WO2015181984A1 - Photocurable resin composition - Google Patents
Photocurable resin composition Download PDFInfo
- Publication number
- WO2015181984A1 WO2015181984A1 PCT/JP2014/064534 JP2014064534W WO2015181984A1 WO 2015181984 A1 WO2015181984 A1 WO 2015181984A1 JP 2014064534 W JP2014064534 W JP 2014064534W WO 2015181984 A1 WO2015181984 A1 WO 2015181984A1
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- WIPO (PCT)
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- component
- meth
- resin composition
- acrylate
- photocurable resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
- C08F222/1025—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate of aromatic dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
Abstract
Description
<1>(A)成分として、下記一般式(1)で表されるフルオレン系化合物、
(B)成分として、脂環式炭化水素基を有する単官能(メタ)アクリレート
(C)成分として、1個の芳香環を有する単官能(メタ)アクリレート
(D)成分として、光ラジカル重合開始剤、
を含有し、(A)~(C)成分の合計100質量部中、前記(A)成分の含有割合が10~70質量部であり、前記(B)成分の含有割合が5~65質量部であり、前記(C)成分の含有割合が5~65質量部である光硬化性樹脂組成物である。
<2>(B)成分は、ホモポリマーのガラス転移温度が40℃以上180℃以下であることが好ましい。
<3>更に(E)成分として、シランカップリング剤を含有することが好ましい。
<4>(E)成分は、フェニル基又は(メタ)アクリロイル基から選ばれる1個以上の官能基を有するシランカップリング剤であることが好ましい。
<5>温度25℃、波長589nmでの液屈折率が1.50以上であり、硬化物屈折率が1.53以上であることが好ましい。
<6>光硬化性樹脂組成物からなる被覆材であることが好ましい。
<7>被覆材を有する基材であることが好ましい。
<8>光硬化性樹脂組成物からなる層を基板上に形成した後に、前記の光硬化性樹脂組成物より低い屈折率を有する層を形成してなる膜であることが好ましい。
<9>膜を有する基材であることが好ましい。
<10>基材を有する素子であることが好ましい。
<11>光硬化性樹脂組成物からなる接着剤であることが好ましい。
<12>接着剤で接着された接合体であることが好ましい。
<13>接合体を有する光学部品であることが好ましい。 The present invention is as follows.
<1> As a component (A), a fluorene compound represented by the following general formula (1),
(B) Monofunctional (meth) acrylate having an alicyclic hydrocarbon group as component (C) Monofunctional (meth) acrylate having one aromatic ring as component (C) Photoradical polymerization initiator as component (D) ,
In a total of 100 parts by mass of the components (A) to (C), the content of the component (A) is 10 to 70 parts by mass, and the content of the component (B) is 5 to 65 parts by mass. And a content ratio of the component (C) is 5 to 65 parts by mass.
As for <2> (B) component, it is preferable that the glass transition temperature of a homopolymer is 40 degreeC or more and 180 degrees C or less.
<3> Furthermore, it is preferable to contain a silane coupling agent as a component (E).
<4> The component (E) is preferably a silane coupling agent having one or more functional groups selected from a phenyl group or a (meth) acryloyl group.
<5> The liquid refractive index at a temperature of 25 ° C. and a wavelength of 589 nm is preferably 1.50 or more, and the cured product refractive index is preferably 1.53 or more.
It is preferable that it is a coating material which consists of a <6> photocurable resin composition.
It is preferable that it is a base material which has a <7> coating material.
<8> A film formed by forming a layer made of a photocurable resin composition on a substrate and then forming a layer having a refractive index lower than that of the photocurable resin composition.
<9> A substrate having a film is preferred.
It is preferable that it is an element which has a <10> base material.
It is preferable that it is an adhesive agent which consists of a <11> photocurable resin composition.
<12> A bonded body bonded with an adhesive is preferable.
<13> An optical component having a joined body is preferable.
本明細書において、被覆材とは、ガラス基板、プラスチックフィルム、プラスチックシート等の基材上を、表面保護や意匠性を付与したり、及び反射防止や光導波といった機能性を付与したりすることを目的に被覆する材料を意味する。 <Explanation of terms>
In the present specification, the covering material is to impart surface protection, designability, or functionality such as antireflection or optical waveguide on a substrate such as a glass substrate, a plastic film, or a plastic sheet. It means a material coated for the purpose.
本実施形態の樹脂組成物は、(A)成分として、下記一般式(1)で表されるフルオレン系化合物を有する。
The resin composition of this embodiment has a fluorene compound represented by the following general formula (1) as the component (A).
本実施形態の樹脂組成物は(B)成分として、脂環式炭化水素基を有する単官能(メタ)アクリレートを含有する。 <(B) component: (meth) acrylate having an alicyclic hydrocarbon group>
The resin composition of this embodiment contains the monofunctional (meth) acrylate which has an alicyclic hydrocarbon group as (B) component.
本実施形態の樹脂組成物は(C)成分として、より屈折率を高めることを目的に1個の芳香環を有する単官能(メタ)アクリレートを含有する。 <(C) component: monofunctional (meth) acrylate having an aromatic ring>
The resin composition of this embodiment contains a monofunctional (meth) acrylate having one aromatic ring for the purpose of further increasing the refractive index as the component (C).
本実施の樹脂組成物は、(D)光ラジカル重合開始剤を含有する。光ラジカル重合開始剤は、エネルギー線を照射することによりラジカルが発生する化合物であれば、特に制限されない。 <(D) component: radical photopolymerization initiator>
The resin composition of the present embodiment contains (D) a radical photopolymerization initiator. The radical photopolymerization initiator is not particularly limited as long as it is a compound that generates radicals when irradiated with energy rays.
本発明の一実施形態として、樹脂組成物は、ガラス面への密着性を一層向上させることを目的に、(E)成分として、シランカップリング剤を更に含有することができる。シランカップリングとしては、γ-クロロプロピルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリクロルシラン、ビニルトリエトキシシラン、ビニル-トリス(β-メトキシエトキシ)シラン、γ-メタクリロイロキシプロピルトリメトキシシラン、γ-アクリロイロキシプロピルトリメトキシシラン、β-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、γ-メルカプトプロピルトリメトキシシラン、γ-アミノプロピルトリエトキシシラン、N-β-(アミノエチル)-γ-アミノプロピルトリメトキシシラン、N-β-(アミノエチル)-γ-アミノプロピルメチルジメトキシシラン、γ-ユレイドプロピルトリエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、p-スチリルトリメトキシシラン等が挙げられる。これらの中では、(メタ)アクリロイル基を有するシランカップリング剤、エポキシ基を有するシランカップリング剤、フェニル基を有するシランカップリング剤からなる群のうちの1種以上が好ましく、(メタ)アクリロイル基を有するシランカップリング剤とフェニル基を有するシランカップリング剤からなる群のうちの1種以上がより好ましい。(メタ)アクリロイル基を有するシランカップリング剤としては、γ-メタクリロイロキシプロピルトリメトキシシラン、γ-アクリロイロキシプロピルトリメトキシシラン等が挙げられる。エポキシ基を有するシランカップリング剤としては、γ-グリシドキシプロピルトリメトキシシラン、β-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン等が挙げられる。フェニル基を有するシランカップリング剤としては、フェニルトリメトキシシラン、フェニルトリエトキシシラン等が挙げられる。 <(E) component: Silane coupling agent>
As one embodiment of the present invention, the resin composition can further contain a silane coupling agent as the component (E) for the purpose of further improving the adhesion to the glass surface. Silane coupling includes γ-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ -Acryloyloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, phenyltrimethoxysilane, E sulfonyl triethoxysilane, p- styryltrimethoxysilane and the like. In these, 1 or more types in the group which consists of the silane coupling agent which has a (meth) acryloyl group, the silane coupling agent which has an epoxy group, and the silane coupling agent which has a phenyl group is preferable, (meth) acryloyl One or more members selected from the group consisting of a silane coupling agent having a group and a silane coupling agent having a phenyl group are more preferred. Examples of the silane coupling agent having a (meth) acryloyl group include γ-methacryloyloxypropyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, and the like. Examples of the silane coupling agent having an epoxy group include γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. Examples of the silane coupling agent having a phenyl group include phenyltrimethoxysilane and phenyltriethoxysilane.
本実施形態の目的を損なわない範囲で、酸化防止剤、アクリルゴム、ウレタンゴム等の各種エラストマー、光増感剤、光安定剤、溶剤、増量材、充填剤、補強材、可塑剤、増粘剤、染料、顔料、難燃剤及び界面活性剤等の添加剤を含有しても良い。 <Other additives>
As long as the purpose of the present embodiment is not impaired, various elastomers such as antioxidants, acrylic rubbers, urethane rubbers, photosensitizers, light stabilizers, solvents, fillers, fillers, reinforcing materials, plasticizers, thickeners You may contain additives, such as an agent, dye, a pigment, a flame retardant, and surfactant.
(A-1)9,9-ビス[4-(2-アクリロイルオキシエトキシ)フェニル]フルオレン(大阪ガスケミカル社製「BPFEA」)
(A-2)9,9-ビス[4-(2-アクリロイルオキシジエトキシ)フェニル]フルオレン(大阪ガスケミカル社製「オクゾールEA-0200」) (A) Fluorene compound (A-1) 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (Osaka Gas Chemical Co., Ltd. “BPFEA”)
(A-2) 9,9-bis [4- (2-acryloyloxydiethoxy) phenyl] fluorene (“Ocsol EA-0200” manufactured by Osaka Gas Chemical Company)
(B-1)ジシクロペンテニルオキシエチルメタクリレート(日立化成工業社製「ファンクリルFA-512M」、ホモポリマーTg:46℃)
(B-2)シクロヘキシルメタクリレート(共栄社化学社製「ライトエステルCH」、ホモポリマーTg:66℃)
(B-3)イソボルニルアクリレート(共栄社化学社製「ライトアクリレートIB-XA」、ホモポリマーTg:94℃)
(B-4)ジシクロペンテニルアクリレート(日立化成工業社製「ファンクリルFA-511AS」、ホモポリマーTg:120℃)
(B-5)2-メチル-2-アダマンチルメタクリレート(出光興産社製「アダマンテートMM」、ホモポリマーTg:170℃)
(B-6)ジシクロペンタニルメタクリレート(日立化成工業社製「ファンクリルFA-513M」、ホモポリマーTg:175℃)
(B-7)イソボルニルメタクリレート(共栄社化学社製「ライトエステルIB-X」、ホモポリマーTg:180℃) (B) (Meth) acrylate having an alicyclic hydrocarbon group (B-1) dicyclopentenyloxyethyl methacrylate (“Fancryl FA-512M” manufactured by Hitachi Chemical Co., Ltd., homopolymer Tg: 46 ° C.)
(B-2) Cyclohexyl methacrylate (Kyoeisha Chemical Co., Ltd. “Light Ester CH”, homopolymer Tg: 66 ° C.)
(B-3) Isobornyl acrylate (“Light acrylate IB-XA” manufactured by Kyoeisha Chemical Co., homopolymer Tg: 94 ° C.)
(B-4) Dicyclopentenyl acrylate (“Fancryl FA-511AS” manufactured by Hitachi Chemical Co., Ltd., homopolymer Tg: 120 ° C.)
(B-5) 2-Methyl-2-adamantyl methacrylate (“Adamantate MM” manufactured by Idemitsu Kosan Co., Ltd., homopolymer Tg: 170 ° C.)
(B-6) Dicyclopentanyl methacrylate (“Fancryl FA-513M” manufactured by Hitachi Chemical Co., Ltd., homopolymer Tg: 175 ° C.)
(B-7) Isobornyl methacrylate (Kyoeisha Chemical Co., Ltd. “Light Ester IB-X”, homopolymer Tg: 180 ° C.)
(C-1)フェノキシエチルアクリレート(共栄社化学社製「ライトアクリレートPO-A」)
(C-2)フェノキシエチルメタクリレート(共栄社化学社製「ライトエステルPO」)
(C-3)ベンジルアクリレート(大阪有機化学工業社製「ビスコート#160」)
(C-4)ベンジルメタクリレート(共栄社化学社製「ライトエステルBZ」) (C) Monofunctional (meth) acrylate having aromatic ring (C-1) Phenoxyethyl acrylate (“Light acrylate PO-A” manufactured by Kyoeisha Chemical Co., Ltd.)
(C-2) Phenoxyethyl methacrylate (Kyoeisha Chemical Co., Ltd. “Light Ester PO”)
(C-3) Benzyl acrylate (Osaka Organic Chemical Co., Ltd. “Biscoat # 160”)
(C-4) benzyl methacrylate (“Light Ester BZ” manufactured by Kyoeisha Chemical Co., Ltd.)
(D-1)1-ヒドロキシ-シクロヘキシルフェニルケトン(BASF社製「イルガキュアー184」)
(D-2)ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(BASF社製「イルガキュアー819」)
(D-3)ベンジルジメチルケタール(BASF社製「イルガキュアー651」) (D) Photoradical polymerization initiator (D-1) 1-hydroxy-cyclohexyl phenyl ketone (“IRGACURE 184” manufactured by BASF)
(D-2) Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (“Irgacure 819” manufactured by BASF)
(D-3) Benzyldimethyl ketal ("Irgacure 651" manufactured by BASF)
(E-1)γ-メタクリロイロキシプロピルトリメトキシシラン(信越シリコーン社製「KBM-503」)
(E-2)フェニルトリメトキシシラン(信越シリコーン社製「KBM-103」)
(E-3)フェニルトリエトキシシラン(信越シリコーン社製「KBE-103」) (E) Silane coupling agent (E-1) γ-methacryloyloxypropyltrimethoxysilane (“KBM-503” manufactured by Shin-Etsu Silicone)
(E-2) Phenyltrimethoxysilane (“KBM-103” manufactured by Shin-Etsu Silicone)
(E-3) Phenyltriethoxysilane (“KBE-103” manufactured by Shin-Etsu Silicone)
(F-1)2-エチルヘキシルメタクリレート(共栄社化学社製「ライトエステルEH」、ホモポリマーTg:-10℃)
(F-2)ビスフェノールAエチレンオキサイド変性ジアクリレート(東亞合成社製「アロニックスM-211B」)
(F-3)ビスフェノールFエチレンオキサイド変性ジアクリレート(東亞合成社製「アロニックスM-208」)
(F-4)エチレングリコールジメタクリレート(新中村化学工業社製「NKエステル1G」
(F-5)2-(o-フェニルフェノキシ)エチルアクリレート(新中村化学工業社製「NKエステルA-LEN-10」) As a comparative example, the following (meth) acrylate not corresponding to the above (B) and (C) was used.
(F-1) 2-Ethylhexyl methacrylate (“Eye ester EH” manufactured by Kyoeisha Chemical Co., homopolymer Tg: −10 ° C.)
(F-2) Bisphenol A ethylene oxide-modified diacrylate (“Aronix M-211B” manufactured by Toagosei Co., Ltd.)
(F-3) Bisphenol F ethylene oxide modified diacrylate (“Aronix M-208” manufactured by Toagosei Co., Ltd.)
(F-4) Ethylene glycol dimethacrylate (“Nk ester 1G” manufactured by Shin-Nakamura Chemical Co., Ltd.)
(F-5) 2- (o-phenylphenoxy) ethyl acrylate (“NK Ester A-LEN-10” manufactured by Shin-Nakamura Chemical Co., Ltd.)
表1~表4に示す種類の原材料を、表1~表4に示す含有割合(単位は質量部)で混合し、被覆材用樹脂組成物を調製し、後述の評価を実施した。各種評価結果を表1~表4に示す。特記しない限り、23℃、湿度50%の環境下で実施した。 (Examples 1 to 30, Comparative Examples 1 to 10)
The raw materials of the types shown in Tables 1 to 4 were mixed in the content ratios (units are parts by mass) shown in Tables 1 to 4 to prepare a resin composition for a coating material, and the evaluation described below was performed. Various evaluation results are shown in Tables 1 to 4. Unless otherwise specified, the test was carried out in an environment of 23 ° C. and 50% humidity.
〔粘度〕
E型粘度計を用いて、温度25℃のときの粘度を測定した。
〔固着時間〕
耐熱ガラス(商品名「耐熱パイレックス(登録商標)ガラス」、25mm×25mm×2.0mm)を使用した。一方の耐熱ガラスに接着剤を膜厚30μmで塗布した後に、他方の耐熱ガラスを重ねた。超高圧水銀ランプ搭載装置(HOYA社製「UL-750」)にて、365nmの波長の照射強度30mW/cm2の条件で、紫外線を照射させながら、耐熱ガラスに4kgの荷重を負荷し、耐熱ガラスを動かした。紫外線を照射してから、荷重を負荷しても耐熱ガラスが動かなくなるまでの時間を測定した。 〔Evaluation methods〕
〔viscosity〕
The viscosity at a temperature of 25 ° C. was measured using an E-type viscometer.
[Fixing time]
Heat-resistant glass (trade name “Heat-resistant Pyrex (registered trademark) glass”, 25 mm × 25 mm × 2.0 mm) was used. After applying the adhesive to one heat-resistant glass with a film thickness of 30 μm, the other heat-resistant glass was stacked. A 4 kg load was applied to the heat-resistant glass while irradiating it with ultraviolet rays under the condition of an irradiation intensity of 30 mW / cm 2 at a wavelength of 365 nm with an ultra-high pressure mercury lamp mounting device (“UL-750” manufactured by HOYA). I moved the glass. The time until the heat-resistant glass stopped moving even when a load was applied was measured after irradiation with ultraviolet rays.
(1)液屈折率
液屈折率の評価は、多波長アッベ屈折率計(アタゴ社製「DR-M2」)を用いて、温度25℃、波長589nmにおける屈折率を測定した。
(2)硬化物屈折率
接着剤組成物を容積15mm×15mm×1.0mmのシリコーンゴム製の型枠に流し込んだ。超高圧水銀ランプ搭載装置(HOYA社製「UL-750」)にて、365nmの波長の照射強度30mW/cm2、積算光量3,000mJ/cm2の条件にて硬化した硬化物試験片を作製し、屈折率を評価した。屈折率の評価は、多波長アッベ屈折率計(アタゴ社製「DR-M2」)を用いて、温度25℃、波長589nmにおける屈折率を測定した。 (Evaluation of refractive index)
(1) Liquid Refractive Index The liquid refractive index was evaluated by measuring the refractive index at a temperature of 25 ° C. and a wavelength of 589 nm using a multi-wavelength Abbe refractometer (“DR-M2” manufactured by Atago Co., Ltd.).
(2) Cured Product Refractive Index The adhesive composition was poured into a silicone rubber mold having a volume of 15 mm × 15 mm × 1.0 mm. A cured product test piece cured under the conditions of an irradiation intensity of 30 mW / cm 2 at a wavelength of 365 nm and an integrated light quantity of 3,000 mJ / cm 2 using an ultra-high pressure mercury lamp mounting device (“UL-750” manufactured by HOYA) And the refractive index was evaluated. The refractive index was evaluated by measuring the refractive index at a temperature of 25 ° C. and a wavelength of 589 nm using a multiwavelength Abbe refractometer (“DR-M2” manufactured by Atago Co., Ltd.).
樹脂組成物を耐熱ガラス(商品名「耐熱パイレックス(登録商標)ガラス」、25mm×25mm×2.0mm)上に膜厚30μmで塗布した後に、超高圧水銀ランプ搭載装置(HOYA社製「UL-750」)にて、365nmの波長の照射強度30mW/cm2、積算光量3,000mJ/cm2の条件にて硬化した試験片を作製した。紫外-可視分光光度計(島津製作所社製「UV-2550」)を用いて、リファレンスを耐熱ガラスとして、400nmの透過率を測定した。 [Evaluation of spectral transmittance]
The resin composition was applied on a heat-resistant glass (trade name “heat-resistant Pyrex (registered trademark) glass”, 25 mm × 25 mm × 2.0 mm) with a film thickness of 30 μm, and then an ultra-high pressure mercury lamp mounting device (“UL-” manufactured by HOYA). 750 "), a test piece cured under conditions of an irradiation intensity of a wavelength of 365 nm of 30 mW / cm 2 and an integrated light amount of 3,000 mJ / cm 2 was produced. Using a UV-visible spectrophotometer (“UV-2550” manufactured by Shimadzu Corporation), the transmittance was measured at 400 nm using heat resistant glass as a reference.
125μm厚のポリエステルフィルム(東洋紡績社製「コスモシャインA4100」)上に、超高圧水銀ランプ搭載装置(HOYA社製「UL-750」)にて、365nmの波長の照射強度30mW/cm2、積算光量3,000mJ/cm2、窒素雰囲気下の条件にて、樹脂組成物を硬化し、形状が20mm×20mm×80μmの樹脂組成物の硬化膜を形成した試験片を作製した。
このようにして得られた各試験片に対して、温度23℃、相対湿度50%の環境下で、硬化膜に縦2mm×横2mm×25マスになるようにカットラインを入れた後、セロファンテープ(ニチバン社製型式CT-405AP:幅24mm、粘着力23N/10mm)を貼り付けて180°剥離を実施した。180°剥離後に残ったマスの数を数え、評価した。その他、特に明示のない条件はJIS K 5600-5-6に従った。 [Adhesion evaluation (cross cut test)]
On a 125 μm-thick polyester film (“Cosmo Shine A4100” manufactured by Toyobo Co., Ltd.), with an ultra-high pressure mercury lamp mounting device (“UL-750” manufactured by HOYA), irradiation intensity of a wavelength of 365 nm is 30 mW / cm 2 . A test piece in which the resin composition was cured under the conditions of a light intensity of 3,000 mJ / cm 2 and a nitrogen atmosphere to form a cured film of the resin composition having a shape of 20 mm × 20 mm × 80 μm was produced.
For each test piece obtained in this manner, a cut line was placed in the cured film so as to be 2 mm long × 2 mm wide × 25 squares in an environment of a temperature of 23 ° C. and a relative humidity of 50%, and then cellophane. A tape (model CT-405AP manufactured by Nichiban Co., Ltd .: width 24 mm, adhesive strength 23 N / 10 mm) was applied and 180 ° peeling was performed. The number of cells remaining after 180 ° peeling was counted and evaluated. Other conditions that were not specified were in accordance with JIS K 5600-5-6.
耐熱ガラス(商品名「耐熱パイレックス(登録商標)ガラス」、25mm×25mm×2.0mm)上に、樹脂組成物を、直径8mmの円状に膜厚80μmで塗布した後に、超高圧水銀ランプ搭載装置(HOYA社製「UL-750」)にて、365nmの波長の照射強度30mW/cm2、積算光量3,000mJ/cm2の条件にて硬化した試験片を作製した。作製した試験片は、23℃、湿度50%RHの環境で、引張試験機を使用して、引張速度10mm/分で引張せん断接着強さを測定した。 [Evaluation of tensile shear bond strength]
A resin composition is applied to a heat-resistant glass (trade name “heat-resistant Pyrex (registered trademark) glass”, 25 mm × 25 mm × 2.0 mm) in a circular shape with a diameter of 8 mm and a film thickness of 80 μm, and then mounted on an ultra-high pressure mercury lamp. A cured test piece was prepared with an apparatus (“UL-750” manufactured by HOYA) under conditions of an irradiation intensity of a wavelength of 365 nm of 30 mW / cm 2 and an integrated light amount of 3,000 mJ / cm 2 . The produced test piece was measured for tensile shear bond strength at a tensile rate of 10 mm / min using a tensile tester in an environment of 23 ° C. and humidity 50% RH.
耐熱ガラス(商品名「耐熱パイレックス(登録商標)ガラス」、25mm×25mm×2.0mm)上に、樹脂組成物を、膜厚30μmで塗布した後に、超高圧水銀ランプ搭載装置(HOYA社製「UL-750」)にて、365nmの波長の照射強度30mW/cm2、積算光量3,000mJ/cm2の条件にて硬化した試験片を作製した。耐光試験機(スガ試験機社製「キセノンウェザメーターX75」)を用いて、照度50W/m2の光を、作製した試験片の樹脂側に100時間連続照射した。照射後の試験片について、紫外-可視分光光度計(島津製作所社製「UV-2550」)を用いて、400nmの透過率を測定した。尚、リファレンスには耐熱ガラスを用いた。 [Evaluation of light resistance (light resistance test)]
After applying the resin composition to heat-resistant glass (trade name “heat-resistant Pyrex (registered trademark) glass”, 25 mm × 25 mm × 2.0 mm) with a film thickness of 30 μm, an ultra-high pressure mercury lamp mounting device (manufactured by HOYA “ UL-750 "), a test piece cured under conditions of an irradiation intensity of a wavelength of 365 nm of 30 mW / cm 2 and an integrated light amount of 3,000 mJ / cm 2 was produced. Using a light resistance tester (“Xenon Weather Meter X75” manufactured by Suga Test Instruments Co., Ltd.), light having an illuminance of 50 W / m 2 was continuously irradiated to the resin side of the prepared test piece for 100 hours. About the test piece after irradiation, the transmittance | permeability of 400 nm was measured using the ultraviolet-visible spectrophotometer (Shimadzu Corporation "UV-2550"). In addition, heat resistant glass was used for the reference.
Claims (13)
- (A)成分として、下記一般式(1)で表されるフルオレン系化合物、
(B)成分として、脂環式炭化水素基を有する単官能(メタ)アクリレート
(C)成分として、1個の芳香環を有する単官能(メタ)アクリレート
(D)成分として、光ラジカル重合開始剤、
を含有し、(A)~(C)成分の合計100質量部中、前記(A)成分の含有割合が10~70質量部であり、前記(B)成分の含有割合が5~65質量部であり、前記(C)成分の含有割合が5~65質量部である光硬化性樹脂組成物。 As the component (A), a fluorene compound represented by the following general formula (1),
(B) Monofunctional (meth) acrylate having an alicyclic hydrocarbon group as component (C) Monofunctional (meth) acrylate having one aromatic ring as component (C) Photoradical polymerization initiator as component (D) ,
In a total of 100 parts by mass of the components (A) to (C), the content of the component (A) is 10 to 70 parts by mass, and the content of the component (B) is 5 to 65 parts by mass. A photocurable resin composition wherein the content of the component (C) is 5 to 65 parts by mass. - (B)成分は、ホモポリマーのガラス転移温度が40℃以上180℃以下である請求項1に記載の光硬化性樹脂組成物。 The photocurable resin composition according to claim 1, wherein the component (B) has a glass transition temperature of the homopolymer of 40 ° C or higher and 180 ° C or lower.
- 更に(E)成分として、シランカップリング剤を含有する請求項1~2のいずれか1項に記載の光硬化性樹脂組成物。 The photocurable resin composition according to claim 1, further comprising a silane coupling agent as component (E).
- (E)成分は、フェニル基又は(メタ)アクリロイル基から選ばれる1個以上の官能基を有するシランカップリング剤である請求項3に記載の光硬化性樹脂組成物。 The photocurable resin composition according to claim 3, wherein the component (E) is a silane coupling agent having one or more functional groups selected from a phenyl group or a (meth) acryloyl group.
- 温度25℃、波長589nmでの液屈折率が1.50以上であり、硬化物屈折率が1.53以上である請求項1~4のいずれか1項に記載の光硬化性樹脂組成物。 The photocurable resin composition according to any one of claims 1 to 4, wherein the liquid refractive index at a temperature of 25 ° C and a wavelength of 589 nm is 1.50 or more and the refractive index of the cured product is 1.53 or more.
- 請求項1~5のいずれか1項に記載の光硬化性樹脂組成物からなる被覆材。 A coating material comprising the photocurable resin composition according to any one of claims 1 to 5.
- 請求項6に記載の被覆材を有する基材。 A base material having the coating material according to claim 6.
- 請求項1~5のいずれか1項に記載の光硬化性樹脂組成物からなる層を基板上に形成した後に、前記の光硬化性樹脂組成物より低い屈折率を有する層を形成してなる膜。 A layer having a refractive index lower than that of the photocurable resin composition is formed after a layer made of the photocurable resin composition according to any one of claims 1 to 5 is formed on a substrate. film.
- 請求項8に記載の膜を有する基材。 A substrate having the film according to claim 8.
- 請求項9に記載の基材を有する素子。 An element having the base material according to claim 9.
- 請求項1~5のいずれか1項に記載の光硬化性樹脂組成物からなる接着剤。 An adhesive comprising the photocurable resin composition according to any one of claims 1 to 5.
- 請求項11に記載の接着剤で接着された接合体。 A joined body bonded with the adhesive according to claim 11.
- 請求項12に記載の接合体を有する光学部品。 An optical component having the joined body according to claim 12.
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CN114787210A (en) * | 2020-03-03 | 2022-07-22 | 电化株式会社 | Composition comprising a metal oxide and a metal oxide |
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