JP2021088650A - Ultraviolet-curable resin composition - Google Patents

Ultraviolet-curable resin composition Download PDF

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JP2021088650A
JP2021088650A JP2019219194A JP2019219194A JP2021088650A JP 2021088650 A JP2021088650 A JP 2021088650A JP 2019219194 A JP2019219194 A JP 2019219194A JP 2019219194 A JP2019219194 A JP 2019219194A JP 2021088650 A JP2021088650 A JP 2021088650A
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JP7426218B2 (en
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佑紀 中野
Yuuki Nakano
佑紀 中野
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Aica Kogyo Co Ltd
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Abstract

To provide a resin composition for injection molding, excellent in curability even when an LED light source is used and excellent in storage stability, which is an ultraviolet-curable resin suitable for handcrafted accessories such as brooches and small articles.SOLUTION: An ultraviolet-curable resin composition is provided, comprising a polyfunctional urethane acrylate oligomer having at least two functional groups, a (meth)acrylate monomer, a photopolymerization initiator, a phosphate, a thiol having four or more functional groups, and a stabilizer, in which the compounding amount of the thiol is 1.0 to 15 pts.wt. and the compounding amount of the stabilizer is 0.01 to 3 pts.wt. relative to total 100 pts.wt. of the urethane acrylate oligomer and the (meth)acrylate monomer.SELECTED DRAWING: None

Description

本発明は、紫外線硬化型で保存安定性に優れた樹脂組成物に関する。 The present invention relates to a resin composition that is ultraviolet curable and has excellent storage stability.

アクリル系の光硬化型樹脂は、プラスチックフィルムやプラスチック成型物表面に特別な性能を付与するために多くの分野で使用されている。例えばPET(ポリエチレンテレフタレート)フィルム上に塗布して高硬度を付与したハードコートフィルムは、タッチパネル製品で大量に使用されており、また当該フィルムに粘性を付与した粘着フィルムはフラットパネルディスプレイ製品で最終製品をはじめ、製造工程における保護フィルムとしても使用されている。 Acrylic-based photocurable resins are used in many fields to impart special performance to the surfaces of plastic films and plastic moldings. For example, hard coat films that are applied on PET (polyethylene terephthalate) film to give high hardness are used in large quantities in touch panel products, and adhesive films that give viscosity to the film are final products of flat panel display products. It is also used as a protective film in the manufacturing process.

こうしたプラスチック表面に薄膜で塗布し、特別な性能を付与する分野以外でも、アクリル樹脂はその硬さや透明性を生かし、ブローチや小物などのアクセサリーを自作するための注形用樹脂として使用されている(特許文献1)。そして過去に出願人は、同用途でポリエーテル骨格の数平均分子量が1,000〜7,000の2官能のウレタン(メタ)アクリレート樹脂と、単官能メタクリレートモノマーまたは芳香族アクリレートモノマーまたは極性基を持たない脂肪族アクリレートモノマーと、光重合開始剤からなる組成物を発明している(特許文献2)。 Acrylic resin is used as a casting resin for making accessories such as brooches and small items by taking advantage of its hardness and transparency, even outside the field of applying a thin film to the plastic surface to give it special performance. (Patent Document 1). In the past, applicants have used bifunctional urethane (meth) acrylate resins with a polyether skeleton with a number average molecular weight of 1,000 to 7,000 and monofunctional methacrylate monomers or aromatic acrylate monomers or polar groups for the same purpose. He has invented a composition comprising an aliphatic acrylate monomer which does not have and a photopolymerization initiator (Patent Document 2).

この発明は、ブラックライト光源で硬化させても、べとつきなどを残さず充分に硬化するという特徴を有した優れたものであった。しかしながら、保存安定性という点では十分でなく、特に高温環境下では増粘しやすいという課題があり、LED光源であっても硬化性が高く、尚且つ高温環境下でも増粘しにくく保存安定性が高いという異なる要求性能を両立させる点で改善の余地があった。 The present invention was excellent in that it was sufficiently cured without leaving stickiness even when cured with a black light light source. However, it is not sufficient in terms of storage stability, and there is a problem that it is easy to thicken even in a high temperature environment. Even an LED light source has high curability, and it is difficult to thicken even in a high temperature environment. There was room for improvement in terms of achieving both the different required performances of high LED.

特開平10-264184号公報Japanese Unexamined Patent Publication No. 10-264184 特許6335853号公報Japanese Patent No. 6335583

本発明の課題は、ブローチや小物などのアクセサリーを自作するような注形成型に適した紫外線硬化樹脂で、紫外線照射光源がLEDでも硬化性に優れ、且つ高温環境下でも増粘しにくく保存安定性にすぐれた樹脂組成物を提供する事にある。 The subject of the present invention is an ultraviolet curable resin suitable for a casting type such as making accessories such as brooches and small items by oneself, which has excellent curability even when the ultraviolet irradiation light source is an LED, and is hard to thicken even in a high temperature environment and is stable in storage. It is an object of the present invention to provide a resin composition having excellent properties.

請求項1の発明は、2官能を少なくとも含む多官能ウレタンアクリレートオリゴマー(A)と、(メタ)アクリレートモノマー(B)と、光重合開始剤(C)と、リン酸エステル(D)と、4官能以上のチオール(E)と、安定剤(F)を含み、前記(A)と(B)の合計100重量部に対する(E)の配合量が1.0〜15重量部で、(F)の配合量が0.01〜3重量部であることを特徴とする紫外線硬化樹脂組成物を提供する。 The invention of claim 1 comprises a polyfunctional urethane acrylate oligomer (A) containing at least a bifunctionality, a (meth) acrylate monomer (B), a photopolymerization initiator (C), a phosphoric acid ester (D), and 4 (F) contains 1.0 to 15 parts by weight of (E) with respect to 100 parts by weight of the total of (A) and (B), which contains a functional or higher thiol (E) and a stabilizer (F). Provided is an ultraviolet curable resin composition characterized by a blending amount of 0.01 to 3 parts by weight.

また、請求項2の発明は、前記(B)の(メタ)アクリレートモノマーが水酸基を含む単官能(メタ)アクリレートモノマー及び/又は2官能直鎖骨格(メタ)アクリレートモノマーを含むことを特徴とする請求項1記載の光硬化性樹脂組成物を提供する。 The invention of claim 2 is characterized in that the (meth) acrylate monomer of (B) contains a monofunctional (meth) acrylate monomer containing a hydroxyl group and / or a bifunctional linear skeleton (meth) acrylate monomer. The photocurable resin composition according to claim 1 is provided.

また、請求項3の発明は、前記(A)と(B)の合計に対する(A)の配合量が50重量%以上であることを特徴とする請求項1又は2いずれか記載の光硬化性樹脂組成物を提供する。 The photocurable according to claim 1, wherein the blending amount of (A) with respect to the total of (A) and (B) is 50% by weight or more. A resin composition is provided.

また、請求項4の発明は、更に重合禁止剤(G)を含むことを特徴とする、請求項1〜3いずれか記載の光硬化性樹脂組成物を提供する。 The invention of claim 4 further provides the photocurable resin composition according to any one of claims 1 to 3, further comprising a polymerization inhibitor (G).

また、請求項5の発明は、注形成型用樹脂であることを特徴とする、請求項1〜4いずれか記載の光硬化性樹脂組成物を提供する。 The invention of claim 5 provides the photocurable resin composition according to any one of claims 1 to 4, characterized in that it is a injection-forming resin.

本発明の組成物は、紫外線照射光源がLEDでも硬化性に優れ、且つ高温環境下でも増粘しにくく保存安定性にすぐれており、ブローチや小物などのアクセサリーを自作する手芸用途に適した紫外線硬化型の注形成型用組成物として有用である。 The composition of the present invention has excellent curability even when the ultraviolet irradiation light source is an LED, is hard to thicken even in a high temperature environment, and has excellent storage stability, and is suitable for handicraft use for making accessories such as brooches and accessories. It is useful as a curable injection-forming composition.

本発明の紫外線硬化樹脂組成物の構成は、多官能ウレタン(メタ)アクリレートオリゴマー(A)と、(メタ)アクリレートモノマー(B)と、光重合開始剤(C)と、リン酸エステル(D)と、4官能以上チオール(E)と、安定剤(F)である。なお、本明細書において、(メタ)アクリレートは、アクリレートとメタクリレートとの双方を包含する。 The composition of the ultraviolet curable resin composition of the present invention comprises a polyfunctional urethane (meth) acrylate oligomer (A), a (meth) acrylate monomer (B), a photopolymerization initiator (C), and a phosphoric acid ester (D). , A tetrafunctional or higher thiol (E), and a stabilizer (F). In addition, in this specification, (meth) acrylate includes both acrylate and methacrylate.

本発明に使用される多官能ウレタン(メタ)アクリレートオリゴマー(A)は、硬化皮膜を構成する主要成分の1つで、例えばポリオールとポリイソシアネートを反応して得られる化合物の両末端に、更にヒドロキシ(メタ)アクリレートを反応させて生成され、1分子中に2個以上の(メタ)アクリロイル基とウレタン結合を有する構造が挙げられる。官能基数としては反応性、硬化収縮、保存安定性のバランスが良好な点で2官能のウレタン(メタ)アクリレートオリゴマーを含む。 The polyfunctional urethane (meth) acrylate oligomer (A) used in the present invention is one of the main components constituting the cured film, and is further hydroxy at both ends of a compound obtained by reacting a polyol with a polyisocyanate, for example. Examples thereof include a structure produced by reacting (meth) acrylate and having two or more (meth) acryloyl groups and urethane bonds in one molecule. The number of functional groups includes a bifunctional urethane (meth) acrylate oligomer in that it has a good balance of reactivity, curing shrinkage, and storage stability.

前記ポリオールとしてはポリエーテル系、ポリエステル系、ポリカーボネート系、ポリジエン系などが挙げられるが、これらの中では高伸度のポリエーテル系が好ましく、ポリテトラメチレングリコール(以下PTMG)が更に好ましい。またポリイソシアネートとしては芳香族系、脂肪族系、脂環族系などが挙げられるが、これらの中では耐候性に優れる非芳香族系が好ましく、硬度を高くできるイソホロンジイソシアネート(以下IPDI)が更に好ましい。 Examples of the polyol include polyether-based, polyester-based, polycarbonate-based, and polydiene-based, and among these, polyether-based products having high elongation are preferable, and polytetramethylene glycol (hereinafter referred to as PTMG) is more preferable. Examples of the polyisocyanate include aromatics, aliphatics, and alicyclics. Among these, non-aromatics having excellent weather resistance are preferable, and isophorone diisocyanate (hereinafter, IPDI) capable of increasing hardness is further used. preferable.

前記(A)における2官能ウレタン(メタ)アクリレートオリゴマーの配合比率は30〜100重量%であることが好ましく、80〜100重量%であることが更に好ましく、90〜100重量%であることが特に好ましい。30重量%以上とすることで、十分な保存安定性を確保できるが、80重量%以上とすることで更に安定性を向上させることができる。 The blending ratio of the bifunctional urethane (meth) acrylate oligomer in (A) is preferably 30 to 100% by weight, more preferably 80 to 100% by weight, and particularly preferably 90 to 100% by weight. preferable. When the content is 30% by weight or more, sufficient storage stability can be ensured, but when the content is 80% by weight or more, the stability can be further improved.

前記(A)の重量平均分子量(以下Mw)は、1000〜20000であることが好ましく、1500〜10000であることが更に好ましく、1500〜5000であることが特に好ましい。1000以上とすることで十分な硬度の硬化物とすることができ、20000以下とすることで作業性に適した粘度に調整しやすくなる。なおMwは、ゲル浸透クロマトグラフィーにより、スチレンジビニルベンゼン基材の充填材を用いたカラムでテトラハイドロフラン溶離液を用いて、標準ポリスチレン換算の分子量を測定、算出した。 The weight average molecular weight (hereinafter referred to as Mw) of (A) is preferably 1000 to 20000, more preferably 1500 to 10000, and particularly preferably 1500 to 5000. When it is 1000 or more, a cured product having sufficient hardness can be obtained, and when it is 20000 or less, it becomes easy to adjust the viscosity to be suitable for workability. Mw was calculated by measuring and calculating the molecular weight in terms of standard polystyrene by gel permeation chromatography using a tetrahydrofuran eluent on a column using a filler based on styrenedivinylbenzene.

前記(A)の配合量は、固形分全量に対し40〜75重量%が好ましく、45〜70重量%が更に好ましい。40重量%以上とすることで充分な硬化性を確保することが可能となり、75重量%以下とすることで作業性に適した粘度に調整しやすくなる。 The blending amount of (A) is preferably 40 to 75% by weight, more preferably 45 to 70% by weight, based on the total solid content. When it is 40% by weight or more, sufficient curability can be ensured, and when it is 75% by weight or less, it becomes easy to adjust the viscosity to be suitable for workability.

本発明に使用される(メタ)アクリレートモノマー(B)は、作業性の良い粘度に調整するための反応性希釈剤として配合される。官能基数は、2官能以下の(メタ)アクリレートモノマーの比率が(B)全体に対し80重量%以上を占めることが好ましい。80重量%未満の場合は硬化性が低下し、硬化物の表面にベタツキが残りやすくなり、また3官能以上の比率が多くなるにつれ硬化収縮が大きくなる傾向がある。 The (meth) acrylate monomer (B) used in the present invention is blended as a reactive diluent for adjusting the viscosity to have good workability. As for the number of functional groups, it is preferable that the ratio of the bifunctional or less functional (meth) acrylate monomer accounts for 80% by weight or more with respect to the whole (B). If it is less than 80% by weight, the curability is lowered, stickiness tends to remain on the surface of the cured product, and the curing shrinkage tends to increase as the ratio of trifunctional or higher increases.

前記2官能以下の(メタ)アクリレートモノマーとしては、例えば直鎖(分岐)アルキル骨格、脂肪族環式骨格、エーテル骨格、芳香環含有、水酸基含有、アミノ基含有、ヘテロ環含有などの(メタ)アクリレートモノマーが挙げられ、単独あるいは2種以上を組み合わせて使用することができる。これらの中では、硬化性が良好な点で、水酸基含有の(メタ)アクリレートモノマー、及び直鎖骨格の(メタ)アクリレートモノマーが好ましく、例えば2−ヒドロキシエチル(メタ)アクリレート、2‐ヒドロキシプロピル(メタ)アクリレート、2−ヒドロキシブチル(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、(ポリ)エチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、(ポリ)プロピレングリコールジ(メタ)アクリレート、1.4−ブタンジオールジ(メタ)アクリレート、1.6−ヘキサンジオールジ(メタ)アクリレートなどがが挙げられ、特に2‐ヒドロキシプロピルメタクリレート、1.6−ヘキサンジオールジアクリレート、ポリエチレングリコールジアクリレート(n<10)が好ましい。 Examples of the bifunctional or lower (meth) acrylate monomer include (meth) such as a linear (branched) alkyl skeleton, an aliphatic cyclic skeleton, an ether skeleton, an aromatic ring-containing, a hydroxyl group-containing, an amino group-containing, and a heterocyclic skeleton. Examples thereof include acrylate monomers, which can be used alone or in combination of two or more. Among these, a hydroxyl group-containing (meth) acrylate monomer and a linear skeleton (meth) acrylate monomer are preferable in terms of good curability, and for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( Meta) acrylate, 2-hydroxybutyl (meth) acrylate, ethylene glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate , 1.4-Butanediol di (meth) acrylate, 1.6-hexanediol di (meth) acrylate and the like, and in particular 2-hydroxypropyl methacrylate, 1.6-hexanediol diacrylate, polyethylene glycol diacrylate and the like. (N <10) is preferable.

前記(B)の配合量は、固形分全量に対し10〜40重量%が好ましく、15〜35重量%が更に好ましい。10重量%以上とすることで作業性に適した粘度に調整しやすくなりすることができ、40重量%以下とすることで充分な硬化性を確保できる。 The blending amount of (B) is preferably 10 to 40% by weight, more preferably 15 to 35% by weight, based on the total solid content. When it is 10% by weight or more, it is easy to adjust the viscosity to be suitable for workability, and when it is 40% by weight or less, sufficient curability can be ensured.

本発明で使用される光重合開始剤(C)は、紫外線や電子線などの照射でラジカルを生じ、そのラジカルが重合反応のきっかけとなるもので、ベンジルケタール系、アセトフェノン系、フォスフィンオキサイド系等汎用の光重合開始剤が使用できる。重合開始剤の光吸収波長を任意に選択することによって、紫外線領域から可視光領域にいたる広い波長範囲にわたって硬化性を付与することができる。具体的にはベンジルケタール系として2.2-ジメトキシ-1.2-ジフェニルエタン-1-オンが、α−ヒドロキシアセトフェノン系として1−ヒドロキシ−シクロヘキシル−フェニル−ケトン及び1−[4−(2−ヒドロキシエトキシ)−フェニル]−2−ヒドロキシ−2−メチル−1−プロパン−1−オンが、α-アミノアセトフェノン系として2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン-1-オンが、アシルフォスフィンオキサイド系として2.4.6-トリメチルベンゾイル-ジフェニル-フォスフィンオキサイド及びビス(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等があり、単独または2種以上を組み合わせて使用できる。 The photopolymerization initiator (C) used in the present invention generates radicals by irradiation with ultraviolet rays, electron beams, etc., and the radicals trigger a polymerization reaction, and is benzylketal-based, acetophenone-based, or phosphine oxide-based. A general-purpose photopolymerization initiator can be used. By arbitrarily selecting the light absorption wavelength of the polymerization initiator, curability can be imparted over a wide wavelength range from the ultraviolet region to the visible light region. Specifically, 2.2-dimethoxy-1.2-diphenylethane-1-one as a benzyl ketal system, 1-hydroxy-cyclohexyl-phenyl-ketone and 1- [4- (2- (2- (2-)) as an α-hydroxyacetophenone system. Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one is a 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1 as an α-aminoacetophenone system. -On includes 2.4.6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2.4.6-trimethylbenzoyl) -phenylphosphine oxide as acylphosphine oxide systems, alone or in combination of two or more. Can be used in combination.

前記(C)の中では、黄変しにくいα−ヒドロキシアセトフェノン系、及び内部硬化性に優れるアシルフォスフィンオキサイド系を含むことが好ましい。特に注形成型のように硬化皮膜が100μm以上と厚膜化する場合は、アシルフォスフィンオキサイド系の配合が効果的であり、更に両者の併用が好ましい。市販品としてはα−ヒドロキシアセトフェノン系でOmnirad184が、フォスフィンオキサイド系でOmnirad TPO H(商品名:iGM Resins社製)などがある。 In the above (C), it is preferable to contain an α-hydroxyacetophenone type that is hard to yellow and an acylphosphine oxide type that is excellent in internal curability. In particular, when the cured film is thickened to 100 μm or more as in the injection type, the acylphosphine oxide system is effective, and the combined use of both is preferable. Commercially available products include α-hydroxyacetophenone-based Omnirad 184 and phosphine oxide-based Omnirad TPO H (trade name: manufactured by iGM Resins).

前記(C)の配合量は、ラジカル重合性成分100重量部に対して、1〜25重量部配合することが好ましく、10〜20重量部が更に好ましく、12〜18重量部が特に好ましい。この範囲で配合する事により、組成物を効率的に硬化させる事ができる。α−ヒドロキシアセトフェノン系とアシルフォスフィンオキサイド系を併用する場合の配合比率は、α−ヒドロキシアセトフェノン系100重量部に対し、アシルフォスフィンオキサイド系20〜60重量部が好ましい。 The blending amount of (C) is preferably 1 to 25 parts by weight, more preferably 10 to 20 parts by weight, and particularly preferably 12 to 18 parts by weight with respect to 100 parts by weight of the radically polymerizable component. By blending in this range, the composition can be cured efficiently. When the α-hydroxyacetophenone system and the acylphosphine oxide system are used in combination, the blending ratio is preferably 20 to 60 parts by weight of the acylphosphine oxide system with respect to 100 parts by weight of the α-hydroxyacetophenone system.

本発明に使用されるリン酸エステル(D)は、高温たとえば60℃での保存時における粘度増加を抑える役割で配合する。硬化皮膜からのブリードが発生しにくくなるよう、(メタ)アクリロイル基等の光反応官能基を有することが好ましい。市販品としてはPM-2(商品名:日本化薬社製)及びPM−21(商品名:同社製)などがある。 The phosphoric acid ester (D) used in the present invention is blended in a role of suppressing an increase in viscosity during storage at a high temperature, for example, 60 ° C. It is preferable to have a photoreactive functional group such as a (meth) acryloyl group so that bleeding from the cured film is less likely to occur. Commercially available products include PM-2 (trade name: manufactured by Nippon Kayaku Co., Ltd.) and PM-21 (trade name: manufactured by Nippon Kayaku Co., Ltd.).

前記(D)の配合量は、(A)と(B)の合計100重量部に対し0.1〜4.5重量部であることが好ましく、0.3〜4重量部であることが更に好ましく、0.4〜3.5重量部であることが特に好ましい。この範囲内とすることで、60℃での保存でも粘度増加を抑えることが可能となり、十分な保存安定性を確保できる。 The blending amount of (D) is preferably 0.1 to 4.5 parts by weight, more preferably 0.3 to 4 parts by weight, based on 100 parts by weight of the total of (A) and (B). It is preferably 0.4 to 3.5 parts by weight, and particularly preferably 0.4 to 3.5 parts by weight. Within this range, it is possible to suppress an increase in viscosity even when stored at 60 ° C., and sufficient storage stability can be ensured.

本発明に使用される4官能以上チオール(E)は、紫外線硬化反応を促進させる役割で配合し、酸素による硬化阻害を抑制できるエンチオール反応が可能で、4官能以上と官能基数が多いため反応性が非常に高いチオールである。例えば4官能ではペンタエリスリトールテトラキス(3‐メルカプトプロピオネート)が、6官能ではジペンタエリスリトールヘキサ−3−メルカプトプロピオネート等があり、単独あるいは2種以上を組み合わせて使用することができる。4官能未満のチオールでは反応性が十分でなく、紫外線照射後の硬化物表面にべとつきが残り不可である。また反応性が高い点で2級よりも1級チオールであることが好ましい。 The tetrafunctional or higher functional thiol (E) used in the present invention is blended in a role of accelerating the ultraviolet curing reaction, and is capable of an enthiol reaction capable of suppressing curing inhibition by oxygen. Is a very high thiol. For example, pentaerythritol tetrakis (3-mercaptopropionate) is used for 4-functionality, and dipentaerythritol hexa-3-mercaptopropionate is used for 6-functionality, which can be used alone or in combination of two or more. Thiols with less than tetrafunctionality do not have sufficient reactivity, and stickiness cannot remain on the surface of the cured product after irradiation with ultraviolet rays. Further, in terms of high reactivity, a primary thiol is preferable to a secondary thiol.

前記(E)の配合量は、(A)と(B)の合計100重量部に対し1.0〜15重量部であり、1.5〜12重量部が好ましく、2.0〜5.0重量部が更に好ましい。1.0重量部以上で硬化性を向上させ硬化後の皮膜表面にべとつきを無くすことができ、15重量部以下することで高温環境下での保存安定性を確保できる。市販品ではPEMP(商品名:SC有機化学社製、4官能)及びDPMP(商品名:同社製、6官能)がある。 The blending amount of (E) is 1.0 to 15 parts by weight, preferably 1.5 to 12 parts by weight, and 2.0 to 5.0 parts by weight with respect to 100 parts by weight in total of (A) and (B). Parts by weight are more preferred. Curability can be improved at 1.0 part by weight or more to eliminate stickiness on the surface of the film after curing, and storage stability in a high temperature environment can be ensured at 15 parts by weight or less. Commercially available products include PEMP (trade name: manufactured by SC Organic Chemistry Co., Ltd., 4-functional) and DPMP (trade name: manufactured by the same company, 6-functional).

本発明に使用される安定剤(F)は、前記(D)同様、高温保存時における粘度増加を抑える役割で配合する。安定剤の種類としては光安定剤及び酸化防止剤などが挙げられ、具体的にはベンゾトリアゾール系やトリアジン系に代表される紫外線吸収剤、ヒンダードアミン系、ヒンダードフェノール系、ホスファイト系、チオエーテル系の酸化防止剤が挙げられ、単独あるいは2種以上を組み合わせて使用することができる。 The stabilizer (F) used in the present invention is blended in a role of suppressing an increase in viscosity during high-temperature storage, as in the case of (D). Examples of stabilizers include light stabilizers and antioxidants. Specifically, UV absorbers typified by benzotriazoles and triazines, hindered amines, hindered phenols, phosphites, and thioethers. Antioxidants can be mentioned, and can be used alone or in combination of two or more.

前記(F)の配合量は、(A)と(B)の合計100重量部に対し0.01〜3.0重量部であり、0.05〜2重量部が好ましく、0.08〜1.5重量部が更に好ましい。0.01重量部以上とすることで高温下での粘度上昇を抑える効果があり、3.0重量部以下とすることで硬化時の表面べとつきを抑えることが可能となる。市販品ではヒンダードアミン系としてTinuvin123及びTinuvin249(商品名:BASFジャパン社製)、ヒンダードフェノール系としてIrganox1076(商品名:BASFジャパン社製)、チオエーテル系としてAO−503(商品名:アデカ社製)がある。 The blending amount of (F) is 0.01 to 3.0 parts by weight, preferably 0.05 to 2 parts by weight, and 0.08 to 1 by weight, based on 100 parts by weight of the total of (A) and (B). .5 parts by weight is more preferred. When it is 0.01 parts by weight or more, it has an effect of suppressing an increase in viscosity at a high temperature, and when it is 3.0 parts by weight or less, it is possible to suppress surface stickiness at the time of curing. Commercially available products include Tinuvin123 and Tinuvin249 (trade name: manufactured by BASF Japan) as hindered amines, Irganox1076 (trade name: manufactured by BASF Japan) as hindered phenols, and AO-503 (trade name: manufactured by Adeka) as thioethers. is there.

本願組成物には、高温保存時における粘度増加を抑える役割で、更に重合禁止剤(G)を含むことが好ましい。(G)を少量添加することで、前記(D)及び(F)の性能を効果的に引き出すことが可能となり、その配合量も低減できる。具体的にはジブチルヒドロキシトルエンが挙げられ、配合量としては光反応性成分100重量部に対し0.03〜0.3重量部が好ましい。 The composition of the present application preferably further contains a polymerization inhibitor (G) in a role of suppressing an increase in viscosity during storage at a high temperature. By adding a small amount of (G), the performances of (D) and (F) can be effectively brought out, and the blending amount thereof can be reduced. Specific examples thereof include dibutylhydroxytoluene, and the blending amount is preferably 0.03 to 0.3 parts by weight with respect to 100 parts by weight of the photoreactive component.

本発明の組成物には性能を損なわない範囲で、必要によりレベリング剤、可塑剤、粘着付与剤、顔料、染料、消泡剤、増粘剤、及び濡れ性調整剤等の各種添加剤が含まれていても良い。 The composition of the present invention contains various additives such as a leveling agent, a plasticizer, a tackifier, a pigment, a dye, an antifoaming agent, a thickener, and a wettability adjusting agent as long as the performance is not impaired. It may be.

本組成物の25℃における粘度は、500〜15000mPa・sであることが好ましく、1000〜10000mPa・sであることが更に好ましい。500mPa・s以上とすることで作業性が向上し注形作業がしやすくなり、15000mPa・s以下とすることで注形型の再現性や気泡抜けが良好となる。 The viscosity of the composition at 25 ° C. is preferably 500 to 15000 mPa · s, more preferably 1000 to 10000 mPa · s. When it is 500 mPa · s or more, workability is improved and casting work becomes easy, and when it is 15000 mPa · s or less, the reproducibility of casting and air bubble removal are improved.

本組成物の保存安定性については、加速試験として60℃環境下における増粘率を測定することに
より判断できる。具体的には60℃で14日間放置後の組成物粘度が、初期粘度に対し増加率が20%以下が好ましく、10%以下であることが更に好ましい。20%以下であれば実用上の保存性は十分あると判断される。
The storage stability of this composition can be determined by measuring the thickening rate in an environment of 60 ° C. as an accelerated test. Specifically, the viscosity of the composition after being left at 60 ° C. for 14 days preferably has an increase rate of 20% or less, more preferably 10% or less, based on the initial viscosity. If it is 20% or less, it is judged that the storage stability is sufficient for practical use.

以下、本発明について実施例及び比較例を挙げてより詳細に説明するが、具体例を示すものであって、特にこれらに限定するものではない。なお表記が無い場合は、室温は25℃相対湿度65%の条件下で測定を行った。また配合量は重量部を示す。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but specific examples are shown, and the present invention is not particularly limited thereto. Unless otherwise specified, the measurement was performed under the conditions of room temperature of 25 ° C. and relative humidity of 65%. The blending amount indicates the part by weight.

実施例1
遮光ビンに、前記(A)として2官能ウレタン(メタ)アクリレートオリゴマー(PTMGとIPDIの反応物にヒドロキシ(メタ)アクリレートを反応、Mw.3000)及び6官能ウレタン(メタ)アクリレートオリゴマーを、(B)としてライトエステルHOP(N)(商品名:共栄社化学社製、2−ヒドロキシプロピルメタクリレート)を、(C)としてOmnirad184(iGM社製、α-ヒドロキシアセトフェノン系)及びOmnirad TPO H(G)(iGM社製、アシルフォスフィンオキサイド系)を、(D)としてPM−21(商品名:日本化薬社製)を、(E)としてPEMP(商品名:SC有機化学社製、ペンタエリスリトールテトラキス(3‐メルカプトプロピオネート))を、(F)としてTinuvin249(商品名:BASFジャパン社製、ヒンダードアミン系)を、(G)としてジブチルヒドロキシトルエンを、レベリング剤としてKL−700(商品名:共栄社化学社製、有機基含有ポリジメチルシロキサン)を、表1に示す量入れ、撹拌脱泡機を用いて均一になるまで15分以上撹拌し実施例1の樹脂組成物を調整した。
Example 1
In the light-shielding bottle, as (A), a bifunctional urethane (meth) acrylate oligomer (reacting a hydroxy (meth) acrylate with a reaction product of PTMG and IPDI, Mw.3000) and a hexafunctional urethane (meth) acrylate oligomer (B). ) As light ester HOP (N) (trade name: Kyoeisha Chemical Co., Ltd., 2-hydroxypropyl methacrylate), and as (C), Omnirad184 (manufactured by iGM, α-hydroxyacetophenone type) and Omnirad TPO H (G) (iGM). (Acylphosphine oxide type) as (D), PM-21 (trade name: Nippon Kayakusha) as (D), PEMP (trade name: SC Organic Chemistry, pentaerythritol tetrakis) (3) -Mercaptopropionate)), Tinuvin249 (trade name: BASF Japan, hindered amine type) as (F), dibutylhydroxytoluene as (G), and KL-700 (trade name: Kyoeisha Chemical Co., Ltd.) as a leveling agent. The resin composition of Example 1 was prepared by adding the amount of polydimethylsiloxane (organic group-containing polydimethylsiloxane) shown in Table 1 and stirring with a stirring defoamer for 15 minutes or more until the mixture became uniform.

実施例2〜15
実施例1で用いた材料の他、前記(B)として1.6HX−A(商品名:共栄社化学社製、1.6ヘキサンジオールジアクリレート)及びM−240(商品名:東亜合成社製、ポリエチレングリコール(n≒4)ジアクリレート)を、(D)としてPM−2(商品名:日本化薬社製)を、前記(E)としてDPMP(商品名:SC有機化学社製、ジペンタエリスリトールヘキサ−3−メルカプトプロピオネート)を、(F)としてIrganox1076(商品名:BASFジャパン社製)及びAO−503(商品名:アデカ社製)を、表2記載の配合にて撹拌脱泡機を用いて均一になるまで15分以上撹拌し実施例2〜15の樹脂組成物を調製した。
Examples 2 to 15
In addition to the materials used in Example 1, 1.6HX-A (trade name: manufactured by Kyoeisha Chemical Co., Ltd., 1.6 hexanediol diacrylate) and M-240 (trade name: manufactured by Toa Synthetic Co., Ltd.) as (B) above. Polyethylene glycol (n≈4) diacrylate), PM-2 (trade name: manufactured by Nippon Kayaku Co., Ltd.) as (D), and DPMP (trade name: SC organic chemical company, dipentaerythritol) as (E). Hexa-3-mercaptopropionate) as (F), Irganox 1076 (trade name: manufactured by BASF Japan) and AO-503 (trade name: manufactured by Adeca) are stirred and defoamed with the formulations shown in Table 2. The resin compositions of Examples 2 to 15 were prepared by stirring for 15 minutes or more until the mixture became uniform.

比較例1〜6
実施例で用いた材料の他、3官能チオールとしてTMMP-LV(商品名:SC有機化学社製、トリメチロールプロパン トリス(3-メルカプトプロピオネート))及びTEMPIC(商品名:SC有機化学社製、トリス-[(3-メルカプトプロピオニルオキシ)-エチル]-イソシアヌレート)を用い、表2記載の配合にて撹拌脱泡機を用いて均一になるまで15分以上撹拌し比較例1〜6の樹脂組成物を調製した。
Comparative Examples 1 to 6
In addition to the materials used in the examples, TMMP-LV (trade name: manufactured by SC Organic Chemistry Co., Ltd., trimethylpropantris (3-mercaptopropionate)) and TEMPIC (trade name: manufactured by SC Organic Chemical Co., Ltd.) as trifunctional thiols. , Tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate), and stir for 15 minutes or more using a stirring defoamer with the formulation shown in Table 2 until uniform. A resin composition was prepared.

硬化物の作製
室温の樹脂組成物3gを、シリコーン型(エルベール社製、シリコーンモチーフRSSD-2、20mm×32mm×t5mm)に投入し、樹脂面より4cmの高さから、LED照射機SUN mini(パーツクラブ製)を用い、出力6W、照度6mW/cm2(365nm)(13W/cm2(405nm))で1分間、更に裏面から1分間照射して硬化させた。その後シリコーン型から硬化物を取り出し、23±2℃にて30分放置して作製した。
Preparation of cured product 3 g of the resin composition at room temperature was put into a silicone mold (manufactured by Herbert, silicone motif RSSD-2, 20 mm × 32 mm × t5 mm), and LED irradiation was performed from a height of 4 cm from the resin surface. Using a machine SUN mini (manufactured by Parts Club), the mixture was cured by irradiating with an output of 6 W and an illuminance of 6 mW / cm2 (365 nm) (13 W / cm2 (405 nm)) for 1 minute and further from the back surface for 1 minute. Then, the cured product was taken out from the silicone mold and left at 23 ± 2 ° C. for 30 minutes to prepare the product.

表1

Figure 2021088650
Table 1
Figure 2021088650

表2

Figure 2021088650
Table 2
Figure 2021088650

評価方法は以下の通りとした。 The evaluation method was as follows.

粘度:東機産業製のコーンプレート型粘度計RC−550を用い、コーン角3°R17.65で25±1℃、回転数は500〜2000mPa・sは20rpm、2000〜5000mPa・sは10rpm、5000〜10000mPa・sは5rpmで測定した。 Viscosity: Using a cone plate type viscometer RC-550 manufactured by Toki Sangyo, the cone angle is 3 ° R17.65, 25 ± 1 ° C., the rotation speed is 20 rpm for 500 to 2000 mPa · s, and 10 rpm for 2000 to 5000 mPa · s. 5000-10000 mPa · s was measured at 5 rpm.

硬化性:前記硬化物のLEDライト照射面のべたつき度合いを指触により確認し、べたつきが無い場合は○、ある場合は×とした。 Curability: The degree of stickiness of the LED light irradiation surface of the cured product was confirmed by touching the finger, and was marked with ◯ when there was no stickiness and x when there was.

外観:前記硬化物の透明性、色味を目視にて確認し、無色透明を○、白濁や変色等の異常が見られた場合を×とした。 Appearance: The transparency and color of the cured product were visually confirmed, and colorless and transparent were marked with ◯, and abnormalities such as cloudiness and discoloration were marked with x.

硬化収縮:前記硬化物の反りや気泡の有無を目視にて確認し、気泡がなく反りが2mm未満の場合を○、気泡がある場合、又は反りが2mm以上ある場合は×とした。 Curing shrinkage: The presence or absence of warpage or air bubbles in the cured product was visually confirmed, and the case where there were no air bubbles and the warp was less than 2 mm was evaluated as ◯, and the case where there were air bubbles or the warpage was 2 mm or more was evaluated as x.

保存性:50mLの遮光ボトルに樹脂組成物を20g量り取り、60℃の恒温槽で14日間保管後、粘度を測定し、初期粘度からの増粘率が10%以下を◎、10%超〜20%を○、20%超を×とした。 Preservation: Weigh 20 g of the resin composition in a 50 mL light-shielding bottle, store it in a constant temperature bath at 60 ° C for 14 days, measure the viscosity, and determine that the viscosity increase rate from the initial viscosity is 10% or less. 20% was marked with ◯, and over 20% was marked with x.

実施例の評価結果を表2に示す。
表3

Figure 2021088650
The evaluation results of the examples are shown in Table 2.
Table 3
Figure 2021088650

比較例の評価結果を表4に示す。
表4

Figure 2021088650
The evaluation results of the comparative examples are shown in Table 4.
Table 4
Figure 2021088650

実施例の樹脂組成物は粘度、硬化性、外観、硬化収縮、保存性のいずれも良好であった。 The resin composition of the example had good viscosity, curability, appearance, curing shrinkage, and storage stability.

一方、2官能のウレアクを含まない比較例1、(F)を含まない比較例5は保存安定性が劣り、(E)の配合量が少ない比較例2、4官能未満のチオールを用いた比較例3〜4、(F)の配合量が多い比較例6は硬化性が劣り、いずれも本願発明に適さないものであった。 On the other hand, Comparative Example 1 not containing the bifunctional ureac and Comparative Example 5 not containing (F) are inferior in storage stability, and the amount of (E) blended is small. Comparative Examples 6 in which the amounts of Examples 3 to 4 and (F) were large were inferior in curability, and none of them was suitable for the present invention.

本発明の紫外線硬化樹脂組成物は、LED光源を使用しても硬化性に優れると共に、高温下での粘度増加率が低く、保存性が良好であるため、ブローチや小物などのアクセサリーを自作する手芸用途に適した注形成型用樹脂として有用である。


The ultraviolet curable resin composition of the present invention has excellent curability even when an LED light source is used, has a low viscosity increase rate at high temperatures, and has good storage stability. Therefore, accessories such as brooches and accessories are made by oneself. It is useful as a casting type resin suitable for handicraft applications.


Claims (5)

2官能を少なくとも含む多官能ウレタンアクリレートオリゴマー(A)と、(メタ)アクリレートモノマー(B)と、光重合開始剤(C)と、リン酸エステル(D)と、4官能以上のチオール(E)と、安定剤(F)を含み、前記(A)と(B)の合計100重量部に対する(E)の配合量が1.0〜15重量部で、(F)の配合量が0.01〜3重量部であることを特徴とする紫外線硬化樹脂組成物。 A polyfunctional urethane acrylate oligomer (A) containing at least bifunctionality, a (meth) acrylate monomer (B), a photopolymerization initiator (C), a phosphoric acid ester (D), and a tetrafunctional or higher functional thiol (E). And the stabilizer (F) is included, the blending amount of (E) is 1.0 to 15 parts by weight, and the blending amount of (F) is 0.01 with respect to 100 parts by weight of the total of (A) and (B). An ultraviolet curable resin composition characterized by being ~ 3 parts by weight. 前記(B)の(メタ)アクリレートモノマーが水酸基を含む単官能(メタ)アクリレートモノマー及び/又は2官能直鎖骨格(メタ)アクリレートモノマーを含むことを特徴とする請求項1記載の光硬化性樹脂組成物。 The photocurable resin according to claim 1, wherein the (meth) acrylate monomer of (B) contains a monofunctional (meth) acrylate monomer containing a hydroxyl group and / or a bifunctional linear skeleton (meth) acrylate monomer. Composition. 前記(A)と(B)の合計に対する(A)の配合量が50重量%以上であることを特徴とする請求項1又は2いずれか記載の光硬化性樹脂組成物。 The photocurable resin composition according to any one of claims 1 or 2, wherein the blending amount of (A) with respect to the total of (A) and (B) is 50% by weight or more. 更に重合禁止剤(G)を含むことを特徴とする、請求項1〜3いずれか記載の光硬化性樹脂組成物。 The photocurable resin composition according to any one of claims 1 to 3, further comprising a polymerization inhibitor (G). 注形成型用樹脂であることを特徴とする、請求項1〜4いずれか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 resin is a casting type resin.




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JP2018027944A (en) * 2016-08-12 2018-02-22 株式会社サクラクレパス Tackifier-containing photocurable artificial nail composition
JP2018177924A (en) * 2017-04-11 2018-11-15 三洋化成工業株式会社 Active energy ray-curable resin composition

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