JP2018161863A - Method for producing resin molded product and method for producing optical component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a resin molded product which hardly causes occurrence of air bubbles when a curable composition is applied to a mold having a pattern shape in imprint molding.SOLUTION: A method for producing a resin molded product includes: a conductive substrate application step S1 of applying a dielectric curable composition having a contact angle of 50° or less with respect to a mold having a pattern shape onto a conductive substrate; a mold application step S2 of facing a surface where the dielectric curable composition of the conductive substrate is applied and a surface where the mold has the pattern shape, and applying a voltage between the conductive substrate and the mold, and thereby bringing the dielectric curable composition applied onto the conductive substrate into contact with a curable composition unapplied portion of the mold, and applying the dielectric curable composition thereto; and a curing step S6 of curing the dielectric curable composition applied to the mold to obtain a resin molded product.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a method for producing a resin molded product and a method for producing an optical component. More specifically, the present invention relates to a method for manufacturing a resin molded product by imprint molding and a method for manufacturing an optical component using the resin molded product.

  In recent years, mobile electronic devices such as mobile phones and smartphones have been improved in product value by mounting sensors and cameras. Every year, miniaturization and thinning have progressed, and optical components such as lenses used for them have been required to be smaller and thinner. Conventionally, such demands have been dealt with by manufacturing optical parts by injection molding, but the injection molding method has a limit in dealing with downsizing and thinning. Therefore, an imprint molding technique is attracting attention as a new molding method that replaces the injection molding method (see Patent Document 1).

JP 2010-266664 A

  When a resin molded product having a fine shape is molded by imprint molding, the mold to be used is provided with a fine pattern shape corresponding to the fine shape of the resin molded product. However, the present inventor, when molding a resin molded product by imprint molding using a mold having such a fine pattern shape, is cured when a curable composition that forms the resin molded product is applied to the mold. It has been found that bubbles are easily generated (foaming) in the composition. The air bubbles are particularly likely to be generated near the bottom of a concave portion having a fine pattern provided in the mold (the portion that becomes the tip of the convex portion of the resin molded product after molding).

  Accordingly, an object of the present invention is to provide a method for producing a resin molded product in which bubbles are not easily generated when a curable composition is applied to a mold having a pattern shape in imprint molding, and an optical system using the resin molded product. It is to provide a method for manufacturing a component.

  As a result of intensive studies to achieve the above object, the present inventor has used a curable composition having a small contact angle with a mold and having a dielectric property as a curable composition for forming a resin molded product. Is applied on a conductive substrate, and then a voltage is applied between the conductive substrate and the mold to bring the curable composition applied on the conductive substrate into contact with the pattern shape of the mold. It has been found that, by applying, it is possible to make it difficult for bubbles to occur when a curable composition is applied to a mold having a pattern shape. The present invention has been completed based on these findings.

  That is, the present invention is a method for producing a resin molded product by imprint molding, which comprises applying a dielectric curable composition having a contact angle to a mold having a pattern shape of 50 ° or less on a conductive substrate. A substrate coating step, the conductive curable composition coated surface of the conductive substrate is opposed to a surface having a pattern shape of the mold, and a voltage is applied between the conductive substrate and the mold to conduct the conductive A mold application process including a voltage application application step of applying the dielectric curable composition applied on the conductive substrate to a part where the curable composition of the mold is not applied, and the dielectric applied to the mold Provided is a method for producing a resin molded product, which has a curing step for obtaining a resin molded product by curing a curable composition.

  After the mold application step, the dielectric curable composition is applied to the mold coated with the dielectric curable composition obtained through the mold application step, through the conductive substrate application step and the mold application step. It is preferable to have a mold closing process in which another mold coated with is laminated so that the dielectric curable compositions come into contact with each other.

  Preferably, the mold application step includes a step of applying the dielectric curable composition to the mold at a coating speed of 100 ml / min or more after the voltage application step.

  The dielectric curable composition preferably contains an epoxy compound.

  It is preferable to have a defoaming step for defoaming under reduced pressure after the mold application step.

  It is preferable that the pattern shape in the mold is a concavo-convex shape, and the height difference between the bottom of the concave portion and the top of the convex portion is 0.05 mm or more.

  The resin molded product is preferably a microlens array.

  Moreover, this invention provides the manufacturing method of the optical component using the resin molded product obtained by the manufacturing method of the said resin molded product.

  According to the method for producing a resin molded product of the present invention, it is possible to make it difficult for bubbles to occur when a curable composition is applied to a mold having a pattern shape. In particular, even when a mold having a fine pattern shape is used, bubbles are unlikely to occur. Therefore, a resin molded product having a fine shape can be easily manufactured with excellent shape accuracy.

It is a schematic diagram showing a mode that a dielectric curable composition is made to contact and apply | coat to a mold by the application of a voltage in a mold application | coating process. It is process drawing which shows one Embodiment of the manufacturing method of the resin molded product of this invention. It is a schematic diagram which shows an example of a Fresnel lens, (1-a) is sectional drawing, (1-b) is the figure seen from right above. It is a schematic diagram showing an angle θ formed by the lens surface 4 and the non-lens surface 5 and the lens surface 4 and the reference surface 6 in the Fresnel lens cross section.

  The method for producing a resin molded product of the present invention is a method for producing a resin molded product by imprint molding, and a dielectric curable composition having a contact angle with a mold having a pattern shape of 50 ° or less is applied on a conductive substrate. Applying a voltage between the conductive substrate and the mold so that the surface of the conductive substrate coated with the dielectric curable composition is opposite to the surface having the pattern shape of the mold. A mold application step including a voltage application step of applying the dielectric curable composition applied on the conductive substrate to a portion where the curable composition of the mold is not applied is applied, and applied to the mold. And curing the obtained dielectric curable composition to obtain a resin molded product. In the present specification, the method for producing a resin molded product of the present invention may be simply referred to as “the production method of the present invention”.

  In addition, when calling it "a curable composition" in this specification, it means all the curable compositions for forming a resin molding including the said dielectric curable composition and another curable composition. .

  As described above, the production method of the present invention is a method for producing a resin molded product by imprint molding, and a curable composition for forming a resin molded product is applied to a substrate, and the applied curable composition is applied. Another substrate is stacked so as to be sandwiched, and then the curable composition is cured to produce a resin molded product. In the production method of the present invention, a mold having a pattern shape is used as at least one substrate, and a dielectric curable composition is applied to the mold having this pattern shape (hereinafter sometimes simply referred to as “mold”). Apply by applying voltage.

(Conductive substrate coating process)
The conductive substrate application step is a step of applying a dielectric curable composition having a contact angle of 50 ° or less to a mold having a pattern shape for imparting a desired shape to a resin molded product on the conductive substrate. .

  The dielectric curable composition is a composition that cures to form a resin molded product. The dielectric curable composition has a contact angle with respect to the mold of 50 ° or less. As a result, the wettability of the dielectric curable composition with respect to the mold is increased, so that even when the pattern shape has a fine structure, when the dielectric material adheres to the mold during application by voltage application, The curable composition easily conforms to the pattern shape and does not easily generate bubbles. The contact angle is preferably 45 ° or less, more preferably 40 ° or less. The contact angle can be measured by a known or common method.

  The dielectric curable composition contains a curable compound (curable compound). As said dielectric curable composition, the dielectric composition used for well-known or usual imprint molding can be used, and it selects suitably according to the kind of the target resin molded product. Examples of the curable compound include a cationic curable compound, a radical curable compound, and an anion curable compound. Examples of the cationic curable compound include an epoxy group-containing compound (epoxy compound), an oxetanyl group-containing compound (oxetane compound), and a vinyl ether group-containing compound (vinyl ether compound), and preferably an epoxy compound. The said curable compound may use only 1 type and may use 2 or more types.

  As said epoxy compound, the well-known thru | or usual compound which has 1 or more epoxy groups (oxirane ring) in a molecule | numerator can be used, Although it does not specifically limit, For example, an alicyclic epoxy compound (alicyclic epoxy resin) ), Aromatic epoxy compounds (aromatic epoxy resins), aliphatic epoxy compounds (aliphatic epoxy resins), and the like.

  Examples of the alicyclic epoxy compound include known or conventional compounds having one or more alicyclic rings and one or more epoxy groups in the molecule, and are not particularly limited. For example, (1) A compound having an epoxy group (referred to as “alicyclic epoxy group”) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring; (2) the epoxy group is directly bonded to the alicyclic ring by a single bond. (3) compounds having an alicyclic ring and a glycidyl ether group in the molecule (glycidyl ether type epoxy compound) and the like.

As said (1) compound which has an alicyclic epoxy group in a molecule | numerator, the compound represented by following formula (i) is mentioned.

  In the above formula (i), Y represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include divalent hydrocarbon groups, alkenylene groups in which part or all of carbon-carbon double bonds are epoxidized, carbonyl groups, ether bonds, ester bonds, carbonate groups, amide groups, and the like. And a group in which a plurality of are connected. In addition, a substituent such as an alkyl group may be bonded to one or more carbon atoms constituting the cyclohexane ring (cyclohexene oxide group) in the formula (i).

  As said bivalent hydrocarbon group, a C1-C18 linear or branched alkylene group, a bivalent alicyclic hydrocarbon group, etc. are mentioned. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclopentylene group, And divalent cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group, and cyclohexylidene group.

  Examples of the alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond is epoxidized (sometimes referred to as “epoxidized alkenylene group”) include, for example, a vinylene group, a propenylene group, and a 1-butenylene group. , A 2-butenylene group, a butadienylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group, etc., and a linear or branched alkenylene group having 2 to 8 carbon atoms. In particular, the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, more preferably 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized. Alkenylene group.

Representative examples of the alicyclic epoxy compound represented by the above formula (i) include (3,4,3 ′, 4′-diepoxy) bicyclohexyl, the following formulas (i-1) to (i-10). ) And the like. In the following formulas (i-5) and (i-7), l and m each represent an integer of 1 to 30. R ′ in the following formula (i-5) is an alkylene group having 1 to 8 carbon atoms, and among them, a linear or branched chain having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group, and an isopropylene group. -Like alkylene groups are preferred. N1-n6 in following formula (i-9) and (i-10) show the integer of 1-30, respectively. Other examples of the alicyclic epoxy compound represented by the above formula (i) include 2,2-bis (3,4-epoxycyclohexyl) propane and 1,2-bis (3,4-epoxycyclohexane). -1-yl) ethane, 1,2-epoxy-1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, bis (3,4-epoxycyclohexylmethyl) ether and the like.

Examples of the compound (2) in which the epoxy group is directly bonded to the alicyclic ring with a single bond include compounds represented by the following formula (ii).

In formula (ii), R ″ is a group (p-valent organic group) obtained by removing p hydroxyl groups (—OH) from the structural formula of a p-valent alcohol, and p and n each represent a natural number. Examples of the valent alcohol [R ″ (OH) _p ] include polyhydric alcohols (such as alcohols having 1 to 15 carbon atoms) such as 2,2-bis (hydroxymethyl) -1-butanol. p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or more, n in each group in () (inside the outer parenthesis) may be the same or different. Specific examples of the compound represented by the above formula (ii) include 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol [for example, , Trade name “EHPE3150” (manufactured by Daicel Corporation), etc.].

  Examples of the compound (3) having an alicyclic ring and a glycidyl ether group in the molecule include glycidyl ethers of alicyclic alcohols (particularly alicyclic polyhydric alcohols). More specifically, for example, 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, 2,2-bis [3,5-dimethyl-4- (2,3-epoxypropoxy) Compound obtained by hydrogenating bisphenol A type epoxy compound such as cyclohexyl] propane (hydrogenated bisphenol A type epoxy compound); bis [o, o- (2,3-epoxypropoxy) cyclohexyl] methane, bis [o , P- (2,3-epoxypropoxy) cyclohexyl] methane, bis [p, p- (2,3-epoxypropoxy) cyclohexyl] methane, bis [3,5-dimethyl-4- (2, 3-epoxypropoxy) cyclohexyl] a compound obtained by hydrogenating a bisphenol F-type epoxy compound such as methane (hydrogenated bisphenol F-type epoxy compound); Hydrogenated phenol novolac epoxy compound; Hydrogenated cresol novolac epoxy compound; Hydrogenated cresol novolac epoxy compound of bisphenol A; Hydrogenated naphthalene epoxy compound; Epoxy compound obtained from trisphenolmethane Hydrogenated epoxy compounds; hydrogenated epoxy compounds of the following aromatic epoxy compounds and the like.

  Examples of the aromatic epoxy compound include epibis type glycidyl ether type epoxy resins obtained by condensation reaction of bisphenols [for example, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol and the like] and epihalohydrin; High molecular weight epibis type glycidyl ether type epoxy resin obtained by addition reaction of bis type glycidyl ether type epoxy resin with the above bisphenols; phenols [eg, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, bisphenol S, etc.] and aldehyde [eg, formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, salicy A novolak alkyl type glycidyl ether type epoxy resin obtained by further condensing a polyhydric alcohol obtained by a condensation reaction with an aldehyde etc. with an epihalohydrin; two phenol skeletons are bonded to the 9-position of the fluorene ring. In addition, an epoxy compound in which a glycidyl group is bonded to an oxygen atom obtained by removing a hydrogen atom from the hydroxy group of the phenol skeleton, either directly or via an alkyleneoxy group.

  Examples of the aliphatic epoxy compound include a glycidyl ether of an alcohol having no q-valent cyclic structure (q is a natural number); a monovalent or polyvalent carboxylic acid [for example, acetic acid, propionic acid, butyric acid, stearic acid, Adipic acid, sebacic acid, maleic acid, itaconic acid, etc.] glycidyl ester; epoxidized oils and fats having double bonds such as epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil; polyolefins such as epoxidized polybutadiene (poly Epoxidized product of alkadiene). Examples of the alcohol having no q-valent cyclic structure include monohydric alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, and 1-butanol; ethylene glycol, 1,2-propanediol, 1 , 3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and other dihydric alcohols; Examples include trihydric or higher polyhydric alcohols such as glycerin, diglycerin, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol. That. The q-valent alcohol may be polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, or the like.

  Examples of the oxetane compound include known or commonly used compounds having one or more oxetane rings in the molecule, and are not particularly limited. For example, 3,3-bis (vinyloxymethyl) oxetane, 3-ethyl-3- (Hydroxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3- Ethyl-3- (chloromethyl) oxetane, 3,3-bis (chloromethyl) oxetane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis {[1-ethyl (3- Oxetanyl)] methyl} ether, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] bisi Chlohexyl, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] cyclohexane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 3-ethyl-3- {[(3-ethyloxetane-3-yl) methoxy] methyl)} oxetane, xylylene bisoxetane, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane, oxetanylsilsesquioxane And phenol novolac oxetane.

  The vinyl ether compound may be a known or conventional compound having one or more vinyl ether groups in the molecule, and is not particularly limited. For example, 2-hydroxyethyl vinyl ether (ethylene glycol monovinyl ether), 3-hydroxy Propyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl vinyl ether, 1-methyl-3 -Hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1-hydroxymethylpropyl vinyl ether 4-hydroxycyclohexyl vinyl ether, 1,6-hexanediol monovinyl ether, 1,6-hexanediol divinyl ether, 1,8-octanediol divinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, 1,4-cyclohexanedi Methanol divinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanol divinyl ether, 1,2-cyclohexanedimethanol monovinyl ether, 1,2-cyclohexanedimethanol divinyl ether, p-xylene glycol monovinyl ether P-xylene glycol divinyl ether, m-xylene glycol monovinyl ether, m-xylene glycol divinyl ether, o-xy Glycol monovinyl ether, o-xylene glycol divinyl ether, ethylene glycol divinyl ether, diethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, tetraethylene glycol monovinyl ether, tetraethylene glycol divinyl ether, penta Ethylene glycol monovinyl ether, pentaethylene glycol divinyl ether, oligoethylene glycol monovinyl ether, oligoethylene glycol divinyl ether, polyethylene glycol monovinyl ether, polyethylene glycol divinyl ether, dipropylene glycol monovinyl ether, dipropylene glycol Coal divinyl ether, tripropylene glycol monovinyl ether, tripropylene glycol divinyl ether, tetrapropylene glycol monovinyl ether, tetrapropylene glycol divinyl ether, pentapropylene glycol monovinyl ether, pentapropylene glycol divinyl ether, oligopropylene glycol monovinyl ether, oligopropylene glycol di Vinyl ether, polypropylene glycol monovinyl ether, polypropylene glycol divinyl ether, isosorbide divinyl ether, oxanorbornene divinyl ether, phenyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octyl vinyl ether, cyclohexyl vinyl ether, ha Droquinone divinyl ether, 1,4-butanediol divinyl ether, cyclohexane dimethanol divinyl ether, trimethylolpropane divinyl ether, trimethylolpropane trivinyl ether, bisphenol A divinyl ether, bisphenol F divinyl ether, hydroxyoxanorbornane methanol divinyl ether, 1, Examples include 4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, and dipentaerythritol hexavinyl ether.

  Although content of the curable compound (especially epoxy compound) in the said dielectric curable composition is not specifically limited, It is 10 to 95 weight% with respect to the total amount (100 weight%) of a dielectric curable composition. Is more preferable, more preferably 15 to 90% by weight, still more preferably 20 to 85% by weight. When the content is 10% by weight or more, the curability of the dielectric curable composition, the heat resistance, light resistance, and transparency of the resin molded product tend to be excellent.

  The dielectric curable composition preferably contains a photopolymerization initiator together with the curable compound, and particularly preferably contains a photocationic polymerization initiator. A cationic photopolymerization initiator is a compound that generates an acid upon irradiation with light and initiates a curing reaction of a curable compound (particularly a cationic curable compound) contained in the dielectric curable composition, and absorbs light. A cation portion and an anion portion which is a source of acid.

  Examples of the photocationic polymerization initiator include diazonium salt compounds, iodonium salt compounds, sulfonium salt compounds, phosphonium salt compounds, selenium salt compounds, oxonium salt compounds, ammonium salt compounds, bromine salt compounds. Etc. In the present invention, it is particularly preferable to use a sulfonium salt compound in that a resin molded product having excellent curability can be formed.

  Examples of the cation moiety of the sulfonium salt compound include triphenylsulfonium ion, diphenyl [4- (phenylthio) phenyl] sulfonium ion, tri-p-tolylsulfonium ion, (4-hydroxyphenyl) methylbenzylsulfonium ion, 4 Examples include arylsulfonium ions (particularly triarylsulfonium ions) such as-(4-biphenylylthio) phenyl-4-biphenylylphenylsulfonium ions.

As the anion moiety, for example, [(X) _s B (Phf) _4-s ] ⁻ (wherein X represents a phenyl group or a biphenylyl group. Phf is a perfluoroalkyl group, at least one of hydrogen atoms is A perfluoroalkoxy group and a phenyl group substituted with at least one selected from the group consisting of halogen atoms, s is an integer of 0 to 3), BF ₄ ⁻ , [(Rf) _n PF _{6−; n} ] ⁻ (Rf: an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms, n: an integer of 0 to 5), AsF ₆ ⁻ , SbF ₆ ⁻ , pentafluorohydroxyantimonate and the like.

  Examples of the photocationic polymerization initiator include (4-hydroxyphenyl) methylbenzylsulfonium tetrakis (pentafluorophenyl) borate, 4- (4-biphenylylthio) phenyl-4-biphenylylphenylsulfonium tetrakis (pentafluorophenyl). ) Borate, 4- (phenylthio) phenyldiphenylsulfonium phenyltris (pentafluorophenyl) borate, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium phenyltris (pentafluorophenyl) borate, diphenyl [ 4- (phenylthio) phenyl] sulfonium tris (pentafluoroethyl) trifluorophosphate, diphenyl [4- (phenylthio) phenyl] sulfonium tetraki (Pentafluorophenyl) borate, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate, 4- (4-biphenylylthio) phenyl-4-biphenylylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, bis [ 4- (diphenylsulfonio) phenyl] sulfide phenyltris (pentafluorophenyl) borate, [4- (2-thioxanthonylthio) phenyl] phenyl-2-thioxanthonylsulfonium phenyltris (pentafluorophenyl) borate, commodity Names “Syracure UVI-6970”, “Syracure UVI-6974”, “Syracure UVI-6990”, “Syracure UVI-950” (above, Union Carbide, USA) "Irgacure 250", "Irgacure 261", "Irgacure 264" (manufactured by Ciba Specialty Chemicals), "SP-150", "SP-151", "SP-170", "Optomer SP-171" (Above, manufactured by ADEKA Corporation), "CG-24-61" (produced by Ciba Specialty Chemicals), "DAICAT II" (produced by Daicel Corporation), "UVAC1590", "UVAC1591" (above, Manufactured by Daicel-Cytec Co., Ltd.), “CI-2064”, “CI-2639”, “CI-2624”, “CI-2481”, “CI-2734”, “CI-2855”, “CI-2823” , “CI-2758”, “CIT-1682” (manufactured by Nippon Soda Co., Ltd.), “PI-2074” (manufactured by Rhodia, Tetra) (Pentafluorophenylborate) tolylcumyl iodonium salt), “FFC509” (manufactured by 3M), “BBI-102”, “BBI-101”, “BBI-103”, “MPI-103”, “TPS-” 103 "," MDS-103 "," DTS-103 "," NAT-103 "," NDS-103 "(manufactured by Midori Chemical Co., Ltd.)," CD-1010 "," CD-1011 "," Commercial products such as “CD-1012” (manufactured by Sartomer, USA), “CPI-100P”, “CPI-101A”, and “CPI-200K” (manufactured by San Apro Co., Ltd.) can be used.

  Only 1 type may be used for the said photoinitiator, and 2 or more types may be used for it. The amount used (blending amount) is preferably 0.01 to 15 parts by weight, more preferably 0, per 100 parts by weight of the curable compound (particularly cationic curable compound) contained in the dielectric curable composition. .05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight. By using the photopolymerization initiator within the above range, a resin molded product having excellent curability, heat resistance, light resistance, transparency, optical properties and the like can be obtained.

  The dielectric curable composition comprises the curable compound, the photopolymerization initiator, and other components as required (for example, a solvent, an antioxidant, a photosensitizer, an antifoaming agent, a leveling agent, a cup Ring agents, surfactants, flame retardants, ultraviolet absorbers, colorants, etc.). As said dielectric curable composition, commercial items, such as a brand name "CELVENUS OUH106" (made by Daicel Corporation), can also be used, for example.

  As the conductive substrate, a known or commonly used conductive material substrate can be used. Examples of the conductive substrate include a metal substrate (metal substrate) such as gold, silver, copper, nickel, chromium, aluminum, and iron; a semiconductor substrate (semiconductor substrate) such as silicon. Moreover, you may use what gave the electroconductivity by giving the metal plating process to the surface of the resin substrate. Further, the conductive substrate may be a mold having conductivity described later.

  The application to the conductive substrate can be performed by a known or conventional application method. Examples of the coating include spin coating, roll coating, spray coating, dispense coating, dip coating, and inkjet coating.

(Mold application process)
The mold application step includes a surface having the pattern shape of the dielectric curable composition application surface of the conductive substrate and a mold (a mold having a pattern shape for imparting a desired shape to a resin molded product). The dielectric curable composition applied on the conductive substrate is applied to the curable composition uncoated portion of the mold by placing the electrodes facing each other and applying a voltage between the conductive substrate and the mold. A step of contacting and applying (sometimes referred to as a “voltage application step”). In the present specification, applying a dielectric curable composition to a mold by applying a voltage as described above may be referred to as “voltage application application”.

  The “mold curable composition unapplied portion” is a portion to which a curable composition (the dielectric curable composition and other curable compositions) for forming a resin molded product is to be applied and is still applied. It is the part of the pattern shape of the mold which is not done. That is, in the voltage application step, when a curable composition for forming a resin molded product is applied to the mold, a dielectric having a contact angle of 50 ° or less as the curable composition to be applied to the mold first. A pattern shape of the mold was imparted to the dielectric curable composition applied on the conductive substrate by applying a voltage between the conductive substrate and the mold using the curable composition. The dielectric curable composition is applied to the mold in contact with the part. For example, when the mold release agent is applied to the mold, the dielectric curable composition is applied to the mold to which the mold release agent is applied, and when the mold release agent is not applied to the mold surface. To do.

  In the production method of the present invention, as described above, when a curable composition for forming a resin molded product is applied to a mold, the contact angle with respect to the mold is 50 ° or less as the curable composition that is first applied to the mold. The dielectric curable composition is used, and the dielectric curable composition is applied in contact with the mold by applying a voltage between the conductive substrate and the mold. . As a result, the dielectric curable composition easily conforms to the pattern shape when it adheres to the mold during application by application of voltage, and bubbles are less likely to be generated. Further, according to the manufacturing method of the present invention in which application is performed by applying a voltage, it is assumed that the mold is deformed by applying the voltage, and the pattern is formed by the synergistic effect of the deformation of the dielectric curable composition and the deformation of the mold. It is conceivable that the shape following ability and the suppression of bubble generation are improved.

  With reference to FIG. 1, a state in which a dielectric curable composition is applied in contact with a mold by applying a voltage in a mold application process will be described. As shown in FIG. 1 (a), a mold 1 having a pattern shape on one side and a conductive substrate 3 coated with the dielectric curable composition 2 prepared in the conductive substrate coating step are molded into a mold 1. The surface having the pattern shape (the lower surface in FIG. 1) and the surface (the upper surface in FIG. 1) coated with the dielectric curable composition 2 of the conductive substrate 3 are disposed so as to face each other (opposite). And connect with the conducting wire with switch. Then, a voltage is applied between the mold 1 and the conductive substrate 3 by turning on the switch. As a result, as shown in FIG. 1B, the dielectric curable composition 2 on the conductive substrate 3 extends in the direction of the mold 1 and comes into contact with the pattern-shaped portion of the mold 1. Product 2 is applied. And as shown in FIG.1 (c), the mold 1 by which the dielectric curable composition 2 was apply | coated to the pattern shape part is obtained. In addition, the position of the power supply and switch in a conducting wire is not specifically limited. Further, the positive electrode and the negative electrode of the power supply may be reversed. Further, the positional relationship between the mold 1 and the conductive substrate 3 is such that the vertical upper side may be the mold 1 and the vertical lower side may be the conductive substrate 3, and the vertical lower side is the mold 1 as shown in FIG. The upper vertical side may be the conductive substrate 3.

  The distance between the conductive substrate and the mold in the voltage application application is appropriately set within a range in which the dielectric curable composition on the conductive substrate can come into contact with the mold by applying a voltage. Moreover, the voltage to apply is suitably set within the range which the dielectric curable composition on an electroconductive board | substrate can contact a mold by application of a voltage, for example, is 100-500V.

  The mold is provided with a reverse concave / convex pattern shape (inverted shape of the desired resin molded product) corresponding to the shape for giving the resin molded product a desired shape. The mold may have a contact angle with respect to the mold of the dielectric curable composition forming the resin molded product of 50 ° or less and be conductive, but is preferably made of resin. The resin forming the mold is selected in consideration of the contact angle of the dielectric curable composition, the releasability of the molded resin product after curing, and examples thereof include silicone resins (dimethylpolysiloxane, etc.), fluorine Resin, polyolefin resin (polyethylene, polypropylene, polycyclic olefin, etc.), polyethersulfone resin, polycarbonate resin, polyester resin (polyarylate, polyethylene terephthalate, polyethylene naphthalate, etc.), polyamide resin, polymethyl methacrylate Etc. Among these resins, silicone resins are preferable. When a silicone resin is used, it is excellent in compatibility with a dielectric curable composition containing an epoxy compound, and the contact angle tends to be small. Moreover, since it is excellent also in the mold release property of a resin molded product, and the softness | flexibility of a mold, a resin molded product can be taken out more easily.

  The resin mold may contain a conductive material such as metal in order to exhibit conductivity. Examples of the resin mold having conductivity include, for example, a resin mold containing conductive particles, a resin mold having a conductive film such as a metal film on at least the pattern-shaped portion surface, and the inside of the resin mold (in particular, Examples include those in which a conductive substrate such as a metal plate is embedded in the vicinity of the pattern shape portion inside the resin mold, and those having a conductive film such as a metal film on the opposite side of the pattern shape portion of the resin mold. . Moreover, in order to exhibit electroconductivity, the resin mold may be subjected to plasma treatment on at least the pattern shape portion. Moreover, the electroconductive particle and the electrically conductive film may be partially arrange | positioned according to the pattern shape and pattern period of resin-made molds. Examples of the conductive material include those exemplified as conductive materials such as metals constituting the conductive substrate described above. The metal film can be provided on the mold surface by a known or common method such as metal vapor deposition.

A commercial item may be used for the above-mentioned mold, and what was manufactured may be used for it. In the case of producing a mold, for example, it can be produced by molding (preferably imprint molding) a resin composition forming the mold and then thermosetting. The metal mold | die which has an uneven | corrugated shape can be used, for example, can be manufactured with the method of following (1), (2).
(1) A method in which a mold is pressed against a coating film of a resin composition applied on a substrate and the coating film of the resin composition is cured, and then the mold is peeled off. (2) A resin composition with respect to the mold A method of peeling a mold after applying a product directly, adhering a substrate from the top, and curing a coating film of a resin composition

  The mold may have a release agent applied to at least a part of the pattern shape. If the mold release agent is applied to the mold before the voltage application, the formed resin molded product can be easily released from the mold (released). In this case, since the release layer is usually released from the mold at the same time, the obtained resin molded product has at least one release layer on the surface.

  Examples of the release agent include a fluorine release agent, a silicone release agent, and a wax release agent. The said mold release agent may use 1 type and may use 2 or more types. Examples of the method for applying the release agent include spraying, spin coating, and screen printing.

  In the mold application step, the voltage application is preferably performed until it can be visually confirmed that a coating film of the dielectric curable composition is formed on at least the entire pattern shape. The voltage application may be performed until the entire amount of the curable composition for forming a resin molded product is applied, and a coating film of the dielectric curable composition is formed on the entire pattern shape. After applying the above-mentioned voltage application until it can be visually confirmed, the remaining total amount of the curable composition for forming a resin molded product may be applied by another application method. As said other application | coating method, the method of apply | coating at the application | coating speed | rate of 100 ml / min or more (preferably 1000 ml / min or more) from a viewpoint of productivity is preferable. That is, the mold application step preferably includes a step of applying the curable composition to the mold at an application rate of 100 ml / min or more (preferably 1000 ml / min or more) after the voltage application application step. In addition, the said curable composition applied with the said other coating method may be the said dielectric curable composition, and another curable composition may be sufficient as it. Further, other curable compositions may or may not have dielectric properties.

  The other coating methods described above can be performed by known or common coating methods. Examples of other coatings include spin coating, roll coating, spray coating (spray spraying), dispense coating, dip coating, ink jet coating, air brush coating (air brush spraying), and ultrasonic coating (ultrasonic spraying). Etc.

  In the mold application step, the voltage-setting application, and then application by the other application method as necessary is performed to apply (fill) the curable composition containing the dielectric curable composition to the pattern shape portion. ) Is obtained.

(Defoaming process)
The manufacturing method of this invention may have the process (defoaming process) of defoaming the bubble in the apply | coated curable composition after the said mold application | coating process. In the production method of the present invention, the generation of bubbles in the curable composition is considerably suppressed in the mold application step, but slightly generated bubbles can be removed by the defoaming step.

  The defoaming can be performed by a known or conventional defoaming method, and defoaming by reduced pressure (vacuum defoaming, vacuum defoaming) is preferable. The vacuum degassing can be performed, for example, by leaving the mold filled with the curable composition in an environment of pressure 0.1 to 20 kPa for 1 to 10 minutes.

(Mold closing process)
The mold coated with (filled with) the curable composition obtained through the mold coating process (if necessary, the defoaming process) is overlapped with another substrate so as to sandwich the coated curable composition. A matching step (mold closing step) is performed. That is, using the mold coated with the curable composition and the other substrate as the upper mold and the lower mold, respectively, the upper mold and the lower mold are closed so as to sandwich the curable composition. . At this time, either may be an upper mold or a lower mold.

  The other substrate may be a mold having a pattern shape (another mold different from the mold subjected to the voltage application application) or a substrate having no pattern shape (a flat substrate). For example, when manufacturing a resin molded product having a concavo-convex shape on only one surface, the flat substrate can be used as the other substrate, and when manufacturing a resin molded product having a concavo-convex shape on both sides, the other The other mold can be used as the substrate.

  As said other mold, the thing similar to the mold which performs the above-mentioned voltage application application can be used. The two molds described above may be formed of different materials or may be formed of the same material. Moreover, said two molds may have the same pattern shape and may have a different pattern shape.

  Examples of the planar substrate include a glass plate; a semiconductor such as silicon, gallium arsenide, and gallium nitride; a resin substrate such as polycarbonate, polypropylene, and polyethylene; a metal substrate; and a combination of these materials. The planar substrate may have a pattern structure such as an optical structure such as a fine wiring, a crystal structure, an optical waveguide, or holography.

  The curable composition may or may not be applied to the other substrate. When the curable composition is applied to the other substrate, a substrate on which the curable composition is applied (filled) through the mold application step (if necessary, a defoaming step) for applying voltage is applied. It may be used. In particular, when a mold is used as the other substrate (that is, when a resin molded product having concavo-convex shapes on both sides is manufactured), the mold as the other substrate includes the conductive substrate application step and the mold application step ( If necessary, it is preferable to use a mold coated (filled) with a curable composition through a defoaming step. When using a substrate coated with a curable composition as the other substrate (particularly, a mold coated with the curable composition through the conductive substrate coating step and the mold coating step), the mold closing step includes: The upper mold and the lower mold are overlapped so that the curable compositions are in contact with each other.

  As described above, a dielectric mold can be used as the conductive substrate. In this case, it is not necessary to perform application to the upper mold and application of the dielectric curable composition to the lower mold. For example, after application to a mold having dielectric properties as the lower mold, the dielectric properties as the upper mold are increased. The dielectric curable composition is brought into contact with the upper mold while applying a voltage to the mold having the mold and the lower mold, and at the same time, the mold is closed and pressed in a pressing process described later. In this case, the process of separately applying the upper mold and the lower mold is batched, so that the effect of shortening the process is obtained and the workability is excellent.

(Pressing process)
The manufacturing method of this invention may have the process (press process) pressed from the upper part of an upper mold | type after the said mold closing process. Thereby, the thickness variation of the resin molded product obtained can be made small. The pressure at the time of pressing is, for example, 0.01 to 100 MPa.

(Curing process)
In the curing step, the curable composition applied (filled) to the mold is cured to obtain a resin molded product. Specifically, the curable composition is cured by advancing a polymerization reaction of a curable compound (particularly a cationic curable compound) contained in the curable composition such as the dielectric curable composition. Can do. The curing method can be appropriately selected from well-known or conventional methods, and is not particularly limited, and examples thereof include a method of irradiation with active energy rays and / or heating. As the active energy ray, for example, any of infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α rays, β rays, γ rays and the like can be used. Among these, ultraviolet rays are preferable in terms of excellent handleability.

  A high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, or the like is used as a light source when performing ultraviolet irradiation. Although the irradiation time varies depending on the type of light source, the distance between the light source and the coating surface, and other conditions, it is several tens of seconds at the longest. Illuminance is, for example, about 5 to 200 mW. After active energy ray irradiation, curing may be promoted by heating (post-cure) as necessary.

  Through the curing step, the curable composition is cured and a resin molded product can be obtained. After the curing step, the upper mold and the lower mold are opened, and the resin molded product can be taken out from the mold.

  FIG. 2 is a process diagram showing an embodiment of the production method of the present invention. The manufacturing method of the present invention shown in FIG. 2 includes a conductive substrate coating step S1 for applying a dielectric curable composition having a contact angle of 50 ° or less to a mold having a pattern shape on a conductive substrate, The dielectric applied on the conductive substrate by applying a voltage between the conductive substrate and the mold, with the dielectric curable composition application surface and the surface having the pattern shape of the mold facing each other. Mold application step S2 including a voltage application step of applying and applying the curable composition to the curable composition uncoated portion of the mold, and defoaming step S3 of defoaming bubbles in the applied curable composition A mold closing step S4 for superimposing a mold coated (filled) with the curable composition on another substrate so as to sandwich the applied curable composition, and a pressing step S for pressing from above the upper mold. And a curing step S6 to obtain a resin molded article by curing a curable composition applied to the mold, has, in this order.

  The resin molded product obtained by the production method of the present invention is, for example, a lens, a prism, an LED, an organic EL element, a semiconductor laser, a transistor, a solar cell, a CCD image sensor, an optical waveguide, an optical fiber, an alternative glass (for example, a display substrate) , Hard disk substrate, polarizing film) and the like can be preferably used.

  When manufacturing a lens as the optical component, for example, a microlens array [for example, a structure having a shape in which a plurality of microlenses are arranged in a matrix in the vertical and horizontal directions] may be obtained. That is, the mold preferably has a pattern shape corresponding to the shape of the microlens array.

  As the size of the optical component, for example, when the optical component is a microlens array, the size of one microlens is about 0.01 to 100 mm in diameter and about 0.1 to 2.0 mm in thickness, for example. The pitch width in the microlens array is, for example, about 10 to 1000 μm.

  In particular, the optical component is preferably a Fresnel lens array. As shown in FIG. 3, the Fresnel lens is a prism composed of a lens surface 4 on the surface and a non-lens surface 5 facing the lens surface, and a plurality of prisms having a cross section in a mountain shape. It is a formed lens. The angle θ formed by the lens surface 4 and the reference surface 6 continuously decreases (or increases) toward the center. When only the lens surface 1 is continuous, one convex lens (or concave lens) is formed. Form (see FIG. 4). Since the mold for molding the Fresnel lens array has fine irregularities as shown in FIGS. 3 and 4, bubbles are particularly likely to be generated when the curable composition is applied. However, the method for producing a resin molded product of the present invention can suppress the generation of bubbles during application even to a mold for producing a resin molded product having a particularly fine uneven shape such as a Fresnel lens array. it can.

  The repeat interval in the Fresnel lens array (distance between the tops of the convex parts or the deepest part of the concave parts, that is, the pitch width of the prism shape) is not particularly limited, but is preferably 0.5 mm or less, more preferably 0.2 mm or less, More preferably, it is 0.1 mm or less. The lower limit is, for example, 0.05 mm. The narrower the repetition interval, the higher the difficulty of preventing the generation of bubbles. However, according to the method for producing a resin molded product of the present invention, the generation of bubbles at the time of application even to a mold corresponding to such a repetition interval. Can be suppressed.

  The sharpness in the Fresnel lens array (the convex tip portion R or the concave valley portion R, that is, the sharpness of the sharpness angle / cutting angle) is not particularly limited, but is preferably R0.01 mm or less, more preferably R0.005 mm or less, More preferably, it is R0.001 mm or less. The lower limit is, for example, 0.0005 mm. The smaller the R is, the higher the difficulty of preventing the generation of bubbles. However, according to the method for producing a resin molded product of the present invention, the generation of bubbles during application to a mold corresponding to such a sharpness is also achieved. Can be suppressed.

  The height interval in the Fresnel lens array (the difference in height between the top of the convex part and the deepest part of the concave part) is not particularly limited, but is preferably 0.05 mm or more, more preferably 0.5 mm or more, and even more preferably 5 mm or more. . The upper limit is 10 mm, for example. The higher the height interval, the higher the difficulty of preventing the generation of bubbles. According to the method for producing a resin molded product of the present invention, the bubbles at the time of application can be applied to a mold corresponding to such a height interval. Can be suppressed.

S1 Conductive substrate coating process S2 Mold coating process S3 Defoaming process S4 Mold closing process S5 Pressing process S6 Curing process

Claims (8)

A method for producing a resin molded product by imprint molding,
A conductive substrate coating step of applying a dielectric curable composition having a contact angle of 50 ° or less to a mold having a pattern shape on the conductive substrate;
By applying a voltage between the conductive substrate and the mold, the dielectric curable composition application surface of the conductive substrate and the surface having the pattern shape of the mold are opposed to each other on the conductive substrate. A mold application step including a voltage application step of applying and applying the applied dielectric curable composition to an uncoated portion of the mold.
And a method for producing a resin molded product, comprising a curing step of curing the dielectric curable composition applied to the mold to obtain a resin molded product.   After the mold application step, the dielectric curable composition is applied to the mold coated with the dielectric curable composition obtained through the mold application step, through the conductive substrate application step and the mold application step. The method for producing a resin molded product according to claim 1, further comprising: a mold closing step in which another mold to which is applied is overlapped with the dielectric curable composition so as to contact each other.   The resin molded product according to claim 1, wherein the mold application step includes a step of applying the dielectric curable composition to the mold at a coating speed of 100 ml / min or more after the voltage application step. Manufacturing method.   The manufacturing method of the resin molded product of any one of Claims 1-3 in which the said dielectric curable composition contains an epoxy compound.   The manufacturing method of the resin molded product of any one of Claims 1-4 which has the defoaming process which defoams by pressure reduction after the said mold application | coating process.   The manufacturing method of the resin molded product of any one of Claims 1-5 whose pattern shape in the said mold is uneven | corrugated shape, and the height difference of a recessed part bottom part and a convex part top part is 0.05 mm or more.   The method for producing a resin molded product according to any one of claims 1 to 6, wherein the resin molded product is a microlens array.   The manufacturing method of the optical component using the resin molded product obtained by the manufacturing method of the resin molded product of any one of Claims 1-7.

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