)
In a 200mL brown bottle, 35 parts by mass of a polypentaerythritol polyacrylate ("Viscoat) # 802" manufactured by Osaka organic Chemical industries, Ltd., "UM-90 (1/3) DA" 45 parts by mass ("UM-90 (1/3) DA") manufactured by Uyu Kyoho Chemical industries, Ltd., "NK Ester (NK Ester) A-400" manufactured by Xinzhou village Chemical industries, Ltd., "China titanium solid (Runtecure) 1104" manufactured by China titanium Chemical industries, Ltd., "20 parts by mass of a polyethylene glycol diacrylate (" NK Ester (NK Ester) A-400 ") and 1 part by mass of a photopolymerization initiator (" China titanium solid (Runtecure)1104 ") were blended, and the mixture was uniformly dissolved and defoamed at 60 ℃ for 30 minutes to obtain an active energy ray-curable resin composition (R3).
Comparative example 4 preparation of resin composition curable with active energy ray (R4)
A200 mL brown bottle was charged with 35 parts by mass of a polypentaerythritol polyacrylate ("NK Ester (NK Ester) TPOA-30") manufactured by Xinzhongcun Chemical industries, Ltd., "UM-90 (1/3) DA" 45 parts by mass manufactured by Yuguxing products, Ltd., "NK Ester (NK Ester) A-400") 20 parts by mass of a polyethylene glycol diacrylate ("NK Ester (NK Ester) A-400") manufactured by Xinzhongcun Chemical industries, Ltd., "Hua Tiguo (Runtecure) 1104") 1 part by mass of a photopolymerization initiator ("Hua Tiguo (Runte cure) 1104") manufactured by HuaTio Chemical industries, and heated at 60 ℃ for 30 minutes to be uniformly dissolved and defoamed, thereby obtaining an active energy ray-curable resin composition (R4).
The following evaluations were carried out using the active energy ray-curable resin compositions obtained in the examples and comparative examples. The evaluation results are shown in tables 1 and 2.
[ method of measuring refractive index ]
The active energy ray-curable compositions obtained in examples and comparative examples were poured into a triangular prism mold (thickness: 5mm, length of one side: 10mm), and irradiated with 3,000mJ/cm using a belt conveyor type ultraviolet irradiation apparatus (120W metal halide lamp) manufactured by Qi (Eyegraphics) Ltd 2 The cured product of the triangular prism shape is produced by the ultraviolet ray of (1). The refractive index of the resulting cured product was measured using a Kalnew precision refractometer "KPR-3000" manufactured by Shimadzu corporation. Further, a matching fluid having a refractive index (nD) closest to the refractive index (nD) of the cured product is appropriately selected and used.
[ method for measuring Abbe number ]
The active energy ray-curable compositions obtained in examples and comparative examples were poured into a triangular prism mold (thickness: 5mm, length of one side: 10mm), and irradiated with 3,000mJ/cm using a belt conveyor type ultraviolet irradiation apparatus (120W metal halide lamp) manufactured by Qi (Eyegraphics) Ltd 2 The cured product of the triangular prism shape is produced by the ultraviolet ray of (1). The Abbe number of the obtained cured product was measured using a Kalnew precision refractometer "KPR-3000" manufactured by Shimadzu corporation. Further, a matching fluid having a refractive index (nD) closest to the refractive index (nD) of the cured product is appropriately selected and used.
[ Table 1]
[ Table 2]
Example 14 production of laminate (1)
The active energy ray-curable resin composition (1) obtained in example 1 was added dropwise to a composition which was subjected to adhesion treatment with a silane coupling agent ("KBM-5103" manufactured by shin-Etsu chemical industries, Ltd.) using a pipetteThe glass substrate was sandwiched by a mold, and an LED light irradiation device ("LHPUV 365" manufactured by Kawasaki electric Co., Ltd.) was used to irradiate the glass substrate with an irradiation intensity of 50mW/cm 2 The cumulative light quantity was 450mJ/cm 2 The mold is then removed from the mold by semi-curing. After the uncured resin composition on the obtained semi-cured product was washed using cyclopentanone as a solvent, the irradiation intensity was 50mW/cm using the LED irradiation apparatus 2 And the cumulative light amount of 7550mJ/cm 2 Allowing it to harden completely. Subsequently, the cured product was placed in an oven heated to 100 ℃ and annealed for 90 minutes to obtain a cured product. Using a magnetron sputtering apparatus ("HSR-522" manufactured by Shimadzu corporation), a sputtering target was prepared by: SiO 2 2 Introducing gas: ar, gas flow rate: 15sccm, room temperature 25 ℃, sputtering time: the hardened material obtained in the above manner was sputtered under a condition of 55min, and SiO was laminated on the surface of the hardened material in a thickness of 0.6 μm 2 And (3) forming a film to obtain a laminate (1).
Example 15 production of laminate (2)
A laminate (2) was obtained in the same manner as in example 14, except that the active energy ray-curable resin composition (2) was used in place of the active energy ray-curable resin composition (1) used in example 14.
Example 16 production of laminate (3)
A laminate (3) was obtained in the same manner as in example 14, except that the active energy ray-curable resin composition (3) was used in place of the active energy ray-curable resin composition (1) used in example 14.
Example 17 production of laminate (4)
A laminate (4) was obtained in the same manner as in example 14, except that the active energy ray-curable resin composition (4) was used in place of the active energy ray-curable resin composition (1) used in example 14.
Example 18 production of laminate (5)
A laminate (5) was obtained in the same manner as in example 14, except that the active energy ray-curable resin composition (5) was used in place of the active energy ray-curable resin composition (1) used in example 14.
Example 19 production of laminate (6)
A laminate (6) was obtained in the same manner as in example 14, except that the active energy ray-curable resin composition (6) was used in place of the active energy ray-curable resin composition (1) used in example 14.
Example 20 production of laminate (7)
A laminate (7) was obtained in the same manner as in example 14, except that the active energy ray-curable resin composition (7) was used in place of the active energy ray-curable resin composition (1) used in example 14.
Example 21 production of laminate (8)
A laminate (8) was obtained in the same manner as in example 14, except that an active energy ray-curable resin composition (8) was used in place of the active energy ray-curable resin composition (1) used in example 14.
Example 22 preparation of laminate (9)
A laminate (9) was obtained in the same manner as in example 14, except that the active energy ray-curable resin composition (9) was used in place of the active energy ray-curable resin composition (1) used in example 14.
Example 23 production of laminate (10)
A laminate (10) was obtained in the same manner as in example 14, except that the active energy ray-curable resin composition (10) was used in place of the active energy ray-curable resin composition (1) used in example 14.
Example 24 production of laminate (11)
A laminate (11) was obtained in the same manner as in example 14, except that the active energy ray-curable resin composition (11) was used in place of the active energy ray-curable resin composition (1) used in example 14.
Example 25 production of laminate (12)
A laminate (11) was obtained in the same manner as in example 14, except that the active energy ray-curable resin composition (12) was used in place of the active energy ray-curable resin composition (1) used in example 14.
Example 26 production of laminate (13)
A laminate (13) was obtained in the same manner as in example 14, except that an active energy ray-curable resin composition (13) was used in place of the active energy ray-curable resin composition (1) used in example 14.
Comparative example 5 production of laminate (R1)
A laminate (R1) was obtained in the same manner as in example 14, except that the active energy ray-curable resin composition (R1) was used in place of the active energy ray-curable resin composition (1) used in example 14.
Comparative example 6 production of laminate (R2)
A laminate (R2) was obtained in the same manner as in example 14, except that an active energy ray-curable resin composition (R2) was used in place of the active energy ray-curable resin composition (1) used in example 14.
Comparative example 7 production of laminate (R3)
A laminate (R3) was obtained in the same manner as in example 11, except that an active energy ray-curable resin composition (R3) was used in place of the active energy ray-curable resin composition (1) used in example 14.
Comparative example 8 production of laminate (R4)
A laminate (R4) was obtained in the same manner as in example 14, except that an active energy ray-curable resin composition (R4) was used in place of the active energy ray-curable resin composition (1) used in example 14.
The laminates obtained in the examples and comparative examples were used to perform the following evaluations.
[ method for evaluating crack resistance ]
The laminates (1) to (10) obtained in examples 11 to 20 and the laminates (R1) to (R7) obtained in comparative examples 8 to 14 were placed in an oven heated to 175 ℃ and subjected to a heat treatment for 5 minutes, and then the surface of the laminate (inorganic layer) was observed with a microscope ("VHX 900" manufactured by Keyence corporation) and evaluated according to the following criteria.
O: no cracks were generated on the laminate surface.
And (delta): 1 to 3 cracks were generated on the surface of the laminate.
X: at least 4 cracks were generated on the surface of the laminate.
The evaluation results of the laminates (1) to (10) obtained in examples 11 to 20 and the laminates (R1) to (R7) obtained in comparative examples 8 to 14 are shown in tables 3 and 4.
[ Table 3]
[ Table 4]
| TABLE 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 |
| Laminated body | (R1) | (R2) | (R3) | (R4) |
| Crack resistance | × | × | × | × |
Examples 1 to 26 shown in tables 1 and 3 are examples of the active energy ray-curable resin composition containing the multibranched polymer compound (a) having a (meth) acryloyl group. It was confirmed that the laminate having the resin layer containing the active energy ray-curable resin composition had excellent crack resistance, while generation of cracks in the inorganic layer formed on the resin layer was suppressed.
On the other hand, comparative examples 1 to 8 are examples of the active energy ray-curable resin composition not containing the multi-branched polymer compound (a) having a (meth) acryloyl group. Since 4 or more cracks were generated on the surface of the laminate having the resin layer containing the active energy ray-curable resin composition after heat treatment at 175 ℃ for 5 minutes, it was confirmed that the crack resistance for suppressing the generation of cracks in the inorganic layer formed on the resin layer was significantly insufficient.
Claims (7)
1. An actinic energy ray-curable resin composition for forming a resin layer, which is an actinic energy ray-curable resin composition for forming a resin layer, comprising a laminate of a resin layer and an inorganic layer, wherein the actinic energy ray-curable resin composition contains a multi-branched polymer compound (A) having a (meth) acryloyl group.
2. The active energy ray-curable resin composition for forming a resin layer according to claim 1, wherein the multi-branched polymer compound (A) is at least one selected from the group consisting of a compound having a dendrimer structure, a compound having a hyperbranched structure, and a compound having a star-shaped structure.
3. A cured product of the active energy ray-curable resin composition according to claim 1 or 2.
4. A cured product according to claim 3, wherein Abbe number vD is 53 or more.
5. A cured product according to claim 3, wherein the refractive index nD at a wavelength of 589nm is 1.48 or more.
6. A laminate, characterized by comprising: a resin layer comprising a cured product according to any one of claims 3 to 5; and an inorganic layer.
7. A lens comprising the laminate of claim 6.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020-018810 | 2020-02-06 | ||
| JP2020018810 | 2020-02-06 | ||
| PCT/JP2021/004015 WO2021157632A1 (en) | 2020-02-06 | 2021-02-04 | Active energy ray-curable resin composition, cured product, multilayer body and lens |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115066329A true CN115066329A (en) | 2022-09-16 |
Family
ID=77200887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202180012833.8A Pending CN115066329A (en) | 2020-02-06 | 2021-02-04 | Active energy ray-curable resin composition, cured product, laminate, and lens |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP7388456B2 (en) |
| KR (1) | KR20220139873A (en) |
| CN (1) | CN115066329A (en) |
| TW (1) | TW202130668A (en) |
| WO (1) | WO2021157632A1 (en) |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004307579A (en) * | 2003-04-03 | 2004-11-04 | Mitsubishi Chemicals Corp | Active energy ray-curable coating composition and molded article having cured coating film obtained from the composition |
| JP2006010829A (en) * | 2004-06-23 | 2006-01-12 | Fuji Photo Film Co Ltd | Anti-reflection coating, anti-reflection film, polarizing plate, and image display device using same |
| JP2006072346A (en) * | 2004-08-04 | 2006-03-16 | Sanyo Chem Ind Ltd | Resin composition for optical lens |
| TW200906873A (en) | 2007-05-30 | 2009-02-16 | Toagosei Co Ltd | Active energy ray curable composition, coating composition, coating member, and optical material |
| JP2011074280A (en) * | 2009-09-30 | 2011-04-14 | Fujifilm Corp | Star polymer, and curable resin composition |
| JP5611705B2 (en) * | 2010-08-02 | 2014-10-22 | 富士フイルム株式会社 | Curable resin composition and molded body |
| JP5981750B2 (en) * | 2012-03-29 | 2016-08-31 | 大阪ガスケミカル株式会社 | Hard coat resin composition, cured product thereof, and method for producing cured product |
| JP2014052424A (en) * | 2012-09-05 | 2014-03-20 | Jsr Corp | Photosensitive resin composition |
| US9873799B2 (en) * | 2013-03-29 | 2018-01-23 | Hoya Corporation | Coating composition |
| WO2018105441A1 (en) * | 2016-12-08 | 2018-06-14 | Dic株式会社 | Active-energy-beam-curable resin composition, and laminate |
-
2021
- 2021-02-04 JP JP2021575842A patent/JP7388456B2/en active Active
- 2021-02-04 WO PCT/JP2021/004015 patent/WO2021157632A1/en active Application Filing
- 2021-02-04 CN CN202180012833.8A patent/CN115066329A/en active Pending
- 2021-02-04 TW TW110104267A patent/TW202130668A/en unknown
- 2021-02-04 KR KR1020227026721A patent/KR20220139873A/en active Search and Examination
Also Published As
| Publication number | Publication date |
|---|---|
| WO2021157632A1 (en) | 2021-08-12 |
| JP7388456B2 (en) | 2023-11-29 |
| TW202130668A (en) | 2021-08-16 |
| KR20220139873A (en) | 2022-10-17 |
| JPWO2021157632A1 (en) | 2021-08-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2013146483A1 (en) | Transparent electroconductive laminate | |
| JP2010052334A (en) | Hard coat film for in-mold shaping, in-mold label, and resin molding | |
| WO2014189124A1 (en) | Resin composition for sealing organic el element, and cured product thereof | |
| JP6108136B2 (en) | Gas barrier film with a protective coating layer containing inorganic particles | |
| KR101912668B1 (en) | Method for producing curable composition for imprints | |
| JP6092200B2 (en) | Photo-curable resin composition for imprint, production method and structure | |
| JP2016502465A (en) | Coating method for reducing damage to the barrier layer | |
| WO2020189707A1 (en) | Anti-reflection film laminate, anti-reflection film, and method for manufacturing anti-reflection film laminate | |
| JP4536417B2 (en) | Gas barrier film | |
| TW201636216A (en) | Transparent conductive film | |
| KR101583119B1 (en) | Gas barrier film | |
| WO2016076302A1 (en) | Photocurable resin composition and method for producing laminate using same | |
| CN115066329A (en) | Active energy ray-curable resin composition, cured product, laminate, and lens | |
| JP2008310119A (en) | Antireflection film | |
| KR102502398B1 (en) | Composition for forming hard coating and hard coating film using the same | |
| JP6603595B2 (en) | Transparent conductive film and touch panel, and method for producing transparent conductive film | |
| JPWO2019124156A1 (en) | Active energy ray-curable composition, its cured product, and a lens | |
| JP6828281B2 (en) | Active energy ray-polymerizable resin composition | |
| JP7559386B2 (en) | Active energy ray curable composition, cured product, lens and camera module | |
| KR20170111922A (en) | A composition for making hard coating layer and transparent conductive film using the same | |
| JP7468685B2 (en) | Active energy ray curable composition, cured product, lens and camera module | |
| JP3799990B2 (en) | Plastic sheet which is not easily damaged and laminate using the same | |
| JP2022087497A (en) | Active energy ray curable resin composition, cured object, laminate and lens | |
| CN112912411B (en) | Photocurable composition, cured film, and laminate | |
| CN108290970A (en) | Photocurable resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |