TWI782938B - Water-based resin composition, laminate using same, optical film and image display device - Google Patents

Water-based resin composition, laminate using same, optical film and image display device Download PDF

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TWI782938B
TWI782938B TW106145467A TW106145467A TWI782938B TW I782938 B TWI782938 B TW I782938B TW 106145467 A TW106145467 A TW 106145467A TW 106145467 A TW106145467 A TW 106145467A TW I782938 B TWI782938 B TW I782938B
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water
resin
mass
based resin
meth
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TW201833216A (en
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小柳達史
岩男武志
北田滿
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日商迪愛生股份有限公司
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
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    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
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    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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    • C09D175/06—Polyurethanes from polyesters
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    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/006—Anti-reflective coatings
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
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Abstract

提供一種水性樹脂組成物，其可作為底漆使用，即使係如聚酯薄膜這種難接著的基材，亦可大幅提升該基材與活性能量射線硬化性組成物的硬化塗膜的密合性。本發明係使用水性樹脂組成物，其係包含含有乙烯酯樹脂及具有芳香環之胺基甲酸酯樹脂的複合樹脂、水性樹脂、水性媒介的水性樹脂組成物，其特徵為：該乙烯酯樹脂係選自包含酚醛清漆型環氧樹脂及雙酚型環氧樹脂之群組的1種以上的環氧樹脂與具有酸基及聚合性不飽和基之化合物的反應物；該胺基甲酸酯樹脂係多元醇與聚異氰酸酯的反應物，多元醇包含具有芳香環之多元醇及具有親水性基之多元醇。 To provide a water-based resin composition that can be used as a primer to greatly improve the adhesion between the substrate and the cured coating film of the active energy ray-curable composition even if it is a difficult-to-adhesive substrate such as a polyester film sex. The present invention uses a water-based resin composition, which is a water-based resin composition comprising a composite resin containing a vinyl ester resin and a urethane resin having an aromatic ring, a water-based resin, and a water-based medium, and is characterized in that: the vinyl ester resin It is a reactant of one or more epoxy resins selected from the group consisting of novolak epoxy resins and bisphenol epoxy resins and a compound having an acid group and a polymerizable unsaturated group; the urethane Resin-based polyol and polyisocyanate reactant, polyol includes polyol with aromatic ring and polyol with hydrophilic group.

Description

水性樹脂組成物、使用其之積層體、光學薄膜及影像顯示裝置 Water-based resin composition, laminate using same, optical film and image display device

本發明係關於在基材的單面或是雙面上形成活性能量射線硬化性組成物之硬化塗膜時，可作為提升基材與該硬化塗膜之密合性的底漆使用的水性樹脂組成物、使用其之積層體及光學薄膜。 The present invention relates to a water-based resin that can be used as a primer for improving the adhesion between the base material and the cured coating film when forming a cured coating film of an active energy ray-curable composition on one or both sides of a base material Compositions, laminates and optical films using them.

水性樹脂組成物，特別是水性胺基甲酸酯樹脂組成物，一般對於基材具有良好的密合性，從可形成柔軟塗膜的觀點來看，其被使用於以塗布劑及黏著劑為首的各種用途中。其中，近年來討論將其應用於光學用途的薄膜及片材。作為該光學用途，具體而言，可列舉：液晶顯示器、觸控式面板等。該液晶顯示器等的顯示裝置，通常為了顯示鮮明的影像，而係將具有各種功能的多個光學薄膜積層而構成，作為此種光學薄膜，可列舉：抗反射膜、相位差膜、稜鏡鏡片等。 Water-based resin compositions, especially water-based urethane resin compositions, generally have good adhesion to substrates, and are used in coating agents and adhesives from the viewpoint of forming a soft coating film. of various uses. Among them, applications to films and sheets for optical applications have been discussed in recent years. As this optical use, a liquid crystal display, a touch panel, etc. are mentioned specifically,. Display devices such as liquid crystal displays are generally composed of a plurality of optical films having various functions in order to display clear images. Wait.

從光學特性、機械強度、耐久性優良的觀點來看，可使用聚酯薄膜，特別是聚對苯二甲酸乙二酯(PET)薄膜作為該等光學薄膜的基材。又，光學用途中，具有藉由在聚酯薄膜的表面上塗布活性能量射線硬化性組成 物並進行硬化以形成硬塗層的情況，以及設置將活性能量射線硬化性組成物澆注的層以將聚酯薄膜作為稜鏡鏡片的情況，但聚酯薄膜因為結晶性高，而具有與活性能量射線硬化性組成物的硬化塗膜的密合性低這樣的問題。 From the viewpoint of excellent optical characteristics, mechanical strength, and durability, polyester films, especially polyethylene terephthalate (PET) films can be used as base materials for such optical films. Also, in optical applications, there is a case where a hard coat layer is formed by coating an active energy ray-curable composition on the surface of a polyester film and curing it, and a layer in which the active energy ray-curable composition is cast is provided to cover In the case of a polyester film used as a tinted lens, the polyester film has a problem of low adhesion to a cured coating film of an active energy ray-curable composition due to its high crystallinity.

目前為止，作為提升聚酯薄膜與活性能量射線硬化性組成物的硬化塗膜之密合性的方法，有人提出一種在作為基材的聚酯薄膜與活性能量射線硬化性組成物之硬化塗膜之間，設置包含丙烯酸樹脂的底漆層者(例如，參照專利文獻1)。然而，即使設置包含丙烯酸樹脂的底漆層，聚酯薄膜與活性能量射線硬化性組成物之硬化塗膜的密合性亦並不充分。 So far, as a method of improving the adhesion between a polyester film and a cured coating film of an active energy ray-curable composition, a method of adding a cured coating film of a polyester film as a base material to an active energy ray-curable composition has been proposed. In between, a primer layer containing an acrylic resin is provided (for example, refer to Patent Document 1). However, even if a primer layer containing an acrylic resin is provided, the adhesion between the polyester film and the cured coating film of the active energy ray-curable composition is not sufficient.

於是，要求一種可用於底漆層的材料，其可使聚酯薄膜與活性能量射線硬化性組成物之硬化塗膜的密合性充分。 Therefore, there is a demand for a material that can provide sufficient adhesion between the polyester film and the cured coating film of the active energy ray-curable composition, which can be used for the primer layer.

[先前技術文獻] [Prior Art Literature] [專利文獻] [Patent Document]

[專利文獻1]日本特開2010-215843號公報 [Patent Document 1] Japanese Unexamined Patent Publication No. 2010-215843

本發明欲解決之課題，係提供一種水性樹脂組成物，其可作為底漆使用，即使如聚酯薄膜這種難以接著的基材，其亦可大幅提升該基材與活性能量射線硬化性組成物的硬化塗膜之密合性；以及使用其之積層 體、光學薄膜及影像顯示裝置。 The problem to be solved by the present invention is to provide a water-based resin composition, which can be used as a primer, and can greatly improve the composition of the base material and active energy ray hardening properties even for difficult-to-bond substrates such as polyester films. The adhesiveness of the hardened coating film of the object; and the laminated body, optical film and image display device using it.

本案發明人等為了解決上述課題而詳細研究，結果發現藉由使用含有特定複合樹脂與水性樹脂的水性樹脂組成物作為底漆，即使是如聚酯薄膜這種難以接著的基材，亦可大幅提升該基材與活性能量射線硬化組成物的硬化塗膜的密合性，進而完成本發明。 The inventors of the present case have studied in detail to solve the above-mentioned problems. As a result, they have found that by using a water-based resin composition containing a specific composite resin and a water-based resin as a primer, even a base material that is difficult to bond such as a polyester film can be greatly improved. The present invention has been completed by improving the adhesion between the base material and the cured coating film of the active energy ray curable composition.

亦即，本發明係關於一種水性樹脂組成物，其係包含具有乙烯酯樹脂(a1)及具有芳香環的胺基甲酸酯樹脂(a2)的複合樹脂(A)、水性樹脂(B)、及水性媒介(C)的水性樹脂組成物，其特徵為：該乙烯酯樹脂(a1)係選自包含酚醛清漆型環氧樹脂及雙酚型環氧樹脂之群組的1種以上的環氧樹脂(a1-1)與具有酸基及聚合性不飽和基的化合物(a1-2)的反應物，該胺基甲酸酯樹脂(a2)係多元醇(a2-1)與聚異氰酸酯(a2-2)的反應物，該多元醇(a2-1)含有具有芳香環的多元醇及具有親水性基的多元醇；以及使用其之積層體、光學薄膜及影像顯示裝置。 That is, the present invention relates to a water-based resin composition comprising a composite resin (A) having a vinyl ester resin (a1) and a urethane resin (a2) having an aromatic ring, a water-based resin (B), and the water-based resin composition of the water-based medium (C), wherein the vinyl ester resin (a1) is one or more epoxy resins selected from the group consisting of novolac-type epoxy resins and bisphenol-type epoxy resins. A reaction product of a resin (a1-1) and a compound (a1-2) having an acid group and a polymerizable unsaturated group, the urethane resin (a2) is a polyol (a2-1) and a polyisocyanate (a2 A reactant of -2), wherein the polyol (a2-1) contains a polyol having an aromatic ring and a polyol having a hydrophilic group; and a laminate, an optical film, and an image display device using the same.

本發明之水性樹脂組成物可作為底漆使用，即使係如聚酯薄膜這種難以接著的基材，其亦可大幅提升該基材與活性能量射線硬化性組成物之硬化塗膜的密合性，故適用於以聚酯薄膜作為基材並在其表面上形成活性能量射線硬化性組成物之硬化塗膜而成的積層體。作為這種積層體，可列舉例如：抗反射膜、相位差膜、稜鏡鏡片等的光學薄膜。又，該等的光學薄膜，可應用於以液晶顯示器為首的影像顯示裝置。 The water-based resin composition of the present invention can be used as a primer, and it can greatly improve the adhesion between the substrate and the cured coating film of the active energy ray-curable composition even if it is a difficult-to-bond substrate such as a polyester film Therefore, it is suitable for laminates in which a polyester film is used as a substrate and a cured coating film of an active energy ray-curable composition is formed on the surface. Examples of such laminates include optical films such as antireflection films, retardation films, and galvanized lenses. Moreover, these optical films can be applied to image display devices including liquid crystal displays.

[實施發明之形態] [Mode of Implementing the Invention]

本發明之水性樹脂組成物包含：複合樹脂(A)，其含有乙烯酯樹脂(a1)及具有芳香環的胺基甲酸酯樹脂(a2)；水性樹脂(B)；及水性媒介(C)。 The water-based resin composition of the present invention comprises: composite resin (A), which contains vinyl ester resin (a1) and urethane resin (a2) having an aromatic ring; water-based resin (B); and water-based medium (C) .

該複合樹脂(A)含有乙烯酯樹脂(a1)及具有芳香環的胺基甲酸酯樹脂(a2)。 The composite resin (A) contains a vinyl ester resin (a1) and a urethane resin (a2) having an aromatic ring.

該乙烯酯樹脂(a1)係例如包含：選自包含酚醛清漆型環氧樹脂及雙酚型環氧樹脂之群組的1種以上的環氧樹脂(a1-1)與具有酸基及聚合性不飽和基的化合物(a1-2)的反應物。 The vinyl ester resin (a1) includes, for example, one or more epoxy resins (a1-1) selected from the group consisting of novolak epoxy resins and bisphenol epoxy resins and having acid groups and polymerizability. A reactant of the unsaturated group compound (a1-2).

該環氧樹脂(a1-1)係含有選自包含酚醛清漆型環氧樹脂及雙酚型環氧樹脂之群組的1種以上者，具體而言可使用以下所述者。 This epoxy resin (a1-1) contains 1 or more types selected from the group containing a novolak type epoxy resin and a bisphenol type epoxy resin, Specifically, what is mentioned below can be used.

作為該酚醛清漆型環氧樹脂，可列舉例如：甲酚酚醛清漆型環氧樹脂、苯酚酚醛清漆型環氧樹脂等。又，作為該雙酚型環氧樹脂，可列舉例如：雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚AD型環氧樹脂、雙酚S型環氧樹脂、四溴雙酚A型環氧樹脂等。該等的環氧樹脂(a1-1)可單獨使用，亦可併用2種以上。 As this novolac-type epoxy resin, a cresol novolac-type epoxy resin, a phenol novolak-type epoxy resin, etc. are mentioned, for example. In addition, examples of the bisphenol epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, bisphenol S epoxy resin, tetrabromobis Phenol A type epoxy resin, etc. These epoxy resins (a1-1) may be used individually, and may use 2 or more types together.

該環氧樹脂(a1-1)之中，較佳為使用具有多個環氧基的酚醛清漆型環氧樹脂，該環氧基可與該化合物(a1-2)所具有之酸基反應。 Among the epoxy resins (a1-1), it is preferable to use a novolak-type epoxy resin having a plurality of epoxy groups that can react with the acid groups that the compound (a1-2) has.

又，該環氧樹脂(a1-1)的環氧當量較佳為150~2,000g/eq.的範圍，更佳為160~1,000g/eq.的範圍。 In addition, the epoxy equivalent of the epoxy resin (a1-1) is preferably in the range of 150 to 2,000 g/eq., more preferably in the range of 160 to 1,000 g/eq.

再者，較佳係使該環氧樹脂(a1-1)所具有之環氧基的總量中的80~100莫耳%與該化合物(a1-2)的酸基反應，更佳係使該環氧基皆與該化合物(a1-2)的酸基反應。 Furthermore, it is preferable to make 80~100 mole % of the total amount of epoxy groups in the epoxy resin (a1-1) react with the acid groups of the compound (a1-2), more preferably to make The epoxy groups all react with the acid groups of the compound (a1-2).

該化合物(a1-2)係具有酸基及聚合性不飽和基者。藉由使該化合物(a1-2)所具有之酸基與該環氧樹脂(a1-1)所具有之環氧基反應，可將聚合性不飽和基導入該乙烯酯樹脂(a1)。 This compound (a1-2) has an acid group and a polymerizable unsaturated group. A polymerizable unsaturated group can be introduced into the vinyl ester resin (a1) by reacting the acid group of the compound (a1-2) with the epoxy group of the epoxy resin (a1-1).

因為該化合物(a1-2)所具有之聚合性不飽和基，在與該環氧樹脂的反應中與其反應無關，結果，該乙烯酯樹脂(a1)具有源自該化合物(a1-2)的聚合性不飽和基。該乙烯酯樹脂(a1)所具有之聚合性不飽和基，與後述活性能量射線硬化性組成物中所含之樹脂或單體所具有之聚合性不飽和基進行聚合反應，藉此形成共價鍵，而成為與包含本發明之水性樹脂組成物的底漆層穩固密合者。 Because the polymerizable unsaturated group possessed by the compound (a1-2) has nothing to do with the reaction with the epoxy resin, as a result, the vinyl ester resin (a1) has polymerizable unsaturated group. The polymerizable unsaturated group of the vinyl ester resin (a1) polymerizes with the polymerizable unsaturated group of the resin or monomer contained in the active energy ray curable composition described later to form a covalent bond, and become the one that firmly adheres to the primer layer comprising the water-based resin composition of the present invention.

作為該具有酸基及聚合性不飽和基的化合物(a1-2)，可列舉例如：丙烯酸、甲基丙烯酸、伊康酸、2-丙烯醯基氧基乙基琥珀酸酯、2-甲基丙烯醯基氧基乙基琥珀酸酯、2,2,2,-參丙烯醯基氧基甲基乙基苯二甲酸等。該等的化合物之中，較佳為丙烯酸，其可將容易與後述活性能量射線硬化性組成物中的樹脂或單體所具有 之聚合性不飽和基進行聚合反應的丙烯醯基導入該乙烯酯樹脂(a1)。又，該等的化合物(a1-2)可單獨使用，亦可併用2種以上，但較佳係在該化合物(a1-2)的總量中使用50質量%以上的丙烯酸。 Examples of the compound (a1-2) having an acid group and a polymerizable unsaturated group include: acrylic acid, methacrylic acid, itaconic acid, 2-acryloxyethyl succinate, 2-methyl Acryloxyethyl succinate, 2,2,2,- reference acryloxymethylethylphthalic acid, etc. Among these compounds, acrylic acid is preferable, which can introduce acryl group that can easily polymerize with the polymerizable unsaturated group of the resin or monomer in the active energy ray-curable composition described later into the vinyl ester. Resin (a1). Moreover, these compounds (a1-2) may be used alone or in combination of two or more, but it is preferable to use 50% by mass or more of acrylic acid in the total amount of the compounds (a1-2).

該環氧樹脂(a1-1)與該化合物(a1-2)的反應溫度較佳為60~150℃的範圍，更佳為80~120℃的範圍。 The reaction temperature between the epoxy resin (a1-1) and the compound (a1-2) is preferably in the range of 60-150°C, more preferably in the range of 80-120°C.

又，使該環氧樹脂(a1-1)與該化合物(a1-2)反應時，為了防止該化合物(a1-2)所具有之聚合性不飽和基的熱聚合，較佳係使用聚合抑制劑。聚合抑制劑的添加量，相對於該環氧樹脂(a1-1)及該化合物(a1-2)的總質量，較佳為500~5,000ppm的範圍。 Also, when the epoxy resin (a1-1) is reacted with the compound (a1-2), in order to prevent thermal polymerization of the polymerizable unsaturated group contained in the compound (a1-2), it is preferable to use a polymerization inhibitor. agent. The addition amount of the polymerization inhibitor is preferably in the range of 500 to 5,000 ppm relative to the total mass of the epoxy resin (a1-1) and the compound (a1-2).

作為該聚合抑制劑，可列舉例如：2,6-雙(第三丁基)-4-甲基苯酚、氫醌、甲基氫醌、氫醌單甲醚(methoquinone)、對第三丁基兒茶酚、硝基苯、硝基苯甲酸、鄰二硝基苯、間二硝基苯、對二硝基苯、2,4-二硝基苯酚、三硝基苯等。該等的聚合抑制劑可單獨使用，亦可併用2種以上。 Examples of the polymerization inhibitor include 2,6-bis(tert-butyl)-4-methylphenol, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether (methoquinone), p-tert-butyl Catechol, nitrobenzene, nitrobenzoic acid, o-dinitrobenzene, m-dinitrobenzene, p-dinitrobenzene, 2,4-dinitrophenol, trinitrobenzene, etc. These polymerization inhibitors may be used alone or in combination of two or more.

再者，使該環氧樹脂(a1-1)與該化合物(a1-2)反應時，可使用反應觸媒。該反應觸媒的使用量，相對於該環氧樹脂(a1-1)100質量份，較佳為0.1~5質量份的範圍。 In addition, when making this epoxy resin (a1-1) and this compound (a1-2) react, a reaction catalyst can be used. The usage-amount of this reaction catalyst is preferably the range of 0.1-5 mass parts with respect to 100 mass parts of this epoxy resin (a1-1).

作為該反應觸媒，可列舉例如：胺觸媒、咪唑觸媒、磷觸媒、硼觸媒、磷-硼觸媒等。具體而言，可列舉：乙基胍、三甲基胍、苯基胍、二苯基胍等的烷基 取代胍；3-(3,4-二氯苯基)-1,1-二甲基尿素、3-苯基-1,1-二甲基尿素、3-(4-氯苯基)-1,1-二甲基尿素等的3-取代苯基-1,1-二甲基尿素；2-甲基咪唑啉、2-苯基咪唑啉、2-十一基咪唑啉、2-十七基咪唑啉等的咪唑啉；2-胺基吡啶等的單胺基吡啶；N,N-二甲基-N-(2-羥基-3-烯丙氧基丙基)胺-N’-乳醯亞胺等的胺化醯亞胺；乙基膦、丙基膦、丁基膦、苯基膦、三甲基膦、三乙基膦、三丁基膦、三辛基膦、三苯基膦、三環己基膦、三苯基膦-三苯基硼烷錯合物、四苯基鏻四苯基硼酸酯等的有機磷觸媒；1,8-二氮雜雙環[5.4.0]十一烯-7,1,4-二氮雜雙環[2.2.2]辛烷等的二氮雜雙環十一烯觸媒等。該等的反應觸媒可單獨使用，亦可併用2種以上。 As this reaction catalyst, an amine catalyst, an imidazole catalyst, a phosphorus catalyst, a boron catalyst, a phosphorus-boron catalyst etc. are mentioned, for example. Specifically, alkyl-substituted guanidines such as ethylguanidine, trimethylguanidine, phenylguanidine, and diphenylguanidine; 3-(3,4-dichlorophenyl)-1,1-dimethyl 3-substituted phenyl-1,1-dimethyl urea, 3-phenyl-1,1-dimethyl urea, 3-(4-chlorophenyl)-1,1-dimethyl urea, etc. Urea; imidazolines such as 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, etc.; monoaminopyridines such as 2-aminopyridine; N, Aminated imides such as N-dimethyl-N-(2-hydroxy-3-allyloxypropyl)amine-N'-lactimide; ethylphosphine, propylphosphine, butylphosphine , phenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine-triphenylborane complex, tetra Organophosphorus catalysts such as phenylphosphonium tetraphenyl borate; 1,8-diazabicyclo[5.4.0]undecene-7,1,4-diazabicyclo[2.2.2]octane and other diazabicycloundecene catalysts, etc. These reaction catalysts may be used alone or in combination of two or more.

作為以該方法所得之乙烯酯樹脂(a1)的重量平均分子量，從提升樹脂粒子的分散穩定性的觀點來看，較佳為500~10,000的範圍，更佳為1,000~6,000的範圍。 The weight average molecular weight of the vinyl ester resin (a1) obtained by this method is preferably in the range of 500 to 10,000, more preferably in the range of 1,000 to 6,000, from the viewpoint of improving the dispersion stability of the resin particles.

本說明書中，重量平均分子量、數量平均分子量可作為以凝膠滲透層析法測量之聚苯乙烯換算值而求得。 In this specification, weight average molecular weight and number average molecular weight can be calculated|required as the polystyrene conversion value measured by gel permeation chromatography.

該乙烯酯樹脂(a1)所具有之聚合性不飽和基的當量較佳為250~2,000g/eq.的範圍。 The equivalent weight of the polymerizable unsaturated group contained in the vinyl ester resin (a1) is preferably in the range of 250 to 2,000 g/eq.

該具有芳香環的胺基甲酸酯樹脂(a2)包含多元醇(a2-1)與聚異氰酸酯(a2-2)的反應物；該多元醇(a2-1)包含具有芳香環的多元醇及具有親水性基的多元醇。 The urethane resin (a2) having an aromatic ring comprises a reactant of a polyol (a2-1) and a polyisocyanate (a2-2); the polyol (a2-1) comprises a polyol having an aromatic ring and Polyols with hydrophilic groups.

藉由將該具有芳香環的多元醇作為該胺基甲酸酯樹脂(a2)的原料使用，該胺基甲酸酯樹脂(a2)成為具 有芳香環者。又，該具有芳香環的多元醇中的芳香環濃度較佳為1.5~8mol/kg的範圍，更佳為1.6~5mol/kg的範圍。再者，多元醇(a2-1)中所含的該具有芳香環的多元醇的比例，從更提升對基材之密合性的觀點來看，較佳為40~98質量%的範圍，更佳為60~98質量%的範圍。 By using the polyol having an aromatic ring as a raw material of the urethane resin (a2), the urethane resin (a2) becomes one having an aromatic ring. Also, the aromatic ring concentration in the polyol having an aromatic ring is preferably in the range of 1.5 to 8 mol/kg, more preferably in the range of 1.6 to 5 mol/kg. Furthermore, the ratio of the polyol having an aromatic ring contained in the polyol (a2-1) is preferably in the range of 40 to 98% by mass from the viewpoint of further improving the adhesion to the substrate, More preferably, it is the range of 60-98 mass %.

作為該具有芳香環的多元醇，可列舉例如：芳香族聚酯多元醇、芳香族聚碳酸酯多元醇、芳香族聚醚多元醇、雙酚的伸烷基氧化物加成物等。該等之中，從基材密合性與防結塊性優良的觀點來看，較佳為芳香族聚酯多元醇、雙酚的伸烷基氧化物加成物。又，該雙酚的伸烷基氧化物加成物中較佳為雙酚A的伸烷基氧化物加成物。另外，該等的具有芳香環的多元醇可單獨使用，亦可併用2種以上。 Examples of the polyol having an aromatic ring include aromatic polyester polyols, aromatic polycarbonate polyols, aromatic polyether polyols, alkylene oxide adducts of bisphenols, and the like. Among them, aromatic polyester polyols and alkylene oxide adducts of bisphenols are preferable from the viewpoint of excellent substrate adhesion and blocking resistance. Moreover, among the alkylene oxide adducts of bisphenols, the alkylene oxide adducts of bisphenol A are preferable. In addition, these polyhydric alcohols which have an aromatic ring may be used individually, and may use 2 or more types together.

該芳香族聚酯多元醇，雖係使多元羧酸與多元醇進行酯化反應所得之反應物，但在該多元羧酸及多元醇之中，係使用至少1個具有芳香環者。 The aromatic polyester polyol is a reactant obtained by esterifying a polycarboxylic acid and a polyol, but at least one of the polycarboxylic acid and the polyol has an aromatic ring.

作為該多元羧酸之中，具有芳香環者，可列舉例如：鄰苯二甲酸、間苯二甲酸、對苯二甲酸、萘二羧酸等的芳香族二羧酸或是其酯化物。又，作為無芳香環者，可列舉例如：琥珀酸、戊二酸、己二酸、馬來酸、庚二酸、辛二酸、壬二酸、伊康酸、癸二酸、氯橋酸、1,2,4-丁烷-三羧酸、癸烷二羧酸、環己烷二羧酸、二聚物酸、富馬酸等的脂肪族二羧酸或是其酯化物。該等的多元羧酸或是其酯化物可單獨使用，亦可併用2種以上。 Among the polyvalent carboxylic acids, those having an aromatic ring include, for example, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalene dicarboxylic acid, or esterified products thereof. Moreover, those without an aromatic ring include, for example, succinic acid, glutaric acid, adipic acid, maleic acid, pimelic acid, suberic acid, azelaic acid, itaconic acid, sebacic acid, and chloroporic acid. , 1,2,4-butane-tricarboxylic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid, fumaric acid and other aliphatic dicarboxylic acids or their esterified products. These polyvalent carboxylic acids or their esterified products may be used alone or in combination of two or more.

作為該多元醇之中，具有芳香環者，可列舉 例如：苯二甲醇、甲苯二甲醇、二甲苯二甲醇等的芳香族二醇。又，作為無芳香環者，可列舉例如：乙二醇、丙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、1,8-辛二醇、二乙二醇、三乙二醇、環己烷-1,4-二醇、環己烷-1,4-二甲醇、新戊二醇乙二醇等的脂肪族多元醇。該等的多元醇可單獨使用，亦可併用2種以上。 Among such polyhydric alcohols, those having an aromatic ring include, for example, aromatic diols such as benzenedimethanol, toluenedimethanol, and xylenedimethanol. Moreover, as those without an aromatic ring, for example: ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, diethylene glycol, Aliphatic polyhydric alcohols such as diol, triethylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, and neopentyl glycol. These polyols may be used alone or in combination of two or more.

該具有芳香環的多元醇的含有率，在該多元醇中，較佳為70質量%以下，更佳為50質量%以下，再佳為30質量%以下，再更佳為10質量%以下，特佳為5質量%以下，下限為0質量%。 The content of the polyol having an aromatic ring in the polyol is preferably at most 70% by mass, more preferably at most 50% by mass, further preferably at most 30% by mass, still more preferably at most 10% by mass, Most preferably, it is 5 mass % or less, and the lower limit is 0 mass %.

製造該芳香族聚酯多元醇時的酯化反應中，以促進酯化反應為目的，較佳為使用酯化觸媒。該酯化觸媒，可列舉例如：鈦、錫、鋅、鋁、鋯、鎂、鉿、鍺等的金屬；四異丙氧基鈦、四丁氧基鈦、乙醯丙酮氧化鈦、二丁基氧化錫、二丁基錫二乙酸酯、二丁基錫二月桂酸酯、辛酸錫、2-乙基己烷錫、乙醯丙酮鋅、4氯化鋯、4氯化鋯四氫呋喃錯合物、4氯化鉿、4氯化鉿四氫呋喃錯合物、氧化鍺、四乙氧基鍺等的金屬化合物等。 In the esterification reaction at the time of producing this aromatic polyester polyol, it is preferable to use an esterification catalyst for the purpose of promoting an esterification reaction. The esterification catalyst, for example: metals such as titanium, tin, zinc, aluminum, zirconium, magnesium, hafnium, germanium; tetraisopropoxytitanium, tetrabutoxytitanium, titanium acetylacetonate, dibutyl Base tin oxide, dibutyl tin diacetate, dibutyl tin dilaurate, tin octoate, 2-ethylhexyl tin, zinc acetylacetonate, 4 zirconium chloride, 4 zirconium chloride tetrahydrofuran complex, 4 chloride Metal compounds such as hafnium chloride, hafnium chloride tetrahydrofuran complex, germanium oxide, tetraethoxygermanium, etc.

該雙酚A的伸烷基氧化物加成物，係對於雙酚A所具有之酚性羥基加成伸烷基氧化物者。作為該伸烷基氧化物，可列舉：氧化乙烯、氧化丙烯等。又，相對於1莫耳雙酚A，伸烷基氧化物的平均加成莫耳數，較佳為1~8的範圍，更佳為1~4的範圍。 The alkylene oxide adduct of bisphenol A is one in which an alkylene oxide is added to the phenolic hydroxyl group possessed by bisphenol A. Ethylene oxide, propylene oxide, etc. are mentioned as this alkylene oxide. Also, the average added mole number of the alkylene oxide is preferably in the range of 1 to 8, more preferably in the range of 1 to 4, relative to 1 mole of bisphenol A.

該具有芳香環的多元醇的重量平均分子量，較佳為500~10,000，更佳為1,000~6,000。 The weight average molecular weight of the polyol having an aromatic ring is preferably 500-10,000, more preferably 1,000-6,000.

作為該具有親水性基的多元醇，可列舉：具有陰離子性基的多元醇、具有陽離子性基的多元醇、具有非離子性基的多元醇。該等之中，較佳為具有陰離子性基的多元醇。 As a polyol which has this hydrophilic group, the polyol which has an anionic group, the polyol which has a cationic group, and the polyol which has a nonionic group are mentioned. Among these, polyhydric alcohols having anionic groups are preferred.

作為該具有陰離子性基的多元醇，可列舉例如：具有羧基的多元醇、具有磺酸基的多元醇等。 As a polyhydric alcohol which has this anionic group, the polyhydric alcohol which has a carboxyl group, the polyhydric alcohol which has a sulfonic acid group, etc. are mentioned, for example.

作為該具有羧基的多元醇，可列舉例如：2,2-二羥甲基丙酸、2,2-二羥甲基丁酸、2,2-二羥甲基戊酸等。該等之中，較佳為2,2-二羥甲基丙酸。又，亦可使用具有「使該具有羧基之多元醇與多元羧酸反應所得之羧基」的聚酯多元醇。 As a polyhydric alcohol which has this carboxyl group, 2, 2- dimethylol propionic acid, 2, 2- dimethylol butyric acid, 2, 2- dimethylol pentanoic acid etc. are mentioned, for example. Among these, 2,2-dimethylolpropionic acid is preferred. Moreover, the polyester polyol which has "the carboxyl group obtained by reacting the said polyhydric alcohol which has a carboxyl group, and a polycarboxylic acid" can also be used.

作為該具有磺酸基的多元醇，可列舉例如：使5-磺酸基間苯二甲酸、磺酸基對苯二甲酸、4-磺酸基鄰苯二甲酸、5-(4-磺酸基苯氧基)間苯二甲酸等的二羧酸或是該等的鹽，與乙二醇、丙二醇、1,4-丁二醇、1,6-己二醇、二乙二醇、新戊二醇等的低分子多元醇反應所得之聚酯多元醇等。 As the polyhydric alcohol having the sulfonic acid group, for example, 5-sulfonic acid isophthalic acid, sulfonic acid terephthalic acid, 4-sulfonic acid phthalic acid, 5-(4-sulfonic acid Dicarboxylic acids such as phenyloxy) isophthalic acid or their salts, and ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, new Polyester polyols obtained by the reaction of low-molecular polyols such as pentylene glycol, etc.

該具有羧基的多元醇及該具有磺酸基的多元醇，較佳係在該胺基甲酸酯樹脂(a2)的酸價為2~70mgKOH/g的範圍內使用，更佳係在10~50mgKOH/g的範圍內使用。另外，本發明所指的酸價，係根據該胺基甲酸酯樹脂(a2)的製造中所使用之具有羧基或磺酸基之多元醇等的含酸基化合物的使用量所算出的理論值。 The polyhydric alcohol with carboxyl group and the polyhydric alcohol with sulfonic acid group are preferably used in the range where the acid value of the urethane resin (a2) is 2 to 70 mgKOH/g, more preferably in the range of 10 to 70 mgKOH/g. Use within the range of 50mgKOH/g. In addition, the acid value referred to in the present invention is a theory calculated from the amount of acid group-containing compounds such as polyols having carboxyl groups or sulfonic acid groups used in the production of the urethane resin (a2). value.

又，從可賦予該胺基甲酸酯樹脂(a2)良好的水分散性的觀點來看，較佳係以鹼性化合物等將該陰離 子性基的一部份或是全部中和。 Also, from the viewpoint of imparting good water dispersibility to the urethane resin (a2), it is preferable to neutralize part or all of the anionic groups with a basic compound or the like.

作為該鹼性化合物，可列舉例如：氨；三乙胺、

Figure 106145467-A0202-12-0011-5
啉、單乙醇胺、二乙基乙醇胺等的有機胺；氫氧化鈉、氫氧化鉀、氫氧化鋰等的金屬氫氧化物等。從更提升本發明之水性樹脂組成物的水分散穩定性的觀點來看，該鹼性化合物的使用量，以鹼性化合物與陰離子性基的莫耳比[鹼性化合物/陰離子性基]計，較佳為0.5~3的範圍，更佳為0.7~1.5的範圍。 As the basic compound, for example: ammonia; triethylamine,
Figure 106145467-A0202-12-0011-5
Organic amines such as morphine, monoethanolamine, diethylethanolamine, etc.; metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. From the point of view of improving the water dispersion stability of the water-based resin composition of the present invention, the amount of the basic compound used is calculated by the molar ratio of the basic compound to the anionic group [basic compound/anionic group] , preferably in the range of 0.5-3, more preferably in the range of 0.7-1.5.

又，該多元醇(a2-1)，除了上述的多元醇以外，亦可因應需求使用其他多元醇。 Moreover, this polyol (a2-1) can use other polyols as needed besides the above-mentioned polyols.

作為該其他多元醇，可列舉例如：乙二醇、二乙二醇、1,2-丙二醇、二丙二醇、新戊二醇、2-丁基-2-乙基-1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、3-甲基-1,5-戊二醇、1,4-環己二醇、1,6-己二醇、環己烷二甲醇等的較低分子量(例如小於500，較佳為400以下)的多元醇。該等的其他多元醇可單獨使用，亦可併用2種以上。 Examples of such other polyhydric alcohols include ethylene glycol, diethylene glycol, 1,2-propanediol, dipropylene glycol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 1 ,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, 1,6-hexanediol, cyclohexanedimethanol etc. lower molecular weight (eg less than 500, preferably less than 400) polyols. These other polyols may be used alone or in combination of two or more.

作為可與該多元醇(a2-1)反應的聚異氰酸酯(a2-2)，可列舉例如：4,4’-二苯基甲烷二異氰酸酯、2,4’-二苯基甲烷二異氰酸酯、碳二亞胺改質二苯基甲烷二異氰酸酯、粗二苯基甲烷二異氰酸酯、伸苯基二異氰酸酯、二異氰酸甲伸苯酯、萘二異氰酸酯等的芳香族聚異氰酸酯；二異氰酸六亞甲酯、離胺酸二異氰酸酯、二甲苯二異氰酸酯、四甲基二甲苯二異氰酸酯等的脂肪族聚異氰酸酯；環己烷二異氰酸酯、二環己基甲烷二異氰酸酯、異佛酮二異氰酸酯等。該等的聚異氰酸酯(a2-2)可單獨使 用，亦可併用2種以上。 Examples of the polyisocyanate (a2-2) that can react with the polyol (a2-1) include 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, carbon Diimine-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, methylene diisocyanate, naphthalene diisocyanate and other aromatic polyisocyanates; hexadiisocyanate Aliphatic polyisocyanates such as methylene esters, lysine diisocyanate, xylene diisocyanate, and tetramethylxylene diisocyanate; cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, and the like. These polyisocyanates (a2-2) may be used alone or in combination of two or more.

該聚異氰酸酯(a2-2)之中，從更提升對基材之密合性的觀點來看，較佳為包含芳香族聚異氰酸酯。此時的該聚異氰酸酯(a2-2)中的芳香族聚異氰酸酯的含量較佳為15~35質量%的範圍。 Among the polyisocyanates (a2-2), it is preferable to include an aromatic polyisocyanate from the viewpoint of further improving the adhesiveness to the substrate. At this time, the content of the aromatic polyisocyanate in the polyisocyanate (a2-2) is preferably in the range of 15 to 35% by mass.

例如，可在無溶劑下或是有機溶劑的存在下，使該多元醇(a2-1)與該聚異氰酸酯(a2-2)混合，於40~120℃的溫度，使其反應3~20小時，藉此可製造該胺基甲酸酯樹脂(a2)。又，製造該胺基甲酸酯樹脂(a2)時，亦可因應需求使用鏈延長劑。 For example, the polyol (a2-1) can be mixed with the polyisocyanate (a2-2) in the absence of a solvent or in the presence of an organic solvent, and reacted at a temperature of 40 to 120°C for 3 to 20 hours , thereby producing the urethane resin (a2). Moreover, when producing this urethane resin (a2), you may use a chain extender as needed.

該多元醇(a2-1)與該聚異氰酸酯(a2-2)的反應，較佳係在該多元醇(a2-1)所具有之羥基與該聚異氰酸酯(a2-2)所具有之異氰酸酯基的當量比[異氰酸酯基/羥基]為0.5~3.5的範圍進行，更佳係在0.9~2.5的範圍進行。 The reaction between the polyol (a2-1) and the polyisocyanate (a2-2) is preferably between the hydroxyl group of the polyol (a2-1) and the isocyanate group of the polyisocyanate (a2-2). The equivalent ratio [isocyanate group/hydroxyl group] is carried out in the range of 0.5 to 3.5, more preferably in the range of 0.9 to 2.5.

作為在製造該胺基甲酸酯樹脂(a2)時可使用的有機溶劑，可列舉例如：丙酮、甲乙酮等的酮溶劑；四氫呋喃、二

Figure 106145467-A0202-12-0012-6
烷(dioxane)等的醚溶劑；乙酸乙酯、乙酸丁酯等的乙酸酯溶劑；乙腈等的腈溶劑；二甲基甲醯胺、N-甲基吡咯啶酮等的醯胺溶劑等。該等的有機溶劑可單獨使用，亦可併用2種以上。 Examples of organic solvents usable when producing the urethane resin (a2) include ketone solvents such as acetone and methyl ethyl ketone; tetrahydrofuran, di
Figure 106145467-A0202-12-0012-6
ether solvents such as dioxane; acetate solvents such as ethyl acetate and butyl acetate; nitrile solvents such as acetonitrile; amide solvents such as dimethylformamide and N-methylpyrrolidone, and the like. These organic solvents may be used alone or in combination of two or more.

以上述方法所得之該胺基甲酸酯樹脂(a2)的重量平均分子量，從更提升基材與活性能量射線硬化性組成物的硬化塗膜之密合性的觀點來看，較佳為3,000~200,000的範圍，更佳為3,000~100,000的範圍。 The weight average molecular weight of the urethane resin (a2) obtained by the above method is preferably 3,000 from the viewpoint of further improving the adhesion between the base material and the cured coating film of the active energy ray-curable composition. The range of ~200,000, more preferably the range of 3,000~100,000.

該複合樹脂(A)係包含該乙烯酯樹脂(a1)及具有芳香環的胺基甲酸酯樹脂(a2)者，該乙烯酯樹脂(a1)及該胺基甲酸酯樹脂(a2)較佳為分散於水性媒介中。此時，在該水性媒介中，較佳係形成該乙烯酯樹脂(a1)的一部分或是全部存在於該胺基甲酸酯樹脂(a2)粒子內部的樹脂粒子。更具體而言，較佳為該乙烯酯樹脂(a1)形成核部，該胺基甲酸酯樹脂(a2)形成殼部的核/殼型的樹脂粒子。 The composite resin (A) is composed of the vinyl ester resin (a1) and the urethane resin (a2) having an aromatic ring, and the vinyl ester resin (a1) and the urethane resin (a2) are more Preferably dispersed in an aqueous medium. In this case, in the aqueous medium, it is preferable to form resin particles in which part or all of the vinyl ester resin (a1) exists inside the urethane resin (a2) particles. More specifically, it is preferable that the vinyl ester resin (a1) forms a core portion and the urethane resin (a2) forms a shell portion, in a core/shell type resin particle.

該複合樹脂(A)可以下述方法製造：預先製造該乙烯酯樹脂(a1)及該胺基甲酸酯樹脂(a2)，接著，在該胺基甲酸酯樹脂(a2)中，混合該乙烯酯樹脂(a1)、將該胺基甲酸酯樹脂(a2)所具有之陰離子性基中和的鹼性化合物以及水性媒介。 This composite resin (A) can be produced by the method of preparing the vinyl ester resin (a1) and the urethane resin (a2) in advance, and then mixing the urethane resin (a2) with the A vinyl ester resin (a1), a basic compound for neutralizing the anionic group of the urethane resin (a2), and an aqueous medium.

該乙烯酯樹脂(a1)與該胺基甲酸酯樹脂(a2)的質量比例[(a1)/(a2)]，從更提升與活性能量射線硬化性組成物的硬化塗膜之密合性的觀點來看，較佳為60/40~10/90的範圍，更佳為55/45~20/80的範圍。 The mass ratio of the vinyl ester resin (a1) to the urethane resin (a2) [(a1)/(a2)] improves the adhesion to the cured coating film of the active energy ray curable composition. From the point of view, it is preferably in the range of 60/40~10/90, more preferably in the range of 55/45~20/80.

在該水性樹脂組成物的非揮發成分中，該複合樹脂(A)的含有率較佳為50質量%以上，更佳為80質量%以上，再佳為85質量%以上，特佳為90質量%以上，較佳為99.9質量%以下。 In the non-volatile components of the aqueous resin composition, the content of the composite resin (A) is preferably at least 50% by mass, more preferably at least 80% by mass, even more preferably at least 85% by mass, and most preferably at least 90% by mass. % or more, preferably 99.9 mass % or less.

作為該水性樹脂(B)，可列舉例如：胺基甲酸酯樹脂(b1)、聚酯樹脂、丙烯酸樹脂等。該等之中，從可形成對於難以接著之基材具有優良密合性的塗膜的觀點來看，較佳為胺基甲酸酯樹脂(b1)。又，該等的水性 樹脂可單獨使用，亦可併用2種以上。 As this aqueous resin (B), a urethane resin (b1), a polyester resin, an acrylic resin, etc. are mentioned, for example. Among these, the urethane resin (b1) is preferable from the viewpoint that it can form a coating film having excellent adhesion to a substrate that is difficult to bond. Also, these water-based resins may be used alone, or two or more of them may be used in combination.

作為該胺基甲酸酯樹脂(b1)，可使用與上述胺基甲酸酯樹脂(a2)相同者。 As this urethane resin (b1), the thing similar to the said urethane resin (a2) can be used.

該複合樹脂(A)與該水性樹脂(B)的質量比例[(A)/(B)]，從摻合穩定性及與以下記載之硬塗劑之密合性的觀點來看，較佳為99/1~80/20的範圍。 The mass ratio [(A)/(B)] of the composite resin (A) to the water-based resin (B) is preferable from the viewpoint of blending stability and adhesion to the hard coating agent described below. It is in the range of 99/1~80/20.

作為該水性媒介(C)，可列舉：水、與水混和的有機溶劑以及該等的混合物。作為與水混和的有機溶劑，可列舉例如：甲醇、乙醇、正丙醇、異丙醇等的醇溶劑；丙酮、甲乙酮等的酮溶劑；乙二醇、二乙二醇、丙二醇等的聚伸烷基二醇；聚伸烷基二醇的烷基醚溶劑；N-甲基-2-吡咯啶酮等的內醯胺溶劑等。該等與水混和的有機溶劑可單獨使用，亦可併用2種以上。 Examples of the aqueous medium (C) include water, organic solvents mixed with water, and mixtures thereof. As the organic solvent mixed with water, for example: alcohol solvents such as methanol, ethanol, n-propanol, and isopropanol; ketone solvents such as acetone and methyl ethyl ketone; Alkyl glycols; alkyl ether solvents of polyalkylene glycols; lactamide solvents such as N-methyl-2-pyrrolidone, etc. These water-miscible organic solvents may be used alone or in combination of two or more.

又，該水性媒介(C)，若考量安全性及降低對於環境之負荷，則較佳係僅為水，或是水及與水混和之有機溶劑的混合物，更佳係僅為水。 In addition, the aqueous medium (C) is preferably only water, or a mixture of water and an organic solvent mixed with water, more preferably only water, in consideration of safety and reduction of environmental load.

本發明之水性樹脂組成物總量中，較佳係以10~60質量%的範圍，更佳係以20~50質量%的範圍包含該水性媒介(C)。 In the total amount of the water-based resin composition of the present invention, the water-based medium (C) is preferably included in the range of 10-60% by mass, more preferably in the range of 20-50% by mass.

使該複合樹脂(A)與該水性樹脂(B)分散於該水性媒介(C)中，可得到本發明之水性樹脂組成物。 The composite resin (A) and the water-based resin (B) are dispersed in the water-based medium (C) to obtain the water-based resin composition of the present invention.

又，本發明之水性樹脂組成物，可更包含非水溶性的添加劑。 Also, the water-based resin composition of the present invention may further contain water-insoluble additives.

該非水溶性的添加劑，較佳係預先分散於該水性樹脂(B)之水分散體中以使用。 The water-insoluble additive is preferably pre-dispersed in the water dispersion of the water-based resin (B) for use.

作為該非水溶性的添加劑，可列舉例如：抗氧化劑、紫外線吸收劑等。該等的非水溶性的添加劑可單獨使用，亦可併用2種以上。 As this water-insoluble additive, antioxidant, a ultraviolet absorber, etc. are mentioned, for example. These water-insoluble additives may be used individually, and may use 2 or more types together.

作為該抗氧化劑，可列舉：酚系抗氧化劑、磷系抗氧化劑、硫系抗氧化劑、胺系抗氧化劑等。該等之中，從可形成對於難以接著之基材具有優良密合性之塗膜，再者，從可形成耐熱性、耐熱變色及自動抑制氧化為優良之塗膜的觀點來看，較佳為酚系抗氧化劑、磷系抗氧化劑。又，該等的抗氧化劑可單獨使用，亦可併用2種以上。 As this antioxidant, a phenolic antioxidant, a phosphorus antioxidant, a sulfur antioxidant, an amine antioxidant, etc. are mentioned. Among these, it is preferable from the viewpoint of forming a coating film having excellent adhesion to substrates that are difficult to adhere to, and furthermore, from the viewpoint of forming a coating film excellent in heat resistance, heat discoloration resistance, and self-oxidation inhibition. It is a phenolic antioxidant and a phosphorus antioxidant. Moreover, these antioxidants may be used individually, and may use 2 or more types together.

該抗氧化劑，分子量若太小則容易移動至塗膜表面，導致對於基材的密合性降低，另一方面，分子量若太大，則與該水性樹脂(B)的相溶性變差，從此觀點來看，較佳為重量平均分子量在500~1,000之範圍者。 The antioxidant, if the molecular weight is too small, it will easily move to the surface of the coating film, resulting in reduced adhesion to the base material; From a viewpoint, it is preferable that the weight average molecular weight is in the range of 500-1,000.

又，該抗氧化劑，若熔點低則塗膜表面容易結塊，另一方面，若熔點高則與該水性樹脂(B)的相溶性變差，從此觀點來看，較佳為熔點在80~180℃的範圍者。 Also, if the antioxidant has a low melting point, the surface of the coating film is likely to agglomerate. On the other hand, if the melting point is high, the compatibility with the water-based resin (B) will be poor. Those in the range of 180°C.

該添加劑的含量，相對於該複合樹脂(A)100質量份，較佳為0.001質量份以上，更佳為0.005質量份以上，再佳為0.01質量份以上，較佳為1質量份以下，更佳為0.5質量份以下，再佳為0.3質量份以下。 The content of the additive is preferably not less than 0.001 part by mass, more preferably not less than 0.005 part by mass, more preferably not less than 0.01 part by mass, more preferably not more than 1 part by mass, and more preferably not more than 1 part by mass relative to 100 parts by mass of the composite resin (A). It is preferably at most 0.5 parts by mass, more preferably at most 0.3 parts by mass.

本發明之水性樹脂組成物中，除了該非水溶性的添加劑以外，亦可因應需求摻合成膜助劑、硬化劑、交聯劑、塑化劑、抗靜電劑、石蠟、光穩定劑、流動控制劑、染料、均染劑、流變控制劑、光觸媒性化合物、無機顏料、有機顏料、體質顏料等的添加劑。 In the water-based resin composition of the present invention, in addition to the non-water-soluble additives, film-forming aids, hardeners, cross-linking agents, plasticizers, antistatic agents, paraffin, light stabilizers, flow control agents, etc. Additives, dyes, leveling agents, rheology control agents, photocatalyst compounds, inorganic pigments, organic pigments, extender pigments, etc.

作為該交聯劑，可列舉例如：三聚氰胺化合物、環氧化物、

Figure 106145467-A0202-12-0016-7
唑啉化合物、碳二亞胺化合物、異氰酸酯化合物等。作為該三聚氰胺化合物，可列舉例如：烷基化羥甲基三聚氰胺樹脂。該烷基化羥甲基三聚氰胺樹脂，例如，係使羥甲基化三聚氰胺樹脂與甲醇、丁醇等的低級醇(碳原子數1~6的醇)反應所得者。作為該羥甲基化三聚氰胺樹脂，可列舉例如：使三聚氰胺與甲醛縮合所得之具有胺基的羥甲基三聚氰胺樹脂、具有亞胺基的羥甲基三聚氰胺樹脂、三甲氧基羥甲基三聚氰胺樹脂、六甲氧基羥甲基三聚氰胺樹脂等。該等之中，較佳為三甲氧基羥甲基三聚氰胺樹脂、六甲氧基羥甲基三聚氰胺樹脂。又，作為該烷基化羥甲基三聚氰胺樹脂，可列舉：具有亞胺基的烷基化羥甲基三聚氰胺樹脂、具有胺基的烷基化羥甲基三聚氰胺樹脂等。 Examples of the crosslinking agent include melamine compounds, epoxides,
Figure 106145467-A0202-12-0016-7
Azoline compounds, carbodiimide compounds, isocyanate compounds, etc. As this melamine compound, an alkylation methylolmelamine resin is mentioned, for example. The alkylated methylolmelamine resin is, for example, obtained by reacting a methylolated melamine resin with a lower alcohol (alcohol having 1 to 6 carbon atoms) such as methanol or butanol. Examples of the methylolated melamine resin include methylol melamine resins having amino groups obtained by condensing melamine and formaldehyde, methylol melamine resins having imine groups, trimethoxymethylol melamine resins, Hexamethoxymethylolmelamine resin, etc. Among them, trimethoxymethylolmelamine resin and hexamethoxymethylolmelamine resin are preferable. Moreover, as this alkylation methylolmelamine resin, the alkylation methylolmelamine resin which has an imine group, the alkylation methylolmelamine resin which has an amino group, etc. are mentioned.

本發明之積層體，具有使用該水性樹脂組成物在基材的單面或是雙面上形成的底漆層，且具有使用活性能量射線硬化性組成物而形成於該底漆層之表面上的硬化塗膜。 The laminate of the present invention has a primer layer formed on one or both sides of a substrate using the aqueous resin composition, and has a primer layer formed on the surface of the primer layer using an active energy ray-curable composition. hardened coating.

作為該活性能量射線硬化性組成物，較佳係包含具有聚合性不飽和基的樹脂與具有聚合性不飽和基之單體者；該等具有聚合性不飽和基之樹脂及具有聚合性不飽和基之單體的種類，較佳係因應該活性能量射線硬化性組成物的硬化塗膜所要求之特性適當選擇。 As the active energy ray-curable composition, it is preferable to include a resin having a polymerizable unsaturated group and a monomer having a polymerizable unsaturated group; the resin having a polymerizable unsaturated group and the resin having a polymerizable unsaturated The type of the monomer of the base is preferably appropriately selected according to the properties required for the cured coating film of the active energy ray curable composition.

作為該具有聚合性不飽和基之樹脂，可列舉：胺基甲酸酯(甲基)丙烯酸酯樹脂、不飽和聚酯樹脂、環氧(甲基)丙烯酸酯樹脂、聚酯(甲基)丙烯酸酯樹脂、丙烯酸(甲基)丙烯酸酯樹脂、具有馬來醯亞胺基的樹脂等。該等的具有聚合性不飽和基之樹脂可單獨使用，亦可併用2種以上。 Examples of the resin having a polymerizable unsaturated group include: urethane (meth)acrylate resin, unsaturated polyester resin, epoxy (meth)acrylate resin, polyester (meth)acrylic acid Ester resins, acrylic (meth)acrylate resins, resins having maleimide groups, and the like. These polymerizable unsaturated group-containing resins may be used alone or in combination of two or more.

本發明中，「(甲基)丙烯酸酯」係指丙烯酸酯及甲基丙烯酸酯的一者或是兩者；「(甲基)丙烯醯基」係指丙烯醯基及甲基丙烯醯基一者或是兩者。 In the present invention, "(meth)acrylate" refers to one or both of acrylate and methacrylate; "(meth)acryl" refers to acryl and methacryl. or both.

作為該胺基甲酸酯(甲基)丙烯酸酯樹脂，可列舉例如：具有使脂肪族聚異氰酸酯或是芳香族聚異氰酸酯與具有羥基之(甲基)丙烯酸酯進行胺基甲酸酯化反應所得之胺基甲酸酯鍵與(甲基)丙烯醯基的樹脂等。 Examples of the urethane (meth)acrylate resin include those obtained by urethanizing an aliphatic polyisocyanate or an aromatic polyisocyanate with a (meth)acrylate having a hydroxyl group. Urethane bond and (meth)acryl-based resin, etc.

作為該脂肪族聚異氰酸酯，可列舉例如：二異氰酸四亞甲酯、二異氰酸五亞甲酯、二異氰酸六亞甲酯、二異氰酸七亞甲酯、二異氰酸八亞甲酯、二異氰酸十亞甲酯、2-甲基-1,5-戊烷二異氰酸酯、3-甲基-1,5-戊烷二異氰酸酯、二異氰酸十二亞甲酯、二異氰酸2-甲基五亞甲酯、二異氰酸2,2,4-三甲基六亞甲酯、二異氰酸2,4,4-三甲基六亞甲酯、異佛酮二異氰酸酯、降莰烷二異氰酸酯、加氫二苯基甲烷二異氰酸酯、加氫甲伸苯基二異氰酸酯、加氫二甲苯二異氰酸酯、加氫四甲基二甲苯二異氰酸酯、二異氰酸環己酯等。又，作為該芳香族聚異氰酸酯，可列舉：二異氰酸甲伸苯酯、4,4’-二苯基甲烷二異氰酸酯、二甲苯二異氰酸酯、1,5-萘二異氰酸酯、 聯甲苯胺二異氰酸酯、二異氰酸對伸苯酯等。 Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, diisocyanate octamethylene diisocyanate, decamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, dodecylene diisocyanate Methyl ester, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate ester, isophorone diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated methylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated tetramethylxylene diisocyanate, di Cyclohexyl isocyanate, etc. Moreover, examples of the aromatic polyisocyanate include methylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylene diisocyanate, 1,5-naphthalene diisocyanate, benzidine diisocyanate, Isocyanate, p-phenylene diisocyanate, etc.

作為該具有羥基之(甲基)丙烯酸酯，可列舉例如：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸4-羥基丁酯、1,5-戊二醇單(甲基)丙烯酸酯、1,6-己二醇單(甲基)丙烯酸酯、新戊二醇單(甲基)丙烯酸酯、羥基三甲基乙酸新戊二醇單(甲基)丙烯酸酯等的2元醇的單(甲基)丙烯酸酯；三羥甲基丙烷二(甲基)丙烯酸酯、乙氧基化三羥甲基丙烷(甲基)丙烯酸酯、丙氧基化三羥甲基丙烷二(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、雙(2-(甲基)丙烯醯基氧基乙基)羥基乙基異氰脲酸酯等的3元醇的單或是二(甲基)丙烯酸酯，或是，以ε-己內酯將該等的醇性羥基的一部份改質而得的具有羥基之單及二(甲基)丙烯酸酯；新戊四醇三(甲基)丙烯酸酯、二三羥甲基丙烷三(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯等的具有1官能的羥基與3官能以上的(甲基)丙烯醯基的化合物，或是，更以ε-己內酯將該化合物改質而得的具有羥基的多官能(甲基)丙烯酸酯；二丙二醇單(甲基)丙烯酸酯、二乙二醇單(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯、聚乙二醇單(甲基)丙烯酸酯等的具有氧基伸烷基鏈的(甲基)丙烯酸酯化合物；聚乙二醇-聚丙二醇單(甲基)丙烯酸酯、聚氧基丁稀-聚氧基丙烯單(甲基)丙烯酸酯等的具有嵌段構造之氧基伸烷基鏈的(甲基)丙烯酸酯化合物；聚(乙二醇-四亞甲基二醇)單(甲基)丙烯酸酯、聚(丙二醇-四亞甲基二醇)單(甲基)丙烯酸酯等的具有無規構 造之氧基伸烷基鏈的(甲基)丙烯酸酯化合物等。 As the (meth)acrylate having a hydroxyl group, for example: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, ( 4-Hydroxybutyl methacrylate, 1,5-pentanediol mono(meth)acrylate, 1,6-hexanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate mono(meth)acrylates of dihydric alcohols such as hydroxytrimethylacetate neopentyl glycol mono(meth)acrylate; trimethylolpropane di(meth)acrylate, ethoxylated trimethylolpropane Methylolpropane (meth)acrylate, propoxylated trimethylolpropane di(meth)acrylate, glycerol di(meth)acrylate, bis(2-(meth)acryloxy Mono- or di-(meth)acrylates of trihydric alcohols such as ethyl) hydroxyethyl isocyanurate, or modifying part of their alcoholic hydroxyl groups with ε-caprolactone The resulting mono- and di(meth)acrylates with hydroxyl groups; neopentylthritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, A compound having a monofunctional hydroxyl group and a trifunctional or more (meth)acryl group such as acrylate, or a polyfunctional ( Meth)acrylate; dipropylene glycol mono(meth)acrylate, diethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, etc. (meth)acrylate compounds with oxyalkylene chains; polyethylene glycol-polypropylene glycol mono(meth)acrylate, polyoxybutylene-polyoxypropylene mono(meth)acrylate, etc. (Meth)acrylate compound having an oxyalkylene chain of block structure; poly(ethylene glycol-tetramethylene glycol) mono(meth)acrylate, poly(propylene glycol-tetramethylene glycol) ) (meth)acrylate compounds such as mono(meth)acrylate having an oxyalkylene chain having a random structure, and the like.

該不飽和聚酯樹脂，係藉由α,β-不飽和雙質子酸或是其酸酐、芳香族飽和雙質子酸或是其酸酐及二醇的聚縮合所得之硬化性樹脂。作為該α,β-不飽和雙質子酸或是其酸酐，可列舉例如：馬來酸、馬來酸酐、富馬酸、伊康酸、焦檸檬酸、氯馬來酸、及該等的酯等。作為該芳香族飽和雙質子酸或是其酸酐，可列舉：鄰苯二甲酸、鄰苯二甲酸酐、間苯二甲酸、對苯二甲酸、硝基鄰苯二甲酸、四氫鄰苯二甲酸酐、內亞甲基四氫鄰苯二甲酸酐、鹵化鄰苯二甲酸酐及該等的酯等。作為脂肪族或是脂環族飽和雙質子酸，可列舉：草酸、丙二酸、琥珀酸、己二酸、癸二酸、壬二酸、戊二酸、六氫鄰苯二甲酸酐及該等的酯等。作為該二醇，可列舉：乙二醇、丙二醇、二乙二醇、二丙二醇、1,3-丁二醇、1,4-丁二醇、2-甲基丙-1,3-二醇、新戊二醇、三乙二醇、四乙二醇、1,5-戊二醇、1,6-己二醇、雙酚A、氫化雙酚A、乙二醇碳酸酯、2,2-二-(4-羥基丙氧基二苯基)丙烷等，其他亦可相同地使用氧化乙烯、氧化丙烯等的氧化物。 The unsaturated polyester resin is a curable resin obtained by polycondensation of α,β-unsaturated diprotic acid or its anhydride, aromatic saturated diprotic acid or its anhydride and diol. Examples of the α,β-unsaturated diprotic acid or its anhydride include maleic acid, maleic anhydride, fumaric acid, itaconic acid, pyrocitric acid, chloromaleic acid, and esters thereof. Wait. Examples of the aromatic saturated diprotic acid or its anhydride include: phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic acid Anhydrides, endomethylenetetrahydrophthalic anhydrides, halogenated phthalic anhydrides and their esters, etc. Examples of aliphatic or alicyclic saturated diprotic acids include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, and the like. etc. Esters etc. Examples of the diol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, and 2-methylpropane-1,3-diol , neopentyl glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2 - Bis-(4-hydroxypropoxydiphenyl)propane, etc. Other oxides such as ethylene oxide and propylene oxide can also be used in the same manner.

作為該環氧(甲基)丙烯酸酯樹脂，可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂等的使環氧樹脂之環氧基與(甲基)丙烯酸反應所得者。 As this epoxy (meth)acrylate resin, the use of bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin etc. is mentioned It is obtained by reacting the epoxy group of epoxy resin with (meth)acrylic acid.

作為該聚酯(甲基)丙烯酸酯樹脂，可列舉例如：使聚酯多元醇的羥基與(甲基)丙烯酸反應所得者。 As this polyester (meth)acrylate resin, what made the hydroxyl group of a polyester polyol react with (meth)acrylic acid is mentioned, for example.

作為該丙烯酸(甲基)丙烯酸酯樹脂，可列舉 例如：使甲基丙烯酸環氧丙酯，及因應需求之(甲基)丙烯酸烷酯等的(甲基)丙烯酸酯單體聚合而得到具有環氧基之丙烯酸樹脂之後，使該環氧基與(甲基)丙烯酸反應所得者。 As the acrylic (meth)acrylate resin, for example, a resin having a ring can be obtained by polymerizing a (meth)acrylate monomer such as glycidyl methacrylate and, if necessary, an alkyl (meth)acrylate. It is obtained by reacting the epoxy group with (meth)acrylic acid after the acrylic resin of the oxygen group.

作為該具有馬來醯亞胺基的樹脂，可列舉：將N-羥基乙基馬來醯亞胺與異佛酮二異氰酸酯進行胺基甲酸酯化所得之2官能馬來醯亞胺胺基甲酸酯化合物、使馬來醯亞胺乙酸與聚四亞甲基二醇進行酯化所得之2官能馬來醯亞胺酯化物、使馬來醯亞胺己酸與新戊四醇的四乙烯氧化物加成物進行酯化所得之4官能馬來醯亞胺酯化物、使馬來醯亞胺乙酸與多元醇化合物進行酯化所得之多官能馬來醯亞胺酯化物等。 Examples of the resin having a maleimide group include bifunctional maleimide amino groups obtained by urethanizing N-hydroxyethylmaleimide and isophorone diisocyanate. Formate compound, bifunctional maleimide ester compound obtained by esterifying maleimide acetic acid and polytetramethylene glycol, tetramethylene glycol Tetrafunctional maleimide esterified products obtained by esterifying ethylene oxide adducts, polyfunctional maleimide esterified products obtained by esterifying maleimide acetic acid and polyol compounds, etc.

作為該具有聚合性不飽和基之單體，可列舉例如：乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、數量平均分子量在150~1000之範圍的聚乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、數量平均分子量在150~1000之範圍的聚丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、羥基三甲基乙酸酯新戊二醇二(甲基)丙烯酸酯、雙酚A二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基丙烷二(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸 酯、二新戊四醇五(甲基)丙烯酸酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十二酯、(甲基)丙烯酸十八酯、(甲基)丙烯酸異十八酯等的(甲基)丙烯酸脂肪族烷酯、甘油(甲基)丙烯酸酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸3-氯-2-羥基丙酯、(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸2-丁氧基乙酯、(甲基)丙烯酸2-(二乙基胺基)乙酯、(甲基)丙烯酸2-(二甲基胺基)乙酯、γ-(甲基)丙烯醯氧基丙基三甲氧基矽烷、(甲基)丙烯酸酯2-甲氧基乙酯、甲氧基二乙二醇(甲基)丙烯酸酯、甲氧基二丙二醇(甲基)丙烯酸酯、壬基苯氧基聚乙二醇(甲基)丙烯酸酯、壬基苯氧基聚丙二醇(甲基)丙烯酸酯、(甲基)丙烯酸苯氧基乙酯、苯氧基二丙二醇(甲基)丙烯酸酯、苯氧基聚丙二醇(甲基)丙烯酸酯、聚丁二烯(甲基)丙烯酸酯、聚乙二醇-聚丙二醇(甲基)丙烯酸酯、聚乙二醇-聚丁二醇(甲基)丙烯酸酯、聚苯乙烯基乙基(甲基)丙烯酸酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸異莰酯、甲氧基化環癸三烯(甲基)丙烯酸酯、(甲基)丙烯酸苯酯；馬來醯亞胺、N-甲基馬來醯亞胺、N-乙基馬來醯亞胺、N-丙基馬來醯亞胺、N-丁基馬來醯亞胺、N-己基馬來醯亞胺、N-辛基馬來醯亞胺、N-十二基馬來醯亞胺、N-十八基馬來醯亞胺、N-苯基馬來醯亞胺、 N-環己基馬來醯亞胺、2-馬來醯亞胺乙基-乙基碳酸酯、2-馬來醯亞胺乙基-丙基碳酸酯、N-乙基-(2-馬來醯亞胺乙基)胺基甲酸酯、N,N-六亞甲基雙馬來醯亞胺、聚丙二醇-雙(3-馬來醯亞胺丙基)醚、雙(2-馬來醯亞胺乙基)碳酸酯、1,4-二馬來醯亞胺環己烷等的馬來醯亞胺化合物等。該等的具有聚合性不飽和基之單體可單獨使用，亦可併用2種以上。 Examples of the monomer having a polymerizable unsaturated group include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and triethylene glycol di(meth)acrylate. , Polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate with a number average molecular weight in the range of 150~1000 ester, polypropylene glycol di(meth)acrylate with number average molecular weight in the range of 150~1000, neopentyl glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1 ,4-Butanediol Di(meth)acrylate, 1,6-Hexanediol Di(meth)acrylate, Hydroxytrimethylacetate Neopentyl Glycol Di(meth)acrylate, Bisphenol A di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane di(meth)acrylate, neopentylthritol tetra(meth)acrylate, neopentyl tetra Alcohol tri(meth)acrylate, diperythritol hexa(meth)acrylate, diperythritol penta(meth)acrylate, dicyclopentenyl (meth)acrylate, (meth) Methyl acrylate, propyl (meth)acrylate, butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, (Meth) decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, etc. Aliphatic alkyl acrylate, glycerin (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, Allyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-(diethylamino)ethyl (meth)acrylate, 2-(dimethyl)acrylate Amino)ethyl ester, γ-(meth)acryloxypropyltrimethoxysilane, 2-methoxyethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate , Methoxy Dipropylene Glycol (Meth) Acrylate, Nonylphenoxy Polyethylene Glycol (Meth) Acrylate, Nonylphenoxy Polypropylene Glycol (Meth) Acrylate, (Meth) Phenoxy Acrylate Ethyl Ester, Phenoxy Dipropylene Glycol (Meth) Acrylate, Phenoxy Polypropylene Glycol (Meth) Acrylate, Polybutadiene (Meth) Acrylate, Polyethylene-Polypropylene Glycol (Meth) Acrylates, polyethylene glycol-polybutylene glycol (meth)acrylate, polystyrene ethyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, ( Dicyclopentyl (meth)acrylate, Dicyclopentenyl (meth)acrylate, Isobornyl (meth)acrylate, Methoxylated cyclodecatriene (meth)acrylate, Benzene (meth)acrylate Esters; maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N- Hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide Maleimide, N-octadecylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 2-maleimide ethyl-ethyl carbonate , 2-maleimide ethyl-propyl carbonate, N-ethyl-(2-maleimide ethyl) carbamate, N, N-hexamethylene bismaleyl imine, polypropylene glycol-bis(3-maleimide propyl) ether, bis(2-maleimide ethyl) carbonate, 1,4-dimaleimide cyclohexane, etc. Maleimide compounds, etc. These monomers having a polymerizable unsaturated group may be used alone or in combination of two or more.

該活性能量射線硬化性組成物，在塗布於基材等之後，藉由照射活性能量射線可成為硬化塗膜。作為該活性能量射線，可列舉：紫外線、電子束、α射線、β射線、γ射線等的游離輻射線。照射紫外線作為活性能量射線以使該活性能量射線硬化性組成物成為硬化塗膜的情況，較佳係在該活性能量射線硬化性組成物中添加光聚合起始劑，以提升硬化性。又，若有需要，可更添加光敏劑，亦可提升硬化性。另一方面，照射電子線、α線、β線或是γ線作為活性能量射線以使該活性能量射線硬化性組成物成為硬化塗膜的情況，即使不使用光聚合起始劑及光敏劑亦可快速硬化，故無需添加光聚合起始劑及光敏劑。 This active energy ray curable composition can become a cured coating film by irradiating an active energy ray after coating on a base material etc. Examples of the active energy rays include ionizing radiation rays such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When irradiating ultraviolet rays as active energy rays to make the active energy ray-curable composition a cured coating film, it is preferable to add a photopolymerization initiator to the active energy ray-curable composition to improve curability. Also, if necessary, a photosensitizer can be added to improve the curability. On the other hand, when irradiating electron beams, α-rays, β-rays, or γ-rays as active energy rays so that the active energy ray-curable composition becomes a cured coating film, even without using a photopolymerization initiator and a photosensitizer It can harden quickly, so there is no need to add photopolymerization initiators and photosensitizers.

作為該光聚合起始劑，可列舉例如：1-羥基環己基苯基酮、2-羥基-2-甲基-1-苯基丙-1-酮、1-[4-(2-羥基乙氧基)-苯基]-2-羥基-甲基-1-丙-1-酮、2-甲基-1-[4-(甲硫基)苯基]-2-

Figure 106145467-A0202-12-0022-8
啉基丙-1-酮、2-苄基-2-二甲基胺基-1-(4-
Figure 106145467-A0202-12-0022-9
啉基苯基)-丁酮、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基戊基膦氧化物、雙(2,4,6-三甲基苯甲醯 基)-苯基膦氧化物等。 Examples of the photopolymerization initiator include: 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethyl Oxygen)-phenyl]-2-hydroxy-methyl-1-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-
Figure 106145467-A0202-12-0022-8
Linylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-
Figure 106145467-A0202-12-0022-9
Linylphenyl)-butanone, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethyl phenylbenzoyl)-phenylphosphine oxide, etc.

作為該光敏劑，可列舉例如：脂肪族胺、芳香族胺等的胺化合物、鄰甲苯基硫代尿素等的尿素化合物、二乙基二硫代磷酸鈉、s-苄基硫脲對甲苯磺酸鹽(s-benzylthiuronium-p-toluenesulfonate)等的硫化物等。 Examples of the photosensitizer include amine compounds such as aliphatic amines and aromatic amines, urea compounds such as o-tolylthiourea, sodium diethyldithiophosphate, s-benzylthiourea p-toluenesulfonate Sulfides such as s-benzylthiuronium-p-toluenesulfonate, etc.

作為用於本發明之積層體的基材，可列舉例如：金屬基材、塑膠基材、玻璃基材、紙基材、木材基材、纖維質基材等。該等的基材之中，為了提升該活性能量射線硬化性組成物的硬化塗膜與基材的密合性，而使用本發明之水性樹脂組成物作為底漆的情況，較佳為塑膠基材。 As a base material used for the laminated body of this invention, a metal base material, a plastic base material, a glass base material, a paper base material, a wood base material, a fibrous base material etc. are mentioned, for example. Among these base materials, in order to improve the adhesion between the cured coating film of the active energy ray curable composition and the base material, when using the water-based resin composition of the present invention as a primer, plastic-based material.

作為該塑膠基材的材質，可列舉：聚酯、丙烯酸樹脂(聚丙烯酸甲酯等)、聚碳酸酯、丙烯腈-丁二烯-苯乙烯共聚物(ABS樹脂)、ABS樹脂與聚碳酸酯的複合樹脂、聚苯乙烯、聚胺基甲酸酯、環氧樹脂、聚氯乙烯、聚醯胺、聚烯烴(聚乙烯、聚丙烯、聚環烯烴(COP)等)、三醋酸纖維素(TAC)等。 As the material of the plastic substrate, polyester, acrylic resin (polymethyl acrylate, etc.), polycarbonate, acrylonitrile-butadiene-styrene copolymer (ABS resin), ABS resin and polycarbonate Composite resin, polystyrene, polyurethane, epoxy resin, polyvinyl chloride, polyamide, polyolefin (polyethylene, polypropylene, polycycloolefin (COP), etc.), cellulose triacetate ( TAC) and so on.

本發明之水性樹脂組成物，在上述的塑膠基材之中，作為聚酯基材的底漆非常有用。作為該聚酯的具體例，可列舉：聚對苯二甲酸乙二酯(PET)、聚對苯二甲酸丁二酯(PBT)等。 The water-based resin composition of the present invention is very useful as a primer for polyester substrates among the above-mentioned plastic substrates. Specific examples of the polyester include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and the like.

作為該塑膠基材，可列舉例如：行動電話、家電產品、汽車內外裝材料、OA設備等的塑膠成形品。又，亦可列舉以塑膠為材料的薄膜基材。以薄膜基材作為本發明之積層體的基材的情況中，可用於抗反射膜、 相位差膜、稜鏡鏡片等的光學薄膜；鋁蒸鍍膜等的食品包裝等的高機能薄膜。 Examples of the plastic base material include plastic molded articles of mobile phones, home electric appliances, interior and exterior materials for automobiles, and OA equipment. In addition, film substrates made of plastics can also be used. When a film substrate is used as the substrate of the laminate of the present invention, it can be used for optical films such as antireflection films, retardation films, and galvanized lenses; and high-performance films such as food packaging such as aluminum vapor-deposited films.

又，以本發明之積層體作為抗反射膜、相位差膜、稜鏡鏡片等的光學薄膜的情況中，可作為液晶顯示器(LCD)、有機EL顯示器(OLED)、電漿顯示器(PDP)等的各種畫面顯示裝置的構件使用。 In addition, in the case of using the laminate of the present invention as an optical film such as an antireflection film, a retardation film, and a galvanized lens, it can be used as a liquid crystal display (LCD), an organic EL display (OLED), a plasma display (PDP), etc. It is used as a component of various screen display devices.

本發明之水性樹脂組成物，例如，可直接塗布於該基材的表面上，接著使其乾燥、硬化，藉此可在基材的表面上形成塗膜。作為使本發明之水性樹脂組成物乾燥以進行硬化的方法，亦可為在常溫下進行固化1~10日左右的方法，但為了迅速進行硬化，較佳係以100℃~150℃的溫度，加熱1~600秒左右的方法。又，使用在較高溫下容易變形或變色之塑膠基材的情況中，較佳係以70℃~100℃左右的較低溫加熱。 The water-based resin composition of the present invention, for example, can be directly coated on the surface of the substrate, and then dried and hardened to form a coating film on the surface of the substrate. As a method of drying the water-based resin composition of the present invention to harden, it can also be cured at room temperature for about 1 to 10 days, but in order to harden quickly, it is preferably at a temperature of 100°C to 150°C. The method of heating for about 1 to 600 seconds. Also, in the case of using a plastic substrate that is easily deformed or discolored at a relatively high temperature, it is preferable to heat at a relatively low temperature of about 70°C to 100°C.

在該基材的表面上塗布本發明之水性樹脂組成物的方法，可列舉例如：使用凹版塗布機、輥塗布機、缺角輪塗布機(comma coater)、刀塗布機、氣刀塗布機、簾幕塗布機、吻合式塗布機、沖淋塗布機、氣流塗布機、旋轉塗布機、浸漬、網版印刷、噴霧、刷塗、散佈機(applicator)、棒塗布機等的塗布方法。 The method for coating the water-based resin composition of the present invention on the surface of the substrate includes, for example: using a gravure coater, a roll coater, a comma coater, a knife coater, an air knife coater, Coating methods such as curtain coater, kiss coater, shower coater, air flow coater, spin coater, dipping, screen printing, spraying, brushing, applicator, bar coater, etc.

使用本發明之水性樹脂組成物所形成之塗膜的膜厚，可因應所使用之用途適當調整，但通常較佳係在0.01~20μm的範圍。 The film thickness of the coating film formed by using the water-based resin composition of the present invention can be adjusted appropriately according to the application, but usually it is preferably in the range of 0.01-20 μm.

在如上述所得之本發明之水性樹脂組成物的塗膜、即底漆層的表面上，更塗布該活性能量射線硬化 性組成物，並且照射活性能量射線以形成該活性能量射線硬化性組成物的硬化塗膜，藉此可得到本發明之積層體。另外，該活性能量射線硬化性組成物的塗布方法，可使用與上述本發明之水性樹脂組成物的塗布方法相同之方法。 The active energy ray-curable composition is further coated on the surface of the coating film of the aqueous resin composition of the present invention obtained as described above, that is, the primer layer, and irradiated with active energy rays to form the active energy ray-curable composition. The hardened coating film can obtain the laminate of the present invention. In addition, as the coating method of the active energy ray curable composition, the same method as the coating method of the above-mentioned aqueous resin composition of the present invention can be used.

[實施例] [Example]

以下以實施例及比較例具體說明本發明。 The present invention will be specifically described below with examples and comparative examples.

(合成例1：聚酯多元醇(1)的合成) (Synthesis Example 1: Synthesis of Polyester Polyol (1))

一邊在具備溫度計、氮氣導入管、攪拌機的反應容器中導入氮氣，一邊加入27.6質量份的間苯二甲酸、27.6質量份的對苯二甲酸、11.7質量份的乙二醇、19.9質量份的二乙二醇及0.03質量份的二丁基氧化錫，於180~230℃下至酸價成為1以下為止，以230℃進行聚縮合反應24小時，得到聚酯多元醇(1)[酸價0.6，羥基價50.0，芳香環濃度4.41mol/Kg]。 Nitrogen gas was introduced into a reaction vessel equipped with a thermometer, a nitrogen introduction pipe, and a stirrer, while 27.6 parts by mass of isophthalic acid, 27.6 parts by mass of terephthalic acid, 11.7 parts by mass of ethylene glycol, and 19.9 parts by mass of Ethylene glycol and 0.03 parts by mass of dibutyltin oxide are subjected to polycondensation reaction at 230°C for 24 hours at 180-230°C until the acid value becomes 1 or less to obtain polyester polyol (1) [acid value 0.6 , hydroxyl value 50.0, aromatic ring concentration 4.41mol/Kg].

(合成例2：聚酯多元醇(2)的合成) (Synthesis Example 2: Synthesis of Polyester Polyol (2))

一邊在具備溫度計、氮氣導入管、攪拌機的反應容器中導入氮氣，一邊加入間苯二甲酸35.4質量份、癸二酸17.8質量份、己二酸7.8質量份、乙二醇6.2質量份、新戊二醇22.9質量份、1,6-己二醇11.7質量份及二丁基氧化錫0.03質量份，於180~230℃下至酸價成為1以下為止，以230℃進行聚縮合反應24小時，得到聚酯多元醇(2)[酸價0.6，羥基價42.5，芳香環濃度2.51mol/Kg]。 Nitrogen gas was introduced into a reaction vessel equipped with a thermometer, a nitrogen introduction pipe, and a stirrer, while 35.4 parts by mass of isophthalic acid, 17.8 parts by mass of sebacic acid, 7.8 parts by mass of adipic acid, 6.2 parts by mass of ethylene glycol, neopentyl 22.9 parts by mass of diol, 11.7 parts by mass of 1,6-hexanediol, and 0.03 parts by mass of dibutyltin oxide were subjected to a polycondensation reaction at 230°C for 24 hours at 180-230°C until the acid value became 1 or less. A polyester polyol (2) [acid value 0.6, hydroxyl value 42.5, aromatic ring concentration 2.51 mol/Kg] was obtained.

(合成例3：乙烯酯樹脂(I)的合成) (Synthesis Example 3: Synthesis of Vinyl Ester Resin (I))

在反應容器中加入46.7質量份的甲酚酚醛清漆型環氧樹脂(DIC股份有限公司製「EPICLON N-673-80M」，固體成分環氧當量=209g/eq，非揮發成分=80質量%，溶劑：甲乙酮)、丙烯酸13.3質量份、氫醌單甲醚0.08質量份、甲乙酮13.3質量份，將其攪拌以使其均勻混合。接著，加入三苯基膦0.37質量份，於反應溫度80℃下使其反應至酸價成為1.5以下為止，得到乙烯酯樹脂(I)。 46.7 parts by mass of cresol novolac type epoxy resin ("EPICLON N-673-80M" manufactured by DIC Co., Ltd., solid content epoxy equivalent=209g/eq, non-volatile content=80 mass %, was added to the reaction container. Solvent: methyl ethyl ketone), 13.3 parts by mass of acrylic acid, 0.08 parts by mass of hydroquinone monomethyl ether, and 13.3 parts by mass of methyl ethyl ketone were stirred so as to be uniformly mixed. Next, 0.37 parts by mass of triphenylphosphine was added, and it was made to react at reaction temperature 80 degreeC until the acid value became 1.5 or less, and vinylester resin (I) was obtained.

(合成例4：胺基甲酸酯樹脂(II-1)的合成) (Synthesis Example 4: Synthesis of Urethane Resin (II-1))

在反應容器中，於減壓下以100℃使75.7質量份的合成例1之聚酯多元醇(1)脫水，之後冷卻至80℃後加入67.89質量份的甲乙酮，並進行攪拌以使其均勻混合。接著，加入6.1質量份的2,2-二羥甲基丙酸，接著加入20.3質量份的異佛酮二異氰酸酯，以80℃使其反應12小時，以實施胺基甲酸酯化步驟。確認異氰酸酯值成為0.1%以下後，加入正丁醇0.3質量份，再使其反應2小時後，冷卻至50℃，得到非揮發成分為60質量%的具有芳香環的胺基甲酸酯樹脂(II-1)。 In a reaction vessel, 75.7 parts by mass of polyester polyol (1) in Synthesis Example 1 was dehydrated at 100°C under reduced pressure, then cooled to 80°C, and 67.89 parts by mass of methyl ethyl ketone was added and stirred to make it uniform mix. Next, 6.1 parts by mass of 2,2-dimethylolpropionic acid was added, followed by 20.3 parts by mass of isophorone diisocyanate, and reacted at 80° C. for 12 hours to implement a urethanization step. After confirming that the isocyanate value was 0.1% or less, 0.3 parts by mass of n-butanol was added and allowed to react for 2 hours, and then cooled to 50° C. to obtain a urethane resin having an aromatic ring with a non-volatile content of 60 mass % ( II-1).

(合成例5：胺基甲酸酯樹脂(II-2)的合成) (Synthesis Example 5: Synthesis of Urethane Resin (II-2))

在反應容器中，於減壓下以100℃將69質量份的合成例2的聚酯多元醇(2)脫水，之後冷卻至80℃後，加入93.3質量份的甲乙酮，並進行攪拌以使其均勻混合。接 著，加入3.0質量份的1,4-丁二醇，6.1質量份的2,2-二羥甲基丙酸，接著，加入19.4質量份的二異氰酸甲伸苯酯，以80℃使其反應12小時，以實施胺基甲酸酯化步驟。確認異氰酸酯值成為0.1%以下後，加入正丁醇0.3質量份，更使其反應2小時後，冷卻至50℃，得到非揮發成分51質量%的具有芳香環的胺基甲酸酯樹脂(II-2)。 In a reaction vessel, 69 parts by mass of polyester polyol (2) in Synthesis Example 2 was dehydrated at 100°C under reduced pressure, and after cooling to 80°C, 93.3 parts by mass of methyl ethyl ketone was added and stirred so that Mix well. Next, add 3.0 parts by mass of 1,4-butanediol, 6.1 parts by mass of 2,2-dimethylolpropionic acid, and then add 19.4 parts by mass of methylene diisocyanate, and make the It was reacted for 12 hours to carry out the urethanization step. After confirming that the isocyanate value was 0.1% or less, 0.3 parts by mass of n-butanol was added and allowed to react for 2 hours, and then cooled to 50° C. to obtain a urethane resin (II -2).

(合成例6：胺基甲酸酯樹脂(II-3)的合成) (Synthesis Example 6: Synthesis of Urethane Resin (II-3))

在反應容器中加入76.1質量份的聚四亞甲醚二醇(平均分子量2000)、43.1質量份的甲乙酮，並進行攪拌以使其均勻混合。接著，加入6.0質量份的2,2-二羥甲基丙酸，接著加入18.7質量份的異佛酮二異氰酸酯，以80℃使其反應12小時，以實施胺基甲酸酯化步驟。確認異氰酸酯值成為0.1%以下後，加入0.3質量份的正丁醇，再使其反應2小時後，冷卻至50℃，得到非揮發成分為70質量%的胺基甲酸酯樹脂(II-3)。 76.1 parts by mass of polytetramethylene ether glycol (average molecular weight: 2000) and 43.1 parts by mass of methyl ethyl ketone were added to the reaction container, and stirred so as to be uniformly mixed. Next, 6.0 parts by mass of 2,2-dimethylolpropionic acid was added, followed by 18.7 parts by mass of isophorone diisocyanate, and it was made to react at 80 degreeC for 12 hours, and the urethanization process was implemented. After confirming that the isocyanate value was 0.1% or less, 0.3 parts by mass of n-butanol was added and allowed to react for 2 hours, and then cooled to 50°C to obtain a urethane resin (II-3 ).

(製造例1：複合樹脂組成物(A-1)的調製) (Production Example 1: Preparation of Composite Resin Composition (A-1))

在合成例4中所得之具有芳香環的胺基甲酸酯樹脂(II-1)中，加入136.1質量份的合成例3中所得之乙烯酯樹脂(I)、5.5質量份的三乙胺，緩慢添加938.5質量份的離子交換水，以使其溶解於水中。接著在減壓下，於30~50℃去除甲乙酮，得到非揮發成分為40質量%的複合樹脂組成物(A-1)。 In the urethane resin (II-1) having an aromatic ring obtained in Synthesis Example 4, the vinyl ester resin (I) obtained in Synthesis Example 3 of 136.1 mass parts, the triethylamine of 5.5 mass parts, 938.5 parts by mass of ion-exchanged water were slowly added to be dissolved in water. Next, under reduced pressure, methyl ethyl ketone was removed at 30 to 50° C. to obtain a composite resin composition (A-1) having a non-volatile content of 40% by mass.

(製造例2：水性樹脂(B-1)水分散體的調製) (Manufacturing example 2: Preparation of water-based resin (B-1) aqueous dispersion)

在合成例4中所得之具有芳香環的胺基甲酸酯樹脂(II-1)中加入1.28質量份的酚系抗氧化劑(1)(分子量：640，熔點：160℃)、1.28質量份的磷系抗氧化劑，並進行攪拌以使其均勻混合。接著，加入4.8質量份的三乙胺，緩慢添加510質量份的離子交換水，以使其溶解於水中。接著在減壓下，於30~50℃去除甲乙酮，調製非揮發成分為23質量%的水性樹脂(B-1)水分散體。 Add 1.28 parts by mass of phenolic antioxidant (1) (molecular weight: 640, melting point: 160°C), 1.28 parts by mass of urethane resin (II-1) having an aromatic ring obtained in Synthesis Example 4, Phosphorus-based antioxidants, and stir to mix evenly. Next, 4.8 parts by mass of triethylamine was added, and 510 parts by mass of ion-exchanged water was gradually added so as to be dissolved in water. Next, under reduced pressure, methyl ethyl ketone was removed at 30 to 50° C., and an aqueous resin (B-1) aqueous dispersion having a nonvolatile content of 23% by mass was prepared.

(製造例3：水性樹脂(B-2)水分散體的調製) (Manufacturing example 3: Preparation of water-based resin (B-2) aqueous dispersion)

在合成例4中所得之具有芳香環的胺基甲酸酯樹脂(II-1)中加入2.56質量份的酚系抗氧化劑(1)、2.56質量份的磷系抗氧化劑，並進行攪拌以使其均勻混合。接著，加入4.8質量份的三乙胺，緩慢添加548質量份的離子交換水，以使其溶解於水中。接著在減壓下，於30~50℃去除甲乙酮，調製非揮發成分為23.5質量%的水性樹脂(B-2)水分散體。 Add 2.56 parts by mass of phenolic antioxidant (1) and 2.56 parts by mass of phosphorus antioxidant to the urethane resin (II-1) having an aromatic ring obtained in Synthesis Example 4, and stir to make It mixes well. Next, 4.8 parts by mass of triethylamine was added, and 548 parts by mass of ion-exchanged water was gradually added so as to be dissolved in water. Next, under reduced pressure, methyl ethyl ketone was removed at 30 to 50° C., and an aqueous resin (B-2) aqueous dispersion having a nonvolatile content of 23.5% by mass was prepared.

(製造例4：水性樹脂(B-3)水分散體的調製) (Manufacturing example 4: Preparation of water-based resin (B-3) aqueous dispersion)

於合成例5中所得之具有芳香環的胺基甲酸酯樹脂(II-2)中加入1.22質量份的酚系抗氧化劑，1.22質量份的磷系抗氧化劑，並進行攪拌以使其均勻混合。接著，加入4.6質量份的三乙胺，緩慢添加390質量份的離子交換水，以使其溶解於水中。接著在減壓下，於30~50℃去除甲乙酮，調製非揮發成分為22.9質量%的水性樹脂 (B-3)水分散體。 Add 1.22 parts by mass of phenolic antioxidant and 1.22 parts by mass of phosphorus antioxidant to the urethane resin (II-2) having an aromatic ring obtained in Synthesis Example 5, and stir to make it uniformly mixed . Next, 4.6 parts by mass of triethylamine was added, and 390 parts by mass of ion-exchanged water was gradually added to be dissolved in water. Next, under reduced pressure, methyl ethyl ketone was removed at 30 to 50° C. to prepare an aqueous resin (B-3) aqueous dispersion having a non-volatile content of 22.9% by mass.

(製造例5：水性樹脂(B-4)水分散體的調製) (Manufacturing example 5: Preparation of water-based resin (B-4) aqueous dispersion)

於合成例6中所得之胺基甲酸酯樹脂(II-3)中加入1.26質量份的酚系抗氧化劑、1.26質量份的磷系抗氧化劑，並進行攪拌以使其均勻混合。接著，加入4.8質量份的三乙胺，緩慢添加410質量份的離子交換水，以使其溶解於水中。接著在減壓下，於30~50℃去除甲乙酮，調製非揮發成分為23.3質量%的水性樹脂(B-4)水分散體。 1.26 mass parts of phenolic antioxidants and 1.26 mass parts of phosphorus antioxidants were added to the urethane resin (II-3) obtained by the synthesis example 6, and it stirred so that it may mix uniformly. Next, 4.8 parts by mass of triethylamine was added, and 410 parts by mass of ion-exchanged water was gradually added so as to be dissolved in water. Next, under reduced pressure, methyl ethyl ketone was removed at 30 to 50° C., and an aqueous resin (B-4) aqueous dispersion having a nonvolatile content of 23.3% by mass was prepared.

(製造例6：水性樹脂(B-5)水分散體的調製) (Manufacture example 6: Preparation of water-based resin (B-5) aqueous dispersion)

在合成例4中所得之具有芳香環的胺基甲酸酯樹脂(II-1)中加入1.28質量份的酚系氧化劑、1.28質量份的紫外線吸收劑，並進行攪拌以使其均勻混合。接著，加入4.8質量份的三乙胺，緩慢添加510質量份的離子交換水，以使其溶解於水中。接著在減壓下，於30~50℃去除甲乙酮，調製非揮發成分為23質量%的水性樹脂(B-5)水分散體。 1.28 mass parts of phenolic oxidizing agents and 1.28 mass parts of ultraviolet absorbers were added to the urethane resin (II-1) which has an aromatic ring obtained in the synthesis example 4, and it stirred so that it may mix uniformly. Next, 4.8 parts by mass of triethylamine was added, and 510 parts by mass of ion-exchanged water was gradually added so as to be dissolved in water. Next, under reduced pressure, methyl ethyl ketone was removed at 30 to 50° C., and an aqueous resin (B-5) aqueous dispersion having a nonvolatile content of 23% by mass was prepared.

(製造例7：水性樹脂(B-6)水分散體的調製) (Manufacture example 7: Preparation of aqueous resin (B-6) aqueous dispersion)

在合成例4中所得之具有芳香環的胺基甲酸酯樹脂(II-1)中加入2.56質量份的酚系氧化劑，並進行攪拌以使其均勻混合。接著，加入4.8質量份的三乙胺，緩慢添加510質量份的離子交換水，以使其溶解於水中。接 著在減壓下，於30~50℃去除甲乙酮，調製非揮發成分為23質量%的水性樹脂(B-6)水分散體。 2.56 mass parts of phenolic oxidizing agents were added to the urethane resin (II-1) which has an aromatic ring obtained in the synthesis example 4, and it stirred so that it might mix uniformly. Next, 4.8 parts by mass of triethylamine was added, and 510 parts by mass of ion-exchanged water was gradually added so as to be dissolved in water. Next, methyl ethyl ketone was removed at 30 to 50° C. under reduced pressure to prepare an aqueous resin (B-6) aqueous dispersion having a nonvolatile content of 23% by mass.

(製造例8：水性樹脂(B-7)水分散體的調製) (Manufacture Example 8: Preparation of water-based resin (B-7) aqueous dispersion)

在合成例4中所得之具有芳香環的胺基甲酸酯樹脂(II-1)中加入2.56質量份的磷系氧化劑，並進行攪拌以使其均勻混合。接著，加入4.8質量份的三乙胺，緩慢添加510質量份的離子交換水，以使其溶解於水中。接著在減壓下，於30~50℃去除甲乙酮，調製非揮發成分為23質量%的水性樹脂(B-7)水分散體。 2.56 parts by mass of phosphorus-based oxidizing agents were added to the urethane resin (II-1) having an aromatic ring obtained in Synthesis Example 4, and stirred so as to be uniformly mixed. Next, 4.8 parts by mass of triethylamine was added, and 510 parts by mass of ion-exchanged water was gradually added so as to be dissolved in water. Next, under reduced pressure, methyl ethyl ketone was removed at 30 to 50° C., and an aqueous resin (B-7) aqueous dispersion having a nonvolatile content of 23% by mass was prepared.

(製造例9：水性樹脂(B-8)水分散體的調製) (Manufacture example 9: Preparation of water-based resin (B-8) aqueous dispersion)

在合成例4中所得之具有芳香環的胺基甲酸酯樹脂(II-1)中加入2.56質量份的紫外線吸收劑，並進行攪拌以使其均勻混合。接著，加入4.8質量份的三乙胺，緩慢添加510質量份的離子交換水，以使其溶解於水中。接著在減壓下，於30~50℃去除甲乙酮，調製非揮發成分為23質量%的水性樹脂(B-8)水分散體。 2.56 parts by mass of ultraviolet absorbers were added to the urethane resin (II-1) having an aromatic ring obtained in Synthesis Example 4, and stirred so as to be uniformly mixed. Next, 4.8 parts by mass of triethylamine was added, and 510 parts by mass of ion-exchanged water was gradually added so as to be dissolved in water. Next, under reduced pressure, methyl ethyl ketone was removed at 30 to 50° C., and an aqueous resin (B-8) aqueous dispersion having a nonvolatile content of 23% by mass was prepared.

(製造例10：水性樹脂(B-9)水分散體的調製) (Manufacture example 10: Preparation of water-based resin (B-9) aqueous dispersion)

在合成例4中所得之胺基甲酸酯樹脂(II-1)中加入2.56質量份的酚系抗氧化劑(2)(分子量：1180，熔點：120℃)，並進行攪拌以使其均勻混合。接著，加入4.8質量份的三乙胺，緩慢添加510質量份的離子交換水，以使其溶解於水中。接著在減壓下，於30~50℃去除甲 乙酮，調製非揮發成分為23質量%的水性樹脂(B-9)水分散體。 Add 2.56 parts by mass of phenolic antioxidant (2) (molecular weight: 1180, melting point: 120°C) to the urethane resin (II-1) obtained in Synthesis Example 4, and stir to make it uniformly mixed . Next, 4.8 parts by mass of triethylamine was added, and 510 parts by mass of ion-exchanged water was gradually added so as to be dissolved in water. Next, under reduced pressure, methyl ethyl ketone was removed at 30 to 50° C. to prepare an aqueous resin (B-9) aqueous dispersion having a non-volatile content of 23% by mass.

(製造例11：水性樹脂(B-10)水分散體的調製) (Manufacture Example 11: Preparation of water-based resin (B-10) aqueous dispersion)

在合成例4中所得之胺基甲酸酯樹脂(II-1)中加入2.56質量份的酚系抗氧化劑(3)(分子量：350，熔點：120℃)，並進行攪拌以使其均勻混合。接著，加入4.8質量份的三乙胺，緩慢添加510質量份的離子交換水，以使其溶解於水中。接著在減壓下，於30~50℃去除甲乙酮，調製非揮發成分為23質量%的水性樹脂(B-10)水分散體。 Add 2.56 parts by mass of phenolic antioxidant (3) (molecular weight: 350, melting point: 120°C) to the urethane resin (II-1) obtained in Synthesis Example 4, and stir to make it uniformly mixed . Next, 4.8 parts by mass of triethylamine was added, and 510 parts by mass of ion-exchanged water was gradually added so as to be dissolved in water. Next, under reduced pressure, methyl ethyl ketone was removed at 30 to 50° C., and an aqueous resin (B-10) aqueous dispersion having a nonvolatile content of 23% by mass was prepared.

(製造例12：水性樹脂(B-11)水分散體的調製) (Manufacture Example 12: Preparation of water-based resin (B-11) aqueous dispersion)

在合成例4中所得之胺基甲酸酯樹脂(II-1)中加入2.56質量份的酚系抗氧化劑(4)(分子量：780，熔點：240℃)，並進行攪拌以使其均勻混合。接著，加入4.8質量份的三乙胺，緩慢添加510質量份的離子交換水，以使其溶解於水中。接著在減壓下，於30~50℃去除甲乙酮，調製非揮發成分為23質量%的水性樹脂(B-11)水分散體。 2.56 parts by mass of phenolic antioxidant (4) (molecular weight: 780, melting point: 240°C) was added to the urethane resin (II-1) obtained in Synthesis Example 4, and stirred to make it uniformly mixed . Next, 4.8 parts by mass of triethylamine was added, and 510 parts by mass of ion-exchanged water was gradually added so as to be dissolved in water. Next, under reduced pressure, methyl ethyl ketone was removed at 30 to 50° C., and an aqueous resin (B-11) aqueous dispersion having a nonvolatile content of 23% by mass was prepared.

(製造例13：水性樹脂(B-12)水分散體的調製) (Manufacture Example 13: Preparation of water-based resin (B-12) aqueous dispersion)

在合成例4中所得之胺基甲酸酯樹脂(II-1)中加入2.56質量份的酚系抗氧化劑(5)(分子量：530，熔點：50℃)，並進行攪拌以使其均勻混合。接著，加入4.8質 量份的三乙胺，緩慢添加410質量份的離子交換水，以使其溶解於水中。接著在減壓下，於30~50℃去除甲乙酮，調製非揮發成分為23質量%的水性樹脂(B-12)水分散體。 Add 2.56 parts by mass of phenolic antioxidant (5) (molecular weight: 530, melting point: 50°C) to the urethane resin (II-1) obtained in Synthesis Example 4, and stir to make it uniformly mixed . Next, 4.8 parts by mass of triethylamine was added, and 410 parts by mass of ion-exchanged water was slowly added to dissolve in water. Next, under reduced pressure, methyl ethyl ketone was removed at 30 to 50° C., and an aqueous resin (B-12) aqueous dispersion having a nonvolatile content of 23% by mass was prepared.

(製造例14：水性樹脂(B-13)水分散體的調製) (Manufacture Example 14: Preparation of water-based resin (B-13) aqueous dispersion)

在合成例4中所得之胺基甲酸酯樹脂(II-1)中加入4.8質量份的三乙胺，緩慢添加405質量份的離子交換水，以使其溶解於水中。接著在減壓下，於30~50℃去除甲乙酮，調製非揮發成分為23質量%的水性樹脂(B-13)水分散體。 4.8 parts by mass of triethylamine was added to the urethane resin (II-1) obtained in Synthesis Example 4, and 405 parts by mass of ion-exchanged water was gradually added and dissolved in water. Next, under reduced pressure, methyl ethyl ketone was removed at 30 to 50° C., and an aqueous resin (B-13) aqueous dispersion having a nonvolatile content of 23% by mass was prepared.

製造例2~14中所使用的胺基甲酸酯樹脂、抗氧化劑及紫外線吸收劑顯示於表1。 Table 1 shows the urethane resins, antioxidants, and ultraviolet absorbers used in Production Examples 2 to 14.

Figure 106145467-A0202-12-0033-1
Figure 106145467-A0202-12-0033-1

(實施例1：水性樹脂組成物(1)的調製) (Example 1: Preparation of water-based resin composition (1))

將100質量份的製造例1中所得之複合樹脂組成物(A-1)、2質量份的製造例2中所得之水性樹脂(B-1)水分散體與302.6質量份的離子交換水混合，藉此得到非揮發成分10質量%的水性樹脂組成物(1)。 Mix 100 parts by mass of the composite resin composition (A-1) obtained in Production Example 1, 2 parts by mass of the aqueous resin (B-1) aqueous dispersion obtained in Production Example 2, and 302.6 parts by mass of ion-exchanged water , thereby obtaining an aqueous resin composition (1) having a non-volatile content of 10% by mass.

(實施例2~15：水性樹脂組成物(2)~(15)的調製) (Example 2~15: preparation of water-based resin composition (2)~(15))

使用製造例3~13中所得之水性樹脂水分散體，代替實施例1中所使用之水性樹脂(B-1)水分散體，除此之外，與實施例1相同地進行，得到水性樹脂組成物(2)~(15)。 Use the water-based resin water dispersion obtained in manufacturing examples 3 to 13 to replace the water-based resin (B-1) water dispersion used in Example 1, except that it is carried out in the same manner as in Example 1 to obtain a water-based resin Composition (2)~(15).

實施例1~15中所使用的複合樹脂及水性樹脂顯示於表2。 The composite resins and water-based resins used in Examples 1-15 are shown in Table 2.

Figure 106145467-A0202-12-0035-2
Figure 106145467-A0202-12-0035-2

(調製例1：光硬化性樹脂組成物(UV-1)的調製) (Preparation example 1: Preparation of photocurable resin composition (UV-1))

將70質量份的UNIDIC V-5500(DIC股份有限公司製，環氧丙烯酸酯樹脂)、30質量份的三丙二醇二丙烯酸酯及3質量份的IRGACURE 184(BASF公司製，光聚合起始劑)混合，藉此得到光硬化性樹脂組成物(UV-1)。 70 parts by mass of UNIDIC V-5500 (manufactured by DIC Co., Ltd., epoxy acrylate resin), 30 parts by mass of tripropylene glycol diacrylate, and 3 parts by mass of IRGACURE 184 (manufactured by BASF, photopolymerization initiator) By mixing, a photocurable resin composition (UV-1) was obtained.

(實施例16：積層體(1)的製作) (Example 16: Production of laminate (1))

在聚對苯二甲酸乙二酯(以下簡記為「PET」)製薄膜基材(厚度125μm)的表面上，以使乾燥後的膜厚成為約1μm的方式，塗布實施例1中所得之水性樹脂組成物(1)，以150℃加熱5分鐘，藉此在該基材的表面上形成底漆層(P-1)。 On the surface of a polyethylene terephthalate (hereinafter abbreviated as "PET") film substrate (thickness 125 μm), the aqueous The resin composition (1) was heated at 150° C. for 5 minutes to form a primer layer (P-1) on the surface of the substrate.

接著，於該底漆層的表面上，以15μm的塗膜厚，塗布調製例1中所得之光硬化性樹脂組成物(UV-1)，以高壓水銀燈作為光源，於照射強度0.5J/cm2下照射紫外線，藉此得到在該基材的表面上具有底漆層，該底漆層的表面上具有紫外線硬化性組成物的硬化塗膜(以下簡記為「UV塗膜」)的積層體(1)。 Next, on the surface of the primer layer, the photocurable resin composition (UV-1) obtained in Preparation Example 1 was coated with a film thickness of 15 μm, and a high-pressure mercury lamp was used as a light source under an irradiation intensity of 0.5 J/cm 2 UV rays are irradiated to obtain a laminate having a primer layer on the surface of the base material and a cured coating film (hereinafter abbreviated as "UV coating film") of an ultraviolet curable composition on the surface of the primer layer. (1).

(實施例17~30：積層體(2)~(15)的製作) (Examples 17-30: Fabrication of laminates (2)-(15))

使用實施例2~15中所得之水性樹脂組成物(2)~(15)作為底漆層(P-2)~(P-15)，以代替實施例16中所使用的水性樹脂組成物(1)，除此之外，與實施例16相同地進行，得到積層體(2)~(15)。 Use the water-based resin composition (2)～(15) gained in embodiment 2～15 as primer layer (P-2)～(P-15), to replace the water-based resin composition used in embodiment 16 ( 1), except that, it carried out similarly to Example 16, and obtained laminated body (2)-(15).

使用上述實施例及比較例中所得之水性樹脂組成物及積層體，進行下述密合性的評價。 Using the water-based resin compositions and laminates obtained in the above Examples and Comparative Examples, the following adhesive evaluations were performed.

[基材與底漆層的密合性(初期)的評價方法] [Evaluation method of adhesion (initial stage) between substrate and primer layer]

在膜厚125μm的包含聚對苯二甲酸乙二酯的基材表面上，以使乾燥時的膜厚成為約1μm的方式塗布底漆，以150℃加熱5分鐘，藉此製作試驗板，其包含在該基材之表面上積層底漆層的構件。接著，使用該試驗板進行1mm棋盤格剝離試驗。具體而言，在該試驗板的底漆層的表面上，以1mm間隔製作100個棋盤格，於其上貼附NICHIBAN股份有限公司製的寬度24mm的黏著膠帶。 On the surface of a substrate containing polyethylene terephthalate with a film thickness of 125 μm, a primer was applied so that the film thickness at the time of drying was about 1 μm, and heated at 150° C. for 5 minutes to prepare a test panel. A member comprising a primer layer laminated on the surface of the substrate. Next, a 1 mm checkerboard peeling test was performed using this test panel. Specifically, on the surface of the primer layer of this test board, 100 checkerboards were produced at intervals of 1 mm, and an adhesive tape with a width of 24 mm manufactured by NICHIBAN Co., Ltd. was attached thereto.

接著，在相對該底漆層垂直的方向上將該黏著膠帶撕起，根據該黏著膠帶從底漆層的表面剝離時，該底漆層的表面上殘存的格子數量進行評價。 Next, the adhesive tape was torn off in a direction perpendicular to the primer layer, and evaluated based on the number of grids remaining on the surface of the primer layer when the adhesive tape was peeled off from the surface of the primer layer.

[底漆層與UV塗膜的密合性(初期)的評價方法] [Evaluation method of adhesion between primer layer and UV coating film (initial stage)]

使用實施例及比較例中所得之積層體，進行1mm棋盤格剝離試驗。在構成實施例及比較例中所得之積層體的UV塗膜的表面上，以1mm間隔製作100個的棋盤格，於其上貼附NICHIBAN股份有限公司製的寬度24mm的黏著膠帶。 Using the laminates obtained in Examples and Comparative Examples, a 1 mm checkerboard peeling test was performed. On the surface of the UV coating film constituting the laminate obtained in Examples and Comparative Examples, 100 checkerboards were formed at intervals of 1 mm, and an adhesive tape with a width of 24 mm manufactured by NICHIBAN Co., Ltd. was attached thereto.

接著，在相對該UV塗膜垂直的方向上將該黏著膠帶撕起，根據該黏著膠帶從UV塗膜的表面剝離時，該UV塗膜的表面上殘存的格子數量進行評價。 Next, the adhesive tape was torn off in a direction perpendicular to the UV coating film, and evaluated based on the number of grids remaining on the surface of the UV coating film when the adhesive tape was peeled off from the surface of the UV coating film.

[基材與底漆層之密合性(UV照射循環試驗後)的評價方法] [Evaluation method of adhesion between substrate and primer layer (after UV irradiation cycle test)]

以高壓水銀燈作為光源，在照射強度0.5J/cm2下，以既定次數對於該所得之積層體照射紫外線後，取出該積層體，以與該[基材與底漆層的密合性(初期)]同樣的方法評價基材與底漆層的密合性。另外，本發明所指的UV照射循環試驗，係指預先對底漆層進行既定次數的UV照射，蓄意地使塗膜劣化，以評價在更嚴苛之條件下的密合性的方法，其係使用該方法實施基材與底漆層之密合性及底漆層與UV塗膜之密合性的評價。 Using a high-pressure mercury lamp as a light source, under the irradiation intensity of 0.5J/cm 2 , after irradiating ultraviolet rays to the obtained laminated body for a predetermined number of times, the laminated body was taken out to check the adhesion between the substrate and the primer layer (initial stage) )] The same method was used to evaluate the adhesion between the substrate and the primer layer. In addition, the UV irradiation cycle test referred to in the present invention refers to a method in which the primer layer is subjected to UV irradiation for a predetermined number of times in advance to deliberately deteriorate the coating film to evaluate the adhesion under more severe conditions. This method is used to evaluate the adhesion between the substrate and the primer layer and the adhesion between the primer layer and the UV coating film.

[底漆層與UV塗膜之密合性(UV照射循環試驗後)的評價方法] [Evaluation method of adhesion between primer layer and UV coating film (after UV irradiation cycle test)]

對於該所得之積層體，以高壓水銀燈作為光源，以照射強度0.5J/cm2下以既定次數照射紫外線後，於該底漆層的表面上，以15μm的塗膜厚度，塗布調製例1中所得之光硬化性樹脂組成物(UV-1)，以高壓水銀燈作為光源，再次以照射強度0.5J/cm2照射紫外線，藉此得到在該基材的表面上具有底漆層，該底漆層的表面上具有UV塗膜的積層體。 After the obtained laminate was irradiated with ultraviolet rays for a predetermined number of times at an irradiation intensity of 0.5 J/cm 2 using a high-pressure mercury lamp as a light source, the coating in Preparation Example 1 was applied on the surface of the primer layer with a coating film thickness of 15 μm. The resulting photocurable resin composition (UV-1) was irradiated with ultraviolet light at an irradiation intensity of 0.5J/ cm2 again with a high-pressure mercury lamp as a light source, thereby obtaining a primer layer on the surface of the base material. A laminate having a UV coating film on the surface of the layer.

接著，取出該積層體，以與該[底漆層與UV塗膜的密合性(初期)]同樣的方法評價底漆層與UV塗膜的密合性。 Next, this laminated body was taken out, and the adhesiveness of a primer layer and a UV coating film was evaluated by the method similar to this [adhesion (initial stage) of a primer layer and a UV coating film].

[薄膜外觀的評價方法(霧度值的測量)] [Evaluation method of film appearance (measurement of haze value)]

使用霧度計(Suga Test Instruments股份有限公司製)測量上述中所得之積層板的霧度值。以依照JIS試驗方法(JIS K7136：2000)的方法進行測量。以下述算式算出霧度值(H)。又，亦僅測量PET基材的霧度值，其霧度值為2.05%。 The haze value of the laminate obtained above was measured using a haze meter (manufactured by Suga Test Instruments Co., Ltd.). Measurement was performed by a method in accordance with JIS test method (JIS K7136:2000). The haze value (H) was calculated by the following formula. Also, only the haze value of the PET substrate was measured, and the haze value was 2.05%.

H(%)=Td/Tt×100 H(%)=Td/Tt×100

H：霧度(霧度值)(%) H: haze (haze value) (%)

Td：擴散透光率(%) Td: diffuse transmittance (%)

Tt：全光線穿透率(%) Tt: total light transmittance (%)

實施例16~30中所得之積層體(1)~(15)中所使用的基材及底漆與評價結果顯示於表3。 Table 3 shows the substrates, primers and evaluation results used in the laminates (1) to (15) obtained in Examples 16 to 30.

Figure 106145467-A0202-12-0040-3
Figure 106145467-A0202-12-0040-3

(比較例1：水性樹脂組成物(C1)的調製) (Comparative Example 1: Preparation of Aqueous Resin Composition (C1))

將100質量份的製造例1中所得之複合樹脂組成物(A-1)與300質量份的離子交換水混合，藉此得到非揮發成分10質量%的水性樹脂組成物(C1)。 100 mass parts of composite resin compositions (A-1) obtained in manufacture example 1 were mixed with 300 mass parts of ion-exchanged water, and the aqueous resin composition (C1) of 10 mass % of non-volatile components was obtained.

(比較例2：水性樹脂組成物(C2)的調製) (Comparative Example 2: Preparation of Aqueous Resin Composition (C2))

將100質量份的製造例2中所得之水性樹脂(B-1)水分散體與130質量份的離子交換水混合，藉此得到非揮發成分10質量%的水性樹脂組成物(C2)。 The aqueous resin composition (C2) of 10 mass % of non-volatile components was obtained by mixing 100 mass parts of aqueous resin (B-1) aqueous dispersions obtained by the manufacture example 2, and 130 mass parts of ion exchanged water.

(比較例3：水性樹脂組成物(C3)的調製) (Comparative example 3: Preparation of water-based resin composition (C3))

將100質量份的製造例4中所得之水性樹脂(B-3)水分散體與130質量份的離子交換水混合，藉此得到非揮發成分10質量%的水性樹脂組成物(C3)。 The aqueous resin composition (C3) of 10 mass % of non-volatile components was obtained by mixing 100 mass parts of aqueous resin (B-3) aqueous dispersions obtained by the manufacture example 4, and 130 mass parts of ion exchanged water.

(比較例4：積層體(R1)的作成) (Comparative example 4: Preparation of laminate (R1))

在PET製薄膜基材(厚度125μm)的表面上，以使乾燥後的膜厚成為約1μm的方式，塗布比較例1中所得之水性樹脂組成物(C1)，以150℃加熱5分鐘，藉此在該基材的表面上形成底漆層(P’-1)。 On the surface of a PET film substrate (thickness 125 μm), the water-based resin composition (C1) obtained in Comparative Example 1 was applied so that the film thickness after drying was about 1 μm, and heated at 150° C. for 5 minutes. This forms a primer layer (P'-1) on the surface of the substrate.

接著，在該底漆層的表面上，以15μm的塗膜厚塗布調製例1中所得之光硬化性樹脂組成物(UV-1)，以高壓水銀燈作為光源，在照射強度0.5J/cm2下照射紫外線，藉此得到在該基材的表面上具有底漆 層，該底漆層的表面上具有UV塗膜的積層體(R1)。 Next, on the surface of the primer layer, the photocurable resin composition (UV-1) obtained in Preparation Example 1 was coated with a film thickness of 15 μm, and a high-pressure mercury lamp was used as a light source under an irradiation intensity of 0.5 J/cm 2 . UV rays are irradiated down to obtain a laminate (R1) having a primer layer on the surface of the substrate and a UV coating film on the surface of the primer layer.

(比較例2~3：積層體(R2)~(R3)的製作) (Comparative Examples 2~3: Fabrication of laminates (R2)~(R3))

使用比較例2~3中所得之水性樹脂組成物(C2)~(C3)作為底漆層(P’-2)~(P’-3)以代替比較例1中所使用的水性樹脂組成物(C1)，除此之外，與比較例1相同地進行，得到積層體(R2)~(R3)。 Use the water-based resin composition (C2)~(C3) obtained in Comparative Example 2~3 as the primer layer (P'-2)~(P'-3) to replace the water-based resin composition used in Comparative Example 1 Except for (C1), it carried out similarly to the comparative example 1, and obtained the laminated body (R2)-(R3).

比較例1~3中所得之積層體(R1)~(R3)中所使用的基材及底漆與評價結果顯示於表4。 Table 4 shows the substrates, primers and evaluation results used in the laminates (R1) to (R3) obtained in Comparative Examples 1 to 3.

Figure 106145467-A0202-12-0042-4
Figure 106145467-A0202-12-0042-4

表3中所示的實施例15~28係使用本發明之水性樹脂組成物的例子。從實施例15~28的評價結果，可確認使用本發明之水性樹脂組成物形成的底漆層，與 基材的密合性優良，且與UV塗膜的密合性亦優良。 Examples 15-28 shown in Table 3 are examples using the water-based resin composition of the present invention. From the evaluation results of Examples 15 to 28, it can be confirmed that the primer layer formed using the water-based resin composition of the present invention has excellent adhesion to the substrate, and also excellent adhesion to the UV coating film.

另一方面，比較例2係使用含有比較例1中所得之複合樹脂的水性樹脂組成物的例子，其係未使用本發明之水性樹脂(B)的例子。可確認使用該比較例1的水性樹脂組成物所形成之底漆層，在UV照射循環試驗前(初期)的基材與底漆層的密合性、及底漆層與UV塗膜的密合性優良，但在UV照射循環試驗後的密合性明顯不足。 On the other hand, Comparative Example 2 is an example using the water-based resin composition containing the composite resin obtained in Comparative Example 1, which is an example not using the water-based resin (B) of the present invention. The primer layer formed using the water-based resin composition of Comparative Example 1, the adhesion between the base material and the primer layer, and the adhesion between the primer layer and the UV coating film before the UV irradiation cycle test (initial stage) can be confirmed. Adhesion is excellent, but the adhesion after UV irradiation cycle test is obviously insufficient.

又，比較例3係使用製造例2中所得之水性樹脂(B-1)的例子，其係未使用本發明之複合樹脂(A)的例子。可確認該比較例3的底漆層，在UV照射循環試驗前(初期)的基材與底漆層的密合性、及UV照射循環試驗後的基材與底漆層的密合性優良，但底漆層與UV塗膜的密合性明顯不足。 Moreover, the comparative example 3 is the example which used the water-based resin (B-1) obtained in the manufacture example 2, and it is the example which did not use the composite resin (A) of this invention. It can be confirmed that the primer layer of Comparative Example 3 is excellent in the adhesion between the substrate and the primer layer before the UV irradiation cycle test (initial stage) and the adhesion between the substrate and the primer layer after the UV irradiation cycle test , but the adhesion between the primer layer and the UV coating film is obviously insufficient.

又，比較例4係使用製造例4中所得之水性樹脂(B-3)的例子，其係未使用本發明之複合樹脂(A)的例子。可確認該比較例4的底漆層，與比較例3相同地，在UV照射循環試驗前(初期)的基材與底漆層的密合性，及UV照射循環試驗後的基材與底漆層的密合性優良，但底漆層與UV塗膜的密合性明顯不足。 Moreover, the comparative example 4 is the example which used the water-based resin (B-3) obtained in the manufacture example 4, and it is the example which did not use the composite resin (A) of this invention. In the primer layer of Comparative Example 4, as in Comparative Example 3, the adhesion between the base material and the primer layer before (initial) UV irradiation cycle test, and the adhesion between the base material and the primer layer after UV irradiation cycle test can be confirmed. The adhesion of the paint layer is excellent, but the adhesion between the primer layer and the UV coating film is obviously insufficient.

Claims (8)

一種水性樹脂組成物，其係包含含有乙烯酯樹脂(a1)及具有芳香環之胺基甲酸酯樹脂(a2)的複合樹脂(A)、水性樹脂(B)、水性媒介(C)、及非水溶性之添加劑的水性樹脂組成物，其特徵為：該乙烯酯樹脂(a1)係選自包含酚醛清漆型環氧樹脂及雙酚型環氧樹脂之群組的1種以上的環氧樹脂(a1-1)與具有酸基及聚合性不飽和基之化合物(a1-2)的反應物；該胺基甲酸酯樹脂(a2)係多元醇(a2-1)與聚異氰酸酯(a2-2)的反應物，該多元醇(a2-1)含有具有芳香環之多元醇及具有親水性基之多元醇；其中該水性樹脂(B)係胺基甲酸酯樹脂(b1)，該胺基甲酸酯樹脂(b1)為多元醇(a2-1)與聚異氰酸酯(a2-2)的反應物，該多元醇(a2-1)含有具有芳香環之多元醇及具有親水性基之多元醇；該非水溶性的添加劑係選自包含抗氧化劑、紫外線吸收劑之群組的1種以上的添加劑；該複合樹脂(A)與水性樹脂(B)的質量比例[(A)/(B)]在99/1~80/20的範圍。 A water-based resin composition comprising a composite resin (A) containing a vinyl ester resin (a1) and a urethane resin (a2) having an aromatic ring, a water-based resin (B), a water-based medium (C), and A water-based resin composition with water-insoluble additives, characterized in that the vinyl ester resin (a1) is at least one epoxy resin selected from the group consisting of novolac-type epoxy resins and bisphenol-type epoxy resins (a1-1) reactant with a compound (a1-2) having an acid group and a polymerizable unsaturated group; the urethane resin (a2) is polyol (a2-1) and polyisocyanate (a2- 2) the reactant, the polyol (a2-1) contains a polyol with an aromatic ring and a polyol with a hydrophilic group; wherein the water-based resin (B) is a urethane resin (b1), and the amine The urethane resin (b1) is a reaction product of a polyol (a2-1) and a polyisocyanate (a2-2). The polyol (a2-1) contains a polyhydric alcohol having an aromatic ring and a polyhydric alcohol having a hydrophilic group. Alcohol; the water-insoluble additive is selected from one or more additives of the group comprising antioxidants and ultraviolet absorbers; the mass ratio of the composite resin (A) to the water-based resin (B) [(A)/(B) ] in the range of 99/1~80/20. 如請求項1之水性樹脂組成物，其中該抗氧化劑係選自包含酚系抗氧化劑、磷系抗氧化劑之群組的1種以上的抗氧化劑。 The water-based resin composition according to claim 1, wherein the antioxidant is at least one antioxidant selected from the group consisting of phenolic antioxidants and phosphorus antioxidants. 如請求項1之水性樹脂組成物，其中該抗氧化劑的重量平均分子量為500~1,000的範圍。 The water-based resin composition according to claim 1, wherein the weight average molecular weight of the antioxidant is in the range of 500-1,000. 如請求項1至3中任一項之水性樹脂組成物，其中該抗氧化劑的熔點在80~180℃的範圍。 The water-based resin composition according to any one of claims 1 to 3, wherein the melting point of the antioxidant is in the range of 80-180°C. 一種積層體，其特徵為：在基材的單面或是雙面上具有使用如請求項1至4中任一項之水性樹脂組成物形成的底漆層，該底漆層的表面上具有活性能量射線硬化性組成物的硬化塗膜。 A kind of laminated body, it is characterized in that: on one or both sides of the base material, there is a primer layer formed by using the water-based resin composition according to any one of claims 1 to 4, and the surface of the primer layer has A cured coating film of an active energy ray curable composition. 如請求項5之積層體，其特徵為：該活性能量射線硬化性樹脂組成物包含具有聚合性不飽和基之樹脂與具有聚合性不飽和基之單體。 The laminate according to claim 5 is characterized in that: the active energy ray curable resin composition includes a resin having a polymerizable unsaturated group and a monomer having a polymerizable unsaturated group. 一種光學薄膜，其特徵為具有：如請求項5或6之積層體。 An optical film characterized by having: the laminate according to claim 5 or 6. 一種影像顯示裝置，其特徵為具有：如請求項7之光學薄膜。 An image display device, characterized by having: the optical film according to claim 7.
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