JP2018161864A - 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 pattern-shaped part of a mold in imprint molding.SOLUTION: A method for producing a resin molded product includes: a conductive composition application step S1 of applying a curable composition having a contact angle of 50° or less with respect to a mold having a pattern-shaped part subjected to wettability improvement treatment onto a curable composition unapplied portion of the mold; and a curing step S5 of curing the curable composition applied to the mold to obtain the resin molded product.SELECTED DRAWING: Figure 1

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

  Therefore, an object of the present invention is to use a method for producing a resin molded product in which bubbles are less likely to occur when a curable composition is applied to a mold having a pattern shape portion in imprint molding, and the resin molded product. It is to provide a method for manufacturing an optical component.

  As a result of intensive studies to achieve the above object, the present inventor has found that the surface of the mold having the pattern shape portion subjected to the wettability improving process has not been subjected to the wettability improving process on the uncoated portion of the curable composition. It has been found that by applying a curable composition having a small contact angle to the mold, it is possible to make it difficult for bubbles to occur when the curable composition is applied to the pattern shape portion of the mold. 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, wherein the wettability is applied to the curable composition uncoated portion of a mold having a pattern shape portion subjected to wettability improvement treatment on the surface. A curable composition application step for applying a curable composition having a contact angle of 50 ° or less with respect to the mold before the improvement treatment, and curing for obtaining a resin molded product by curing the curable composition applied to the mold. Provided is a method for producing a resin molded product having a process.

  The wettability improving treatment is preferably one or more treatments selected from the group consisting of plasma discharge treatment, corona discharge treatment, ozone exposure treatment, and excimer treatment.

The plasma discharge treatment or the corona discharge treatment is preferably a discharge treatment with a discharge amount of 50 W · min / m ² or more.

  After the curable composition application step, the mold to which the curable composition obtained through the curable composition application step is applied is applied to the mold through the curable composition application step. It is preferable to have a mold closing process in which the other mold is overlapped so that the curable compositions are in contact with each other.

  The curable composition preferably contains an epoxy compound.

  It is preferable to have the defoaming process by pressure reduction after the said curable composition application | coating process.

  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 pattern shape portion of a mold. In particular, even when a mold having a fine pattern shape portion is used, the generation of bubbles is difficult to occur. Therefore, a resin molded product having a fine shape can be easily manufactured with excellent shape accuracy.

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 a lens surface 1 and a non-lens surface 2 and a lens surface 1 and a reference surface 3 in a Fresnel lens cross section.

  The method for producing a resin molded product according to the present invention is a method for producing a resin molded product by imprint molding, wherein the curable composition uncoated part of the mold having a pattern shape portion subjected to wettability improvement treatment on the surface A curable composition coating step of applying a curable composition having a contact angle of 50 ° or less with respect to the mold before the wettability improving treatment, and curing the curable composition applied to the mold to form a resin. It has a curing step for obtaining a 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”.

  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 portion is used as at least one substrate, and the pattern shape portion of the mold having this pattern shape portion (hereinafter sometimes simply referred to as “mold”) is cured. Apply the composition.

(Curable composition application process)
In the curable composition coating step, a curable composition uncoated portion of a mold having a pattern shape portion subjected to wettability improvement treatment on the surface (that is, a curable composition forming a resin molded product should be applied) This is a step of applying a curable composition having a contact angle with respect to the mold of 50 ° or less to a portion that has not been applied yet.

  The curable composition can be applied by a known or conventional application method. Examples of the application include spin coat application, roll coat application, spray application (spray spray), dispense coat, dip coat, ink jet application, air brush application (air brush spray), and ultrasonic application (ultrasonic spray). Can be mentioned.

  The said curable composition is a composition which hardens | cures and forms a resin molded product. The curable composition has a contact angle of 50 ° or less with respect to the mold before being subjected to the wettability improving treatment. As a result, the wettability of the curable composition with respect to the mold is increased, so that even when the pattern shape portion has a fine structure, the pattern is not adhered to the mold when the curable composition is applied. The curable composition easily spreads along the shape and bubbles are not easily generated. 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 curable composition contains a curable compound (curable compound). As said curable composition, the composition used for well-known thru | or usual imprint molding can be used, According to the kind of the target resin molded product, it selects suitably. 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 curable composition is not specifically limited, 10-95 weight% is preferable with respect to the total amount (100 weight%) of a curable composition, More Preferably it is 15 to 90 weight%, More preferably, it is 20 to 85 weight%. When the content is 10% by weight or more, the curability of the curable composition, the heat resistance, light resistance, and transparency of the resin molded product tend to be excellent.

  The 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 curable composition, and absorbs light. Part and an anion part 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 use amount (blending amount) is preferably 0.01 to 15 parts by weight, more preferably 0.05 to 100 parts by weight of the curable compound (particularly cationic curable compound) contained in the curable composition. -10 parts by weight, more preferably 0.1-5 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 curable composition includes the curable compound, the photopolymerization initiator, and other components as necessary (for example, a solvent, an antioxidant, a photosensitizer, an antifoaming agent, a leveling agent, a coupling agent). , Surfactants, flame retardants, ultraviolet absorbers, colorants, etc.). As said curable composition, commercial items, such as a brand name "CELVENUS OUH106" (made by Daicel Corporation), can also be used, for example.

  The mold is provided with a reverse concave / convex pattern shape (inverted shape of a desired resin molded product) corresponding to the shape for giving the resin molded product a desired shape. Although the said mold should just have a contact angle with respect to the mold of the curable composition which forms a resin molded product, it is preferable that it is resin. The resin for forming the mold is selected in consideration of the contact angle of the curable composition, the peelability of the molded resin product after curing, and the like, for example, a silicone resin (dimethylpolysiloxane, etc.), a fluorine resin , Polyolefin resins (polyethylene, polypropylene, polycyclic olefins, etc.), polyethersulfone resins, polycarbonate resins, polyester resins (polyarylate, polyethylene terephthalate, polyethylene naphthalate, etc.), polyamide resins, polymethyl methacrylate, etc. Can be mentioned. Among these resins, silicone resins are preferable. When a silicone resin is used, it is excellent in compatibility with a 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 mold has a wettability improving process applied to the surface of the pattern shape portion. The wettability improving treatment is preferably plasma discharge treatment, corona discharge treatment, ozone exposure treatment, or excimer treatment, and more preferably plasma discharge treatment or corona discharge treatment. By applying these wettability improving treatments to the mold, the wettability of the curable composition is improved. And by combining with the use of the curable composition having a contact angle of 50 ° or less, the compatibility of the curable composition and the mold is further improved, and the fine pattern shape portion formed in the mold It is easy for the curable composition to reach the tip of the concave portion of the cavities, and the generation of bubbles can be suppressed.

  The plasma discharge treatment is a treatment for processing the mold surface by generating positive and negative charged particles activated by discharging in the atmosphere. The corona discharge treatment is a treatment for processing the mold surface by generating a non-uniform electric field around a sharp electrode (needle electrode) and generating a continuous discharge. The ozone exposure treatment is, for example, a treatment for processing the mold surface by generating ozone by ultraviolet irradiation using a low-pressure mercury lamp or the like in the presence of oxygen. The excimer process is a process for processing the mold surface by ultraviolet irradiation or laser irradiation using an excimer lamp in a vacuum state.

In the plasma discharge treatment or the corona discharge treatment, although not particularly limited, the discharge amount is preferably 50 W · min / m ² or more, and more preferably 80 W · min / m ² or more. When the discharge amount is 50 W · min / m ² or more, the wettability of the curable composition is further improved, and bubbles are less likely to occur after coating.

A commercial item may be used for the above-mentioned mold, and what was manufactured may be used for it. When manufacturing a mold, for example, it is manufactured by molding (preferably imprint molding) a resin composition that forms the mold, thermosetting, and then applying wettability improving treatment to the surface of the pattern portion of the mold. Can do. A mold having a concavo-convex shape can be used for molding the resin composition, and for example, it can be produced by the following methods (1) and (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

  In the mold, a release agent may be applied to at least a part of the pattern shape portion. If the mold release agent is applied to the mold before the application of the curable composition, it can be easily released when the formed resin molded product is taken out (released) from the mold. 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.

  As described above, in the curable composition application step, a mold in which the curable composition is applied (filled) to the pattern shape portion whose surface has been subjected to wettability improvement processing 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 curable composition application | coating process. In the production method of the present invention, in the curable composition coating step, the generation of bubbles in the curable composition is considerably suppressed, but the 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 curable composition coating step (if necessary, the defoaming step) is placed in another manner so as to sandwich the coated curable composition. A process of superimposing on the substrate (mold closing process) 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 portion (other mold different from the mold used in the curable composition coating step), and a substrate having no pattern shape portion (planar substrate). It may be. 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 in which the above-mentioned wettability improvement process was performed 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 part, and may have a different pattern shape part.

  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 a curable composition is applied to the other substrate, the curable composition application step (if necessary, a defoaming step) using a mold having a pattern shape portion subjected to wettability improvement treatment on the surface. ) Through which the curable composition is applied (filled) may be used. Therefore, in the case of producing a resin molded product having concavo-convex shapes on both surfaces, the mold as the other substrate is the curable composition application step using a mold having a pattern shape portion subjected to wettability improvement processing on the surface. It is preferable to use a mold filled with the curable composition through (if necessary, a defoaming step). The substrate on which the curable composition is applied as the other substrate (particularly, the curable composition is subjected to the curable composition application step using the mold having the pattern shape portion subjected to the wettability improving process on the surface). In the case of using an applied mold), in the mold closing step, the upper mold and the lower mold are overlapped so that the curable compositions are in contact with each other.

(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 can be cured by advancing a polymerization reaction of a curable compound (particularly a cationic curable compound) contained in the curable composition. 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. 1 is a process diagram showing an embodiment of the production method of the present invention. In the manufacturing method of the present invention shown in FIG. 1, the contact angle with respect to the mold before the wettability improving treatment is applied to the curable composition uncoated portion of the mold having the pattern shape portion subjected to the wettability improving treatment on the surface. A curable composition coating step S1 for applying a curable composition of 50 ° or less, a defoaming step S2 for defoaming bubbles in the applied curable composition, and the curable composition applied (filled). A mold closing step S3 for overlapping the mold with another substrate so as to sandwich the applied curable composition, a pressing step S4 for pressing from the upper part of the upper mold, and the curable composition applied to the mold is cured. The curing step S5 for obtaining a resin molded product is provided 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. 2, the Fresnel lens is a prism composed of a lens surface 1 on the surface and a non-lens surface 2 opposite to 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 1 and the reference surface 3 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. 3). Since the mold for molding the Fresnel lens array has fine irregularities as shown in FIGS. 2 and 3, 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 curable composition coating process S2 defoaming process S3 mold closing process S4 pressing process S5 curing process

Claims (9)

  A method for producing a resin molded product by imprint molding, wherein the mold before the wettability improvement treatment is applied to a curable composition uncoated portion of a mold having a pattern shape portion subjected to wettability improvement treatment on the surface. Resin molding having a curable composition coating step of coating a curable composition having a contact angle with respect to 50 ° or less and a curing step of curing the curable composition applied to the mold to obtain a resin molded product Product manufacturing method.   The method for producing a resin molded product according to claim 1, wherein the wettability improving treatment is one or more treatments selected from the group consisting of plasma discharge treatment, corona discharge treatment, ozone exposure treatment, and excimer treatment. The method for producing a resin molded product according to claim 2, wherein the plasma discharge treatment or the corona discharge treatment is a discharge treatment with a discharge amount of 50 W · min / m ² or more.   After the curable composition application step, the mold to which the curable composition obtained through the curable composition application step is applied is applied to the mold through the curable composition application step. The manufacturing method of the resin molded product of any one of Claims 1-3 which has a mold closing process which overlaps so that another curable composition and the said curable composition may contact.   The manufacturing method of the resin molded product of any one of Claims 1-4 in which the said curable composition contains an epoxy compound.   The manufacturing method of the resin molded product of any one of Claims 1-5 which has the defoaming process by pressure reduction after the said curable composition application | coating process.   The manufacturing method of the resin molded product of any one of Claims 1-6 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 manufacturing method of the resin molded product of any one of Claims 1-7 whose said resin molded product is a micro lens 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 1-8.

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