JP2020097126A - Light molding kit, and manufacturing method of molding member - Google Patents

Abstract

To provide a light molding kit capable of improving repetitive utilization of a molding die made of a resin, and to provide a molding member using the light molding kit.SOLUTION: According to a light molding kit including a molding die made of a resin and a light molding photocurable type composition, the light molding kit has 5.0 mN/m or more as an absolute value of a difference between surface free energy of the molding die made of a resin and surface free energy of a cured material made from the light molding photocurable type composition. A manufacturing method of a molding member using the light molding kit comprises the steps of: filling the light molding photocurable type composition in a recess of the molding die made of a resin, in which the recess is formed; arranging the molding die in such a manner that the composition having been filled in and a substrate are closely attached to each other; curing the composition by irradiating UV rays and/or visible rays from a molding die side; and releasing the cured material obtained in the step of curing the composition from the molding die.SELECTED DRAWING: None

Description

The present invention relates to an optical molding kit and a method for manufacturing a molding member.

As a method for producing a member having an uneven shape on its surface, a method of forming an uneven shape made of a cured product of an active energy ray-curable composition on a transparent substrate by “die transfer” is widely known (for example, , Patent Documents 1 and 2). Here, the mold transfer means that the composition is applied to a mold (a nickel stamper or the like) on which an inverted structure corresponding to the concavo-convex shape of the target member is formed, and the composition is attached to a transparent substrate, or It means that the composition is applied to a transparent substrate, the composition is attached to the same die, the active substrate is irradiated with an active energy ray from the transparent substrate to cure the composition, and then the die is released.

On the other hand, as a method for manufacturing a member having a concavo-convex shape on its surface, transfer using a less expensive resin molding die (also referred to as resin mold) is being studied, rather than transfer using an expensive mold.

Patent Document 3 discloses a specific example in which a PET film having an uneven shape formed of an ultraviolet curable resin is used as a resin molding die.

JP, 2013-216748, A International Publication No. 2013/151119 JP, 2011-228674, A

However, in the method described in Patent Document 3, when the difference in surface free energy between the cured product of the active energy ray-curable composition and the resin molding die is not appropriate, the cured product adheres to the resin molding die. Can be a problem. According to the study by the present inventors, it has been found that the adhesion causes the cured product to accumulate as the resin molding die is repeatedly used, and as a result, the releasability of the cured product gradually deteriorates. In this case, not only the productivity is inferior because the resin molding die needs to be replaced with a new one at a constant frequency, but there is also a great cost problem.
The present invention has been made in view of the above circumstances, and an object thereof is to provide an optical molding kit capable of improving the reusability of a resin molding die. Another object of the present invention is to provide a method for manufacturing a molding member using the above-mentioned photomolding kit.

As a result of intensive studies to solve the above problems, the present inventors have determined that the absolute value of the difference between the surface free energy of the resin molding die and the surface free energy of the cured product of the photocurable composition is a specific value or more. It was found that the reusability of the resin molding die can be improved by the above, and the present invention was completed.
This is particularly effective when ultraviolet rays and/or visible rays are irradiated from the resin molding die side.

The present invention is as follows.
[1] A photomolding kit comprising a resin molding mold and a photocurable photocurable composition, wherein the surface free energy of the resin molding mold and a cured product of the photocurable photocurable composition. A kit for optical molding, wherein the absolute value of the difference in surface free energy is 5.0 mN/m or more.
[2] The photomolding kit according to [1], wherein the resin molding die has a surface free energy of 30 to 60 mN/m.
[3] The material of the resin molding die is a material selected from the group consisting of polyacetal resin, fluorine resin, polyolefin resin, polymethylmethacrylate resin, polycarbonate resin and polyamide resin. [1] ] Or the photomolding kit according to [2].
[4] The photoforming kit according to any one of [1] to [3], wherein the resin-made molding die having a thickness of 1 mm has a transmittance of 405 nm of 50% or more.
[5] The photomolding kit according to any one of [1] to [4], wherein the cured product of the photocurable composition for photomolding has a surface free energy of 35 to 65 mN/m.
[6] The photomolding kit according to any one of [1] to [5], wherein the photocurable composition for photomolding contains an oligomer having two or more (meth)acryloyl groups.
[7] The photoforming kit according to [6], wherein the oligomer contains at least one selected from the group consisting of polyester (meth)acrylate, epoxy (meth)acrylate, and urethane (meth)acrylate.
[8] Either of [6] or [7], wherein the content ratio of the oligomer is 40% by mass to 95% by mass with respect to 100% by mass of the curable component in the photocurable composition for photomolding. The optical molding kit according to item 1.
[9] The optical molding kit according to any one of [1] to [8], which is applied to a display-related member.
[10] The photoforming kit according to any one of [1] to [8], which is applied to a building material-related member.
[11] The photoforming kit according to any one of [1] to [8], which is applied to automobile-related members.
[12] A method for producing a molding member using the photomolding kit according to any one of [1] to [11],
A step of filling a photo-curable composition for photo-molding into the concave part of the resin molding die in which the concave part is formed,
Arranging the molding die such that the filled composition and the substrate are in close contact,
Curing the composition by irradiating ultraviolet rays and/or visible rays from the molding die side;
And a step of releasing the cured product obtained in the step of curing the composition from the molding die,
Manufacturing method of molded member.

According to the photo-molding kit of the present invention, the reusability of the resin molding die can be improved.

Hereinafter, various embodiments of the technology disclosed in the present specification will be described in detail. In the present specification, acrylate and/or methacrylate are represented by (meth)acrylate, acryloyl group and/or methacryloyl group are represented by (meth)acryloyl group, and acrylic acid and/or methacrylic acid are represented by (meth)acrylic acid. ..

The present invention is a photomolding kit including a resin mold and a photocurable photocurable composition, wherein the surface free energy of the resin mold and curing of the photocurable photocurable composition. The present invention relates to a photo-molding kit having an absolute value of a difference in surface free energy of 5.0 mN/m or more and a method for manufacturing a molding member.

In the present invention, the surface free energy of the resin molding die, and the surface free energy of the cured product of the photocurable composition for photomolding are the contact angles of water and diiodomethane measured using a known contact angle measuring device. By doing so, it can be obtained by the Wu theoretical formula.

Here, in the theoretical formula of Wu, the dispersion component of the surface free energy of the solid is γ _Sd , the polar component of the surface free energy of the solid is γ _Sp , the dispersion component of the surface free energy of the liquid is γ _Ld , and the surface free energy of the liquid is _Let γ _{Lp be} the polar component of energy and γ _L (=γ _Ld +γ _Lp) be the surface free energy of the liquid.
(Γ _Sd γ _Ld /(γ _Sd +γ _Ld ))+(γ _Sp γ _Lp /(γ _Sp +γ _Lp )=γ _L (1+cos θ)/4 (1)
The respective components γ _Sd and γ _Sp of the surface free energy of the solid can be obtained by measuring the contact angles of two kinds of liquids having different surface free energies.

Specifically, first, the contact angles θ of water and diiodomethane of the resin molding die are measured.
Next, the θ, the dispersion component γ _{Ld of} each of water and diiodomethane, the polar component γ _Lp , and the surface free energy γ _L (=γ _Ld +γ _Lp ) obtained above are substituted into the equation (1), and the simultaneous equations are substituted. From this, the dispersion component γ _Sd and the polar component γ _Sp of the surface free energy of the resin mold are obtained.
-Water γ _Ld : 22.6 mN/m, γ _Lp : 50.20 mN/m, γ _L : 72.8 mN/m
-Diiodomethane γ _Ld : 49.0 mN/m, γ _Lp : 1.8 mN/m, γ _L : 50.8 mN/m
The sum of γ _Sd and γ _Sp (γ _Sd +γ _Sd ) is the surface free energy γ _S of the resin molding die.
The surface free energy of the cured product of the photocurable composition for photoforming can also be determined by the same method.

Hereinafter, a resin molding die, a photocurable photocurable composition and a method for producing the same, and a molding member and a method for producing the same will be described in detail.

1. Resin-Molding Mold The surface free energy of the resin-molding mold according to the present invention is preferably 30 to 60 mN/m, and preferably 30 to 50 mN/m, from the viewpoint of repeatability of the molding mold. Is more preferable, and 30-40 mN/m is even more preferable.
As the resin-made molding die, a cured product having various sizes and shapes can be easily prepared by simply adjusting the recess of the mold frame having the recess to a desired size.

Examples of the material of the resin molding die according to the present invention include polyacetal resin, fluorine resin, polyolefin resin, polymethylmethacrylate resin, polycarbonate resin and polyamide resin.

The polyacetal resin is a resin having an oxymethylene unit as a main repeating unit, and specific examples thereof include a homopolymer obtained by a polymerization reaction of formaldehyde or trioxane as a main raw material, other than oxymethylene unit and oxymethylene unit. Examples thereof include copolymers composed of structural units.
Specific examples of the fluorine-based resin include polytetrafluoroethylene, fluorinated ethylene-propylene copolymer resin, perfluoroalkoxy resin, and fluorinated epoxy resin.
Specific examples of the polyolefin resin include cycloolefin polymer, polypropylene, polyethylene and the like.
The polymethylmethacrylate-based resin means a homopolymer of methylmethacrylate or a copolymer containing 50% by mass or more of a methylmethacrylate component, and a component which is copolymerizable with the methylmethacrylate component is a (meth)acrylic acid ester. And maleimides, (meth)acrylic acid, styrenes and the like.
Examples of the polycarbonate resin include aromatic polycarbonate resins and aliphatic polycarbonate resins, and specific examples thereof include bisphenol A-based polycarbonate which is a general-purpose polycarbonate.
Examples of the polyamide resin include an aliphatic polyamide resin and an aromatic polyamide resin, and specific examples thereof include 6 nylon, 66 nylon, 610 nylon, copolyparaphenylene/3.4'oxydiphenylene/ Examples thereof include terephthalamide, polyparaphenylene terephthalamide, polymetaphenylene isophthalamide and the like.
Among these, polyacetal-based resins, fluorine-based resins and polyolefin-based resins are particularly preferable in that the effect of the present invention is particularly large.

As the resin-made molding die, a die whose surface is untreated can be used, and a die whose surface is release-treated may be used. Specific examples of the release treatment include surface treatments such as silicone treatment, long-chain alkyl treatment and fluorine treatment.
Examples of the form of the resin molding die include a film form, a sheet form and a plate form.

2. Photocurable Photocurable Composition for Photoforming In the photocurable composition for photoforming according to the present invention, the absolute value of the difference between the surface free energy of the resin molding die and the surface free energy of the cured product of the composition is 5. The composition is 0 mN/m or more.
The surface free energy of the cured product of the composition is preferably 35 to 65 mN/m, more preferably 35 to 60 mN/m, and still more preferably 35 to 55 mN/m from the viewpoint of repeatability of the molding die. More preferably m.

As the viscosity of the photocurable composition for photoforming according to the present invention, the applicability that can be used in the manufacturing process of the molding member, that is, it may be appropriately set in order to obtain a coated surface having excellent smoothness. Based on this, those skilled in the art can easily set the value.

The photocurable composition for photomolding according to the present invention preferably contains an ethylenically unsaturated group-containing compound, more preferably contains a photopolymerization initiator, and various other components are mixed depending on the purpose. be able to.

Examples of the ethylenically unsaturated group include a (meth)acryloyl group, a (meth)acrylamide group, a vinyl group and a (meth)allyl group, and a (meth)acryloyl group is preferable from the viewpoint of photocurability.

As the ethylenically unsaturated group-containing compound, a compound having two or more (meth)acryloyl groups (hereinafter, referred to as "polyfunctional (meth)acrylate"), having one (meth)acryloyl group in the molecule A compound (henceforth "a monofunctional (meth)acrylate") etc. are mentioned.

As the polyfunctional (meth)acrylate, an oligomer having two or more (meth)acryloyl groups, and a compound having two or more (meth)acryloyl groups other than the oligomer (hereinafter, referred to as “other polyfunctional (meth)acrylate”). "Acrylate".) and the like.
The polyfunctional (meth)acrylate preferably contains an oligomer having two or more (meth)acryloyl groups from the viewpoint of improving the toughness of the cured product, and the oligomer includes polyester (meth)acrylate and epoxy. It is more preferable to contain at least one selected from the group consisting of (meth)acrylate and urethane (meth)acrylate.

Hereinafter, polyester (meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate, other polyfunctional (meth)acrylate, monofunctional (meth)acrylate, photopolymerization initiator and other components will be described below.

2-1. Polyester (meth)acrylate Examples of the polyester (meth)acrylate include dehydration condensation products of polyester polyol and (meth)acrylic acid.

Here, examples of the polyester polyol include a reaction product of the polyol and a carboxylic acid or an anhydride thereof.
Specific examples of the polyol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, tetramethylene glycol, hexamethylene. Low molecular weight polyols such as glycol, neopentyl glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, trimethylolpropane, glycerin, pentaerythritol and dipentaerythritol, and alkylenes thereof. Examples thereof include oxide adducts.
Specific examples of the carboxylic acid or its anhydride include dibasic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, adipic acid, succinic acid, fumaric acid, maleic acid, hexahydrophthalic acid, tetrahydrophthalic acid and trimellitic acid. Or the anhydride etc. are mentioned.
Examples of polyester poly(meth)acrylates other than these include compounds such as those described on pages 74 to 76 of the document "UV/EB curing material".
In the above, as the alkylene oxide of the alkylene oxide adduct, ethylene oxide, propylene oxide and the like are preferable.
Here, the curable component is a component that is cured by irradiation with light and means an ethylenically unsaturated group-containing compound.
The polyester (meth)acrylate may be a dendrimer type (meth)acrylate.

Commercially available products of polyester (meth)acrylate include Aronix (registered trademark) M-6100, M-6200, M-6250, M-6500, M-7100, M-7300K, M-8030, M-8060, M-. 8100, M-8530, M-8560, 9050 (above, Toagosei Co., Ltd. product) etc. are mentioned.

The content ratio of the polyester (meth)acrylate is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and 40 parts by mass in view of improving the toughness of the cured product when the curable component is 100 parts by mass. The above is particularly preferable, 100 parts by mass or less is preferable, 97 parts by mass or less is more preferable, and 95 parts by mass or less is particularly preferable.

2-2. Epoxy (meth)acrylate The epoxy (meth)acrylate in the present invention is a compound obtained by addition-reacting (meth)acrylic acid with an epoxy resin, and is described in the above-mentioned document "UV/EB curing material" [CMC, Inc., 1992]. Annual publication], pages 74 to 75, and the like.

Examples of the epoxy resin include aromatic epoxy resins and aliphatic epoxy resins.
Specific examples of the aromatic epoxy resin include resorcinol diglycidyl ether; di- or polyglycidyl ether of bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene or its alkylene oxide adduct; phenol novolac type epoxy resin and cresol novolac type epoxy resin. Examples thereof include novolak type epoxy resins such as resins; glycidyl phthalimide; o-phthalic acid diglycidyl ester.

Specific examples of the aliphatic epoxy resin include diglycidyl ethers of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol; diglycidyl ethers of polyethylene glycol and polypropylene glycol. Diglycidyl ether of polyalkylene glycol; neopentyl glycol, dibromoneopentyl glycol and its alkylene oxide adduct diglycidyl ether; trimethylolethane, trimethylolpropane, glycerin and its alkylene oxide adduct di or triglycidyl ether, and Polyglycidyl ethers of polyhydric alcohols such as pentaerythritol and its alkylene oxide adducts such as di-, tri- or tetraglycidyl ethers; Di- or polyglycidyl ethers of hydrogenated bisphenol A and its alkylene oxide adducts; tetrahydrophthalic acid diglycidyl ether And hydroquinone diglycidyl ether and the like.

In addition to these aromatic epoxy resins and aliphatic epoxy resins, epoxy compounds having a triazine nucleus in the skeleton, such as TEPIC [Nissan Kagaku Co., Ltd.] and Denacol EX-310 [Nagase Kasei Co., Ltd.] can be mentioned.

Commercially available epoxy (meth)acrylates include lipoxy SP-1507, SP-1509, SP-4010, VR-60, VR-90 (above, Showa Denko KK), denacol acrylate DA111, DA212, DA721. (Above, manufactured by Nagase Chemtex Co., Ltd.), epoxy ester 40EM, 70PA, 80MFA, 200PA, 3000A (all manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

The content ratio of the epoxy (meth)acrylate when the curable component is 100 parts by mass,
From the viewpoint that the toughness of the cured product can be improved, it is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, particularly preferably 40 parts by mass or more, and preferably 100 parts by mass or less, more preferably 97 parts by mass or less. , 95 parts by mass or less is particularly preferable.

2-3. Urethane (meth)acrylate Urethane (meth)acrylate is a reaction product of a polyhydric alcohol, an organic polyvalent isocyanate and a hydroxyl group-containing (meth)acrylate compound, and a reaction product of an organic polyvalent isocyanate and a hydroxyl group-containing (meth)acrylate (hereinafter , "Urethane adduct").

Specific examples of the polyhydric alcohol include polypropylene glycol, polyether polyols such as polytetramethylene glycol, polyester polyols obtained by reacting the polyhydric alcohol with the polybasic acid, the polyhydric alcohol and the polybasic acid. Examples thereof include a caprolactone polyol obtained by the reaction of ε-caprolactone, and a polycarbonate polyol (for example, a polycarbonate polyol obtained by the reaction of 1,6-hexanediol and diphenyl carbonate).

Specific examples of the organic polyvalent isocyanate include diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate and dicyclopentanyl diisocyanate;
And organic polyisocyanates having three or more isocyanate groups such as hexamethylene diisocyanate trimer and isophorone diisocyanate trimer.

Specific examples of the hydroxyl group-containing (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, and hydroxyhexyl (meth). Hydroxyl group-containing mono(meth)acrylates such as acrylates and hydroxyoctyl(meth)acrylates, trimethylolpropane mono(meth)acrylates and pentaerythritol mono(meth)acrylates;
And hydroxyl groups such as trimethylolpropane di(meth)acrylate, pentaerythritol di- or tri(meth)acrylate, di- or tri(meth)acrylate of ditrimethylolpropane and di-, tri-, tetra- or penta(meth)acrylate of dipentaerythritol Examples include contained polyfunctional (meth)acrylates.

As the urethane (meth)acrylate, one obtained by a conventional method using the above compound can be used.

As a method for producing a reaction product of a polyhydric alcohol, an organic polyvalent isocyanate and a hydroxyl group-containing (meth)acrylate compound, specifically, in the presence of an addition catalyst such as dibutyltin dilaurate, the organic isocyanate to be used and the polyol component are heated and stirred. It is obtained by carrying out an addition reaction, further adding a hydroxyalkyl (meth)acrylate, stirring with heating and carrying out an addition reaction.

The urethane adduct can be produced by heating and stirring the organic isocyanate used and the hydroxyalkyl (meth)acrylate in the presence of an addition catalyst such as dibutyltin dilaurate to cause an addition reaction.

Examples of urethane poly(meth)acrylates other than these include compounds such as those described on pages 70 to 74 of the above-mentioned document "UV/EB curing material".

Commercially available urethane (meth)acrylates include RX8-3-6, RX43-21 (above, manufactured by Asia Industry Co., Ltd.), Shikotsu UV-3000B, UV-3200B (above, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.). , UN-7600, 9200 (all manufactured by Negami Kogyo Co., Ltd.), Aronix (registered trademark) M-1100, M-1200 (all manufactured by Toagosei Co., Ltd.) and the like.

The content ratio of urethane (meth)acrylate is 100 parts by mass of the curable component,
20 parts by mass or more is preferable, 30 parts by mass or more is more preferable, 40 parts by mass or more is particularly preferable, and 100 parts by mass or less is preferable, and 97 parts by mass or less is more preferable, in that the toughness of the cured product can be improved. It is particularly preferably 95 parts by mass or less.

2-4. Other polyfunctional (meth)acrylate The photocurable composition for photomolding according to the present invention may contain other polyfunctional (meth)acrylate for the purpose of improving curability and coatability.

Specific examples of other polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate and 1, Di(meth)acrylate of aliphatic diol such as 9-nonanediol di(meth)acrylate;
Di(meth)acrylates of alicyclic diols such as cyclohexane dimethylol di(meth)acrylate and tricyclodecane dimethylol di(meth)acrylate;
Alkylene glycol di(meth)acrylates such as diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate and tripropylene glycol di(meth)acrylate;
Esterification reaction product of neopentyl glycol, hydroxypivalic acid and (meth)acrylic acid;
Bisphenol A alkylene oxide adduct di(meth)acrylate and other bisphenol compound alkylene oxide adduct di(meth)acrylate;
Hydrogenated bisphenol A di(meth)acrylate such as di(meth)acrylate of hydrogenated bisphenol A;
Trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol di, tri or tetra(meth)acrylate, dipentaerythritol penta or hexa(meth)acrylate polyol poly(meth)acrylate;
Tri(meth)acrylate of trimethylolpropane alkylene oxide adduct, tetra(meth)acrylate of ditrimethylolpropane alkylene oxide adduct, tri or tetra(meth)acrylate of pentaerythritol alkylene oxide adduct, dipentaerythritol alkylene oxide adduct And a poly(meth)acrylate of a polyol alkylene oxide adduct such as penta or hexa(meth)acrylate.
In the alkylene oxide adduct, examples of the alkylene oxide include ethylene oxide and propylene oxide.

Further, as the other polyfunctional (meth)acrylate, a (meth)acrylate having a tertiary amino group which is a Michael adduct of the other polyfunctional (meth)acrylate and a primary and/or secondary amine compound (so-called amine modified (Meth)acrylate) may be included.

The content ratio of the other polyfunctional (meth)acrylate can be appropriately set in consideration of the viscosity of the photocurable composition for photomolding according to the present invention in consideration of the viscosity of the composition. Is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, still more preferably 40 parts by mass or more, and preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and 70 parts by mass. More preferably, it is not more than part.

2-5. Monofunctional (meth)acrylate A monofunctional (meth)acrylate is a compound having one (meth)acryloyl group in the molecule. The photocurable composition for photoforming according to the present invention may contain a monofunctional (meth)acrylate for the purpose of improving coatability.
Specific examples of the monofunctional (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2- Aliphatic alkyl (meth)acrylates such as ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate and stearyl (meth)acrylate;
Alicyclic alkyl (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate and dicyclopentenyloxyethyl (meth)acrylate;
Benzyl (meth)acrylate, (meth)acrylate of a phenol alkylene oxide adduct, (meth)acrylate of a p-cumylphenol alkylene oxide adduct, (meth)acrylate of an o-phenylphenol alkylene oxide adduct and nonylphenol alkylene oxide addition Aromatic (meth)acrylates such as (meth)acrylates of products;
2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethylol mono (meth)acrylate, pentanediol mono (meth) Acrylate, hexanediol mono(meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, tetraethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, dipropylene glycol Mono(meth)acrylate, tripropylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate and 2-hydroxy-3-butoxypropyl(meth). Hydroxyl group-containing (meth)acrylate such as acrylate;
Alkoxyalkyl (meth)acrylates such as 2-methoxyethyl (meth)acrylate and ethoxyethoxyethyl (meth)acrylate;
Imido group-containing (meth)acrylates such as N-(meth)acryloyloxyethyl hexahydrophthalimide and N-(meth)acryloyloxyethyl tetrahydrophthalimide;
Alkoxysilyl group-containing (meth)acrylates such as 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyldimethoxymethylsilane and 3-(meth)acryloyloxypropyltriethoxysilane;
Tetrahydrofurfuryl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl (meth)acrylate, (2-ethyl-2-methyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, (2-isobutyl-2- Methyl-1,3-dioxolan-4-yl)methyl(meth)acrylate, (1,4-dioxaspiro[4,5]decane-2-yl)methyl(meth)acrylate, glycidyl(meth)acrylate, 3,4 -Epoxy cyclohexylmethyl (meth)acrylate, (3-ethyloxetane-3-yl)methyl (meth)acrylate, 2-(meth)acryloyloxyethyl isocyanate, allyl (meth)acrylate, 2-(meth)acryloyloxyethyl hexa Examples thereof include hydrophthalic acid, 2-(meth)acryloyloxyethylsuccinic acid, ω-carboxy-polycaprolactone mono(meth)acrylate, and 2-(meth)acryloyloxyethyl acid phosphate.
In the alkylene oxide adduct, examples of the alkylene oxide include ethylene oxide and propylene oxide.

The content ratio of the monofunctional (meth)acrylate can be appropriately set in consideration of the viscosity of the photocurable composition for photomolding according to the present invention in consideration of the viscosity of the composition. When it is 100 parts by mass, 20 parts by mass or more is preferable, 30 parts by mass or more is more preferable, 40 parts by mass or more is further preferable, 90 parts by mass or less is preferable, 80 parts by mass or less is more preferable, 70 parts by mass. The following are more preferable.

2-6. Photopolymerization initiator Specific examples of the photopolymerization initiator include a cleavage type photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator.
Examples of the cleavage-type photopolymerization initiator include α-phenylglyoxylic acid ester compounds (hereinafter referred to as “(a1) component”) and α-aminoalkylphenone compounds (hereinafter referred to as “(a2) component”). ), an acylphosphine oxide compound (hereinafter referred to as “(a3) component”), an oxime compound (hereinafter referred to as “(a4) component”), a germanium compound (hereinafter referred to as “(a5) component”). ) And the like.

Specific examples of the component (a1) include 2-[2-oxo-2-phenylacetoxyethoxy]ethyl oxyphenylacetate and a mixture of 2-(2-hydroxyethoxy)ethyl oxyphenylacetic acid, methyl benzoylformate. Etc.

Specific examples of the component (a2) include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one.

Specific examples of the component (a3) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and phenyl(2,4,6-trimethylbenzoyl)phosphinic acid. Ethyl (, other acylphosphine oxide compounds such as SPEEDCURE XKM manufactured by LAMBSON, etc. may be mentioned.

Specific examples of the component (a4) include 1-[4-(phenylthio)phenyl]octane-1,2-dione 2-(O-benzoyloxime), ethanone, 1-[9-ethyl-6-(2- Methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) and the like.

Specific examples of the component (a5) include bis(4-methoxybenzoyl)diethylgermanium. The main cleavage products are presumed to be benzoyl radicals and germyl radicals.

The hydrogen abstraction type photopolymerization initiator is referred to as a thioxanthone compound (hereinafter referred to as “(a6) component”) and a photopolymerization initiator other than (a6) (hereinafter referred to as “(a7) component”). ) Is mentioned.

Specific examples of the component (a6) include other thioxanthone compounds such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, chlorothioxanthone, and isopropoxychlorothioxanthone.

Specific examples of the component (a7) include 4-phenylbenzophenone, 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, 4-benzoyl 4'-methyl diphenyl sulfide etc. are mentioned.

The photopolymerization initiator is preferably a cleavage type photopolymerization initiator in terms of excellent photocurability and reusability of a resin molding die, and among these, (a2) component, (a3) component, (a4 ) Component and (a5) component are more preferable, and (a2) component, (a3) component and (a5) component are more preferable.

Further, when it is necessary to increase the film thickness of the cured product, for example, when it is required to be 50 μm or more, in order to improve the curability inside the cured product, and when an ultraviolet absorber or a pigment is used in combination, For the purpose of improving the curability of the composition, it is preferable to use a plurality of kinds of compounds selected from the component (a2), the component (a3) and the component (a6) in combination.

The content ratio of the photopolymerization initiator can be appropriately set depending on the coating thickness of the composition, and is preferably 0.05 parts by mass or more and less than 10 parts by mass with respect to 100 parts by mass of the total amount of the curable components, and is 0.1. It is more preferably 05 parts by mass or more and 9 parts by mass or less, further preferably 0.05 parts by mass or more and 8 parts by mass or less, more preferably 0.05 parts by mass or more and 7 parts by mass or less, and 0.05 parts by mass or more and 6 parts by mass or less. It is even more preferable, and 0.05 parts by mass or more and 5 parts by mass or less is particularly preferable. By setting the proportion of the photopolymerization initiator to 0.05 parts by mass or more, the photocurability of the composition can be improved and the adhesiveness can be made excellent, and by setting it to less than 10 parts by mass, a cured product can be obtained. The internal curability of the can be improved, and the adhesion to the substrate can be improved.

2-7. Other components As other components, as long as the effects of the present invention are not impaired, a thermal polymerization initiator, an ultraviolet absorber, a light stabilizer, an antioxidant, a polymerization inhibitor, a silane coupling agent, a non-reactive polymer, a filler, a metal. Examples thereof include fine particles, metal oxide fine particles, ion trap agents, defoaming agents, leveling agents, dyes and pigments.

Of the other components, the thermal polymerization initiator will be described below.
The photocurable composition for photoforming according to the present invention may be mixed with a thermal polymerization initiator for the purpose of further improving the reaction rate after photocuring.
Various compounds can be used as the thermal polymerization initiator, and organic peroxides and azo initiators are preferable.
Specific examples of the organic peroxide include 1,1-bis(t-butylperoxy)2-methylcyclohexane, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, and ,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2 ,2-bis(4,4-di-butylperoxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-Butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di(m-toluoylperoxy)hexane, t-butylperoxy Oxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxyacetate, 2, 2-bis(t-butylperoxy)butane, t-butylperoxybenzoate, n-butyl-4,4-bis(t-butylperoxy)valerate, di-t-butylperoxyisophthalate, α, α '-Bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl Peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3 , 3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide and the like.
Specific examples of the azo compound include 1,1′-azobis(cyclohexane-1-carbonitrile), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile. , Azodi-t-octane, azodi-t-butane and the like.
These may be used alone or in combination of two or more. Also, the redox reaction can be carried out by combining the organic peroxide with a reducing agent.

The mixing ratio of the thermal polymerization initiator is preferably 10 parts by mass or less based on 100 parts by mass of the total amount of the curable components.

3. As a method for producing an optical molding photocurable composition according to the production method the present invention an optical molding photocurable composition may according to a conventional method, the curable component, and, further photopolymerizable optionally It can be produced by stirring and mixing the initiator and other components according to a conventional method. In this case, heating or heating can be performed as needed.

4. Molded Member and Manufacturing Method Thereof The molded member according to the present invention is a molded member composed of a substrate and a cured product of the photocurable composition for photoforming according to the present invention.
As the method for producing the molded member of the present invention, a conventional method may be used, and various usage methods can be adopted depending on the purpose. Specifically, the following modes can be mentioned.

<Aspect 1>
The step of filling the photo-curable composition for photo-molding according to the present invention into the concave part of the resin-made molding die in which the concave part is formed, and the above-mentioned molding so that the filled composition and the substrate are in close contact with each other. The step of arranging the mold, the step of curing the composition by irradiating ultraviolet rays and/or visible light from the side of the molding die, and the cured product obtained in the step of curing the composition are used for the molding. A method of manufacturing a molded member, the method including a step of releasing from a mold.

<Aspect 2>
The step of applying the photocurable composition for photomolding according to the present invention to the substrate, and the above-mentioned molding so that the coated composition and the recess of the resin molding die in which the recess is formed are in close contact with each other. The step of arranging the mold, the step of curing the composition by irradiating ultraviolet rays and/or visible rays from the side of the molding die, and the cured product obtained in the step of curing the composition are used for the molding. A method of manufacturing a molded member, the method including a step of releasing from a mold.

Examples of the base material include plastics other than the resin molding die, glass, paper and the like.
Specific examples of plastics other than resin-made molding dies include cellulose acetate resins such as polyester, polyarylate, polyether sulfone, polyvinyl alcohol, triacetyl cellulose and diacetyl cellulose.
Specific examples of the glass include soda glass, non-alkali glass, and quartz glass.
Specific examples of the paper include high-quality paper, coated paper, art paper, imitation paper, thin paper, thick paper, synthetic paper and filter paper.
Examples of the form of the base material include a film form, a sheet form, and a plate form. In the case of use as a filter element, a chrysanthemum-like cylindrical form may be used.
When the base material is a material having poor adhesion, an activation treatment can be performed on the surface of the base material before applying the photocurable composition for photoforming according to the present invention. Examples of the surface activation treatment include plasma treatment, corona discharge treatment, chemical treatment, roughening treatment and etching treatment, and flame treatment, which may be used in combination.

The photo-curable photocurable composition according to the present invention may be applied to a substrate by a conventionally known method, such as a natural coater, a knife belt coater, a floating knife, a knife over roll, a knife-on-blanket, a spray, Various methods such as a dispenser, a dip, a kiss roll, a squeeze roll, a reverse roll, an air blade, a curtain flow coater, a comma coater, a gravure coater, a micro gravure coater, and a die coater can be used.

The coating thickness of the photocurable composition for photoforming according to the present invention may be selected according to the substrate used and the application, but is preferably 10 μm to 2 mm, more preferably 20 μm to 2 mm, and 30 μm to 2 mm is more preferable, 40 μm to 2 mm is even more preferable, 50 μm to 2 mm is still more preferable, 100 μm to 2 mm is even more preferable, and 200 μm to 2 mm is particularly preferable.

As a light source when curing the photocurable composition for photoforming according to the present invention, a high pressure mercury lamp, a metal halide lamp, a xenon lamp, an electrodeless discharge lamp, a carbon arc lamp, an LED light source (emission wavelength is 405, 395, 385, 365 nm, etc.) and the like. The light sources may be used alone or in combination of two or more, and may be used in combination with other active energy ray irradiation devices such as an electron beam irradiation device.
The irradiation amount varies depending on the thickness of the coating film, the illuminance, etc., but may be appropriately set according to the emission wavelength of the light source and the composition.

Examples of applications of the obtained molded member include display-related members such as lens sheets, building material-related members such as heat ray reflective films, and automobile-related members such as filtration elements.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention is not limited to these examples.

<Production Examples 1 to 6>
1. Production of Photocurable Composition The compounds shown in Table 1 below were stirred and mixed in the proportions shown in Table 1 to produce a photocurable composition.
The obtained photocurable composition shown in Table 1 was used for the evaluation described below. The results are shown in Table 1.

The numbers in the curable components and photopolymerization initiators in Table 1 mean parts by mass.
The abbreviations in Table 1 mean the following.

(Curable component)
◆Oligomer having two or more (meth)acryloyl groups M8100: polyfunctional polyester (meth)acrylate, Aronix (registered trademark) M-8100 manufactured by Toagosei Co., Ltd. (However, residual toluene 6% by mass is distilled off under reduced pressure. To use)
SP1509: Bifunctional epoxy (meth)acrylate (main chain: bisphenol A), Showa Denko KK Lipoxy SP-1509
-RX43: Bifunctional urethane (meth)acrylate (main chain: polyester type), RX43-21 manufactured by Asia Industry Co., Ltd.

◆Other polyfunctional (meth)acrylate V230:1,6-hexanediol acrylate, Viscoat #230 manufactured by Osaka Organic Chemical Industry Co., Ltd.

(Photopolymerization initiator)
-I369: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, IRGACURE369 manufactured by BASF Japan Ltd.

2. Evaluation of reusability of resin mold
<Examples 1-28, Comparative Examples 1-8>
In this evaluation, resin molding dies (mold size: 12.5 mm × 15 mm × thickness 1 mm, groove: width 8 mm × depth 0.5 mm, square, untreated surface) each made of the following materials were used in this evaluation. .. The 405 nm transmittance of each resin molding die having a thickness of 1 mm was represented by T ₄₀₅ .

◆Material of resin molding die・POM: Polyacetal (T ₄₀₅ =62%)
・PFA: Perfluoroalkoxyalkane (T ₄₀₅ =84%)
・PP: Polypropylene (T ₄₀₅ =70%)
・PMMA: Polymethylmethacrylate (T ₄₀₅ =71%)
・PC: Polycarbonate (T ₄₀₅ =87%)
・NY: 6,6-nylon (T ₄₀₅ =45%)

1. The photocurable composition obtained in 1. is heated appropriately according to the viscosity, and then filled in the resin molding die, and a 100 μm-thick easily-adhesive PET film [TOYOBO CO., LTD. Cosmoshine A4300, The size: 100 mm in length×100 mm in width] was pressed so that the curable composition was in contact, and the temperature was kept at 25° C.
Next, using an UV irradiator manufactured by Eye Graphics (light source: metal halide lamp, peak intensity at 405 nm through a molding die: 700 mW/cm ² (UIT-250 UVD-C405 manufactured by Ushio), from the molding die side, Irradiation energy: 800 mJ/cm ² (UIT-250 UVD-C405 manufactured by Ushio Co., Ltd.) as a value through the molding die was applied to obtain a cured product.
When the cured product could not be released from the molding die, it was evaluated as "x".
On the other hand, in the case where the cured product could be released from the molding die, the cured product could be released from the molded die after the curing was performed under the same conditions as described above using the molding die after release ( That is, when the molding die could be reused), the "reusability of the molding die" was counted as 1 time, and 3. In, the surface free energy of the cured product was measured.
Furthermore, the same experiment was subsequently repeated, and the "reusability of the molding die" was counted until the cured product could not be released from the mold. When the "repeating usability of the molding die" is 1 to 9 times, it is evaluated as "△", and when the "repeating usability of the molding die" is 10 times, it is evaluated as "○". However, when the “reusability of use of the molding die” was 20 times, it was evaluated as “⊚” without performing further curing experiments. The results are shown in Table 1.

3. Surface Free Energy Measurement of Cured Product of Photocurable Composition and Photoforming Mold First, the above 2. Of the photocurable composition (each corresponding to Production Examples 1 to 6) obtained in Examples 1, 6, 11, 16, 21, and 25 of Example 1, and a resin molding die (POM, PFA, PP). , PMMA, PC, NY) using a contact angle measuring device (SCA20 manufactured by Eiko Instruments Co., Ltd.) to measure the water contact angle and the diiodomethane contact angle at a room temperature of 23° C. and 50% RH in a dropping amount of 5 microliters. After standing for 30 seconds, measurement was performed.
Then, using the water contact angle and the diiodomethane contact angle obtained above, the cured product of the photocurable composition and the resin molding by the method using the theoretical formula of Wu described in paragraphs [0011] to [0013]. The surface free energy of the mold was calculated. The results are shown in Table 1.

4. Evaluation Results As is clear from the results of Examples 1 to 28, when the photomolding kit of the present invention was used, the reusability of the resin molding mold was at a practical level.
On the other hand, Comparative Examples 1 to 8 in which the absolute value of the difference between the surface free energy of the resin molding die and the surface free energy of the cured product of the composition is less than 5.0 mN/m is the resin molding. The reusability of the mold was poor, and it was far from the practical level.

The photomolding kit of the present invention is excellent in reusability of a resin molding die. Therefore, it can be applied to various applications such as display-related members, building material-related members, and automobile-related members.

Claims (12)

A photomolding kit comprising a resin molding mold and a photocurable photocurable composition,
An optical molding kit, wherein an absolute value of a difference between a surface free energy of the resin molding die and a surface free energy of a cured product of the photocurable photocurable composition is 5.0 mN/m or more. The photomolding kit according to claim 1, wherein the resin molding die has a surface free energy of 30 to 60 mN/m. The material of the resin molding die is a material selected from the group consisting of polyacetal resin, fluorine resin, polyolefin resin, polymethylmethacrylate resin, polycarbonate resin and polyamide resin. Item 2. The photoforming kit according to item 2. The optical molding kit according to any one of claims 1 to 3, wherein the resin molding die having a thickness of 1 mm has a transmittance of 405 nm of 50% or more. The photomolding kit according to any one of claims 1 to 4, wherein the cured product of the photocurable photocurable composition has a surface free energy of 35 to 65 mN/m. The photomolding kit according to claim 1, wherein the photocurable photocurable composition contains an oligomer having two or more (meth)acryloyl groups. The photo-molding kit according to claim 6, wherein the oligomer contains at least one selected from the group consisting of polyester (meth)acrylate, epoxy (meth)acrylate and urethane (meth)acrylate. The content rate of the said oligomer is 40 mass%-95 mass% with respect to 100 mass% of curable components in the said photocurable composition for photomolding, Either of Claim 6 or Claim 7. The photo-molding kit described in. The optical molding kit according to any one of claims 1 to 8, which is applied to a display-related member. The optical molding kit according to any one of claims 1 to 8, which is applied to a building material-related member. The optical molding kit according to any one of claims 1 to 8, which is applied to an automobile-related member. A method for manufacturing a molding member using the photomolding kit according to claim 1.
A step of filling a photo-curable composition for photo-molding into the concave part of the resin molding die in which the concave part is formed,
Arranging the molding die such that the filled composition and the substrate are in close contact,
Curing the composition by irradiating ultraviolet rays and/or visible rays from the molding die side;
And a step of releasing the cured product obtained in the step of curing the composition from the molding die,
Manufacturing method of molded member.