JP2018170327A - Manufacturing method of resin molded product and manufacturing method of optical component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a resin molded product in which misalignment is unlikely to occur before and after curing in imprint molding. SOLUTION: This is a method of manufacturing a resin molded product by imprint molding, in which a first substrate, which is a mold having a pattern-shaped portion, and a second substrate are superposed so as to sandwich a curable composition. The temperature of the laminate preparation step for preparing the laminated laminate and the temperature of the portion A where the horizontal surface end portion of the pattern-shaped portion and the portion A overlapping in the thickness direction of the laminate exceeds 0 ° C. and 30 ° C. or lower. Light is placed on a temperature control plate in which the temperature of the portion B overlapping the horizontal center of the pattern-shaped portion in the thickness direction of the laminate is 10 to 90% of the temperature of the portion A. It has a curing step of curing the curable composition by irradiation to obtain a resin molded product. [Selection diagram] Fig. 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

  Generally, when a curable composition is cured by imprint molding or the like, the resulting resin molded product contracts with respect to the curable composition before curing. As a result, there is a problem that the size of the resin molded product obtained is smaller than the mold of the mold, and the position of each part in the resin molded product is shifted before and after curing, from the design position reflected in the mold of the mold. There is a problem of shifting. In particular, when an assembly of multiple products is formed by a single molding by imprint molding, as the product is far from the center, the positional deviation before and after curing increases, and the position at the time of design (position before curing) ) Tends to be closer to the center.

  When an aggregate of a plurality of products is formed by a single molding by imprint molding, after curing, the product is cut into individual products by dicing and then picked up as individual products. Here, when the position of each product is greatly deviated from the position at the time of design, there is a problem that the cutting position is shifted at the time of cutting, and the product cannot be picked up well at the time of picking up.

  In recent years, the optical parts and the like are required to have higher accuracy. For example, in a product at a position about 30 mm from the center, a deviation of about 20 μm may occur before and after curing. In the case of molding an assembly of a plurality of products by being cured by ultraviolet irradiation, this degree of deviation has not been regarded as a problem so far, but in recent years there is a tendency to require more positional accuracy.

  Accordingly, an object of the present invention is to provide a method for producing a resin molded product in which positional displacement hardly occurs before and after curing in imprint molding, and a method for producing an optical component using the resin molded product.

  As a result of intensive studies to achieve the above object, the present inventor, in a method for producing a resin molded product by imprint molding, the temperature of the portion overlapping the horizontal end of the pattern shape portion exceeds 0 ° C. and is 30 ° C. or less. The mold is filled with the curable composition on the temperature control plate in which the temperature of the portion overlapping the center of the horizontal plane of the pattern shape portion is set to 10 to 90% of the temperature of the portion overlapping the end portion of the horizontal plane. It has been found that by irradiating the curable composition with light in a state where the resin is placed, it is possible to make it difficult to cause a positional shift before and after curing of the resin molded product to be obtained. 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 first substrate, which is a mold having a pattern shape portion, and the second substrate sandwich the curable composition. A laminate preparing step for preparing a stacked laminate, and a temperature of a portion A that overlaps the horizontal plane end of the pattern shape portion and the thickness direction of the laminate in the laminate is over 30 ° C. And in a state where the temperature of the portion B overlapping the center of the horizontal plane of the pattern shape portion and the thickness direction of the laminate is 10 to 90% of the temperature of the portion A. The manufacturing method of the resin molded product which has a hardening process which hardens the said curable composition by light irradiation and obtains a resin molded product is provided.

  It is preferable that the aspect ratio of the horizontal shape of the pattern shape portion of the mold is 0.1-1.

  In the curing step, the temperature control plate preferably has a gradation so that the temperature increases from the portion B to the portion A.

  The curable composition preferably contains an epoxy compound.

  The mold is preferably made of silicone resin.

  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 to cause a positional shift before and after curing of the obtained resin molded product. For example, at a position about 30 mm from the center, the deviation before and after curing can be made less than 20 μm. For this reason, the manufacturing method of the resin molded product of this invention is especially suitable for manufacture of the aggregate | assembly (especially the aggregate | assembly of a some optical component (optical element)) of several products in which especially high positional accuracy is calculated | required.

It is process drawing which shows one Embodiment of the manufacturing method of the resin molded product of this invention. It is the schematic (perspective view) which shows an example before superimposing the 1st board | substrate and the 2nd board | substrate. It is the schematic (sectional drawing) which shows an example of the state by which the laminated body obtained at the laminated body preparation process was mounted on the temperature control board.

  In FIG. 1, one Embodiment of the manufacturing method of the resin molded product of this invention is shown. The method for producing a resin molded product of the present invention shown in FIG. 1 is a method for producing a resin molded product by imprint molding, and includes a first substrate that is a mold having a pattern shape portion, and a second substrate. A laminate preparation step S1 for preparing a laminate laminated so as to sandwich the curable composition, and a portion A in which the laminate is overlapped in the thickness direction of the laminate and the horizontal end portion of the pattern shape portion The temperature of the part B that overlaps the horizontal plane center of the pattern shape part and the thickness direction of the laminate is 10% to 90% of the temperature of the part A. In a state of being placed on the temperature control plate, there is a curing step S2 in which the curable composition is cured by light irradiation 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”. Further, in the temperature control plate, a portion overlapping the horizontal plane end of the pattern shape portion and the thickness direction of the laminate is “part A”, and a portion overlapping the horizontal plane center of the pattern shape portion and the thickness direction of the laminate. May be referred to as “part B”.

  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. Note that a mold having a pattern shape portion (hereinafter sometimes simply referred to as “mold”) is used as at least one of the substrates (first substrate).

(Laminate preparation process)
In the laminate preparation step S1, a laminate is prepared in which a first substrate, which is a mold having a pattern shape portion, and a second substrate are stacked so as to sandwich the curable composition.

  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. When the said curable composition contains an epoxy compound, the position shift before and behind hardening is much less likely to occur. 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 which is the first substrate is provided with a reverse uneven pattern shape (inverted shape of the desired resin molded product) corresponding to the shape for giving the resin molded product a desired shape. Although the shape of the horizontal surface of the pattern shape portion of the mold is not particularly limited, the aspect ratio is preferably 0.1 to 1, more preferably 0.5 to 1, and the closer to 1, the more preferable. The aspect ratio is the ratio of the length in the vertical direction to the length in the horizontal direction when the longest direction in the horizontal plane is the horizontal direction. When the aspect ratio is within the above range, the degree of curing tends to be uniform over the entire resin molded product, the shrinkage of the entire resin molded product is further suppressed, and positional deviation is less likely to occur before and after curing. The shape of the horizontal plane is, for example, a shape seen from the upper surface when the first substrate is placed in a horizontal position so that the pattern shape portion is the upper surface.

  The mold is preferably made of resin. The resin forming the mold is selected in consideration of compatibility with the curable composition (wetting properties, etc.), shape accuracy of the resin molded product after curing, releasability (release property), etc. Silicone resin (dimethylpolysiloxane, etc.), fluorine resin, polyolefin resin (polyethylene, polypropylene, polycyclic olefin, etc.), polyethersulfone resin, polycarbonate resin, polyester resin (polyarylate, polyethylene terephthalate, polyethylene naphthalate) Phthalate, etc.), polyamide resins, polymethyl methacrylate, and the like. 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 shape accuracy. 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.

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. For molding the resin composition, a mold having a desired concavo-convex shape can be used, 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.

  The second substrate may be a mold having a pattern shape portion or a flat substrate. For example, a flat substrate can be used as the second substrate when manufacturing a resin molded product having an uneven shape on only one surface, and a second substrate when manufacturing a resin molded product having an uneven shape on both sides. A mold can be used.

  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.

  When the second substrate is a mold, the two molds that are the first substrate and the second substrate 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.

  A curable composition is applied to at least one of the first substrate and the second substrate before being overlaid. In addition, it is preferable to use what applied the curable composition to this pattern shape part of the mold which has a pattern shape part as a 1st board | substrate. In this case, the curable composition may or may not be applied to the second substrate. That is, the second substrate may be a second substrate coated with a curable composition.

  Application | coating of the curable composition to the said board | substrate can be performed by a well-known thru | or usual coating 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.

  FIG. 2 shows a schematic diagram (perspective view) of an example of a state before the first substrate and the second substrate are overlaid. The 1st board | substrate 1a is a mold which has a perfect circular pattern shape part, and the curable composition 2 is apply | coated to the pattern shape part. In FIG. 2, F represents the horizontal surface of the pattern shape portion, and the circumference of F corresponds to the circumscribed circle of the shape of the horizontal surface of the pattern shape portion. And the 2nd board | substrate 1b is piled up on the surface by which the curable composition 2 of the 1st board | substrate 1a is apply | coated. In FIG. 2, the second substrate 1b is a mold having a pattern shape portion, and the surface (the lower surface in FIG. 2) on which the pattern shape portion of the second substrate 1b is formed is the first substrate 1a. The first substrate 1a and the second substrate 1b are overlapped so as to sandwich the curable composition 2 so as to face (oppose) the surface to which the curable composition 2 is applied.

  In the curing step, since the curable composition is irradiated with light, at least one of the first substrate and the second substrate is transparent, and both are preferably transparent from the viewpoint of curability.

  Substrate to which the curable composition is applied (when the curable composition is applied to both the first substrate and the second substrate, the first substrate and the second substrate to which the curable composition is applied) Each of the substrates) is preferably defoamed when there are bubbles in the applied curable composition.

  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 substrate on which the curable composition is applied in an environment with a pressure of 0.1 to 20 kPa for 1 to 10 minutes.

  Substrate to which the curable composition is applied (when the curable composition is applied to both the first substrate and the second substrate, the first substrate and the second substrate to which the curable composition is applied) If the bubbles remain even after the above defoaming, each of the substrates may remove the bubbles by directly sucking the liquid and removing the bubbles, or by vibration of the liquid.

  The first substrate and the second substrate are used as an upper mold and a lower mold, respectively, after the defoaming is applied to the first substrate and the second substrate as necessary, and the curable composition is sandwiched between the first substrate and the second substrate. The upper mold and the lower mold are overlapped to close the mold. At this time, either may be an upper mold or a lower mold.

  The laminate obtained by closing the mold may then be pressed from the upper part of the upper mold. 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.

  In this way, it is possible to obtain a laminate in which the first substrate coated with the curable composition and the second substrate are overlapped so as to sandwich the curable composition. In the obtained laminate, a mold is used as at least one of the first substrate and the second substrate, so that the curable composition is filled in the pattern shape portion of the mold.

(Curing process)
In the curing step S2, the curable composition is applied by light irradiation in a state where the laminate obtained in the laminate preparation step S1 is placed on a temperature control plate set to a specific temperature state. Cured to obtain a resin molded product.

  The said temperature control board is a board | substrate for controlling the temperature of the said laminated body in the case of hardening of the said curable composition. In the temperature control plate, when the curable composition is cured, the temperature of the portion (part A) that overlaps the horizontal end of the pattern shape portion of the first substrate and the thickness direction of the laminate exceeds 0 ° C. And the temperature of the part (part B) that overlaps the horizontal plane center of the pattern shape part and the thickness direction of the laminate is 10 to 90% of the temperature of the part A. ing.

  When the curable composition is cured by light irradiation, the amount of accumulated light near the center of the curable composition surface is larger than that of other parts (especially the end of the curable composition surface) and the temperature rises. It tends to be easy. For this reason, hardening near the center of the curable composition surface is more likely to proceed than other parts (particularly, the end of the surface of the curable composition), and shrinkage near the center is likely to proceed. On the other hand, according to the production method of the present invention, when the curable composition is cured, light irradiation is performed in a state of being placed on the temperature control plate set to the specific temperature state. The degree of cure of the resin molded product is sufficient, and the degree of cure tends to be uniform at the center of the horizontal plane and the end of the horizontal plane of the resin molded product. As a result, shrinkage in the vicinity of the center is suppressed, and the resin molded product In each part, misalignment hardly occurs before and after curing.

  The horizontal surface of the pattern shape corresponds to the surface of the curable composition in a state where the pattern shape portion of the first substrate is filled with the curable composition so as not to protrude from the pattern shape portion. The center of the horizontal plane of the pattern shape portion is the center of the circumscribed circle of the shape of the horizontal plane of the pattern shape portion, that is, when the mold is placed in a horizontal position so that the pattern shape portion is the upper surface. It is the midpoint of the diameter of the circumscribed circle of the pattern shape portion. For example, when the pattern shape portion viewed from the top is a circle, the horizontal plane center is the center of the circle. The horizontal plane end portion is a portion of the horizontal plane that is farthest from the horizontal plane center, and is a portion on the circumference of the circumscribed circle. When both the first substrate and the second substrate have the pattern shape portion, the horizontal surface may be that of the pattern shape portion of either substrate, but is preferably the larger horizontal surface. .

  Moreover, the temperature control board which the said horizontal surface edge part and the part (part A) which overlaps in the thickness direction of the said laminated body overlaps with the said horizontal surface edge part in the perpendicular direction in the state which mounted the said laminated body on the temperature control board. It is the surface part that exists inside. In addition, a portion (part B) that overlaps the horizontal plane center and the thickness direction of the laminate on the temperature control plate surface that overlaps the horizontal plane center in the vertical direction in a state where the laminate is placed on the temperature control plate. It is a part that exists.

  The laminate may be placed on the first substrate side or on the second substrate side on the temperature control plate. Further, the laminate may be placed on the temperature control plate via another layer within a range not impairing the effects of the present invention, or directly placed without any other layer. It may be.

  In FIG. 3, the schematic (sectional drawing) of an example of the state which mounted the laminated body obtained at the laminated body preparation process on the temperature control board is shown. In FIG. 3, the laminate 1 that is superimposed so as to sandwich the curable composition 2 between the first substrate 1 a and the second substrate 1 b is placed on the temperature control plate 3 on the first substrate 1 a side. It is placed directly without intervening other layers. F is a horizontal plane of the pattern shape portion in the first substrate. 2b is the horizontal plane center of the pattern shape portion, and 2a is a portion on the circumscribed circle of the horizontal plane end of the pattern shape portion, that is, the horizontal plane farthest from the horizontal plane center 2b. 3b is a portion B in the temperature control plate 3 (surface of the temperature control plate 3) that overlaps the horizontal plane center 2b of the pattern shape portion and the thickness direction of the laminate (vertical direction in FIG. 3). 3a is a portion A in the temperature control plate 3 (surface of the temperature control plate 3) overlapping the horizontal end 2a of the pattern shape portion and the thickness direction of the laminate (vertical direction in FIG. 3).

  The temperature of the part A at the time of light irradiation exceeds 0 degreeC and is 30 degrees C or less as mentioned above, Preferably it is 5-20 degreeC, More preferably, it is 5-15 degreeC.

  The temperature of the part B at the time of light irradiation is 10 to 90% of the temperature of the part A as described above, preferably 20 to 80%, more preferably 30 to 70%. When the ratio of the temperature of the part B at the time of the light irradiation is within the above range, a sufficient degree of curing can be obtained, and the degree of curing tends to be uniform throughout the resin molded product, and the entire resin molded product shrinks. It is further suppressed and misalignment is less likely to occur before and after curing.

  The temperature control plate preferably has a gradation so that the temperature increases from a portion B overlapping the horizontal plane center of the laminate to a portion A overlapping the horizontal plane end. In other words, it is preferable that the temperature is gradually increased from the portion B to the portion A in a concentric shape centering on the portion B so as to gradually increase in gradation. By irradiating light in such a state, the degree of curing tends to be uniform throughout the entire resin molded product, the shrinkage of the entire resin molded product is further suppressed, and positional displacement is less likely to occur before and after curing. The temperature of the part A is set to be higher than the temperature of the part B.

  The distance from the part B to the part A (radius of the circumscribed circle) is, for example, about 5 to 200 mm, preferably 7 to 100 mm, more preferably 10 to 70 mm, and still more preferably 20 to 40 mm. When the distance is within the above range, shrinkage before and after curing is less likely to occur in the entire resin molded product, and positional deviation before and after curing is less likely to occur.

  In the curing step, 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 said hardening is performed by light irradiation (especially irradiation of an active energy ray). 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 / cm ² . After active energy ray irradiation, curing may be promoted by heating (post-cure) as necessary. The temperature of the said post cure is 80-200 degreeC, for example, Preferably it is 100-180 degreeC.

  In the manufacturing method of this invention, you may have other processes other than a laminate preparation process and a hardening process.

  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. Moreover, since the film | membrane of the hardened | cured material of a curable composition may remain in the used mold, it is preferable to perform the process (residual film process) which removes this film | membrane. When taking out the resin molded product from the mold, for example, it can be taken out by attaching and peeling an adhesive tape on the surface of the resin molded product fitted in the upper mold or the lower mold after opening.

  The resin molded product obtained by the production method of the present invention preferably has a deviation of 30 mm or less before and after curing at a distance of 30 mm from the center of the horizontal plane, more preferably 25 μm or less, and even more preferably less than 20 μm. .

  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.

  The method for producing a resin molded product of the present invention can make it difficult to cause a positional shift before and after curing of the obtained resin molded product. For this reason, the resin molded product obtained by the production method of the present invention is particularly preferably an aggregate of a plurality of products (particularly an aggregate of a plurality of optical components) that requires particularly high positional accuracy.

  For example, when manufacturing a lens as the optical component, a microlens array that is an assembly of the plurality of optical components [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 as That is, the mold preferably has a pattern shape corresponding to the shape of the microlens array.

  When the obtained resin molded product is an assembly (particularly, a microlens array) of the plurality of optical parts, the size of each individual optical part (particularly, microlens) is, for example, about 0.01 to 100 mm in diameter. The thickness is preferably about 0.1 to 2.0 mm, for example. Moreover, it is preferable that the pitch width in the aggregate | assembly (especially micro lens array) of a some optical component is about 10-1000 micrometers, for example.

S1 Laminate Preparation Step S2 Curing Step 1 Laminate 1a First Substrate 1b Second Substrate 2 Curable Composition 2a Horizontal Plane End of Pattern Shaped Part 2b Horizontal Plane Center of Pattern Shaped Part 3 Temperature Control Plate 3a Part A (Pattern The part in the temperature control plate that overlaps the horizontal end of the shape part and the thickness direction of the laminate)
3b Part B (the part in the temperature control plate that overlaps the horizontal center of the pattern-shaped part and the thickness direction of the laminate)
F Horizontal plane of the pattern shape portion of the first substrate

Claims (8)

  A method for producing a resin molded product by imprint molding, in which a first substrate, which is a mold having a pattern shape portion, and a second substrate are laminated so as to sandwich a curable composition The temperature of the laminate preparation step for preparing the laminate, and the portion A that overlaps the horizontal direction end of the pattern shape portion and the thickness direction of the laminate is greater than 0 ° C. and 30 ° C. or less, and The curing is performed by light irradiation in a state where the temperature of the portion B overlapping the center of the horizontal plane of the pattern shape portion and the thickness direction of the laminate is 10 to 90% of the temperature of the portion A. The manufacturing method of a resin molded product which has a hardening process which hardens a property composition and obtains a resin molded product.   The manufacturing method of the resin molded product of Claim 1 whose aspect ratio of the shape of the horizontal surface of the pattern shape part which the said mold has is 0.1-1.   3. The method for manufacturing a resin molded product according to claim 1, wherein, in the curing step, the temperature control plate has a gradation such that the temperature increases from the portion B to the portion A. 4.   The manufacturing method of the resin molding of any one of Claims 1-3 in which the said curable composition contains an epoxy compound.   The method for producing a resin molded product according to any one of claims 1 to 4, wherein the mold is made of a silicone resin.   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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