JP2018161862A - Manufacturing method of resin molded product and manufacturing method of optical component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a resin molded product which hardly causes occurrence of air bubbles when a curable composition is applied to a mold having a pattern shape in imprint molding.SOLUTION: A method for producing a resin molded product includes: a curable composition application step of applying a curable composition having a contact angle with respect to a mold having a pattern shape of 50° or less to a curable composition unapplied portion of the mold so that a particle diameter of a fine particle of the curable composition when being deposited to the mold is 0.5 mm or less; and a curing step of curing the curable composition applied to the mold to obtain a 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 corresponding to the fine shape of the resin molded product. However, the present inventor, when molding a resin molded product by imprint molding using a mold having such a fine pattern shape, is cured when a curable composition that forms the resin molded product is applied to the mold. It has been found that bubbles are easily generated (foaming) in the composition. The air bubbles are particularly likely to be generated near the bottom of a concave portion having a fine pattern provided in the mold (the portion that becomes the tip of the convex portion of the resin molded product after molding).

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

  As a result of intensive investigations to achieve the above object, the present inventor cured a mold having a pattern shape by finely applying a curable composition having a small contact angle to the mold having a pattern shape. It has been found that the generation of bubbles can be made difficult to occur when an adhesive composition is applied. 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, and a curable composition having a contact angle with respect to the mold of 50 ° or less on a curable composition uncoated portion of a mold having a pattern shape. A curable composition application step including a fine particle application step of applying the fine particle size of the curable composition when adhering to the mold to be 0.5 mm or less, and the mold applied to the mold Provided is a method for producing a resin molded product, which has a curing step for obtaining a resin molded product by curing a curable composition.

  In the fine particle application step, it is preferable to apply the curable composition so that the aspect ratio of the fine particles of the curable composition when adhering to the mold is 0.1 or more.

  The coating in the fine particle coating step is preferably spray coating.

  In the curable composition coating step, the curable composition is coated such that the particle size of the curable composition when adhering to the curable composition coated on the mold exceeds 0.1 mm after the fine particle coating step. Preferably, the method includes a step of applying a composition to the mold.

  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 mold having a pattern shape. In particular, even when a mold having a fine pattern shape is used, bubbles are unlikely to occur. For this reason, a resin molded product and an optical component 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 of the present invention is a method for producing a resin molded product by imprint molding, and a contact angle with respect to the mold is 50 ° or less at a curable composition uncoated portion of a mold having a pattern shape. A curable composition coating step including a fine particle coating step of coating the curable composition of the curable composition so that the particle size of the fine particles of the curable composition when adhering to the mold is 0.5 mm or less, and the mold A curing step of curing the curable composition applied to the substrate 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”.

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

(Curable composition application process)
The said curable composition application | coating process is a curable composition uncoated part (namely, part which should apply | coat the curable composition which forms a resin molded product, and is not apply | coated) of the mold which has a pattern shape The step of applying a curable composition having a contact angle of 50 ° or less to the mold so that the particle size of the curable composition when adhering to the mold is 0.5 mm or less (“particulate application”) Sometimes referred to as “stage”). In the present specification, the application so that the particle diameter of the fine particles of the curable composition when adhering to the mold is 0.5 mm or less may be referred to as “fine particle application”.

  That is, in the fine particle application step, when the curable composition is applied to the mold, the curable composition having a contact angle of 50 ° or less as the curable composition for forming a resin molded product is first applied to the mold. The product is applied to the portion to which the pattern shape has been applied so that the particle size of the fine particles of the curable composition at the time of adhesion is 0.5 mm or less. For example, when the mold release agent is applied to the mold, the mold with the mold release agent is applied. When the mold release agent is not applied, the mold surface is coated with the fine particles of the curable composition. To do.

  The said curable composition is a composition which hardens | cures and forms a resin molded product. The curable composition has a contact angle with respect to the mold of 50 ° or less. As a result, the wettability of the curable composition with respect to the mold increases, so that even when the pattern shape has a fine structure, it is cured along the pattern shape when attached to the mold during fine particle application. Property composition easily spreads 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 particle size of the fine particles of the curable composition at the time of adhering to the mold at the time of applying fine particles (more specifically, immediately before adhering) is 0.5 mm or less as described above, preferably 0.1 mm. Below, more preferably 0.05 mm or less. Although a minimum is not specifically limited, For example, it is 0.001 mm. By setting the particle size to 0.5 mm or less, the surface free energy of the fine particles of the curable composition can be reduced. In combination with the contact angle being 50 ° or less, the compatibility of the curable composition with the mold is improved, and the curable composition reaches the tip of the concave portion having a fine pattern shape formed in the mold. The generation of bubbles can be suppressed easily.

  The particle size of the fine particles of the curable composition can be adjusted by the nozzle diameter (discharge port diameter), the discharge speed, etc. of the apparatus (application apparatus) used for applying the curable composition. When the curable composition is intermittently applied in the form of particles, the particle size of the fine particles of the curable composition is smaller than the nozzle diameter of the coating apparatus. For example, when the curable composition is intermittently applied in the form of particles using a coating device having a nozzle diameter of 0.5 mm in cross section, the particle size of the fine particles of the curable composition is determined to be 0.5 mm or less. can do. In addition, as a method of measuring the particle size of the actual fine particles, the granular curable composition was shot at a high shutter speed until the fine particles of the curable composition discharged from the coating apparatus landed on the mold. A method for measuring the particle diameter from an image is mentioned.

  The aspect ratio of the fine particles of the curable composition when adhering to the mold at the time of applying fine particles (more specifically, immediately before adhering) is not particularly limited, but is preferably 0.1 or more, more preferably 0. .3 or more. When the aspect ratio is 0.1 or more, the fine particles of the curable composition become closer to a sphere, the surface free energy of the fine particles of the curable composition can be further reduced, and the fine shape 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 aspect ratio is “horizontal length (shorter length) / vertical length (longer length)”.

  The aspect ratio can be adjusted by a nozzle diameter (discharge port diameter), a discharge speed, and the like of a coating apparatus that performs fine particle coating. The aspect ratio can be measured from a photographed image of a granular curable composition until fine particles of the curable composition discharged from the coating apparatus land on the mold at a high shutter speed.

  Examples of the fine particle coating method include spray coating (spray spraying), air brush coating (air brush spraying), and ultrasonic coating (ultrasonic spraying). By applying by these application methods, the curable composition is applied so that the particle size of the fine particles when adhering to the mold is 0.5 mm or less (and the aspect ratio is 0.1 or more). Becomes easy.

  For the fine particle coating, a known or conventional coating apparatus can be used. The nozzle diameter (discharge port diameter) of the coating apparatus is preferably 0.5 mm or less, more preferably 0.1 mm or less, and still more preferably 0.05 mm or less. Although a minimum is not specifically limited, For example, it is 0.001 mm. Therefore, the fine particle coating is preferably performed by discharging the curable composition from a nozzle having a nozzle diameter of 0.5 mm or less.

  The application speed (discharge speed) at the time of applying the fine particles is preferably 55 ml / min or less, more preferably 30 ml / min or less, and still more preferably 10 ml / min or less. The lower limit is, for example, 0.1 ml / min from the viewpoint of productivity. When the coating speed is 55 ml / min or less, wetting of the curable composition with respect to the mold can be controlled, and generation of bubbles can be further suppressed.

  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 the 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.

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

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

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

  In the curable composition coating step, the fine particle coating is preferably performed until it can be visually confirmed that a coating film of the curable composition is formed on at least the entire pattern shape. The fine particle application may be performed until the entire amount of the curable composition for forming the resin molded product is applied, but from the viewpoint of productivity, the coating film of the curable composition is formed on the entire pattern shape. After performing the above-mentioned fine particle coating until it can be confirmed visually, the remaining total amount of the curable composition for forming a resin molded product is applied to the curable composition applied to the mold in the fine particle coating stage. It is preferable to apply so that the particle size of the curable composition when adhering exceeds 0.1 mm. That is, in the curable composition coating step, the particle size of the curable composition when adhering to the curable composition coated on the mold is greater than 0.1 mm after the fine particle coating step. It is preferable to include a step of applying a curable composition to the mold. In the present specification, coating so that the particle size of the curable composition exceeds 0.1 mm may be referred to as “normal coating” with respect to “fine particle coating”.

  The normal coating can be performed by a known or common coating method. Examples of the normal coating include spin coating, roll coating, spray coating, dispensing coating, dip coating, and inkjet coating.

  In the curable composition application step, the mold in which the curable composition is applied (filled) in a pattern shape is obtained by applying the fine particles and then applying the normal application as necessary.

(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, the mold closing process of the upper mold and the lower mold is performed using the mold coated with the curable composition and the other substrate as the upper mold and the lower mold, respectively, and sandwiching the curable compound. At this time, either may be an upper mold or a lower mold.

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

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

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

  The curable composition may or may not be applied to the other substrate. When the curable composition is applied to the other substrate, the curable composition is applied (filled) through the curable composition application step (defoaming step, if necessary) for applying fine particles. A substrate may be used. In particular, when a mold is used as the other substrate (that is, when a resin molded product having an uneven shape on both sides is produced), the mold as the other substrate includes the fine particle application step. It is preferable to use a mold coated (filled) with the curable composition through (if necessary, a defoaming step). When using the board | substrate with which the curable composition was apply | coated as said other board | substrate, the said mold closing process overlaps an upper mold | type and a lower mold | type so that curable compositions may contact.

(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 adhesion degree of an upper mold | type and a lower mold | type can be improved, and thickness variation can be prevented. 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 / cm ² . 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 production method of the present invention shown in FIG. 1, the curable composition having a contact angle with respect to the mold of 50 ° or less is attached to the mold on the mold-uncoated portion of the mold having a pattern shape. Curable composition application step S1 including a fine particle application step of applying the fine particles of the curable composition so that the particle diameter thereof is 0.5 mm or less, and a defoaming step of defoaming bubbles in the applied curable composition S2, a mold closing step S3 in which the mold coated (filled) with the curable composition is overlapped 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 a curing step S5 for curing the curable composition applied to the mold to obtain a resin molded product 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.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Production Example 1
As silicone resin, 50 parts by weight of trade name “X-32-3094-2” (manufactured by Shin-Etsu Chemical Co., Ltd.), 50 parts by weight of trade name “KE-1606” (manufactured by Shin-Etsu Chemical Co., Ltd.), curing agent As described above, 5 parts by weight of the product name “CX-32-3094-2” (manufactured by Shin-Etsu Chemical Co., Ltd.) and 5 parts by weight of the product name “CAT-RG” (manufactured by Shin-Etsu Chemical Co., Ltd.) are mixed and stirred. Thus, a resin composition was prepared. Next, a Teflon spacer having a length of 40 mm, a width of 20 mm, and a thickness of 1.0 mm was prepared, and released from the mold (trade name “OPTOOL HD1000”, manufactured by Daikin Co., Ltd. and left in a draft for 24 hours). The slide glass (trade name “S2111”, manufactured by Matsunami Glass Co., Ltd.) was subjected to scissoring. Then, after casting the resin composition obtained above in a gap, the resin composition is allowed to stand at room temperature for 2 hours and cured by heating in an oven at 150 ° C. for 30 minutes, and an array of Fresnel lenses as shown in FIG. A silicone mold (thickness: 1.0 mm) having a pattern shape for production was produced. (Interval: 0.2 mm, sharpness: R 0.005 mm, height interval: 0.2 mm)

Example 1
A curable composition (trade name “CELVENUS OUH106” (contact angle with respect to the following silicone mold: 28 °, manufactured by Daicel Corporation) was used as an application device with an air brush (trade name “air brush kit EA121DF” (application nozzle diameter: 0). 2 mm), manufactured by Esco Corporation), the distance from the nozzle to the silicone mold in the silicone mold obtained in Production Example 1 is 50 mm, the discharge rate is 5 ml / min, and the coating amount is 5 ± 0.00 mm. 1 g (visually confirmed that a coating film of the curable composition is formed on the entire pattern shape) was applied.The particle size of the curable composition when contacting the silicone mold was 0.2 mm. It was the following.
After the application, the number of bubbles in the curable composition applied on the pattern shape of the silicone mold was visually confirmed, and the number of bubbles was about 20.

Example 2
Curing was carried out in the same manner as in Example 1 except that an ultrasonic spray device (trade name “40K50ST” (coating nozzle diameter: 0.08 mm), manufactured by Sonear) was used as the coating device, and the discharge speed was 50 ml / min. The composition was applied. In addition, the particle size of the said curable composition at the time of contacting the said silicone mold was 0.08 mm or less.
After the application, the number of bubbles in the curable composition applied on the pattern shape of the silicone mold was visually confirmed, and the number of bubbles was about 20.

Example 3
The curable composition was applied in the same manner as in Example 1 except that an air spray nozzle (application nozzle diameter: 0.40 mm) was used as the application device and the discharge speed was 3 ml / min. In addition, the particle size of the said curable composition at the time of contacting the said silicone mold was 0.45 mm or less.
After the application, the number of bubbles in the curable composition applied onto the pattern shape of the silicone mold was visually confirmed, and the number of bubbles was 10 or less.

Comparative Example 1
The curable composition was applied in the same manner as in Example 1 except that a dropper with a coating nozzle diameter of 1 mm or more was used as the coating apparatus and the discharge speed was about 60 ml / min.
After the application, the number of bubbles in the curable composition applied on the pattern shape of the silicone mold was visually confirmed, and the number of bubbles was about 1000. In addition, the particle size of the said curable composition at the time of contacting the said silicone mold was 1 mm or more.

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 a curable composition having a contact angle with respect to the mold of 50 ° or less is attached to the mold on a curable composition uncoated portion of a mold having a pattern shape A curable composition application step including a fine particle application step of applying the fine particles of the curable composition so as to have a particle size of 0.5 mm or less, and curing the curable composition applied to the mold A method for producing a resin molded product, comprising a curing step for obtaining a resin molded product.   2. The resin molded product according to claim 1, wherein in the fine particle application step, the curable composition is applied so that an aspect ratio of the fine particles of the curable composition when adhering to the mold is 0.1 or more. Manufacturing method.   The method for producing a resin molded product according to claim 1, wherein the coating in the fine particle coating step is spray coating.   The curable composition is applied such that the particle size of the curable composition exceeds 0.1 mm when adhering to the curable composition applied to the mold after the fine particle application step. The manufacturing method of the resin molded product of any one of Claims 1-3 including the step which apply | coats a composition to the said mold.   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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