TW201345935A - A resin composition for coating material - Google Patents

A resin composition for coating material Download PDF

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TW201345935A
TW201345935A TW102110835A TW102110835A TW201345935A TW 201345935 A TW201345935 A TW 201345935A TW 102110835 A TW102110835 A TW 102110835A TW 102110835 A TW102110835 A TW 102110835A TW 201345935 A TW201345935 A TW 201345935A
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resin composition
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meth
polymer
weight
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TW102110835A
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TWI490242B (en
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Yosuke Tsuge
Tomokazu Iwasaki
Tomoaki Hiwatashi
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Mitsubishi Chem Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • 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
    • G02B1/14—Protective coatings, e.g. hard coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/148—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • 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
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/253—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates
    • G11B2007/25303—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Optical Record Carriers And Manufacture Thereof (AREA)

Abstract

Provided are a non-aqueous resin composition capable of inhibiting the generation of defect in a formed film because of lower foaming properties and excellent deforming properties in a case of foaming; and further a resin composition capable of forming a cured film which gives excellent hardness, scratch resistance, transparence, contamination resistance and durability to objects. A resin composition comprises a polymer which has hydroxyl group and fluoroalkyl group, whose weight-average molecular weight is 1000 or more, a hydrocarbon-based monomer which contains one or more types selected from (metha)acryloyl group and vinyl group, 0.01 to 25 wt% of a saturated hydrocarbon, and a solvent whose solubility parameter(SP value)is 10.0 or less.

Description

塗佈塗料用樹脂組成物 Resin composition for coating

本發明係關於一種可用作耐污染性賦予劑之塗佈塗料用樹脂組成物、以及使用該組成物之硬化物及光記錄媒體等物品，該塗佈塗料用樹脂組成物於組成物之狀態下難以起泡，因此硬化後之硬化膜之均染性優異，進而具有優異之硬度及耐損傷性。本發明尤其是關於一種提供即便為薄膜亦具有該等充分之性能之硬化膜的組成物等。 The present invention relates to a resin composition for a coating material which can be used as a stain resistance imparting agent, and a cured product and an optical recording medium using the composition, and a resin composition for coating a coating material in a state of a composition Since it is difficult to foam, the cured film after hardening is excellent in the leveling property, and further has excellent hardness and damage resistance. More particularly, the present invention relates to a composition or the like which provides a cured film having such sufficient properties even in the form of a film.

本發明係關於一種光學物品，尤其是唯讀光碟、光記錄碟片、磁光記錄碟片等光記錄媒體，或者觸控面板或液晶電視之類之光學顯示器用透明物品。 The present invention relates to an optical article, particularly an optical recording medium such as a CD-ROM, an optical recording disk, a magneto-optical recording disk, or a transparent article for an optical display such as a touch panel or a liquid crystal television.

塑膠製品、例如聚碳酸酯、聚甲基丙烯酸甲酯、聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、丙烯腈-丁二烯-苯乙烯共聚合體(ABS(Acrylonitrile-Butadiene-Styrene))、甲基丙烯酸甲酯-苯乙烯共聚合體(MS(Methyl Methacrylate Styrene)樹脂)、丙烯腈-苯乙烯共聚合體(AS(Acrylonitrile-Styrene)樹脂)等苯乙烯系樹脂、氯乙烯系樹脂、三乙酸纖維素等乙酸纖維素等樹脂素材由於其輕量性、易加工性、耐衝擊性等尤其優異，故而可用於容器、汽車之儀錶板(instrument panel)或外板、窗戶材料、屋頂材料、包裝材料、各種外罩(housing)材料、光碟基板、塑膠透鏡、液晶顯示器或電漿顯示器、投影TV等顯示機器之基 材等各種用途。 Plastic products such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, acrylonitrile-butadiene-styrene copolymer (ABS (Acrylonitrile-Butadiene) -Styrene)), styrene resin such as methyl methacrylate-styrene copolymer (MS (Methyl Methacrylate Styrene) resin), acrylonitrile-styrene copolymer (AS (Acrylonitrile-Styrene) resin), vinyl chloride A resin material such as cellulose acetate such as resin or cellulose triacetate is particularly excellent in light weight, easy processability, impact resistance, etc., and thus can be used for an instrument panel or an outer panel of a container or a car, a window material, Roofing materials, packaging materials, various housing materials, optical disc substrates, plastic lenses, liquid crystal displays or plasma displays, projection TVs, etc. Materials and other uses.

然而，該等塑膠製品表面硬度較低而容易損傷，聚碳酸酯或聚對苯二甲酸乙二酯之類之透明樹脂存在該樹脂所具有之原本之透明性或外觀明顯受損之缺點，而難以將塑膠製品用於必需耐磨耗性之領域中。因此，業界謀求用以提高該等塑膠製品之表面硬度而賦予耐磨耗性之表面硬化膜(被覆材料)。 However, such plastic products have low surface hardness and are easily damaged, and transparent resins such as polycarbonate or polyethylene terephthalate have the disadvantages that the original transparency or appearance of the resin is significantly impaired. It is difficult to use plastic articles in fields where wear resistance is required. Therefore, the industry has sought to provide a surface-hardened film (coating material) for improving the surface hardness of such plastic products and imparting abrasion resistance.

此種表面硬化膜通常係藉由使樹脂組成物溶解或懸浮於溶劑中，以塗料之形態塗佈於製品之表面後使之硬化而獲得。於藉由塗佈獲得塗膜，進而獲得硬化膜之情形時，對該樹脂組成物要求均染性。其原因在於，若均染性較差，則塗膜或硬化膜中會產生所謂凹凸不均之表面粗糙或塗敷不全部位，於硬化膜之生產中可能成為重大障礙。作為凹凸不均之原因，可舉出塗佈液或塗膜中產生氣泡或該氣泡難以消失。 Such a surface-cured film is usually obtained by dissolving or suspending a resin composition in a solvent, coating it on the surface of the article in the form of a coating, and hardening it. When a coating film is obtained by coating to obtain a cured film, the resin composition is required to have a leveling property. The reason for this is that if the leveling property is inferior, surface roughness or uneven coating which causes unevenness in the coating film or the cured film may become a major obstacle in the production of the cured film. The reason why the unevenness is uneven is that bubbles are generated in the coating liquid or the coating film, and the bubbles are hard to disappear.

通常，關於水系塗料，容易產生氣泡，而採取用以解決上述凹凸不均之問題之對策。例如已知使含有界面活性劑之水系塗料中含有飽和烴以消除起因於該界面活性劑之氣泡(專利文獻1)。另一方面，關於非水系塗料，由於通常使用非極性溶劑，故而先前以來一直認為難以產生泡。 In general, as for the water-based paint, bubbles are easily generated, and countermeasures for solving the above problem of unevenness of unevenness are taken. For example, it is known that a water-based paint containing a surfactant contains a saturated hydrocarbon to eliminate bubbles caused by the surfactant (Patent Document 1). On the other hand, as for the non-aqueous paint, since a non-polar solvent is usually used, it has been considered that it is difficult to generate bubbles.

且說，對於光碟、觸控面板顯示器、液晶電視或電漿TV之類之大畫面平板TV顯示器中所使用之表面硬化膜，不僅要求表面硬度或耐久性，而且亦要求以高水準賦予耐污染性。又，對於下一代型之光資訊媒體或觸控面板等光學物品而言，近年來，問題是指紋污垢等污染物質不僅對外觀而且亦對性能造成影響，該問題已逐步受到重視。 Moreover, the surface-hardened film used in a large-screen flat-panel TV display such as a compact disc, a touch panel display, a liquid crystal television, or a plasma TV requires not only surface hardness or durability but also high level of pollution resistance. . Further, in the case of optical articles such as the next-generation optical information medium or the touch panel, in recent years, the problem has been that the pollutants such as fingerprints and the like have an influence not only on the appearance but also on the performance, and this problem has been gradually taken seriously.

於此種狀況下，業界開發有含有具有活性能量射線硬化性基之氟系化合物之非水系塗佈塗料用樹脂組成物，使其硬化而獲得之硬化膜顯示出優異之耐污染性，因而備受矚目(例如，專利文獻2)。本發明者等人迄今為止亦發現含有特定之全氟烷基與環氧基的特定之共聚合體或其(甲基)丙烯酸反應物作為具有優異之污染物質拭除性或其耐久性之耐污染性賦予劑而有效(專利文獻3~4)。 Under such circumstances, the resin composition for a non-aqueous coating material containing a fluorine-based compound having an active energy ray-curable group is developed, and the cured film obtained by curing has excellent stain resistance. Subject to attention (for example, Patent Document 2). The present inventors have hitherto found that a specific copolymer containing a specific perfluoroalkyl group and an epoxy group or a (meth)acrylic acid reactant thereof is resistant to contamination with excellent contaminant erasability or durability thereof. It is effective as a sex-imparting agent (patent documents 3 to 4).

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利特開2001-261908公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-261908

[專利文獻2]日本專利特開2005-112900號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2005-112900

[專利文獻3]國際公開2006/059702公報 [Patent Document 3] International Publication No. 2006/059702

[專利文獻4]日本專利特開2009-102513號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2009-102513

然而，於開發含有具有氟烷基與羥基之聚合體的樹脂組成物之過程中，本發明者等人發現，儘管該等通常係被認為難以起泡之非水系塗料，但起泡性仍較高，因此於製成塗膜並硬化時均染性降低。因此，面臨改善所獲得之塗膜或硬化膜之均染性之新課題。 However, in the process of developing a resin composition containing a polymer having a fluoroalkyl group and a hydroxyl group, the inventors have found that although these are generally non-aqueous coatings which are considered to be difficult to foam, the foaming property is still relatively high. It is high, so the leveling property is lowered when the coating film is formed and hardened. Therefore, there is a new problem of improving the leveling property of the obtained coating film or cured film.

若如關於水系塗料之專利文獻1般僅藉由添加飽和烴，則無法獲得充分之消泡性。進而如上所述之聚合體對飽和烴之溶解性較低，若飽和烴之添加量增多，則會發生白濁而使所獲得之硬化膜之透明性受損，因此難以應用於光學物品用之塗佈塗料中。 If only a saturated hydrocarbon is added as in the patent document 1 regarding a water-based paint, sufficient defoaming property cannot be obtained. Further, as described above, the polymer has a low solubility in a saturated hydrocarbon, and when the amount of the saturated hydrocarbon is increased, white turbidity occurs and the transparency of the obtained cured film is impaired, so that it is difficult to apply it to an optical article. In the cloth coating.

又，為抑制組成物之起泡，通常添加各種添加劑作為消 泡劑。然而，通常此種添加劑多為固體組分，可能對由樹脂組成物獲得之塗膜或硬化膜之特性造成影響。又，添加劑多為價格昂貴者，而存在工業生產上成本增加之問題。又，於具有與樹脂組成物之構成成分之親和性，樹脂組成物與添加劑之親和性較差之情形時，亦有使樹脂組成物本身之特性降低之可能性，添加劑必須根據不同樹脂組成物個別地選定，業界謀求一種對於作為含有具有氟烷基與羥基之聚合體之樹脂組成物之非水系塗料整體，可不損及其特性地應用之消泡方法。 Further, in order to suppress foaming of the composition, various additives are usually added as a consumer. Foaming agent. However, usually such additives are mostly solid components, which may affect the properties of the coating film or the cured film obtained from the resin composition. Moreover, additives are mostly expensive, and there is a problem of an increase in cost in industrial production. Further, when the affinity between the resin composition and the additive is inferior to the affinity of the constituent component of the resin composition, the properties of the resin composition itself may be lowered, and the additive must be individually determined depending on the resin composition. In the field, the industry has devised a defoaming method which can be applied to a non-aqueous coating material containing a resin composition having a polymer of a fluoroalkyl group and a hydroxyl group as long as it does not impair its properties.

本發明鑒於上述狀況，其目的在於提供一種起泡性較小，即便有起泡之情況消泡性亦優異，其結果所形成之塗膜難以產生缺陷的非水系樹脂組成物。進而，本發明之目的在於提供一種可提供賦予優異之硬度、耐損傷性、透明性、耐污染性及其耐久性之硬化膜的樹脂組成物。 In view of the above, it is an object of the present invention to provide a nonaqueous resin composition which is less foaming and which is excellent in defoaming properties even when foaming occurs, and as a result, the coating film formed is less likely to cause defects. Further, an object of the present invention is to provide a resin composition which can provide a cured film which imparts excellent hardness, scratch resistance, transparency, stain resistance and durability.

又，本發明之目的在於提供一種上述組成物之硬化物、及表面包含該硬化物之物品，尤其是光記錄媒體、觸控面板顯示器等光學用途之物品中表面具有高硬度及耐磨耗性且亦具有優異之耐污染性及耐污染性之耐久性的物品。 Further, an object of the present invention is to provide a cured product of the above composition and an article including the cured product on the surface thereof, in particular, an object for optical use such as an optical recording medium or a touch panel display, which has high hardness and wear resistance on the surface. It also has excellent durability against stains and stains.

本發明者等人為解決上述課題而進行努力研究，結果發現藉由含有具有羥基及氟烷基且重量平均分子量為1000以上之聚合體、包含選自(甲基)丙烯醯基及乙烯基中之1種或2種以上之烴系單體、特定量之飽和烴、及溶解度參數(SP，Solubility Parameter)值為10.0以下之溶劑，可減小樹脂組成物之起泡性。 The present inventors have made an effort to solve the above problems, and as a result, it has been found to contain a polymer having a hydroxyl group and a fluoroalkyl group and having a weight average molecular weight of 1,000 or more, and comprising a group selected from a (meth) acrylonitrile group and a vinyl group. One or two or more kinds of hydrocarbon-based monomers, a specific amount of saturated hydrocarbons, and a solvent having a Solubility Parameter (SP) value of 10.0 or less can reduce the foaming property of the resin composition.

又，發現藉由含有具有羥基及氟烷基且重量平均分子量為1000以上之聚合體、包含選自(甲基)丙烯醯基及乙烯基中之1種或2種以上之 烴系單體、表面張力降低能力為2mN/m以上之含氟基之寡聚物(oligomer)、及SP值為10.0以下之溶劑，亦可減小樹脂組成物之起泡性。 In addition, it has been found that a polymer having a hydroxyl group and a fluoroalkyl group and having a weight average molecular weight of 1,000 or more, and one or more selected from the group consisting of a (meth)acryl fluorenyl group and a vinyl group are contained. The hydrocarbon-based monomer, an oligomer having a fluorine-containing group having a surface tension reducing ability of 2 mN/m or more, and a solvent having an SP value of 10.0 or less can also reduce the foaming property of the resin composition.

進而發現，於上述聚合體為具有聚矽氧烷構造，且該聚矽氧烷構造末端之矽或該矽上所鍵結之飽和烴基經由氧原子或硫原子鍵結於上述聚合體之主鏈上的聚合體之情形時，成為亦表現出較高之撥水撥油性之尤其優異之樹脂組成物，從而完成本發明。 Further, it is found that the polymer has a polyoxane structure, and the terminal of the polyoxyalkylene structure or the saturated hydrocarbon group bonded to the crucible is bonded to the main chain of the polymer via an oxygen atom or a sulfur atom. In the case of the above polymer, the resin composition which exhibits particularly high water repellency and oil repellency is excellent, and the present invention has been completed.

即，本發明如下所述。 That is, the present invention is as follows.

[1]一種樹脂組成物，其含有：具有羥基及氟烷基且重量平均分子量為1000以上之聚合體、包含選自(甲基)丙烯醯基及乙烯基中之1種或2種以上之烴系單體、飽和烴0.01~25重量%、及SP值為10.0以下之溶劑。 [1] A resin composition comprising a polymer having a hydroxyl group and a fluoroalkyl group and having a weight average molecular weight of 1,000 or more, and one or more selected from the group consisting of a (meth)acryl fluorenyl group and a vinyl group. A hydrocarbon monomer, a saturated hydrocarbon of 0.01 to 25% by weight, and a solvent having an SP value of 10.0 or less.

[2]如[1]之樹脂組成物，其中，上述飽和烴之碳數為5~18。 [2] The resin composition according to [1], wherein the saturated hydrocarbon has a carbon number of 5 to 18.

[3]一種樹脂組成物，其含有：具有羥基及氟烷基且重量平均分子量為1000以上之聚合體、包含選自(甲基)丙烯醯基及乙烯基中之1種或2種以上之烴系單體、表面張力降低能力為2mN/m以上之含氟基之寡聚物、及SP值為10.0以下之溶劑。 [3] A resin composition comprising a polymer having a hydroxyl group and a fluoroalkyl group and having a weight average molecular weight of 1,000 or more, and one or more selected from the group consisting of a (meth)acryl fluorenyl group and a vinyl group. The hydrocarbon-based monomer, a fluorine-containing oligomer having a surface tension reducing ability of 2 mN/m or more, and a solvent having an SP value of 10.0 or less.

[4]如[1]至[3]中任一項之樹脂組成物，其中，上述聚合體中之羥基之含量為0.2~5.0重量%。 [4] The resin composition according to any one of [1] to [3] wherein the content of the hydroxyl group in the polymer is 0.2 to 5.0% by weight.

[5]如[1]至[4]中任一項之樹脂組成物，其中，上述聚合體中之氟原子之含量為1.0~34.0重量%。 [5] The resin composition according to any one of [1] to [4] wherein the content of the fluorine atom in the polymer is 1.0 to 34.0% by weight.

[6]如[1]至[5]中任一項之樹脂組成物，其中，上述聚合體於側鏈上具有不飽和雙鍵基。 [6] The resin composition according to any one of [1] to [5] wherein the polymer has an unsaturated double bond group in a side chain.

[7]如[1]至[6]中任一項之樹脂組成物，其中，上述聚合體具有聚矽氧烷構造。 [7] The resin composition according to any one of [1] to [6] wherein the polymer has a polyoxane structure.

[8]如[7]之樹脂組成物，其中，上述聚矽氧烷構造末端之矽或該矽上所鍵結之飽和烴基經由氧原子或硫原子鍵結於上述聚合體之主鏈上。 [8] The resin composition according to [7], wherein the hydrazine at the end of the polyoxyalkylene structure or the saturated hydrocarbon group bonded to the oxime is bonded to the main chain of the polymer via an oxygen atom or a sulfur atom.

[9]如[1]至[8]中任一項之樹脂組成物，其中，上述烴系單體為1分子中具有3個以上之(甲基)丙烯醯基之多官能(甲基)丙烯酸酯。 The resin composition of any one of [1] to [8], wherein the hydrocarbon-based monomer is a polyfunctional (methyl) group having three or more (meth) acrylonitrile groups in one molecule. Acrylate.

[10]如[3]至[9]中任一項之樹脂組成物，其中，上述含氟基之寡聚物之重量平均分子量為5000以上。 [10] The resin composition according to any one of [3] to [9] wherein the fluoro group-containing oligomer has a weight average molecular weight of 5,000 or more.

[11]如[3]至[10]中任一項之樹脂組成物，其中，上述含氟基之寡聚物為非離子性。 [11] The resin composition according to any one of [3] to [10] wherein the fluoro group-containing oligomer is nonionic.

[12]如[3]至[11]中任一項之樹脂組成物，其中，樹脂組成物中之含氟基之寡聚物之含量為樹脂組成物整體之0.005~10重量%。 [12] The resin composition according to any one of [3] to [11] wherein the content of the fluorine-containing oligomer in the resin composition is 0.005 to 10% by weight based on the entire resin composition.

[13]如[1]至[12]中任一項之樹脂組成物，其中，上述溶劑為選自由酮系溶劑、醇系溶劑、醚系溶劑、酯系溶劑及芳香族烴溶劑所組成之群組中之至少一種溶劑。 [13] The resin composition according to any one of [1] to [12] wherein the solvent is selected from the group consisting of a ketone solvent, an alcohol solvent, an ether solvent, an ester solvent, and an aromatic hydrocarbon solvent. At least one solvent in the group.

[14]如[3]至[13]中任一項之樹脂組成物，其含有碳數為5~18之飽和烴。 [14] The resin composition according to any one of [3] to [13] which contains a saturated hydrocarbon having 5 to 18 carbon atoms.

[15]如[1]至[14]中任一項之樹脂組成物，其含有自由基聚合性光起始劑。 [15] The resin composition according to any one of [1] to [14] which contains a radical polymerizable photoinitiator.

[16]一種硬化物，其係使如[1]至[15]中任一項之組成物硬化而獲得。 [16] A cured product obtained by hardening a composition according to any one of [1] to [15].

[17]如[16]之硬化物，其係藉由對上述組成物照射活性能量射線而獲得。 [17] The cured product according to [16], which is obtained by irradiating the above composition with an active energy ray.

[18]一種成形品，其包含如[16]或[17]之硬化物。 [18] A molded article comprising the cured product of [16] or [17].

[19]如[18]之成形品，其係用於光學用途。 [19] The molded article according to [18], which is used for optical use.

[20]如[19]之成形品，其為光記錄媒體或光學顯示器用積層體。 [20] The molded article according to [19], which is a laminate for an optical recording medium or an optical display.

根據本發明，可提供一種起泡性較小，即便有起泡之情況消泡性亦優異，因此所形成之塗膜難以產生缺陷的樹脂組成物。本發明進而提供一種若將上述樹脂組成物較薄地塗佈於物品等之表面並使其硬化，則對該物品等賦予優異之硬度、耐損傷性、透明性、耐污染性及其耐久性的硬化膜。 According to the present invention, it is possible to provide a resin composition which is less foaming and which is excellent in defoaming property even in the case of foaming, so that the formed coating film is less likely to cause defects. Further, the present invention provides a method in which the resin composition is applied to a surface of an article or the like and is cured, thereby imparting excellent hardness, scratch resistance, transparency, stain resistance, and durability to the article or the like. Hardened film.

因此，本發明之樹脂組成物可較佳地應用於光記錄媒體表面之保護、觸控面板或平面顯示器等光學顯示器、行動電話殼體、汽車透明零件保護、農業用塑膠棚(vinyl house)等之透明部之保護等廣泛之用途。 Therefore, the resin composition of the present invention can be preferably applied to the protection of the surface of an optical recording medium, an optical display such as a touch panel or a flat panel display, a mobile phone case, a transparent part of a car, a vinyl house for agriculture, etc. A wide range of uses such as protection of the transparent portion.

以下，對本發明之實施形態進行詳細說明，但以下所記載之構成要件之說明為本發明之實施樣態之代表例，本發明並不限定於該等內容，可於其主旨之範圍內進行各種變化而實施。以下，對本發明之實施形態進行詳細說明。 Hereinafter, the embodiments of the present invention will be described in detail, but the description of the constituent elements described below is a representative example of the embodiment of the present invention, and the present invention is not limited to the above, and various types can be made within the scope of the gist of the present invention. Implemented by change. Hereinafter, embodiments of the present invention will be described in detail.

再者，本案說明書中，所謂「~」，係以包含其前後記載之數值作為下限值及上限值之含義使用。 In addition, in the present specification, the term "~" is used in the meaning of including the numerical values described before and after the lower limit and the upper limit.

又，本發明中所謂之「聚合」只要無特別說明，則為亦包含所謂之「共聚合」之廣義之聚合。因此，於本發明中，「聚合體」中亦包含「共聚合體」。 In addition, the "polymerization" in the present invention is a generalized polymerization which also includes so-called "copolymerization" unless otherwise specified. Therefore, in the present invention, "polymer" also includes "copolymer".

又，本發明中所謂之「室溫」係指進行其實驗等之場所之溫度， 例如意指15~30℃之溫度、更佳為20~25℃。 In addition, the term "room temperature" as used in the present invention means the temperature at which the experiment or the like is performed. For example, it means a temperature of 15 to 30 ° C, more preferably 20 to 25 ° C.

又，所謂「通常氧濃度」，意指18~22%、更佳為19~21%。 Further, the term "normal oxygen concentration" means 18 to 22%, more preferably 19 to 21%.

又，「(甲基)丙烯酸酯」意指「丙烯酸酯及/或甲基丙烯酸酯」，關於「(甲基)丙烯醯基」、「(甲基)丙烯酸基」亦相同。 Further, "(meth) acrylate" means "acrylate and/or methacrylate", and the same applies to "(meth)acryloyl group" and "(meth)acrylic group".

<1.樹脂組成物> <1. Resin composition>

作為本發明之一樣態之樹脂組成物(以下，有時簡稱為「本發明之樹脂組成物(A)」)含有具有羥基及氟烷基且重量平均分子量為1000以上之聚合體、包含選自(甲基)丙烯醯基及乙烯基中之1種或2種以上之烴系單體、飽和烴0.01重量%~25重量%、及SP值為10.0以下之溶劑作為必需成分。 The resin composition (hereinafter, simply referred to as "the resin composition (A) of the present invention) of the present invention contains a polymer having a hydroxyl group and a fluoroalkyl group and having a weight average molecular weight of 1,000 or more, and is selected from the group consisting of a polymer having a weight average molecular weight of 1,000 or more. A solvent such as one or two or more kinds of hydrocarbon-based monomers of (meth)acrylonyl group and vinyl group, 0.01% by weight to 25% by weight of saturated hydrocarbon, and a solvent having an SP value of 10.0 or less are essential components.

又，作為本發明之另一樣態之樹脂組成物(以下，有時簡稱為「本發明之樹脂組成物(B)」)含有具有羥基及氟烷基且重量平均分子量為1000以上之聚合體、包含選自(甲基)丙烯醯基及乙烯基中之1種或2種以上之烴系單體、表面張力降低能力為2mN/m以上之含氟基之寡聚物、及SP值為10.0以下之溶劑作為必需成分。 In addition, the resin composition (hereinafter, simply referred to as "the resin composition (B) of the present invention)" of the present invention contains a polymer having a hydroxyl group and a fluoroalkyl group and having a weight average molecular weight of 1,000 or more. An oligomer containing one or more hydrocarbon monomers selected from the group consisting of a (meth) acrylonitrile group and a vinyl group, and a fluorine group having a surface tension reducing ability of 2 mN/m or more, and an SP value of 10.0 The following solvents are essential ingredients.

<1-1.聚合體> <1-1. Polymer>

作為本發明之樹脂組成物之必需成分的聚合體具有羥基及氟烷基，且重量平均分子量為1000以上。重量平均分子量只要為1000以上，則並無特別限定，較佳為1000~30000，更佳為1000~20000。此處，重量平均分子量係指利用凝膠滲透層析儀(GPC，Gel Permeation Chromatography)(東梭公司製造之「HLC-8120GPC」)，使用四氫呋喃作為溶劑，使用聚苯乙烯作為標準樣品而測定者。 The polymer which is an essential component of the resin composition of the present invention has a hydroxyl group and a fluoroalkyl group, and has a weight average molecular weight of 1,000 or more. The weight average molecular weight is not particularly limited as long as it is 1000 or more, and is preferably from 1,000 to 30,000, more preferably from 1,000 to 20,000. Here, the weight average molecular weight refers to a gel permeation chromatograph (GPC, Gel Permeation Chromatography) ("HLC-8120GPC" manufactured by Tosoh Corporation), using tetrahydrofuran as a solvent, and using polystyrene as a standard sample. .

又，就樹脂組成物之硬化之觀點而言，上述聚合體較佳為側鏈上具有不飽和雙鍵基者。 Further, from the viewpoint of curing the resin composition, the polymer preferably has an unsaturated double bond group in its side chain.

又，就對硬化膜賦予均染性、滑動性、剝離性之觀點而言，上述聚合體較佳為具有聚矽氧烷構造者。於此情形時，更佳為上述聚矽氧烷構造末端之矽或該矽上所鍵結之飽和烴基經由氧原子或硫原子鍵結於上述聚合體之主鏈上者。 Moreover, from the viewpoint of imparting leveling property, slidability, and peelability to the cured film, the polymer preferably has a polyoxyalkylene structure. In this case, it is more preferred that the terminal of the polyoxyalkylene structure or the saturated hydrocarbon group bonded to the crucible is bonded to the main chain of the polymer via an oxygen atom or a sulfur atom.

本發明之樹脂組成物中之聚合體可藉由使以下說明之聚合性單體聚合而製造。以下記述聚合體之較佳之製造方法。 The polymer in the resin composition of the present invention can be produced by polymerizing a polymerizable monomer described below. A preferred method of producing the polymer will be described below.

再者，以下有時將作為本發明之聚合體之製造原料之單體混合物100重量份中的各成分之量(重量份)稱為「使用量」。 In the following, the amount (parts by weight) of each component in 100 parts by weight of the monomer mixture as a raw material for the production of the polymer of the present invention is referred to as "amount of use".

作為製造聚合體之聚合性單體，首先對具有羥基之(甲基)丙烯酸酯進行說明。若例示具有羥基之(甲基)丙烯酸酯之若干代表性之具體例，則可舉出丙烯酸2-羥乙酯、季戊四醇三丙烯酸酯等，但並不受該等之任何限定，亦可為具有藉由反應而生成羥基之官能基之單體。具有羥基之(甲基)丙烯酸酯之使用量少，由樹脂組成物獲得之硬化膜之硬度差，均欠佳。 As a polymerizable monomer for producing a polymer, first, a (meth) acrylate having a hydroxyl group will be described. Specific examples of the representative examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl acrylate and pentaerythritol triacrylate, but are not limited thereto, and may have A monomer which generates a functional group of a hydroxyl group by a reaction. The amount of the (meth) acrylate having a hydroxyl group is small, and the hardness of the cured film obtained from the resin composition is poor.

關於具有藉由反應而生成羥基之官能基之單體，作為此種反應，可舉出環氧基與羰基之反應、或氧基矽烷骨架之開環反應或加成反應等作為例子。 The monomer having a functional group which generates a hydroxyl group by the reaction may, for example, be a reaction between an epoxy group and a carbonyl group, or a ring opening reaction or an addition reaction of an oxydecane skeleton.

若例示具有環氧基之(甲基)丙烯酸酯之若干代表性之具體例，則可舉出：丙烯酸環氧丙酯、甲基丙烯酸環氧丙酯等具有環氧丙基之(甲基)丙烯酸酯；3,4-環氧環己基丙烯酸酯、3,4-環氧環己基甲基丙烯酸酯、3,4-環氧環己基丙烯酸甲酯、3,4-環氧環己基甲基丙烯酸甲酯等在脂環構造上直接鍵結有環氧基之(甲基)丙烯酸酯，但並不受該等之任何限定。 Specific examples of the representative examples of the (meth) acrylate having an epoxy group include (meth) epoxidized propyl acrylate and glycidyl methacrylate; Acrylate; 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate The methyl ester or the like is directly bonded to the (meth) acrylate of the epoxy group in the alicyclic structure, but is not limited to these.

該等之中，就獲取之容易性、由(甲基)丙烯酸改質之容易性而言， 尤佳為甲基丙烯酸環氧丙酯、3,4-環氧環己基丙烯酸酯、3,4-環氧環己基甲基丙烯酸酯、3,4-環氧環己基丙烯酸甲酯、3,4-環氧環己基甲基丙烯酸甲酯等。 Among these, in terms of ease of acquisition and ease of upgrading with (meth)acrylic acid, Especially preferred are glycidyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate, methyl 3,4-epoxycyclohexyl acrylate, 3,4 - Epoxycyclohexylmethyl methacrylate or the like.

此種具有環氧基之(甲基)丙烯酸酯可單獨使用1種，亦可混合2種以上而使用。 The (meth) acrylate having an epoxy group may be used singly or in combination of two or more.

若具有環氧基之(甲基)丙烯酸酯之使用量較少，則無法表現出由具有(甲基)丙烯醯基之羧酸改質引起之光自由基聚合之高硬化性或高硬度化效果、表面硬化性之提高效果等，若使用量較多，則有可見到聚合體溶液之增黏或溶液穩定性之降低之情況，又，亦未見到進一步之高硬化性或高硬度化，故而均欠佳。 When the (meth) acrylate having an epoxy group is used in a small amount, high photohardness or high hardness of photoradical polymerization caused by modification of a carboxylic acid having a (meth) acrylonitrile group cannot be exhibited. When the amount of use is large, the viscosity of the polymer solution or the stability of the solution is lowered, and further high hardenability or high hardness is not observed. Therefore, they are all poor.

若例示具有羰基之(甲基)丙烯酸酯之若干代表性之具體例，則可舉出：丙烯酸、甲基丙烯酸、琥珀酸變質季戊四醇三丙烯酸酯等，但並不受該等之任何限定。 Specific examples of the representative examples of the (meth) acrylate having a carbonyl group include acrylic acid, methacrylic acid, succinic acid-modified pentaerythritol triacrylate, and the like, but are not limited thereto.

本發明之樹脂組成物中的聚合體中之羥基之含量並無特別限定，於本發明之樹脂組成物(A)或樹脂組成物(B)之情形時，作為下限值，較佳為0.2重量%以上，更佳為0.4重量%以上，進而較佳為0.5重量%以上，尤佳為0.7重量%以上，最佳為1.0重量%以上。作為上限值，較佳為5.0重量%以下，更佳為4.0重量%以下，進而較佳為3.5重量%以下，最佳為3.0重量%以下。 The content of the hydroxyl group in the polymer in the resin composition of the present invention is not particularly limited, and in the case of the resin composition (A) or the resin composition (B) of the present invention, the lower limit is preferably 0.2. The weight% or more is more preferably 0.4% by weight or more, further preferably 0.5% by weight or more, particularly preferably 0.7% by weight or more, and most preferably 1.0% by weight or more. The upper limit is preferably 5.0% by weight or less, more preferably 4.0% by weight or less, still more preferably 3.5% by weight or less, and most preferably 3.0% by weight or less.

於製造聚合體時，以成為該範圍之方式調整具有羥基之單體之使用量。 When the polymer is produced, the amount of the monomer having a hydroxyl group is adjusted so as to be in this range.

又，於製造聚合體之單體混合物中，具有羥基之單體相對於單體整體之使用量較佳為5~50重量%，進而較佳為10~30重量%。 Further, in the monomer mixture for producing a polymer, the amount of the monomer having a hydroxyl group relative to the entire monomer is preferably from 5 to 50% by weight, more preferably from 10 to 30% by weight.

作為聚合體之製造中所使用之單體，對具有氟烷基之單 體進行說明。作為該單體，較佳地可舉出含有氟烷基之(甲基)丙烯酸酯。作為含有氟烷基之(甲基)丙烯酸酯，並無特別限制，較佳為具有碳數8以上之直鏈之全氟烷基之(甲基)丙烯酸酯以外含有氟烷基之(甲基)丙烯酸酯。其原因在於，若使用大量具有碳數為8以上且為直鏈之全氟烷基之(甲基)丙烯酸酯，則本發明之聚合體溶液或使用該聚合體之組成物溶液之起泡性明顯提高而成為問題。再者，具有碳數8以上之直鏈之全氟烷基之(甲基)丙烯酸酯並非不可使用。 As a monomer used in the manufacture of a polymer, for a single having a fluoroalkyl group The body is explained. As the monomer, a (meth) acrylate containing a fluoroalkyl group is preferred. The fluoroalkyl group-containing (meth) acrylate is not particularly limited, and it is preferably a fluoroalkyl group other than a (meth) acrylate having a linear perfluoroalkyl group having 8 or more carbon atoms. )Acrylate. The reason for this is that if a large amount of (meth) acrylate having a carbon number of 8 or more and a linear perfluoroalkyl group is used, the foaming property of the polymer solution of the present invention or the composition solution using the polymer is used. Significantly improved and become a problem. Further, a (meth) acrylate having a linear perfluoroalkyl group having 8 or more carbon atoms is not unusable.

作為較佳之具有氟烷基之(甲基)丙烯酸酯，可舉出具有碳數4~7之直鏈之氟烷基之(甲基)丙烯酸酯，例如較佳為全氟己基(甲基)丙烯酸乙酯、全氟己基環氧丙基醚之(甲基)丙烯酸加成物、全氟庚基環氧丙基醚之(甲基)丙烯酸加成物等。又，亦可舉出具有碳數為6以上且末端為二氟甲基之氟烷基之(甲基)丙烯酸酯，例如較佳為(甲基)丙烯酸1H,1H,7H-十二氟庚酯、(甲基)丙烯酸1H,1H,9H-十六氟壬酯等。 Preferred examples of the (meth) acrylate having a fluoroalkyl group include a (meth) acrylate having a linear fluoroalkyl group having 4 to 7 carbon atoms, and preferably, for example, a perfluorohexyl group (methyl). Ethyl acrylate, (meth)acrylic acid adduct of perfluorohexylepoxypropyl ether, (meth)acrylic acid adduct of perfluoroheptylepoxypropyl ether, and the like. Further, a (meth) acrylate having a fluoroalkyl group having a carbon number of 6 or more and a terminal difluoromethyl group may be mentioned, and for example, 1H, 1H, 7H-didofluoroheptyl (meth)acrylate is preferable. Ester, (meth)acrylic acid 1H, 1H, 9H-hexadecafluorodecyl ester, and the like.

該等之中，尤佳為具有碳數6之直鏈、飽和氟烷基之(甲基)丙烯酸酯，例如全氟己基(甲基)丙烯酸乙酯、全氟己基環氧丙醚之(甲基)丙烯酸加成物。 Among them, a (meth) acrylate having a carbon number of 6 linear and saturated fluoroalkyl groups, such as ethyl perfluorohexyl (meth) acrylate or perfluorohexyl epoxypropyl ether (A) Base) acrylic acid adduct.

該等具有氟烷基之(甲基)丙烯酸酯可單獨使用1種，亦可混合2種以上而使用。 These fluoroalkyl group-containing (meth) acrylates may be used alone or in combination of two or more.

作為具有碳數8以上之直鏈之全氟烷基之(甲基)丙烯酸酯，例如可舉出：全氟辛基(甲基)丙烯酸乙酯、全氟癸基(甲基)丙烯酸乙酯、2-(全氟-7-甲基辛基)(甲基)丙烯酸乙酯、(甲基)丙烯酸十七氟壬烯酯、全氟辛基環氧丙醚之(甲基)丙烯酸加成物等中之1種或2種以上。 Examples of the (meth) acrylate having a linear perfluoroalkyl group having 8 or more carbon atoms include ethyl perfluorooctyl (meth) acrylate and ethyl perfluorodecyl (meth) acrylate. , 2-(perfluoro-7-methyloctyl)ethyl (meth)acrylate, heptafluorodecenyl (meth)acrylate, (meth)acrylic acid addition of perfluorooctyl epoxidized propyl ether One or two or more of the substances.

本發明之樹脂組成物中的聚合體中之氟原子之含量並無特別限定，於本發明之樹脂組成物(A)或樹脂組成物(B)之情形時，作 為下限值，較佳為1.0重量%以上，更佳為4.0重量%以上，進而較佳為4.5重量%以上，尤佳為5.0重量%以上，最佳為10.0重量%以上。作為上限值，較佳為34.0重量%以下，更佳為30.0重量%以下，進而較佳為25.0重量%以下。若氟原子之含量未滿該下限值，則無法充分表現出源自氟烷基之撥油性的耐油性污垢性之提高等效果，若超過該上限值，則有聚合體與其他成分之相溶性降低，或硬化膜之硬度降低而使表面之耐損傷性或鉛筆硬度降低的可能性。於製造聚合體時，以成為該範圍之方式調整具有氟烷基之單體之使用量。 The content of the fluorine atom in the polymer in the resin composition of the present invention is not particularly limited, and in the case of the resin composition (A) or the resin composition (B) of the present invention, The lower limit is preferably 1.0% by weight or more, more preferably 4.0% by weight or more, still more preferably 4.5% by weight or more, still more preferably 5.0% by weight or more, and most preferably 10.0% by weight or more. The upper limit is preferably 34.0% by weight or less, more preferably 30.0% by weight or less, still more preferably 25.0% by weight or less. When the content of the fluorine atom is less than the lower limit, the effect of improving the oil-repellent fouling property derived from the oil-repellency of the fluoroalkyl group cannot be sufficiently exhibited. When the content exceeds the upper limit, the polymer and other components are present. The compatibility is lowered, or the hardness of the cured film is lowered to reduce the damage resistance of the surface or the pencil hardness. When the polymer is produced, the amount of the monomer having a fluoroalkyl group is adjusted so as to be in this range.

又，於製造聚合體之單體混合物中，具有全氟烷基之(甲基)丙烯酸酯相對於單體整體之使用量較佳為80.0重量%以下，進而較佳為60.0重量%以下。 Further, in the monomer mixture for producing a polymer, the amount of the (meth) acrylate having a perfluoroalkyl group relative to the entire monomer is preferably 80.0% by weight or less, and more preferably 60.0% by weight or less.

又，如上所述，本發明中之聚合體較佳為具有聚矽氧烷構造。此處，所謂聚矽氧烷構造，較佳為具有下述通式(1)所表示之重複構造單位者。 Further, as described above, the polymer of the present invention preferably has a polyoxyalkylene structure. Here, the polysiloxane structure preferably has a repeating structural unit represented by the following general formula (1).

-(SiR1R2-O)- (1) -(SiR 1 R 2 -O)- (1)

式中，R1及R2分別獨立地表示可具有取代基之烷基或可具有取代基之苯基，較佳為可經羥基或烷氧基取代之烷基(更佳為烷氧基及烷基之碳數為1~3)，進而較佳為不具有取代基之碳數1~3之烷基，最佳為甲基。 Wherein R 1 and R 2 each independently represent an alkyl group which may have a substituent or a phenyl group which may have a substituent, preferably an alkyl group which may be substituted with a hydroxyl group or an alkoxy group (more preferably an alkoxy group and The alkyl group has 1 to 3 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms which does not have a substituent, and is preferably a methyl group.

於本發明中，具有聚矽氧烷構造之聚合體為具有相當於如下構造之構造者：使包含除羥基或環氧基及氟烷基以外亦具有聚矽氧烷結構之(甲基)丙烯酸酯或二硫醇等的單體混合物之自由基聚合體的環氧基之至少一部分、與具有(甲基)丙烯醯基之羧酸反應而成之構造；或者使具有羥基及氟烷基之單體混合物之自由基聚合體的環氧基 之至少一部分、與具有聚矽氧烷構造之羧酸、或硫醇、胺等反應而成之構造。 In the present invention, the polymer having a polyoxymethane structure is a structure having a structure corresponding to a structure in which a (meth)acrylic acid having a polyoxyalkylene structure other than a hydroxyl group or an epoxy group and a fluoroalkyl group is contained. a structure in which at least a part of an epoxy group of a radical polymer of a monomer mixture such as an ester or a dithiol is reacted with a carboxylic acid having a (meth) acrylonitrile group; or a hydroxyl group and a fluoroalkyl group Epoxy group of free radical polymer of monomer mixture At least a part of the structure is a reaction with a carboxylic acid having a polyoxyalkylene structure or a thiol or an amine.

此種具有聚矽氧烷構造之聚合體之製造中所使用之單體較佳為具有上述式(1)所表示之重複構造單位連結2個以上而成之聚矽氧烷構造的(甲基)丙烯酸酯或二硫醇。作為此種單體之例子，可舉出：一末端具有甲基丙烯醯基之聚二甲基矽氧烷(JNC(原Chisso)公司製造之「Silaplane FM-0725」)、兩末端具有甲基丙烯醯基之聚二甲基矽氧烷(例如信越化學製造之「X-22-164A」)、兩末端具有環氧基之聚二甲基矽氧烷、兩末端及側鏈上具有環氧基之聚二甲基矽氧烷、側鏈上具有丙烯醯基之聚二甲基矽氧烷衍生物(例如Evonik Degussa Japan製造之「Tego-Rad」)、兩末端具有丙烯醯基之聚二甲基矽氧烷(例如Gelest公司製造之「DMS-U22」)、兩末端具有巰基之聚二甲基矽氧烷(例如信越化學工業公司製造之「X-22-167B」)、主鏈或側鏈上具有聚二甲基矽氧烷且側鏈及/或末端具有丙烯醯基及/或環氧基之共聚合體等。 The monomer used in the production of the polymer having a polyoxyalkylene structure is preferably a polyoxane structure having two or more repeating structural units represented by the above formula (1). ) acrylate or dithiol. Examples of such a monomer include polydimethyl methoxy oxane having a methacryl fluorenyl group at one end ("Silaplane FM-0725" manufactured by JNC (formerly Chisso) Co., Ltd.) and a methyl group at both ends. A propylene fluorenyl polydimethyl siloxane (for example, "X-22-164A" manufactured by Shin-Etsu Chemical Co., Ltd.), a polydimethyl siloxane having an epoxy group at both ends, and an epoxy at both ends and side chains. Polydimethyl methoxy oxane, polydimethyl methoxy olefin derivative having an acryl fluorenyl group in a side chain (for example, "Tego-Rad" manufactured by Evonik Degussa Japan), and poly propylene having a fluorenyl group at both ends Methyl decane (for example, "DMS-U22" manufactured by Gelest Corporation), polydimethyl methoxy oxane having sulfhydryl groups at both ends (for example, "X-22-167B" manufactured by Shin-Etsu Chemical Co., Ltd.), main chain or A copolymer having a polydimethylsiloxane and a side chain and/or a terminal having an acryloyl group and/or an epoxy group in the side chain.

又，如上所述，本發明之聚合體中之聚矽氧烷構造較佳為其末端之矽或該矽上所鍵結之飽和烴基經由氧原子或硫原子鍵結於上述聚合體之主鏈上。作為用以製造此種聚合體之具有聚矽氧烷構造之單體，若以甲基丙烯酸酯進行例示，則例如有二甲基聚矽烷氧基丙基甲基丙烯酸酯、α-丁基-ω-(3-甲基丙烯醯氧基丙基)聚二甲基矽氧烷，並不受該等之任何限定。又，若以二硫醇進行例示，則例如有α,ω-二巰基聚二甲基矽氧烷、α,ω-二巰基聚二乙基矽氧烷、α,ω-二巰基聚甲基乙基矽氧烷、α,ω-二巰基聚二羥基甲基矽氧烷、α,ω-二巰基聚二甲氧基甲基矽氧烷等。其中，較佳為α,ω-二巰基聚二甲基矽氧烷，且該巰基可直接連結於聚矽氧烷基，亦可經由伸烷基而連結於聚矽氧烷基。更 佳為巰基經由伸丙基而連結於聚矽氧烷基之聚矽氧烷(α,ω-二巰基丙基聚二甲基矽氧烷)。但，並不受該等之任何限定。 Further, as described above, the polyoxyalkylene structure in the polymer of the present invention is preferably such that the terminal or the saturated hydrocarbon group bonded to the oxime is bonded to the main chain of the above polymer via an oxygen atom or a sulfur atom. on. As a monomer having a polyoxyalkylene structure for producing such a polymer, if exemplified by methacrylic acid, for example, dimethylpolydecyloxypropyl methacrylate or α-butyl- Omega-(3-methacryloxypropyl)polydimethyloxane is not limited by these. Further, when exemplified by dithiol, for example, α,ω-dimercaptopolydimethyloxane, α,ω-dimercaptopolydimethoxydecane, α,ω-dimercaptopolymethyl group Ethyl decane, α, ω-dimercaptopolydihydroxymethyl decane, α, ω-dimercaptopolydimethoxymethyl decane, and the like. Among them, α,ω-dimercaptopolydimethyloxane is preferable, and the fluorenyl group may be directly bonded to the polyoxyalkylene group or may be bonded to the polyoxyalkylene group via an alkyl group. more Preferably, the sulfhydryl group is bonded to the polyoxyalkylene polyoxyalkylene (α,ω-dimercaptopropylpolydimethyloxane) via a propyl group. However, it is not subject to any limitation.

為良好地達成平衡耐污染性與硬度，具有聚矽氧烷構造之(甲基)丙烯酸酯或二硫醇之數量平均分子量較佳為1000~10000左右。此處，數量平均分子量係指利用GPC(東梭公司製造之「HLC-8120GPC」)，使用四氫呋喃作為溶劑，聚苯乙烯作為標準樣品而測定者。 In order to achieve a good balance between contamination resistance and hardness, the number average molecular weight of the (meth) acrylate or dithiol having a polyoxyalkylene structure is preferably about 1,000 to 10,000. Here, the number average molecular weight is measured by using GPC ("HLC-8120GPC" manufactured by Hokusto Co., Ltd.), using tetrahydrofuran as a solvent, and polystyrene as a standard sample.

具有聚矽氧烷構造之(甲基)丙烯酸酯或二硫醇可單獨使用1種，亦可混合2種以上而使用。 The (meth) acrylate or the dithiol having a polyoxyalkylene structure may be used singly or in combination of two or more.

又，具有聚矽氧烷構造之(甲基)丙烯酸酯或二硫醇之使用量於製造聚合體之單體混合物中，相對於單體整體為0.01~30重量%，較佳為0.1~25重量%，更佳為1~20重量%。若具有聚矽氧烷構造之(甲基)丙烯酸酯或二硫醇之使用量未滿0.01重量%，則耐污染性賦予不充分，若超過30重量%，則所獲得之聚合體與其他成分之相溶性(聚合反應時之體系之均勻相溶性、以及製成組成物時之聚合體與其他成分之相溶性)降低，或硬化膜之硬度降低，故而欠佳。 Further, the amount of the (meth) acrylate or dithiol having a polyoxyalkylene structure is from 0.01 to 30% by weight, preferably from 0.1 to 25, based on the total amount of the monomer mixture in the production of the polymer. The weight % is more preferably 1 to 20% by weight. When the amount of the (meth) acrylate or the dithiol having a polyoxyalkylene structure is less than 0.01% by weight, the contamination resistance is insufficient, and if it exceeds 30% by weight, the obtained polymer and other components are obtained. The compatibility (the uniform compatibility of the system at the time of polymerization and the compatibility of the polymer with other components in the case of forming a composition) is lowered, or the hardness of the cured film is lowered, which is not preferable.

較佳為具有聚矽氧烷構造之(甲基)丙烯酸酯或二硫醇之使用量為0.1重量%以上，進而較佳為1重量%以上。 The amount of the (meth) acrylate or dithiol having a polyoxyalkylene structure is preferably 0.1% by weight or more, and more preferably 1% by weight or more.

又，較佳為具有聚矽氧烷構造之(甲基)丙烯酸酯或二硫醇之使用量為25重量%以下，進而較佳為20重量%以下。 Further, the amount of the (meth) acrylate or dithiol having a polyoxyalkylene structure is preferably 25% by weight or less, and more preferably 20% by weight or less.

於製造本發明中之聚合體時所調製之單體混合物中亦可含有其他(甲基)丙烯酸酯。作為其他(甲基)丙烯酸酯，並無特別限定，但較佳為謀求與環氧基之反應性較低而不會降低生成聚合體之穩定性者、或骨架為剛性而不會降低硬度者、可進一步提高耐污染性者 等。 Other (meth) acrylates may also be included in the monomer mixture prepared in the manufacture of the polymer of the present invention. The other (meth) acrylate is not particularly limited, but it is preferably one which is low in reactivity with an epoxy group, does not lower the stability of the polymer formed, or has rigidity in the skeleton and does not lower the hardness. Can further improve the pollution resistance Wait.

若舉出此種其他(甲基)丙烯酸酯之若干具體例，則可例示：苯乙烯或其低級(碳數1~4之)烷基、烯基取代衍生物、碳數1~20之烷基(甲基)丙烯酸酯、烷基(甲基)丙烯醯胺、具有碳數5~20之(聚)環烷基側鏈之(甲基)丙烯酸環烷基酯、(甲基)丙烯醯胺類等自由基聚合性單體等。 Specific examples of such other (meth) acrylates include styrene or a lower alkyl group having 1 to 4 carbon atoms, an alkenyl substituted derivative, and an alkyl group having 1 to 20 carbon atoms. (meth) acrylate, alkyl (meth) acrylamide, cycloalkyl (meth) acrylate having a (poly) cycloalkyl side chain of 5 to 20, (meth) propylene hydride A radically polymerizable monomer such as an amine.

其他(甲基)丙烯酸酯可單獨使用1種，亦可混合2種以上而使用。 The other (meth) acrylate may be used singly or in combination of two or more.

其他(甲基)丙烯酸酯之使用量為50重量%以下。若其他(甲基)丙烯酸酯之使用量超過50重量%，則聚合體之硬度降低，表面之耐損傷性或鉛筆硬度降低，故而仍然欠佳。 The other (meth) acrylate is used in an amount of 50% by weight or less. When the amount of the other (meth) acrylate used exceeds 50% by weight, the hardness of the polymer is lowered, and the scratch resistance of the surface or the pencil hardness is lowered, so that it is still unsatisfactory.

較佳為其他(甲基)丙烯酸酯之使用量為45重量%以下，進而較佳為40重量%以下。 The amount of the other (meth) acrylate to be used is preferably 45% by weight or less, and more preferably 40% by weight or less.

於製造本發明之聚合體時，使上述單體之混合物進行自由基聚合，為提高其反應之均勻性，亦可於單體混合物中添加溶劑。 In the production of the polymer of the present invention, the mixture of the above monomers is subjected to radical polymerization, and in order to improve the uniformity of the reaction, a solvent may be added to the monomer mixture.

作為此種溶劑，可舉出丙酮、甲基乙基酮(MEK)、甲基異丁基酮(MIBK)等酮系溶劑；乙醇、甲醇、異丙醇(IPA)、異丁醇等醇系溶劑；乙二醇二甲醚、丙二醇單甲醚等醚系溶劑；乙酸乙酯、丙二醇單甲醚乙酸酯、2-乙氧基乙酸乙酯等酯系溶劑；甲苯等芳香族烴溶劑；及水作為較佳例。 Examples of such a solvent include ketone solvents such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK); and alcohols such as ethanol, methanol, isopropanol (IPA), and isobutanol. Solvent; ether solvent such as ethylene glycol dimethyl ether or propylene glycol monomethyl ether; ester solvent such as ethyl acetate, propylene glycol monomethyl ether acetate or 2-ethoxyethyl acetate; aromatic hydrocarbon solvent such as toluene; And water is a preferred example.

該等溶劑可單獨使用1種，亦可混合2種以上而使用。 These solvents may be used alone or in combination of two or more.

包含上述成分之單體混合物之自由基聚合中較佳為使用自由基聚合起始劑。 It is preferred to use a radical polymerization initiator in the radical polymerization of the monomer mixture containing the above components.

作為自由基聚合起始劑，可使用通常用於自由基聚合之公知之起始劑，可舉出過氧化苯甲醯、過氧化二(三級丁基)等有機過氧化物，2,2'- 偶氮雙丁腈、2,2'-偶氮雙(2,4-二甲基戊腈)、2,2'-偶氮雙(4-甲氧-2,4-二甲基戊腈)等偶氮化合物作為較佳例。 As the radical polymerization initiator, a known initiator generally used for radical polymerization can be used, and examples thereof include organic peroxides such as benzamidine peroxide and di(tertiary butyl peroxide), 2, 2 '- Azobisbutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) An azo compound is preferred.

該等自由基聚合起始劑可單獨使用1種，亦可混合2種以上而使用。 These radical polymerization initiators may be used alone or in combination of two or more.

於包含上述成分之單體混合物中進而視需要使用溶劑及自由基聚合起始劑進行自由基聚合時，單體成分與溶劑之混合、溶解方法等並無特別限制，例如較佳為於單體成分與溶劑之混合後，在一定時間以內、較佳為3小時以內添加自由基聚合起始劑而開始聚合。 In the case where the monomer mixture containing the above components is subjected to radical polymerization using a solvent or a radical polymerization initiator as needed, the method of mixing and dissolving the monomer component with the solvent is not particularly limited, and for example, it is preferably a monomer. After mixing the components with the solvent, the polymerization is started by adding a radical polymerization initiator within a certain period of time, preferably within 3 hours.

供至自由基聚合之反應液中的單體成分之總和濃度較佳為10重量%以上、60重量%以下，自由基聚合起始劑較佳為相對於單體成分之合計，較佳為使用0.1重量%以上，更佳為使用0.2重量%以上，且較佳為使用10重量%以下，更佳為使用2重量%以下。 The total concentration of the monomer components in the reaction liquid to be subjected to radical polymerization is preferably 10% by weight or more and 60% by weight or less, and the radical polymerization initiator is preferably used in combination with the monomer components, preferably used. 0.1% by weight or more, more preferably 0.2% by weight or more, and preferably 10% by weight or less, more preferably 2% by weight or less.

又，較佳之聚合條件根據所使用之自由基聚合起始劑而有所不同，聚合溫度為20~150℃，聚合時間為1~72小時，進而較佳為聚合溫度通常為50~100℃，聚合時間為3~36小時。 Further, preferred polymerization conditions vary depending on the radical polymerization initiator used, the polymerization temperature is 20 to 150 ° C, the polymerization time is 1 to 72 hours, and further preferably the polymerization temperature is usually 50 to 100 ° C. The polymerization time is 3 to 36 hours.

本發明中之聚合體較佳為對以如上所述之方式獲得之自由基聚合體的環氧基之至少一部分加成具有(甲基)丙烯醯基之羧酸、較佳為加成1分子內具有1~5個(甲基)丙烯醯基之羧酸而成者。其原因在於，(甲基)丙烯醯基成為交聯點使聚合體具有交聯構造，藉此污染物質之拭除性及其耐久性提高。 The polymer in the present invention is preferably a carboxylic acid having a (meth) acrylonitrile group, preferably one molecule, added to at least a part of the epoxy group of the radical polymer obtained as described above. It is a carboxylic acid having 1 to 5 (meth) acrylonitrile groups. The reason for this is that the (meth)acryl fluorenyl group serves as a crosslinking point, and the polymer has a crosslinked structure, whereby the wiping property of the contaminant and the durability thereof are improved.

作為此處所使用之具有(甲基)丙烯醯基之羧酸，例如可舉出：(甲基)丙烯酸、2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基乙基六氫酞酸、季戊四醇三(甲基)丙烯酸酯與琥珀酸酐、鄰苯二甲酸酐、六氫肽酐等酸酐之加成物、及二新戊四醇五(甲基)丙烯酸酯與琥 珀酸酐、鄰苯二甲酸酐、六氫肽酐等酸酐之加成物等。其可單獨使用1種，亦可混合2種以上而使用。 Examples of the carboxylic acid having a (meth) acrylonitrile group used herein include (meth)acrylic acid, 2-(meth)acryloxyethyl succinic acid, and 2-(methyl) propylene. An adduct of an oxiranyl ethyl hexahydrophthalic acid, pentaerythritol tri(meth) acrylate with an anhydride such as succinic anhydride, phthalic anhydride or hexahydropeptidic anhydride, and dipentaerythritol penta (methyl) Acrylate and amber An adduct of an acid anhydride such as phenolic anhydride, phthalic anhydride or hexahydropeptidic anhydride. These may be used alone or in combination of two or more.

於該加成反應中，自由基聚合體所具有之環氧基與具有(甲基)丙烯醯基之羧酸之羧基反應。 In the addition reaction, the epoxy group of the radical polymer reacts with the carboxyl group of the carboxylic acid having a (meth) acrylonitrile group.

自由基聚合體與具有(甲基)丙烯醯基之羧酸較佳為以使自由基聚合體之環氧基與具有(甲基)丙烯醯基之羧酸之羧基的比(以下，有時簡稱為「環氧基/羧基」)成為1以上之比例使用。又，環氧基/羧基較佳為10以下，更佳為5以下，進而較佳為2以下。 The radical polymer and the carboxylic acid having a (meth) acrylonitrile group are preferably a ratio of an epoxy group of a radical polymer to a carboxyl group of a carboxylic acid having a (meth) acrylonitrile group (hereinafter, sometimes The abbreviated as "epoxy group/carboxy group" is used in a ratio of 1 or more. Further, the epoxy group/carboxy group is preferably 10 or less, more preferably 5 or less, still more preferably 2 or less.

若環氧基/羧基為該下限值以上，則可防止由因未反應而殘存之具有(甲基)丙烯醯基之羧酸引起的穩定性之降低，若為該上限值以下則可防止由殘存之環氧基引起的穩定性之降低，故而較佳。 When the epoxy group/carboxy group is at least the lower limit value, it is possible to prevent a decrease in stability due to a carboxylic acid having a (meth) acrylonitrile group remaining unreacted, and if it is at most the upper limit value, It is preferred to prevent a decrease in stability caused by the remaining epoxy group.

又，自由基聚合體所具有之環氧基之中，較佳為50~99%與具有(甲基)丙烯醯基之羧酸之羧基反應，進而較佳為70~98%。 Further, among the epoxy groups of the radical polymer, 50 to 99% is preferably reacted with a carboxyl group of a carboxylic acid having a (meth) acrylonitrile group, and more preferably 70 to 98%.

該加成反應較佳為於50~110℃下進行3~50小時，進而較佳為於80~110℃下進行3~30小時。 The addition reaction is preferably carried out at 50 to 110 ° C for 3 to 50 hours, and more preferably at 80 to 110 ° C for 3 to 30 hours.

又，於本反應中，為促進反應，例如可使用三乙胺、三丁胺、三伸乙二胺、N,N-二甲基苄胺、苄基三甲基氯化銨及三苯基膦等公知之觸媒之1種或2種以上。其使用量相對於反應混合物(即，自由基聚合體與具有(甲基)丙烯醯基之羧酸之合計)，較佳為0.01重量%以上，更佳為0.05重量%以上。又，較佳為2重量%以下，更佳為1重量%以下。 Further, in the present reaction, in order to promote the reaction, for example, triethylamine, tributylamine, triethylenediamine, N,N-dimethylbenzylamine, benzyltrimethylammonium chloride, and triphenyl can be used. One or two or more kinds of known catalysts such as phosphine. The amount thereof to be used is preferably 0.01% by weight or more, and more preferably 0.05% by weight or more based on the reaction mixture (i.e., the total of the radical polymer and the carboxylic acid having a (meth)acrylonitrile group). Further, it is preferably 2% by weight or less, more preferably 1% by weight or less.

又，於本反應中，為防止由具有(甲基)丙烯醯基之羧酸之(甲基)丙烯醯基引起之自由基聚合，例如較佳為使用對苯二酚、對苯二酚單甲醚、鄰苯二酚、對三級丁鄰苯二酚、酚噻等聚合抑制劑之1 種或2種以上。聚合抑制劑之使用量相對於反應混合物，較佳為0.01重量%以上，更佳為0.05重量%以上。又，較佳為1重量%以下，更佳為5重量%以下。 Further, in the present reaction, in order to prevent radical polymerization caused by a (meth) acrylonitrile group of a carboxylic acid having a (meth) acrylonitrile group, for example, hydroquinone or hydroquinone is preferably used. Methyl ether, catechol, p-tert-butyl catechol, phenol thiophene One or two or more kinds of polymerization inhibitors. The amount of the polymerization inhibitor to be used is preferably 0.01% by weight or more, and more preferably 0.05% by weight or more based on the reaction mixture. Further, it is preferably 1% by weight or less, more preferably 5% by weight or less.

以上，舉出具體例對本發明中之聚合體之製造方法進行了說明，但於本發明中聚合體只要具有上述所說明之構造即可，並不限定於利用上述製造法獲得者。 In the above, the method for producing the polymer in the present invention has been described with reference to specific examples. However, in the present invention, the polymer may have the structure described above, and is not limited to those obtained by the above-described production method.

本發明之樹脂組成物中可僅含有1種上述聚合體，亦可含有2種以上之上述聚合體。 The resin composition of the present invention may contain only one type of the above polymer, or may contain two or more kinds of the above polymer.

本發明之組成物中之聚合體之含量亦根據組成物之用途或所使用之聚合體之種類、其他含有成分之組成而有所不同，較佳為0.5重量%以上，更佳為1重量%以上，又，較佳為20重量%以下，更佳為15重量%以下。若聚合體之含量為0.5重量%以上，則耐污染性變得更良好，若為20重量%以下，則硬度變高，塗佈性優異。 The content of the polymer in the composition of the present invention varies depending on the use of the composition or the type of the polymer to be used and the composition of other components, and is preferably 0.5% by weight or more, more preferably 1% by weight. The above is further preferably 20% by weight or less, and more preferably 15% by weight or less. When the content of the polymer is 0.5% by weight or more, the stain resistance is further improved, and when the content is 20% by weight or less, the hardness is high and the coating property is excellent.

<1-2.烴系單體> <1-2. Hydrocarbon monomer>

作為本發明之樹脂組成物之必需成分之烴系單體含有選自(甲基)丙烯醯基及乙烯基中之1種或2種以上，較佳為含有(甲基)丙烯醯基。 The hydrocarbon-based monomer which is an essential component of the resin composition of the present invention contains one or more selected from the group consisting of a (meth) acrylonitrile group and a vinyl group, and preferably contains a (meth) acrylonitrile group.

本成分對由樹脂組成物獲得之硬化膜提供良好之硬度。再者，本案說明書中所謂之「烴系單體」亦可含有包含碳、氫以外之原子之鍵。 This component provides good hardness to the cured film obtained from the resin composition. In addition, the "hydrocarbon type monomer" as used in the present specification may also contain a bond containing atoms other than carbon or hydrogen.

作為含有乙烯基之烴系單體，例如可舉出：苯乙烯、對氯苯乙烯、對甲氧基苯乙烯、二乙烯苯、N-乙烯吡咯啶酮、N-乙烯基己內醯胺、丙烯腈、乙二醇二乙烯醚、季戊四醇二乙烯醚、1,6-己二醇二乙烯醚、三羥甲丙烷二乙烯醚、環氧乙烷改質對苯二酚二乙烯醚、環氧乙烷改質雙酚A二乙烯醚、季戊四醇三乙烯醚、二新戊四醇六乙烯醚、二-三羥甲丙烷聚乙烯醚等。 Examples of the vinyl group-containing hydrocarbon-based monomer include styrene, p-chlorostyrene, p-methoxystyrene, divinylbenzene, N-vinylpyrrolidone, and N-vinylcaprolactam. Acrylonitrile, ethylene glycol divinyl ether, pentaerythritol divinyl ether, 1,6-hexanediol divinyl ether, trimethylolpropane divinyl ether, ethylene oxide modified hydroquinone divinyl ether, epoxy Ethane is modified with bisphenol A divinyl ether, pentaerythritol trivinyl ether, dipentaerythritol hexavinyl ether, di-trimethylolpropane polyvinyl ether and the like.

作為含有(甲基)丙烯醯基之烴系單體，可舉出1分子中具有1個或2個以上之(甲基)丙烯醯基者。 Examples of the hydrocarbon-based monomer containing a (meth) acrylonitrile group include one or two or more (meth) acrylonitrile groups in one molecule.

作為1分子中具有1個(甲基)丙烯醯基者，可舉出：(甲基)丙烯酸、烷基(甲基)丙烯酸酯(C1~C18)、(甲基)丙烯酸苯氧乙酯、(甲基)丙烯酸乙氧乙酯、(甲基)丙烯酸甲氧乙酯、(甲基)丙烯酸丁氧乙酯、(甲基)丙烯酸N,N-二乙胺乙酯、(甲基)丙烯酸N,N-二甲胺乙酯、(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-甲氧基乙氧基乙酯、(甲基)丙烯酸2-乙氧基乙氧基乙酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯、(甲基)丙烯醯基磷酸2-羥基乙酯、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸二環戊二烯酯、雙環戊二烯乙氧基(甲基)丙烯酸酯、(甲基)丙烯酸對苄基苯氧乙酯、1,6-己二醇單(甲基)丙烯酸酯、新戊二醇單(甲基)丙烯酸酯、甘油單(甲基)丙烯酸酯、三羥甲丙烷單(甲基)丙烯酸酯、季戊四醇單(甲基)丙烯酸酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、(甲基)丙烯酸2-羥基-3-辛氧基丙酯、二乙二醇單(甲基)丙烯酸酯、聚乙二醇400單(甲基)丙烯酸酯、2-(全氟辛基)(甲基)丙烯酸乙酯、CH2=C(CH3)COO(CH2)3Si(OCH3)3等。 Examples of the one having one (meth) acrylonitrile group in one molecule include (meth)acrylic acid, alkyl (meth) acrylate (C 1 to C 18 ), and phenoxy (meth) acrylate. Ester, ethoxyethyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, N,N-diethylamine (meth)acrylate, (methyl) N,N-dimethylamine ethyl acrylate, glycidyl (meth)acrylate, allyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy(meth)acrylate Ethyl ester, 2-methoxyethoxyethyl (meth)acrylate, 2-ethoxyethoxyethyl (meth)acrylate, benzyl (meth)acrylate, cyclomethacrylate Ester, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acryloylphosphonate, tetrahydrofurfuryl (meth)acrylate , dicyclopentadienyl (meth) acrylate, dicyclopentadienyl ethoxy (meth) acrylate, p-benzylphenoxyethyl (meth) acrylate, 1,6-hexanediol mono (A) Acrylate, neopentyl glycol mono (meth) acrylate, glycerol mono (meth) acrylate, trishydroxyl Alkenyl mono (meth) acrylate, pentaerythritol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3- octyloxy (meth) acrylate Ester, diethylene glycol mono (meth) acrylate, polyethylene glycol 400 mono (meth) acrylate, 2-(perfluorooctyl) ethyl (meth) acrylate, CH 2 = C (CH 3 COO(CH 2 ) 3 Si(OCH 3 ) 3 or the like.

作為1分子中具有2個以上之(甲基)丙烯醯基者，包含該技術領域中通常稱作多官能(甲基)丙烯酸酯或特殊(甲基)丙烯酸酯者、或稱作預聚合體、基底樹脂(base resin)、寡聚物、或丙烯酸系寡聚物者，具體而言，可舉出以下之(i)~(v)。 Those having two or more (meth) acrylonitrile groups in one molecule include those generally referred to in the art as polyfunctional (meth) acrylates or special (meth) acrylates, or prepolymers. Specific examples of the base resin, the oligomer, or the acrylic oligomer include the following (i) to (v).

(i)於多元醇上鍵結有2個以上之(甲基)丙烯酸而成之多元(甲基)丙烯酸酯。 (i) A poly (meth) acrylate in which two or more (meth)acrylic groups are bonded to a polyhydric alcohol.

(ii)於藉由多元醇與多元酸之反應而獲得的聚酯多元醇上鍵結有2 個以上之(甲基)丙烯酸而成之聚酯丙烯酸酯。 (ii) the polyester polyol obtained by the reaction of the polyol with the polybasic acid has 2 bonds More than one (meth)acrylic acid polyester acrylate.

作為上述(i)及(ii)中之多元醇，為乙二醇、1,4-丁二醇、1,6-己二醇、二乙二醇、三羥甲丙烷、二丙烯甘醇、聚乙二醇、聚丙二醇、季戊四醇、二新戊四醇等。又，作為多元酸，可舉出：鄰苯二甲酸、己二酸、順丁烯二酸、偏苯三甲酸、亞甲基丁二酸、琥珀酸、對苯二甲酸、烯基琥珀酸等。 The polyols in the above (i) and (ii) are ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, trimethylolpropane, and dipropylene glycol. Polyethylene glycol, polypropylene glycol, pentaerythritol, dipentaerythritol, and the like. Further, examples of the polybasic acid include phthalic acid, adipic acid, maleic acid, trimellitic acid, methylene succinic acid, succinic acid, terephthalic acid, alkenyl succinic acid, and the like. .

(iii)利用(甲基)丙烯酸將環氧樹脂之環氧基酯化而形成(甲基)丙烯醯基作為官能基的環氧丙烯酸酯。 (iii) An epoxy acrylate obtained by esterifying an epoxy group of an epoxy resin with (meth)acrylic acid to form a (meth)acryl fluorenyl group as a functional group.

作為上述(iii)中之環氧樹脂，可舉出：雙酚A-表氯醇型、苯酚酚醛清漆-表氯醇型、脂環式樹脂等。 Examples of the epoxy resin in the above (iii) include a bisphenol A-epichlorohydrin type, a phenol novolak-epichlorohydrin type, and an alicyclic resin.

(iv)使含羥基之(甲基)丙烯酸酯與多元異氰酸酯化合物反應而獲得之聚胺基甲酸酯丙烯酸酯。 (iv) Polyurethane acrylate obtained by reacting a hydroxyl group-containing (meth) acrylate with a polyvalent isocyanate compound.

作為上述(iv)中之多元異氰酸酯化合物，可舉出分子中央部具有聚酯、聚醚、聚胺基甲酸乙酯等構造且兩端含有異氰酸酯基者等。 The polyisocyanate compound in the above (iv) includes a structure having a structure such as a polyester, a polyether or a polyurethane at the center of the molecule, and an isocyanate group at both ends.

(v)上述以外之聚醚(甲基)丙烯酸酯、三聚氰胺(甲基)丙烯酸酯、醇酸(甲基)丙烯酸酯、異氰尿酸酯(甲基)丙烯酸酯、矽(甲基)丙烯酸酯等。 (v) Polyether (meth) acrylate, melamine (meth) acrylate, alkyd (meth) acrylate, isocyanurate (meth) acrylate, hydrazine (meth) acrylate other than the above Ester and the like.

作為該等之更具體之化合物之例子，可舉出：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、二伸乙甘醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、聚乙二醇400二(甲基)丙烯酸酯、羥基三甲基乙酸新戊二醇二(甲基)丙烯酸酯、三伸丙二醇二(甲基)丙烯酸酯、1,3-雙(3"-丙烯醯氧基乙氧基-2'-羥丙基)5,5-二甲內醯脲、三羥甲丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、三羥甲丙烷二(甲基)丙烯酸酯、雙酚A二(甲基)丙烯酸 酯、二新戊四醇單羥基五(甲基)丙烯酸酯、異氰尿酸三(丙烯醯氧基乙基)酯、異氰尿酸雙(丙烯醯氧基乙基)酯、日立化成股份有限公司製造之FA-731A、下述通式(2)~(7)(其中，R6為H或-CH3，n及x分別為1~10之整數)，但並不限定於該等。 Examples of such more specific compounds include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1,6-hexyl Diol (meth) acrylate, diethylene glycol di(meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol 400 di(meth) acrylate, hydroxy three Methyl acetic acid neopentyl glycol di(meth) acrylate, tri-propylene glycol di(meth) acrylate, 1,3-bis(3"-propylene methoxy ethoxy-2'-hydroxypropyl) 5,5-dimethyl carbazide, trimethylolpropane tri(meth) acrylate, pentaerythritol tri(meth) acrylate, dipentaerythritol hexa(meth) acrylate, pentaerythritol tetra (methyl) Acrylate, trimethylolpropane di(meth)acrylate, bisphenol A di(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, isocyanuric acid tris(propylene decyloxy) Ethyl) ester, bis(acryloxyethyl) isocyanurate, FA-731A manufactured by Hitachi Chemical Co., Ltd., and the following general formula (2) to (7) (wherein R 6 is H or - CH 3 , n and x are integers from 1 to 10, respectively, but are not limited thereto.

於本發明中，上述1分子中具有2個以上之(甲基)丙烯醯基者之中，更佳為具有3個以上之(甲基)丙烯醯基之多官能(甲基)丙烯酸酯。其原因在於，藉由使用此種烴系單體，可進一步提高由樹脂組成物獲得之硬化膜之硬度。 In the present invention, among the ones having two or more (meth) acrylonitrile groups in one molecule, more preferably a polyfunctional (meth) acrylate having three or more (meth) acrylonitrile groups. This is because the hardness of the cured film obtained from the resin composition can be further improved by using such a hydrocarbon-based monomer.

具體而言，可例示：季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、三羥甲丙烷三(甲基)丙烯酸酯、二-三羥甲丙烷四(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯類、多官能胺基甲酸酯(甲基)丙烯酸酯類、聚環氧(甲基)丙烯酸酯類、具有異氰尿酸酯環之三乙氧基(甲基)丙烯酸酯(例如東亞合成製造之ARONIX M315、M313等)，但並不限定於該等。該等之中，就硬度等性能面良好之方面而言，較佳為多官能丙烯酸酯，較佳為異氰尿酸三(丙烯醯氧基乙基)酯、異氰尿酸雙(丙烯醯氧基乙基)酯、季戊四醇三(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯。 Specifically, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate may be exemplified. , trimethylolpropane tri (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, polyester (meth) acrylate, polyfunctional urethane (meth) acrylate a polyepoxy (meth) acrylate, a triethoxy (meth) acrylate having an isocyanurate ring (for example, ARONIX M315, M313, etc. manufactured by Toagosei Co., Ltd.), but is not limited thereto. Wait. Among these, a polyfunctional acrylate is preferable in terms of a good performance surface such as hardness, and preferably tris(propylene methoxyethyl) isocyanurate or bis(propylene oxy oxy) Ethyl)ester, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate.

上述所舉出之各種烴系單體可單獨使用1種，亦可混合2種以上而使用。 The various hydrocarbon-based monomers mentioned above may be used alone or in combination of two or more.

又，關於組成物中之該等之較佳之含量，只要其合計含量不脫離本發明之主旨，則並無特別限定，但於用作尤其需要較高硬度之組成物之情形時，作為烴系單體/聚合體之重量比，較佳為使聚合體多於99.9/0.1，尤佳為使聚合體多於99/1，較佳為使聚合體少於50/50，進而較佳為使聚合體少於80/20，尤佳為使聚合體少於85/15。藉由將聚合體設為該上限以下，所獲得之硬化物可保持更高之硬度，故而較佳，藉由設為該下限以上，所獲得之硬化物可表現出更良好之耐污染性，故而較佳。 Further, the preferred content of the composition is not particularly limited as long as the total content thereof does not deviate from the gist of the present invention, but is used as a hydrocarbon system when used as a composition requiring a particularly high hardness. The weight ratio of the monomer/polymer is preferably such that the polymer is more than 99.9/0.1, and more preferably the polymer is more than 99/1, preferably the polymer is less than 50/50, and further preferably The polymer is less than 80/20, and more preferably the polymer is less than 85/15. When the polymer is set to be equal to or lower than the upper limit, the obtained cured product can maintain a higher hardness. Therefore, it is preferred that the cured product obtained exhibits better stain resistance by setting it as the lower limit or more. Therefore, it is better.

<1-3.飽和烴> <1-3. Saturated hydrocarbons>

作為本發明之樹脂組成物(A)之必需成分之飽和烴，可廣泛採用公知者，較佳為碳數為5~18者。碳數未滿5者於室溫下為氣體，碳數為18以上者於室溫下為固體，難以操作。作為較佳例，可舉出：己烷、庚烷、辛烷、環己烷、環庚烷等。 As the saturated hydrocarbon which is an essential component of the resin composition (A) of the present invention, a known one can be widely used, and those having a carbon number of 5 to 18 are preferable. Those having a carbon number of less than 5 are gas at room temperature, and those having a carbon number of 18 or more are solid at room temperature and are difficult to handle. Preferable examples thereof include hexane, heptane, octane, cyclohexane, and cycloheptane.

又，本發明之樹脂組成物(B)亦較佳為含有飽和烴。飽和烴與本發明之樹脂組成物(A)之情形同樣地可廣泛採用公知者，較佳為碳數為5~18者。 Further, the resin composition (B) of the present invention preferably further contains a saturated hydrocarbon. The saturated hydrocarbon can be widely used in the same manner as in the case of the resin composition (A) of the present invention, and preferably has a carbon number of 5 to 18.

本發明之樹脂組成物(A)中之飽和烴之含量為0.01~25重量%，較佳為0.5重量%以上，更佳為1重量%以上。 The content of the saturated hydrocarbon in the resin composition (A) of the present invention is 0.01 to 25% by weight, preferably 0.5% by weight or more, and more preferably 1% by weight or more.

本發明之樹脂組成物(B)中之飽和烴之含量亦根據組成物之用途或所使用之聚合體之種類、其他含有成分之組成而有所不同，較佳為0.01重量%以上，更佳為0.5重量%以上，進而較佳為1重量%以上，又，較佳為25重量%以下，更佳為23重量%以下，尤佳為20重量%以下。若聚合體之含量少於該下限值，則無法賦予消泡性，若多於該上限值，則有聚合體析出之虞。 The content of the saturated hydrocarbon in the resin composition (B) of the present invention varies depending on the use of the composition, the type of the polymer to be used, and the composition of other components, and is preferably 0.01% by weight or more, more preferably It is 0.5% by weight or more, more preferably 1% by weight or more, further preferably 25% by weight or less, more preferably 23% by weight or less, and still more preferably 20% by weight or less. When the content of the polymer is less than the lower limit, the defoaming property cannot be imparted, and if it exceeds the upper limit, the polymer is precipitated.

又，於本發明之樹脂組成物中，作為必需成分之聚合體與飽和烴以重量比計較佳為5：1~1：20。其原因在於，藉由使該比為該範圍，容易藉由兩成分之相互作用抑制樹脂組成物之起泡性，又，容易提高消泡性。 Further, in the resin composition of the present invention, the polymer as an essential component and the saturated hydrocarbon are preferably 5:1 to 1:20 by weight. The reason for this is that by setting the ratio to the range, it is easy to suppress the foaming property of the resin composition by the interaction of the two components, and it is easy to improve the defoaming property.

<1-4.表面張力降低能力為2mN/m以上之含氟基之寡聚物> <1-4. A fluorine-containing oligomer having a surface tension reducing ability of 2 mN/m or more>

作為本發明之樹脂組成物(B)之必需成分的表面張力降低能力為2mN/m以上之含氟基之寡聚物可廣泛採用公知者。此處，所謂表面張力 降低能力，意指溶解含氟基之寡聚物1質量%時的PGMAc(1-甲氧基丙基-2-乙酸酯)之表面張力之降低量(「表面張力降低能力」=「PGMAc之表面張力」-「1%PGMAc溶液之表面張力」)。 The fluorinated group-containing oligomer having a surface tension reducing ability of 2 mN/m or more as an essential component of the resin composition (B) of the present invention can be widely used. Here, the surface tension The ability to reduce the surface tension of PGMac (1-methoxypropyl-2-acetate) when the fluorine-containing oligomer is dissolved at 1% by mass ("surface tension reducing ability" = "PGMAc Surface tension" - "surface tension of 1% PGMAc solution").

含氟基之寡聚物之表面張力降低能力只要為2mN/m以上，則並無特別限定，作為上限值，較佳為15mN/m以下，更佳為12mN/m以下，尤佳為10mN/m以下。又，作為下限值，較佳為2mN/m以上，更佳為3.5mN/m以上，尤佳為5mN/m以上。若為該上限值以下，則相溶性良好，故而較佳，若為該下限值以上，則消泡性良好，故而較佳。再者，上述表面張力降低能力係使用表面張力計(協和界面化學公司製造之「DropMaster系列」)算出之值。又，表面張力降低能力係由添加劑之分子構造決定之數值，且由如下情況而決定：若具有含有氟原子或Si原子之構造，則有表面張力降低能力變大之傾向，若含有較多極性基，則有表面張力降低能力變小之傾向。 The surface tension reducing ability of the fluorine-containing oligomer is not particularly limited as long as it is 2 mN/m or more, and is preferably 15 mN/m or less, more preferably 12 mN/m or less, and particularly preferably 10 mN. /m below. Further, the lower limit is preferably 2 mN/m or more, more preferably 3.5 mN/m or more, and still more preferably 5 mN/m or more. When the value is at most the upper limit value, the compatibility is good. Therefore, when the amount is more than the lower limit value, the defoaming property is good, which is preferable. Further, the surface tension reducing ability is a value calculated using a surface tension meter ("DropMaster Series" manufactured by Kyowa Interface Chemical Co., Ltd.). In addition, the surface tension reducing ability is determined by the molecular structure of the additive, and is determined by the fact that if the structure contains a fluorine atom or a Si atom, the surface tension reducing ability tends to increase, and if the polarity is more The base has a tendency to reduce the surface tension reduction ability.

含氟基之寡聚物只要表面張力降低能力為2mN/m以上，則關於其他方面，並無特別限定，作為重量平均分子量之下限值，較佳為5000以上，更佳為6000以上，尤佳為7000以上。又，作為上限值，較佳為40000以下，更佳為20000以下，尤佳為15000以下。若為該上限值以下，則與其他成分之相溶性良好，故而較佳。若為該下限值以上，則消泡性良好，故而較佳。此處，重量平均分子量係指利用GPC(東梭公司製造之「HLC-8120GPC」)，使用四氫呋喃作為溶劑，使用聚苯乙烯作為標準樣品而測定者。 The fluorine-containing oligomer is not particularly limited as long as the surface tension reducing ability is 2 mN/m or more, and is preferably 5,000 or more, and more preferably 6,000 or more, as the lower limit of the weight average molecular weight. Good for 7000 or above. Further, the upper limit is preferably 40,000 or less, more preferably 20,000 or less, and still more preferably 15,000 or less. When it is below this upper limit, it is preferable because compatibility with other components is favorable. If it is at least the lower limit value, the defoaming property is good, which is preferable. Here, the weight average molecular weight is measured by using GPC ("HLC-8120GPC" manufactured by Hokusto Co., Ltd.), using tetrahydrofuran as a solvent, and using polystyrene as a standard sample.

又，含氟基之寡聚物較佳為不含有丙烯醯基者，其原因在於消泡性良好。 Further, the fluorine-containing oligomer is preferably one which does not contain an acrylonitrile group because the defoaming property is good.

進而，含氟基之寡聚物較佳為非離子性，其原因在於消泡性優異。 具體而言，例如可舉出：NEOS公司之Ftergent 710FM、DIC公司製造之Megafac F-555、Daikin公司製造之NS-9013等。上述寡聚物亦可混合數種而使用。 Further, the fluorine-containing oligomer is preferably nonionic, which is because the defoaming property is excellent. Specific examples include Ftergent 710FM manufactured by NEOS Corporation, Megafac F-555 manufactured by DIC Corporation, and NS-9013 manufactured by Daikin Corporation. The above oligomers may be used in combination of several kinds.

本發明之樹脂組成物(B)中的含氟基之寡聚物之較佳含量只要不脫離本發明之主旨，則並無特別限定，較佳為本發明之樹脂組成物(B)整體之0.005~10重量%，進而較佳為0.01~5重量%。若該含量少於0.005重量%，則有無法抑制樹脂組成物之起泡之情況，若大於10重量%，則有塗敷樹脂組成物時產生條紋或凹凸不均等缺陷之情況。 The preferred content of the fluorine-containing oligomer in the resin composition (B) of the present invention is not particularly limited as long as it does not deviate from the gist of the present invention, and is preferably the resin composition (B) of the present invention as a whole. 0.005 to 10% by weight, more preferably 0.01 to 5% by weight. When the content is less than 0.005% by weight, foaming of the resin composition may not be inhibited. When the content is more than 10% by weight, defects such as streaks or unevenness may occur when the resin composition is applied.

本發明之樹脂組成物(A)亦較佳為含有含氟基之寡聚物，更佳為含有非離子性之含氟基之寡聚物。其原因在於，可進一步提高樹脂組成物之起泡防止。 The resin composition (A) of the present invention is also preferably a fluorine-containing group-containing oligomer, more preferably a nonionic fluorine-containing group-containing oligomer. This is because the foaming prevention of the resin composition can be further improved.

作為非離子性之含氟基之寡聚物，較佳為聚合平均分子量為5000~20000者，更佳為聚合平均分子量為5000~10000者。例如可舉出：NEOS公司之Ftergent 710FM、DIC公司製造之Megafac F-554、Megafac F-555、Megafac F-556、Megafac RS-75、Daikin公司製造之NS-9013、DSN-403N等，較佳為Ftergent 710FM、Megafac F-555、NS-9013。此處，聚合平均分子量係指利用GPC(東梭公司製造之「HLC-8120GPC」)，使用四氫呋喃作為溶劑，使用聚苯乙烯作為標準樣品而測定者。 The nonionic fluorinated group-containing oligomer preferably has a polymerization average molecular weight of 5,000 to 20,000, more preferably a polymerization average molecular weight of 5,000 to 10,000. For example, Fergent 710FM of NEOS, Megafac F-554 by DIC, Megafac F-555, Megafac F-556, Megafac RS-75, NS-9013 by Daikin, DSN-403N, etc. are preferable. For Ftergent 710FM, Megafac F-555, NS-9013. Here, the polymerization average molecular weight is measured by using GPC ("HLC-8120GPC" manufactured by Hokusto Co., Ltd.), using tetrahydrofuran as a solvent, and using polystyrene as a standard sample.

本發明之樹脂組成物(A)中的非離子性之含氟基之寡聚物之含量並無特別限定，較佳為本發明之樹脂組成物(A)整體之0.005~10重量%，進而較佳為0.01~5重量%，尤佳為0.1~2重量%。若該含量少於0.005重量%，則有無法抑制樹脂組成物之起泡之情況，若大 於10重量%，則有塗敷樹脂組成物時產生條紋或凹凸不均等缺陷之情況。 The content of the nonionic fluorine-containing oligomer in the resin composition (A) of the present invention is not particularly limited, but is preferably 0.005 to 10% by weight based on the entire resin composition (A) of the present invention. It is preferably 0.01 to 5% by weight, particularly preferably 0.1 to 2% by weight. If the content is less than 0.005% by weight, there is a possibility that the foaming of the resin composition cannot be suppressed. When the resin composition is applied at 10% by weight, defects such as streaks or unevenness may occur.

<1-5.溶劑> <1-5. Solvent>

作為本發明之樹脂組成物之必需成分之溶劑為SP值10.0以下者，較佳為9.5以下，更佳為9.3以下，尤佳為9.0以下。若為該上限值以下，則消泡性良好，故而較佳。又，作為下限值，較佳為7.5以上，更佳為7.8以上，進而較佳為8.0以上，尤佳為8.2以上，最佳為8.5以上。若為該下限值以上，則相溶性良好，故而較佳。 The solvent which is an essential component of the resin composition of the present invention has an SP value of 10.0 or less, preferably 9.5 or less, more preferably 9.3 or less, and still more preferably 9.0 or less. If it is at most the upper limit value, the defoaming property is good, which is preferable. Further, the lower limit is preferably 7.5 or more, more preferably 7.8 or more, still more preferably 8.0 or more, still more preferably 8.2 or more, and most preferably 8.5 or more. If it is more than this lower limit, compatibility is good, and it is preferable.

所謂SP值，係表示溶解度參數，該值係藉由Fedors等人提出之方法而計算者。具體而言，望參照「POLYMER ENGINEERING AND SCIENCE,FEBRUARY,1974,Vol.14,No.2,ROBERT F.FEDORS.(147~154頁)」。又，SP值係由分子之疏水性基或親水性基之含量所決定之物性值，於使用混合溶劑之情形時，亦可將SP值較小之溶劑與較大之溶劑混合而適當調製。 The SP value is a solubility parameter which is calculated by the method proposed by Fedors et al. Specifically, it is referred to "POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (pp. 147-154)". Further, the SP value is a physical property value determined by the content of the hydrophobic group or the hydrophilic group of the molecule. When a mixed solvent is used, a solvent having a small SP value may be mixed with a larger solvent to appropriately prepare it.

通常於溶解聚合體之樹脂組成物中，若使用SP值較高之溶劑，則親水性基變多，因此變得容易形成膠體而容易起泡，若使用SP值較低之溶劑，則可防止起泡。然而，為提高作為本發明之樹脂組成物之必需成分的聚合體之溶解性，使用某種程度上SP值較高之溶劑可獲得均勻之溶液，故而較佳。因此，作為本發明中之溶劑，可使用於上述範圍內具有SP值者。 In the resin composition in which the polymer is dissolved, when a solvent having a high SP value is used, the hydrophilic group is increased, so that it is easy to form a colloid and foaming easily, and if a solvent having a low SP value is used, it can be prevented. Foaming. However, in order to improve the solubility of the polymer which is an essential component of the resin composition of the present invention, it is preferred to use a solvent having a high SP value to obtain a uniform solution. Therefore, as the solvent in the present invention, it can be used for those having the SP value within the above range.

作為本發明中之溶劑，只要SP值為上述範圍，則可廣泛採用公知者，可舉出丙酮、甲基乙基酮(MEK)、甲基異丁基酮(MIBK)等酮系溶劑；乙醇、甲醇、異丙醇(IPA)、異丁醇等醇系溶劑；乙二醇二甲基醚、丙二醇單甲醚等醚系溶劑；乙酸乙酯、乙酸丁酯、丙二醇 單甲醚乙酸酯、2-乙酸乙氧乙酯等酯系溶劑；甲苯等芳香族烴溶劑等作為較佳例。其中，就起泡性較低且與本發明之聚合體之相溶性亦較高之觀點而言，進而較佳為酮系溶劑之甲基乙基酮(MEK)、甲基異丁基酮(MIBK)。 As a solvent in the present invention, as long as the SP value is in the above range, a known one can be widely used, and examples thereof include a ketone solvent such as acetone, methyl ethyl ketone (MEK) or methyl isobutyl ketone (MIBK); and ethanol. , alcoholic solvents such as methanol, isopropanol (IPA), isobutanol; ether solvents such as ethylene glycol dimethyl ether and propylene glycol monomethyl ether; ethyl acetate, butyl acetate, propylene glycol An ester solvent such as monomethyl ether acetate or 2-acetoxyethyl acetate; an aromatic hydrocarbon solvent such as toluene or the like is preferable. Among them, from the viewpoint of low foaming property and high compatibility with the polymer of the present invention, methyl ethyl ketone (MEK) and methyl isobutyl ketone of a ketone solvent are further preferable. MIBK).

該等溶劑可單獨使用1種，亦可混合2種以上而使用。 These solvents may be used alone or in combination of two or more.

本發明之樹脂組成物尤其於如下所述般用於塗佈用途之情形時，較佳為藉由含有該等有機溶劑，將其固形份濃度調製成10重量%以上、尤其是20重量%以上，且90重量%以下、尤其是70重量%以下。 When the resin composition of the present invention is used for coating applications as described below, it is preferred to prepare the solid content of the resin composition to be 10% by weight or more, particularly 20% by weight or more by containing the organic solvent. And 90% by weight or less, especially 70% by weight or less.

<1-6.自由基聚合性光起始劑> <1-6. Radical Polymerizable Photoinitiator>

本發明之樹脂組成物較佳為除上述必需成分以外亦進而含有自由基聚合性起始劑。其原因在於，可有效率地進行樹脂組成物之硬化。通常，樹脂組成物之硬化係藉由照射活性能量射線而進行，但於如電子束(EB，electron beam)般照射能量非常強，無需添加自由基聚合性起始劑之情形時可省略。 The resin composition of the present invention preferably further contains a radical polymerizable initiator in addition to the above-mentioned essential components. The reason for this is that the hardening of the resin composition can be performed efficiently. Usually, the curing of the resin composition is carried out by irradiation with an active energy ray, but the irradiation energy is very strong as in the case of an electron beam (EB), and it is not necessary to add a radical polymerizable initiator.

作為自由基聚合性光起始劑，可廣泛採用公知者，較佳地可舉出：烷基苯酮型化合物(α-羥基苯乙酮系、α-胺基苯乙酮系、苄基縮酮系等)、醯基膦氧化型化合物、肟酯化合物、氧苯基乙酸酯類、安息香醚類、苯基甲酸酯類、酮/胺化合物等。具體而言，較佳為安息香甲醚、安息香***、安息香丙醚、安息香丁醚、二乙氧基苯乙酮、苄基二甲基縮酮、2-羥-2-甲基苯丙酮、1-羥基環己基苯基酮、二苯基酮、2,4,6-三甲基安息香二苯基氧化膦、2-甲基-[4-(甲硫基)苯基]-2-啉基-1-丙酮、2-苄基-2-二甲胺基-1-(4-啉基苯基)-丁烷-1-酮、苯甲醯甲酸甲酯、米其勒酮、N,N-二甲胺基苯甲酸異戊酯、2-氯-9-氧硫、2,4-二乙基-9-氧硫等。 As a radically polymerizable photoinitiator, a known one can be widely used, and an alkylphenone type compound (α-hydroxyacetophenone type, α-aminoacetophenone type, benzyl group) is preferable. A ketone system or the like, a mercaptophosphine oxide compound, an oxime ester compound, an oxyphenyl acetate, a benzoin ether, a phenyl formate, a ketone/amine compound, and the like. Specifically, it is preferably benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin butyl ether, diethoxy acetophenone, benzyl dimethyl ketal, 2-hydroxy-2-methyl phenyl ketone, 1 -hydroxycyclohexyl phenyl ketone, diphenyl ketone, 2,4,6-trimethylbenzoin diphenylphosphine oxide, 2-methyl-[4-(methylthio)phenyl]-2- Lolinyl-1-propanone, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butan-1-one, methyl benzhydrazide, mischrone, isoamyl N,N-dimethylaminobenzoate, 2-chloro-9-oxosulfur 2,4-diethyl-9-oxosulfur Wait.

該等自由基聚合性光起始劑可單獨使用1種，亦可混合2種以上而使用。 These radically polymerizable photoinitiators may be used singly or in combination of two or more.

本發明之樹脂組成物中之自由基聚合性光起始劑之含量可根據所使用之自由基聚合性光起始劑之種類而適當決定，相對於組成物中之聚合體、其他下述之以矽酸膠(colloidal silica)為主成分之無機氧化物微粒子上具有經由-O-Si-R-鍵(R表示碳數2~10之直鏈或支鏈之伸烷基)鍵結之(甲基)丙烯醯基的有機無機複合體、自由基聚合性之有機(甲基)丙烯酸酯化合物及/或自由基聚合性之有機(甲基)丙烯醯胺化合物、本發明之聚合體以外之具有自由基聚合性基之聚合體等組成物中之聚合性成分之總和，較佳為10重量%以下，更佳為8重量%以下，且較佳為0.5重量%以上。若自由基聚合性光起始劑之含量少於該範圍，則硬化變得不充分，若多於該範圍，則有產生硬度之降低或耐污染性之降低之情況。 The content of the radically polymerizable photoinitiator in the resin composition of the present invention can be appropriately determined depending on the kind of the radically polymerizable photoinitiator to be used, and the polymer in the composition, other The inorganic oxide fine particles mainly composed of colloidal silica have a bond via a -O-Si-R- bond (R represents a linear or branched alkyl group having 2 to 10 carbon atoms) ( An organic-inorganic composite of a methyl) acrylonitrile group, a radically polymerizable organic (meth) acrylate compound, and/or a radically polymerizable organic (meth) acrylamide compound, other than the polymer of the present invention The total of the polymerizable components in the composition such as the polymer having a radical polymerizable group is preferably 10% by weight or less, more preferably 8% by weight or less, and still more preferably 0.5% by weight or more. When the content of the radically polymerizable photoinitiator is less than the above range, the curing becomes insufficient, and if it is more than this range, the hardness may be lowered or the stain resistance may be lowered.

再者，作為自由基聚合性光起始劑，若自由基聚合性光起始劑成分中之20重量%以上使用2-甲基-[4-(甲硫基)苯基]-2-啉基-1-丙酮、2-苄基-2-二甲胺基-1-(4-啉基苯基)-丁烷-1-酮等α-胺基苯乙酮系起始劑，Ciba Specialty Chemicals公司製造之Irgacure OXE-01等肟酯系起始劑，1-羥基環己基苯基酮、米其勒酮等α-羥基酮系起始劑與二苯基酮系增感劑之混合物之1種或2種以上，則有進一步減輕由氧引起之阻聚，可見到表面硬化性、薄膜硬化性之進一步之提高而尤佳之情況。 In addition, as a radically polymerizable photoinitiator, 2-methyl-[4-(methylthio)phenyl]-2- is used as a 20% by weight or more of the radically polymerizable photoinitiator component. Lolinyl-1-propanone, 2-benzyl-2-dimethylamino-1-(4- α-Aminoacetophenone-based initiator such as phenylphenyl)-butan-1-one, oxime ester-based initiator such as Irgacure OXE-01 manufactured by Ciba Specialty Chemicals, 1-hydroxycyclohexylphenyl One or two or more kinds of a mixture of an α-hydroxyketone-based initiator such as a ketone or a ketone ketone and a diphenyl ketone-based sensitizer further reduce the inhibition by oxygen, and the surface hardenability is observed. Further improvement of the film hardenability is particularly preferable.

<1-7.其他任意成分> <1-7. Other optional ingredients>

為實現將組成物製成塗膜時之硬度等塗膜物性或組成物之黏度等液物性之調整，本發明之樹脂組成物中亦可進而含有選自本發明之聚 合體以外之具有自由基聚合性基之聚合體、以矽酸膠為主成分之無機氧化物微粒子上具有經由-O-Si-R-鍵(R表示碳數2~10之直鏈或支鏈之伸烷基)鍵結之(甲基)丙烯醯基的有機無機複合體、及無機微粒子中之1種或2種以上。 The resin composition of the present invention may further contain a polymer selected from the present invention in order to adjust the physical properties such as the hardness of the coating film or the viscosity of the composition when the composition is formed into a coating film. A polymer having a radical polymerizable group other than the complex, and an inorganic oxide fine particle containing a phthalic acid gel as a main component has a linear or branched chain via a -O-Si-R- bond (R represents a carbon number of 2 to 10) One or two or more kinds of the organic-inorganic composites of the (meth)acryloyl group bonded to the alkyl group and the inorganic fine particles.

該等之含量只要不脫離本發明之主旨，則並無特別限定，較佳為樹脂組成物整體之0.1~50重量%，進而較佳為1~30重量%。若該含量小於0.1重量%，則難以藉由該等進一步之成分之添加獲得所期望之效果(例如提高塗膜之硬度或抑制捲曲等)，又，若大於50重量%，則有耐污染性等塗膜物性降低之情況。 The content of the present invention is not particularly limited as long as it does not deviate from the gist of the present invention, and is preferably 0.1 to 50% by weight, and more preferably 1 to 30% by weight based on the entire resin composition. If the content is less than 0.1% by weight, it is difficult to obtain a desired effect by the addition of the further components (for example, to increase the hardness of the coating film or to suppress curling, etc.), and if it is more than 50% by weight, it is resistant to contamination. When the physical properties of the coating film are lowered.

此處，作為本發明之聚合體以外之聚合體，較佳地可舉出側鏈上具有丙烯醯基、甲基丙烯醯基之類之自由基聚合性基的本發明之聚合體以外之(甲基)丙烯酸酯系聚合體，及此種聚合體與苯乙烯等其他自由基聚合性單體之共聚合體。具體而言，較佳為對以丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯、3,4-環氧環己基丙烯酸酯、3,4-環氧環己基甲基丙烯酸酯、3,4-環氧環己基丙烯酸甲酯、3,4-環氧環己基甲基丙烯酸甲酯為主成分聚合而成之聚合體加成(甲基)丙烯酸而獲得的於側鏈上具有(甲基)丙烯醯基之聚合體。當然，並不排除該等以外者。該等可單獨使用1種，亦可混合2種以上而使用。 Here, the polymer other than the polymer of the present invention is preferably a polymer other than the polymer of the present invention having a radical polymerizable group such as an acrylonitrile group or a methacryl group in the side chain ( A methyl acrylate polymer, and a copolymer of such a polymer and another radical polymerizable monomer such as styrene. Specifically, it is preferably a glycidyl acrylate, a glycidyl methacrylate, a 3,4-epoxycyclohexyl acrylate, a 3,4-epoxycyclohexyl methacrylate, a 3,4-ring. Methyl oxycyclohexyl acrylate and 3,4-epoxycyclohexyl methacrylate as a main component polymerized by addition of (meth)acrylic acid, having (meth) propylene fluorene in a side chain Base polymer. Of course, it is not excluded. These may be used alone or in combination of two or more.

進而，為賦予各種功能性，本發明之樹脂組成物中除上述成分以外亦可調配其他成分。 Further, in order to impart various functionalities, the resin composition of the present invention may be blended with other components in addition to the above components.

例如，若調配紫外線吸收劑、受阻胺系光安定劑，則有耐候性進一步顯著提高而較佳之情況。作為紫外線吸收劑，可舉出苯并***系、二苯基酮系、水楊酸系、氰基丙烯酸酯系、三系紫外線吸收劑等作為較佳例。此外，為改良塗膜物性，亦可調配抗氧化劑(例如受阻酚系、 硫系、磷系抗氧化劑等)、抗結塊劑、助滑劑、均染劑等調配於該種耐污染性賦予劑中之各種添加劑。作為該等添加劑之調配量，相對於其他固形份，分別較佳為設為0.01重量%以上、2重量%以下。 For example, when a UV absorber or a hindered amine light stabilizer is blended, the weather resistance is further remarkably improved, which is preferable. Examples of the ultraviolet absorber include a benzotriazole-based, a diphenylketone-based, a salicylic acid-based, a cyanoacrylate-based, and a third. A UV absorber or the like is preferably used. In addition, in order to improve the physical properties of the coating film, an antioxidant (for example, a hindered phenol system, a sulfur-based or a phosphorus-based antioxidant), an anti-caking agent, a slip agent, a leveling agent, or the like may be formulated to impart such contamination resistance. Various additives in the agent. The amount of the additives to be added is preferably 0.01% by weight or more and 2% by weight or less based on the other solid content.

又，為進一步提高硬度或耐結塊性等，本發明之樹脂組成物中亦可直接調配未經處理之於上述有機無機複合體(C2)中所使用之無機氧化物微粒子。 Further, in order to further improve the hardness, the blocking resistance, and the like, the inorganic oxide fine particles used in the above-mentioned organic-inorganic composite (C2) may be directly formulated in the resin composition of the present invention.

又，亦可輔助性地含有矽系化合物等市售之消泡劑。 Further, a commercially available antifoaming agent such as a lanthanoid compound may be contained in an auxiliary manner.

<1-8.消泡性> <1-8. Defoaming property>

本發明之樹脂組成物具有優異之消泡性。因此，成為如下者：於用作塗佈塗料時，塗膜中不產生凹凸不均，由該塗膜獲得之硬化膜之均染性優異。 The resin composition of the present invention has excellent defoaming properties. Therefore, when used as a coating material, unevenness does not occur in the coating film, and the cured film obtained from the coating film is excellent in leveling property.

此處，消泡性優異係將使固形份(作為樹脂組成物之必需成分之聚合體及烴系單體)以固形份濃度為50重量%且固體成分中之該聚合體之比例成為5重量%之方式溶解於作為樹脂組成物之必需成分之飽和烴(溶解液整體之10重量%)及同為必需成分之溶劑中而成之溶液15mL添加至內徑1.5cm之30mL容量之有底圓筒形狀之容器中，於5秒內振盪20次並靜置，以目視測定直至所生成之溶液表面之氣泡消失為止之時間。較佳為溶液表面之氣泡於未滿15分鐘內消失，更佳為於未滿2分鐘內消失。 Here, the excellent defoaming property is such that the solid content (polymer and hydrocarbon monomer as an essential component of the resin composition) is 50% by weight in solid content and 5 parts by weight in the solid content. % of the solution is dissolved in a saturated hydrocarbon (10% by weight of the entire solution) which is an essential component of the resin composition, and a solution of 15 mL of a solvent which is an essential component is added to a bottomed circle of a volume of 30 mL having an inner diameter of 1.5 cm. In a cylindrical container, the mixture was shaken 20 times in 5 seconds and allowed to stand, and the time until the bubble on the surface of the generated solution disappeared was visually observed. Preferably, the bubbles on the surface of the solution disappear within less than 15 minutes, more preferably within less than 2 minutes.

<1-9.本發明發揮效果之理由> <1-9. Reasons for the effect of the present invention>

作為本發明發揮效果之理由，推測如下。通常，於SP值較高之溶劑中，如本發明之具有羥基與氟烷基之聚合體、即具有親水性與疏水性之基之聚合體以疏水性之基為外部進行排列，由此形成溶液之氣泡。因此，於本發明之第一樣態中，可推測如下：藉由使用SP值為特 定值以下之溶劑並添加飽和烴，而提高溶劑之疏水性，抑制聚合體形成氣泡，藉此消泡性變得良好；以及飽和烴使形成氣泡之具有親水性與疏水性之基之聚合體於溶液中分子排列崩解，藉此成為消泡之起點，從而發揮出本發明之效果。又，同樣地於本發明之第二樣態中，可推測如下：藉由使用SP值為特定值以下之溶劑並添加表面張力降低能力為一定程度以上之添加劑，而提高溶劑之疏水性，抑制聚合體形成氣泡，藉此消泡性變得良好；以及含氟基之寡聚物使形成氣泡之具有親水性與疏水性之基之聚合體於溶液中分子排列崩解，藉此成為消泡之起點，從而發揮出本發明之效果。 The reason why the present invention exerts an effect is presumed as follows. In general, in a solvent having a high SP value, a polymer having a hydroxyl group and a fluoroalkyl group, that is, a polymer having a hydrophilicity and a hydrophobicity, is arranged externally with a hydrophobic group, thereby forming Bubbles in solution. Therefore, in the first aspect of the present invention, it can be presumed as follows: by using the SP value The solvent below the constant value and the addition of a saturated hydrocarbon increase the hydrophobicity of the solvent, inhibit the formation of bubbles in the polymer, whereby the defoaming property becomes good; and the polymer of the hydrophilic and hydrophobic group which forms a bubble by the saturated hydrocarbon The molecular arrangement in the solution disintegrates, thereby becoming the starting point of defoaming, thereby exerting the effects of the present invention. Further, in the second aspect of the present invention, it is presumed that the hydrophobicity of the solvent is suppressed by using an additive having a SP value of a specific value or less and an additive having a surface tension reducing ability of a certain degree or more. The polymer forms bubbles, whereby the defoaming property becomes good; and the fluorine-containing oligomer causes the polymer having a hydrophilic and hydrophobic group forming a bubble to disintegrate in a molecular arrangement in the solution, thereby becoming a defoaming The starting point is to exert the effects of the present invention.

<2.硬化物> <2. Hardened matter>

藉由使本發明之樹脂組成物硬化，可獲得下述顯示優異物性之硬化膜。 By curing the resin composition of the present invention, the following cured film exhibiting excellent physical properties can be obtained.

塗佈本發明之樹脂組成物之後，藉由溶劑乾燥形成塗膜之後，照射活性能量射線，藉此可使組成物中之聚合性成分聚合而獲得硬化膜。作為塗佈方法，可舉出旋轉塗佈、浸漬塗佈、淋塗(flow coat)、噴塗、棒式塗佈、凹板塗佈、輥塗、刀塗佈、氣刀塗佈等作為較佳例。進行塗佈、乾燥、聚合、硬化所得之覆膜之厚度並無特別限定，例如可為5μm以上，亦可為2μm以下。即，本發明之樹脂組成物就薄膜化/厚膜化兩者均可之方面而言極有意義。硬化膜之厚度尤佳為0.01μm以上、50μm以下，於重視硬度之情形時，尤佳為2μm以上、20μm以下，相對而言於不重視硬度之情形時，尤佳為0.04μm以上、2μm以下。 After the resin composition of the present invention is applied, the coating film is formed by drying with a solvent, and then the active energy ray is irradiated, whereby the polymerizable component in the composition is polymerized to obtain a cured film. Examples of the coating method include spin coating, dip coating, flow coating, spray coating, bar coating, gravure coating, roll coating, knife coating, air knife coating, and the like. example. The thickness of the coating film obtained by coating, drying, polymerizing, and hardening is not particularly limited, and may be, for example, 5 μm or more, or 2 μm or less. That is, the resin composition of the present invention is extremely significant in terms of both thin film formation and thick film formation. The thickness of the cured film is preferably 0.01 μm or more and 50 μm or less. When the hardness is important, it is preferably 2 μm or more and 20 μm or less. When the hardness is not important, it is preferably 0.04 μm or more and 2 μm or less. .

作為活性能量射線照射，可使用自氙氣燈、低壓水銀燈、高壓水銀燈、超高壓水銀燈、金屬鹵化物燈、碳弧燈、鎢絲燈等 光源發出之紫外線或通常自20~2000kV之粒子加速器掠出之電子束、α射線、β射線、γ射線等活性能量射線，將該等活性能量射線照射至塗膜，使之硬化而形成硬化膜。 As the active energy ray irradiation, a xenon lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a tungsten lamp, or the like can be used. An ultraviolet ray emitted from a light source or an active energy ray such as an electron beam, an alpha ray, a beta ray, or a gamma ray which is usually picked up by a particle accelerator of 20 to 2000 kV, and the active energy ray is irradiated onto the coating film to be hardened to form a cured film. .

以此種利用活性能量射線之照射所形成之硬化膜的生產性、物性之平衡性優異，故而尤佳。 It is particularly preferable that the cured film formed by the irradiation with the active energy ray has excellent balance between productivity and physical properties.

本發明之硬化物為對上述本發明之樹脂組成物照射活性能量射線，使組成物中之聚合性成分聚合而成者，尤佳為滿足以下較佳之物性。又，包含本發明之樹脂組成物之塗膜之硬化不限於紫外線，亦可使用電子束、α射線、β射線、γ射線等活性能量射線，作為本發明中之「照射活性能量射線進行聚合」，可舉出光自由基聚合或光陽離子聚合作為較佳例。再者，以下，紫外線照射均於通常氧濃度環境下進行。 In the cured product of the present invention, the resin composition of the present invention is irradiated with an active energy ray to polymerize the polymerizable component in the composition, and it is particularly preferable to satisfy the following preferable physical properties. Further, the curing of the coating film containing the resin composition of the present invention is not limited to ultraviolet rays, and an active energy ray such as an electron beam, an α-ray, a β-ray or a γ-ray may be used as the "polymerization of an active energy ray for irradiation" in the present invention. A photoradical polymerization or photocationic polymerization is exemplified as a preferred example. Further, in the following, ultraviolet irradiation is performed in a normal oxygen concentration environment.

<2-1.硬化物之性質> <2-1. Properties of hardened material>

使本發明之樹脂組成物硬化而獲得之硬化物具有以下物性。 The cured product obtained by hardening the resin composition of the present invention has the following physical properties.

<2-1-1.硬度> <2-1-1. Hardness>

本發明之硬化物顯示較高之硬度。此處，所謂硬度較高，係指於鉛筆硬度JIS K-5400之規格之條件下為HB以上之硬度。再者，鉛筆硬度自柔軟者起依序規定為6B、5B、…、B、HB、F、H、2H、3H、…、9H。 The cured product of the present invention exhibits a higher hardness. Here, the term "hardness" means a hardness of HB or more under the conditions of the pencil hardness JIS K-5400. Further, the pencil hardness is defined as 6B, 5B, ..., B, HB, F, H, 2H, 3H, ..., 9H in order from the softer.

藉由將本發明之樹脂組成物塗佈於188μm厚之易接著PET基材上，對所獲得之塗膜使用輸出密度120W/cm之高壓水銀燈，以成為500mJ/cm2之累積光量之方式照射波長254nm之紫外線而形成的膜厚5μm之硬化膜之鉛筆硬度較佳為B以上，尤佳為HB以上。 By coating the resin composition of the present invention on a 188 μm thick easy-to-extend PET substrate, a high-pressure mercury lamp having an output density of 120 W/cm was used for the obtained coating film, and irradiation was performed in a cumulative light amount of 500 mJ/cm 2 . The pencil hardness of the cured film having a film thickness of 5 μm formed by ultraviolet rays having a wavelength of 254 nm is preferably B or more, and more preferably HB or more.

尤其於本發明之樹脂組成物含有二新戊四醇六丙烯酸 酯之情形時，藉由將其塗佈於188μm厚之易接著PET基材上，對所獲得之塗膜使用輸出密度120W/cm之高壓水銀燈，以成為500mJ/cm2之累積光量之方式照射波長254nm之紫外線而形成的膜厚5μm之硬化膜之鉛筆硬度較佳為3H以上。 In particular, when the resin composition of the present invention contains dipentaerythritol hexaacrylate, an output density of 120 W/cm is used for the obtained coating film by coating it on a 188 μm thick easy-to-extend PET substrate. In the high-pressure mercury lamp, the pencil hardness of the cured film having a thickness of 5 μm formed by irradiating ultraviolet rays having a wavelength of 254 nm to a cumulative light amount of 500 mJ/cm 2 is preferably 3H or more.

其中，該鉛筆硬度之評價中所使用之組成物係僅使用1-羥基環己基苯基酮作為自由基聚合性光起始劑，且相對於1-羥基環己基苯基酮以外之固形份100重量份而調配1-羥基環己基苯基酮2.5重量份者。 Among them, the composition used in the evaluation of the pencil hardness was only 1-hydroxycyclohexyl phenyl ketone as a radical polymerizable photoinitiator, and a solid content 100 other than 1-hydroxycyclohexyl phenyl ketone. 2 parts by weight of 1-hydroxycyclohexyl phenyl ketone was blended in parts by weight.

<2-1-2.撥水撥油性> <2-1-2. Water and oil repellency>

本發明之硬化物顯示優異之撥水撥油性。 The cured product of the present invention exhibits excellent water repellency.

此處，撥水撥油性優異可藉由如下方式進行評價：藉由將本發明之樹脂組成物塗佈於188μm厚之易接著PET基材上，對所獲得之塗膜使用輸出密度120W/cm之高壓水銀燈，以成為500mJ/cm2之累積光量之方式照射波長254nm之紫外線而形成的膜厚5μm之硬化膜之表面相對於水之接觸角為100度以上、120度以下，尤其是102度以上、115度以下，相對於十六烷之接觸角為50度以上、90度以下，尤其是52度以上、75度以下。再者，該接觸角之測定方法於下述之實施例中說明詳情。 Here, the excellent water repellency can be evaluated by applying the resin composition of the present invention to a 188 μm thick easy-to-extend PET substrate, and using an output density of 120 W/cm for the obtained coating film. In the high-pressure mercury lamp, the contact angle of the surface of the cured film having a thickness of 5 μm formed by irradiating ultraviolet rays having a wavelength of 254 nm to a cumulative light amount of 500 mJ/cm 2 with respect to water is 100 degrees or more and 120 degrees or less, especially 102 degrees. Above 115 degrees, the contact angle with respect to hexadecane is 50 degrees or more and 90 degrees or less, especially 52 degrees or more and 75 degrees or less. Further, the method of measuring the contact angle is described in the following examples.

<2-1-3.耐污染性及其耐久性> <2-1-3. Pollution resistance and durability>

本發明之硬化物之耐污染性優異，進而該性質之耐久性優異。尤其對油脂性污垢顯示優異之防污性。 The cured product of the present invention is excellent in stain resistance and further excellent in durability of this property. In particular, it exhibits excellent antifouling properties against greasy dirt.

耐污染性優異可藉由如下耐指紋性極高者進行評價：於使黑色標記油墨(black magic)附著於本發明之樹脂組成物之硬化物或硬化膜之表面，在負重200g下利用衛生紙(tissue paper)進行拭除之情形時，利用往返3次以內之拭除操作、更佳為往返2次以內之操作，可將指紋 完全去除。 The excellent stain resistance can be evaluated by adhering the black fingerprint to the surface of the cured product or the cured film of the resin composition of the present invention, and using toilet paper under a load of 200 g ( Tissue paper) In the case of erasing, the fingerprint can be used by using an erase operation within 3 times or more, preferably within 2 times of round-trip operation. Completely removed.

又，耐污染性之耐久性優異可藉由附著黑色標記油墨，於負重200g下利用衛生紙往返3次進行擦拭即便重複5次如下之拭除操作，指紋去除性亦未降低而進行評價，其為本發明之硬化物之更大之特徵。 Moreover, the durability of the stain-resistant property is excellent by the adhesion of the black mark ink, and it is wiped back and forth three times by using the toilet paper under a load of 200 g. Even if the following wiping operation is repeated five times, the fingerprint removal property is not lowered and evaluated. A larger feature of the cured product of the present invention.

即便使用可以較少之拭除次數拭除之耐污染性賦予劑，對於先前者而言，由於硬度不足或未固定於膜表面，故而若重複附著、拭除操作，則亦於數次~數十次時表面產生細微傷痕，其間隙中進入指紋(或人工指紋液)，或者耐污染性賦予劑本身自表面消失，指紋去除性之耐久性較差。另一方面，本發明之樹脂組成物由於硬化後之硬度較高且固定於膜表面，故而具有如下特徵，即，具備即便重複5次以上、較佳為10次以上之操作，黑色標記油墨之拭除性亦不會降低的極高之拭除性能耐久性。 Even if the antifouling agent is removed by a small number of erasing times, the former is insufficient or not fixed to the surface of the film, so if the adhesion and erasing operations are repeated, it is also several times to several times. Ten times, the surface is slightly scratched, and the fingerprint (or artificial fingerprint liquid) enters the gap, or the stain-resistant agent itself disappears from the surface, and the durability of fingerprint removal is poor. On the other hand, since the resin composition of the present invention has high hardness after curing and is fixed to the surface of the film, it is characterized in that it has an operation of repeating five or more times, preferably 10 times or more, of black marking ink. Abrasiveness does not reduce the extremely high erase performance durability.

<3.包含硬化膜之成形品> <3. A molded article containing a cured film>

如上所述，對本發明之樹脂組成物照射活性能量射線使組成物中之聚合性成分聚合而成之硬化物的耐污染性、硬度等特性優異。 As described above, the cured resin composition obtained by polymerizing the resin composition of the present invention with an active energy ray to polymerize the polymerizable component in the composition is excellent in properties such as stain resistance and hardness.

因此，表面包含對本發明之樹脂組成物照射活性能量射線而獲得之硬化膜的物品之耐污染性、硬度等特性優異。 Therefore, the article containing the cured film obtained by irradiating the resin composition of the present invention with an active energy ray is excellent in properties such as stain resistance and hardness.

該硬化膜可於物品本體之表面塗佈本發明之樹脂組成物後，照射活性能量射線使之聚合而形成，亦可另外製作照射活性能量射線使之聚合而形成之硬化膜後將其積層於物品而形成。 The cured film may be formed by applying a resin composition of the present invention to the surface of the article body, irradiating with an active energy ray to polymerize it, or separately forming a cured film formed by polymerizing an active energy ray to polymerize it, and then laminating it. Formed by objects.

以下，對具備本發明之硬化物、尤其是硬化膜之物品進行說明。 Hereinafter, an article comprising the cured product of the present invention, particularly a cured film, will be described.

本發明之硬化膜可應用於各種物品，例如可應用於光記錄媒體、 光學顯示器、農業用塑膠溫室之透明薄膜(由於需要有效吸收太陽光，故而需要耐污染功能)、太陽電池之表面保護透明薄膜(為防止電池效率降低而需要耐污染功能)、逆向反射標識表面保護用透明薄膜(為於前照燈光或外部光相對較暗之亮度下亦能容易地觀察到標識之文字而需要透明性與耐污染功能)、光學透鏡、光學稜鏡、稜鏡片(prism sheet)、汽車之窗戶材料、建造物之窗戶材料、眼鏡片(spectacle lens)等。尤佳為應用於要求較高之透明性之光學物品。 The cured film of the present invention can be applied to various articles, for example, to optical recording media, Optical display, transparent film for agricultural plastic greenhouse (requires pollution resistance due to effective absorption of sunlight), surface protection transparent film for solar cells (requires pollution resistance to prevent battery efficiency reduction), retroreflective marking surface protection Transparent film (transparent and stain resistant functions are required for easy viewing of the logo text in the light of the relatively dark light of the front or external light), optical lens, optical cymbal, prism sheet , window materials for automobiles, window materials for construction materials, spectacle lenses, etc. It is especially preferred for optical articles that require higher transparency.

本發明之樹脂組成物可較佳地用以塗佈於各種基材上並進行乾燥、硬化而形成硬塗層。於此情形時，基材之種類並無特別限定，但就高接著性等而言，較佳為由樹脂組成之基材。樹脂基材可為板狀、片狀、薄膜狀之任一種，亦可為任意形狀之成形品。又，基材可為積層體之一部分，亦可於基材與硬化膜之間介隔其他層。 The resin composition of the present invention can be preferably applied to various substrates and dried and hardened to form a hard coat layer. In this case, the type of the substrate is not particularly limited, but a substrate composed of a resin is preferable in terms of high adhesion and the like. The resin substrate may be in the form of a plate, a sheet, or a film, and may be a molded article of any shape. Further, the substrate may be a part of the laminate, and another layer may be interposed between the substrate and the cured film.

樹脂基材可為熱塑性樹脂，亦可為藉由熱或活性能量射線而硬化之硬化樹脂。 The resin substrate may be a thermoplastic resin or a hardened resin which is hardened by heat or active energy rays.

作為熱塑性樹脂，例如可舉出：聚對苯二甲酸乙二酯(PET)或聚2,6萘二甲酸乙二酯等聚酯，聚甲基丙烯酸甲酯(PMMA)、含甲基丙烯酸甲酯(MMA)之共聚合體(甲基丙烯酸甲酯-苯乙烯共聚合樹脂(MS樹脂))、聚碳酸酯(PC)、三乙酸纖維素、丙烯腈-丁二烯-苯乙烯共聚合體(ABS樹脂)、改質聚烯烴樹脂、氟樹脂(例如聚偏二氟乙烯樹脂(PVDF)、聚氟乙烯樹脂(PVF)等)、氫化聚苯乙烯樹脂、環烯烴系樹脂(例如JSR製造之ARTON，日本ZEON製造之ZEONEX、ZEONOR，三井化學製造之APEL)等。 Examples of the thermoplastic resin include polyesters such as polyethylene terephthalate (PET) or polyethylene-2,6-naphthalate, polymethyl methacrylate (PMMA), and methacrylic acid-containing Copolymer (MMA) copolymer (methyl methacrylate-styrene copolymer resin (MS resin)), polycarbonate (PC), cellulose triacetate, acrylonitrile-butadiene-styrene copolymer (ABS) Resin), modified polyolefin resin, fluororesin (for example, polyvinylidene fluoride resin (PVDF), polyvinyl fluoride resin (PVF), etc.), hydrogenated polystyrene resin, cycloolefin resin (for example, ARTON manufactured by JSR) ZEONEX, ZEONOR manufactured by ZEON, Japan, APEL manufactured by Mitsui Chemicals, etc.

作為硬化樹脂，例如可舉出：環氧樹脂、胺基甲酸乙酯樹脂、熱硬化性或光硬化性之丙烯酸系樹脂之硬化物、熱硬化性或光 硬化性之有機無機混成樹脂等之硬化物等。 Examples of the cured resin include an epoxy resin, a urethane resin, a cured product of a thermosetting or photocurable acrylic resin, and thermosetting or light. A cured product such as a curable organic-inorganic hybrid resin.

該等基材例如其本身可為塗佈形成之膜，亦可為利用各種成形法形成之成形品。 These base materials may be, for example, a film formed by coating, or may be a molded article formed by various molding methods.

本發明之硬化膜由於透明性優異，耐污染性、硬度優異，故而若應用於要求較高之透明性之光學物品，則非常有用。此時，於基材亦必需為透明之情形時，基材較理想為利用塗佈法、熔融擠出成形法、溶劑澆鑄法之任一者形成而成。又，於基材含有可利用活性能量射線或熱而硬化之官能基之情形時，有藉由活性能量射線照射或加熱而硬化之更佳之情況。又，為提高基材之硬度或減少硬化收縮，較佳為含有無機氧化物微粒子及/或胺基甲酸酯丙烯酸酯。再者，所謂透明，通常係指目標波長之光之穿透率為80%以上。 Since the cured film of the present invention is excellent in transparency and excellent in stain resistance and hardness, it is very useful when applied to an optical article requiring high transparency. In this case, when the substrate is required to be transparent, the substrate is preferably formed by any one of a coating method, a melt extrusion molding method, and a solvent casting method. Further, in the case where the substrate contains a functional group which can be cured by active energy rays or heat, it is more preferably cured by irradiation with active energy rays or heating. Further, in order to increase the hardness of the substrate or to reduce the hardening shrinkage, it is preferred to contain inorganic oxide fine particles and/or urethane acrylate. Further, the term "transparent" generally means that the transmittance of light of a target wavelength is 80% or more.

又，本發明之硬化膜可較佳地用作光記錄媒體之耐污染性硬塗層。 Further, the cured film of the present invention can be preferably used as a stain-resistant hard coat layer of an optical recording medium.

本發明之樹脂組成物亦可較佳地用於光學顯示器用途。尤其是作為應用於平面顯示器(液晶顯示器、電漿顯示器、背投影顯示器、前投影儀用螢幕、無機電致發光(EL，Electroluminescence)顯示器、有機EL顯示器等)之顯示面板表面之耐污染性賦予劑而較佳，其中，可較佳地用作汽車導航系統、行動電話、移動終端裝置(個人數位助理(PDA，Personal Digital Assistant)等)、個人電腦屏幕(Personal Computer Monitor，PC屏幕)等中具有觸控面板輸入功能之顯示器、或於家庭中廣為利用之平面TV(尤其是液晶電視)之表面之硬塗層。 The resin composition of the present invention can also be preferably used for optical display applications. In particular, it is imparted to the surface of a display panel for use in a flat panel display (liquid crystal display, plasma display, rear projection display, front projector screen, inorganic electroluminescence (EL) display, organic EL display, etc.). Preferably, it is preferably used as a car navigation system, a mobile phone, a mobile terminal device (PDA, Personal Digital Assistant, etc.), a personal computer monitor (PC screen), or the like. A hard-coated surface having a touch panel input function or a surface of a flat TV (especially a liquid crystal television) widely used in the home.

於將本發明之樹脂組成物應用於此種光記錄媒體或顯示器中所使用之積層體之情形時，較佳為使用透明樹脂基材，於積層體之至少一側之最表面形成對本發明之樹脂組成物照射活性能量射線 使之聚合而成之硬化膜。 When the resin composition of the present invention is applied to a laminate used in such an optical recording medium or display, it is preferred to use a transparent resin substrate to form the outermost surface of at least one side of the laminate. Resin composition irradiates active energy ray A cured film obtained by polymerization.

對本發明之樹脂組成物照射活性能量射線使之聚合而成之硬化物的耐污染性、硬度等特性優異。 The cured product obtained by irradiating the resin composition of the present invention with an active energy ray is excellent in properties such as stain resistance and hardness.

表面包含對本發明之樹脂組成物照射活性能量射線使之聚合而成之膜的物品之耐污染性、硬度等特性優異。可於物品之表面塗佈組成物之後照射活性能量射線使之聚合，亦可將照射活性能量射線使之聚合而成之膜積層於物品。 The article containing the film obtained by irradiating the resin composition of the present invention with an active energy ray to be polymerized is excellent in properties such as stain resistance and hardness. The composition may be coated on the surface of the article, and then irradiated with an active energy ray to polymerize it, or a film obtained by polymerizing the active energy ray may be laminated on the article.

[實施例] [Examples]

以下，藉由實施例更詳細地說明本發明，但本發明只要不超出其主旨，則並不限定於以下實施例。 Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the following examples as long as the present invention is not exceeded.

以下，舉出實施例更具體地說明本發明。以下實施例中所示之材料、使用量、比例、處理內容、處理順序等只要不脫離本發明之主旨，則可適當變更。因此，本發明之範圍並不限定於以下所示之具體例。 Hereinafter, the present invention will be more specifically described by way of examples. The materials, the amounts used, the ratios, the contents of the treatment, the order of the treatment, and the like, which are shown in the following examples, can be appropriately changed without departing from the gist of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

再者，例中之「份」及「%」分別表示「重量份」及「重量%」。 In addition, the "parts" and "%" in the examples represent "parts by weight" and "% by weight", respectively.

<合成例1：聚合體(A-01)之合成> <Synthesis Example 1: Synthesis of Polymer (A-01)>

添加全氟己基甲基丙烯酸乙酯55g、甲基丙烯酸月桂酯11g、甲基丙烯酸環氧丙酯34g、十二硫醇0.9g(M(a1)/M(a3)=1.78)、1-甲氧基-2-丙醇200g，使內溫於氮氣氣流下升溫至約60℃。其後，分2次添加合計1.2g之2,2'-偶氮雙(2,4-二甲基戊腈)(V65)，於65℃下持續攪拌6小時。其後，將內溫上升至80℃，使V65完全失活之後，恢復至室溫。固形份濃度為約34%。 Adding 55 g of perfluorohexyl methacrylate, 11 g of lauryl methacrylate, 34 g of glycidyl methacrylate, 0.9 g of dodecyl mercaptan (M(a1)/M(a3)=1.78), 1-A 200 g of oxy-2-propanol was allowed to warm to an internal temperature of about 60 ° C under a nitrogen gas stream. Thereafter, a total of 1.2 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (V65) was added in two portions, and stirring was continued at 65 ° C for 6 hours. Thereafter, the internal temperature was raised to 80 ° C, and after V65 was completely deactivated, it was returned to room temperature. The solids concentration was about 34%.

其次，於7%氧氣環境下加熱至90℃之後，添加對甲氧苯酚0.5g、三苯基膦4.6g。5分鐘後，將季戊四醇三(甲基)丙烯酸酯127.2g溶解於1-甲氧基丙基-2-乙酸酯54.5g中，歷時30分鐘滴加。 其間使液溫保持於90~105℃。其後，使液溫上升至110℃，於該溫度下維持12小時之後，恢復至室溫。固形份為35%(A-01)。 Next, after heating to 90 ° C in an 7% oxygen atmosphere, 0.5 g of p-methoxyphenol and 4.6 g of triphenylphosphine were added. After 5 minutes, 127.2 g of pentaerythritol tri(meth)acrylate was dissolved in 54.5 g of 1-methoxypropyl-2-acetate, and added dropwise over 30 minutes. The liquid temperature is maintained at 90 to 105 ° C during this period. Thereafter, the liquid temperature was raised to 110 ° C, and after maintaining at this temperature for 12 hours, it was returned to room temperature. The solid content is 35% (A-01).

再者，由添加之重量算出之氟原子之含量為12.3重量%，羥基之含量為1.6重量%。 Further, the content of the fluorine atom calculated from the added weight was 12.3% by weight, and the content of the hydroxyl group was 1.6% by weight.

<合成例2：聚合體(A-02)之合成> <Synthesis Example 2: Synthesis of Polymer (A-02)>

添加全氟己基甲基丙烯酸乙酯50g、甲基丙烯酸月桂酯10g、α,ω-二巰基丙基聚二甲基矽氧烷(數量平均分子量1600)10g、甲基丙烯酸環氧丙酯30g、十二硫醇0.9g、1-甲氧基-2-丙醇200g，使內溫於氮氣氣流下升溫至約60℃。其後，分2次添加合計1.2g之2,2'-偶氮雙(2,4-二甲基戊腈)(V65)，於65℃下持續攪拌6小時。其後，將內溫上升至80℃，使V65完全失活之後，恢復至室溫。固形份濃度為約34%。 50 g of perfluorohexyl methacrylate, 10 g of lauryl methacrylate, 10 g of α,ω-dimercaptopropyl polydimethyl decane (number average molecular weight 1600), 30 g of glycidyl methacrylate, 30 g, 0.9 g of dodecanol and 200 g of 1-methoxy-2-propanol were allowed to raise the internal temperature to about 60 ° C under a nitrogen gas stream. Thereafter, a total of 1.2 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (V65) was added in two portions, and stirring was continued at 65 ° C for 6 hours. Thereafter, the internal temperature was raised to 80 ° C, and after V65 was completely deactivated, it was returned to room temperature. The solids concentration was about 34%.

其次，於7%氧氣環境下加熱至90℃之後，添加對甲氧苯酚0.5g、三苯基膦4.6g。5分鐘後，將丙烯酸15.5g溶解於1-甲氧基丙基-2-乙酸酯54.5g中，歷時30分鐘滴加。其間使液溫保持於90~105℃。其後，使液溫上升至110℃，於該溫度下維持12小時之後，恢復至室溫。固形份為30%(A-02)。 Next, after heating to 90 ° C in an 7% oxygen atmosphere, 0.5 g of p-methoxyphenol and 4.6 g of triphenylphosphine were added. After 5 minutes, 15.5 g of acrylic acid was dissolved in 54.5 g of 1-methoxypropyl-2-acetate, and the mixture was added dropwise over 30 minutes. The liquid temperature is maintained at 90 to 105 ° C during this period. Thereafter, the liquid temperature was raised to 110 ° C, and after maintaining at this temperature for 12 hours, it was returned to room temperature. The solid content is 30% (A-02).

<合成例3：聚合體(A-03)之合成> <Synthesis Example 3: Synthesis of Polymer (A-03)>

添加全氟己基甲基丙烯酸乙酯50g、甲基丙烯酸月桂酯10g、α,ω-二巰基丙基聚二甲基矽氧烷(數量平均分子量1600)10g、甲基丙烯酸環氧丙酯30g、十二硫醇0.9g、1-甲氧基-2-丙醇200g，使內溫於氮氣氣流下升溫至約60℃。其後，分2次添加合計1.2g之2,2'-偶氮雙(2,4-二甲基戊腈)(V65)，於65℃下持續攪拌6小時。其後，將內溫上升至80℃，使V65完全失活之後，恢復至室溫。固形份濃度為約34%。 50 g of perfluorohexyl methacrylate, 10 g of lauryl methacrylate, 10 g of α,ω-dimercaptopropyl polydimethyl decane (number average molecular weight 1600), 30 g of glycidyl methacrylate, 30 g, 0.9 g of dodecanol and 200 g of 1-methoxy-2-propanol were allowed to raise the internal temperature to about 60 ° C under a nitrogen gas stream. Thereafter, a total of 1.2 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (V65) was added in two portions, and stirring was continued at 65 ° C for 6 hours. Thereafter, the internal temperature was raised to 80 ° C, and after V65 was completely deactivated, it was returned to room temperature. The solids concentration was about 34%.

其次，於7%氧氣環境下加熱至90℃之後，添加對甲氧 苯酚0.5g、三苯基膦4.6g。5分鐘後，將季戊四醇三(甲基)丙烯酸酯127.2g溶解於1-甲氧基丙基-2-乙酸酯54.5g中，歷時30分鐘滴加。其間使液溫保持於90~105℃。其後，使液溫上升至110℃，於該溫度下維持12小時之後，恢復至室溫。固形份為35%(A-03)。 Secondly, after heating to 90 ° C in 7% oxygen atmosphere, add methoxy 0.5 g of phenol and 4.6 g of triphenylphosphine. After 5 minutes, 127.2 g of pentaerythritol tri(meth)acrylate was dissolved in 54.5 g of 1-methoxypropyl-2-acetate, and added dropwise over 30 minutes. The liquid temperature is maintained at 90 to 105 ° C during this period. Thereafter, the liquid temperature was raised to 110 ° C, and after maintaining at this temperature for 12 hours, it was returned to room temperature. The solid content is 35% (A-03).

再者，由添加之重量算出之氟原子之含量為12.1重量%，羥基之含量為1.5重量%。 Further, the content of the fluorine atom calculated from the added weight was 12.1% by weight, and the content of the hydroxyl group was 1.5% by weight.

<合成例4：聚合體(A-04)之合成> <Synthesis Example 4: Synthesis of Polymer (A-04)>

添加全氟己基甲基丙烯酸乙酯50g、甲基丙烯酸月桂酯10g、含聚二甲基矽氧烷之甲基丙烯酸酯(數量平均分子量1000，Chisso公司，FMO711)10g、甲基丙烯酸環氧丙酯30g、十二硫醇0.9g、1-甲氧基-2-丙醇200g，使內溫於氮氣氣流下升溫至約60℃。其後，分2次添加合計1.2g之2,2'-偶氮雙(2,4-二甲基戊腈)(V65)，於65℃下持續攪拌6小時。其後，將內溫上升至80℃，使V65完全失活之後，恢復至室溫。固形份濃度為約34%。 Adding 50 g of perfluorohexyl methacrylate, 10 g of lauryl methacrylate, methacrylate containing polydimethyl siloxane (quantitative molecular weight 1000, Chisso, FMO711) 10 g, propylene glycol methacrylate 30 g of ester, 0.9 g of dodecyl mercaptan, and 200 g of 1-methoxy-2-propanol were allowed to raise the internal temperature to about 60 ° C under a nitrogen gas stream. Thereafter, a total of 1.2 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (V65) was added in two portions, and stirring was continued at 65 ° C for 6 hours. Thereafter, the internal temperature was raised to 80 ° C, and after V65 was completely deactivated, it was returned to room temperature. The solids concentration was about 34%.

其次，於7%氧氣環境下加熱至90℃之後，添加對甲氧苯酚0.5g、三苯基膦4.6g。5分鐘後，將季戊四醇三(甲基)丙烯酸酯127.2g溶解於1-甲氧基丙基-2-乙酸酯54.5g中，歷時30分鐘滴加。其間使液溫保持於90~105℃。其後，使液溫上升至110℃，於該溫度下維持12小時之後，恢復至室溫。固形份為35%(A-04)。 Next, after heating to 90 ° C in an 7% oxygen atmosphere, 0.5 g of p-methoxyphenol and 4.6 g of triphenylphosphine were added. After 5 minutes, 127.2 g of pentaerythritol tri(meth)acrylate was dissolved in 54.5 g of 1-methoxypropyl-2-acetate, and added dropwise over 30 minutes. The liquid temperature is maintained at 90 to 105 ° C during this period. Thereafter, the liquid temperature was raised to 110 ° C, and after maintaining at this temperature for 12 hours, it was returned to room temperature. The solid content was 35% (A-04).

再者，由添加之重量算出之氟原子之含量為12.1重量%，羥基之含量為1.5重量%。 Further, the content of the fluorine atom calculated from the added weight was 12.1% by weight, and the content of the hydroxyl group was 1.5% by weight.

<參考合成例1：聚合體(X-01)之合成> <Reference Synthesis Example 1: Synthesis of Polymer (X-01)>

添加甲基丙烯酸甲酯2g、甲基丙烯酸環氧丙酯98g、巰基丙基三甲氧基矽烷3.3g、1-甲氧基-2-丙醇200g，使內溫於氮氣氣流下升溫 至約60℃。其後，分2次添加合計1.5g之2,2'-偶氮雙(2,4-二甲基戊腈)(V65)，於65℃下持續攪拌6小時。其後，將內溫上升至80℃，使V65完全失活之後，恢復至室溫。固形份濃度為約34%。 2 g of methyl methacrylate, 98 g of glycidyl methacrylate, 3.3 g of mercaptopropyltrimethoxydecane, and 200 g of 1-methoxy-2-propanol were added to raise the internal temperature under a nitrogen gas stream. Up to about 60 ° C. Thereafter, a total of 1.5 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (V65) was added in two portions, and stirring was continued at 65 ° C for 6 hours. Thereafter, the internal temperature was raised to 80 ° C, and after V65 was completely deactivated, it was returned to room temperature. The solids concentration was about 34%.

其次，於空氣環境下加熱至90℃之後，添加對甲氧苯酚0.1g、三苯基膦0.5g。5分鐘後，將丙烯酸50.6g溶解於1-甲氧基-2-丙醇19g中，歷時30分鐘滴加。其間使液溫保持於90~105℃。其後，使液溫上升至110℃，於該溫度下維持12小時之後，恢復至室溫。固形份為35%(X-01)。 Next, after heating to 90 ° C in an air atmosphere, 0.1 g of p-methoxyphenol and 0.5 g of triphenylphosphine were added. After 5 minutes, 50.6 g of acrylic acid was dissolved in 19 g of 1-methoxy-2-propanol, and the mixture was added dropwise over 30 minutes. The liquid temperature is maintained at 90 to 105 ° C during this period. Thereafter, the liquid temperature was raised to 110 ° C, and after maintaining at this temperature for 12 hours, it was returned to room temperature. The solid content is 35% (X-01).

<參考合成例2：聚合體(X-02)之合成> <Reference Synthesis Example 2: Synthesis of Polymer (X-02)>

添加全氟己基甲基丙烯酸乙酯22g、甲基丙烯酸月桂酯10g、甲基丙烯酸甲酯68g、十二硫醇0.9g、1-甲氧基-2-丙醇200g，使內溫於氮氣氣流下升溫至約60℃。其後，分2次添加合計1.2g之2,2'-偶氮雙(2,4-二甲基戊腈)(V65)，於65℃下持續攪拌6小時。其後，將內溫上升至80℃，使V65完全失活之後，恢復至室溫。固形份濃度為約34%(X-02)。 22 g of perfluorohexyl methacrylate, 10 g of lauryl methacrylate, 68 g of methyl methacrylate, 0.9 g of dodecyl mercaptan, and 200 g of 1-methoxy-2-propanol were added to make the internal temperature in a nitrogen gas stream. The temperature was raised to about 60 °C. Thereafter, a total of 1.2 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (V65) was added in two portions, and stirring was continued at 65 ° C for 6 hours. Thereafter, the internal temperature was raised to 80 ° C, and after V65 was completely deactivated, it was returned to room temperature. The solids concentration was about 34% (X-02).

[實施例1-1~1-11] [Examples 1-1 to 1-11]

<樹脂組成物之調製及評價> <Modulation and evaluation of resin composition>

按照表1中所示之調配(重量比)調製實施例1-1~1-11及比較例1~9之樹脂組成物。 The resin compositions of Examples 1-1 to 1-11 and Comparative Examples 1 to 9 were prepared in accordance with the formulation (weight ratio) shown in Table 1.

對如上所述般調製之實施例1-1~1-9及比較例1~9之樹脂組成物評價消泡性。 The defoaming properties of the resin compositions of Examples 1-1 to 1-9 and Comparative Examples 1 to 9 prepared as described above were evaluated.

評價方法如下所述。將實施例1-1~1-9及比較例1~9之樹脂組成物15mL分別添加至內徑1.5cm之30mL容量之有底圓筒形狀之容器中，於5秒內振盪20次(振幅10~20cm)之後靜置，以目視測定直至溶液表面之氣泡消失為止所需之時間，以3個等級(◎：未滿3分鐘，○：3分鐘以上且未滿20分鐘，×：20分鐘以上)評價「消泡性」。又，觀察振盪前之溶液之透明性、均勻性，作為「外觀」以2個等級(○：透明，×：存在白濁或沈澱)進行評價。將結果示於表2。 The evaluation method is as follows. 15 mL of the resin compositions of Examples 1-1 to 1-9 and Comparative Examples 1 to 9 were respectively added to a bottomed cylindrical container having a diameter of 1.5 cm and a volume of 30 mL, and oscillated 20 times in 5 seconds (amplitude After 10 to 20 cm), the time required for the measurement until the bubbles on the surface of the solution disappeared was visually observed in three grades (◎: less than 3 minutes, ○: 3 minutes or more and less than 20 minutes, ×: 20 minutes) The above) evaluates "defoaming property". Further, the transparency and uniformity of the solution before the shaking were observed, and the "appearance" was evaluated in two grades (○: transparent, ×: white turbidity or precipitation). The results are shown in Table 2.

如表2所示，實施例1-1~1-9之樹脂組成物顯示出優異之消泡性。另一方面，比較例1~7之樹脂組成物容易起泡，且氣泡不容易消失。尤其是比較例3中，溶液白濁而難以觀察，無法進行消泡 性之評價。再者，如使用具有羥基而不具有氟烷基之聚合體之比較例8或使用不具有羥基而具有氟烷基之聚合體之比較例9所示，樹脂組成物之氣泡係起因於存在於聚合體中之羥基及氟烷基。 As shown in Table 2, the resin compositions of Examples 1-1 to 1-9 exhibited excellent defoaming properties. On the other hand, the resin compositions of Comparative Examples 1 to 7 were easily foamed, and the bubbles did not easily disappear. In particular, in Comparative Example 3, the solution was cloudy and difficult to observe, and defoaming could not be performed. Evaluation of sex. Further, as shown in Comparative Example 8 using a polymer having a hydroxyl group instead of a fluoroalkyl group or Comparative Example 9 using a polymer having a hydroxyalkyl group and having no hydroxy group, the bubble of the resin composition is caused by a hydroxyl group and a fluoroalkyl group in the polymer.

<硬化膜之製作及評價> <Manufacture and evaluation of cured film>

將如上所述般調製之實施例1-4、1-5、1-7及1-9以及比較例2之樹脂組成物分別以形成膜厚3~4μm之硬化膜之方式塗佈於PET基材(厚度188μm)，其後，於80℃下進行乾燥，去除溶劑而形成乾燥覆膜。對該塗膜使用輸出密度120W/cm之高壓水銀燈，以成為累積光量500mJ/cm2之方式於通常氧濃度環境下照射波長254nm之紫外線使之硬化而獲得硬化膜。 The resin compositions of Examples 1-4, 1-5, 1-7, and 1-9 and Comparative Example 2 prepared as described above were respectively applied to a PET base by forming a cured film having a film thickness of 3 to 4 μm. The material (thickness: 188 μm) was dried at 80 ° C, and the solvent was removed to form a dried film. A high-pressure mercury lamp having an output density of 120 W/cm was used for the coating film, and ultraviolet rays having a wavelength of 254 nm were irradiated in a normal oxygen concentration atmosphere so as to have a cumulative light amount of 500 mJ/cm 2 to obtain a cured film.

針對如上所述般製作之硬化膜，對以下之(1)~(6)之項目進行評價。 The following items (1) to (6) were evaluated for the cured film produced as described above.

(1)透明性：依據JIS K-7105，使用霧度計(HAZE METER)(村上色彩技術研究所製造之「HAZE METER HM-65W」)，測定硬化膜之霧度值。 (1) Transparency: The haze value of the cured film was measured using a haze meter (HAZE METER) ("HAZE METER HM-65W" manufactured by Murakami Color Research Laboratory) in accordance with JIS K-7105.

(2)硬度：使用JIS標準鉛筆硬度計(太佑機材公司製造)，基於JIS K-5400之條件進行測定，以不產生傷痕之最硬之鉛筆之硬度號數表示。 (2) Hardness: It was measured based on the conditions of JIS K-5400 using a JIS standard pencil hardness tester (manufactured by Taisho Machinery Co., Ltd.), and was expressed by the hardness number of the hardest pencil which did not cause scratches.

(3)撥水撥油性：將硬化膜於溫度23℃、濕度60%RH之恆溫室內靜置24小時而調整狀態之後，利用接觸角計(協和界面科學公司製造之「DropMaster DM500」)，對硬化膜滴加0.002mL之純水或十六烷，1分鐘後使用接觸角計(協和界面科學股份有限公司製造，DropMaster 500」)，分別測定相對於水之接觸角及相對於十六烷之接觸角(單位：度)。 (3) Water-repellent property: After the cured film is allowed to stand in a constant temperature room at a temperature of 23 ° C and a humidity of 60% RH for 24 hours, the contact angle meter ("DropMaster DM500" manufactured by Kyowa Interface Science Co., Ltd.) is used. To the hardened film, 0.002 mL of pure water or hexadecane was added dropwise, and after 1 minute, a contact angle meter (Draft Master 500, manufactured by Kyowa Interface Science Co., Ltd.) was used, and the contact angle with respect to water and relative to hexadecane were measured, respectively. Contact angle (unit: degree).

(4)密接性：利用JIS K5400中所記載之棋盤格法進行試驗。於硬 化膜上以1mm間隔形成100個棋盤格，使用透明膠帶(Nichiban公司製造)進行試驗。重複5次相同操作(透明膠帶通常使用新膠帶)，將完全未產生傷痕或剝離者設為○，將產生10%以下之傷痕或剝離者設為△，將其以外者設為×而以3個等級進行評價。 (4) Adhesion: The test was carried out by the checkerboard method described in JIS K5400. Hard 100 checkerboards were formed on the film at intervals of 1 mm, and tested using a transparent tape (manufactured by Nichiban Co., Ltd.). The same operation is repeated five times (a new tape is usually used for the scotch tape), and ○ is not caused by scratches or peeling at all, and 10% or less of scratches or peelings are set to Δ, and others are set to × and 3 Ratings are evaluated.

(5)耐標記油墨附著性：利用油性魔術彩色筆(magic marker)(ZEBRA製造，Mac-Care極細(黑色)之細端)對硬化膜畫線，30秒後，若去掉線則設為○，若去不掉則設為×而以2個等級進行評價。 (5) Marking ink adhesion: Use a magical magic marker (manufactured by ZEBRA, Mac-Care's fine (black) thin end) to draw a line on the cured film. After 30 seconds, if the line is removed, set it to ○. If it cannot be removed, it is set to × and evaluated in two levels.

(6)標記油墨拭除耐久性：利用油性魔術彩色筆(ZEBRA製造，Mac-Care極細(黑色)之細端)對硬化膜畫線，10秒後，利用衛生紙(製造商：CRECIA)對表面進行擦拭，重複該操作，根據直至變得無法拭除為止之次數，將8~5次設為○，將4~2次設為△，將1次設為×而以3個等級進行評價。 (6) Marking ink erasing durability: Using an oily magic color pen (manufactured by ZEBRA, fine end of Mac-Care (black)), the hardened film was drawn, and after 10 seconds, the surface was treated with toilet paper (manufacturer: CRECIA). This was repeated, and the operation was repeated, and 8 to 5 times were set to ○, 4 to 2 times to Δ, and once to ×, and to be evaluated in three levels.

將硬化膜之評價結果示於表3。 The evaluation results of the cured film are shown in Table 3.

使本發明之樹脂組成物硬化而獲得之硬化膜的透明性、硬度、撥水撥油性、密接性、耐污染性、耐污染性之耐久性之任一者均良好。 Any of the cured films obtained by curing the resin composition of the present invention has good transparency, hardness, water repellency, adhesion, stain resistance, and stain resistance.

根據上述實施例可明確，本發明之樹脂組成物之起泡性較小，均染性優異。進而可明確，本發明之樹脂組成物藉由硬化可實現硬度較高，耐污染性及其耐久性、撥水撥油性、以及密接性優異之 硬化物。 According to the above examples, it is clear that the resin composition of the present invention has a small foaming property and is excellent in leveling property. Further, it is clear that the resin composition of the present invention can achieve high hardness, stain resistance, durability, water repellency, and adhesion by hardening. Hardened material.

[實施例2-1~2-25] [Examples 2-1 to 2-25]

<樹脂組成物之調製及評價> <Modulation and evaluation of resin composition>

按照表4所示之調配(重量比)調製實施例及比較例之樹脂組成物。具體而言，將上述合成例中所合成之聚合體、多官能丙烯酸酯按照表4中所記載之比率混合成合計100重量份，相對於聚合體與多官能丙烯酸酯之混合物100重量份，按照表4中所記載之比率分別混合起始劑及添加劑。於其中按照表4中所記載之重量比添加溶劑，實施例2-4、2-5、2-10、2-11、2-15~2-18中亦添加飽和烴而調製樹脂組成物。 The resin compositions of the examples and the comparative examples were prepared in accordance with the formulation (weight ratio) shown in Table 4. Specifically, the polymer and the polyfunctional acrylate synthesized in the above Synthesis Example are mixed in a ratio of those shown in Table 4 to a total of 100 parts by weight, based on 100 parts by weight of the mixture of the polymer and the polyfunctional acrylate. The ratios shown in Table 4 were mixed with an initiator and an additive, respectively. A solvent was added thereto in accordance with the weight ratio shown in Table 4, and saturated hydrocarbons were also added to Examples 2-4, 2-5, 2-10, 2-11, 2-15 to 2-18 to prepare a resin composition.

再者，實施例及比較例中所使用之添加劑之物性值之測定方法如下所述。溶劑之SP值係使用文獻值(IUPAC Gold Book-solubility parameter)。 Further, the methods for measuring the physical property values of the additives used in the examples and the comparative examples are as follows. The SP value of the solvent is the IUPAC Gold Book-solubility parameter.

表面張力降低能力係使用表面張力計(協和界面化學公司製造之「DropMaster系列」)，測定含氟基之寡聚物之1%PGMAc溶液之表面張力，以「表面張力降低能力=PGMAc之表面張力-1%PGMAc溶液之表面張力」算出。 The surface tension reduction ability was measured by using a surface tension meter ("DropMaster Series" manufactured by Kyowa Interface Chemical Co., Ltd.) to determine the surface tension of a 1% PGMAc solution of a fluorine-containing oligomer, "surface tension reducing ability = surface tension of PGMAc" The surface tension of the -1% PGMAc solution was calculated.

重量平均分子量係指利用GPC(東梭公司製造之「HLC-8120GPC」)，使用四氫呋喃作為溶劑，使用聚苯乙烯作為標準樣品而測定者。又，將寡聚物之物性測定結果示於表5。 The weight average molecular weight is measured by using GPC ("HLC-8120GPC" manufactured by Hokusto Co., Ltd.), using tetrahydrofuran as a solvent, and using polystyrene as a standard sample. Further, the measurement results of the physical properties of the oligomer are shown in Table 5.

對如上所述般調製之實施例及比較例之樹脂組成物評價消泡性。 The defoaming property of the resin compositions of the examples and the comparative examples prepared as described above was evaluated.

評價方法如下所述。將實施例及比較例之樹脂組成物15mL分別添加至內徑1.5cm之30mL容量之有底圓筒形狀之容器中，於5秒內振盪20次(振幅10~20cm)之後靜置，以目視測定直至溶液表面之氣泡消失為止所需之時間。15分鐘以上者實際上生產性較差，因此作為比較例。又，觀察振盪前之溶液之透明性、均勻性，作為「外觀」以2個等級(○：透明，×：存在白濁或沈澱)進行評價。將結果示於表6。 The evaluation method is as follows. 15 mL of the resin compositions of the examples and the comparative examples were respectively added to a bottomed cylindrical container having a diameter of 1.5 cm and a volume of 30 mL, and the mixture was shaken 20 times (amplitude 10 to 20 cm) in 5 seconds, and then allowed to stand still. The time required until the bubbles on the surface of the solution disappeared were measured. Those who are more than 15 minutes actually have poor productivity, and therefore are used as comparative examples. Further, the transparency and uniformity of the solution before the shaking were observed, and the "appearance" was evaluated in two grades (○: transparent, ×: white turbidity or precipitation). The results are shown in Table 6.

如表6所示，實施例之樹脂組成物顯示出優異之消泡性。另一方面，比較例之樹脂組成物容易起泡，且氣泡不容易消失。 As shown in Table 6, the resin composition of the examples showed excellent defoaming properties. On the other hand, the resin composition of the comparative example was easily foamed, and the bubbles did not easily disappear.

<硬化膜之製作及評價> <Manufacture and evaluation of cured film>

將如上所述般調製之實施例2-2、2-4、2-8及2-10以及比較例10之樹脂組成物分別以形成膜厚3~4μm之硬化膜之方式塗佈於PET基材(厚度188μm)上，其後，於80℃下進行乾燥，去除溶劑而形成乾燥覆膜。對該塗膜使用輸出密度120W/cm之高壓水銀燈，以成為累積光量500mJ/cm2之方式於通常氧濃度環境下照射波長254nm之紫外線使之硬化而獲得硬化膜。 The resin compositions of Examples 2-2, 2-4, 2-8, and 2-10 and Comparative Example 10 prepared as described above were respectively applied to a PET base by forming a cured film having a film thickness of 3 to 4 μm. The material (thickness: 188 μm) was dried at 80 ° C, and the solvent was removed to form a dried film. A high-pressure mercury lamp having an output density of 120 W/cm was used for the coating film, and ultraviolet rays having a wavelength of 254 nm were irradiated in a normal oxygen concentration atmosphere so as to have a cumulative light amount of 500 mJ/cm 2 to obtain a cured film.

針對如上所述般製作之硬化膜，對以下之(1)~(6)之項目進行評價。 The following items (1) to (6) were evaluated for the cured film produced as described above.

(1)透明性：依據JIS K-7105，使用霧度計(HAZE METER)(村上色彩技術研究所製造之「HAZE METER HM-65W」)，測定硬化膜之霧度值。 (1) Transparency: The haze value of the cured film was measured using a haze meter (HAZE METER) ("HAZE METER HM-65W" manufactured by Murakami Color Research Laboratory) in accordance with JIS K-7105.

(2)硬度：使用JIS標準鉛筆硬度計(太佑機材公司製造)，基於JIS K-5400之條件進行測定，以不產生傷痕之最硬之鉛筆之硬度號數表示。 (2) Hardness: It was measured based on the conditions of JIS K-5400 using a JIS standard pencil hardness tester (manufactured by Taisho Machinery Co., Ltd.), and was expressed by the hardness number of the hardest pencil which did not cause scratches.

(3)撥水撥油性：將硬化膜於溫度23℃、濕度60%RH之恆溫室內靜置24小時而調整狀態之後，利用接觸角計(協和界面科學公司製造之「DropMaster DM500」)，對硬化膜滴加0.002mL之純水或十六烷，1秒後使用接觸角計(協和界面科學股份有限公司製造，DropMaster 500」)，分別測定相對於水之接觸角及相對於十六烷之接觸角(單位：度)。 (3) Water-repellent property: After the cured film is allowed to stand in a constant temperature room at a temperature of 23 ° C and a humidity of 60% RH for 24 hours, the contact angle meter ("DropMaster DM500" manufactured by Kyowa Interface Science Co., Ltd.) is used. To the hardened film, 0.002 mL of pure water or hexadecane was added dropwise, and after 1 second, a contact angle meter (Draft Master 500, manufactured by Kyowa Interface Science Co., Ltd.) was used, and the contact angle with respect to water and relative to hexadecane were measured, respectively. Contact angle (unit: degree).

(4)密接性：利用JIS K5400中所記載之棋盤格法進行試驗。於硬化膜上以1mm間隔形成100個棋盤格，使用透明膠帶(Nichiban公司製造)進行試驗。重複5次相同操作(透明膠帶通常使用新膠帶)，將完全未產生傷痕或剝離者設為○，將產生10%以下之傷痕或剝離者設為△，將其以外者設為×而以3個等級進行評價。 (4) Adhesion: The test was carried out by the checkerboard method described in JIS K5400. 100 checkerboards were formed on the cured film at intervals of 1 mm, and tested using a transparent tape (manufactured by Nichiban Co., Ltd.). The same operation is repeated five times (a new tape is usually used for the scotch tape), and ○ is not caused by scratches or peeling at all, and 10% or less of scratches or peelings are set to Δ, and others are set to × and 3 Ratings are evaluated.

(5)耐標記油墨附著性：利用油性魔術彩色筆(ZEBRA製造，Mac-Care極細(黑色)之細端)對硬化膜畫線，30秒後，若去掉線則設為○，若去不掉則設為×而以2個等級進行評價。 (5) Marking ink adhesion: Use an oily magic color pen (manufactured by ZEBRA, the fine end of Mac-Care (black)) to draw a line on the cured film. After 30 seconds, if the line is removed, set it to ○, if not When it is off, it is set to × and it is evaluated in two levels.

(6)標記油墨拭除耐久性：利用油性魔術彩色筆(ZEBRA製造，Mac-Care極細(黑色)之細端)對硬化膜畫線，10秒後，利用衛生紙(製造商：CRECIA)對表面進行擦拭，重複該操作，根據直至變得無法拭除為止之次數，將8~5次設為○，將4~2次設為△，將1次設為×而以3個等級進行評價。 (6) Marking ink erasing durability: Using an oily magic color pen (manufactured by ZEBRA, fine end of Mac-Care (black)), the hardened film was drawn, and after 10 seconds, the surface was treated with toilet paper (manufacturer: CRECIA). This was repeated, and the operation was repeated, and 8 to 5 times were set to ○, 4 to 2 times to Δ, and once to ×, and to be evaluated in three levels.

將硬化膜之評價結果示於表7。 The evaluation results of the cured film are shown in Table 7.

使本發明之樹脂組成物硬化而獲得之硬化膜的透明性、硬度、撥水撥油性、密接性、耐污染性、耐污染性之耐久性之任一者均良好。 Any of the cured films obtained by curing the resin composition of the present invention has good transparency, hardness, water repellency, adhesion, stain resistance, and stain resistance.

根據上述實施例可明確，本發明之樹脂組成物之起泡性較小，均染性優異。進而可明確，本發明之樹脂組成物藉由硬化可實現一種硬度較高，耐污染性及其耐久性、撥水撥油性、以及密接性優異之硬化物。 According to the above examples, it is clear that the resin composition of the present invention has a small foaming property and is excellent in leveling property. Further, it is understood that the resin composition of the present invention can achieve a cured product having high hardness, stain resistance, durability, water repellency, and adhesion by hardening.

(產業上之可利用性) (industrial availability)

根據本發明，可提供一種起泡性較小，即便有起泡之情況消泡性亦優異，因此所形成之塗膜難以產生缺陷的樹脂組成物。本發明進而提供一種若將上述樹脂組成物較薄地塗佈於物品等之表面並使其硬化，則對該物品等賦予優異之硬度、耐損傷性、透明性、耐污染性及其耐久性的硬化膜。因此，本發明之樹脂組成物可較佳地應用於光記錄媒體表面之保護、觸控面板或平面顯示器等光學顯示器、行動電話殼體、汽車透明零件保護、農業用塑膠溫室等之透明部之保護等廣泛之用途，因此於產業上非常有用。 According to the present invention, it is possible to provide a resin composition which is less foaming and which is excellent in defoaming property even in the case of foaming, so that the formed coating film is less likely to cause defects. Further, the present invention provides a method in which the resin composition is applied to a surface of an article or the like and is cured, thereby imparting excellent hardness, scratch resistance, transparency, stain resistance, and durability to the article or the like. Hardened film. Therefore, the resin composition of the present invention can be preferably applied to the protection of the surface of an optical recording medium, the optical display such as a touch panel or a flat panel display, the mobile phone case, the transparent part protection of an automobile, the transparent part of an agricultural plastic greenhouse, etc. It is widely used in industry and is therefore very useful in industry.

Claims (20)

一種樹脂組成物，其含有：具有羥基及氟烷基且重量平均分子量為1000以上之聚合體、含有選自(甲基)丙烯醯基及乙烯基中之1種或2種以上之烴系單體、飽和烴0.01~25重量%、及SP值為10.0以下之溶劑。 A resin composition containing a polymer having a hydroxyl group and a fluoroalkyl group and having a weight average molecular weight of 1,000 or more, and a hydrocarbon system containing one or more selected from the group consisting of a (meth) acrylonitrile group and a vinyl group A solvent having a body, a saturated hydrocarbon of 0.01 to 25% by weight, and an SP value of 10.0 or less. 如申請專利範圍第1項之樹脂組成物，其中，上述飽和烴之碳數為5~18。 The resin composition of claim 1, wherein the saturated hydrocarbon has a carbon number of 5 to 18. 一種樹脂組成物，其含有：具有羥基及氟烷基且重量平均分子量為1000以上之聚合體、含有選自(甲基)丙烯醯基及乙烯基中之1種或2種以上之烴系單體、表面張力降低能力為2mN/m以上之含氟基之寡聚物、及SP值為10.0以下之溶劑。 A resin composition containing a polymer having a hydroxyl group and a fluoroalkyl group and having a weight average molecular weight of 1,000 or more, and a hydrocarbon system containing one or more selected from the group consisting of a (meth) acrylonitrile group and a vinyl group A fluorine-containing oligomer having a body and a surface tension reducing ability of 2 mN/m or more, and a solvent having an SP value of 10.0 or less. 如申請專利範圍第1至3項中任一項之樹脂組成物，其中，上述聚合體中之羥基之含量為0.2~5.0重量%。 The resin composition according to any one of claims 1 to 3, wherein the content of the hydroxyl group in the polymer is 0.2 to 5.0% by weight. 如申請專利範圍第1至4項中任一項之樹脂組成物，其中，上述聚合體中之氟原子之含量為1.0~34.0重量%。 The resin composition according to any one of claims 1 to 4, wherein the content of the fluorine atom in the polymer is 1.0 to 34.0% by weight. 如申請專利範圍第1至5項中任一項之樹脂組成物，其中，上述聚合體於側鏈上具有不飽和雙鍵基。 The resin composition according to any one of claims 1 to 5, wherein the polymer has an unsaturated double bond group in a side chain. 如申請專利範圍第1至6項中任一項之樹脂組成物，其中，上述聚合體具有聚矽氧烷構造。 The resin composition according to any one of claims 1 to 6, wherein the polymer has a polyoxyalkylene structure. 如申請專利範圍第7項之樹脂組成物，其中，上述聚矽氧烷構造末 端之矽或該矽上所鍵結之飽和烴基經由氧原子或硫原子鍵結於上述聚合體之主鏈上。 The resin composition of claim 7 of the patent scope, wherein the polypyroxane is constructed at the end The terminal or the saturated hydrocarbon group bonded to the crucible is bonded to the main chain of the above polymer via an oxygen atom or a sulfur atom. 如申請專利範圍第1至8項中任一項之樹脂組成物，其中，上述烴系單體為1分子中具有3個以上之(甲基)丙烯醯基之多官能(甲基)丙烯酸酯。 The resin composition according to any one of claims 1 to 8, wherein the hydrocarbon-based monomer is a polyfunctional (meth) acrylate having three or more (meth) acrylonitrile groups in one molecule. . 如申請專利範圍第3至9項中任一項之樹脂組成物，其中，上述含氟基之寡聚物之重量平均分子量為5000以上。 The resin composition according to any one of claims 3 to 9, wherein the fluorine-containing group oligomer has a weight average molecular weight of 5,000 or more. 如申請專利範圍第3至10項中任一項之樹脂組成物，其中，上述含氟基之寡聚物為非離子性。 The resin composition according to any one of claims 3 to 10, wherein the fluoro group-containing oligomer is nonionic. 如申請專利範圍第3至11項中任一項之樹脂組成物，其中，樹脂組成物中之含氟基之寡聚物之含量為樹脂組成物整體之0.005~10重量%。 The resin composition according to any one of claims 3 to 11, wherein the content of the fluorine-containing oligomer in the resin composition is 0.005 to 10% by weight based on the entire resin composition. 如申請專利範圍第1至12項中任一項之樹脂組成物，其中，上述溶劑為選自由酮系溶劑、醇系溶劑、醚系溶劑、酯系溶劑及芳香族烴溶劑所組成之群組中之至少一種溶劑。 The resin composition according to any one of claims 1 to 12, wherein the solvent is selected from the group consisting of a ketone solvent, an alcohol solvent, an ether solvent, an ester solvent, and an aromatic hydrocarbon solvent. At least one solvent. 如申請專利範圍第3至13項中任一項之樹脂組成物，其含有碳數為5~18之飽和烴。 The resin composition according to any one of claims 3 to 13, which contains a saturated hydrocarbon having 5 to 18 carbon atoms. 如申請專利範圍第1至14項中任一項之樹脂組成物，其含有自由基聚合性光起始劑。 The resin composition according to any one of claims 1 to 14, which contains a radical polymerizable photoinitiator. 一種硬化物，其係使申請專利範圍第1至15項中任一項之樹脂組成物硬化而獲得。 A cured product obtained by hardening a resin composition according to any one of claims 1 to 15. 如申請專利範圍第16項之硬化物，其係藉由對上述組成物照射活性能量射線而獲得。 The cured product of claim 16 is obtained by irradiating the above composition with an active energy ray. 一種成形品，其具有申請專利範圍第16或17項之硬化物。 A molded article having a cured product of claim 16 or 17. 如申請專利範圍第18項之成形品，其係用於光學用途。 For example, the molded article of claim 18 is used for optical use. 如申請專利範圍第19項之成形品，其為光記錄媒體或光學顯示器用積層體。 The molded article of claim 19, which is a laminate for an optical recording medium or an optical display.
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