WO2019230977A1

WO2019230977A1 - Led-curable composition for photomolding and use thereof

Info

Publication number: WO2019230977A1
Application number: PCT/JP2019/021876
Authority: WO
Inventors: 晶作末岡; 浩之神村
Original assignee: 東亞合成株式会社
Priority date: 2018-06-01
Filing date: 2019-05-31
Publication date: 2019-12-05
Also published as: CN112204056B; CN112204056A; JP7424287B2; JPWO2019230977A1

Abstract

[Problem] To provide an LED-curable composition for photomolding excellent in LED curability and reusability of a mold, and a molded member using the same. [Solution] An LED curable composition for photomolding, comprising the following components (A) and (B). Component (A): photopolymerization initiator having a molar extinction coefficient at 385 nm of 20 L·mol^-1·cm^-1 or more; and Component (B): an ethylenically-unsaturated group-containing compound; wherein the content ratio of the component (A) is 0.05 parts by mass or more and less than 10 parts by mass with respect to 100 parts by mass of the component (B).

Description

LED curable composition for light molding and use thereof

The present invention relates to a photo-molding LED curable composition and use thereof.

Photo-curable compositions are used in various applications such as coating agents, inks, resists, adhesives and sealants, and UV lamps such as high-pressure mercury lamps and metal halide lamps have been widely used as curing systems as light sources.

In recent years, an ultraviolet irradiation device using a light emitting diode (hereinafter referred to as “LED”) as a light source has been developed as a curing system replacing these ultraviolet lamps.
This is because the LED light source has the advantages of a long light source life and excellent energy saving, but has the disadvantage that the surface curability of the coating film made of the composition is greatly inferior to the conventional ultraviolet lamp light source. This is a monochromatic light source and does not emit light in a short wavelength region of 300 nm or less compared to an ultraviolet lamp light source that emits ultraviolet light of a wide wavelength, so that the amount of radicals generated from the photopolymerization initiator is small. Therefore, the polymerization reaction is easily affected by oxygen inhibition.

In such a background, especially in the field of paints such as clear coating agents and printing fields such as offset inks, which are irradiated with ultraviolet rays in an air atmosphere, surface curability is often a problem and is compatible with LED light sources. The manufacturing method of the cured film to perform and the composition used for it are examined (patent document 1).

On the other hand, in the fields (Patent Documents 2 and 3) such as display-related members such as lens sheets and building material-related members such as heat ray reflective films, which are irradiated with ultraviolet rays in a state where the composition is shielded from air, Studies have been made using the above advantages. In the production of lens sheets, heat ray reflective films, etc., a molding die such as a mold (stamper) is used, so that diffusion of oxygen in the air to the composition is reduced and oxygen polymerization inhibition during LED curing is reduced. Can do.

JP 2011-213965 A International Publication No. 2012/011434 International Publication No. 2013/151119

However, in the composition used for manufacturing a lens sheet, a heat ray reflective film, etc., when the LED curability is insufficient, an unreacted component is formed by a molding die only by the effect of reducing oxygen polymerization inhibition by the molding die. It becomes a problem to adhere to.
According to the study of the present inventors, as a result of the adhesion, the unreacted components are deposited with repeated use of the molding die, and the unreacted components are cured each time the ultraviolet rays or the visible light is irradiated. It was found that the releasability of objects gradually deteriorated. In this case, it is not only a problem that productivity is inferior because it is necessary to replace the molding die with a new one at a constant frequency, but it is also a big problem in terms of cost.
This invention is made | formed in view of the said situation, The objective is to provide LED curable composition for photoforming which can improve LED sclerosis | hardenability and the reusability of a shaping | molding die. Moreover, it is providing the shaping | molding member using the said LED curable composition for photoforming.

As a result of intensive studies to solve the above problems, the present inventors have found that an LED curable composition containing a photopolymerization initiator having a specific molar extinction coefficient and an ethylenically unsaturated group-containing compound is an LED curable composition. And it discovered that the reusability of a shaping | molding die can be improved, and completed this invention.

The present invention is as follows.
[1] A photocurable LED curable composition comprising the following components (A) and (B).
Component (A): Photopolymerization initiator having a molar extinction coefficient at 385 nm of 20 L · mol ⁻¹ · cm ⁻¹ or more (B) Component: Ethylenically unsaturated group-containing compound [2] The component (A) is α- The LED curable composition for photomolding according to claim 1, which is at least one selected from the group consisting of an aminoalkylphenone compound, an acylphosphine oxide compound, and a germanium compound.
[3] The photomolding according to [1] or [2], wherein the content ratio of the component (A) is 0.05 parts by mass or more and less than 10 parts by mass with respect to 100 parts by mass of the component (B). LED curable composition.
[4] The LED curable mold for photomolding according to any one of [1] to [3], wherein the component (B) comprises a component (B1); an oligomer having two or more (meth) acryloyl groups Composition.
[5] The component (B) includes the component (B1) and the component (B2); includes one (meth) acryloyl group, and the component (B2) includes an aromatic ring and one (meth) acryloyl group. The LED curable composition for photomolding according to [4], which comprises a compound having
[6] The component (B) includes a component (B1) and a component (B2), and the component (B2) includes a compound having a hydroxyl group and one (meth) acryloyl group, [4] or [5 ] LED curable composition for photo-molding of description.
[7] The component (B) includes a component (B1) and a component (B2), and as the component (B2), a compound having an aromatic ring and one (meth) acryloyl group, a hydroxyl group and one ( 5. The compound having a (meth) acryloyl group, and one or more selected from the group consisting of a compound having an aromatic ring, a hydroxyl group and one (meth) acryloyl group in one molecule. 5. The LED curable composition for photomolding according to 5.
[8] The photocurable LED curable composition for photomolding according to any one of [1] to [7], wherein the obtained cured composition has a hot strength at 170 ° C. of 0.3 MPa or more.
[9] The LED curable composition for photomolding according to any one of [1] to [8], which is applied to a display-related member.
[10] The LED curable composition for photomolding according to any one of [1] to [8], which is applied to a building material-related member.
[11] The LED curable composition for photomolding according to any one of [1] to [8], which is applied to automobile-related members.
[12] A step of filling the LED curable composition for photomolding according to any one of [1] to [11] into a recess of the molding die in which the recess is formed;
Arranging the mold so that the filled composition and the substrate are in close contact with each other;
From the side of the base material or the molding die, the LED light having a wavelength of 365 nm or more is irradiated from the side that transmits light of a wavelength of 365 nm or longer, and the composition is applied by the light transmitted through the base material or the molding die. A step of curing,
Manufacturing method of molded member.
[13] The method for producing a molded member according to [12], further including a step of releasing the cured product obtained in the step of curing the composition from the mold.
[14] The method for producing a molded member according to [12] or [13], wherein the material of the molding die is a material selected from the group consisting of a metal, a fluorine resin, and a polyolefin resin.
A photocurable LED curable composition comprising a photopolymerization initiator (A) having a molar extinction coefficient at 385 nm of 20 L · mol ⁻¹ · cm ⁻¹ or more and an ethylenically unsaturated group-containing compound (B).
[15] The method for producing a molded member according to any one of [12] to [14], wherein the obtained molded member has a heat resistance of 170 ° C. and a hot strength of 0.3 MPa or more.
[16] The method for producing a molded member according to any one of [12] to [15], wherein the obtained molded member has a thickness of 0.5 mm or more.

According to the photocurable LED curable composition of the present invention, the LED curability and the reusability of the mold can be improved.

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

The present invention is a photo-molding comprising (A) component (photopolymerization initiator having a molar extinction coefficient at 385 nm of 20 L · mol ⁻¹ · cm ⁻¹ or more) and (B) component (ethylenically unsaturated group-containing compound). The present invention relates to an LED curable composition (hereinafter also simply referred to as “composition”).
In the present invention, photomolding is a use different from thin film coating such as clear varnish, ink and hard coat, and cures a curable composition on a substrate using an LED that emits ultraviolet light or visible light. Means that.
For the purpose of reducing inhibition of oxygen polymerization during LED curing, there is a method of irradiating ultraviolet rays or visible rays by reducing oxygen diffusion in the air to the composition using a mold such as a mold (stamper). Preferably, specific uses thereof include a photocurable composition for a lens sheet used for a display-related member, a photocurable composition for a heat ray reflective film used for a building-related member, and an automobile-related member. Examples thereof include a sealing agent for a filter element used for the purpose.

In addition, since the composition of this invention is excellent in LED sclerosis | hardenability, it is not limited to the aspect which uses a shaping | molding die, The insulation for electronic substrates which irradiates the said composition to an ultraviolet-ray or visible light in an air atmosphere The present invention can also be applied to electronic material-related members such as coating materials and potting materials.

Hereinafter, the component (A), the component (B), other components, the composition, the molded member, and the manufacturing method thereof will be described in detail.

1. Component (A) Component (A) is a photopolymerization initiator having a molar extinction coefficient at 385 nm (hereinafter referred to as “ε385”) of 20 L · mol ⁻¹ · cm ⁻¹ or more.

Specific examples of the component (A) include a cleavage type photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator having ε385 of 20 L · mol ⁻¹ · cm ⁻¹ or more.
Examples of the cleavage type photopolymerization initiator include α-phenylglyoxylic acid ester compounds (hereinafter referred to as “component (a1)”) having an ε385 of 20 L · mol ⁻¹ · cm ⁻¹ or more, α-aminoalkylphenone. Compounds (hereinafter referred to as “component (a2)”), acylphosphine oxide compounds (hereinafter referred to as “component (a3)”), oxime compounds (hereinafter referred to as “component (a4)”), and , And a germanium compound (hereinafter referred to as “component (a5)”) having ε385 of 20 L · mol ⁻¹ · cm ⁻¹ or more.

Specific examples of the component (a1) include a mixture of oxyphenylacetic acid 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid 2- (2-hydroxyethoxy) ethyl ester (ε385: 39L · mol ^{^-1} · cm ^-1), benzoyl methyl formate ^{(ε385: 21L · mol -1 ·} cm -1) , and the like.

Specific examples of the component (a2) include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (ε385: 245 L · mol ⁻¹ · cm ⁻¹ ) and the like. .

Specific examples of the component (a3) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (ε385: 501 L · mol ⁻¹ · cm ⁻¹ ), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide ( ε385: 745 L · mol ⁻¹ · cm ⁻¹ ), ethyl phenyl (2,4,6-trimethylbenzoyl) phosphinate (ε385: 185 L · mol ⁻¹ · cm ⁻¹ ), other acyl phosphines such as SPEDDCURE XKM manufactured by LAMBSON And oxide compounds (ε385: 20 L · mol ⁻¹ · cm ⁻¹ or more).

Specific examples of the component (a4) include 1- [4- (phenylthio) phenyl] octane-1,2-dione 2- (O-benzoyloxime), (ε385: 519 L · mol ⁻¹ · cm ⁻¹ ), Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (ε385: 69 L · mol ⁻¹ · cm ⁻¹ ), etc. Is mentioned.

Specific examples of the component (a5) include bis (4-methoxybenzoyl) diethylgermanium (ε385: 538 L · mol ⁻¹ · cm ⁻¹ ). The main cleavage products are presumed to be benzoyl radicals and germyl radicals.

Examples of the hydrogen abstraction type photopolymerization initiator include thioxanthone compounds having ε385 of 20 L · mol ⁻¹ · cm ⁻¹ or more (hereinafter referred to as “component (a6)”), and photopolymerization other than (a6). Initiators (hereinafter referred to as “component (a7)”).

Specific examples of the component (a6) include other thioxanthone compounds such as 2,4-diethylthioxanthone (ε385: 4016 L · mol ⁻¹ · cm ⁻¹ ), 2-isopropylthioxanthone, chlorothioxanthone, and isopropoxychlorothioxanthone ( ε385: 20 L · mol ⁻¹ · cm ⁻¹ or more).

Specific examples of the component (a7) include 4-phenylbenzophenone (ε385: 23 L · mol ⁻¹ · cm ⁻¹ ), 1- [4- (4-benzoylphenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenyl sulfonyl) propan-1-one ^{(ε385: 63L · mol -1 ·} cm -1), 4- benzoyl-4'-methyl diphenyl sulfide ^{(ε385: 66L · mol -1 ·} cm -1) and the like Can be mentioned.

As the component (A), a cleavage type photopolymerization initiator is preferable from the viewpoint of excellent LED curability of the composition and reusability of the molding die.

The component (A) ε385 is 20 L · mol ⁻¹ · cm ⁻¹ or more, and 50 L · mol ⁻¹ · cm ^{−1 in} view of excellent LED curability of the composition and repeated use of the mold. Or more, preferably 100 L · mol ⁻¹ · cm ⁻¹ or more, more preferably 200 L · mol ⁻¹ · cm ⁻¹ or more, still more preferably 300 L · mol ⁻¹ · cm ⁻¹ or more, and 500 L · mol ^{− 1} · cm ⁻¹ or more is even more preferable, and 600 L · mol ⁻¹ · cm ⁻¹ or more is particularly preferable.
As the component (A), the component (a2), the component (a3), the component (a4), and the component (a5) are preferable because the LED curability of the composition and the reusability of the molding die are excellent. The component a2), the component (a3), and the component (a5) are more preferable.

Also, when it is necessary to increase the 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, or when using an ultraviolet absorber or a pigment together For the purpose of improving the curability of the composition, it is preferable to use a plurality of compounds selected from the components (a2), (a3) and (a6) in combination.

The content ratio of the component (A) can be appropriately set depending on the value of ε385 of the component (A) and the coating thickness of the composition, and 0.05 part by mass with respect to 100 parts by mass of the total component (B). It is preferably 10 parts by mass or less, more preferably 0.05 parts by mass or more and 9 parts by mass or less, still more preferably 0.05 parts by mass or more and 8 parts by mass or less, and even more preferably 0.05 parts by mass or more and 7 parts by mass or less. The amount is more preferably 0.05 parts by mass or more and 6 parts by mass or less, and particularly preferably 0.05 parts by mass or more and 5 parts by mass or less. By making the proportion of the component (A) 0.05 parts by mass or more, the photocurability of the composition can be improved and the adhesiveness can be improved, and by setting it to less than 10 parts by mass, the cured product The internal curability can be improved, and the adhesion to the substrate can be improved.

2. Component (B) The component (B) is an ethylenically unsaturated group-containing compound.
Examples of the ethylenically unsaturated group in component (B) include (meth) acryloyl group, (meth) acrylamide group, vinyl group and (meth) allyl group, and (meth) acryloyl in terms of excellent LED curability. Groups are preferred.

Examples of the compound having a (meth) acryloyl group in the component (B) include an oligomer having two or more (meth) acryloyl groups (hereinafter referred to as “component (B1)”), one ( A compound having a (meth) acryloyl group (hereinafter referred to as “component (B2)”) and a compound having two or more (meth) acryloyl groups in the molecule (however, the component (B1) is excluded. And the like ”.
Among these, it is preferable that (B1) component is included at the point which can improve the toughness etc. of hardened | cured material.
Hereinafter, the component (B1), the component (B2), and the polyfunctional (meth) acrylate will be described.
In the following, a compound having one (meth) acryloyl group in the molecule is sometimes referred to as “monofunctional (meth) acrylate”.

2-1. Component (B1) The component (B1) is an oligomer having two or more (meth) acryloyl groups.
The molecular weight of the component (B1) is preferably 600 to 30,000, more preferably 600 to 20,000 in terms of weight average molecular weight (hereinafter referred to as “Mw”).
In the present invention, Mw means a value obtained by converting the molecular weight measured by gel permeation chromatography (GPC) into polystyrene.
The component (B1) preferably includes at least one selected from the group consisting of epoxy (meth) acrylate, urethane (meth) acrylate, and polyester (meth) acrylate.
Hereinafter, epoxy (meth) acrylate, urethane (meth) acrylate, and polyester (meth) acrylate will be described.

2-1-1. Epoxy (meth) acrylate In the present invention, epoxy (meth) acrylate is a compound obtained by addition reaction of (meth) acrylic acid to an epoxy resin, and the document “UV / EB Curing Material” [CMC, 1992]. Issue], pages 74 to 75, and the like.
And the compounds described on pages 74 to 75.

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 adducts; phenol novolac type epoxy resin and cresol novolac type epoxy Examples thereof include novolak-type epoxy resins such as resins; glycidyl phthalimide; o-phthalic acid diglycidyl ester and the like.
In addition to these, the document “Epoxy Resin-Recent Advances” (Shojodo, published in 1990), Chapter 2 and the document “Polymer Processing”, Volume 9, Volume 22 Special Issue Epoxy Resin [Polymer Publications, Compounds published on pages 4 to 6 and pages 9 to 16 of 1973.

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; and diglycidyl ethers of polyethylene glycol and polypropylene glycol. Diglycidyl ethers of polyalkylene glycols; diglycidyl ethers of neopentyl glycol, dibromoneopentyl glycol and its alkylene oxide adducts; di- or triglycidyl ethers of trimethylolethane, trimethylolpropane, glycerin and its alkylene oxide adducts; and Polyglycerides of polyhydric alcohols such as di, tri or tetraglycidyl ethers of pentaerythritol and its alkylene oxide adducts Ether; hydrogenated bisphenol A and di- or polyglycidyl ethers of alkylene oxide adducts; tetrahydrophthalic acid diglycidyl ether; hydroquinone diglycidyl ether, and the like.
In addition to these, the compounds described on pages 3 to 6 of the above-mentioned document “Polymer Processing”, separate volume epoxy resin, can be mentioned.

Besides these aromatic epoxy resins and aliphatic epoxy trees, epoxy compounds having a triazine nucleus in the skeleton, such as TEPIC [Nissan Chemical Co., Ltd.], Denacol EX-310 [Nagase Kasei Co., Ltd.], etc. Examples thereof include compounds described on pages 289 to 296 of the above-mentioned document “Polymer Processing”, separate volume epoxy resin.

As commercially available products of epoxy (meth) acrylate, lipoxy SP-1507, SP-1509, SP-4010, VR-60, VR-90 (manufactured by Showa Denko KK), Denacol acrylate DA111, DA212, DA721 (Nagase ChemteX Co., Ltd.), epoxy ester 40EM, 70PA, 80MFA, 200PA, 3000A (above, manufactured by Kyoeisha Chemical Co., Ltd.).

The content ratio of the epoxy (meth) acrylate is preferably 10% by mass or more and 100% by mass or less in terms of being able to improve the toughness of the cured product in the total 100% by mass of the component (B), and is preferably 30% by mass. As mentioned above, it is more preferable to contain 95 mass% or less, and it is especially preferable to contain 50 mass% or more and 90 mass% or less.

2-1-2. Urethane (meth) acrylate Urethane (meth) acrylate is a reaction product of polyhydric alcohol, organic polyisocyanate and hydroxyl group-containing (meth) acrylate compound, and a reaction product of organic polyisocyanate and hydroxyl group-containing (meth) acrylate (hereinafter referred to as “reaction product”) , "Urethane adduct").

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

Specific examples of the organic polyisocyanate 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-containing mono (meth) acrylates such as acrylate and 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, ditrimethylolpropane di or tri (meth) acrylate and dipentaerythritol di, tri, tetra or penta (meth) acrylate Examples thereof include polyfunctional (meth) acrylates.

Urethane (meth) acrylate can be obtained by a conventional method using the above compound.

Specifically, as a method for producing a reaction product of a polyhydric alcohol, an organic polyisocyanate, and a hydroxyl group-containing (meth) acrylate compound, 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 can be obtained by addition reaction, further adding hydroxyalkyl (meth) acrylate, stirring and heating to cause addition reaction.

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

Examples of urethane poly (meth) acrylates other than these include compounds described on pages 70 to 74 of the above-mentioned document “UV / EB Curing Material”.

As commercially available products of urethane (meth) acrylate, RX8-3-6, RX43-21 (above, manufactured by Asia Industries), purple light UV-3000B, UV-3200B (above, 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 the urethane (meth) acrylate is preferably 10% by mass or more and 100% by mass or less, preferably 20% by mass in terms of improving the toughness of the cured product in the total 100% by mass of the component (B). As mentioned above, it is more preferable to contain 95 mass% or less, and it is especially preferable to contain 30 mass% or more and 90 mass% or less.

2-1-3. Examples of polyester (meth) acrylate polyester (meth) acrylate include dehydration condensate of polyester polyol and (meth) acrylic acid.

Here, examples of the polyester polyol include a reaction product of a polyol and a carboxylic acid or an anhydride thereof.
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, 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 And 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 described on pages 74 to 76 of the above-mentioned document “UV / EB Curing Material”.
In the above, the alkylene oxide of the alkylene oxide adduct is preferably ethylene oxide or propylene oxide.
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 (above, manufactured by Toagosei Co., Ltd.) and the like.

The content ratio of the polyester (meth) acrylate is preferably 10% by mass or more and 100% by mass or less in terms of being able to improve the toughness of the cured product in the total 100% by mass of the component (B), and 20% by mass. As mentioned above, it is more preferable to contain 95 mass% or less, and it is especially preferable to contain 30 mass% or more and 90 mass% or less.

2-2. Component (B2) The component (B2) is a compound having one (meth) acryloyl group in the molecule. The composition of the present invention may contain a component (B2) for the purpose of improving applicability.
Specific examples of the component (B2) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl ( Aliphatic alkyl (meth) acrylates such as meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate and isobornyl (meth) acrylate;
Cycloaliphatic 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 addition Aromatic monofunctional (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, 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, mono (meth) acrylate of tripropylene glycol, mono (meth) acrylate of polypropylene glycol, and 2-hydroxy-3-butoxypropyl Meth) hydroxyl group-containing monofunctional (meth) acrylates such as acrylate;
Monofunctional (meth) acrylates having a hydroxyl group and an aromatic ring such as 2-hydroxy-3-phenoxypropyl (meth) acrylate and 2- (meth) acryloyloxyethyl-2-hydroxyethyl-phthalic acid;
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; and 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) And alkoxysilyl group-containing (meth) acrylates such as acryloyloxypropyldimethoxymethylsilane and 3- (meth) acryloyloxypropyltriethoxysilane.
Examples other than the above include 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-ethyloxetane-3-yl) methyl (meth) acrylate, 2- (meth) acryloyloxyethyl isocyanate, allyl (meth) acrylate, 2- (Meth) acryloyloxyethyl hexahydroph Le acid, 2- (meth) acryloyloxyethyl succinic acid, .omega.-carboxy - polycaprolactone mono (meth) acrylate, and 2- (meth) acryloyloxyethyl acid phosphate, and the like.
In the alkylene oxide adduct, examples of the alkylene oxide include ethylene oxide and propylene oxide.

As the component (B2), among the (meth) acrylates described above, monofunctional (meth) acrylates having an aromatic ring are preferred because they are excellent due to the repeated availability of the mold.
Specific examples of the monofunctional (meth) acrylate having an aromatic ring are the same as those exemplified above for the aromatic monofunctional (meth) acrylate and the monofunctional (meth) acrylate having a hydroxyl group and an aromatic ring. Can be mentioned.
In applications where the cured product requires oil resistance, it is preferable to include a monofunctional (meth) acrylate having a hydroxyl group as the component (B2).
Examples of the monofunctional (meth) acrylate having a hydroxyl group include the same compounds as those exemplified for the hydroxyl group-containing monofunctional (meth) acrylate and the monofunctional (meth) acrylate having a hydroxyl group and an aromatic ring. .

The content ratio of the component (B2) can be appropriately set in consideration of the viscosity of the composition from the viewpoint of applicability of the composition of the present invention, and 10% in a total of 100% by mass of the component (B). The mass% is preferably 90% by mass or less, more preferably 20% by mass or more and 80% by mass or less, and further preferably 30% by mass or more and 70% by mass or less.

2-3. Polyfunctional (meth) acrylate Polyfunctional (meth) acrylate is a compound having two or more (meth) acryloyl groups in the molecule, and is a compound excluding the component (B1). The composition of the present invention may contain a polyfunctional (meth) acrylate for the purpose of improving LED curability and coatability.

Specific examples of the polyfunctional (meth) acrylate 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 1,9 A di (meth) acrylate of an aliphatic diol such as 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;
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) acrylate 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) acrylate.
In the alkylene oxide adduct, examples of the alkylene oxide include ethylene oxide and propylene oxide.

As the polyfunctional (meth) acrylate, a (meth) acrylate having a tertiary amino group which is a Michael adduct of a polyfunctional (meth) acrylate and a primary and / or secondary amine compound (so-called amine-modified (meta) ) Acrylate).

The content ratio of the polyfunctional (meth) acrylate can be appropriately set in consideration of the viscosity of the composition from the viewpoint of applicability of the composition of the present invention. When the component (B) is 100 parts by mass 10 parts by mass or more is preferable, 20 parts by mass or more is more preferable, 30 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, and 70 parts by mass or less is further preferable.

2-4. A preferred combination of the component (B) is a combination of the component (B1) and the component (B2).
The content ratio of the component (B1) and the component (B2) can be appropriately set in consideration of the viscosity of the composition from the viewpoint of applicability of the composition of the present invention. In mass%,
(B1) Component 10% by mass or more, 90% by mass or less, and (B2) Component 10% by mass or more, preferably 90% by mass or less,
More preferably, the component (B1) contains 20% by mass or more and 80% by mass or less, and the component (B2) contains 20% by mass or more and 80% by mass or less,
More preferably, the component (B1) contains 30% by mass to 70% by mass and the component (B2) contains 30% by mass to 70% by mass.

A more preferable combination of the component (B) includes the component (B1) and the component (B2), and the component (B2) includes a monofunctional (meth) acrylate having an aromatic ring.
According to the said (B) component, it becomes excellent by the reusability of a shaping | molding die, and also the obtained hardened | cured material is excellent in heat resistance.
In applications in which conventional molded members are used, in particular, molded members used in display-related members, building material-related members, and automobile-related members, which are the preferred applications described above, the heat resistance may be required. For example, for display-related members, the sealant at the end of the laminate and the adhesive portion with the flexible printed wiring board; for automotive-related members, sealing agent for filtration elements; and for other applications, various industrial gaskets, etc. In some cases, the molded member may require heat resistance.
However, the conventional curable composition cannot satisfy the heat resistance.
In the present invention, those using (meth) acrylates in the above combination as the component (B) not only have excellent reusability of the mold, but also the resulting cured product has excellent heat resistance. .
The proportion of the monofunctional (meth) acrylate having an aromatic ring in the component (B2) is 10 to 100 masses of the monofunctional (meth) acrylate having an aromatic ring based on the total amount of the component (B2) 100 mass%. %, More preferably 20 to 90% by mass.

Furthermore, as a preferable combination of another (B) component, what contains the monofunctional (meth) acrylate which has a hydroxyl group as (B1) component and (B2) component is mentioned.
According to the said (B) component, it becomes excellent by the reusability of a shaping | molding die, and also the obtained hardened | cured material is excellent in oil resistance.
In applications where conventional molded members are used, in particular, molded members used in display-related members, building material-related members, and automobile-related members, which are the preferred applications described above, may come into contact with oily components. In some cases, sex was required. For example, in automobile-related members, sealants for filter elements, and in other applications, there are cases where oil resistance is required for molded members in applications such as gaskets for various industries.
However, conventional curable compositions cannot satisfy the oil resistance.
In the present invention, those using (meth) acrylates in the above combination as the component (B) are not only excellent in the reusability of the molding die but also the obtained cured product is excellent in oil resistance. .
The proportion of the monofunctional (meth) acrylate having a hydroxyl group in the component (B2) is preferably 10 to 100% by mass of the monofunctional (meth) acrylate having a hydroxyl group based on 100% by mass of the total amount of the component (B2). More preferably, it is 20 to 90% by mass.

Furthermore, as a more preferable combination of the component (B), the component (B1) and the component (B2) are included, and the component (B2) includes a monofunctional (meth) acrylate having an aromatic ring and a unit having a hydroxyl group. The thing containing functional (meth) acrylate is mentioned.
According to the said (B) component, it becomes more excellent by the reusability of a shaping | molding die, and the cured | curing material obtained becomes excellent in heat resistance and oil resistance.
The ratio of the monofunctional (meth) acrylate having an aromatic ring and the monofunctional (meth) acrylate having a hydroxyl group in the component (B2) is based on the total amount of the component (B2) 100% by mass. The monofunctional (meth) acrylate having 10 to 90% by mass and the monofunctional (meth) acrylate having a hydroxyl group of 10 to 90% by mass are preferable, and more preferably, the monofunctional (meth) acrylate having an aromatic ring is 20 to 80% by mass. %, And monofunctional (meth) acrylate having a hydroxyl group of 20 to 80% by mass.
In addition, in the case where a monofunctional (meth) acrylate having an aromatic ring and a monofunctional (meth) acrylate having a hydroxyl group are used in combination as the component (B2), a monofunctional (meta) having an aromatic ring and a hydroxyl group in one molecule ) Acrylate can be used alone.
In this case, the ratio of the monofunctional (meth) acrylate having an aromatic ring and a hydroxyl group in one molecule in the component (B2) has an aromatic ring on the basis of 100% by mass of the total amount of the component (B2). The monofunctional (meth) acrylate is preferably 10 to 100% by mass, more preferably 20 to 90% by mass.

3. Other components The composition of the present invention comprises the component (A) and the component (B) as essential components, but various other components can be blended depending on the purpose.

As other components, unless the effect of the present invention is 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, metal fine particles, Examples include metal oxide fine particles, ion trapping agents, antifoaming agents, leveling agents, dyes and pigments.

Hereinafter, among other components, the thermal polymerization initiator will be described.
The composition of the present invention may be blended 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 preferred.
Specific examples of the organic peroxide include 1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, , 1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, , 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- , 5-di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl 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-butyl) Peroxy) 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. Moreover, an organic peroxide can also be made into a redox reaction by combining with a reducing agent.

The blending 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 component (B).

4). LED curable composition for photoforming The LED curable composition for photoforming of the present invention comprises the component (A) and the component (B).

As a method for producing the composition of the present invention, a conventional method may be followed, and the above-described components (A) and (B) and, if necessary, other components may be further stirred and mixed according to a conventional method. can do. In this case, it can be heated or heated as necessary.

The viscosity of the composition of the present invention may be set as appropriate in order to obtain a coating surface that is excellent in smoothness and coating properties that can be used in the manufacturing process of the molded member. It can be set easily.

As a method of using the composition of the present invention, a conventional method may be followed, and various methods of use can be adopted depending on the purpose.

The heat resistance of the cured product of the composition of the present invention is preferably one having a hot strength of 0.3 MPa or more at 170 ° C., more preferably 0.5 to 50 MPa.
In the present invention, the hot strength means the tensile strength at 170 ° C.
The conditions of the tensile test in the measurement of the breaking strength were as follows. The obtained cured product was cut into a No. 3 type dumbbell with a thickness of t1 mm and allowed to stand at 170 ° C. for 5 minutes, and the distance between chucks was 60 mm and 100 mm / min. It is the value carried out in.
In order to achieve the preferable heat resistance, the component (B) includes the component (B1) and the component (B2), and the component (B2) includes a monofunctional (meth) acrylate having an aromatic ring. preferable.

5. Molded member and production method thereof The photocurable LED curable composition of the present invention can be preferably used for the production of a molded member.
Hereinafter, the molded member and the manufacturing method thereof will be described.

5-1. Molded member The molded member produced from the photocurable LED curable composition of the present invention comprises a substrate and a cured product of the composition of the present invention.
The molded member of the present invention uses a mold having no releasability as a mold for molding (hereinafter referred to as “non-releasable mold”), a base material, a cured product of the composition of the present invention, and a non-molded product. It may be a molded member composed of a releasable mold.

As the heat resistance of the molded member of the present invention, as the heat resistance of the cured product, one having a hot strength of 170 MPa at 170 ° C. is preferable, and more preferably 0.5 to 50 MPa.

As a base material on which a cured product of the composition of the present invention is formed, a plastic other than a release-treated material described later and a surface untreated material having peelability (hereinafter collectively referred to as “release material”), Glass, paper, etc. are mentioned.
Specific examples of plastics other than the release material include cellulose acetate resins such as polyvinyl alcohol, triacetyl cellulose and diacetyl cellulose, and cyclic olefins such as acrylic resin, polyester, polycarbonate, polyarylate, polyethersulfone and norbornene as monomers. Examples include cyclic polyolefin resins.
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, filter paper, and the like.
Examples of the form of the substrate include a film shape, a sheet shape, a plate shape, and the like. In the case of a filter element, a chrysanthemum-like cylindrical shape may be used.

The thickness of the molded member may be appropriately set according to the purpose, preferably 10 μm to 2 mm, more preferably 20 μm to 2 mm, further preferably 30 μm to 2 mm, still more preferably 40 μm to 2 mm, and even more preferably 50 μm to 2 mm. Preferably, 100 μm to 2 mm is even more preferable, and 200 μm to 2 mm is particularly preferable.
In particular, a molded member used in a display-related member, a building material-related member, and an automobile-related member, which are preferable uses described later, preferably has a thickness of 0.5 mm or more, and more preferably 0.5 mm or more and 2 mm or less.

Examples of uses of the 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. When the obtained molded member is applied to the above-mentioned use, it is preferable to release the molding die.

5-2. As a method for producing the molded member of the production method the present invention the molded member may according to the conventional method, it is possible to employ various usage according to the purpose.
Specifically, the following embodiments 1 to 4 are preferable.

<Aspect 1>
Filling the concave portion of the molding die formed with the concave portion with the composition of the present invention;
Arranging the mold so that the filled composition and the substrate are in close contact with each other;
Irradiate LED light having a wavelength of 365 nm or more from the side that transmits light having a wavelength of 365 nm or more out of the base material or the molding die, and cure the composition by the light transmitted through the base material or molding die. Including the step of
Manufacturing method of molded member.
<Aspect 2>
In addition to the process of the said aspect 1, the manufacturing method of a molded member including the process of releasing the hardened | cured material obtained at the process of hardening the said composition from the shaping | molding die further.

<Aspect 3>
Applying a composition of the present invention to a substrate;
Arranging the molding die so that the coated composition and the concave portion of the molding die formed with the concave portion are in close contact with each other;
Irradiate LED light having a wavelength of 365 nm or more from the side that transmits light having a wavelength of 365 nm or more out of the base material or the molding die, and cure the composition by the light transmitted through the base material or molding die. Including the step of
Manufacturing method of molded member.
<Aspect 4>
In addition to the process of the said aspect 3, Furthermore, the manufacturing method of a molded member including the process of releasing the hardened | cured material obtained at the process of hardening the said composition from a shaping | molding die.

5-2-1. Mold for molding [also referred to as a mold (stamper). ] Can be any of a peelable mold and a non-releasable mold.
In the first to fourth aspects, a cured product having various sizes and shapes can be easily produced by simply using a molding die having a recess as a molding die and adjusting it to a desired size of the recess of the mold. can do.
Molding die having a recess [also called a mold (stamper). ] Can be used as both a peelable mold and a non-releasable mold, and can be easily adapted to various sizes and shapes just by adjusting the desired size of the recess of the mold having the recess. A cured product can be produced.

Examples of the material constituting the mold that can be peeled include a mold release material (a material subjected to a mold release treatment and a surface untreated material having a peelability).
Examples of the material for the release material include metals, fluorine resins, and polyolefin resins.
Specific examples of the metal include brass and nickel.
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 and the like include surface untreated cycloolefin polymer, surface untreated polypropylene, and surface untreated polyethylene.
In addition to these, silicone-treated polyethylene terephthalate, untreated surface polyethylene terephthalate, and the like can be given.
Among these, polyolefin resins and fluorine resins are particularly preferable in that the effect of the present invention is particularly great.
As a form of a mold release material, it is a shape which can form the shape of the target shaping | molding member, What has a convex part is preferable, A film form, a sheet form, plate shape, etc. may be sufficient.

Examples of the non-releasable mold include plastics other than the mold release material, glass, paper, and the like. Specific examples of these can be the same as those exemplified for the substrate.
Examples of the form of the non-releasable mold include a film form, a sheet form, and a plate form. In the case of a filter element, a chrysanthemum-like cylindrical form may be used.
In addition, when a non-releasable base material is a difficult-to-adhere material, an activation treatment can be performed on the surface of the releasable base material before applying the composition of the present invention. Examples of the surface activation treatment include plasma treatment, corona discharge treatment, chemical solution treatment, surface roughening treatment and etching treatment, and flame treatment, and these may be used in combination.

5-2-2. Coating method The coating method of the composition of the present invention on the mold or substrate may be in accordance with a conventionally known method. Natural coater, knife belt coater, floating knife, knife over roll, knife on blanket, spray, Various methods such as a dispenser, dip, kiss roll, squeeze roll, reverse roll, air blade, curtain flow coater, comma coater, gravure coater, micro gravure coater, and die coater can be used.

The coating thickness of the composition of the present invention on the molding die or substrate may be selected according to the molding die to be used, the substrate and the application, etc., but is preferably 10 μm to 2 mm, preferably 20 μm to 2 mm. More preferably, 30 μm to 2 mm is more preferable, 40 μm to 2 mm is still more preferable, 50 μm to 2 mm is still more preferable, 100 μm to 2 mm is still more preferable, and 200 μm to 2 mm is particularly preferable.
The molded member used in the display-related member, the building material-related member, and the automobile-related member, which are the preferred applications described above, preferably has a coating thickness of 0.5 mm or more, and more preferably 0.5 mm or more and 2 mm or less.

5-2-3. LED
The LED light source for curing the composition of the present invention is an LED that emits visible light or ultraviolet light, and examples of the emission wavelength include various wavelengths such as 405, 395, 385, and 365 nm.
Only one type of LED light source may be used, or two or more types may be used in combination.
The irradiation amount varies depending on the thickness of the coating film, the illuminance, and the like, but may be appropriately set according to the emission wavelength of the LED light source and the composition.

In addition to the LED light source, other active energy ray irradiation devices such as a high pressure mercury lamp, a metal halide lamp, a xenon lamp, an electrodeless discharge lamp, a carbon arc lamp, and an electron beam irradiation device may be used in combination.

5-2-4. Molding A molded member can be obtained by curing the composition by the method described above and releasing the resulting cured product from the molding die.
The resulting molded member can be used for the preferred applications described above.

Hereinafter, the present invention will be described more specifically by showing examples and comparative examples. However, the present invention is not limited to these examples.

1. Examples 1 to 21 and Comparative Examples 1 to 5
1) Production of curable composition The compounds shown in Tables 1 to 3 below were stirred and mixed at the ratios shown in Tables 1 to 3 to produce curable compositions.
The obtained curable compositions shown in Tables 1 to 3 were used and evaluated as described below. The results are shown in Tables 1 to 3. In Tables 1 to 3, the numerical values in parentheses of the components (A) and (A) ′ mean ε385 (unit: L · mol ⁻¹ · cm ⁻¹ ).

The numbers in the photopolymerization initiator and the component (B) in Tables 1 to 3 mean parts by mass.
The abbreviations in Tables 1 to 3 mean the following.

<Photopolymerization initiator>
◆ (A) component · MBF: methyl benzoylformate (ε385: 21 L · mol ^-1 · cm ^-1 ), SPEDDCURE MBF manufactured by Rambson Japan Co., Ltd.
OXE02: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (ε385: 69 L · mol ⁻¹ · cm ^{− 1} ) IRGACURE OXE02 manufactured by BASF Japan
TPOL: Phenyl (2,4,6-trimethylbenzoyl) ethyl phosphinate (ε385: 185 L · mol ⁻¹ · cm ⁻¹ ), TPO-L manufactured by BASF Japan Ltd.
I369: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (ε385: 245 L · mol ⁻¹ · cm ⁻¹ ), IRGACURE 369 manufactured by BASF Japan Ltd.
TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (ε385: 501 L · mol ⁻¹ · cm ⁻¹ ), BASF Japan Ltd. Lucillin TPO
OXE01: 1- [4- (phenylthio) phenyl] octane-1,2-dione 2- (O-benzoyloxime), (3ε385: 519 L · mol ⁻¹ · cm ⁻¹ ), IRGACURE manufactured by BASF Japan Ltd. OXE01
IVO: bis (4-methoxybenzoyl) diethylgermanium (ε385: 538 L · mol ⁻¹ · cm ⁻¹ ), IVOCARIIN made by IVOCLAR VIVADENT
I819: bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (ε385: 745 L · mol ⁻¹ · cm ⁻¹ ), IRGACURE 819 manufactured by BASF Japan Ltd.
DETX: 2,4-diethylthioxanthone (ε385: 4016 L · mol ⁻¹ · cm ⁻¹ ), DETX manufactured by BASF Japan Ltd.

◆ (A) 'component [photopolymerization initiator other than (A) component]
I184: 1-hydroxycyclohexyl phenyl ketone (ε385: 0.8 L · mol ⁻¹ · cm ⁻¹ ), IRGACURE 184 manufactured by BASF Japan Ltd.
I907 :: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (ε385: 14 L · mol ⁻¹ · cm ⁻¹ ), IRGACURE907 manufactured by BASF Japan Ltd.

<(B) component>
◆ Component (B1) SP1509: Bifunctional epoxy (meth) acrylate (main chain: bisphenol A), Lipoxy SP-1509, Showa Denko KK, Mw: 500
DA212: Bifunctional epoxy (meth) acrylate (main chain: 1,6-hexanediol), Denacol acrylate DA-212 manufactured by Nagase ChemteX Corporation
RX43: bifunctional urethane (meth) acrylate (main chain: polyester), RX43-21 manufactured by Asia Industry Co., Ltd., Mw: 8,700
M8100: Multifunctional polyester (meth) acrylate, Aronix (registered trademark) M-8100 manufactured by Toagosei Co., Ltd. (However, 6% by mass of residual toluene was distilled off under reduced pressure), Mw: 1,500

◆ Multifunctional (meth) acrylate V230: 1,6-hexanediol diacrylate, Biscoat # 230 manufactured by Osaka Organic Chemical Industry Co., Ltd.

2) Evaluation
(1) Evaluation of curability (Examples 1 to 21, Comparative Examples 1 to 4)
In this evaluation, as a mold, a mold M1 (material: made of polytetrafluoroethylene, mold size: vertical 50 mm × horizontal 50 mm × thickness 10 mm, groove: square 4 mm wide × 1 mm deep, between the grooves Distance: 2 mm, number of grooves: 8) or molding die M2 (material: made of polypropylene, mold size: 50 mm long x 50 mm wide x 10 mm thick, groove: square 4 mm wide x 1 mm deep, groove The distance between them was 2 mm, and the number of grooves was 8).
1. The curable composition obtained in 1 above was appropriately heated in accordance with the viscosity and then filled into the recesses (grooves) of the molding die M1 or M2, and a 100 μm thick easy-adhesive PET film [Toyobo Co., Ltd. The curable composition was pressed against Cosmo Shine A4300 manufactured by Cosmo Shine A4300, size: vertical 100 mm × horizontal 100 mm, and brought to a state of 25 ° C.
Next, UV-LED irradiation device manufactured by Centec Co., Ltd. (emission wavelength: 385 nm, peak intensity as a value over a mold for molding: 240 mW / cm ² (measured value in UV-A region of UV POWER PUCK manufactured by Heraeus Co., Ltd.)) ), And passing through a conveyor with a lamp height of 8 mm and 3 mm / sec once, irradiation energy of 1,000 mJ / cm ² (Heraeus Co., Ltd.) from the molding die side as a value over the molding die. ) UV irradiation of UV POWER PUCK (measured value in the UV-A region) was made to obtain a cured product.
The cured product obtained above was released from the molding die M1 or M2, and the curability of the composition was determined according to the following three levels using the surface state of the cured product as an index. The results are shown in Tables 1 to 3.
○: Tack free △: Slightly tacky ×: Uncured state

(2) Evaluation of curability (Comparative Example 5)
A metal halide lamp manufactured by Eye Graphics Co., Ltd. was used as the light source, and the conveyor had a lamp height of 21 cm and 4.9 m / min ((peak intensity as a value over the molding die: 240 mW / cm ² , irradiation energy per pass: 500 mJ / cm ² , both measured values in the UV-A region of UV POWER PUCK manufactured by Heraeus Co., Ltd.) were passed twice and UV irradiation was performed at an integrated irradiation energy of 1,000 mJ / cm ^2. The curability was evaluated in the same manner as in 1 to 21 and Comparative Examples 1 to 4. The results are shown in Tables 1 to 3.

(3) Evaluation of Repeatability of Mold for Molding Using the mold for molding after releasing the cured product in (1), curing was performed under the same conditions as in (1), and then the cured product was released from the mold. When it was possible (that is, the molding die could be reused), the “repetitive availability of the molding die” was counted as one time. Further, the same experiment was repeated, and “repetitive availability of molding die” was counted until the cured product could not be released. The results are shown in Tables 1 to 3.
In addition, when the “repetitive usability of the mold” was 20 times, it was described as ≧ 20 times without further curing experiments.

3) Evaluation results As is clear from the results of Examples 1 to 21, when the photocurable LED curable composition of the present invention was used, the LED curability and the reusability of the mold were practical levels. .
Among these, the compositions of Examples 4 to 21 containing a photopolymerization initiator having an ε385 component (A) of 200 L · mol ⁻¹ · cm ⁻¹ or more are particularly excellent in the reusability of the molding die. .
In addition, when the light source is changed from a metal hydride lamp to an LED under the conditions using the polypropylene molding die with the same components of the composition (contrast between Example 21 and Comparative Example 5), the molding die is repeated. It turned out that usability can be improved dramatically.
On the other hand, the compositions of Comparative Examples 1 to 4 containing a photopolymerization initiator having an ε385 of less than 20 L · mol ⁻¹ · cm ⁻¹ are inferior in LED curability. Due to the deposition and its curing, the reusability of the mold was poor and far from the practical level.

2. Examples 22-27
1) Production of curable composition The compounds shown in Table 4 below were stirred and mixed at the ratios shown in Table 4 to produce curable compositions.
The obtained curable composition shown in Table 4 was used and evaluated as described below. The results are shown in Table 4. In Table 4, the numerical value in parentheses of the component (A) means ε385 (unit: L · mol ⁻¹ · cm ⁻¹ ).

In addition, the number in (A) component and (B) component of Table 4 means a mass part.
The abbreviations in Table 4 mean the following, except for those defined above.

<(B) component>
◆ (B2) component M110: paracumylphenol ethylene oxide adduct (1.2 mol adduct) acrylate, Aronix (registered trademark) M-110 manufactured by Toagosei Co., Ltd.
BzA: benzyl acrylate, Osaka Organic Industry Co., Ltd. biscoat # 160
MPE (N): 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, light acrylate HOA-MPE (N) manufactured by Kyoeisha Chemical Co., Ltd.
-HBA: 4-Hydroxybutyl acrylate, Osaka Organic Chemical Industry Co., Ltd. 4-HBA
HEA: 2-Hydroxyethyl acrylate, Acrix HEA manufactured by Toagosei Co., Ltd.
LA: lauryl acrylate, Kyoeisha Chemical Co., Ltd. light acrylate LA

2) Evaluation
(1) Evaluation of curability Evaluation was carried out according to the same method as (1) in Examples 1 to 21 and Comparative Examples 1 to 4.
(2) Evaluation of Repeatability of Molding Mold Evaluation was performed according to the same method as (3) of Examples 1 to 21 and Comparative Examples 1 to 5.

(3) Evaluation of hot strength Using the obtained composition, a mold having a concave indentation having a mold size: length 100 mm × width 100 mm × thickness 1 mm on a 10 mm-thick polytetrafluoroethylene plate Except for the use mold, UV irradiation was performed in the same manner as in Examples 1 to 21 and Comparative Examples 1 to 4, and cured products were obtained.
The obtained cured product was cut into a No. 3 type dumbbell shape having a thickness of t1 mm, allowed to stand at 170 ° C. for 5 minutes, and then subjected to a tensile test at a distance between chucks of 60 mm and 100 mm / min. The stress at the time of rupture was defined as the hot strength.

(4) Evaluation of oil resistance Using the obtained composition, cured products were prepared in the same manner as in Examples 1 to 21 and Comparative Examples 1 to 4, and used as test pieces.
The obtained test piece was immersed in Lubricating Oil 3 (IRM903) defined by JIS K 6258: 2003, and allowed to stand at a temperature of 150 ° C. for 100 hours. Then, the test piece was taken out from the lubricating oil, the appearance was visually observed, and the following two levels were evaluated.
○: No change. X: A crack occurred.

3) Evaluation results As is clear from the results of Examples 22 to 27, when the photocurable LED curable composition of the present invention was used, the LED curability and the reusability of the mold were practical levels. .
In these examples, as component (A), ε385 contains a photopolymerization initiator having 200 L · mol ⁻¹ · cm ⁻¹ or more, and the reusability of the mold was particularly excellent.
The compositions of Examples 23 and 25 to 27 are compositions in which the component (B) includes the component (B1) and the component (B2), and the component (B2) includes a monofunctional acrylate having an aromatic ring. Yes, the component (B) contains the component (B1) and the component (B2), and the component (B2) contains a monofunctional acrylate having a long-chain alkyl group as the component. Was also excellent.
In the compositions of Examples 24 to 27, the component (B) includes a component (B1) and a component (B2), and the component (B2) includes a monofunctional acrylate having a hydroxyl group as the component (B2). ) Component was superior in oil resistance to the composition of Example 22 in which the component (B1) and a monofunctional acrylate having a long-chain alkyl group were used in combination.
In particular, in the compositions of Examples 25 and 26, the component (B) includes the component (B1) and the component (B2), and the component (B2) includes a monofunctional acrylate having an aromatic ring and a unit having a hydroxyl group. A composition containing a functional acrylate, the composition of Example 27, wherein the component (B) includes the component (B1) and the component (B2), and the component (B2) is a monofunctional compound having an aromatic ring and a hydroxyl group. It was a composition containing (meth) acrylate, and the compositions of these examples were excellent in heat resistance and oil resistance.

The light-curing LED curable composition of the present invention is excellent in LED curability and reusability of the mold. Therefore, it can be applied to various uses such as a lens sheet that is a display-related member, a heat ray reflective film that is a building material-related member, and a filter element that is an automobile-related member.

Claims

An LED curable composition for photomolding comprising the following component (A) and component (B).
(A) Component: Photopolymerization initiator having a molar absorption coefficient at 385 nm of 20 L · mol −1 · cm −1 or more (B) Component: Ethylenically unsaturated group-containing compound
2. The LED-curable photomolding for optical molding according to claim 1, wherein the component (A) is at least one selected from the group consisting of α-aminoalkylphenone compounds, acylphosphine oxide compounds, and germanium compounds. Composition.
The photocuring LED curable mold according to claim 1 or 2, wherein a content ratio of the component (A) is 0.05 parts by mass or more and less than 10 parts by mass with respect to 100 parts by mass of the component (B). Composition.
The LED curable composition for photomolding according to any one of claims 1 to 3, wherein the component (B) comprises a component (B1); an oligomer having two or more (meth) acryloyl groups. .
The (B) component is a compound having (B1) component and (B2) component; one (meth) acryloyl group, and (B2) component having an aromatic ring and one (meth) acryloyl group. The LED curable composition for photomolding according to claim 4, comprising:
The said (B) component contains (B1) component and (B2) component, and contains the compound which has a hydroxyl group and one (meth) acryloyl group as (B2) component. LED curable composition for photoforming.
The component (B) includes a component (B1) and a component (B2), and as the component (B2), a compound having an aromatic ring and one (meth) acryloyl group, a hydroxyl group and one (meth) acryloyl The compound which has a group and 1 or more types selected from the group which consists of a compound which has an aromatic ring, a hydroxyl group, and one (meth) acryloyl group in 1 molecule are included in Claim 4 or Claim 5. LED curable composition for photoforming.
The photocurable LED curable composition according to any one of claims 1 to 7, wherein the obtained cured composition has a hot strength of 0.3 MPa or more at 170 ° C.
The LED curable composition for photoforming according to any one of claims 1 to 8, which is applied to a display-related member.
The LED curable composition for photoforming according to any one of claims 1 to 8, which is applied to a building material-related member.
The photocurable LED curable composition according to any one of claims 1 to 8, which is applied to automobile-related members.
Filling the concave portion of the molding die in which the concave portion is formed with the photocurable LED curable composition according to any one of claims 1 to 11,
Arranging the mold so that the filled composition and the substrate are in close contact with each other;
From the side of the base material or the molding die, the LED light having a wavelength of 365 nm or more is irradiated from the side that transmits light of a wavelength of 365 nm or longer, and the composition is applied by the light transmitted through the base material or the molding die. A step of curing,
Manufacturing method of molded member.
Furthermore, the manufacturing method of the molded member of Claim 12 including the process of releasing the hardened | cured material obtained at the process of hardening the said composition from a shaping | molding die.
The method for producing a molded member according to claim 12 or 13, wherein a material of the molding die is a material selected from the group consisting of a metal, a fluorine resin, and a polyolefin resin.
The method for producing a molded member according to any one of claims 12 to 14, wherein the obtained molded member has a heat resistance of 170 ° C and a hot strength of 0.3 MPa or more.
The method for producing a molded member according to any one of claims 12 to 15, wherein the thickness of the obtained molded member is 0.5 mm or more.