JP7268344B2 - Optical molding kit and method for manufacturing molded member - Google Patents

Description

The present invention relates to photomolding kits and methods of making moldings.

As a method for producing a member having an uneven surface, a method of forming an uneven shape composed of a cured product of an active energy ray-curable composition on a transparent substrate by "mold transfer" is widely known (e.g. , Patent Documents 1-2). Here, the mold transfer is performed by applying the composition to a mold (such as a nickel stamper) having an inverted structure corresponding to the uneven shape of the target member, and bonding it to a transparent substrate, or , the composition is applied to a transparent base material, bonded to the same mold, irradiated with an active energy ray from the transparent base material side for curing, and then released from the mold.

On the other hand, as a method of manufacturing a member having an uneven surface, transfer using a less expensive resin mold (also referred to as a resin mold) has been studied instead of transfer using an expensive mold.

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

JP 2013-216748 WO2013/151119 JP 2011-228674 A

However, in the method described in Patent Document 3, if 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 releasability of the cured product gradually deteriorates as a result of the deposition of the cured product with repeated use of the resin molding die. In this case, since it is necessary to replace the resin molding die with a new one at a certain frequency, not only is the productivity inferior, but the cost is also a big problem.
SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an optical molding kit capable of improving the reusability of resin molding molds. Another object of the present invention is to provide a method for manufacturing a molded member using the kit for photomolding.

As a result of intensive studies to solve the above problems, the present inventors have found 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. By doing so, the inventors have found that the reusability of the resin molding die can be improved, and completed the present invention.
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 containing a resin molding mold and a photocurable composition for photomolding,
The photocurable composition for photomolding contains an oligomer having two or more (meth)acryloyl groups, and further contains urethane (meth)acrylate as the oligomer,
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 for photomolding is 5.0 mN/m or more,
The 405 nm transmittance of the resin molding mold having a thickness of 1 mm is 50% or more,
Optical molding kit.
[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-based resin, fluorine-based resin, polyolefin-based resin, polymethylmethacrylate-based resin, polycarbonate-based resin and polyamide-based resin, [1 ] or the photoforming kit according to [2].
[4] The photoforming kit according to any one of [1] to [3], wherein the cured product of the photocurable composition for photoforming has a surface free energy of 35 to 65 mN/m.
[ 5 ] Any one of [ 1 ] to [ 4 ], wherein the content 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. 1. The photoforming kit according to claim 1.
[ 6 ] The optical molding kit according to any one of [1] to [ 5 ], which is applied to a display-related member.
[ 7 ] The optical molding kit according to any one of [1] to [ 5 ], which is applied to a building material-related member.
[ 8 ] The optical molding kit according to any one of [1] to [ 5 ], which is applied to automobile-related members.
[ 9 ] A method for manufacturing a molded member using the photomolding kit according to any one of [1] to [ 8 ],
A step of filling a concave portion of a resin molding mold having a concave portion with a photocurable composition for photoforming;
positioning the mold so that the filled composition and substrate are in intimate contact;
A step of curing the composition by irradiating ultraviolet rays and/or visible light from the molding die side;
and releasing the cured product obtained in the step of curing the composition from the mold.
A method for manufacturing a molded member.

According to the optical molding kit of the present invention, it is possible to improve the reusability of the resin molding mold.

Various embodiments of the technology disclosed herein are described in detail below. In the present specification, acrylate and/or methacrylate are represented as (meth)acrylate, acryloyl group and/or methacryloyl group as (meth)acryloyl group, and acrylic acid and/or methacrylic acid as (meth)acrylic acid. .

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

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 obtained by measuring the contact angles of water and diiodomethane using a known contact angle measuring device. Then, it can be obtained by Wu's theoretical formula.

Here, in Wu's theoretical formula, γ _Sd is the dispersion component of the surface free energy of the solid, γ _Sp is the polar component of the surface free energy of the solid, γ Ld is the dispersion component of the surface free energy of the liquid, and γ _Ld is the surface free energy of the liquid. Assuming that the polar component of the energy is γ _Lp and the surface free energy of the liquid is γ _L (= γ _Ld + γ _Lp ,
(γ _Sd γ _Ld / (γ _Sd + γ _Ld )) + (γ _Sp γ _Lp / (γ _Sp + γ _Lp ) = γ _L (1 + cos θ) / 4 (1)
, and the respective components γ _Sd and γ _Sp of the surface free energy of a solid can be determined by measuring the contact angles of two liquids with different surface free energies.

Specifically, first, the contact angles θ of water and diiodomethane on the resin mold are measured.
Next, θ obtained above, dispersion component γ _Ld , polar component γ _Lp , and surface free energy γ _L (= γ _Ld + γ _Lp ) of water and diiodomethane are substituted into equation (1), and the simultaneous equation Then, the dispersive component γ _Sd and the polar component γ _Sp of the surface free energy of the resin molding die are obtained.
・γ _Ld of water: 22.6 mN/m, γ _Lp : 50.20 mN/m, γ _L : 72.8 mN/m
・γ _Ld of diiodomethane: 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 mold.
The surface free energy of the cured product of the photocurable composition for photomolding can also be obtained by the same method.

Hereinafter, the resin molding die, the photocurable composition for photomolding and its manufacturing method, and the molding member and its manufacturing method 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, more preferably 30 to 50 mN/m, from the standpoint of repeated use of the molding mold. is more preferred, and 30 to 40 mN/m is even more preferred.
As for the resin molding die, it is possible to easily produce cured products having various sizes and shapes simply by adjusting the concave portion of the mold having the concave portion to a desired size.

Examples of materials for the resin molding die according to the present invention include polyacetal-based resins, fluorine-based resins, polyolefin-based resins, polymethylmethacrylate-based resins, polycarbonate-based resins, and polyamide-based resins.

Polyacetal-based resins are resins having oxymethylene units as main repeating units. Specific examples thereof include homopolymers obtained by polymerization reaction using formaldehyde or trioxane as the main raw material, oxymethylene units and units other than oxymethylene units. Examples thereof include copolymers composed of structural units.
Specific examples of fluorine-based resins include polytetrafluoroethylene, fluoroethylene-propylene copolymer resins, perfluoroalkoxy resins, and fluorinated epoxy resins.
Specific examples of polyolefin resins include cycloolefin polymers, polypropylene, and polyethylene.
The polymethyl methacrylate-based resin refers to a homopolymer of methyl methacrylate or a copolymer containing 50% by mass or more of methyl methacrylate component. , maleimides, (meth)acrylic acid, styrenes, and the like.
Polycarbonate-based resins include aromatic polycarbonate resins and aliphatic polycarbonate resins, and specific examples include bisphenol A-based polycarbonates, which are general-purpose polycarbonates.
Examples of polyamide-based resins include aliphatic polyamide-based resins and aromatic polyamide-based resins, and specific examples thereof include nylon 6, nylon 66, nylon 610, copolyparaphenylene, 3.4′ oxydiphenylene, Examples include terephthalamide, polyparaphenylene terephthalamide, polymetaphenylene isophthalamide, and the like.
Among these, polyacetal-based resins, fluorine-based resins and polyolefin-based resins are particularly preferred because the effects of the present invention are particularly large.

As the resin molding mold, a mold with an untreated surface can be used, and a mold with a mold release treatment on the surface 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 shape of the resin molding die include film, sheet and plate shapes.

2. Photo-curable composition for photo-molding The photo-curable composition for photo-molding according to the present invention has an 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 of 5.5. It is a composition that becomes 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, more preferably 35 to 55 mN/m, from the viewpoint of repeated use of the molding die. More preferably m.

The viscosity of the photo-curable composition for photo-molding according to the present invention may be appropriately set in order to obtain a coated surface with excellent smoothness that can be used in the manufacturing process of a molded member. Based on this, a person skilled in the art can easily set.

The photocurable composition for photoforming according to the present invention preferably contains an ethylenically unsaturated group-containing compound, more preferably contains a photopolymerization initiator, and various other components are blended according to 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 the (meth)acryloyl group is preferable from the viewpoint of photocurability.

Examples of ethylenically unsaturated group-containing compounds include compounds having two or more (meth)acryloyl groups (hereinafter referred to as "polyfunctional (meth)acrylates"), and having one (meth)acryloyl group in the molecule. compounds (hereinafter referred to as "monofunctional (meth)acrylates") and the like.

Examples of polyfunctional (meth)acrylates include oligomers having two or more (meth)acryloyl groups, and compounds having two or more (meth)acryloyl groups other than the oligomer (hereinafter referred to as "other polyfunctional (meth) "Acrylate".) and the like.
The polyfunctional (meth) acrylate preferably contains an oligomer having two or more (meth) acryloyl groups in terms of improving the toughness of the cured product. Examples of the oligomer include polyester (meth) acrylate, epoxy More preferably, it contains at least one selected from the group consisting of (meth)acrylates and urethane (meth)acrylates.

Polyester (meth)acrylates, epoxy (meth)acrylates, urethane (meth)acrylates, other polyfunctional (meth)acrylates, monofunctional (meth)acrylates, photopolymerization initiators and other components are described below.

2-1. Polyester (meth)acrylates Examples of polyester (meth)acrylates include dehydration condensates of polyester polyols and (meth)acrylic acid.

Here, examples of polyester polyols include reaction products of polyols and carboxylic acids or their anhydrides.
Specific examples of polyols 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, and 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 Oxide adducts and the like can be mentioned.
Specific examples of carboxylic acids or their anhydrides 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 its anhydride.
Polyester poly(meth)acrylates other than these include compounds described on pages 74 to 76 of "UV/EB Curing Materials".
In the above, the alkylene oxide of the alkylene oxide adduct is preferably ethylene oxide, propylene oxide, or the like.
Here, the curable component is a component that is cured by light irradiation, and means an ethylenically unsaturated group-containing compound.
The polyester (meth)acrylate may be a dendrimer-type (meth)acrylate.

Commercially available polyester (meth)acrylates 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 (manufactured by Toagosei Co., Ltd.) and the like.

The content of the polyester (meth)acrylate is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, more preferably 40 parts by mass, in that the toughness of the cured product can be improved when the curable component is 100 parts by mass. The above is particularly preferable, and 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 reaction of (meth)acrylic acid to an epoxy resin. published in 2003], pp. 74-75.

Epoxy resins include aromatic epoxy resins and aliphatic epoxy resins.
Specific examples of the aromatic epoxy resins include resorcinol diglycidyl ether; bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene or di- or polyglycidyl ethers of alkylene oxide adducts thereof; phenol novolak-type epoxy resins and cresol novolak-type epoxy resins. novolak type epoxy resins such as resins; glycidyl phthalimide; o-diglycidyl phthalate;

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

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

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

The content of epoxy (meth)acrylate is, when the curable component 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 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. , 95 parts by mass or less is particularly preferred.

2-3. Urethane (meth)acrylate Urethane (meth)acrylate is a reaction product of a polyhydric alcohol, an organic polyisocyanate 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 , referred to as “urethane adduct”).

Specific examples of the polyhydric alcohol include polyether polyols such as polypropylene glycol and polytetramethylene glycol, polyester polyols obtained by reacting the polyhydric alcohol and the polybasic acid, and the polyhydric alcohol and the polybasic acid. and ε-caprolactone, and polycarbonate polyols (for example, polycarbonate polyols obtained by reacting 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)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, and hydroxyhexyl (meth)acrylate. acrylates and hydroxyl-containing mono(meth)acrylates such as hydroxyoctyl(meth)acrylate, trimethylolpropane mono(meth)acrylate and pentaerythritol mono(meth)acrylate;
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 Containing polyfunctional (meth)acrylate etc. are mentioned.

The urethane (meth)acrylate can be obtained by a conventional method using the above compounds.

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

The urethane adduct is produced by heating and stirring the organic isocyanate and hydroxyalkyl (meth)acrylate used 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 the compounds described on pages 70 to 74 of the above-mentioned document "UV/EB curable materials".

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

The content of urethane (meth)acrylate is, when the curable component 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 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. 95 parts by mass or less is particularly preferred.

2-4. Other Polyfunctional (Meth)acrylates The photocurable composition for photomolding according to the present invention may contain other polyfunctional (meth)acrylates 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)acrylates of aliphatic diols such as 9-nonanediol di(meth)acrylate;
Di(meth)acrylates of alicyclic diols such as cyclohexanedimethylol di(meth)acrylate and tricyclodecanedimethylol 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;
Di(meth)acrylates of alkylene oxide adducts of bisphenol compounds such as di(meth)acrylates of bisphenol A alkylene oxide adducts;
Di(meth)acrylates of hydrogenated bisphenol compounds such as di(meth)acrylates of hydrogenated bisphenol A;
Polyol poly(meth)acrylates such as trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol di, tri or tetra(meth)acrylate, dipentaerythritol penta or hexa(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 poly(meth)acrylates of polyol alkylene oxide adducts, such as penta or hexa(meth)acrylates.
Examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide and propylene oxide.

In addition, other polyfunctional (meth)acrylates include (meth)acrylates having a tertiary amino group, which are Michael adducts of other polyfunctional (meth)acrylates and primary and/or secondary amine compounds (so-called amine-modified (Meth)acrylate) may be included.

The content ratio of other polyfunctional (meth)acrylates can be appropriately set in consideration of the viscosity of the composition from the viewpoint of the applicability of the photocurable composition for photoforming according to the present invention. is 100 parts by mass, preferably 20 parts by mass or more, more preferably 30 parts by mass or more, further preferably 40 parts by mass or more, preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and 70 parts by mass Part or less is more preferable.

2-5. Monofunctional (meth)acrylate 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 monofunctional (meth)acrylates 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 phenol alkylene oxide adduct, (meth)acrylate of p-cumylphenol alkylene oxide adduct, (meth)acrylate of o-phenylphenol alkylene oxide adduct and nonylphenol alkylene oxide adduct aromatic (meth)acrylates such as (meth)acrylates;
2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethylol mono(meth)acrylate, pentanediol mono(meth)acrylate 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 of tripropylene glycol, mono (meth) acrylate of polypropylene glycol, 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;
imide group-containing (meth)acrylates such as N-(meth)acryloyloxyethylhexahydrophthalimide and N-(meth)acryloyloxyethyltetrahydrophthalimide;
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]decan-2-yl)methyl (meth)acrylate, glycidyl (meth)acrylate, 3,4 -epoxycyclohexylmethyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, 2-(meth)acryloyloxyethyl isocyanate, allyl (meth)acrylate, 2-(meth)acryloyloxyethyl hexa hydrophthalic acid, 2-(meth)acryloyloxyethyl succinic acid, ω-carboxy-polycaprolactone mono(meth)acrylate, 2-(meth)acryloyloxyethyl acid phosphate and the like.
Examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide and propylene oxide.

The content of the monofunctional (meth)acrylate can be appropriately set in consideration of the viscosity of the composition from the viewpoint of the applicability of the photocurable composition for photoforming according to the present invention. When 100 parts by mass, preferably 20 parts by mass or more, more preferably 30 parts by mass or more, further preferably 40 parts by mass or more, preferably 90 parts by mass or less, more preferably 80 parts by mass or less, 70 parts by mass More preferred are:

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

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

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

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

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

As the hydrogen abstraction type photopolymerization initiator, a thioxanthone compound (hereinafter referred to as "(a6) component") and a photopolymerization initiator other than (a6) (hereinafter referred to as "(a7) component"). ).

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

Specific examples of component (a7) include 4-phenylbenzophenone, 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, 4-benzoyl 4'-methyldiphenyl sulfide and the like.

As the photopolymerization initiator, a cleavage-type photopolymerization initiator is preferable from the viewpoint of excellent photocurability and reusability of the resin molding mold. ) and (a5) are more preferred, and (a2), (a3) and (a5) are more preferred.

In addition, when it is necessary to increase the film thickness of the cured product, for example, when it is necessary to make it 50 μm or more, for the purpose of improving the curability inside the cured product, and when using an ultraviolet absorber or pigment in combination For the purpose of improving the curability of the composition, it is preferable to use a plurality of compounds selected from components (a2), (a3) and (a6) in combination.

The content 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 curable components. 05 parts by mass to 9 parts by mass is more preferable, 0.05 parts by mass to 8 parts by mass is more preferable, 0.05 parts by mass to 7 parts by mass is even more preferable, and 0.05 parts by mass to 6 parts by mass is more preferable. More preferably, 0.05 parts by mass or more and 5 parts by mass or less is particularly preferable. By making the proportion of the photopolymerization initiator 0.05 parts by mass or more, the photocurability of the composition can be improved and the adhesion can be made excellent. The internal curability of the resin can be improved, and the adhesion to the substrate can be improved.

2-7. Other components Other components include thermal polymerization initiators, ultraviolet absorbers, light stabilizers, antioxidants, polymerization inhibitors, silane coupling agents, non-reactive polymers, fillers, metals, as long as they do not impair the effects of the present invention. Examples include fine particles, metal oxide fine particles, ion trapping agents, antifoaming agents, leveling agents, dyes and pigments.

Among other components, the thermal polymerization initiator will be described below.
The photocurable composition for photoforming according to the present invention may contain a thermal polymerization initiator after photocuring for the purpose of further improving the reaction rate.
Various compounds can be used as the thermal polymerization initiator, and organic peroxides and azo initiators are preferred.
Specific examples of organic peroxides include 1,1-bis(t-butylperoxy) 2-methylcyclohexane, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1 , 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-butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butyl peroxyacetate, 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 azo compounds 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 organic peroxide can be combined with a reducing agent to cause a redox reaction.

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

3. Method for producing the photocurable composition for photoforming The method for producing the photocurable composition for photoforming according to the present invention may follow a conventional method, and the curable component and, if necessary, further photopolymerization. The initiator and other components can be produced by stirring and mixing in a conventional manner. In this case, it can be heated or warmed as necessary.

4. Molded member and its manufacturing method The molded member according to the present invention is a molded member comprising a substrate and a cured product of the photocurable composition for photoforming according to the present invention.
The molded member of the present invention can be produced by a conventional method, and various methods of use can be adopted depending on the purpose. Specifically, the following aspects are mentioned.

<Aspect 1>
A step of filling the concave portion of a resin molding mold having a concave portion with the photocurable composition for photoforming according to the present invention, and the molding so that the filled composition and the substrate are in close contact. The step of placing a mold, the step of curing the composition by irradiating ultraviolet rays and / or visible light from the side of the molding die, and the step of curing the composition. A method of manufacturing a molded member, comprising the step of releasing from the mold.

<Aspect 2>
applying the photocurable composition for photoforming according to the present invention to a base material; The step of placing a mold, the step of curing the composition by irradiating ultraviolet rays and / or visible light from the side of the molding die, and the step of curing the composition. A method of manufacturing a molded member, comprising the step of releasing from the mold.

Examples of the base material include plastics other than resin molds, glass, paper, and the like.
Specific examples of plastics other than resin molds include polyester, polyarylate, polyethersulfone, polyvinyl alcohol, and cellulose acetate resins such as triacetyl cellulose and diacetyl cellulose.
Specific examples of glass include soda glass, alkali-free glass, quartz glass, and the like.
Specific examples of paper include woodfree paper, coated paper, art paper, imitation paper, thin paper, cardboard, synthetic paper and filter paper.
The form of the substrate includes film, sheet, plate, and the like, and in the case of use as a filter element, it may have a chrysanthemum-like cylindrical shape.
In addition, when the base material is a difficult-to-adhere material, the surface of the base material can be subjected to an activation treatment 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 solution treatment, surface roughening treatment, etching treatment, flame treatment and the like, and these may be used in combination.

Application of the photocurable composition for photoforming according to the present invention to a substrate may be carried out according to conventionally known methods, such as natural coater, knife belt coater, floating knife, knife over roll, knife on blanket, spray, Various methods such as dispenser, dip, kiss roll, squeeze roll, reverse roll, air blade, curtain flow coater, comma coater, gravure coater, micro gravure coater, die coater and the like can be used.

In addition, the coating thickness of the photocurable composition for photoforming according to the present invention may be selected according to the substrate and application to be used. 2 mm is more preferred, 40 μm to 2 mm is more preferred, 50 μm to 2 mm is even more preferred, 100 μm to 2 mm is even more preferred, and 200 μm to 2 mm is particularly preferred.

Light sources for curing the photocurable composition for photomolding according to the present invention include high-pressure mercury lamps, metal halide lamps, xenon lamps, electrodeless discharge lamps, carbon arc lamps, LED light sources (emission wavelengths are 405, 395, 385, 365 nm, etc.). One of the light sources may be used alone, or two or more of them may be used in combination, and other active energy ray irradiation devices such as an electron beam irradiation device may be used in combination.
Although the irradiation dose varies depending on the thickness of the coating film, the illuminance, etc., it may be appropriately set according to the emission wavelength of the light source and the compounding composition.

Applications of the obtained molded member include display-related members such as lens sheets, construction-related members such as heat ray reflective films, and automobile-related members such as filter elements.

EXAMPLES Examples and comparative examples are shown below to describe the present invention more specifically. However, the present invention is not limited by these examples.

<Production Examples 1 to 6>
1. Preparation 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.
Using the obtained photocurable composition in Table 1, the evaluation described later was performed. Those 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)
◆Oligomers with two or more (meth)acryloyl groups
· M8100: Polyfunctional polyester (meth) acrylate, Toagosei Co., Ltd. Aronix (registered trademark) M-8100 (however, 6% by mass of residual toluene is distilled off under reduced pressure and used)
・ SP1509: Bifunctional epoxy (meth) acrylate (main chain: bisphenol A), Lipoxy SP-1509 manufactured by Showa Denko Co., Ltd.
・RX43: Bifunctional urethane (meth)acrylate (main chain: polyester), RX43-21 manufactured by Asia Industry Co., Ltd.

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

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

2. Evaluation of repeatability of resin molds
<Examples 1 to 28, Comparative Examples 1 to 8>
In this evaluation, a resin molding mold (mold size: 12.5 mm × 15 mm × thickness 1 mm, groove: 8 mm width × 0.5 mm depth, square, surface untreated) made of the following materials was used. . The 405 nm transmittance of each resin molding die having a thickness of 1 mm is represented by _T405 .

◆Material of resin mold・POM: Polyacetal (T ₄₀₅ = 62%)
・PFA: Perfluoroalkoxyalkane (T ₄₀₅ =84%)
・PP: Polypropylene ( _T405 = 70%)
- PMMA: polymethyl methacrylate ( _T405 = 71%)
・PC: Polycarbonate (T ₄₀₅ = 87%)
・NY: 6,6-nylon (T ₄₀₅ = 45%)

1. After appropriately heating the photocurable composition obtained in (1) according to the viscosity, it is filled into the resin molding mold described above, and a 100 μm thick easy-adhesive PET film [Cosmoshine A4300 manufactured by Toyobo Co., Ltd., Size: length 100 mm x width 100 mm] was pressed so that the curable composition was in contact with it, and the temperature was kept at 25°C.
Next, using an ultraviolet irradiation device manufactured by Eyegraphics (light source: metal halide lamp, peak intensity at 405 nm through the molding die: 700 mW/cm ² (Ushio UIT-250 UVD-C405), from the molding die side, UV irradiation was performed at an irradiation energy of 800 mJ/cm ² (Ushio UIT-250 UVD-C405) as a value through a molding die to obtain a cured product.
When the cured product could not be released from the mold, it was evaluated as "x".
On the other hand, when the cured product could be released from the mold, the cured product was released after curing under the same conditions as above using the mold after release ( That is, when the molding die could be reused), the "repetitive use of the molding die" is counted as one time, and 3. below is counted. In, the surface free energy of the cured product was measured.
Furthermore, the same experiment was repeated successively, and the "repeated usability of the mold for molding" was counted until the cured product could not be released from the mold. If the "repeated use of the molding die" is 1 to 9 times, it is evaluated as "△", and if the "repeated use of the molding die" is 10 times, it is evaluated as "○". However, when the "repetitive use of the molding die" reached 20 times, it was evaluated as "excellent" without conducting further curing experiments. Those results are shown in Table 1.

3. Measurement of the surface free energy of the cured product of the photocurable composition and the photoforming mold . Cured products of the photocurable compositions obtained in Examples 1, 6, 11, 16, 21, and 25 (corresponding to Production Examples 1 to 6, respectively), and resin molding dies (POM, PFA, PP , PMMA, PC, NY) were measured using a contact angle measuring device (SCA20 manufactured by Eiko Seiki Co., Ltd.) at room temperature of 23 ° C. and 50% RH, with a drop amount of 5 microliters. After standing still for 30 seconds, the measurement was performed.
Next, using the water contact angle and the diiodomethane contact angle obtained above, the method using Wu's theoretical formula described in paragraphs [0011] to [0013] is performed to obtain a cured product of the photocurable composition and a resin molding. The surface free energy of the mold was calculated. Those results are shown in Table 1.

4. Evaluation Results As is clear from the results of Examples 1 to 28, when the optical molding kit of the present invention was used, the reusability of the resin molding mold was at a practical level.
On the other hand, in 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, the resin molding The reusability of the mold was poor, and it was far from a practical level.

The optical molding kit of the present invention is excellent in reusability of the resin molding mold. Therefore, it can be applied to various uses such as display-related members, building-related members, and automobile-related members.

Claims (9)

A photomolding kit containing a resin molding mold and a photocurable composition for photomolding,
The photocurable composition for photomolding contains an oligomer having two or more (meth)acryloyl groups, and further contains urethane (meth)acrylate as the oligomer,
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 for photomolding is 5.0 mN/m or more,
The 405 nm transmittance of the resin molding mold having a thickness of 1 mm is 50% or more,
Optical molding kit. 2. The photomolding kit according to claim 1, wherein the surface free energy of the resin mold is 30 to 60 mN/m. 3. The material of said resin molding die is a material selected from the group consisting of polyacetal resin, fluorine resin, polyolefin resin, polymethyl methacrylate resin, polycarbonate resin and polyamide resin. Item 3. The photoforming kit according to item 2. The photoforming kit according to any one of claims 1 to 3, wherein the surface free energy of a cured product of the photocurable composition for photoforming is 35 to 65 mN/m. A 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, any one of claims 1 to 4 . A photoforming kit as described in . The optical molding kit according to any one of claims 1 to 5 , which is applied to a display-related member. 6. The photoforming kit according to any one of claims 1 to 5 , which is applied to building material-related members. 6. The optical molding kit according to any one of claims 1 to 5 , which is applied to automobile-related members. A method for manufacturing a molded member using the photomolding kit according to any one of claims 1 to 8 ,
A step of filling a concave portion of a resin molding mold having a concave portion with a photocurable composition for photoforming;
positioning the mold so that the filled composition and substrate are in intimate contact;
A step of curing the composition by irradiating ultraviolet rays and/or visible light from the molding die side;
and releasing the cured product obtained in the step of curing the composition from the mold.
A method for manufacturing a molded member.