TWI653282B - Combination - Google Patents

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TWI653282B
TWI653282B TW103140931A TW103140931A TWI653282B TW I653282 B TWI653282 B TW I653282B TW 103140931 A TW103140931 A TW 103140931A TW 103140931 A TW103140931 A TW 103140931A TW I653282 B TWI653282 B TW I653282B
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meth
acrylate
mass
composition
dicarboxylic acid
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TW103140931A
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TW201546159A (en
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石田泰則
比舍佑基
深尾健司
後藤慶次
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日商電化股份有限公司
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    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • 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
    • C08F290/02—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 end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols

Abstract

提供一種深部固化好的組合物。所述組合物含有(P)聚合性乙烯基單體、(C)光聚合引發劑、(D)抗氧化劑、(E)硫醇、(F)二羧酸二酯。 Provided is a deep cured composition. The composition contains (P) a polymerizable vinyl monomer, (C) a photopolymerization initiator, (D) an antioxidant, (E) a thiol, and (F) a dicarboxylic acid diester.

Description

組合物 combination

本發明涉及組合物。 The invention relates to a composition.

搭載在LCD(液晶顯示器)等顯示體上的觸摸屏存在電阻膜式、靜電電容式、電磁誘導式、光學式等。在這些觸摸屏(touch panel)的表面有時粘貼改善外觀的設計性的裝飾板或指定觸摸的位置的圖示片(icon sheet)。靜電電容式觸摸屏具有在透明基板上形成透明電極，在透明電極上粘貼透明板的構造。 Touch screens mounted on display bodies such as LCDs (Liquid Crystal Display) include resistive film type, electrostatic capacitance type, electromagnetic induction type, and optical type. On the surface of these touch panels, a decorative plate that improves the appearance or an icon sheet that designates a touched position may be pasted. The electrostatic capacitance type touch screen has a structure in which a transparent electrode is formed on a transparent substrate, and a transparent plate is pasted on the transparent electrode.

以往，裝飾板與觸摸屏的粘貼、圖示片與觸摸屏的粘貼、以及透明基板與透明板的粘貼使用粘合劑。 Conventionally, adhesives have been used for pasting decorative boards and touch screens, pasting graphics sheets and touch screens, and pasting transparent substrates and transparent boards.

這些圖示片或觸摸屏為了隱藏顯示體的驅動用IC、佈線或LCD的框密封劑，只可以看到顯示區域，並為了提高設計性，有時藉由印刷等覆蓋遮光框。如果存在該遮光框，遮光框下的光可固化粘合劑組合物就被遮光框遮住光，如果不照射光就會不固化，粘合變得不充分。 In order to hide the driving IC of the display body, wiring, or the frame sealant of the LCD in these graphic sheets or touch screens, only the display area can be seen, and in order to improve the design, the light-shielding frame may be covered by printing or the like. If such a light-shielding frame is present, the light-curable adhesive composition under the light-shielding frame is shielded by the light-shielding frame, and if it is not irradiated with light, it will not be cured and the adhesion will be insufficient.

為了解決由於該未固化而導致的不充分的粘合的問題，實施以下方法，即，傾斜或橫向照射光等並調整光的照射角度，或對光可固化粘合劑組合物添加熱固性催化劑，除了光可固化性賦予熱固性，藉由光和熱固化。 In order to solve the problem of insufficient adhesion due to this uncuring, a method is implemented in which light or the like is irradiated obliquely or laterally and the angle of light irradiation is adjusted, or a thermosetting catalyst is added to the photocurable adhesive composition In addition to photocurability, thermosetting properties are imparted by light and heat curing.

但是，在調整光的照射角度的方法中，存在如果遮光框的寬度變寬則難以使遮光框下的光可固化粘合劑組合物全部充分地固化，易於殘留未固化部分的問題。對光可固化粘合劑組合物賦予熱固性，藉由光和熱固化的方法需要將LCD、EL顯示器、LED顯示器等顯示面板升溫到60~80℃並保持30~60分鐘，因此存在可能導致品質劣化或縮短商品壽命的問題。 However, in the method of adjusting the irradiation angle of light, if the width of the light-shielding frame is widened, it is difficult to sufficiently cure all of the light-curable adhesive composition under the light-shielding frame, and it is easy to leave uncured portions. The thermosetting property is imparted to the photocurable adhesive composition, and the display panel such as LCD, EL display, and LED display needs to be heated to 60 to 80 ° C and maintained for 30 to 60 minutes by the light and heat curing method. Problems that degrade or shorten product life.

專利文獻1記載了一種光可固化樹脂組合物，該組成物含有(A)骨架具有聚異戊二烯、聚丁二烯或聚胺酯的(甲基)丙烯酸酯低聚物，(B)軟化成分、以及(C1)(甲基)丙烯酸酯單體，並且該(甲基)丙烯酸酯單體從苯氧基(甲基)丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯、2-羥基-3-苯氧基丙基(甲基)丙烯酸酯、環己基(甲基)丙烯酸酯、壬基苯酚EO加成物(甲基)丙烯酸酯、甲氧基三乙二醇(甲基)丙烯酸酯以及四氫糠(甲基)丙烯酸酯中選擇。 Patent Document 1 describes a photocurable resin composition containing (A) a (meth) acrylate oligomer having a polyisoprene, polybutadiene, or polyurethane skeleton, and (B) a softening component And (C1) (meth) acrylate monomer, and the (meth) acrylate monomer is selected from phenoxy (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, 2 -Hydroxy-3-phenoxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, nonylphenol EO adduct (meth) acrylate, methoxytriethylene glycol (methyl ) Acrylate and tetrahydrofurfuryl (meth) acrylate.

近年來，LCD等顯示體的玻璃變薄。如果玻璃變薄則由於外部應力，LCD易於變形。當將使用薄的玻璃的LCD等的顯示體和亞克力板或聚碳酸酯板等光學功能材料粘貼時，由於玻璃與丙烯酸等的線性膨脹的不同、以及亞克力板或聚碳酸酯等塑膠成型材料在成型時發生變形，在耐熱試驗或 耐濕試驗中發生成型變形的緩解或吸濕/乾燥，發生尺寸變化或彎曲等表面精度變化。專利文獻2記載了主要成分含有氨基甲酸酯(甲基)丙烯酸酯、聚丁二烯(甲基)丙烯酸酯、以及異戊二烯(甲基)丙烯酸酯的固化樹脂。 In recent years, the glass of display bodies such as LCDs has become thinner. If the glass becomes thin, the LCD is easily deformed due to external stress. When a display body such as an LCD using thin glass and an optically functional material such as an acrylic plate or a polycarbonate plate are pasted, due to the difference in linear expansion between glass and acrylic, and plastic molding materials such as an acrylic plate or polycarbonate, Deformation during molding, heat resistance test or In the moisture resistance test, a reduction in molding deformation or moisture absorption / drying occurs, and a change in surface accuracy such as dimensional change or bending occurs. Patent Document 2 describes a cured resin containing urethane (meth) acrylate, polybutadiene (meth) acrylate, and isoprene (meth) acrylate as main components.

在裝飾板與觸摸屏的粘貼、圖示片與觸摸屏的粘貼、以及透明基板與透明板的粘貼等的用途中，希望具有可以與被粘合體在假定使用環境為升溫氣氛下進行的變形相匹配的程度的柔性。 For applications such as pasting decorative boards and touch screens, pasting graphics and touch screens, and pasting transparent substrates and transparent boards, it is desirable to have a deformation that matches the adherend under the assumption that the use environment is a warming atmosphere. Degree of flexibility.

另一方面，當具有可以與被粘合體在假定使用環境為升溫氣氛下進行的變形相匹配的程度的柔性時，存在耐熱試驗後發生著色或變色、在耐濕試驗後強度降低等問題也變得明顯。作為所述問題的解決方案，專利文獻4記載了一種光可固化型粘合組合物，該光可固化型粘合組合物含有從由聚異戊二烯(甲基)丙烯酸酯低聚物、聚丁二烯(甲基)丙烯酸酯低聚物以及聚胺酯(甲基)丙烯酸酯低聚物構成的組中選擇出的一種以上的低聚物和受阻胺。 On the other hand, if it has a degree of flexibility that can match the deformation of the adherend under the assumption that the use environment is a warming atmosphere, there are problems such as coloration or discoloration after the heat resistance test, and strength reduction after the humidity resistance test. Become obvious. As a solution to the problem, Patent Document 4 describes a photocurable adhesive composition containing a polyisoprene (meth) acrylate oligomer, One or more oligomers and hindered amines selected from the group consisting of a polybutadiene (meth) acrylate oligomer and a polyurethane (meth) acrylate oligomer.

在專利文獻5中記載了一種光可固化組合物，其特徵在於，含有(A)特定的含硫(甲基)丙烯酸酯化合物或含有該化合物的自由基活性組合物、(B)紫外線吸收劑、(C)抗氧化劑、以及(D)聚合引發劑。 Patent Document 5 describes a photocurable composition containing (A) a specific sulfur-containing (meth) acrylate compound or a radically active composition containing the compound, and (B) an ultraviolet absorber. (C) an antioxidant, and (D) a polymerization initiator.

在專利文獻6中記載了一種光可固化型透明粘合劑組合物，該組合物含有丙烯酸聚合物(E)、具有兩個以上官能基的氨酯(甲基)丙烯酸酯(A)，且該官能基具有不飽和雙鍵、具有一個官能基的單體(B)，且該官能基具 有不飽和雙鍵、光聚合引發劑(C)、具有兩個以上硫醇基的聚硫醇化合物(D)，該組合物中的氨酯(甲基)丙烯酸酯(A)的重量比為2重量%~30重量%。 Patent Document 6 describes a photocurable transparent adhesive composition containing an acrylic polymer (E), a urethane (meth) acrylate (A) having two or more functional groups, and The functional group has an unsaturated double bond, a monomer (B) having one functional group, and the functional group has There is an unsaturated double bond, a photopolymerization initiator (C), and a polythiol compound (D) having two or more thiol groups. The weight ratio of the urethane (meth) acrylate (A) in the composition is 2% to 30% by weight.

在專利文獻7中，記載了一種將在末端具有烯丙基的烯丙基酯低聚物作為熱固性樹脂組合物來使用，在烯丙基酯低聚物的組成成分中，10~80摩爾%是含有由衣康酸衍生出的有機殘基的脂肪二羧酸，餘量包含由含有衣康酸以外的不飽和基團的脂肪族和/或飽和脂肪族和/或芳香族脂肪二羧酸衍生出的有機殘基、和由多元醇衍生出的有機殘基。 Patent Document 7 describes the use of an allyl ester oligomer having an allyl group at the terminal as a thermosetting resin composition. The composition of the allyl ester oligomer is 10 to 80 mol%. It is an aliphatic dicarboxylic acid containing organic residues derived from itaconic acid, and the balance contains derivatives derived from aliphatic and / or saturated aliphatic and / or aromatic aliphatic dicarboxylic acids containing unsaturated groups other than itaconic acid Organic residues, and organic residues derived from polyols.

【現有技術文獻】 [Existing technical literature]

【專利文獻】 [Patent Literature]

專利文獻1：國際公開第2010/027041號公報 Patent Document 1: International Publication No. 2010/027041

專利文獻2：日本特開2004-77887號公報 Patent Document 2: Japanese Patent Application Laid-Open No. 2004-77887

專利文獻3：日本特開昭64-85209號公報 Patent Document 3: Japanese Patent Application Laid-Open No. 64-85209

專利文獻4：日本特開2012-46658號公報 Patent Document 4: Japanese Patent Application Publication No. 2012-46658

專利文獻5：日本特開2002-097224號公報 Patent Document 5: Japanese Patent Application Laid-Open No. 2002-097224

專利文獻6：日本特開2009-001655號公報 Patent Document 6: Japanese Patent Application Laid-Open No. 2009-001655

專利文獻7：日本特開平7-324123號公報 Patent Document 7: Japanese Patent Application Laid-Open No. 7-324123

然而，所述文獻所記載的以往技術在以下的方面具有改善的餘地。 However, the conventional technology described in the document has room for improvement in the following points.

專利文獻2的方法存在當想要抑制表面精度變化等變形時，粘合面剝離，或LCD裂開，或LCD顯示不均勻等問題。 The method of Patent Document 2 has problems such as peeling of the adhesive surface, cracking of the LCD, or uneven display of the LCD when it is desired to suppress deformation such as a change in surface accuracy.

作為專利文獻2的問題的解決方案，例如有專利文獻3的UV固化型樹脂。但是，在專利文獻3中，是將異冰片(甲基)丙烯酸酯等剛性的骨架單體作為基材的高彈性樹脂，因此在高溫可靠性試驗(耐濕熱性試驗)中不能承受被粘合體的膨脹收縮，並且會發生剝離。 As a solution to the problem of Patent Document 2, there is, for example, a UV curable resin of Patent Document 3. However, since Patent Document 3 is a highly elastic resin using a rigid skeleton monomer such as isoborneol (meth) acrylate as a base material, it cannot withstand adhesion in a high-temperature reliability test (humidity and heat resistance test). The body expands and contracts, and peeling occurs.

另外，在任意一個文獻的技術中，例如當將觸摸屏等顯示體所使用的裝飾板或圖示片粘貼時、將透明基板和透明基板粘貼時、以及將被印刷加工的部分粘貼時，在藉由來自側面的可見光或紫外線對在被粘合體正面由於印刷等的遮光框，從正面可見光或紫外線不能到達的位置進行固化的情況下，遮光框下的固化樹脂組合物發生固化不良的問題也存在。 In addition, in any of the literature technologies, for example, when a decorative plate or a graphic sheet used for a display body such as a touch panel is pasted, when a transparent substrate and a transparent substrate are pasted, and when a printed part is pasted, the borrowing When the light-shielding frame on the front side of the adherend is cured by visible light or ultraviolet rays from the side, the visible light or ultraviolet rays from the front side cannot be cured, and the cured resin composition under the light-shielding frame also suffers from poor curing. presence.

本發明鑒於所述問題而形成，其目的在於提供一種例如當粘貼觸摸屏等顯示體所使用的裝飾板或圖示片時、當粘貼透明基板和透明基板的粘貼時、以及當粘貼顯示體和光學功能材料時，合適地使用的組合物。 The present invention has been made in view of the problems described above, and an object thereof is to provide, for example, when a decorative board or a graphic sheet used for a display body such as a touch screen is attached, when a transparent substrate and a transparent substrate are attached, and when a display body and an optical element are attached Functional materials are suitable compositions.

即，根據本發明，提供含有下述(P)、(C)~(F)的組合物。 That is, according to the present invention, a composition containing the following (P), (C) to (F) is provided.

(P)聚合性乙烯基單體 (P) Polymerizable vinyl monomer

(C)光聚合引發劑 (C) Photopolymerization initiator

(D)抗氧化劑 (D) Antioxidants

(E)硫醇 (E) Thiol

(F)二羧酸二酯 (F) Dicarboxylic acid diester

優選為所述(F)是由式(1)表示的二羧酸二酯的該組合物。 The composition (F) is preferably a dicarboxylic acid diester represented by the formula (1).

優選為所述(E)硫醇是聚硫醇(Polythiol)。 Preferably, the (E) mercaptan is a polythiol.

優選為所述(P)聚合性乙烯基單體含有(A)多官能(甲基)丙烯酸酯以及(B)單官能(甲基)丙烯酸酯的該組合物。 It is preferred that the (P) polymerizable vinyl monomer contains (A) a polyfunctional (meth) acrylate and (B) a monofunctional (meth) acrylate.

另外，優選為所述(A)多官能(甲基)丙烯酸酯是氨酯(甲基)丙烯酸酯(Urethane(meth)acrylate)的該組合物。 In addition, the composition in which the (A) polyfunctional (meth) acrylate is a urethane (meth) acrylate is preferred.

優選為所述(B)單官能(甲基)丙烯酸酯是含有從由羥基烷基(甲基)丙烯酸酯和烷基(甲基)丙烯酸酯構成的組中選擇出的一種以上的該組合物。 The (B) monofunctional (meth) acrylate is preferably a composition containing one or more kinds selected from the group consisting of a hydroxyalkyl (meth) acrylate and an alkyl (meth) acrylate. .

當設(P)聚合性乙烯基單體以及(F)二羧酸二酯合計為100質量份時，優選為所述(F)二羧酸二酯的含量是5~50質量份的該組合物。 When the total of (P) the polymerizable vinyl monomer and (F) the dicarboxylic acid diester is 100 parts by mass, it is preferable that the content of the (F) dicarboxylic acid diester is 5 to 50 parts by mass. Thing.

另外，根據本發明，提供含有該組合物的固化樹脂組合物。 The present invention also provides a cured resin composition containing the composition.

另外，根據本發明，提供含有該組合物的粘合劑組合物。 Moreover, according to this invention, the adhesive composition containing this composition is provided.

另外，根據本發明，提供該粘合劑組合物的固化體。 Moreover, according to this invention, the hardened | cured body of this adhesive composition is provided.

另外，根據本發明，提供由該固化體將被粘合體覆蓋或結合的複合體。 In addition, according to the present invention, there is provided a composite body in which the cured body is covered or bonded with an adherend.

優選為該被粘合體含有從由三醋酸纖維素、含氟聚合物、聚酯纖維、聚碳酸酯、聚烯烴、玻璃、金屬構成的組中選擇出的一種以上的該複合體。 The adherend preferably contains one or more kinds of the composite selected from the group consisting of cellulose triacetate, fluoropolymer, polyester fiber, polycarbonate, polyolefin, glass, and metal.

另外，根據本發明，提供藉由該粘合劑組合物將被粘合體粘貼的觸摸屏層疊體。 Moreover, according to this invention, the touchscreen laminated body by which the to-be-adhered body is stuck with this adhesive composition is provided.

另外，根據本發明，提供由該粘合劑組合物將被粘合體粘貼的液晶面板層疊體。 Moreover, according to this invention, the liquid-crystal-panel laminated body in which the to-be-adhered body was stuck with this adhesive composition is provided.

另外，根據本發明，提供使用該觸摸屏層疊體的顯示器。 Moreover, according to this invention, the display using this touchscreen laminated body is provided.

另外，根據本發明，提供使用該液晶面板層疊體的顯示器。 The present invention also provides a display using the liquid crystal panel laminate.

根據本發明，可以提供深部可固化性好的組合物。 According to the present invention, a composition having good deep curability can be provided.

以下，詳細說明本發明的實施方式。 Hereinafter, embodiments of the present invention will be described in detail.

本發明的組合物含有下述(P)、(C)~(F)。 The composition of the present invention contains the following (P), (C) to (F).

(P)聚合性乙烯基單體 (P) Polymerizable vinyl monomer

(C)光聚合引發劑 (C) Photopolymerization initiator

(D)抗氧化劑 (D) Antioxidants

(E)硫醇 (E) Thiol

(F)二羧酸二酯 (F) Dicarboxylic acid diester

根據該組成，可以提供一種固化樹脂組合物，該固化樹脂組合物例如當粘貼觸摸屏等顯示體所使用的裝飾板或圖示片時、粘貼透明基板和透明基板時、以及粘貼被印刷加工的部分時，在被粘合體正面因印刷等的遮光框使可見光或紫外線不能從正面到達的位置，是藉由來自側面的可見光或紫外線進行固化。 According to this composition, a cured resin composition can be provided, for example, when a decorative board or a graphic sheet used for a display body such as a touch panel is attached, when a transparent substrate and a transparent substrate are attached, and a portion to be printed is attached. At this time, in a position where the visible light or ultraviolet rays cannot be reached from the front side by a light-shielding frame such as printing on the front surface of the adherend, curing is performed by visible light or ultraviolet light from the side surface.

另外，根據該組成，可以提供深部固化好的組合物，因此，例如可以對遮光框下的固化樹脂組合物進行固化，可以具有抑制粘合劑的固化不良的效果。 In addition, according to this composition, since a deep-cured composition can be provided, for example, the cured resin composition under the light-shielding frame can be cured, and the effect of suppressing poor curing of the adhesive can be obtained.

在本發明的一實施方式中，組合物如上述那樣含有(P)、(C)~(F)，因此即使不使用異冰片(甲基)丙烯酸酯那樣的剛性的骨架的單體，也可以承受可靠性試驗。 In one embodiment of the present invention, since the composition contains (P), (C) to (F) as described above, it is possible to use the monomer without a rigid skeleton such as isobornyl (meth) acrylate. Withstand reliability tests.

<(P)聚合性乙烯基單體> <(P) polymerizable vinyl monomer>

作為(P)聚合性乙烯基單體，優選為(甲基)丙烯酸酯，更優選為含有(A)多官能(甲基)丙烯酸酯以及(B)單官能(甲基)丙烯酸酯。 The (P) polymerizable vinyl monomer is preferably a (meth) acrylate, and more preferably contains (A) a polyfunctional (meth) acrylate and (B) a monofunctional (meth) acrylate.

<(A)多官能(甲基)丙烯酸酯> <(A) Multifunctional (meth) acrylate>

所謂(A)多官能(甲基)丙烯酸酯是指具有兩個以上(甲基)丙烯醯基的(甲基)丙烯酸酯。作為多官能(甲基)丙烯酸酯，例如有在低聚物/聚合物末端或側鏈上兩個以上(甲基)丙烯醯化之多官能(甲基)丙烯酸酯的低聚物/聚合物等。 The (A) polyfunctional (meth) acrylate means a (meth) acrylate having two or more (meth) acrylfluorenyl groups. Examples of polyfunctional (meth) acrylates include oligomers / polymers of polyfunctional (meth) acrylates having two or more (meth) acrylic acids at the end or side chain of the oligomer / polymer. Wait.

例如，作為多官能(甲基)丙烯酸酯的低聚物/聚合物，例如有1,2-聚丁二烯末端氨酯(甲基)丙烯酸酯(urethane(meth)acrylate)(例如，日本曹達公司製“TEA-1000”)、1,2-聚丁二烯末端氨酯(甲基)丙烯酸酯的氫氧化物(例如，是指在對1,2-聚丁二烯骨架中的碳-碳結合附加氫的氫化聚丁二烯的兩末端具有(甲基)丙烯醯氧基的氨酯(甲基)丙烯酸酯。例如，日本曹達公司製“TEAI-1000”、大賽璐(DAICEL-ALLNEX)公司製“KRM-8776”、“KRM-8792”)、1，4-聚丁二烯末端氨酯(甲基)丙烯酸酯(例如，大阪有機化學公司製“BAC-45”)、聚異戊二烯末端(甲基)丙烯酸酯、聚酯型氨酯(甲基)丙烯酸酯(Urethane(meth)acrylate)(例如，日本合成公司製“UV-2000B”、“UV-3000B”、“UV-7000B”、根上工業公司製“KHP-11”、“KHP-17”)、聚醚氨酯(甲基)丙烯酸酯(例如，日本合成公司製“UV-3700B”、“UV-6100B”)、雙酚A型環氧(甲基)丙烯酸酯等。 For example, as an oligomer / polymer of a polyfunctional (meth) acrylate, there is 1,2-polybutadiene-terminated urethane (meth) acrylate (for example, Soda Japan "TEA-1000" manufactured by the company), 1,2-polybutadiene terminal urethane (meth) acrylate hydroxide (for example, refers to the carbon in the 1,2-polybutadiene skeleton- Carbon-bonded hydrogenated polybutadiene is a urethane (meth) acrylate having (meth) acryloxy groups at both ends. For example, "TEAI-1000" manufactured by Soda Co., Ltd., and DAICEL-ALLNEX ) "KRM-8776" and "KRM-8792" made by the company), 1,4-polybutadiene terminal urethane (meth) acrylate (for example, "BAC-45" made by Osaka Organic Chemical Co., Ltd.), polyiso Pentadiene-terminated (meth) acrylate, Urethane (meth) acrylate (for example, "UV-2000B", "UV-3000B", "UV" -7000B "," KHP-11 "and" KHP-17 "manufactured by Genjo Industrial Co., Ltd., and polyether urethane (meth) acrylate (for example," UV-3700B "and" UV-6100B "manufactured by Nippon Gosei) Bisphenol A epoxy ( Yl) acrylate.

另外，聚丁二烯末端(甲基)氨酯丙烯酸酯的分子結構的末端為(甲基)丙烯酸酯。 The molecular structure of the polybutadiene-terminated (meth) urethane acrylate is (meth) acrylate.

在上述記載的多官能(甲基)丙烯酸酯的低聚物/聚合物中，從效果大出發，優選氨酯(甲基)丙烯酸酯。 Among the polyfunctional (meth) acrylate oligomers / polymers described above, urethane (meth) acrylate is preferred because of its large effect.

另外，在氨酯(甲基)丙烯酸酯中，優選為由聚丁二烯氨酯(甲基)丙烯酸酯、聚丁二烯末端氨酯(甲基)丙烯酸酯的氫氧化物、聚酯型氨酯(甲基)丙烯酸酯以及聚醚氨酯(甲基)丙烯酸酯構成的組中的一種以上，更優選為聚丁二烯氨酯(甲基)丙烯酸酯和/或聚丁二烯末端氨酯(甲基)丙烯酸酯的氫氧化物，最優選聚丁二烯末端氨酯(甲基)丙烯酸酯的氫氧化物。 Among the urethane (meth) acrylates, polybutadiene urethane (meth) acrylate, polybutadiene-terminated urethane (meth) acrylate hydroxide, and polyester type are preferred. One or more of the group consisting of a urethane (meth) acrylate and a polyether urethane (meth) acrylate, more preferably a polybutadiene urethane (meth) acrylate and / or a polybutadiene terminal The urethane (meth) acrylate hydroxide is most preferably a polybutadiene-terminated urethane (meth) acrylate hydroxide.

另外，在聚丁二烯末端氨酯(甲基)丙烯酸酯的氫氧化物中，優選為1,2-聚丁二烯末端氨酯(甲基)丙烯酸酯的氫氧化物。在聚丁二烯氨酯(甲基)丙烯酸酯中，優選1，4-聚丁二烯末端氨酯(甲基)丙烯酸酯。 The hydroxide of the polybutadiene-terminated urethane (meth) acrylate is preferably a hydroxide of 1,2-polybutadiene-terminated urethane (meth) acrylate. Among polybutadiene urethane (meth) acrylates, 1,4-polybutadiene terminal urethane (meth) acrylates are preferred.

在此，所謂氨酯(甲基)丙烯酸酯是指在分子內具有氨酯鍵的氨酯(甲基)丙烯酸酯，所述氨酯(甲基)丙烯酸酯藉由使多元醇化合物(以下，以X表示)、有機聚異氰酸酯化合物(以下，以Y表示)以及羥基(甲基)丙烯酸酯(以下，以Z表示)進行反應(例如，縮聚反應)來得到。 Here, the urethane (meth) acrylate refers to a urethane (meth) acrylate having a urethane bond in the molecule, and the urethane (meth) acrylate is obtained by using a polyol compound (hereinafter, It is represented by X), an organic polyisocyanate compound (hereinafter, represented by Y), and a hydroxy (meth) acrylate (hereinafter, represented by Z) are reacted (for example, a polycondensation reaction) to obtain it.

作為多元醇化合物(X)，例如有乙二醇、二甘醇、三甘醇、四乙二醇、聚乙二醇、丙二醇、二丙二醇、聚丙二醇、丁二醇、1,4-丁二醇、聚丁二醇、1,5-戊二醇、1,6-己二醇、1,8-辛二醇、1,9-壬次甲基二醇、3-甲基-1,5-戊二醇、2,4-二乙基-1,5-戊二醇、2,2-丁基乙基-1,3-丙二醇、新戊二醇、環己烷二甲醇、氫化雙酚A、聚己內酯、三羥甲基乙烷、三羥甲基丙烷、聚三羥甲基丙烷、 季戊四醇、聚季戊四醇、山梨糖醇、甘露醇、甘油、聚甘油、聚四氫呋喃二醇等多元醇、具有聚氧化乙烯、聚環氧丙烷、環氧乙烷/環氧丙烷的塊或無規共聚合的至少一種結構的聚醚多元醇、作為該多元醇或聚醚多元醇與馬來酸酐、馬來酸、富馬酸、衣康酸酐、衣康酸、己二酸、間苯二甲酸等多元酸的縮合物的聚酯多元醇、己內酯改性聚四亞甲基多元醇等己內酯改性多元醇、聚烯烴多元醇、聚碳酸酯多元醇、聚丁二烯多元醇、聚異戊二烯多元醇、氫化聚丁二烯多元醇、氫化聚異戊二烯多元醇等聚二烯多元醇、聚二甲矽氧烷多元醇等聚矽氧烷多元醇等。 Examples of the polyol compound (X) include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butanediol, and 1,4-butanediol. Alcohol, polybutanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanemethyldiol, 3-methyl-1,5 -Pentanediol, 2,4-diethyl-1,5-pentanediol, 2,2-butylethyl-1,3-propanediol, neopentyl glycol, cyclohexanedimethanol, hydrogenated bisphenol A, polycaprolactone, trimethylolethane, trimethylolpropane, polytrimethylolpropane, Polyols such as pentaerythritol, polypentaerythritol, sorbitol, mannitol, glycerol, polyglycerol, polytetrahydrofurandiol, block or random copolymerization with polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide Polyether polyol with at least one structure, as the polyol or polyether polyol, with maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, isophthalic acid, etc. Acid-condensed polyester polyols, caprolactone-modified polytetramethylene polyols, and other caprolactone-modified polyols, polyolefin polyols, polycarbonate polyols, polybutadiene polyols, poly Polydiene polyols such as isoprene polyol, hydrogenated polybutadiene polyol, hydrogenated polyisoprene polyol, polysiloxanes such as polydimethylsiloxane, and the like.

其中，作為多元醇化合物(X)，優選為含有由聚丁二烯多元醇、氫化聚丁二烯多元醇、聚醚多元醇以及聚酯多元醇構成的組中的一種以上，更有選為氫化聚丁二烯多元醇。在氫化聚丁二烯多元醇中，優選為式(3)表示的化合物(n為正數)。 Among them, the polyol compound (X) is preferably one or more selected from the group consisting of polybutadiene polyol, hydrogenated polybutadiene polyol, polyether polyol, and polyester polyol, and more preferably Hydrogenated polybutadiene polyol. Among hydrogenated polybutadiene polyols, compounds represented by formula (3) (n is a positive number) are preferred.

在此，在聚丁二烯氨酯(甲基)丙烯酸酯中，例如多元醇化合物(X)為聚丁二烯多元醇。另外，在聚酯型氨酯(甲基)丙烯酸酯中，例如，多元醇化合物(X)是聚酯多元醇。另外，在聚酯型氨酯(甲基)丙烯酸酯中，例如多元醇化合物(X)為聚醚多元醇。 Here, in the polybutadiene urethane (meth) acrylate, for example, the polyol compound (X) is a polybutadiene polyol. In the polyester urethane (meth) acrylate, for example, the polyol compound (X) is a polyester polyol. In the polyester urethane (meth) acrylate, for example, the polyol compound (X) is a polyether polyol.

作為有機聚異氰酸酯化合物(Y)，不需要特別地限定，例如可以使用芳香族、脂肪族、環式脂肪族、脂環族等聚異氰酸酯。 The organic polyisocyanate compound (Y) is not particularly limited, and for example, polyisocyanates such as aromatic, aliphatic, cyclic aliphatic, and alicyclic can be used.

在聚異氰酸酯中，恰當地使用甲苯二異氰酸酯(TDI)、二苯基甲烷二異氰酸酯(MDI)、氫化二苯基甲烷二異氰酸酯(H-MDI)、多苯基甲烷多異氰酸酯(polyphenyl methane polyisocyanate)(粗製MDI)、改性二苯基甲烷二異氰酸酯(改性MDI)、氫化苯二亞甲基二異氰酸酯(H-XDI)、苯二亞甲基二異氰酸酯(XDI)、六亞甲基二異氰酸酯(HMDI)，三甲基六亞甲基二異氰酸酯(TMXDI)、四甲基苯二亞甲基二異氰酸酯(m-TMXDI)、異佛爾酮二異氰酸酯(IPDI)、降冰片烯二異氰酸酯(norbornene diisocyanate)(NBDI)，1,3-二(異氰酸根合甲基)環己烷(H6XDI)等聚異氰酸酯、這些聚異氰酸酯的三聚體化合物、或這些聚異氰酸酯與多元醇的反應生成物等。 Among polyisocyanates, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (H-MDI), polyphenylmethane polyisocyanate (polyphenylmethane polyisocyanate) ( Crude MDI), modified diphenylmethane diisocyanate (modified MDI), hydrogenated xylylene diisocyanate (H-XDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate ( HMDI), trimethylhexamethylene diisocyanate (TMXDI), tetramethylxylylene diisocyanate (m-TMXDI), isophorone diisocyanate (IPDI), norbornene diisocyanate (norbornene diisocyanate ) (NBDI), polyisocyanates such as 1,3-bis (isocyanatomethyl) cyclohexane (H6XDI), trimer compounds of these polyisocyanates, or reaction products of these polyisocyanates and polyols, and the like.

在以上之中，作為有機聚異氰酸酯化合物(Y)，優選為氫化苯二亞甲基二異氰酸酯(H-XDI)以及/或異佛爾酮二異氰酸酯(IPDI)，更優選為異佛爾酮二異氰酸酯(IPDI)。 Among the above, the organic polyisocyanate compound (Y) is preferably hydrogenated xylylene diisocyanate (H-XDI) and / or isophorone diisocyanate (IPDI), and more preferably isophorone di Isocyanate (IPDI).

作為羥基(甲基)丙烯酸酯(Z)，例如有2-羥乙基(甲基)丙烯酸酯、2-羥丙基(甲基)丙烯酸酯、2-羥丁基(甲基)丙烯酸酯、2-羥乙基(甲基)丙烯醯基磷酸酯、4-羥丁基(甲基)丙烯酸酯、2-(甲基)丙烯醯氧乙基-2-羥基鄰苯二甲酸酯(2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate)、甘油二(甲基)丙烯酸酯、2-羥基-3-(甲基)丙烯醯氧基丙烯酸酯(2-hydroxy-3-(meth)acryloyloxy acrylate)，己內酯改性2-羥乙基(甲基)丙烯酸酯、季戊 四醇三(甲基)丙烯酸酯，二季戊四醇五(甲基)丙烯酸酯、己內酯改性2-羥乙基(甲基)丙烯酸酯等。 Examples of the hydroxy (meth) acrylate (Z) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylfluorenyl phosphate, 4-hydroxybutyl (meth) acrylate, 2- (meth) acryloxyethyl-2-hydroxyphthalate (2 -(meth) acryloyloxyethyl-2-hydroxypropyl phthalate), glycerol di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxy acrylate (2-hydroxy-3- (meth) acryloyloxy acrylate) , Caprolactone modified 2-hydroxyethyl (meth) acrylate, pentaerythr Tetraol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, and the like.

在這些之中，作為羥基(甲基)丙烯酸酯(Z)，優選為羥基烷基(甲基)丙烯酸酯。在羥基烷基(甲基)丙烯酸酯中，優選含有由2-羥乙基(甲基)丙烯酸酯、2-羥丙基(甲基)丙烯酸酯、2-羥丁基(甲基)丙烯酸酯構成的組中的一種以上。 Among these, the hydroxy (meth) acrylate (Z) is preferably a hydroxyalkyl (meth) acrylate. The hydroxyalkyl (meth) acrylate preferably contains 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate One or more members of the group.

多官能(甲基)丙烯酸酯的重量平均分子量沒有特別地限定，優選為含有1000~60000，更優選為含有1500~40000。重量平均分子量藉由按照下述的條件，作為溶劑使用四氫呋喃，使用GPC系統(東曹公司製SC-8010)等，藉由市售的標準聚苯乙烯製成校正曲線來得到。 The weight average molecular weight of the polyfunctional (meth) acrylate is not particularly limited, but it is preferably 1,000 to 60,000, and more preferably 1,500 to 40,000. The weight average molecular weight is obtained by using a commercially available standard polystyrene as a calibration curve using tetrahydrofuran as a solvent, a GPC system (SC-8010 manufactured by Tosoh Corporation), and the like under the following conditions.

流速：1.0ml/min Flow rate: 1.0ml / min

設定溫度：40℃ Setting temperature: 40 ℃

柱形結構：東曹公司製“TSK guardcolumn MP(×L)”6.0mmID×4.0cm1根、以及東曹公司製“TSK-GELMULTIPOREHXL-M”7.8mmID×30.0cm(邏輯段數16，000段)2根，計3根(作為整體，理論板數32，000板)，樣品注入量：100μl(樣品溶劑濃度1mg/ml) Column structure: "TSK guardcolumn MP (× L)" made by Tosoh Corporation 6.0mmID x 4.0cm 1 and "TSK-GELMULTIPOREHXL-M" made by Tosoh Corporation 7.8mmID x 30.0cm (16,000 logical segments) 2 pcs, 3 pcs (as a whole, theoretical plate number 32,000), sample injection volume: 100 μl (sample solvent concentration 1mg / ml)

送液壓力：39kg/cm2 Delivery pressure: 39kg / cm 2

檢測器：RI檢測器 Detector: RI detector

<(B)單官能(甲基)丙烯酸酯> <(B) Monofunctional (meth) acrylate>

所謂(B)單官能(甲基)丙烯酸酯是指含有一個(甲基)丙烯醯基的(甲基)丙烯酸酯。在(B)單官能(甲基)丙烯酸酯中，優選為由羥基烷基(甲基)丙烯酸酯和烷基(甲基)丙烯酸酯構成的組中的一種以上，更優選並用羥基烷基(甲基)丙烯酸酯和烷基(甲基)丙烯酸酯。 The (B) monofunctional (meth) acrylate means a (meth) acrylate containing one (meth) acrylfluorenyl group. Among (B) monofunctional (meth) acrylates, one or more of the group consisting of a hydroxyalkyl (meth) acrylate and an alkyl (meth) acrylate is preferred, and a hydroxyalkyl ( (Meth) acrylates and alkyl (meth) acrylates.

另外，在本發明的一實施方式中，例如，也可以不使用異冰片(甲基)丙烯酸酯那樣的剛性的骨架的單體。這是因為本發明的一實施方式例如即使不使用異冰片(甲基)丙烯酸酯，在耐濕性試驗也可以示出良好的效果。 Moreover, in one embodiment of the present invention, for example, a rigid skeleton monomer such as isobornyl (meth) acrylate may not be used. This is because an embodiment of the present invention can exhibit a good effect in a moisture resistance test even if isobornyl (meth) acrylate is not used, for example.

在羥基烷基(甲基)丙烯酸酯中，優選由式(2)表示的(甲基)丙烯酸酯。 Among the hydroxyalkyl (meth) acrylates, a (meth) acrylate represented by the formula (2) is preferred.

式(2)Z-O-(R1-O-)p-H (2) ZO- (R 1 -O-) p -H

(Z表示(甲基)丙烯醯基，R1表示烯烴基，p表示1~10的整數。) (Z represents a (meth) acrylfluorenyl group, R1 represents an olefin group, and p represents an integer from 1 to 10.)

另外，式(2)中的R1的烯烴基的碳數優選為1~8，更優選為2~6。 The carbon number of the olefin group of R1 in the formula (2) is preferably 1 to 8, and more preferably 2 to 6.

作為羥基烷基(甲基)丙烯酸酯，例如有2-羥乙基(甲基)丙烯酸酯、2-羥丙基(甲基)丙烯酸酯、2-羥丁基(甲基)丙烯酸酯、二甘醇單(甲基)丙烯酸酯以及聚丙二醇(甲基)丙烯酸酯等。在這些中，在粘合性或耐濕性的方面，優選為2-羥丁基(甲基)丙烯酸酯。 Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and Glycol mono (meth) acrylate, polypropylene glycol (meth) acrylate, and the like. Among these, in terms of adhesiveness or moisture resistance, 2-hydroxybutyl (meth) acrylate is preferred.

在烷基(甲基)丙烯酸酯中，優選為(甲基)丙烯酸烷基酯。在烷基酯中，烷基的碳數優選為1~16，更優選為碳數2~14，最優選為碳數4~ 12，還優選為碳數6~10。烷基優選為飽和脂肪族烴基。另外，烷基優選為非取代。 Among the alkyl (meth) acrylates, alkyl (meth) acrylates are preferred. In the alkyl ester, the carbon number of the alkyl group is preferably 1 to 16, more preferably 2 to 14, and most preferably 4 to 4 carbons. 12, It is also preferably a carbon number of 6 to 10. The alkyl group is preferably a saturated aliphatic hydrocarbon group. The alkyl group is preferably unsubstituted.

作為烷基(甲基)丙烯酸酯，例如有甲基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、丙基(甲基)丙烯酸酯、丁基(甲基)丙烯酸酯、2-乙基己基(甲基)丙烯酸、N-辛基(甲基)丙烯酸酯、異辛基(甲基)丙烯酸酯、癸基(甲基)丙烯酸酯、異癸(甲基)丙烯酸酯、月桂基(甲基)丙烯酸酯、硬脂醯基(甲基)丙烯酸酯、異硬脂醯基(甲基)丙烯酸酯等。其中，在粘合性或耐濕性的方面，優選為辛基(甲基)丙烯酸酯，更優選為N-辛基(甲基)丙烯酸酯。 Examples of the alkyl (meth) acrylate include meth (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2- Ethylhexyl (meth) acrylic acid, N-octyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (Meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, and the like. Among these, in terms of adhesiveness or moisture resistance, an octyl (meth) acrylate is preferred, and an N-octyl (meth) acrylate is more preferred.

當設(P)以及(F)的合計量為100質量份時，(P)聚合性乙烯基單體的含量優選為50~95質量份，更優選為55~90質量份，最優選為60~80質量份。如果(P)聚合性乙烯基單體的含量為50質量份以上，則可以得到更好的固化，如果是95質量份以下，則可以進一步抑制粘合性的降低。另外，(P)聚合性乙烯基單體的含量例如也可以是50、51、54、55、56、59、60、61、65、69、70、71、75、79、80、81、85、89、90、91、94或95質量份，也可以是這些的任意的兩個值的範圍內。 When the total amount of (P) and (F) is 100 parts by mass, the content of the (P) polymerizable vinyl monomer is preferably 50 to 95 parts by mass, more preferably 55 to 90 parts by mass, and most preferably 60. ~ 80 parts by mass. If the content of the (P) polymerizable vinyl monomer is 50 parts by mass or more, better curing can be obtained, and if it is 95 parts by mass or less, a decrease in adhesiveness can be further suppressed. The content of the (P) polymerizable vinyl monomer may be, for example, 50, 51, 54, 55, 56, 59, 60, 61, 65, 69, 70, 71, 75, 79, 80, 81, 85. , 89, 90, 91, 94, or 95 parts by mass, or any two of these values.

當(P)聚合性乙烯基單體含有(A)多官能(甲基)丙烯酸酯以及(B)單官能(甲基)丙烯酸酯時，(A)多官能(甲基)丙烯酸酯以及(B)單官能(甲基)丙烯酸酯的含量在(A)多官能(甲基)丙烯酸酯以及(B)單官能(甲基)丙烯酸酯的合計100質量份中，按照質量比，優選為(A)：(B) =30~95：5~70，更優選為40~90：10~60，最優選為50~70：30~50。 When (P) the polymerizable vinyl monomer contains (A) a polyfunctional (meth) acrylate and (B) a monofunctional (meth) acrylate, (A) a polyfunctional (meth) acrylate and (B) The content of the monofunctional (meth) acrylate is preferably 100% by mass based on the total of (A) the polyfunctional (meth) acrylate and (B) the monofunctional (meth) acrylate. ): (B) = 30 ~ 95: 5 ~ 70, more preferably 40 ~ 90: 10 ~ 60, and most preferably 50 ~ 70: 30 ~ 50.

當(B)單官能(甲基)丙烯酸酯並用羥基烷基(甲基)丙烯酸酯和烷基(甲基)丙烯酸酯時，羥基烷基(甲基)丙烯酸酯和烷基(甲基)丙烯酸酯的含量在羥基烷基(甲基)丙烯酸酯和烷基(甲基)丙烯酸酯的合計100質量份中，按照質量比，優選為羥基烷基(甲基)丙烯酸酯：烷基(甲基)丙烯酸酯=5~70：30~95，更優選為10~50：50~90，最優選為20~40：60~80。 When (B) a monofunctional (meth) acrylate is used in combination with a hydroxyalkyl (meth) acrylate and an alkyl (meth) acrylate, a hydroxyalkyl (meth) acrylate and an alkyl (meth) acrylate The content of the ester is preferably 100% by mass based on the total of the hydroxyalkyl (meth) acrylate and the alkyl (meth) acrylate, and is preferably hydroxyalkyl (meth) acrylate: alkyl (methyl) in terms of mass ratio. ) Acrylate = 5 to 70: 30 to 95, more preferably 10 to 50: 50 to 90, and most preferably 20 to 40: 60 to 80.

<(C)光聚合引發劑> <(C) Photopolymerization Initiator>

(C)光聚合引發劑用於藉由可見光或紫外線的活性光線強化並促進樹脂組合物的光可固化。 (C) The photopolymerization initiator is used to strengthen and promote photo-curability of the resin composition by active light of visible light or ultraviolet light.

作為光聚合引發劑，例如有二苯甲酮及其衍生物、苄及其衍生物、蒽醌及其衍生物、苯偶姻、苯偶姻甲基醚、苯偶姻乙基醚、安息香丙醚、苯偶姻異丁基醚等安息香衍生物、苯偶醯二甲基縮酮、1-羥基環己基苯基甲酮、2-羥基-2-甲基-1-苯基-丙-1-酮等烷基苯衍生物，二乙氧基苯乙酮、4-叔丁基三氯苯乙酮(4-tert-butyl trichloro acetophenone)等苯乙酮衍生物、2-二甲氨基苯甲酸乙酯、p-二甲氨基苯甲酸乙酯、二苯二硫醚、噻噸酮及其衍生物、樟腦醌、7，7-二甲基-2，3-二氧雜二環(dioxobicyclo)〔2.2.1〕庚烷-1-羧酸、7，7-二甲基-2，3-二氧雜二環〔2.2.1〕庚烷-1-羧基-2-溴乙基酯、7，7-二甲基-2，3-二氧雜二環〔2.2.1〕庚烷-1-羧基-2-甲酯、7，7-二甲基-2，3-二氧雜二環〔2.2.1〕庚烷-1-甲醯氯等樟腦醌衍生物、2-甲基-1-〔4-(甲硫基)苯基〕-2-嗎啉基-1-丙酮、2-苄基-2-二甲氨基-1-(4-嗎啉基苯基)-丁酮-1等 α-氨基烷基苯衍生物、苯甲醯二苯基氧化膦、2，4，6-三甲基苯甲醯二苯基氧化膦、苯甲醯二乙氧基氧化膦、2，4，6-三甲基苯甲醯二甲氧基苯基氧化膦、2，4，6-三甲基苯甲醯二乙氧基苯基氧化膦、雙(2，4，6-三甲基苯甲醯)-苯基氧化膦等醯基氧化膦衍生物、氧基-苯基-醋酸2-〔2-氧基-2-苯基-乙醯氧基-乙氧基〕-乙酯以及氧-苯基-醋酸2-〔2-羥基-乙氧基〕-乙酯等。(C)光聚合引發劑可以組合使用一種或兩種以上。在所述中，從效果大的方面出發，(C)光聚合引發劑優選含有從由烷基苯衍生物和醯基氧化膦衍生物構成的群組中選擇出的一種以上，更優選並用烷基苯衍生物和醯基氧化膦衍生物。 Examples of the photopolymerization initiator include benzophenone and its derivatives, benzyl and its derivatives, anthraquinone and its derivatives, benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin Benzoin derivatives such as ether, benzoin isobutyl ether, benzoin dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1 -Alkyl benzene derivatives such as ketones, acetophenone derivatives such as diethoxyacetophenone, 4-tert-butyl trichloro acetophenone, 2-dimethylaminobenzoic acid Ethyl ester, p-dimethylaminobenzoate, diphenyl disulfide, thioxanthone and its derivatives, camphorquinone, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane-1-carboxylic acid, 7,7-dimethyl-2,3-dioxabicyclo [2.2.1] heptane-1-carboxy-2-bromoethyl ester, 7 , 7-dimethyl-2,3-dioxabicyclo [2.2.1] heptane-1-carboxy-2-methyl ester, 7,7-dimethyl-2,3-dioxabicyclo [2.2.1] Camphorquinone derivatives such as heptane-1-formamyl chloride, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinyl-1-acetone, 2- Benzyl-2-dimethylamino-1- (4-morpholine Phenyl) -butanone-1, etc. α-Aminoalkylbenzene derivatives, benzamidinediphenylphosphine oxide, 2,4,6-trimethylbenzamidinediphenylphosphine oxide, benzamidinediethoxyphosphine oxide, 2,4, 6-Trimethylbenzidine dimethoxyphenylphosphine oxide, 2,4,6-trimethylbenzidine diethoxyphenylphosphine oxide, bis (2,4,6-trimethylbenzene Formamidine) fluorenylphosphine oxide derivatives such as phenylphosphine oxide, oxy-phenyl-acetic acid 2- [2-oxy-2-phenyl-acetamido-ethoxy] -ethyl ester, and oxygen -Phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester and the like. (C) One or two or more photopolymerization initiators may be used in combination. Among the above, the (C) photopolymerization initiator preferably contains one or more selected from the group consisting of an alkylbenzene derivative and a fluorenylphosphine oxide derivative from the viewpoint of having a large effect, and it is more preferable to use an alkane in combination. Benzyl derivatives and fluorenyl phosphine oxide derivatives.

當並用烷基苯衍生物和醯基氧化膦衍生物時，其並用比例相對於醯基氧化膦衍生物100質量份，優選為烷基苯衍生物50~400質量份，更優選為100~300質量份，最優選為150~250質量份。 When an alkylbenzene derivative and a fluorenylphosphine oxide derivative are used in combination, the combined ratio is preferably 50 to 400 parts by mass of an alkylbenzene derivative, and more preferably 100 to 300 parts by weight relative to 100 parts by mass of the fluorenylphosphine oxide derivative. It is most preferably 150 to 250 parts by mass.

在烷基苯衍生物中，優選含有從由苯偶醯二甲基縮酮和1-羥基環己基苯基甲酮構成的組中選擇的一種以上。另外，在醯基氧化膦衍生物中，優選含有從由2，4，6-三甲基苯甲醯二苯基氧化膦和雙(2，4，6-三甲基苯甲醯)-苯基氧化膦構成的組中選擇出的一種以上。 The alkylbenzene derivative preferably contains one or more selected from the group consisting of benzophenone dimethyl ketal and 1-hydroxycyclohexylphenylmethyl ketone. In addition, the fluorenylphosphine oxide derivative preferably contains bis (2,4,6-trimethylbenzidine) -benzene from 2,4,6-trimethylbenzylhydrazone diphenylphosphine oxide. One or more selected from the group consisting of phosphine oxides.

當設(P)以及(F)的合計量為100質量份時，(C)光聚合引發劑的含量優選為0.01~10質量份，更優選為0.05~5質量份，最優選為0.1~1質量份。如果光聚合引發劑的含量為0.01質量份以上，則可以得到更好的固化，如果是10質量份以下，則可以得到更良好的深部固化。另外，(C)光聚合引發劑例如可以是0.01、0.02、0.03、0.04、0.05、0.06、0.09、1、1.01、 1.5、1.9、2、3、4、4.5、4.9、5、6、7、8、9或10質量份，也可以是這些的任意兩個值的範圍內。 When the total amount of (P) and (F) is 100 parts by mass, the content of the (C) photopolymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and most preferably 0.1 to 1 Parts by mass. If the content of the photopolymerization initiator is 0.01 parts by mass or more, better curing can be obtained, and if it is 10 parts by mass or less, deeper curing can be obtained more favorably. The (C) photopolymerization initiator may be, for example, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.09, 1, 1.01, or the like. 1.5, 1.9, 2, 3, 4, 4.5, 4.9, 5, 6, 7, 8, 9 or 10 parts by mass may be within a range of any two of these values.

<(D)抗氧化劑> <(D) Antioxidant>

(D)抗氧化劑可以提高儲存穩定性。 (D) Antioxidants can improve storage stability.

作為抗氧化劑，例如有甲基氫醌、對苯二酚、2,2-亞甲基-雙(4-甲基-6-叔丁基苯酚)、6-叔丁基-4-〔3-〔(2，4，8，10-四-tert-二叔丁基二苯〔d，f〕〔1，3，2〕二氧磷雜七-6-基)氧基]丙基]-2-甲基苯酚、鄰苯二酚、對羥基苯甲醚、單叔丁基對苯二酚、2,5-二叔丁基對苯二酚、P-苯醌、2,5-二苯基-P-苯醌、2,5-二叔丁基-P-苯醌、苦味酸、檸檬酸、吩噻嗪、對叔丁基鄰苯二酚、2-丁基-4-羥基茴香醚以及2,6-二叔丁基-p-甲酚等。 Examples of the antioxidant include methylhydroquinone, hydroquinone, 2,2-methylene-bis (4-methyl-6-tert-butylphenol), and 6-tert-butyl-4- [3- [(2,4,8,10-tetra-tert-di-tert-butyldiphenyl [d, f] [1,3,2] dioxo-hepta-6-yl) oxy] propyl] -2 -Methylphenol, catechol, p-hydroxyanisole, mono-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, P-benzoquinone, 2,5-diphenyl -P-benzoquinone, 2,5-di-tert-butyl-P-benzoquinone, picric acid, citric acid, phenothiazine, p-tert-butylcatechol, 2-butyl-4-hydroxyanisole, and 2,6-di-tert-butyl-p-cresol and the like.

(D)當(P)以及(F)的合計量為100質量份時，抗氧化劑的含量優選為含有0.001~0.5質量份，更優選為含有0.005~0.1質量份。如果抗氧化劑的含量為0.001質量份以上，則由於固化樹脂組合物的熱導致的著色或變色小，如果是0.5質量份以下則可以得到更好的深部固化。另外，(D)抗氧化劑例如也可以是0.001、0.002、0.003、0.004、0.005、0.006、0.009、0.010、0.011、0.04、0.05、0.06、0.07、0.08、0.09、0.10、0.20、0.30、0.40、0.45、0.49或0.5質量份，也可以是這些的任意兩個值的範圍內。 (D) When the total amount of (P) and (F) is 100 parts by mass, the content of the antioxidant is preferably 0.001 to 0.5 parts by mass, and more preferably 0.005 to 0.1 parts by mass. If the content of the antioxidant is 0.001 parts by mass or more, the coloring or discoloration due to heat of the cured resin composition is small, and if it is 0.5 parts by mass or less, better deep curing can be obtained. The (D) antioxidant may be, for example, 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.009, 0.010, 0.011, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.20, 0.30, 0.40, 0.45 , 0.49, or 0.5 parts by mass, or any two of these values.

<(E)硫醇> <(E) thiol>

所謂(E)硫醇是指含有一個以上的硫醇基的化合物。在硫醇中，在深部固化方面，優選為聚硫醇。所謂(E)聚硫醇是指含有兩個以上的硫醇基的化合物。作為聚硫醇，例如有季戊四醇四(3-巰基丁酸酯)、季戊四醇四(3-巰基丙酸酯)、三羥甲基丙烷三(3-巰基丙酸酯)、三羥甲基丙烷三硫代丙酸酯、季戊四醇四硫代丙酸酯、二季戊四醇六(3-巰基丙酸酯)、三〔(3-巰基丙醯氧基)-乙基〕異氰脲酸酯、3-巰基丁酸酯衍生物等。這些聚硫醇可以使用一種以上。 The (E) thiol means a compound containing one or more thiol groups. Among the thiols, polythiol is preferred in terms of deep curing. The (E) polythiol means a compound containing two or more thiol groups. Examples of the polythiol include pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tri (3-mercaptopropionate), and trimethylolpropane tri Thiopropionate, pentaerythritol tetrathiopropionate, dipentaerythritol hexa (3-mercaptopropionate), tris [(3-mercaptopropionyloxy) -ethyl] isocyanurate, 3-mercapto Butyrate derivatives, etc. These polythiols can be used in one kind or more.

在聚硫醇中，優選為3-巰基丁酸酯衍生物。作為3-巰基丁酸酯衍生物，例如有1，4-雙(3-巰基丁醯氧基)丁烷、1，3，5-三(3-巰基丁基乙氧基)-1，3，5-三嗪-2，4，6-(1H，3H，5H)-三酮，季戊四醇四(3-巰基丁酸酯)等。在聚硫醇中，優選為二級的聚硫醇。 Among polythiols, 3-mercaptobutyrate derivatives are preferred. Examples of the 3-mercaptobutyrate derivatives include 1,4-bis (3-mercaptobutoxy) butane, 1,3,5-tri (3-mercaptobutylethoxy) -1,3 , 5-triazine-2,4,6- (1H, 3H, 5H) -trione, pentaerythritol tetrakis (3-mercaptobutyrate) and the like. Among polythiols, secondary polythiols are preferred.

當設(P)以及(F)的合計量為100質量份時，(E)硫醇的含量優選為0.1~10質量份，更優選為0.5~5質量份。(E)硫醇的含量相對於(P)以及(F)的合計100質量份，如果是0.1質量份以上則可以得到更好的深部固化，如果是10質量份以下則由於固化樹脂組合物的熱導致的著色或變色變得更小。另外，(E)硫醇例如可以是0.1、0.2、0.3、0.4、0.5、0.6、0.9、1.0、2.0、3.0、4.0、4.5、4.9、5.0、6.0、7.0、8.0、9.0、9.9或10質量份，也可以是這些的任意兩個值的範圍內。 When the total amount of (P) and (F) is 100 parts by mass, the content of (E) mercaptan is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass. (E) The content of thiol is 100 parts by mass with respect to the total of (P) and (F). If it is 0.1 part by mass or more, deeper curing can be obtained better. If it is 10 parts by mass or less, the curing resin composition is The coloration or discoloration caused by heat becomes smaller. The (E) mercaptan may be, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.9, 1.0, 2.0, 3.0, 4.0, 4.5, 4.9, 5.0, 6.0, 7.0, 8.0, 9.0, 9.9, or 10 mass. The value may be within the range of any two of these values.

<(F)二羧酸二酯> <(F) Dicarboxylic acid diester>

作為(F)二羧酸二酯，優選為脂肪族二元酸雙酯。作為脂肪族二元酸雙酯，優選為由式(1)表示的化合物。 The (F) dicarboxylic acid diester is preferably an aliphatic dibasic acid diester. The aliphatic dibasic acid diester is preferably a compound represented by the formula (1).

R1、R2是碳原子數為1~18的烷基，R3是碳原子數為1~10的亞烷基，R1、R2可以相同，也可以不同。 R 1 and R 2 are alkyl groups having 1 to 18 carbon atoms, R 3 is an alkylene group having 1 to 10 carbon atoms, and R 1 and R 2 may be the same or different.

由式(1)表示的化合物的R1、R2優選為飽和脂肪族烴基。另外，所述R1、R2優選為非取代。所述R1、R2優選為碳數2~12的烷基，更優選為碳數4~10的烷基，最優選為碳數8的烷基。由式(1)表示的化合物的R3優選為飽和脂肪族烴基。另外，所述R3優選為非取代。所述R3優選為碳數4~10的烯烴基，更優選為碳數7~8的烯烴基，最優選為碳數8的烯烴基。 R1 and R2 of the compound represented by formula (1) are preferably a saturated aliphatic hydrocarbon group. The R1 and R2 are preferably unsubstituted. The R1 and R2 are preferably an alkyl group having 2 to 12 carbon atoms, more preferably an alkyl group having 4 to 10 carbon atoms, and most preferably an alkyl group having 8 carbon atoms. R3 of the compound represented by formula (1) is preferably a saturated aliphatic hydrocarbon group. In addition, R3 is preferably unsubstituted. The R3 is preferably an olefin group having 4 to 10 carbon atoms, more preferably an olefin group having 7 to 8 carbon atoms, and most preferably an olefin group having 8 carbon atoms.

(F)二羧酸二酯例如是用於使深部固化良好，調整粘度的化合物。作為由(F)化學式(1)表示的二羧酸二酯，例如有草酸二甲酯、草酸二乙酯、草酸二丙酯、草酸二異丙酯、草酸二丁酯、草酸二己酯、草酸二辛酯、丙二酸二異丙酯、丙二酸二丁酯、丁二酸二乙酯、丁二酸二丙酯、丁二酸二異丙酯、丁二酸二丁酯、丁二酸二叔丁基、丁二酸雙(2-乙基己基酯)、丁二酸雙(2-乙氧基乙酯)、戊二酸二乙酯、戊二酸二丁酯、己二酸二甲酯、 己二酸二乙酯、己二酸二丙酯、己二酸二異丙酯、己二酸二丁酯、己二酸二叔丁基、己二酸雙(2-乙基己基酯)、己二酸二辛酯、庚二酸二甲酯、庚二酸二乙酯、庚二酸二異丙酯、庚二酸二丁酯、辛二酸二甲酯、辛二酸二乙酯、辛二酸二丙酯、辛二酸二異丙酯、壬二酸二甲酯、壬二酸二乙酯、壬二酸二丙酯、壬二酸二異丙酯、壬二酸二丁酯、壬二酸雙(2-乙基己基酯)、癸二酸二甲酯、癸二酸二乙酯、癸二酸二丙酯、癸二酸二異丙酯、癸二酸二丁酯、癸二酸雙(2-乙基己基酯)等。這些二羧酸二酯可以使用一種以上。在(F)二羧酸二酯中，最優選癸二酸雙(2-乙基己基酯)。 (F) A dicarboxylic acid diester is a compound for hardening deep part, for example, and adjusting a viscosity. Examples of the dicarboxylic acid diester represented by (F) chemical formula (1) include dimethyl oxalate, diethyl oxalate, dipropyl oxalate, diisopropyl oxalate, dibutyl oxalate, dihexyl oxalate, Dioctyl oxalate, diisopropyl malonate, dibutyl malonate, diethyl succinate, dipropyl succinate, diisopropyl succinate, dibutyl succinate, butyl Di-tert-butyl diacid, bis (2-ethylhexyl) succinate, bis (2-ethoxyethyl) succinate, diethyl glutarate, dibutyl glutarate, adipic acid Dimethyl acid, Diethyl adipate, dipropyl adipate, diisopropyl adipate, dibutyl adipate, di-tert-butyl adipate, bis (2-ethylhexyl adipate), Dioctyl adipate, dimethyl pimelate, diethyl pimelate, diisopropyl pimelate, dibutyl pimelate, dimethyl suberate, diethyl suberate, Dipropyl suberate, Diisopropyl suberate, Dimethyl azelate, Diethyl azelate, Dipropyl azelate, Diisopropyl azelate, Dibutyl azelate , Bis (2-ethylhexyl ester) azelaate, dimethyl sebacate, diethyl sebacate, dipropyl sebacate, diisopropyl sebacate, dibutyl sebacate, Sebacic acid bis (2-ethylhexyl ester) and the like. These dicarboxylic acid diesters may be used singly or in combination. Among the (F) dicarboxylic acid diesters, bis (2-ethylhexyl ester) sebacate is most preferred.

當(P)以及(F)的合計量為100質量份時，(F)二羧酸二酯的含量優選為5~50質量份，更優選為10~45質量份，最優選為20~40質量份。(F)二羧酸二酯的含量如果為5質量份以上則可以得到更好的粘度和深部固化，如果是50質量份以下則可以得到更好的深部固化。另外，(F)二羧酸二酯的含量例如也可以是5、6、7、8、9、10、11、15、20、21、25、29、30、31、35、39、40、41、49或50質量份，也可以是這些的任意兩個值的範圍內。 When the total amount of (P) and (F) is 100 parts by mass, the content of the (F) dicarboxylic acid diester is preferably 5 to 50 parts by mass, more preferably 10 to 45 parts by mass, and most preferably 20 to 40. Parts by mass. (F) If the content of the dicarboxylic acid diester is 5 parts by mass or more, better viscosity and deep curing can be obtained, and if it is 50 parts by mass or less, better deep curing can be obtained. The content of the (F) dicarboxylic acid diester may be, for example, 5, 6, 7, 8, 9, 10, 11, 15, 20, 21, 25, 29, 30, 31, 35, 39, 40, 41, 49, or 50 parts by mass may be in the range of any two of these values.

本發明的一實施方式的組合物在不損害本發明的目的的範圍內，也可以使用一般使用的丙烯酸橡膠、氨酯橡膠、丙烯腈-丁二烯-苯乙烯橡膠等各種彈性體、極性有機溶劑等溶劑、填充劑、強化材料、塑化劑、增稠劑、染料、顏料、阻燃劑、矽烷偶聯劑以及表面活性劑等添加劑。 As long as the composition of one embodiment of the present invention does not impair the object of the present invention, various elastomers such as acrylic rubber, urethane rubber, acrylonitrile-butadiene-styrene rubber, and polar organics that are generally used may be used. Additives such as solvents, fillers, reinforcing materials, plasticizers, thickeners, dyes, pigments, flame retardants, silane coupling agents, and surfactants.

由本發明的一實施方式的組合物粘合的固化體在完全固化之後可以重做(重新利用)。作為重做的方法沒有特別地限制，可以藉由在粘貼的一種或兩種被粘合體間施加0.01~100N的負荷來使被粘合體彼此解體，重新利用解體後的被粘合體。 The cured body bonded with the composition according to an embodiment of the present invention can be redone (reused) after being completely cured. The method of redoing is not particularly limited, and the adherends can be disassembled by applying a load of 0.01 to 100 N between one or two adherends, and the disassembled adherend can be reused.

本發明的一實施方式的組合物例如是固化樹脂組合物，另外，可以作為粘合劑組合物來使用。本發明的一實施方式的組合物是例如在以波長365nm按照100mJ/cm2照射可見光或紫外線時，可以對大於3mm的、優選4mm以上的深部進行固化的組合物。本發明的一實施方式的組合物例如是在由被粘合體的正面側照射可見光或紫外線之後，由被粘合體的側面側照射可見光或紫外線沒有透過的位置，可以將被粘合體粘貼的粘合劑組合物。 The composition according to one embodiment of the present invention is, for example, a cured resin composition, and can also be used as an adhesive composition. The composition according to one embodiment of the present invention is a composition capable of curing a deep portion larger than 3 mm, preferably 4 mm or more, when visible light or ultraviolet light is irradiated at a wavelength of 365 nm at 100 mJ / cm 2 . The composition according to one embodiment of the present invention can irradiate visible light or ultraviolet light from the front side of the adherend, and irradiate the visible light or ultraviolet rays from the side of the adherend at a position where the visible light or ultraviolet rays are not transmitted. Adhesive composition.

本發明的一實施方式的粘合劑組合物例如藉由照射可見光或紫外線可以得到粘合劑組合物的固化體。 The adhesive composition according to one embodiment of the present invention can obtain a cured body of the adhesive composition by irradiating visible light or ultraviolet rays, for example.

藉由本發明的一實施方式的固化體可以得到覆蓋或結合被粘合體的複合體。另外，被粘合體沒有特別地限定，優選含有從三醋酸纖維素、含氟聚合物、聚酯纖維、聚碳酸酯、聚烯烴、玻璃、金屬構成的組中選擇的一種以上。 A cured body according to an embodiment of the present invention can obtain a composite body covering or bonding an adherend. The adherend is not particularly limited, but preferably contains one or more selected from the group consisting of cellulose triacetate, fluoropolymer, polyester fiber, polycarbonate, polyolefin, glass, and metal.

使用本發明的一實施方式的粘合劑組合物，藉由公知方法，可以得到將被粘合體粘貼的觸摸屏層疊體。 By using a pressure-sensitive adhesive composition according to an embodiment of the present invention, a touch screen laminate in which an adherend is pasted can be obtained by a known method.

另外，使用本發明的一實施方式的粘合劑組合物，藉由公知方法，可以製得將被粘合體粘貼的觸摸屏層疊體。另外，使用所述觸摸屏層疊體可以製得顯示器。 In addition, by using a pressure-sensitive adhesive composition according to an embodiment of the present invention, a touch screen laminate in which an adherend is pasted can be produced by a known method. In addition, a display can be produced using the touch screen laminate.

另外，使用本發明的一實施方式的粘合劑組合物，藉由公知方法，可以製得粘貼有被粘合體的液晶面板層疊體。另外，使用所述液晶面板層疊體可以製得顯示器。 In addition, by using a pressure-sensitive adhesive composition according to an embodiment of the present invention, a liquid crystal panel laminate to which an adherend is adhered can be produced by a known method. In addition, a display can be produced using the liquid crystal panel laminate.

【實施例】 [Example]

以下，列舉實驗例，更詳細地說明本發明，但本發明並不限定於此。 Hereinafter, the present invention will be described in more detail by giving experimental examples, but the present invention is not limited thereto.

(實驗例) (Experimental example)

只要沒有特別提及，就在23℃下進行實驗。調製表1、表2所示的組成的固化樹脂組合物並進行評估。表3、表4表示其結果。 Unless specifically mentioned, experiments were performed at 23 ° C. Cured resin compositions having the compositions shown in Tables 1 and 2 were prepared and evaluated. Table 3 and Table 4 show the results.

作為實驗例所述的固化樹脂組合物中的各成分，選擇以下的化合物。 As each component in the cured resin composition described in the experimental example, the following compounds were selected.

其中，表的KRM-8776記載了Daicel-Cytec製“KRM-8776”中所含有的氨酯丙烯酸酯的量。表的NOAA記載了Daicel-Cytec製“KRM-8776”中所含有的n-辛基丙烯酸酯的量。當不使用Daicel-Cytec製“KRM-8776”時，使用大阪有機化學公司製的n-辛基丙烯酸酯。 Here, KRM-8776 in the table describes the amount of urethane acrylate contained in "KRM-8776" manufactured by Daicel-Cytec. The NOAA in the table describes the amount of n-octyl acrylate contained in "KRM-8776" manufactured by Daicel-Cytec. When "KRM-8776" manufactured by Daicel-Cytec is not used, n-octyl acrylate manufactured by Osaka Organic Chemical Co., Ltd. is used.

<(P)聚合性乙烯基單體的(A)多官能(甲基)丙烯酸酯> <(A) Polyfunctional (meth) acrylate of (P) polymerizable vinyl monomer>

作為(A)成分的多官能(甲基)丙烯酸酯，選擇以下的化合物。 As the polyfunctional (meth) acrylate of the component (A), the following compounds were selected.

(A-1)聚酯型氨酯丙烯酸酯低聚物(根上工業公司製“KHP-11”，結 構如以下那樣，多元醇化合物是具有作為1,4-丁二醇與己二酸的縮合物的聚酯多元醇和作為乙二醇與己二酸的縮合物的聚酯多元醇的化合物(作為1,4-丁二醇與己二酸的縮合物的聚酯多元醇：作為乙二醇與己二酸的縮合物的聚酯多元醇=2：3(摩爾比))，有機聚異氰酸酯化合物為異佛爾酮二異氰酸酯，羥基(甲基)丙烯酸酯為2-丙烯酸羥乙酯，基於GPC的聚苯乙烯換算的重量平均分子量為25000) (A-1) Polyester type urethane acrylate oligomer ("KHP-11" manufactured by Genjo Industrial Co., Ltd., The polyol compound is a compound having a polyester polyol as a condensate of 1,4-butanediol and adipic acid and a polyester polyol as a condensate of ethylene glycol and adipic acid (as Polyester polyol of the condensation product of 1,4-butanediol and adipic acid: polyester polyol as the condensation product of ethylene glycol and adipic acid = 2: 3 (molar ratio)), organic polyisocyanate compound Isophorone diisocyanate, hydroxy (meth) acrylate is 2-hydroxyethyl acrylate, and weight average molecular weight in terms of polystyrene based on GPC is 25,000)

(A-2)聚酯型氨酯丙烯酸酯低聚物(日本合成化學公司製“UV-3000B”，另外，結構如以下那樣，多元醇化合物是作為氫化聚丁二烯多元醇與己二酸的縮合物的聚酯多元醇，有機聚異氰酸酯化合物是異佛爾酮二異氰酸酯，羥基(甲基)丙烯酸酯是4-羥基丁基丙烯酸酯，基於GPC的聚苯乙烯換算的重量平均分子量為15000，氫化聚丁二烯多元醇是由式(3)表示的化合物(n為正數)) (A-2) Polyester-type urethane acrylate oligomer ("UV-3000B" manufactured by Nippon Synthetic Chemical Co., Ltd.). The structure is as follows. The polyol compound is a hydrogenated polybutadiene polyol and adipic acid. Condensed polyester polyol, the organic polyisocyanate compound is isophorone diisocyanate, the hydroxy (meth) acrylate is 4-hydroxybutyl acrylate, and the weight-average molecular weight in terms of polystyrene based on GPC is 15,000 , Hydrogenated polybutadiene polyol is a compound represented by formula (3) (n is a positive number)

(A-3)聚丁二烯氨酯丙烯酸酯(Daicel-Cytec製“KRM-8776”是具有氫化聚丁二烯骨架的氨酯丙烯酸酯。另外，結構如以下那樣，多元醇化合物是氫化聚丁二烯多元醇，有機聚異氰酸酯化合物是異佛爾酮二異氰酸酯，羥基(甲基)丙烯酸酯是2-丙烯酸羥乙酯，基於GPC的聚苯乙烯換算的重量平均分子量為19000，氫化聚丁二烯多元醇為由式(3)表示的化合物(n為正數)，其中，作為稀釋單體含有n-辛基丙烯酸酯30質量%) (A-3) Polybutadiene urethane acrylate ("KRM-8776" manufactured by Daicel-Cytec is a urethane acrylate having a hydrogenated polybutadiene skeleton. In addition, the structure is as follows, and the polyol compound is a hydrogenated polymer Butadiene polyol, the organic polyisocyanate compound is isophorone diisocyanate, the hydroxy (meth) acrylate is 2-hydroxyethyl acrylate, the weight-average molecular weight in terms of polystyrene based on GPC is 19,000, and the hydrogenated polybutylene The diene polyol is a compound represented by the formula (3) (n is a positive number, and contains 30% by mass of n-octyl acrylate as a diluting monomer)

<(P)聚合性乙烯基單體的單官能(甲基)丙烯酸酯> <(P) Monofunctional (meth) acrylate of polymerizable vinyl monomer>

作為(B)成分的單官能(甲基)丙烯酸酯，選擇以下的化合物。 As the monofunctional (meth) acrylate of the component (B), the following compounds were selected.

(B-1)丙烯酸十二酯(大阪有機化學公司製“LA”) (B-1) Dodecyl acrylate ("LA" manufactured by Osaka Organic Chemical Co., Ltd.)

(B-2)2-羥基丁基丙烯酸酯(共榮公司化學公司製“HOB-A”) (B-2) 2-hydroxybutyl acrylate ("HOB-A" manufactured by Kyoei Chemical Co., Ltd.)

(B-3)n-辛基丙烯酸酯(以下簡稱為“NOAA”) (B-3) n-octyl acrylate (hereinafter referred to as "NOAA")

<(C)光聚合引發劑> <(C) Photopolymerization Initiator>

作為(C)成分的光聚合引發劑，選擇以下的化合物。 As the photopolymerization initiator of the component (C), the following compounds were selected.

(C-1)1-羥基環己基苯基甲酮(BASF公司製“Irgacure184”，以下簡稱為“I-184”) (C-1) 1-hydroxycyclohexyl phenyl ketone ("Irgacure184" manufactured by BASF, hereinafter referred to as "I-184")

(C-2)2，4，6-三甲基苯甲醯二苯基氧化膦(BASF公司製“LucirinTPO”，以下簡稱為“TPO”) (C-2) 2,4,6-trimethylbenzidine diphenylphosphine oxide ("LucirinTPO" manufactured by BASF, hereinafter referred to as "TPO")

<(D)抗氧化劑> <(D) Antioxidant>

作為(D)成分的抗氧化劑，選擇以下的化合物。 As the antioxidant of the component (D), the following compounds were selected.

(D-1)6-叔丁基-4-〔3-〔(2，4，8，10-四-叔丁基二苯〔d，f〕〔1，3，2］二氧磷雜七-6-基)氧〕丙基〕-2-甲酚(住友化學工業公司製“Sumilizer GP”)(以下簡稱為“GP”) (D-1) 6-tert-butyl-4- [3-[(2,4,8,10-tetra-tert-butyldiphenyl [d, f] [1,3,2] dioxophosphate -6-yl) oxy] propyl] -2-cresol ("Sumilizer GP" manufactured by Sumitomo Chemical Industries, Ltd.) (hereinafter referred to as "GP")

<(E)硫醇> <(E) thiol>

硫醇化合物選擇以下的化合物。 As the thiol compound, the following compounds were selected.

(E-1)季戊四醇四(3-巰基丁酸酯)(昭和電工公司製“Karenz MT PE1”)(以下簡稱為“MT-PE1”) (E-1) Pentaerythritol tetrakis (3-mercaptobutyrate) ("Karenz MT PE1" manufactured by Showa Denko Corporation) (hereinafter referred to as "MT-PE1")

(E-2)季戊四醇四(3-巰基丙酸酯)(SC有機化學製“PBMP”) (E-2) Pentaerythritol tetrakis (3-mercaptopropionate) ("PBMP" manufactured by SC Organic Chemistry)

(E-3)1-正十二硫醇(Sigma-Aldrich公司製“DDT”) (E-3) 1-N-dodecyl mercaptan ("DDT" manufactured by Sigma-Aldrich)

<(F)二羧酸二酯> <(F) Dicarboxylic acid diester>

作為將(F)由式(1)表示的二羧酸二酯，選擇以下的化合物。 As the dicarboxylic acid diester represented by the formula (1) (F), the following compounds were selected.

(F-1)癸二酸雙(2-乙基己基酯)(Sebacic acid bis(2-ethylhexyl))(新日本理化公司製“Sansocizer DOS”)(以下簡稱為“DOS”) (F-1) Sebacic acid bis (2-ethylhexyl) ("Sansocizer DOS" manufactured by Shin Nippon Chemical Co., Ltd.) (hereinafter referred to as "DOS")

(F-2)癸二酸二丁酯(Dibutyl sebacate)(和光純藥公司製)(以下簡稱為“DBS”) (F-2) Dibutyl sebacate (manufactured by Wako Pure Chemical Industries, Ltd.) (hereinafter referred to as "DBS")

(F-3)壬二酸雙(2-乙基己基酯)(Azelaic acid bis(2-ethylhexyl))(和光純藥公司製)(以下簡稱為“DOZ”) (F-3) Azelaic acid bis (2-ethylhexyl) (manufactured by Wako Pure Chemical Industries, Ltd.) (hereinafter referred to as "DOZ")

(F-4)己二酸雙(2-乙基己基酯)(Adipic acid bis(2-ethylhexyl))(和光純藥公司製)(以下簡稱為“DOA”) (F-4) Adipic acid bis (2-ethylhexyl) (manufactured by Wako Pure Chemical Industries, Ltd.) (hereinafter referred to as "DOA")

各種特性如以下那樣測量。 Various characteristics were measured as follows.

〔光可固化性〕 [Photocurable]

以溫度23℃來測量。關於光可固化性，對Tempax玻璃(寬度25mm×長度25mm×厚度2mm)的表面塗布厚度為0.1mm的固化樹脂組合物。之後，利用使用無極放電燈的Fusion公司製的固化裝置，以累積光量2000mJ/cm2的條件照射波長為365nm的UV光，並固化。 Measured at a temperature of 23 ° C. Regarding photocurability, a surface of Tempax glass (width 25 mm × length 25 mm × thickness 2 mm) was coated with a cured resin composition having a thickness of 0.1 mm. Thereafter, UV light having a wavelength of 365 nm was irradiated with a curing device made by Fusion Corporation using an electrodeless discharge lamp under a condition of a cumulative light amount of 2000 mJ / cm 2 and cured.

固化率使用FT-IR，根據以下的式子計算。碳與碳的雙鍵的吸收光譜使 用1600cm-1附近的峰值。 The curing rate was calculated using the following formula using FT-IR. The absorption spectrum of the carbon-carbon double bond uses a peak near 1600 cm -1 .

(固化率)=100-(固化後的、碳與碳的雙鍵的吸收光譜的強度)/(固化前的、碳與碳的雙鍵的吸收光譜的強度)×100(%) (Cure rate) = 100- (Intensity of absorption spectrum of carbon and carbon double bond after curing) / (Intensity of absorption spectrum of carbon and carbon double bond before curing) × 100 (%)

〔固化收縮率〕 〔Cure shrinkage rate〕

對比重瓶填充固化樹脂組合物，測量大氣中的品質以及純水中的品質，計算液體比重。進一步藉由〔光可固化〕所述的方法將固化樹脂組合物固化，製成寬度25mm×長度25mm×厚度2mm的固化物，測量大氣中的品質以及純水中的品質，計算固化物比重。根據液體比重以及固化物比重的比率計算固化收縮率。 The weight of the cured resin composition was compared with a heavy bottle, and the quality in the atmosphere and the quality in pure water were measured to calculate the specific gravity of the liquid. Further, the cured resin composition was cured by the method described in [Photocurable] to produce a cured product having a width of 25 mm × a length of 25 mm × a thickness of 2 mm. The quality in the atmosphere and the quality in pure water were measured to calculate the specific gravity of the cured product. The cure shrinkage was calculated from the ratio of the specific gravity of the liquid and the specific gravity of the cured product.

固化收縮率=((固化物比重-液比重)/固化物比重)×100(%) Curing shrinkage ratio = ((specific gravity of solidified product-specific gravity of liquid) / specific gravity of solidified product) × 100 (%)

〔深部固化〕 [Deep curing]

對直徑5mmφ的開有孔的長度20mm的黑色管填充固化樹脂組合物，從上部由不可見光照射100秒(累積光量為100mJ/cm2)1mW/cm2(365nm)的光。之後，從黑色管中取出固化物，除去未固化部分，由千分尺測量固化的部分的厚度。 A black tube having a hole length of 5 mm and a diameter of 20 mm was filled with a cured resin composition, and light from an upper part was irradiated with invisible light for 100 seconds (cumulative light amount was 100 mJ / cm 2 ) at 1 mW / cm 2 (365 nm). After that, the cured product was taken out from the black tube, the uncured portion was removed, and the thickness of the cured portion was measured with a micrometer.

〔聚對苯二甲酸乙二酯(PET)粘合性評估(聚對苯二甲酸乙二酯試驗片間的剝離粘合強度)〕 [Evaluation of polyethylene terephthalate (PET) adhesion (peel adhesion strength between polyethylene terephthalate test pieces)]

將固化樹脂組合物作為粘合劑組合物來使用，按照粘合層的厚度30μm 設粘合面積為縱向40mm×橫向10mm將雙軸向延伸PET膜(露米勒(Lumirror)T60、平均厚度190μm、東麗公司製)的試驗片(寬度50mm×長度10mm×厚度0.19mm)彼此粘結。藉由光照射固化後，拉伸由粘合劑組合物粘合的該試驗片沒有結合的兩處，從而使膜彼此結合的部分剝離，測量初始的180°剝離粘合強度。光照射條件按照〔光可固化性〕所述的方法。剝離粘合強度(單位：N/cm)使用拉伸試驗器在溫度23℃、濕度50%的環境下以拉伸速度50mm/分來測量。 The cured resin composition was used as an adhesive composition, and the thickness of the adhesive layer was 30 μm A test piece (width 50 mm × length 10 mm × thickness 0.19 mm) of a biaxially-stretched PET film (Lumirror T60, average thickness 190 μm, manufactured by Toray Co., Ltd.) was set with a bonding area of 40 mm in length and 10 mm in width. Bonding. After curing by light irradiation, two portions where the test piece bonded by the adhesive composition was not bonded were stretched to peel off portions where the films were bonded to each other, and the initial 180 ° peeling adhesive strength was measured. Light irradiation conditions were in accordance with the method described in [Photocurability]. The peeling adhesive strength (unit: N / cm) was measured using a tensile tester under a temperature of 23 ° C and a humidity of 50% at a tensile speed of 50 mm / min.

〔玻璃粘合性評估(耐熱玻璃試驗片間的拉伸粘合強度)〕 [Evaluation of glass adhesion (tensile adhesive strength between heat-resistant glass test pieces)]

將厚度80μm×寬度11.5mm×長度25mm的Teflon(注冊商標)膠帶作為墊片來使用，將固化樹脂組合物作為粘合劑組合物來使用，將耐熱玻璃試驗片(寬度25mm×長度25mm×厚度2.0mm)彼此粘合(粘合面積3cm2)。光照射條件按照〔光可固化〕所述的方法。在以所述條件使粘合劑組合物固化之後，還在試驗片的兩面使用電化學工業公司製的粘合劑組合物“G-55“，將鍍鋅鋼板(寬度100mm×長度25mm×厚度2.0mm，Engineering Test Service公司製)粘合。固化後，使用由粘合劑組合物粘合的該試驗片，扔掉鍍鋅鋼板，測量初始的拉伸剪斷粘合強度。拉伸剪斷粘合強度(單位：MPa)使用拉伸試驗器在溫度23℃、濕度50%的環境下以拉伸速度10mm/分來測量。 A Teflon (registered trademark) tape having a thickness of 80 μm × width 11.5 mm × length 25 mm was used as a gasket, a cured resin composition was used as an adhesive composition, and a heat-resistant glass test piece (width 25 mm × length 25 mm × thickness) was used. 2.0 mm) adhered to each other (adhesive area 3 cm 2 ). Light irradiation conditions were in accordance with the method described in [Photocurable]. After the adhesive composition was cured under the above-mentioned conditions, an adhesive composition "G-55" manufactured by Electrochemical Industries was used on both sides of the test piece, and a galvanized steel sheet (width 100 mm × length 25 mm × thickness 2.0mm, manufactured by Engineering Test Service). After curing, using this test piece bonded with the adhesive composition, the galvanized steel sheet was discarded, and the initial tensile shear adhesive strength was measured. The tensile shear adhesive strength (unit: MPa) was measured using a tensile tester under an environment of a temperature of 23 ° C and a humidity of 50% at a tensile speed of 10 mm / min.

〔環烯烴聚合物(COP)粘合性評估(環烯烴聚合物試驗片間的剝離粘合強度)〕 [Evaluation of cyclic olefin polymer (COP) adhesiveness (peel adhesion strength between cyclic olefin polymer test pieces)]

將固化樹脂組合物作為粘合劑組合物來使用，按照粘合層的厚度10μm設粘合面積為縱向40mm×橫向10mm將COP膜(ZEONOR、平均厚度40μm、日本Zeon公司製)的試驗片(寬度50mm×長度10mm×厚度0.04mm)彼此粘合。在藉由光照射固化後，藉由拉伸由粘合劑粘合的該試驗片沒有結合的兩處的膜端部，來使膜彼此結合的部分剝離，測量初始的180°剝離粘合強度。光照射條件按照〔光可固化〕所述的方法。剝離粘合強度(單位：N/cm)使用拉伸試驗器在溫度23℃、濕度50%的環境下以拉伸速度50mm/分來測量。 The cured resin composition was used as an adhesive composition, and a test piece of a COP film (ZEONOR, average thickness 40 μm, manufactured by Zeon Corporation of Japan) was set with an adhesive area of 40 mm in the longitudinal direction and 10 mm in the transverse direction according to the thickness of the adhesive layer 10 μm. Width 50 mm × length 10 mm × thickness 0.04 mm). After curing by light irradiation, the two end portions of the film that were not bonded by the test piece bonded by the adhesive were stretched to peel the portions where the films were bonded to each other, and the initial 180 ° peeling adhesive strength was measured . Light irradiation conditions were in accordance with the method described in [Photocurable]. The peeling adhesive strength (unit: N / cm) was measured using a tensile tester under a temperature of 23 ° C and a humidity of 50% at a tensile speed of 50 mm / min.

〔三醋酸纖維素粘合性評估(三醋酸纖維素試驗片間的剝離粘合強度)〕 [Evaluation of cellulose triacetate adhesion (peel adhesion strength between cellulose triacetate test pieces)]

將固化樹脂組合物作為粘合劑組合物來使用，按照粘合層的厚度10μm設粘合面積為縱向40mm×橫向10mm將三醋酸纖維素(TAC)膜(平均厚度40μm、富士膜公司製)的試驗片(寬度50mm×長度10mm×厚度0.04mm)彼此粘合。藉由拉伸由粘合劑組合物粘合的該試驗片沒有結合的兩處的膜端部，從而使膜彼此結合的部分剝離，測量初始的180°剝離粘合強度。在光照射進行固化後，藉由拉伸由粘合劑組合物粘合的該試驗片沒有結合的兩處的膜端部，從而使膜彼此結合的部分剝離，測量初始的180°剝離粘合強度。光照射條件按照〔光可固化〕所述的方法。剝離粘合強度(單位：N/cm)使用拉伸試驗器在溫度23℃、濕度50%的環境下以拉伸速度50mm/分進行測量。 A cured resin composition was used as the adhesive composition, and a thickness of the adhesive layer was 10 μm. The adhesive area was set to 40 mm in the vertical direction and 10 mm in the horizontal direction. A cellulose triacetate (TAC) film (average thickness: 40 μm, manufactured by Fujifilm Corporation) The test pieces (width 50 mm × length 10 mm × thickness 0.04 mm) were bonded to each other. The film-bonded portions were peeled off by stretching the film end portions of the test piece bonded by the adhesive composition at two places that were not bonded, and the initial 180 ° peeling adhesive strength was measured. After curing by light irradiation, two end portions of the film which were not bonded by the test piece bonded by the adhesive composition were stretched to peel off the portions where the films were bonded to each other, and the initial 180 ° peel adhesion was measured strength. Light irradiation conditions were in accordance with the method described in [Photocurable]. The peeling adhesive strength (unit: N / cm) was measured using a tensile tester under an environment of a temperature of 23 ° C and a humidity of 50% at a tensile speed of 50 mm / min.

〔含氟聚合物粘合性評估(含氟聚合物試驗片間的剝離粘合強度)〕 [Evaluation of Fluoropolymer Adhesion (Peel Adhesion Strength Between Fluoropolymer Test Pieces)]

將固化樹脂組合物作為粘合劑組合物來使用，按照粘合層的厚度10μm設粘合面積為縱向40mm×橫向10mm將PVDF(Polyvinylidene fluoride)膜(平均厚度40μm、電化學工業公司製“DX膜”)的試驗片(寬度50mm×長度10mm×厚度0.04mm)彼此粘合。藉由拉伸由粘合劑組合物粘合的該試驗片沒有結合的兩處的膜端部，從而使膜彼此結合的部分剝離，測量初始的180°剝離粘合強度。在由光照射固化後，藉由拉伸由粘合劑組合物粘合的該試驗片沒有結合的兩處的膜端部，從而使膜彼此結合的部分剝離，測量初始的180°剝離粘合強度。光照射條件按照〔光可固化〕所述的方法。剝離粘合強度(單位：N/cm)使用拉伸試驗器在溫度23℃、濕度50%的環境下以拉伸速度50mm/分來測量。 A cured resin composition was used as the adhesive composition, and a PVDF (Polyvinylidene fluoride) film (average thickness 40 μm, “DX” manufactured by Electrochemical Industries, Ltd.) was set to have a bonding area of 40 mm in the vertical direction and 10 mm in the lateral direction according to the thickness of the adhesive layer 10 μm. Film ") (50 mm in width x 10 mm in length x 0.04 mm in thickness) were bonded to each other. The film-bonded portions were peeled off by stretching the film end portions of the test piece bonded by the adhesive composition at two places that were not bonded, and the initial 180 ° peeling adhesive strength was measured. After curing by light irradiation, two end portions of the film which were not bonded by the test piece bonded by the adhesive composition were stretched to peel off portions where the films were bonded to each other, and the initial 180 ° peeling adhesion was measured strength. Light irradiation conditions were in accordance with the method described in [Photocurable]. The peeling adhesive strength (unit: N / cm) was measured using a tensile tester under a temperature of 23 ° C and a humidity of 50% at a tensile speed of 50 mm / min.

〔聚碳酸酯粘合性評估(聚碳酸酯試驗片間的拉伸粘合強度)〕 [Polycarbonate adhesion evaluation (tensile adhesive strength between polycarbonate test pieces)]

將厚度80μm×寬度12.5mm×長度25mm的Teflon(注冊商標)膠帶作為墊片來使用，將固化樹脂組合物作為粘合劑組合物來使用，將聚碳酸酯(帝人公司製“Panlite”)試驗片(寬度25mm×長度25mm×厚度2.0mm)彼此粘合(粘合面積3cm2)。光照射條件按照〔光可固化〕所述的方法。拉伸剪斷粘合強度(單位：MPa)使用拉伸試驗器在溫度23℃、濕度50%的環境下以拉伸速度10mm/分鐘進行測量。 A Teflon (registered trademark) tape with a thickness of 80 μm × width 12.5 mm × length 25 mm was used as a gasket, a cured resin composition was used as an adhesive composition, and polycarbonate (“Panlite” manufactured by Teijin Corporation) was tested. The sheets (width 25 mm × length 25 mm × thickness 2.0 mm) were adhered to each other (adhesion area 3 cm 2 ). Light irradiation conditions were in accordance with the method described in [Photocurable]. The tensile shear adhesive strength (unit: MPa) was measured using a tensile tester under an environment of a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / minute.

〔耐濕熱性評估(高溫高濕曝露後的耐熱玻璃試驗片間的拉伸粘合強度)〕 [Evaluation of damp heat resistance (tensile adhesive strength between heat-resistant glass test pieces after high temperature and high humidity exposure)]

將固化樹脂組合物作為粘合劑組合物來使用，按照粘合層的厚度100μm設粘合面積為1.0cm2使Tempax(注冊商標)玻璃(寬度25mm×長度25mm×厚度2mm)彼此粘合，並固化。光照射條件按照〔光可固化〕所述的方法。固化後，使用恒溫恒濕槽將由粘合劑組合物粘合的該試驗片在溫度85℃，相對濕度85%的環境下曝露1000小時。使用曝露後的試驗片，測量拉伸剪斷粘合強度。拉伸剪斷粘合強度(單位：MPa)使用拉伸試驗器在溫度23℃、濕度50%的環境下以拉伸速度10mm/分鐘來測量。 The cured resin composition was used as an adhesive composition, and Tempax (registered trademark) glass (width 25 mm × length 25 mm × thickness 2 mm) was adhered to each other by setting the adhesion area to 1.0 cm 2 according to the thickness of the adhesive layer 100 μm, And cured. Light irradiation conditions were in accordance with the method described in [Photocurable]. After curing, the test piece bonded with the adhesive composition was exposed to an environment of temperature 85 ° C. and relative humidity 85% using a constant temperature and humidity tank for 1000 hours. Using the exposed test piece, the tensile shear adhesive strength was measured. The tensile shear adhesive strength (unit: MPa) was measured using a tensile tester under an environment of a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / minute.

〔耐濕熱性評估(外觀觀察(表面精度變化和黃變度))〕 [Evaluation of Moisture and Heat Resistance (Appearance Observation (Change in Surface Accuracy and Yellowness))]

將固化樹脂組合物作為粘合劑組合物來使用，按照粘合層的厚度100μm設粘合面積為1.0cm2使Tempax(注冊商標)玻璃(寬度25mm×長度25mm×厚度2mm)彼此粘合，並固化。光照射條件按照〔光可固化〕所述的方法。固化後，使用恒溫恒濕槽將由粘合劑組合物粘合的該試驗片在溫度85℃、相對濕度85%的環境下曝露1000小時。曝露後，由顏色測量裝置(SHIMADZU公司製“UV-VISIBLE SPECTROPOHOTOMETER”測量由粘合劑組合物粘合的該試驗片的△b值，作為黃變度。曝露後，目視地觀察粘合部位的外觀，檢查作為表面精度變化，是否發生尺寸變化或彎曲並是否黃變。 The cured resin composition was used as an adhesive composition, and Tempax (registered trademark) glass (width 25 mm × length 25 mm × thickness 2 mm) was adhered to each other by setting the adhesion area to 1.0 cm 2 according to the thickness of the adhesive layer 100 μm, And cured. Light irradiation conditions were in accordance with the method described in [Photocurable]. After curing, the test piece bonded by the adhesive composition was exposed to an environment of a temperature of 85 ° C. and a relative humidity of 85% using a constant temperature and humidity tank for 1000 hours. After the exposure, the Δb value of the test piece bonded with the adhesive composition was measured by a color measuring device ("UV-VISIBLE SPECTROPOHOTOMETER" manufactured by Shimadzu Corporation) as the degree of yellowing. After the exposure, the adhesion portion was visually observed. The appearance is checked as a change in surface accuracy, whether a dimensional change or bending occurs, and whether it has yellowed.

根據實驗例，得到以下的判斷。相當於本發明的實施例的固化樹脂組合物的深部固化性良好。從而，例如，即使從遮光框的傾斜方向或橫向照射光，也可以使遮光框下的固化樹脂組合物固化到深部(即，位於深處的部位)。 Based on the experimental examples, the following judgments were obtained. The cured resin composition corresponding to an example of the present invention has good deep-part curability. Therefore, for example, even if light is irradiated from the oblique direction or the lateral direction of the light-shielding frame, the cured resin composition under the light-shielding frame can be cured to a deep portion (that is, a portion located deep).

另外，相當於本發明的實施例的固化樹脂組合物即使在遮光框下，藉由微弱的光(例如，累積光量1000~3000mJ/cm2的光)也可以固化到深部。 In addition, the cured resin composition corresponding to the embodiment of the present invention can be cured to a deep portion by a weak light (for example, light having a cumulative light amount of 1000 to 3000 mJ / cm 2 ) even under a light-shielding frame.

在相當於本發明的實施例的固化樹脂組合物的實驗例中，固化收縮率小，因此沒有發現耐濕熱性試驗後發生尺寸變化或彎曲等表面精度變化。在實驗例6中，(E)成分中的硫醇基數為一個，因此與使用實驗例2或實驗例3的聚硫醇的固化樹脂組合物相比，深部固化小。 In the experimental examples of the cured resin composition corresponding to the examples of the present invention, the curing shrinkage rate was small, so no change in surface accuracy such as dimensional change or warpage occurred after the moist heat resistance test. In Experimental Example 6, since the number of thiol groups in the component (E) is one, deep curing is smaller than that of the cured resin composition using the polythiol of Experimental Example 2 or Experimental Example 3.

相當於本發明的實施例的固化樹脂組合物不會產生在耐熱試驗後發生著色或變色、在耐濕試驗後發生強度降低等問題。 The cured resin composition corresponding to the examples of the present invention does not cause problems such as coloration or discoloration after the heat resistance test, and reduction in strength after the moisture resistance test.

Claims (14)

一種組合物，其含有(P)聚合性乙烯基單體、(C)光聚合引發劑、(D)抗氧化劑、(E)硫醇、(F)二羧酸二酯，所述(F)二羧酸二酯是由式(1)表示的二羧酸二酯，且所述式(1)為R1、R2是碳原子數為1~18的烷基，R3是碳原子數為1~10的亞烷基，R1、R2為相同或不同，而且，當所述(P)聚合性乙烯基單體以及所述(F)二羧酸二酯的合計為100質量份時，所述(F)二羧酸二酯的含量是5~50質量份。A composition comprising (P) a polymerizable vinyl monomer, (C) a photopolymerization initiator, (D) an antioxidant, (E) a thiol, (F) a dicarboxylic acid diester, and (F) The dicarboxylic acid diester is a dicarboxylic acid diester represented by the formula (1), and the formula (1) is R 1 and R 2 are alkyl groups having 1 to 18 carbon atoms, R 3 is an alkylene group having 1 to 10 carbon atoms, R 1 and R 2 are the same or different, and when (P) When the total of the polymerizable vinyl monomer and the (F) dicarboxylic acid diester is 100 parts by mass, the content of the (F) dicarboxylic acid diester is 5 to 50 parts by mass. 如請求項1所述的組合物，其中，所述(E)硫醇是聚硫醇。The composition according to claim 1, wherein the (E) thiol is a polythiol. 如請求項1或2中所述的組合物，其中，所述(P)聚合性乙烯基單體含有(A)多官能(甲基)丙烯酸酯以及(B)單官能(甲基)丙烯酸酯。The composition according to claim 1 or 2, wherein the (P) polymerizable vinyl monomer contains (A) a polyfunctional (meth) acrylate and (B) a monofunctional (meth) acrylate . 如請求項3所述的組合物，其中，所述(A)多官能(甲基)丙烯酸酯是氨酯(甲基)丙烯酸酯(Urethane(meth)acrylate)。The composition according to claim 3, wherein the (A) polyfunctional (meth) acrylate is a urethane (meth) acrylate. 如請求項3所述的組合物，其中，所述(B)單官能(甲基)丙烯酸酯含有從由羥基烷基(甲基)丙烯酸酯和烷基(甲基)丙烯酸酯構成的群組中選擇出的一種以上。The composition according to claim 3, wherein the (B) monofunctional (meth) acrylate contains a group consisting of a hydroxyalkyl (meth) acrylate and an alkyl (meth) acrylate More than one selected. 一種固化樹脂組合物，其中，含有請求項1~5的任意一項中所述的組合物。A cured resin composition containing the composition described in any one of claims 1 to 5. 一種粘合劑組合物，其中，含有請求項1~5的任意一項中所述的組合物。An adhesive composition containing the composition as described in any one of Claims 1-5. 一種如請求項7所述之粘合劑組合物的固化體。A cured body of the adhesive composition according to claim 7. 一種複合體，其中，藉由如請求項8所述的固化體將被粘合體覆蓋或結合而製得。A composite produced by covering or bonding a cured body according to claim 8 with an adherend. 如請求項9所述的複合體，其中，所述被粘合體含有從由三醋酸纖維素、含氟聚合物、聚酯纖維、聚碳酸酯、聚烯烴、玻璃、金屬構成的群組中選擇出一種以上。The composite according to claim 9, wherein the adherend comprises a group consisting of cellulose triacetate, fluoropolymer, polyester fiber, polycarbonate, polyolefin, glass, and metal Choose more than one. 一種觸摸屏層疊體，其中，藉由如請求項7所述的粘合劑組合物來粘貼被粘合體。A touch screen laminate in which an adherend is adhered with the adhesive composition according to claim 7. 一種液晶面板層疊體，其中，藉由如請求項7所述的粘合劑組合物來粘貼被粘合體。A liquid crystal panel laminate in which an adherend is adhered with the adhesive composition according to claim 7. 一種顯示器，其中，使用如請求項11所述的觸摸屏層疊體。A display using the touch screen laminate according to claim 11. 一種顯示器，其中，使用如請求項12所述的液晶面板層疊體。A display using the liquid crystal panel laminate according to claim 12.
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