TWI781208B - Moisture-curable resin compositions, adhesives for electronic parts, and adhesives for display elements - Google Patents

Moisture-curable resin compositions, adhesives for electronic parts, and adhesives for display elements Download PDF

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TWI781208B
TWI781208B TW107127963A TW107127963A TWI781208B TW I781208 B TWI781208 B TW I781208B TW 107127963 A TW107127963 A TW 107127963A TW 107127963 A TW107127963 A TW 107127963A TW I781208 B TWI781208 B TW I781208B
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moisture
curable resin
meth
resin composition
acrylate
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TW201920521A (en
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結城彰
高橋徹
木田拓身
玉川智一
徐坤
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日商積水化學工業股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09J201/10—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups

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Abstract

本發明之目的在於提供一種著色性及硬化性優異，且可抑制褪色之濕氣硬化型樹脂組成物。又，本發明之目的在於提供一種使用該濕氣硬化型樹脂組成物而成之電子零件用接著劑及顯示元件用接著劑。本發明係一種含有濕氣硬化型樹脂與感光性著色劑之濕氣硬化型樹脂組成物。An object of the present invention is to provide a moisture-curable resin composition that is excellent in colorability and curability, and can suppress discoloration. Moreover, the object of this invention is to provide the adhesive agent for electronic parts and the adhesive agent for display elements which use this moisture hardening type resin composition. The present invention is a moisture-curable resin composition containing moisture-curable resin and photosensitive colorant.

Description

濕氣硬化型樹脂組成物、電子零件用接著劑及顯示元件用接著劑Moisture curable resin composition, adhesive for electronic parts and adhesive for display element

本發明係關於一種著色性及硬化性優異，且可抑制褪色之濕氣硬化型樹脂組成物。又，本發明係關於一種使用該濕氣硬化型樹脂組成物而成之電子零件用接著劑及顯示元件用接著劑。The present invention relates to a moisture-curable resin composition that is excellent in colorability and curability, and can suppress fading. Also, the present invention relates to an adhesive for electronic parts and an adhesive for display elements using the moisture-curable resin composition.

近年來，作為具有薄型、輕量、低耗電等特徵之顯示元件，廣泛使用液晶顯示元件、有機EL顯示元件等。於該等顯示元件中，通常於液晶或發光層之密封、基板、光學膜、保護膜等各種構件之接著等中使用由樹脂組成物構成之接著劑。 又，近年來，對於半導體晶片等電子零件，要求高積體化、小型化，例如進行經由接著劑層將複數個較薄之半導體晶片接合而製成半導體晶片之積層體。此種半導體晶片之積層體例如係藉由於一導體晶片上塗佈接著劑後，經由該接著劑而將另一導體晶片積層，其後使接著劑硬化之方法；或隔開一定之間隔而於所保持之半導體晶片間填充接著劑，其後使接著劑硬化之方法等而製造。In recent years, liquid crystal display elements, organic EL display elements, and the like have been widely used as display elements featuring thinness, light weight, and low power consumption. In these display elements, adhesives made of resin compositions are generally used for sealing liquid crystals and light-emitting layers, and for bonding various members such as substrates, optical films, and protective films. In addition, in recent years, electronic parts such as semiconductor chips have been required to be highly integrated and miniaturized. For example, a plurality of thin semiconductor chips are bonded through an adhesive layer to form a laminate of semiconductor chips. Such a laminate of semiconductor wafers is, for example, a method in which an adhesive is coated on one conductor wafer, another conductor wafer is laminated through the adhesive, and then the adhesive is hardened; Manufactured by filling an adhesive between held semiconductor wafers and then hardening the adhesive.

作為用於顯示元件或電子零件之接著劑，為了確認接著狀態，提高隱蔽性或遮光性，使用含有著色劑之接著劑。例如，於專利文獻1中，揭示有含有著色劑之光硬化性著色接著劑。然而，專利文獻1中所揭示之光硬化性著色接著劑係使用碳黑等作為著色劑，使用以使硬化性樹脂光硬化所照射之紫外線等活性能量線之大部分被該碳黑等著色劑吸收。因此，若為了提高著色性而增加該著色劑之摻合量，則有所獲得之接著劑成為硬化性（深部硬化性）較差者之問題。Adhesives used for display devices and electronic parts use adhesives containing colorants in order to confirm the bonding state and improve concealment or light-shielding properties. For example, Patent Document 1 discloses a photocurable colored adhesive agent containing a colorant. However, the photocurable colored adhesive disclosed in Patent Document 1 uses carbon black or the like as a colorant, and most of the active energy rays such as ultraviolet rays irradiated so that the curable resin is photohardened are absorbed by the colorant such as carbon black. absorb. Therefore, if the blending amount of the coloring agent is increased in order to improve the coloring property, there is a problem that the obtained adhesive is poor in curability (deep curability).

作為一面抑制硬化性之降低一面提高接著劑之著色性之方法，考慮使用感光性著色劑之方法。例如，於專利文獻2中，揭示有使用無色染料（leuco dye）作為感光性著色劑之光硬化性樹脂組成物。然而，於在光硬化性樹脂組成物中摻合此種感光性著色劑之情形時，有即便暫時著色，其後亦有於硬化物產生褪色之情況之問題。 [先前技術文獻] [專利文獻]As a method of improving the colorability of an adhesive while suppressing a decrease in curability, a method of using a photosensitive colorant is conceivable. For example, Patent Document 2 discloses a photocurable resin composition using a leuco dye as a photosensitive colorant. However, when such a photosensitive colorant is mixed with a photocurable resin composition, there is a problem that even if it is colored once, the cured product may fade in color thereafter. [Prior Art Document] [Patent Document]

專利文獻1：日本特開2014-25021號公報 專利文獻2：國際公開第2016/129568號Patent Document 1: Japanese Patent Laid-Open No. 2014-25021 Patent Document 2: International Publication No. 2016/129568

[發明所欲解決之問題][Problem to be solved by the invention]

本發明之目的在於提供一種著色性及硬化性優異，且可抑制褪色之濕氣硬化型樹脂組成物。又，本發明之目的在於提供一種使用該濕氣硬化型樹脂組成物而成之電子零件用接著劑及顯示元件用接著劑。 [解決問題之技術手段]An object of the present invention is to provide a moisture-curable resin composition that is excellent in colorability and curability, and can suppress discoloration. Moreover, the object of this invention is to provide the adhesive agent for electronic parts and the adhesive agent for display elements which use this moisture hardening type resin composition. [Technical means to solve the problem]

本發明係一種含有濕氣硬化型樹脂與感光性著色劑之濕氣硬化型樹脂組成物。 以下，詳細敘述本發明。The present invention is a moisture-curable resin composition containing moisture-curable resin and photosensitive colorant. Hereinafter, the present invention will be described in detail.

本發明者等人驚奇地發現：藉由於含有濕氣硬化型樹脂之濕氣硬化型樹脂組成物中摻合感光性著色劑作為著色劑，可獲得著色性及硬化性優異，且可抑制於使用感光性著色劑之情形時成為問題之褪色之濕氣硬化型樹脂組成物，從而完成本發明。The inventors of the present invention surprisingly found that by blending a photosensitive colorant as a colorant into a moisture-curable resin composition containing a moisture-curable resin, excellent colorability and curability can be obtained, and the use can be suppressed. In the case of a photosensitive colorant, a moisture-curing type resin composition in which discoloration becomes a problem has been solved, and the present invention has been accomplished.

本發明之濕氣硬化型樹脂組成物含有感光性著色劑。藉由含有上述感光性著色劑，而本發明之濕氣硬化型樹脂組成物成為著色性及硬化性（尤其是深部硬化性）優異者。又，本發明之濕氣硬化型樹脂組成物可抑制於使用上述感光性著色劑之情形時成為問題之褪色。 再者，於本說明書中，所謂上述「感光性著色劑」，意指具有藉由光照射而變色（顯色）之特性之材料。The moisture-curable resin composition of the present invention contains a photosensitive colorant. By containing the above-mentioned photosensitive colorant, the moisture-curable resin composition of the present invention is excellent in colorability and curability (particularly, deep curability). Moreover, the moisture-curable resin composition of this invention can suppress the discoloration which becomes a problem when using the said photosensitive colorant. In addition, in this specification, the said "photosensitive colorant" means the material which has the characteristic which changes color (color development) by light irradiation.

作為於本發明之濕氣硬化型樹脂組成物中，即便使用上述感光性著色劑，亦可抑制褪色之理由，考慮如下。 即，上述感光性著色劑通常係藉由光照射而直接或間接地進行反應（著色反應），藉此感光性著色劑之化學結構變化並著色。然而，於著色後進行該著色反應之逆反應之情形時，產生褪色。於本發明之濕氣硬化型樹脂組成物中，藉由著色後之感光性著色劑與下述之濕氣硬化型樹脂反應，而防止著色反應之逆反應進行。其結果為，認為發揮抑制褪色之效果。The reason why discoloration can be suppressed even if the above-mentioned photosensitive colorant is used in the moisture-curable resin composition of the present invention is considered as follows. That is, the above-mentioned photosensitive colorant usually directly or indirectly reacts (coloring reaction) by light irradiation, whereby the chemical structure of the photosensitive colorant is changed and colored. However, when the reverse reaction of the coloring reaction proceeds after coloring, discoloration occurs. In the moisture-curable resin composition of the present invention, the reverse reaction of the coloring reaction is prevented by reacting the colored photosensitive colorant with the moisture-curable resin described below. As a result, it is considered that the effect of suppressing fading is exhibited.

作為上述感光性著色劑，例如可列舉：無色染料、光致變色色素等。其中，就提高光學密度（OD值），呈現更優異之遮光性之觀點而言，較佳為無色染料。As said photosensitive coloring agent, a leuco dye, a photochromic dye, etc. are mentioned, for example. Among these, leuco dyes are preferred from the viewpoint of increasing the optical density (OD value) and exhibiting more excellent light-shielding properties.

作為上述無色染料，例如可列舉：結晶紫內酯、孔雀綠內酯、3,3-雙(對二甲基胺基苯基)-6-胺基酞內酯、3,3-雙(對二甲基胺基苯基)-6-(對甲苯磺醯胺)酞內酯、3,3-雙(2-(對二甲基胺基苯基)-2-(4-甲氧基苯基)乙烯基)-4,5,6,7-四氯酞內酯、3-二甲基胺基-6-甲基-7-氯螢光黃母體、3-二甲基胺基-6-甲基-7-苯胺基螢光黃母體、3-二乙基胺基-7-氯螢光黃母體（3-diethylamino-7-chlorofluoran）、3-二乙基胺基-7-(鄰氯苯胺基)螢光黃母體、3-二乙基胺基-7-(間三氟甲基苯胺基)螢光黃母體、3-二乙基胺基-7-苯基螢光黃母體、3-二乙基胺基-7-苯基螢光黃母體、3-二乙基胺基-7,8-二苯并螢光黃母體、3-二乙基胺基-5-甲基-7-二苄基胺基螢光黃母體、3-二乙基胺基-6-甲基-7-(鄰,對二甲基苯胺基)螢光黃母體、3-二乙基胺基-7-(鄰氟苯胺基)螢光黃母體、3-二乙基胺基-6-甲基-7-氯螢光黃母體、3-二乙基胺基-6-甲基螢光黃母體、3-二乙基胺基-6-甲基-7-苯胺基螢光黃母體、3-二丙基胺基-6-甲基-7-苯胺基螢光黃母體、3-二戊基胺基-6-甲基-7-苯胺基螢光黃母體、3-二乙基胺基苯并[a]螢光黃母體、3-二丁基胺基-7-(鄰氯苯胺基)螢光黃母體、3-二丁基胺基-6-甲基-7-苯胺基螢光黃母體、3-二丁基胺基-7-氟苯胺基螢光黃母體、3-二戊基胺基-6-甲基-7-苯胺基螢光黃母體、3-異戊基乙基胺基-6-甲基-7-苯胺基螢光黃母體、3-(N-甲基-N-丙基胺基)-6-甲基-7-苯胺基螢光黃母體、3-(N-乙基-N-異丁基胺基)-6-甲基-7-苯胺基螢光黃母體、3-環己基胺基-6-氯螢光黃母體、3-吡咯啶酮-6-甲基-7-苯胺基螢光黃母體、3-哌啶基-6-甲基-7-苯胺基螢光黃母體、3-(N-乙基-N-異戊基胺基)-6-甲基-7-苯胺基螢光黃母體、3-(N-甲基-N-環己基胺基)-6-甲基-7-苯胺基螢光黃母體、2-(N-甲基-N-苯基胺基)-6-(N-乙基-N-對甲苯胺基)螢光黃母體、3-(N-乙基-N-對甲苯胺基)-6-甲基-7-苯胺基螢光黃母體、3-(N-乙基-N-四氫呋喃甲基胺基)-6-甲基-7-苯胺基螢光黃母體、1,3,3-三甲基-6'-氯-8'-甲氧基吲哚酮苯并螺吡喃、2'-苯胺基-3'-甲基-6'-(二戊基胺基)螺[異苯并呋喃-1(3H),9'-[9H]口星]-3-酮等。其中，較佳為下述式（1）所表示之化合物。Examples of the above-mentioned leuco dyes include crystal violet lactone, malachite green lactone, 3,3-bis(p-dimethylaminophenyl)-6-aminophthalide, 3,3-bis(p- Dimethylaminophenyl)-6-(p-toluenesulfonamide)phthalide, 3,3-bis(2-(p-dimethylaminophenyl)-2-(4-methoxybenzene Base) vinyl) -4,5,6,7-tetrachlorophthalide, 3-dimethylamino-6-methyl-7-chlorofluorescent yellow precursor, 3-dimethylamino-6 -Methyl-7-anilinofluorescent yellow precursor, 3-diethylamino-7-chlorofluorescent yellow precursor (3-diethylamino-7-chlorofluororan), 3-diethylamino-7-(o Chloroanilino) fluorescent yellow precursor, 3-diethylamino-7-(m-trifluoromethylanilino) fluorescent yellow precursor, 3-diethylamino-7-phenyl fluorescent yellow precursor, 3-diethylamino-7-phenyl fluorescent yellow precursor, 3-diethylamino-7,8-dibenzo fluorescent yellow precursor, 3-diethylamino-5-methyl- 7-dibenzylamino fluorescent yellow precursor, 3-diethylamino-6-methyl-7-(o, p-dimethylanilino) fluorescent yellow precursor, 3-diethylamino- 7-(o-fluoroanilino) fluorescent yellow precursor, 3-diethylamino-6-methyl-7-chloro fluorescent yellow precursor, 3-diethylamino-6-methyl fluorescent yellow precursor , 3-diethylamino-6-methyl-7-anilino fluorescent yellow precursor, 3-dipropylamino-6-methyl-7-anilino fluorescent yellow precursor, 3-dipentyl Amino-6-methyl-7-anilinofluorescent yellow precursor, 3-diethylaminobenzo[a] fluorescent yellow precursor, 3-dibutylamino-7-(o-chloroanilino) Fluorescent yellow precursor, 3-dibutylamino-6-methyl-7-anilinyl fluorescent yellow precursor, 3-dibutylamino-7-fluoroanilinyl fluorescent yellow precursor, 3-dipentyl Amino-6-methyl-7-anilino fluorescent yellow precursor, 3-isoamylethylamino-6-methyl-7-anilino fluorescent yellow precursor, 3-(N-methyl-N -Propylamino)-6-methyl-7-anilinofluorescent yellow precursor, 3-(N-ethyl-N-isobutylamino)-6-methyl-7-anilinofluorescent yellow Parent, 3-cyclohexylamino-6-chlorofluorescent yellow precursor, 3-pyrrolidone-6-methyl-7-anilinofluorescent yellow precursor, 3-piperidinyl-6-methyl-7- Anilino fluorescent yellow precursor, 3-(N-ethyl-N-isopentylamino)-6-methyl-7-anilinyl fluorescent yellow precursor, 3-(N-methyl-N-cyclohexyl Amino)-6-methyl-7-anilinofluorescent yellow precursor, 2-(N-methyl-N-phenylamino)-6-(N-ethyl-N-p-toluidyl)fluoride Light yellow precursor, 3-(N-ethyl-N-p-toluidine)-6-methyl-7-anilinofluorescent yellow precursor, 3-(N-ethyl-N-tetrahydrofuranylamino) -6-methyl-7-anilinofluorescent yellow precursor, 1,3,3-trimethyl-6'-chloro-8'-methoxyindolinone benzospiropyran, 2'-anilino -3'-A Base-6'-(dipentylamino)spiro[isobenzofuran-1(3H),9'-[9H]star]-3-one, etc. Among these, compounds represented by the following formula (1) are preferred.

Figure 02_image001
Figure 02_image001

式（1）中，R1 及R2 係氫原子、碳數1以上且8以下之烷基、苯基、或3-三氟甲基苯基，可分別相同，亦可不同。式（1）中，R3 係氫原子、或碳數1以上且3以下之烷基。In formula (1), R 1 and R 2 are a hydrogen atom, an alkyl group having 1 to 8 carbons, a phenyl group, or a 3-trifluoromethylphenyl group, and may be the same or different. In formula (1), R 3 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

上述感光性著色劑之含量相對於硬化性樹脂成分100重量份，較佳之下限為0.1重量份，較佳之上限為10重量份。藉由上述感光性著色劑之含量為0.1重量份以上，而所獲得之濕氣硬化型樹脂組成物成為著色性更優異者。藉由上述感光性著色劑之含量為10重量份以下，而所獲得之濕氣硬化型樹脂組成物成為硬化性更優異者。上述感光性著色劑之含量之更佳之下限為0.3重量份，更佳之上限為3重量份。 再者，於本說明書中，所謂上述「硬化性樹脂成分」，於濕氣硬化型樹脂組成物不含有下述之光聚合性化合物之情形時，意指「濕氣硬化型樹脂」，於含有下述之光聚合性化合物之情形時，意指「光聚合性化合物與濕氣硬化型樹脂之合計」。With respect to 100 parts by weight of the curable resin component, the lower limit of the content of the photosensitive colorant is preferably 0.1 parts by weight, and the upper limit is preferably 10 parts by weight. When content of the said photosensitive coloring agent is 0.1 weight part or more, the moisture hardening type resin composition obtained becomes what is more excellent in coloring property. When content of the said photosensitive coloring agent is 10 weight part or less, the obtained moisture-curable resin composition becomes what is more excellent in curability. The more preferable lower limit of the content of the said photosensitive coloring agent is 0.3 weight part, and the more preferable upper limit is 3 weight part. In addition, in this specification, the above-mentioned "curable resin component" means "moisture curable resin" when the moisture curable resin composition does not contain the following photopolymerizable compound. In the case of the following photopolymerizable compound, it means "the total of the photopolymerizable compound and the moisture-curable resin".

本發明之濕氣硬化型樹脂組成物亦可於不阻礙本發明之目的之範圍內，除上述感光性著色劑以外，含有非感光性著色劑。 作為上述非感光性著色劑，例如可列舉：氧化鐵、鈦黑、苯胺黑、花青黑、富勒烯、碳黑、樹脂被覆型碳黑等。又，上述非感光性著色劑亦可不為呈現黑色者，只要為具有使可見光區域之光難以穿透之能力之材料，則氧化鈦等作為下述之填充劑所列舉之材料等亦包含於上述非感光性著色劑中。其中，較佳為鈦黑。The moisture-curable resin composition of the present invention may contain a non-photosensitive colorant in addition to the above-mentioned photosensitive colorant within a range that does not hinder the object of the present invention. Examples of the non-photosensitive colorant include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. In addition, the above-mentioned non-photosensitive colorant may not be black, as long as it is a material that has the ability to make it difficult for light in the visible light region to penetrate, titanium oxide and the like are also included in the materials listed below as fillers. In non-photosensitive colorants. Among them, titanium black is preferred.

上述鈦黑係與相對於波長300〜800 nm之光之平均穿透率相比，相對於紫外線區域附近、尤其是波長370〜450 nm之光之穿透率提高之物質。 即，上述鈦黑係藉由充分遮蔽可見光區域之波長之光而對本發明之濕氣硬化型樹脂組成物賦予遮光性，另一方面，具有使紫外線區域附近之波長之光穿透之性質之非感光性著色劑。因此，可藉由使用可藉由上述鈦黑之穿透率提高之波長（370〜450 nm）之光而開始反應者作為下述之光聚合起始劑，而不易阻礙本發明之濕氣硬化型樹脂組成物之光硬化。又，另一方面，作為本發明之濕氣硬化型樹脂組成物中所含之非感光性著色劑，較佳為絕緣性較高之物質，作為絕緣性較高之非感光性著色劑，亦較佳為鈦黑。The above-mentioned titanium black is compared with the average transmittance with respect to the light with a wavelength of 300-800 nm, and is a material that has an improved transmittance with respect to the vicinity of the ultraviolet region, especially with respect to light with a wavelength of 370-450 nm. That is, the above-mentioned titanium black imparts light-shielding properties to the moisture-curable resin composition of the present invention by sufficiently shielding light of wavelengths in the visible region, and on the other hand, has the property of allowing light of wavelengths near the ultraviolet region to pass through. Photosensitive colorant. Therefore, it is not easy to hinder the moisture hardening of the present invention by using the light of the wavelength (370~450 nm) that can start the reaction by using the light of the above-mentioned titanium black whose transmittance is improved as the following photopolymerization initiator Photocuring of type resin compositions. Also, on the other hand, as the non-photosensitive colorant contained in the moisture-curable resin composition of the present invention, it is preferably a material with high insulating properties, and as a non-photosensitive colorant with high insulating property, it is also Titanium black is preferred.

上述鈦黑之光學密度（OD值）較佳為3以上，更佳為4以上。上述鈦黑之遮光性越高越佳，上述鈦黑之OD值較佳之上限並無特別限制，通常成為5以下。又，上述鈦黑之黑色度（L值）較佳為9以上，更佳為11以上。The optical density (OD value) of the above-mentioned titanium black is preferably 3 or more, more preferably 4 or more. The higher the light-shielding property of the above-mentioned titanium black, the better. The upper limit of the OD value of the above-mentioned titanium black is not particularly limited, and it is usually 5 or less. In addition, the blackness (L value) of the above-mentioned titanium black is preferably 9 or more, more preferably 11 or more.

上述鈦黑即便為未經表面處理者，亦發揮充分之效果，亦可使用：表面經偶合劑等有機成分所處理者，經氧化矽、氧化鈦、氧化鍺、氧化鋁、氧化鋯、氧化鎂等無機成分所被覆者等，經表面處理之鈦黑。其中，經有機成分處理者就進一步提高絕緣性之方面而言較佳。Even if the above-mentioned titanium black is not surface-treated, it can also exert sufficient effects. It can also be used: the surface is treated with organic components such as coupling agents, and the surface is treated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, and magnesium oxide. Titanium black coated with other inorganic components, etc., after surface treatment. Among them, those treated with an organic component are preferable in terms of further improving insulation.

上述鈦黑之比表面積之較佳之下限為5 m2 /g，較佳之上限為40 m2 /g，更佳之下限為10 m2 /g，更佳之上限為25 m2 /g。 又，上述鈦黑之片電阻之較佳之下限於與樹脂混合之情形（摻合70%）時，為109 Q/□，更佳之下限為1011 Q/□。The lower limit of the specific surface area of the titanium black is preferably 5 m 2 /g, the upper limit is 40 m 2 /g, the lower limit is 10 m 2 /g, and the upper limit is 25 m 2 /g. Also, the preferable lower limit of the sheet resistance of the above-mentioned titanium black is 10 9 Q/□ when it is mixed with resin (70% blending), and the more preferable lower limit is 10 11 Q/□.

作為上述鈦黑中所市售者，例如可列舉：12S、13M、13M-C、13R-N（均為Mitsubishi Materials公司製造）、Tilack D（AKO KASEI公司製造）等。As what is marketed among the said titanium blacks, 12S, 13M, 13M-C, 13R-N (all are made by Mitsubishi Materials Co., Ltd.), Tilack D (made by AKO KASEI company) etc. are mentioned, for example.

於本發明之濕氣硬化型樹脂組成物中，上述非感光性著色劑之一次粒徑係根據顯示元件之基板間之距離以下等用途而適宜選擇，較佳之下限為30 nm，較佳之上限為500 nm。藉由上述非感光性著色劑之一次粒徑為該範圍，而於不使黏度及觸變性大幅增加之情況下，所獲得之濕氣硬化型樹脂組成物成為於基板之塗佈性及作業性更優異者。上述非感光性著色劑之一次粒徑之更佳之下限為50 nm，更佳之上限為200 nm。 再者，上述非感光性著色劑之一次粒徑可使用NICOMP 380ZLS（PARTICLE SIZING SYSTEMS公司製造），使上述非感光性著色劑分散於溶劑（水、有機溶劑等）中進行測定。In the moisture-curable resin composition of the present invention, the primary particle size of the above-mentioned non-photosensitive colorant is appropriately selected according to the application such as the distance between the substrates of the display element. The preferred lower limit is 30 nm, and the preferred upper limit is 500nm. When the primary particle size of the above-mentioned non-photosensitive colorant is in this range, the obtained moisture-curable resin composition can be applied on the substrate without greatly increasing the viscosity and thixotropy and workability. more excellent. The more preferable lower limit of the primary particle size of the non-photosensitive colorant is 50 nm, and the more preferable upper limit is 200 nm. In addition, the primary particle diameter of the said non-photosensitive colorant can be measured by dispersing the said non-photosensitive colorant in a solvent (water, an organic solvent, etc.) using NICOMP 380ZLS (made by PARTICLE SIZING SYSTEMS).

上述非感光性著色劑之含量相對於硬化性樹脂成分100重量份，較佳之下限為0.05重量份，較佳之上限為0.5重量份。藉由上述非感光性著色劑之含量為該範圍，而所獲得之濕氣硬化型樹脂組成物成為於維持優異之繪圖性、對基板等之接著性、及硬化後之強度的情況下著色性更優異者。上述非感光性著色劑之含量之更佳之下限為0.1重量份。With respect to 100 parts by weight of the curable resin component, the content of the above-mentioned non-photosensitive colorant has a preferable lower limit of 0.05 parts by weight, and a preferable upper limit of 0.5 parts by weight. When the content of the non-photosensitive colorant is within this range, the obtained moisture-curable resin composition has colorability while maintaining excellent drawing properties, adhesion to substrates, etc., and strength after curing. more excellent. The more preferable lower limit of content of the said non-photosensitive colorant is 0.1 weight part.

本發明之濕氣硬化型樹脂組成物含有濕氣硬化型樹脂。 作為上述濕氣硬化型樹脂，較佳為濕氣硬化型胺酯樹脂及含有水解性矽烷基之樹脂之至少任一者。其中，就濕氣硬化時之速硬化性優異之方面而言，更佳為濕氣硬化型胺酯樹脂。上述濕氣硬化型胺酯樹脂具有胺酯鍵與異氰酸基，分子內之異氰酸基與空氣中或被接著體中之水分反應而硬化。The moisture-curable resin composition of the present invention contains a moisture-curable resin. The moisture-curable resin is preferably at least any one of a moisture-curable urethane resin and a hydrolyzable silyl group-containing resin. Among them, a moisture-curable urethane resin is more preferable at the point that it is excellent in quick-curing property at the time of moisture-curing. The above-mentioned moisture-curable urethane resin has urethane bonds and isocyanate groups, and the isocyanate groups in the molecule react with moisture in the air or in the bonded body to harden.

上述濕氣硬化型胺酯樹脂可於1分子中僅具有一個異氰酸基，亦可具有兩個以上。其中，較佳為於分子之主鏈兩封端具有異氰酸基。The said moisture hardening type urethane resin may have only one isocyanate group in 1 molecule, and may have two or more. Among them, it is preferable to have isocyanate groups at both ends of the main chain of the molecule.

上述濕氣硬化型胺酯樹脂可藉由使於1分子中具有兩個以上之羥基之多元醇化合物、與於1分子中具有兩個以上之異氰酸基之聚異氰酸酯化合物反應而獲得。The above moisture-curable urethane resin can be obtained by reacting a polyol compound having two or more hydroxyl groups in one molecule and a polyisocyanate compound having two or more isocyanate groups in one molecule.

上述多元醇化合物與聚異氰酸酯化合物之反應通常係於以多元醇化合物中之羥基（OH）與聚異氰酸酯化合物中之異氰酸基（NCO）之莫耳比計[NCO]/[OH]＝2.0〜2.5之範圍內進行。The reaction between the polyol compound and the polyisocyanate compound is usually based on the molar ratio of the hydroxyl group (OH) in the polyol compound to the isocyanate group (NCO) in the polyisocyanate compound [NCO]/[OH]=2.0 ~2.5 range.

作為上述多元醇化合物，可使用通常用於製造聚胺酯（polyurethane）之公知之多元醇化合物，例如可列舉：聚酯多元醇、聚醚多元醇、聚伸烷基多元醇、聚碳酸酯多元醇等。該等多元醇化合物可單獨使用，亦可將兩種以上組合而使用。As the above-mentioned polyol compound, known polyol compounds generally used in the production of polyurethane (polyurethane) can be used, for example, polyester polyol, polyether polyol, polyalkylene polyol, polycarbonate polyol, etc. . These polyol compounds may be used alone or in combination of two or more.

作為上述聚酯多元醇，例如可列舉：藉由多元羧酸與多元醇之反應所獲得之聚酯多元醇、使ε-己內酯開環聚合所獲得之聚-ε-己內酯多元醇等。Examples of the above-mentioned polyester polyols include polyester polyols obtained by reacting polycarboxylic acids and polyhydric alcohols, and poly-ε-caprolactone polyols obtained by ring-opening polymerization of ε-caprolactone. Wait.

作為成為上述聚酯多元醇之原料之上述多元羧酸，例如可列舉：對苯二甲酸、間苯二甲酸、1,5-萘二甲酸、2,6-萘二甲酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、癸二甲酸、十二烷二甲酸等。Examples of the polyvalent carboxylic acid used as a raw material for the polyester polyol include terephthalic acid, isophthalic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, succinic acid, pentanedicarboxylic acid, and Diacid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, sebacic acid, dodecanedicarboxylic acid, etc.

作為成為上述聚酯多元醇之原料之上述多元醇，例如可列舉：乙二醇、丙二醇、1,3-丙二醇、1,4-丁二醇、新戊二醇、1,5-戊二醇、1,6己二醇、二乙二醇、環己二醇等。Examples of the above-mentioned polyol used as a raw material for the above-mentioned polyester polyol include ethylene glycol, propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, and 1,5-pentanediol , 1,6 hexanediol, diethylene glycol, cyclohexanediol, etc.

作為上述聚醚多元醇，例如可列舉：乙二醇、丙二醇、四氫呋喃之開環聚合物、3-甲基四氫呋喃之開環聚合物、及該等或其衍生物之無規共聚物或嵌段共聚物、雙酚型之聚氧伸烷基改質體等。Examples of the aforementioned polyether polyols include ethylene glycol, propylene glycol, ring-opening polymers of tetrahydrofuran, ring-opening polymers of 3-methyltetrahydrofuran, and random copolymers or blocks of these or their derivatives. Copolymer, polyoxyalkylene modified bisphenol type, etc.

上述雙酚型之聚氧伸烷基改質體係使環氧烷（例如，環氧乙烷、環氧丙烷、環氧丁烷等）與雙酚型分子骨架之活性氫部分進行加成反應所獲得之聚醚多元醇，可為無規共聚物，亦可為嵌段共聚物。上述雙酚型之聚氧伸烷基改質體較佳為使一種或兩種以上之環氧烷於雙酚型分子骨架之兩封端加成。作為上述雙酚型，並無特別限定，可列舉：A型、F型、S型等，較佳為雙酚A型。The above-mentioned bisphenol-type polyoxyalkylene modification system is formed by the addition reaction of alkylene oxide (such as ethylene oxide, propylene oxide, butylene oxide, etc.) and the active hydrogen part of the bisphenol-type molecular skeleton. The obtained polyether polyol can be a random copolymer or a block copolymer. The above-mentioned bisphenol-type polyoxyalkylene modified body is preferably added with one or more than two kinds of alkylene oxides on both ends of the bisphenol-type molecular skeleton. It does not specifically limit as said bisphenol type, A type, F type, S type etc. are mentioned, Preferably it is a bisphenol A type.

作為上述聚伸烷基多元醇，例如可列舉：聚丁二烯多元醇、氫化聚丁二烯多元醇、氫化聚異戊二烯多元醇等。As said polyalkylene polyol, a polybutadiene polyol, a hydrogenated polybutadiene polyol, a hydrogenated polyisoprene polyol, etc. are mentioned, for example.

作為上述聚碳酸酯多元醇，例如可列舉：聚碳酸六亞甲酯多元醇、聚碳酸環己二甲酯多元醇等。As said polycarbonate polyol, polyhexamethylene carbonate polyol, polycyclohexanedimethylene carbonate polyol, etc. are mentioned, for example.

作為成為上述濕氣硬化型胺酯樹脂之原料之聚異氰酸酯化合物，可較佳地使用芳香族聚異氰酸酯化合物、脂肪族聚異氰酸酯化合物。 作為上述芳香族聚異氰酸酯化合物，例如可列舉：二苯基甲烷二異氰酸酯、二苯基甲烷二異氰酸酯之液狀改質物、聚合MDI、甲苯二異氰酸酯、萘-1,5-二異氰酸酯等。 作為上述脂肪族聚異氰酸酯化合物，例如可列舉：六亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯、離胺酸二異氰酸酯、降莰烷二異氰酸酯、反式環己烷-1,4-二異氰酸酯、異佛爾酮二異氰酸酯、氫化苯二甲基二異氰酸酯、氫化二苯基甲烷二異氰酸酯、環己烷二異氰酸酯、雙(異氰酸基甲基)環己烷、二環己基甲烷二異氰酸酯等。 作為上述聚異氰酸酯化合物，其中，就蒸氣壓及毒性較低之方面、操作容易性之方面而言，較佳為二苯基甲烷二異氰酸酯及其改質物。 上述聚異氰酸酯化合物可單獨使用，亦可將兩種以上組合而使用。Aromatic polyisocyanate compounds and aliphatic polyisocyanate compounds can be preferably used as the polyisocyanate compound used as the raw material of the above-mentioned moisture-curable urethane resin. Examples of the aromatic polyisocyanate compound include diphenylmethane diisocyanate, liquid modified products of diphenylmethane diisocyanate, polymerized MDI, toluene diisocyanate, and naphthalene-1,5-diisocyanate. Examples of the aliphatic polyisocyanate compound include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, trans-cyclohexane-1,4 -Diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, cyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanates, etc. Among these polyisocyanate compounds, diphenylmethane diisocyanate and modified products thereof are preferred in terms of low vapor pressure and toxicity, and ease of handling. The said polyisocyanate compound may be used individually or in combination of 2 or more types.

又，上述濕氣硬化型胺酯樹脂較佳為使用具有下述式（2）所表示之結構之多元醇化合物所獲得者。藉由使用具有下述式（2）所表示之結構之多元醇化合物，可獲得接著性優異之組成物、及柔軟且伸長良好之硬化物，成為與下述之光聚合性化合物之相溶性優異者。 其中，較佳為使用由丙二醇、四氫呋喃（THF）化合物之開環聚合化合物、或具有甲基等取代基之四氫呋喃化合物之開環聚合化合物構成之聚醚多元醇者。Moreover, it is preferable that the said moisture-curable urethane resin is obtained using the polyol compound which has the structure represented by following formula (2). By using a polyol compound having a structure represented by the following formula (2), a composition with excellent adhesion and a cured product that is soft and elongated can be obtained, and it has excellent compatibility with the following photopolymerizable compound By. Among them, it is preferable to use a polyether polyol composed of propylene glycol, a ring-opening polymer compound of a tetrahydrofuran (THF) compound, or a ring-opening polymer compound of a tetrahydrofuran compound having a substituent such as a methyl group.

Figure 02_image003
Figure 02_image003

式（2）中，R表示氫原子、甲基、或乙基，I為0〜5之整數，m為1〜500之整數，n為1〜10之整數。I較佳為0〜4，m較佳為50〜200，n較佳為1〜5。 再者，所謂I為0之情形，意指與R鍵結之碳直接與氧鍵之情形。In formula (2), R represents a hydrogen atom, a methyl group, or an ethyl group, I is an integer of 0 to 5, m is an integer of 1 to 500, and n is an integer of 1 to 10. I is preferably 0~4, m is preferably 50~200, and n is preferably 1~5. In addition, the case where I is 0 means the case where the carbon bonded to R is directly bonded to oxygen.

上述含有水解性矽烷基之樹脂係分子內之水解性矽烷基與空氣中或被接著體中之水分反應而硬化。 上述含有水解性矽烷基之樹脂可於1分子中僅具有一個水解性矽烷基，亦可具有兩個以上。其中，較佳為於分子之主鏈兩封端具有水解性矽烷基。The hydrolyzable silyl groups in the above-mentioned resins containing hydrolyzable silyl groups react with moisture in the air or in the bonded body to harden. The above-mentioned hydrolyzable silyl group-containing resin may have only one hydrolyzable silyl group in 1 molecule, or may have two or more. Among them, it is preferable to have a hydrolyzable silyl group at both ends of the main chain of the molecule.

上述水解性矽烷基係下述式（3）所表示。The above-mentioned hydrolyzable silane is represented by the following formula (3).

-SiR4 3-a Xa （3）-SiR 4 3-a X a (3)

式（3）中，R4 分別獨立地為可經取代之碳數1以上且20以下之烷基、碳數6以上且20以下芳基、碳數7以上且20以下之芳烷基、或-OSiR5 3 （R5 分別獨立地為碳數1以上且20以下之烴基）所表示之三有機矽氧基。又，式（3）中，X分別獨立地為羥基或水解性基。進而，式（3）中，a為1〜3之整數。In formula (3), R 4 is independently an optionally substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or - a triorganosilyloxy group represented by OSiR 5 3 (R 5 are each independently a hydrocarbon group having 1 to 20 carbon atoms). Moreover, in formula (3), X is each independently a hydroxyl group or a hydrolyzable group. Furthermore, in formula (3), a is an integer of 1-3.

上述水解性基並無特別限定，例如可列舉：氫原子、鹵素原子、烷氧基、烯氧基、芳氧基、醯氧基、酮肟酸酯基、胺基、醯胺基、(酸)醯胺基、胺氧基、巰基等。其中，就活性較高之方面而言，較佳為鹵素原子、烷氧基、烯氧基、醯氧基，就水解性穩定且操作容易之方面而言，更佳為甲氧基、乙氧基等烷氧基，進而較佳為甲氧基、乙氧基。又，就安全性之觀點而言，較佳為藉由反應而脫離之化合物分別為乙醇、丙酮即乙氧基、異丙烯氧基。The above-mentioned hydrolyzable groups are not particularly limited, and examples thereof include hydrogen atoms, halogen atoms, alkoxy groups, alkenyloxy groups, aryloxy groups, acyloxy groups, ketoxamate groups, amine groups, amide groups, (acid ) amido group, aminooxy group, mercapto group, etc. Among them, halogen atoms, alkoxy groups, alkenyloxy groups, and acyloxy groups are preferred in terms of high activity, and methoxy groups and ethoxy groups are more preferred in terms of stable hydrolysis and easy handling. An alkoxy group such as a group, and more preferably a methoxy group or an ethoxy group. Also, from the viewpoint of safety, the compounds desorbed by the reaction are preferably ethanol, acetone or ethoxy, and isopropenyloxy, respectively.

上述羥基或上述水解性基可相對於1個矽原子，於1〜3個之範圍內鍵結。於上述羥基或上述水解性基相對於1個矽原子鍵結兩個以上之情形時，該等基可相同，亦可不同。The above-mentioned hydroxyl group or the above-mentioned hydrolyzable group may be bonded within a range of 1 to 3 silicon atoms. When two or more of the above-mentioned hydroxyl groups or the above-mentioned hydrolyzable groups are bonded to one silicon atom, these groups may be the same or different.

上述式（3）中之a就硬化性之觀點而言，較佳為2或3，尤佳為3。又，就保存穩定性之觀點而言，a較佳為2。In the above formula (3), a is preferably 2 or 3, particularly preferably 3, from the viewpoint of curability. Moreover, a is preferably 2 from the viewpoint of storage stability.

又，作為上述式（3）中之R4 ，例如可列舉：甲基、乙基等烷基、環己基等環烷基、苯基等芳基、苄基等芳烷基、三甲基矽烷氧基、氯甲基、甲氧基甲基等。其中，較佳為甲基。In addition, examples of R 4 in the above formula (3) include alkyl such as methyl and ethyl, cycloalkyl such as cyclohexyl, aryl such as phenyl, aralkyl such as benzyl, and trimethylsilane. Oxygen, chloromethyl, methoxymethyl, etc. Among them, methyl is preferred.

作為上述水解性矽烷基，例如可列舉：甲基二甲氧基矽烷基、三甲氧基矽烷基、三乙氧基矽烷基、三(2-丙烯基氧基)矽烷基、三乙醯氧基矽烷基、(氯甲基)二甲氧基矽烷基、(氯甲基)二乙氧基矽烷基、(二氯甲基)二甲氧基矽烷基、(1-氯乙基)二甲氧基矽烷基、(1-氯丙基)二甲氧基矽烷基、(甲氧基甲基)二甲氧基矽烷基、(甲氧基甲基)二乙氧基矽烷基、(乙氧基甲基)二甲氧基矽烷基、(1-甲氧基乙基)二甲氧基矽烷基、(胺基甲基)二甲氧基矽烷基、(N,N-二甲基胺基甲基)二甲氧基矽烷基、(N,N-二乙基胺基甲基)二甲氧基矽烷基、(N,N-二乙基胺基甲基)二乙氧基矽烷基、(N-(2-胺基乙基)胺基甲基)二甲氧基矽烷基、(乙醯氧基甲基)二甲氧基矽烷基、(乙醯氧基甲基)二乙氧基矽烷基等。Examples of the hydrolyzable silyl group include: methyldimethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group Silyl, (chloromethyl)dimethoxysilyl, (chloromethyl)diethoxysilyl, (dichloromethyl)dimethoxysilyl, (1-chloroethyl)dimethoxy (1-chloropropyl)dimethoxysilyl, (methoxymethyl)dimethoxysilyl, (methoxymethyl)diethoxysilyl, (ethoxy Methyl)dimethoxysilyl, (1-methoxyethyl)dimethoxysilyl, (aminomethyl)dimethoxysilyl, (N,N-dimethylaminomethyl base) dimethoxysilyl group, (N,N-diethylaminomethyl)dimethoxysilyl group, (N,N-diethylaminomethyl)diethoxysilyl group, ( N-(2-Aminoethyl)aminomethyl)dimethoxysilyl, (Acetyloxymethyl)dimethoxysilyl, (Acetyloxymethyl)diethoxysilane Base etc.

作為上述含有水解性矽烷基之樹脂，例如可列舉：含有水解性矽烷基之(甲基)丙烯酸樹脂、於分子鏈末端或分子鏈末端部位具有水解性矽烷基之有機聚合物、含有水解性矽烷基之聚胺酯樹脂等。Examples of the above-mentioned hydrolyzable silyl group-containing resin include (meth)acrylic resins containing hydrolyzable silyl groups, organic polymers having hydrolyzable silyl groups at molecular chain terminals or molecular chain terminal sites, hydrolyzable silane-containing Based polyurethane resin, etc.

上述含有水解性矽烷基之(甲基)丙烯酸樹脂較佳為於主鏈具有源自含有水解性矽烷基之(甲基)丙烯酸酯及(甲基)丙烯酸烷基酯之重複結構單元。The above-mentioned hydrolyzable silyl group-containing (meth)acrylic resin preferably has repeating structural units derived from hydrolyzable silyl group-containing (meth)acrylates and (meth)acrylic acid alkyl esters in the main chain.

上述含有水解性矽烷基之(甲基)丙烯酸酯，例如可列舉：(甲基)丙烯酸3-(三甲氧基矽基)丙酯、(甲基)丙烯酸3-(三乙氧基矽基)丙酯、(甲基)丙烯酸3-(甲基二甲氧基矽基)丙酯、(甲基)丙烯酸2-(三甲氧基矽基)乙酯、(甲基)丙烯酸2-(三乙氧基矽基)乙酯、(甲基)丙烯酸2-(甲基二甲氧基矽基)乙酯、(甲基)丙烯酸三甲氧基矽基甲酯、(甲基)丙烯酸三乙氧基矽基甲酯、(甲基)丙烯酸(甲基二甲氧基矽基)甲酯等。Examples of (meth)acrylates containing hydrolyzable silyl groups include: 3-(trimethoxysilyl)propyl (meth)acrylate, 3-(triethoxysilyl) (meth)acrylate Propyl ester, 3-(methyldimethoxysilyl)propyl (meth)acrylate, 2-(trimethoxysilyl)ethyl (meth)acrylate, 2-(triethyl)(meth)acrylate Oxysilyl) ethyl ester, 2-(methyldimethoxysilyl) ethyl (meth)acrylate, trimethoxysilylmethyl (meth)acrylate, triethoxy (meth)acrylate Silyl methyl ester, (meth)acrylate (methyldimethoxysilyl) methyl ester, etc.

作為上述(甲基)丙烯酸烷基酯，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸正庚酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸正十二烷酯、(甲基)丙烯酸硬脂酯等。Examples of the alkyl (meth)acrylate include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( n-butyl methacrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclo(meth)acrylate Hexyl ester, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate , n-dodecyl (meth)acrylate, stearyl (meth)acrylate, etc.

作為製造上述含有水解性矽烷基之(甲基)丙烯酸樹脂之方法，具體而言，例如可列舉：國際公開第2016/035718號中記載之含有水解性矽基之(甲基)丙烯酸酯系聚合物之合成方法等。As a method for producing the above-mentioned hydrolyzable silyl group-containing (meth)acrylic resin, specifically, for example, the following: Hydrolyzable silyl group-containing (meth)acrylate-based polymerization described in International Publication No. 2016/035718 Synthetic methods, etc.

上述於分子鏈末端或分子鏈末端部位具有水解性矽烷基之有機聚合物係於主鏈之末端及側鏈之末端之至少任一者具有水解性矽烷基。 上述主鏈之骨架結構並無特別限定，例如可列舉：飽和烴系聚合物、聚氧伸烷基系聚合物、(甲基)丙烯酸酯系聚合物等。The above-mentioned organic polymer having a hydrolyzable silyl group at a molecular chain terminal or at a molecular chain terminal position has a hydrolyzable silyl group at least one of the main chain terminal and the side chain terminal. The skeleton structure of the said main chain is not specifically limited, For example, a saturated hydrocarbon type polymer, a polyoxyalkylene type polymer, (meth)acrylate type polymer etc. are mentioned.

作為上述聚氧伸烷基系聚合物，例如可列舉：具有聚氧乙烯結構、聚氧丙烯結構、聚氧丁烯結構、聚氧四亞甲基結構、聚氧乙烯-聚氧丙烯共聚物結構、聚氧丙烯-聚氧丁烯共聚物結構之聚合物等。Examples of the polyoxyalkylene-based polymers include those having a polyoxyethylene structure, a polyoxypropylene structure, a polyoxybutylene structure, a polyoxytetramethylene structure, and a polyoxyethylene-polyoxypropylene copolymer structure. , Polyoxypropylene-polyoxybutylene copolymer structure polymers, etc.

作為製造上述於分子鏈末端或分子鏈末端部位具有水解性矽烷基之有機聚合物之方法，具體而言，例如可列舉：國際公開第2016/035718號中記載之僅於分子鏈末端或分子鏈末端部位具有交聯性矽烷基之有機聚合物之合成方法。又，作為製造上述於分子鏈末端或分子鏈末端部位具有水解性矽烷基之有機聚合物之其他方法，例如可列舉：國際公開第2012/117902號中記載之含有反應性矽基之聚氧伸烷基系聚合物之合成方法等。As a method for producing the above-mentioned organic polymer having a hydrolyzable silyl group at a molecular chain terminal or at a molecular chain terminal position, specifically, for example, the method described in International Publication No. 2016/035718 that only has a molecular chain terminal or a molecular chain A method for synthesizing an organic polymer having a crosslinkable silyl group at the end. In addition, as another method for producing the above-mentioned organic polymer having a hydrolyzable silyl group at the end of the molecular chain or at the end of the molecular chain, for example, polyoxyalkylene containing a reactive silyl group described in International Publication No. 2012/117902 can be cited. Synthesis methods of alkyl polymers, etc.

作為製造上述含有水解性矽烷基之聚胺酯樹脂之方法，例如可列舉：於使多元醇化合物與聚異氰酸酯化合物反應而製造聚胺酯樹脂時，進而使矽烷偶合劑等含有矽烷基之化合物反應之方法等。具體而言，例如可列舉：日本特開2017-48345號公報中記載之具有水解性矽烷基之胺酯低聚物之合成方法等。As a method of producing the above-mentioned hydrolyzable silyl group-containing polyurethane resin, for example, when producing the polyurethane resin by reacting a polyol compound and a polyisocyanate compound, a method of further reacting a silane group-containing compound such as a silane coupling agent, etc. are mentioned. Specifically, for example, a method for synthesizing an urethane oligomer having a hydrolyzable silyl group described in JP-A-2017-48345 and the like can be mentioned.

作為上述矽烷偶合劑，例如可列舉：乙烯基三氯矽烷、乙烯基三乙氧基矽烷、乙烯基三(β-甲氧基-乙氧基)矽烷、β-(3,4-環氧基環己基)-乙基三甲氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基甲基二乙氧基矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、N-(β-胺基乙基)-γ-胺基丙基三甲氧基矽烷、N-(β-胺基乙基)-γ-胺基丙基三甲基二甲氧基矽烷、N-苯基-γ-胺基丙基三甲氧基矽烷、γ-氯丙基三甲氧基矽烷、γ-巰基丙基三甲氧基矽烷、γ-胺基丙基三甲氧基矽烷、3-異氰酸基丙基三甲氧基矽烷、3-異氰酸基丙基三乙氧基矽烷等。其中，較佳為γ-巰基丙基三甲氧基矽烷、3-異氰酸基丙基三甲氧基矽烷、3-異氰酸基丙基三乙氧基矽烷。該等矽烷偶合劑可單獨使用，亦可將兩種以上組合而使用。Examples of the above-mentioned silane coupling agents include: vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxy-ethoxy)silane, β-(3,4-epoxy Cyclohexyl)-ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxypropyl Trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethyldimethoxy silane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, etc. Among them, γ-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane are preferred. These silane coupling agents may be used alone or in combination of two or more.

作為上述含有水解性矽烷基之樹脂中所市售者，例如可列舉：EXCESTAR S2410、EXCESTAR S2420、EXCESTAR S3430（均為AGC公司製造）、XMAP SA-100S、Cyril MA440（均為Kaneka公司製造）等。Examples of commercially available resins containing hydrolyzable silyl groups include: EXCESTAR S2410, EXCESTAR S2420, EXCESTAR S3430 (all manufactured by AGC Corporation), XMAP SA-100S, Cyril MA440 (all manufactured by Kaneka Corporation), etc. .

進而，上述濕氣硬化型樹脂亦可具有自由基聚合性官能基。作為上述濕氣硬化型樹脂可具有之自由基聚合性官能基，較佳為具有不飽和雙鍵之基，尤其就反應性之方面而言，更佳為(甲基)丙烯醯基。 再者，具有自由基聚合性官能基之濕氣硬化型樹脂不包括於下述之自由基聚合性化合物中，當作濕氣硬化型樹脂處理。Furthermore, the said moisture curable resin may have a radically polymerizable functional group. The radically polymerizable functional group that the moisture-curable resin may have is preferably a group having an unsaturated double bond, and is more preferably a (meth)acryl group in terms of reactivity. Furthermore, moisture-curable resins having radically polymerizable functional groups are not included in the following radically polymerizable compounds, and are treated as moisture-curable resins.

上述濕氣硬化型樹脂之重量平均分子量並無特別限定，較佳之下限為800，較佳之上限為1萬。藉由上述濕氣硬化型樹脂之重量平均分子量為該範圍，而所獲得之濕氣硬化型樹脂組成物於硬化時交聯密度不過度提高而成為柔軟性更優異者，且成為塗佈性更優異者。上述濕氣硬化型樹脂之重量平均分子量之更佳之下限為2000，更佳之上限為8000，進而較佳之下限為2500，進而較佳之上限為6000。 再者，於本說明書中，上述重量平均分子量係利用凝膠滲透層析法（GPC）且使用四氫呋喃作為溶劑進行測定，並藉由聚苯乙烯換算而求出之值。作為藉由GPC測定藉由聚苯乙烯換算之重量平均分子量時之管柱，例如可列舉：Shodex LF-804（昭和電工公司製造）等。又，作為GPC中所使用之溶劑，可列舉：四氫呋喃等。The weight average molecular weight of the moisture-curable resin is not particularly limited, but the lower limit is preferably 800, and the upper limit is 10,000. When the weight average molecular weight of the above-mentioned moisture-curable resin is in this range, the obtained moisture-curable resin composition does not excessively increase the crosslink density during curing, and becomes more excellent in flexibility and has better coating properties. Excellent. The weight average molecular weight of the moisture-curable resin has a more preferably lower limit of 2000, a more preferable upper limit of 8000, a more preferable lower limit of 2500, and a more preferable upper limit of 6000. In addition, in this specification, the said weight average molecular weight is the value calculated|required by the polystyrene conversion which measured using tetrahydrofuran as a solvent by gel permeation chromatography (GPC). As a column at the time of measuring the weight average molecular weight in terms of polystyrene by GPC, Shodex LF-804 (made by Showa Denko Co., Ltd.) etc. are mentioned, for example. Moreover, tetrahydrofuran etc. are mentioned as a solvent used by GPC.

於本發明之濕氣硬化型樹脂組成物含有下述之光聚合性化合物之情形時，上述濕氣硬化型樹脂之含量相對於上述光聚合性化合物與上述濕氣硬化型樹脂之合計100重量份，較佳之下限為20重量份，較佳之上限為90重量份。藉由上述濕氣硬化型樹脂之含量為該範圍，而所獲得之濕氣硬化型樹脂組成物成為濕氣硬化性及光硬化性更優異者。上述濕氣硬化型樹脂之含量之更佳之下限為30重量份，更佳之上限為75重量份，進而較佳之下限為41重量份，進而較佳之上限為70重量份。When the moisture-curable resin composition of the present invention contains the following photopolymerizable compound, the content of the moisture-curable resin is based on 100 parts by weight of the total of the photopolymerizable compound and the moisture-curable resin , the preferred lower limit is 20 parts by weight, and the preferred upper limit is 90 parts by weight. When the content of the moisture-curable resin is within this range, the obtained moisture-curable resin composition is more excellent in moisture curability and photocurability. A more preferable lower limit of the content of the moisture-curable resin is 30 parts by weight, a more preferable upper limit is 75 parts by weight, a more preferable lower limit is 41 parts by weight, and a more preferable upper limit is 70 parts by weight.

本發明之濕氣硬化型樹脂組成物亦可含有光聚合性化合物。於該情形時，可使光硬化與濕氣硬化之兩者之硬化機制發揮作用，故而除藉由濕氣硬化之接著性以外，亦可期待藉由光硬化之形狀穩定性或硬化速度之提高。因此，作為濕氣硬化性樹脂組成物，不僅可較佳地用於半導體晶片之接著，亦可較佳地用於電子零件或殼體之窄邊緣接著。The moisture-curable resin composition of the present invention may also contain a photopolymerizable compound. In this case, the hardening mechanism of both light hardening and moisture hardening can function, so in addition to the adhesiveness by moisture hardening, the shape stability and the improvement of the hardening speed by light hardening can also be expected . Therefore, as a moisture curable resin composition, it can be preferably used not only for bonding of semiconductor wafers, but also for narrow edge bonding of electronic parts or casings.

作為上述光聚合性化合物，可較佳地使用自由基聚合性化合物。作為上述自由基聚合性化合物，只要為具有光聚合性之自由基聚合性化合物即可，若為於分子中具有自由基聚合性官能基之化合物，則並無特別限定，較佳為具有不飽和雙鍵之化合物作為自由基聚合性官能基，尤其就反應性之方面而言，較佳為(甲基)丙烯酸化合物。 再者，於本說明書中，上述「(甲基)丙烯醯基」表示丙烯醯基或甲基丙烯醯基，上述「(甲基)丙烯酸」表示丙烯酸或甲基丙烯酸，上述「(甲基)丙烯酸化合物」表示具有(甲基)丙烯醯基之化合物。As the above-mentioned photopolymerizable compound, a radical polymerizable compound can be preferably used. The above-mentioned radically polymerizable compound is not particularly limited as long as it is a radically polymerizable compound having photopolymerization, and it is not particularly limited as long as it is a compound having a radically polymerizable functional group in the molecule. A compound having a double bond is preferably a (meth)acrylic compound as a radical polymerizable functional group, especially in terms of reactivity. In addition, in this specification, the above-mentioned "(meth)acryl" means acryl or methacryl, the above-mentioned "(meth)acryl" means acrylic or methacryl, and the above-mentioned "(meth)acryl" means acryl or methacryl. "Acrylic compound" means a compound having a (meth)acryl group.

作為上述(甲基)丙烯酸化合物，例如可列舉：(甲基)丙烯酸酯化合物、環氧(甲基)丙烯酸酯、(甲基)丙烯酸胺酯等。 再者，於本說明書中，所謂上述「(甲基)丙烯酸酯」，意指丙烯酸酯或甲基丙烯酸酯。又，成為上述(甲基)丙烯酸胺酯之原料之異氰酸酯化合物之異氰酸基均用於胺酯鍵之形成，上述(甲基)丙烯酸胺酯不具有殘存異氰酸基。As said (meth)acryl compound, a (meth)acrylate compound, epoxy (meth)acrylate, (meth)acrylate amine, etc. are mentioned, for example. In addition, in this specification, the said "(meth)acrylate" means acrylate or methacrylate. Moreover, the isocyanate group of the isocyanate compound used as the raw material of the said amine (meth)acrylate is used for formation of an urethane bond, and the said amine (meth)acrylate does not have a residual isocyanate group.

作為上述(甲基)丙烯酸酯化合物中之單官能者，例如可列舉：N-丙烯醯氧基乙基六氫鄰苯二甲醯亞胺、各種(甲基)丙烯醯亞胺酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸異肉豆蔻酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸2-丁氧基乙酯、(甲基)丙烯酸甲氧基乙二醇酯、(甲基)丙烯酸甲氧基聚乙二醇酯、(甲基)丙烯酸乙基卡必醇酯、(甲基)丙烯酸四氫呋喃甲酯、(甲基)丙烯酸2-苯氧基乙酯、(甲基)丙烯酸苯氧基二乙二醇酯、(甲基)丙烯酸苯氧基聚乙二醇酯、(甲基)丙烯酸2,2,2-三氟乙酯、(甲基)丙烯酸2,2,3,3-四氟丙酯、(甲基)丙烯酸1H,1H,5H-八氟戊酯、(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸二乙基胺基乙酯、丁二酸2-(甲基)丙烯醯氧基乙酯、六氫鄰苯二甲酸2-(甲基)丙烯醯氧基乙酯、鄰苯二甲酸2-(甲基)丙烯醯氧基乙基-2-羥基丙酯、(甲基)丙烯酸縮水甘油酯、磷酸2-(甲基)丙烯醯氧基乙酯等。Examples of the monofunctional ones among the above-mentioned (meth)acrylate compounds include: N-acryloxyethylhexahydrophthalimide, various (meth)acrylimides, (meth) base) methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, (meth)acrylate base) lauryl acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, bicyclo(meth)acrylate Pentenyl ester, Benzyl (meth)acrylate, 2-Hydroxyethyl (meth)acrylate, 2-Hydroxypropyl (meth)acrylate, 2-Hydroxybutyl (meth)acrylate, (meth)acrylic acid 4-Hydroxybutyl, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, (meth)acrylic acid Methoxyethylene glycol ester, methoxypolyethylene glycol (meth)acrylate, ethyl carbitol (meth)acrylate, tetrahydrofurfuryl methyl (meth)acrylate, 2-(meth)acrylate Phenoxyethyl Ester, Phenoxydiethylene Glycol (Meth)acrylate, Phenoxy Polyethylene Glycol (Meth)acrylate, 2,2,2-Trifluoroethyl (Meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, (methyl ) Diethylaminoethyl acrylate, 2-(meth)acryloxyethyl succinate, 2-(meth)acryloxyethyl hexahydrophthalate, 2-phthalate -(meth)acryloxyethyl-2-hydroxypropyl, glycidyl (meth)acrylate, 2-(meth)acryloxyethyl phosphate, etc.

又，作為上述(甲基)丙烯酸酯化合物中之二官能者，例如可列舉：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、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、2-正丁基-2-乙基-1,3-丙二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、環氧乙烷加成雙酚A二(甲基)丙烯酸酯、環氧丙烷加成雙酚A二(甲基)丙烯酸酯、環氧乙烷加成雙酚F二(甲基)丙烯酸酯、二羥甲基二環戊二烯二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、環氧乙烷改質異三聚氰酸二(甲基)丙烯酸酯、2-羥基-3-(甲基)丙烯醯氧基丙基(甲基)丙烯酸酯、碳酸酯二醇二(甲基)丙烯酸酯、聚醚二醇二(甲基)丙烯酸酯、聚酯二醇二(甲基)丙烯酸酯、聚己內酯二醇二(甲基)丙烯酸酯、聚丁二烯二醇二(甲基)丙烯酸酯等。Moreover, examples of the difunctional ones in the above-mentioned (meth)acrylate compounds include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate , 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2-n-butyl 2-ethyl-1,3-propanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate base) acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ethylene oxide Alkane addition bisphenol A di(meth)acrylate, Propylene oxide addition bisphenol A di(meth)acrylate, Ethylene oxide addition bisphenol F di(meth)acrylate, Dimethylol Dicyclopentadiene di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide modified isocyanuric acid di(meth)acrylate, 2-hydroxy-3 -(meth)acryloxypropyl (meth)acrylate, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth)acrylate ) acrylate, polycaprolactone diol di(meth)acrylate, polybutadiene diol di(meth)acrylate, etc.

又，作為上述(甲基)丙烯酸酯化合物中之三官能以上者，例如可列舉：三羥甲基丙烷三(甲基)丙烯酸酯、環氧乙烷加成三羥甲基丙烷三(甲基)丙烯酸酯、環氧丙烷加成三羥甲基丙烷三(甲基)丙烯酸酯、己內酯改質三羥甲基丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、環氧乙烷加成異三聚氰酸三(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯、環氧丙烷加成甘油三(甲基)丙烯酸酯、三(甲基)丙烯醯氧基乙基磷酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、新戊四醇四(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)丙烯酸酯等。In addition, examples of the trimethylolpropane tri(meth)acrylate, ethylene oxide-added trimethylolpropane tri(methyl ) acrylate, propylene oxide added trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, neopentylthritol tri(meth)acrylate Ester, ethylene oxide added isocyanuric acid tri(meth)acrylate, glycerol tri(meth)acrylate, propylene oxide added glycerol tri(meth)acrylate, tri(meth)propylene Acyloxyethyl phosphate, di-trimethylolpropane tetra(meth)acrylate, neopentylthritol tetra(meth)acrylate, dipenteoerythritol penta(meth)acrylate, dinew Pentaerythritol hexa(meth)acrylate, etc.

作為上述環氧基(甲基)丙烯酸酯，例如可列舉：藉由根據常法使環氧基化合物與(甲基)丙烯酸於鹼性觸媒之存在下反應所獲得者等。As said epoxy (meth)acrylate, the thing obtained by making an epoxy compound and (meth)acrylic acid react in presence of a basic catalyst according to a normal method, etc. are mentioned, for example.

作為上述環氧基化合物，例如可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、2,2'-二烯丙基雙酚A型環氧樹脂、氫化雙酚型環氧樹脂、環氧丙烷加成雙酚A型環氧樹脂、間苯二酚型環氧樹脂、聯苯型環氧樹脂、硫醚型環氧樹脂、二苯醚型環氧樹脂、二環戊二烯型環氧樹脂、萘型環氧樹脂、苯酚酚醛清漆型環氧樹脂、鄰甲酚酚醛清漆型環氧樹脂、二環戊二烯酚醛清漆型環氧樹脂、聯苯酚醛清漆型環氧樹脂、萘酚酚醛清漆型環氧樹脂、縮水甘油胺型環氧樹脂、烷基多元醇型環氧樹脂、橡膠改質型環氧樹脂、縮水甘油酯化合物、雙酚A型環硫樹脂等。Examples of the epoxy compounds include bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, 2,2'-diallyl bisphenol A epoxy resins, and bisphenol A epoxy resins. Resin, hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type Epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, o-cresol novolak type epoxy resin, dicyclopentadiene novolac type epoxy resin, Biphenyl novolak type epoxy resin, naphthol novolac type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, glycidyl ester compound, bisphenol A-type episulfide resin, etc.

作為上述環氧(甲基)丙烯酸酯中所市售者，例如可列舉：Daicel Allnex公司製造之環氧(甲基)丙烯酸酯、新中村化學工業公司製造之環氧(甲基)丙烯酸酯、共榮社化學公司製造之環氧(甲基)丙烯酸酯、Nagase chemteX公司製造之環氧(甲基)丙烯酸酯等。 作為上述Daicel Allnex公司製造之環氧(甲基)丙烯酸酯，例如可列舉：EBECRYL 860、EBECRYL 3200、EBECRYL 3201、EBECRYL 3412、EBECRYL 3600、EBECRYL 3700、EBECRYL 3701、EBECRYL 3702、EBECRYL 3703、EBECRYL 3800、EBECRYL 6040、EBECRYL RDX 63182等。 作為上述新中村化學工業公司製造之環氧(甲基)丙烯酸酯，例如可列舉：EA-1010、EA-1020、EA-5323、EA-5520、EA-CHD、EMA-1020等。 作為上述共榮社化學公司製造之環氧(甲基)丙烯酸酯，例如可列舉：Epoxy Ester M-600A、Epoxy Ester 40EM、Epoxy Ester 70PA、Epoxy Ester 200PA、Epoxy Ester 80MFA、Epoxy Ester 3002M、Epoxy Ester 3002A、Epoxy Ester 1600A、Epoxy Ester 3000M、Epoxy Ester 3000A、Epoxy Ester 200EA、Epoxy Ester 400EA等。 作為上述Nagase chemteX公司製造之環氧(甲基)丙烯酸酯，例如可列舉：Denacol Acrylate DA-141、Denacol Acrylate DA-314、Denacol Acrylate DA-911等。As what is marketed among the said epoxy (meth)acrylates, the epoxy (meth)acrylate by Daicel Allnex company, the epoxy (meth)acrylate by Shin-Nakamura Chemical Industry Co., Ltd., etc. are mentioned, for example. Epoxy (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd., epoxy (meth)acrylate manufactured by Nagase ChemteX Co., Ltd., and the like. Examples of the epoxy (meth)acrylate manufactured by Daicel Allnex include: EBECRYL 860, EBECRYL 3200, EBECRYL 3201, EBECRYL 3412, EBECRYL 3600, EBECRYL 3700, EBECRYL 3701, EBECRYL 3702, EBECRYL 3703, 3EBECRYL EBECRYL 6040, EBECRYL RDX 63182, etc. As epoxy (meth)acrylate by said Shin-Nakamura Chemical Industry Co., Ltd., EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 etc. are mentioned, for example. Examples of epoxy (meth)acrylates manufactured by Kyoeisha Chemical Co., Ltd. include Epoxy Ester M-600A, Epoxy Ester 40EM, Epoxy Ester 70PA, Epoxy Ester 200PA, Epoxy Ester 80MFA, Epoxy Ester 3002M, Epoxy Ester 3002A, Epoxy Ester 1600A, Epoxy Ester 3000M, Epoxy Ester 3000A, Epoxy Ester 200EA, Epoxy Ester 400EA, etc. As epoxy (meth)acrylate by said Nagase ChemteX company, Denacol Acrylate DA-141, Denacol Acrylate DA-314, Denacol Acrylate DA-911 etc. are mentioned, for example.

上述(甲基)丙烯酸胺酯例如可藉由相對於異氰酸酯化合物，使具有羥基之(甲基)丙烯酸衍生物於觸媒量之錫系化合物存在下反應而獲得。The amine (meth)acrylate can be obtained, for example, by reacting a (meth)acrylic acid derivative having a hydroxyl group with an isocyanate compound in the presence of a catalytic amount of a tin-based compound.

作為上述異氰酸酯化合物，例如可列舉：異佛爾酮二異氰酸酯、2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、六亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯、二苯基甲烷-4,4'-二異氰酸酯（MDI）、氫化MDI、聚合MDI、1,5-萘二異氰酸酯、降莰烷二異氰酸酯、聯甲苯胺二異氰酸酯、苯二甲基二異氰酸酯（XDI）、氫化XDI、離胺酸二異氰酸酯、三苯基甲烷三異氰酸酯、三(異氰酸基苯基)硫代磷酸酯、四甲基苯二甲基二異氰酸酯、1,6,11-十一烷三異氰酸酯等。Examples of the isocyanate compound include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate, Phenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, benzylidine diisocyanate, xylylene diisocyanate (XDI) , Hydrogenated XDI, Lysine Diisocyanate, Triphenylmethane Triisocyanate, Tris(isocyanatophenyl) Phosphorothioate, Tetramethylxylylene Diisocyanate, 1,6,11-Undecane Triisocyanate etc.

又，作為上述異氰酸酯化合物，亦可使用藉由多元醇與過量之異氰酸酯化合物之反應所獲得的經鏈延長之異氰酸酯化合物。 作為上述多元醇，例如可列舉：乙二醇、丙二醇、甘油、山梨糖醇、三羥甲基丙烷、碳酸酯二醇、聚醚二醇、聚酯二醇、聚己內酯二醇等。In addition, as the above-mentioned isocyanate compound, a chain-extended isocyanate compound obtained by reacting a polyhydric alcohol with an excess of isocyanate compound can also be used. Examples of the above-mentioned polyhydric alcohol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, and the like.

作為上述具有羥基之(甲基)丙烯酸衍生物，例如可列舉：二元醇之單(甲基)丙烯酸酯、三元醇之單(甲基)丙烯酸酯或二(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯等。 作為上述二元醇，例如可列舉：乙二醇、丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、聚乙二醇等。 作為上述三元醇，例如可列舉：三羥甲基乙烷、三羥甲基丙烷、甘油等。 作為上述環氧(甲基)丙烯酸酯，例如可列舉：雙酚A型環氧(甲基)丙烯酸酯等。Examples of (meth)acrylic acid derivatives having a hydroxyl group include mono(meth)acrylates of diols, mono(meth)acrylates or di(meth)acrylates of triols, cyclic Oxy(meth)acrylate, etc. As said dihydric alcohol, ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 3- butanediol, 1, 4- butanediol, polyethylene glycol etc. are mentioned, for example. As said trivalent alcohol, trimethylolethane, trimethylolpropane, glycerin etc. are mentioned, for example. As said epoxy (meth)acrylate, bisphenol A epoxy (meth)acrylate etc. are mentioned, for example.

作為上述(甲基)丙烯酸胺酯中所市售者，例如可列舉：東亞合成公司製造之(甲基)丙烯酸胺酯、Daicel Allnex公司製造之(甲基)丙烯酸胺酯、根上工業公司製造之(甲基)丙烯酸胺酯、新中村化學工業公司製造之(甲基)丙烯酸胺酯、共榮社化學公司製造之(甲基)丙烯酸胺酯等。 作為上述東亞合成公司製造之(甲基)丙烯酸胺酯，例如可列舉：M-1100、M-1200、M-1210、M-1600等。 作為上述Daicel Allnex公司製造之(甲基)丙烯酸胺酯，例如可列舉：EBECRYL 230、EBECRYL 270、EBECRYL 4858、EBECRYL 8402、EBECRYL 8411、EBECRYL 8412、EBECRYL 8413、EBECRYL 8804、EBECRYL 8803、EBECRYL 8807、EBECRYL 9260、EBECRYL 1290、EBECRYL 5129、EBECRYL 4842、EBECRYL 210、EBECRYL 4827、EBECRYL 6700、EBECRYL 220、EBECRYL 2220、KRM7735、KRM-8295等。 作為上述根上工業公司製造之(甲基)丙烯酸胺酯，例如可列舉：Artresin UN-9000H、Artresin UN-9000A、Artresin UN-7100、Artresin UN-1255、Artresin UN-330、Artresin UN-3320HB、Artresin UN-1200TPK、Artresin SH-500B等。 作為上述新中村化學工業公司製造之(甲基)丙烯酸胺酯，例如可列舉：U-2HA、U-2PHA、U-3HA、U-4HA、U-6H、U-6LPA、U-6HA、U-10H、U-15HA、U-122A、U-122P、U-108、U-108A、U-324A、U-340A、U-340P、U-1084A、U-2061BA、UA-340P、UA-4100、UA-4000、UA-4200、UA-4400、UA-5201P、UA-7100、UA-7200、UA-W2A等。 作為上述共榮社化學公司製造之(甲基)丙烯酸胺酯，例如可列舉：AI-600、AH-600、AT-600、UA-101I、UA-101T、UA-306H、UA-306I、UA-306T等。As what is marketed among the above-mentioned amine (meth)acrylates, the amine (meth)acrylate made by Toagosei Co., Ltd., the amine (meth)acrylate made by Daicel Allnex, and the amine made by Negami Kogyo Co., Ltd. are mentioned, for example. Amino (meth)acrylate, amine (meth)acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd., amine (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd., and the like. As the amine (meth)acrylate manufactured by the said Toagosei Co., Ltd., M-1100, M-1200, M-1210, M-1600 etc. are mentioned, for example. Examples of the amine (meth)acrylate manufactured by Daicel Allnex include: EBECRYL 230, EBECRYL 270, EBECRYL 4858, EBECRYL 8402, EBECRYL 8411, EBECRYL 8412, EBECRYL 8413, EBECRYL 8804, EBECRYL 8803, EBECRYL 8413, EBECRYL 8803, EBECRYL 8803, EBECRYL 8413 9260, EBECRYL 1290, EBECRYL 5129, EBECRYL 4842, EBECRYL 210, EBECRYL 4827, EBECRYL 6700, EBECRYL 220, EBECRYL 2220, KRM7735, KRM-8295, etc. Examples of the amine (meth)acrylate manufactured by Negami Industry Co., Ltd. include: Artresin UN-9000H, Artresin UN-9000A, Artresin UN-7100, Artresin UN-1255, Artresin UN-330, Artresin UN-3320HB, Artresin UN-1200TPK, Artresin SH-500B, etc. Examples of the amine (meth)acrylate manufactured by Shin-Nakamura Chemical Co., Ltd. include U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6LPA, U-6HA, U -10H, U-15HA, U-122A, U-122P, U-108, U-108A, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4100 , UA-4000, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A, etc. Examples of the amine (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd. include AI-600, AH-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA -306T etc.

又，亦可適宜使用上述以外之其他自由基聚合性化合物。 作為上述其他自由基聚合性化合物，例如可列舉：(甲基)丙烯醯胺化合物、乙烯系化合物等。 作為上述(甲基)丙烯醯胺化合物，例如可列舉：N,N-二甲基(甲基)丙烯醯胺、N-(甲基)丙烯醯口末啉、N-羥基乙基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N-異丙基(甲基)丙烯醯胺、N,N-二甲基胺基丙基(甲基)丙烯醯胺等。 作為上述乙烯系化合物，例如可列舉：苯乙烯、α-甲基苯乙烯、N-乙烯基-2-吡咯啶酮、N-乙烯基-ε-己內醯胺等。Moreover, other radically polymerizable compounds other than the above can also be used suitably. As said other radically polymerizable compound, a (meth)acrylamide compound, a vinyl compound, etc. are mentioned, for example. Examples of the above-mentioned (meth)acrylamide compounds include: N,N-dimethyl(meth)acrylamide, N-(meth)acryloyl peroline, N-hydroxyethyl(methyl) ) acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide Amines etc. Examples of the vinyl compound include styrene, α-methylstyrene, N-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam, and the like.

上述自由基聚合性化合物就調整硬化性等觀點而言，較佳為含有單官能自由基聚合性化合物與多官能自由基聚合性化合物。藉由含有上述單官能自由基聚合性化合物與上述多官能自由基聚合性化合物，而所獲得之濕氣硬化型樹脂組成物成為硬化性及黏性更優異者。其中，較佳為將作為上述多官能自由基聚合性化合物之(甲基)丙烯酸胺酯與上述單官能自由基聚合性化合物組合而使用。又，上述多官能自由基聚合性化合物較佳為二官能或三官能，更佳為二官能。The radical polymerizable compound preferably contains a monofunctional radical polymerizable compound and a polyfunctional radical polymerizable compound from the viewpoint of curability adjustment and the like. By containing the monofunctional radically polymerizable compound and the polyfunctional radically polymerizable compound, the obtained moisture-curable resin composition is more excellent in curability and viscosity. Among them, it is preferable to use the amine (meth)acrylate which is the above-mentioned polyfunctional radically polymerizable compound in combination with the above-mentioned monofunctional radically polymerizable compound. In addition, the polyfunctional radical polymerizable compound is preferably difunctional or trifunctional, more preferably difunctional.

於上述自由基聚合性化合物含有上述單官能自由基聚合性化合物與上述多官能自由基聚合性化合物之情形時，上述多官能自由基聚合性化合物之含量相對於上述單官能自由基聚合性化合物與上述多官能自由基聚合性化合物之合計100重量份，較佳之下限為2重量份，較佳之上限為45重量份。藉由上述多官能自由基聚合性化合物之含量為該範圍，而所獲得之濕氣硬化型樹脂組成物成為硬化性及黏性更優異者。上述多官能自由基聚合性化合物之含量之更佳之下限為5重量份，更佳之上限為35重量份。When the radical polymerizable compound contains the monofunctional radical polymerizable compound and the polyfunctional radical polymerizable compound, the content of the polyfunctional radical polymerizable compound is relative to the monofunctional radical polymerizable compound and the polyfunctional radical polymerizable compound. For 100 parts by weight of the polyfunctional radically polymerizable compound in total, the lower limit is preferably 2 parts by weight, and the upper limit is 45 parts by weight. When the content of the polyfunctional radically polymerizable compound is within this range, the obtained moisture-curable resin composition is more excellent in curability and viscosity. The more preferable lower limit of the content of the above-mentioned polyfunctional radically polymerizable compound is 5 parts by weight, and the more preferable upper limit is 35 parts by weight.

上述光聚合性化合物之含量相對於上述光聚合性化合物與上述濕氣硬化型樹脂之合計100重量份，較佳之下限為10重量份，較佳之上限為80重量份。藉由上述光聚合性化合物之含量為該範圍，而所獲得之濕氣硬化型樹脂組成物成為光硬化性及濕氣硬化性更優異者。上述光聚合性化合物之含量之更佳之下限為25重量份，更佳之上限為70重量份，進而較佳之下限為30重量份，進而較佳之上限為59重量份。The content of the photopolymerizable compound is preferably 10 parts by weight in the lower limit and 80 parts by weight in the upper limit with respect to 100 parts by weight of the total of the photopolymerizable compound and the moisture-curable resin. When content of the said photopolymerizable compound falls within this range, the obtained moisture-curable resin composition becomes what is more excellent in photocurability and moisture curability. The lower limit of the content of the photopolymerizable compound is preferably 25 parts by weight, the upper limit is 70 parts by weight, the lower limit is 30 parts by weight, and the upper limit is 59 parts by weight.

本發明之濕氣硬化型樹脂組成物亦可含有光聚合起始劑。 作為上述光聚合起始劑，可較佳地使用光自由基聚合起始劑。 作為上述光自由基聚合起始劑，例如可列舉：二苯甲酮系化合物、苯乙酮系化合物、醯基氧化膦系化合物、二茂鈦系化合物、肟酯系化合物、安息香醚系化合物、9-氧硫口山口星等。The moisture-curable resin composition of the present invention may also contain a photopolymerization initiator. As the above photopolymerization initiator, a photoradical polymerization initiator can be preferably used. Examples of the photoradical polymerization initiator include: benzophenone-based compounds, acetophenone-based compounds, acylphosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin ether-based compounds, 9-Oxysulfur Pass and the magnitude of the pass.

作為上述光自由基聚合起始劑中所市售者，例如可列舉：BASF公司製造之光自由基聚合起始劑、東京化成工業公司製造之光自由基聚合起始劑等。 作為上述BASF公司製造之光自由基聚合起始劑，例如可列舉：IRGACURE 184、IRGACURE 369、IRGACURE 379、IRGACURE 651、IRGACURE 784、IRGACURE 819、IRGACURE 907、IRGACURE 2959、IRGACURE OXE01、IRGACURE TPO等。 作為上述東京化成工業公司製造之光自由基聚合起始劑，例如可列舉：安息香甲醚、安息香***、安息香異丙醚等。As what is marketed among the said radical photopolymerization initiators, the radical photopolymerization initiator by BASF company, the radical photopolymerization initiator by Tokyo Chemical Industry Co., Ltd., etc. are mentioned, for example. Irgacure 184, Irgacure 369, Irgacure 379, Irgacure 651, Irgacure 784, Irgacure 819, Irgacure 907, Irgacure 2959, Irgacure OXE01, Irgacure TPO etc. are mentioned as said BASF company make photoradical polymerization initiators, for example. Examples of the photoradical polymerization initiator manufactured by Tokyo Chemical Industry Co., Ltd. include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

上述光聚合起始劑之含量相對於上述光聚合性化合物與上述濕氣硬化型樹脂之合計100重量份，較佳之下限為0.01重量份，較佳之上限為10重量份。藉由上述光聚合起始劑之含量為該範圍，而所獲得之濕氣硬化型樹脂組成物成為光硬化性及保存穩定性更優異者。上述光聚合起始劑之含量之更佳之下限為0.1重量份，更佳之上限為5重量份。The content of the photopolymerization initiator is preferably 0.01 parts by weight in the lower limit and 10 parts by weight in the upper limit with respect to 100 parts by weight of the total of the photopolymerizable compound and the moisture-curable resin. When content of the said photoinitiator is this range, the obtained moisture-curable resin composition becomes what is more excellent in photocurability and storage stability. The more preferable lower limit of the content of the said photopolymerization initiator is 0.1 weight part, and the more preferable upper limit is 5 weight part.

本發明之濕氣硬化型樹脂組成物較佳為含有光酸產生劑。藉由含有上述光酸產生劑，可促進上述感光性著色劑之著色反應。The moisture curable resin composition of the present invention preferably contains a photoacid generator. By containing the said photoacid generator, the coloring reaction of the said photosensitive colorant can be accelerated|stimulated.

上述光酸產生劑只要為藉由光照射而產生質子酸或路易斯酸者，則並無特別限定，可為離子性光酸產生型，亦可為非離子性光酸產生型。The photoacid generator is not particularly limited as long as it generates a protonic acid or a Lewis acid by light irradiation, and may be an ionic photoacid generating type or a nonionic photoacid generating type.

作為上述離子性光酸產生型之光酸產生劑之陰離子部分，例如可列舉：陰離子部分為BF4 - 、PF6 - 、SbF6 - 、(BX4 )- （其中，X表示至少兩個以上之氟或三氟甲基被取代之苯基）等。 作為上述離子性光酸產生型之光酸產生劑，例如可列舉：具有上述陰離子部分之芳香族鋶鹽、芳香族錪鹽、芳香族重氮鎓鹽、芳香族銨鹽、(2,4-二環戊二烯-1-基)((1-甲基乙基)苯)鐵鹽等。Examples of the anion portion of the above-mentioned ionic photoacid generating type photoacid generator include: the anion portion is BF 4 - , PF 6 - , SbF 6 - , (BX 4 ) - (where X represents at least two or more Fluorine or trifluoromethyl substituted phenyl), etc. As the photoacid generator of the above-mentioned ionic photoacid-generating type, for example, aromatic permeic acid salts, aromatic indium salts, aromatic diazonium salts, aromatic ammonium salts, (2,4- Dicyclopentadien-1-yl)((1-methylethyl)benzene)iron salt, etc.

作為上述芳香族鋶鹽，例如可列舉：雙(4-(二苯基鋶基)苯基)硫基雙六氟磷酸鹽、雙(4-(二苯基鋶基)苯基)硫基雙六氟銻酸鹽、雙(4-(二苯基鋶基)苯基)硫基雙四氟硼酸鹽、雙(4-(二苯基鋶基)苯基)硫基四(五氟苯基)硼酸鹽、二苯基-4-(苯硫基)苯基鋶六氟磷酸鹽、二苯基-4-(苯硫基)苯基鋶六氟銻酸鹽、二苯基-4-(苯硫基)苯基鋶四氟硼酸鹽、二苯基-4-(苯硫基)苯基鋶四(五氟苯基)硼酸鹽、三苯基鋶六氟磷酸鹽、三苯基鋶六氟銻酸鹽、三苯基鋶四氟硼酸鹽、三苯基鋶四(五氟苯基)硼酸鹽、雙(4-(二(4-(2-羥基乙氧基))苯基鋶基)苯基)硫基雙六氟磷酸鹽、雙(4-(二(4-(2-羥基乙氧基))苯基鋶基)苯基)硫基雙六氟銻酸鹽、雙(4-(二(4-(2-羥基乙氧基))苯基鋶基)苯基)硫基雙四氟硼酸鹽、雙(4-(二(4-(2-羥基乙氧基))苯基鋶基)苯基)硫基四(五氟苯基)硼酸鹽、三(4-(4-乙醯基苯基)噻吩基)鋶四(五氟苯基)硼酸鹽等。Examples of the above-mentioned aromatic cobaltium salts include: bis(4-(diphenylpermelyl)phenyl)thiobishexafluorophosphate, bis(4-(diphenylpermelyl)phenyl)thiobis Hexafluoroantimonate, bis(4-(diphenylcondyl)phenyl)sulfanyl bistetrafluoroborate, bis(4-(diphenylcondyl)phenyl)thiotetrakis(pentafluorophenyl) ) borate, diphenyl-4-(phenylsulfanyl)phenylpercited hexafluorophosphate, diphenyl-4-(phenylthio)phenylcuredium hexafluoroantimonate, diphenyl-4-( Phenylthio)phenylpercitetetrafluoroborate, diphenyl-4-(phenylthio)phenylpercitetetrakis(pentafluorophenyl)borate, triphenylpercite hexafluorophosphate, triphenylpercite hexafluoroborate Fluoroantimonate, triphenylpermetrafluoroborate, triphenylpermetrakis(pentafluorophenyl)borate, bis(4-(bis(4-(2-hydroxyethoxy))phenylpermedium ) phenyl) sulfenyl bis-hexafluorophosphate, bis (4- (bis (4- (2-hydroxyethoxy)) phenylpermellyl) phenyl) thio bis hexafluoroantimonate, bis (4 -(bis(4-(2-hydroxyethoxy))phenylperidyl)phenyl)thiobistetrafluoroborate, bis(4-(bis(4-(2-hydroxyethoxy))benzene perulidyl)phenyl)sulfanyltetrakis(pentafluorophenyl)borate, tris(4-(4-acetylphenyl)thienyl)perciliumtetrakis(pentafluorophenyl)borate, etc.

作為上述芳香族錪鹽，例如可列舉：二苯基錪六氟磷酸鹽、二苯基錪六氟銻酸鹽、二苯基錪四氟硼酸鹽、二苯基錪四(五氟苯基)硼酸鹽、雙(十二烷基苯基)錪六氟磷酸鹽、雙(十二烷基苯基)錪六氟銻酸鹽、雙(十二烷基苯基)錪四氟硼酸鹽、雙(十二烷基苯基)錪四(五氟苯基)硼酸鹽、4-甲基苯基-4-(1-甲基乙基)苯基錪六氟磷酸酯、4-甲基苯基-4-(1-甲基乙基)苯基錪六氟銻酸鹽、4-甲基苯基-4-(1-甲基乙基)苯基錪四氟硼酸鹽、4-甲基苯基-4-(1-甲基乙基)苯基錪四(五氟苯基)硼酸鹽等。Examples of the above-mentioned aromatic iodonium salts include: diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis(pentafluorophenyl) Borate, bis(dodecylphenyl)iodonium hexafluorophosphate, bis(dodecylphenyl)iodonium hexafluoroantimonate, bis(dodecylphenyl)iodonium tetrafluoroborate, bis(dodecylphenyl)iodonium tetrafluoroborate, (Dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluorophosphate, 4-methylphenyl -4-(1-methylethyl)phenyliodonium hexafluoroantimonate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrafluoroborate, 4-methylbenzene Base-4-(1-methylethyl)phenyliodonium tetrakis(pentafluorophenyl)borate, etc.

作為上述芳香族重氮鎓鹽，例如可列舉：苯基重氮鎓六氟磷酸酯、苯基重氮鎓六氟銻酸鹽、苯基重氮鎓四氟硼酸鹽、苯基重氮鎓四(五氟苯基)硼酸鹽等。Examples of the aromatic diazonium salts include: phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, phenyldiazonium tetrafluoroborate, phenyldiazonium tetrafluoroborate, (Pentafluorophenyl) borate, etc.

作為上述芳香族銨鹽，例如可列舉：1-苄基-2-氰基吡啶鎓六氟磷酸酯、1-苄基-2-氰基吡啶鎓六氟銻酸鹽、1-苄基-2-氰基吡啶鎓四氟硼酸鹽、1-苄基-2-氰基吡啶鎓四(五氟苯基)硼酸鹽、1-(萘基甲基)-2-氰基吡啶鎓六氟磷酸鹽、1-(萘基甲基)-2-氰基吡啶鎓六氟銻酸鹽、1-(萘基甲基)-2-氰基吡啶鎓四氟硼酸鹽、1-(萘基甲基)-2-氰基吡啶鎓四(五氟苯基)硼酸鹽等。Examples of the aromatic ammonium salts include: 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2 -cyanopyridinium tetrafluoroborate, 1-benzyl-2-cyanopyridinium tetrakis(pentafluorophenyl)borate, 1-(naphthylmethyl)-2-cyanopyridinium hexafluorophosphate , 1-(naphthylmethyl)-2-cyanopyridinium hexafluoroantimonate, 1-(naphthylmethyl)-2-cyanopyridinium tetrafluoroborate, 1-(naphthylmethyl) -2-cyanopyridinium tetrakis(pentafluorophenyl) borate and the like.

作為上述(2,4-二環戊二烯-1-基)((1-甲基乙基)苯)-鐵鹽，例如可列舉：(2,4-二環戊二烯-1-基)((1-甲基乙基)苯)-鐵(II)六氟磷酸鹽、(2,4-二環戊二烯-1-基)((1-甲基乙基)苯)-鐵(II)六氟銻酸鹽、(2,4-二環戊二烯-1-基)((1-甲基乙基)苯)-鐵(II)四氟硼酸鹽、(2,4-二環戊二烯-1-基)((1-甲基乙基)苯)-鐵(II)四(五氟苯基)硼酸鹽等。Examples of the (2,4-dicyclopentadien-1-yl)((1-methylethyl)benzene)-iron salt include: (2,4-dicyclopentadien-1-yl )((1-methylethyl)benzene)-iron(II) hexafluorophosphate, (2,4-dicyclopentadien-1-yl)((1-methylethyl)benzene)-iron (II) Hexafluoroantimonate, (2,4-dicyclopentadien-1-yl)((1-methylethyl)benzene)-iron(II)tetrafluoroborate, (2,4- Dicyclopentadien-1-yl)((1-methylethyl)benzene)-iron(II)tetrakis(pentafluorophenyl)borate and the like.

作為上述非離子性光酸產生型之光酸產生劑，例如可列舉：硝基苄酯、磺酸衍生物、磷酸酯、苯酚磺酸酯、重氮萘醌、N-羥基醯亞胺磺酸酯等。Examples of the nonionic photoacid-generating photoacid generator include nitrobenzyl esters, sulfonic acid derivatives, phosphoric acid esters, phenolsulfonic acid esters, diazonaphthoquinone, and N-hydroxyimidesulfonic acid. Esters etc.

作為上述光酸產生劑中所市售者，例如可列舉：SAN-APRO公司製造之光酸產生劑、Midori Kagaku公司製造之光酸產生劑、Union Carbide公司製造之光酸產生劑、ADEKA公司製造之光酸產生劑、3M公司製造之光酸產生劑、BASF公司製造之光酸產生劑、Rhodia公司製造之光酸產生劑等。 作為上述SAN-APRO公司製造之光酸產生劑，例如可列舉：CPI-100P、CPI-200K、CPI-210S等。 作為上述Midori Kagaku公司製造之光酸產生劑，例如可列舉：DTS-200等。 作為上述Union Carbide公司製造之光酸產生劑，例如可列舉：UVI 6990、UVI 6974等。 作為上述ADEKA公司製造之光酸產生劑，例如可列舉：SP-150、SP-170等。 作為上述3M公司製造之光酸產生劑，例如可列舉：FC-508、FC-512等。 作為上述BASF公司製造之光酸產生劑，例如可列舉：IRGACURE 261、IRGACURE 290等。 作為上述Rhodia公司製造之光酸產生劑，例如可列舉：PI 2074等。Examples of commercially available photoacid generators include: photoacid generators manufactured by SAN-APRO Corporation, photoacid generators manufactured by Midori Kagaku Corporation, photoacid generators manufactured by Union Carbide Corporation, and photoacid generators manufactured by ADEKA Corporation. A photoacid generator, a photoacid generator made by 3M, a photoacid generator made by BASF, a photoacid generator made by Rhodia, etc. As a photoacid generator manufactured by the said San-Apro company, CPI-100P, CPI-200K, CPI-210S etc. are mentioned, for example. As a photoacid generator manufactured by the said Midori Kagaku company, DTS-200 etc. are mentioned, for example. As a photoacid generator manufactured by the said Union Carbide company, UVI6990, UVI6974 etc. are mentioned, for example. As the photoacid generator manufactured by the said ADEKA company, SP-150, SP-170 etc. are mentioned, for example. As a photoacid generator manufactured by the said 3M company, FC-508, FC-512 etc. are mentioned, for example. As a photoacid generator manufactured by the said BASF company, IRGACURE 261, IRGACURE 290 etc. are mentioned, for example. As a photoacid generator manufactured by the said Rhodia company, PI2074 etc. are mentioned, for example.

上述光酸產生劑之含量相對於硬化性樹脂成分100重量份，較佳之下限為0.1重量份，較佳之上限為10重量份。藉由上述光酸產生劑之含量為該範圍，而所獲得之濕氣硬化型樹脂組成物成為著色性及接著性更優異者。上述光酸產生劑之含量之更佳之下限為1重量份，更佳之上限為4重量份。With respect to 100 parts by weight of the curable resin component, the lower limit of the content of the photoacid generator is preferably 0.1 parts by weight, and the upper limit is preferably 10 parts by weight. When the content of the photo-acid generator is within this range, the obtained moisture-curable resin composition is more excellent in colorability and adhesiveness. A more preferable lower limit of the content of the photoacid generator is 1 part by weight, and a more preferable upper limit is 4 parts by weight.

本發明之濕氣硬化型樹脂組成物較佳為含有敏化劑。上述敏化劑具有進一步提高藉由上述光酸產生劑之上述感光性著色劑之著色反應之促進效果之作用。The moisture-curable resin composition of the present invention preferably contains a sensitizer. The above-mentioned sensitizer has the effect of further increasing the effect of accelerating the coloring reaction of the above-mentioned photosensitive colorant by the above-mentioned photoacid generator.

作為上述敏化劑，例如可列舉：2-(4-甲基苯基磺醯基)苯酚、脂肪醯胺、醚類、草酸酯類、萘甲酸酯類、對羥基苯甲酸酯類、鄰苯二甲酸二酯類、磺醯胺類、烴化合物、雙酚S衍生物、雙酚A衍生物、各種蠟類、芳香族羧酸與胺之縮合物、高級直鏈二醇類、高級酮類等。 作為上述脂肪醯胺，例如可列舉：十八醯胺、硬脂酸羥甲基醯胺、油醯胺、棕櫚醯胺、椰子油肪醯胺等。 作為上述醚類，例如可列舉：1,2-雙苯氧基乙烷、1,2-二(3-甲基苯氧基)乙烷、1,4-二甲氧基萘、1,4-二苄氧基萘、苄氧基噻吩基醚、2-苄氧基萘、1,2-雙(苯氧基甲基)苯、9,10-二丁氧基蒽、9,10-二乙氧基蒽等。 作為上述草酸酯類，例如可列舉：草酸二苄酯、草酸二(對甲基苄基)酯、草酸二(對氯苄基)酯等。 作為上述萘甲酸酯類，例如可列舉：1-羥基-2-萘甲酸苯酯等。 作為上述對羥基苯甲酸酯類，例如可列舉：苄氧基苯甲酸苄酯、對羥基苯甲酸苄基等。 作為上述鄰苯二甲酸二酯類，例如可列舉：對苯二甲酸二苄酯等。 作為上述磺醯胺類，例如可列舉：N-二苄基甲苯磺醯胺、N-苄基甲苯磺醯胺、對甲苯磺醯胺等。 作為上述烴化合物，例如可列舉：間聯三苯、對苄基聯苯等。 作為上述雙酚S衍生物，例如可列舉：4,4'-二(烯丙氧基)二苯基碸等。Examples of the sensitizer include: 2-(4-methylphenylsulfonyl)phenol, fatty amide, ethers, oxalic acid esters, naphthoic acid esters, p-hydroxybenzoic acid esters, o-phthalic acid esters, Dicarboxylic acid diesters, sulfonamides, hydrocarbon compounds, bisphenol S derivatives, bisphenol A derivatives, various waxes, condensates of aromatic carboxylic acids and amines, higher linear diols, higher ketones Wait. Examples of the aforementioned fatty amide include stearylamide, stearic acid hydroxymethylamide, oleylamide, palmitamide, and coconut fatty amide. Examples of the aforementioned ethers include: 1,2-bisphenoxyethane, 1,2-bis(3-methylphenoxy)ethane, 1,4-dimethoxynaphthalene, 1,4 -Dibenzyloxynaphthalene, benzyloxythienyl ether, 2-benzyloxynaphthalene, 1,2-bis(phenoxymethyl)benzene, 9,10-dibutoxyanthracene, 9,10-di Ethoxyanthracene, etc. As said oxalic acid ester, dibenzyl oxalate, di(p-methylbenzyl) oxalate, bis(p-chlorobenzyl) oxalate, etc. are mentioned, for example. Examples of the above-mentioned naphthoic acid esters include phenyl 1-hydroxy-2-naphthoate and the like. As said paraben, benzyloxybenzoate, benzyl p-hydroxybenzoate, etc. are mentioned, for example. As said phthalic-acid diester, dibenzyl terephthalate etc. are mentioned, for example. Examples of the above-mentioned sulfonamides include N-dibenzyltoluenesulfonamide, N-benzyltoluenesulfonamide, p-toluenesulfonamide, and the like. As said hydrocarbon compound, m-terphenyl, p-benzylbiphenyl, etc. are mentioned, for example. As said bisphenol S derivative, 4,4'- bis(allyloxy) diphenylsulfone etc. are mentioned, for example.

上述敏化劑之含量相對於硬化性樹脂成分100重量份，較佳之下限為0.001重量份，較佳之上限為0.1重量份。藉由上述敏化劑之含量為0.001重量份以上，而進一步發揮敏化效果。可藉由上述敏化劑之含量為0.1重量份以下，而不使吸收過度增大而將光傳達至深部。上述敏化劑之含量之更佳之下限為0.005重量份，更佳之上限為0.05重量份。With respect to 100 parts by weight of the curable resin component, the content of the above-mentioned sensitizer has a preferable lower limit of 0.001 parts by weight, and a preferable upper limit of 0.1 parts by weight. When content of the said sensitizer is 0.001 weight part or more, a sensitization effect is exhibited further. When content of the said sensitizer is 0.1 weight part or less, light can be transmitted to a deep part, without excessively increasing absorption. The more preferable lower limit of the content of the said sensitizer is 0.005 weight part, and the more preferable upper limit is 0.05 weight part.

本發明之濕氣硬化型樹脂組成物較佳為含有填充劑。 藉由含有上述填充劑，而本發明之濕氣硬化型樹脂組成物成為具有較佳之觸變性者，可充分保持塗佈後之形狀。The moisture-curable resin composition of the present invention preferably contains a filler. By containing the above-mentioned filler, the moisture-curable resin composition of the present invention has better thixotropy and can sufficiently maintain the shape after coating.

上述填充劑之一次粒徑之較佳之下限為1 nm，較佳之上限為50 nm。藉由上述填充劑之一次粒徑為該範圍，而所獲得之濕氣硬化型樹脂組成物成為塗佈性及塗佈後之形狀保持性更優異者，尤其成為窄邊緣設計之顯示元件較佳者。上述填充劑之一次粒徑之更佳之下限為5 nm，更佳之上限為30 nm，進而較佳之下限為10 nm，進而較佳之上限為20 nm。 再者，上述填充劑之一次粒徑可使用NICOMP 380ZLS（PARTICLE SIZING SYSTEMS公司製造），使上述填充劑分散於溶劑（水、有機溶劑等）中而測定。 又，上述填充劑有於本發明之濕氣硬化型樹脂組成物中以二次粒子（複數個一次粒子聚集而成者）之形式存在之情形，此種二次粒子之粒徑之較佳之下限為5 nm，較佳之上限為500 nm，更佳之下限為10 nm，更佳之上限為100 nm。上述填充劑之二次粒子之粒徑可使用穿透型電子顯微鏡（TEM）觀察本發明之濕氣硬化型樹脂組成物或其硬化體而測定。The preferred lower limit of the primary particle size of the above-mentioned filler is 1 nm, and the preferred upper limit is 50 nm. When the primary particle diameter of the above-mentioned filler is within this range, the obtained moisture-curable resin composition has better applicability and shape retention after coating, and is especially preferable for display devices with a narrow edge design. By. The lower limit of the primary particle size of the above-mentioned filler is more preferably 5 nm, the upper limit is 30 nm, the lower limit is 10 nm, and the upper limit is 20 nm. In addition, the primary particle diameter of the said filler can be measured by dispersing the said filler in a solvent (water, an organic solvent, etc.) using NICOMP 380ZLS (made by PARTICLE SIZING SYSTEMS). In addition, the above-mentioned filler may exist in the form of secondary particles (a plurality of primary particles aggregated) in the moisture-curable resin composition of the present invention. The preferred lower limit of the particle size of such secondary particles is 5 nm, the upper limit is preferably 500 nm, the lower limit is 10 nm, and the upper limit is 100 nm. The particle size of the secondary particles of the filler can be measured by observing the moisture-curable resin composition of the present invention or its cured body using a transmission electron microscope (TEM).

作為上述填充劑，較佳為無機填充劑，例如可列舉：二氧化矽（silica）、滑石、氧化鈦、氧化鋅、碳酸鈣等。其中，就紫外線穿透性優異之方面而言，較佳為二氧化矽。該等填充劑可單獨使用，亦可將兩種以上組合而使用。As said filler, an inorganic filler is preferable, For example, silicon dioxide (silica), talc, titanium oxide, zinc oxide, calcium carbonate etc. are mentioned. Among these, silicon dioxide is preferable in terms of excellent ultraviolet light penetration. These fillers may be used alone or in combination of two or more.

上述填充劑較佳為進行疏水性表面處理。藉由上述疏水性表面處理，而所獲得之濕氣硬化型樹脂組成物成為塗佈後之形狀保持性更優異者。 作為上述疏水性表面處理，可列舉：矽基化處理、烷基化處理、環氧化處理等。其中，就提高形狀保持性之效果優異之方面而言，較佳為矽基化處理，更佳為三甲基矽基化處理。The aforementioned filler is preferably subjected to a hydrophobic surface treatment. By the above-mentioned hydrophobic surface treatment, the obtained moisture-curable resin composition is more excellent in shape retention after coating. Examples of the above-mentioned hydrophobic surface treatment include silylation treatment, alkylation treatment, epoxidation treatment, and the like. Among these, silylation treatment is preferred, and trimethylsilylation treatment is more preferred, in terms of the excellent effect of improving shape retention.

作為對上述填充劑進行疏水性表面處理之方法，例如可列舉：使用六甲基二矽氮烷等表面處理劑對填充劑之表面進行處理之方法等。 具體而言，例如，上述三甲基矽基化處理二氧化矽可藉由將二氧化矽利用溶膠凝膠法等方法進行合成，於使二氧化矽流動之狀態下噴霧表面處理劑之方法；或於醇、甲苯等有機溶劑中添加二氧化矽，進而添加表面處理劑與水後，利用蒸發器使水與有機溶劑蒸發乾燥之方法等而製作。As a method of subjecting the above-mentioned filler to a hydrophobic surface treatment, for example, a method of treating the surface of the filler with a surface treatment agent such as hexamethyldisilazane, etc. may be mentioned. Specifically, for example, the above-mentioned trimethylsilylation-treated silica can be synthesized by using a sol-gel method and other methods to synthesize silica, and spray a surface treatment agent in a state where the silica is flowing; Alternatively, silicon dioxide is added to an organic solvent such as alcohol or toluene, and then a surface treatment agent and water are added, and then the water and the organic solvent are evaporated and dried by an evaporator.

本發明之濕氣硬化型樹脂組成物100重量份中之上述填充劑之含量之較佳之下限為1重量份，較佳之上限為20重量份。藉由上述填充劑之含量為該範圍，而所獲得之濕氣硬化型樹脂組成物成為塗佈性及塗佈後之形狀保持性更優異者。上述填充劑之含量之更佳之下限為2重量份，更佳之上限為15重量份，進而較佳之下限為3重量份，進而較佳之上限為10重量份，尤佳之下限為4重量份。The preferable lower limit of the content of the above-mentioned filler in 100 parts by weight of the moisture-curable resin composition of the present invention is 1 part by weight, and the upper limit is preferably 20 parts by weight. When the content of the filler is within this range, the obtained moisture-curable resin composition is more excellent in applicability and shape retention after coating. The lower limit of the content of the filler is preferably 2 parts by weight, the upper limit is 15 parts by weight, the lower limit is 3 parts by weight, the upper limit is 10 parts by weight, and the lower limit is 4 parts by weight.

本發明之濕氣硬化型樹脂組成物亦可進而視需要含有離子液體、溶劑、含金屬之粒子、反應性稀釋劑等添加劑。The moisture-curable resin composition of the present invention may further contain additives such as ionic liquids, solvents, metal-containing particles, and reactive diluents as needed.

作為製造本發明之濕氣硬化型樹脂組成物之方法，例如可列舉：使用勻相分散機、均質攪拌機、萬能攪拌器、行星式混合機、捏合機、三輥研磨機等混合機，將濕氣硬化型樹脂、感光性著色劑、及視需要添加之添加劑進行混合之方法等。As a method for producing the moisture-curable resin composition of the present invention, for example, using a mixer such as a homogeneous disperser, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll mill The method of mixing air-curing resin, photosensitive colorant, and additives added if necessary, etc.

本發明之濕氣硬化型樹脂組成物較佳為含有之水分量為100 ppm以下。藉由上述水分量為100 ppm以下，而抑制保存中之上述濕氣硬化型樹脂與水分之反應，使濕氣硬化型樹脂組成物成為保存穩定性更優異者。上述水分量更佳為80 ppm以下。 再者，上述水分量可藉由卡氏水分測定裝置而測定。The moisture curable resin composition of the present invention preferably contains 100 ppm or less of moisture. When the moisture content is 100 ppm or less, the reaction between the moisture-curable resin and moisture during storage is suppressed, and the moisture-curable resin composition is more excellent in storage stability. The above moisture content is more preferably 80 ppm or less. Furthermore, the above-mentioned moisture content can be measured by a Karl Fischer moisture measuring device.

本發明之濕氣硬化型樹脂組成物係於25℃不為固形。 本發明之濕氣硬化型樹脂組成物之使用錐板型黏度計於25℃、1 rpm之條件下所測定之黏度之較佳之下限為30 Pa·s，較佳之上限為500 Pa·s。藉由上述黏度為該範圍，而成為於將濕氣硬化型樹脂組成物用於電子零件用接著劑或顯示元件用接著劑之情形時，塗佈於基板等被接著體時之作業性更優異者。上述黏度之更佳之下限為40 Pa·s，更佳之上限為300 Pa·s。 再者，於本發明之濕氣硬化型樹脂組成物之黏度過高之情形時，可藉由於塗佈時加溫而提高塗佈性。The moisture-curable resin composition of the present invention is not solid at 25°C. The preferred lower limit of the viscosity of the moisture-curable resin composition of the present invention measured using a cone-plate viscometer at 25°C and 1 rpm is 30 Pa·s, and the preferred upper limit is 500 Pa·s. When the above-mentioned viscosity is within this range, when the moisture-curing resin composition is used as an adhesive for electronic parts or an adhesive for display elements, the workability when it is applied to an adherend such as a substrate is more excellent By. A more preferable lower limit of the above-mentioned viscosity is 40 Pa·s, and a more preferable upper limit is 300 Pa·s. Furthermore, when the viscosity of the moisture-curable resin composition of the present invention is too high, the applicability can be improved by heating during coating.

本發明之濕氣硬化型樹脂組成物之搖變指數之較佳之下限為1.3，較佳之上限為5.0。藉由上述搖變指數為該範圍，而所獲得之濕氣硬化型樹脂組成物成為塗佈性及塗佈後之形狀保持性更優異者。該形狀保持性例如於窄邊緣設計之顯示元件中，就可保持塗佈寬度之方面而言，技術上之意義較大。又，於微細之半導體晶片之接著中，就可保持不自接著面溢出之狀態之方面而言，技術上之意義較大。上述搖變指數之更佳之上限為4.0。 再者，於本說明書中，所謂上述搖變指數，意指用使用錐板型黏度計於25℃、1 rpm之條件下所測定之黏度除以使用錐板型黏度計於25℃、10 rpm之條件下所測定之黏度所得之值。The preferred lower limit of the thixotropic index of the moisture-curable resin composition of the present invention is 1.3, and the preferred upper limit is 5.0. When the above-mentioned thixotropy index is in this range, the obtained moisture-curable resin composition is more excellent in applicability and shape retention after coating. This shape retention is technically significant in terms of maintaining the coating width, for example, in a display device with a narrow edge design. In addition, in the bonding of fine semiconductor wafers, it is technically significant in terms of maintaining a state of not overflowing from the bonding surface. A more preferable upper limit of the above-mentioned thixotropy index is 4.0. Furthermore, in this specification, the above-mentioned thixotropy index refers to dividing the viscosity measured with a cone-plate viscometer at 25°C and 1 rpm by the viscosity measured with a cone-plate viscometer at 25°C and 10 rpm. The value obtained from the viscosity measured under the conditions.

本發明之濕氣硬化型樹脂組成物較佳為厚度500 μm之硬化物之光學密度（OD值）為1以上。藉由上述OD值為1以上，而本發明之濕氣硬化型樹脂組成物成為確認接著狀態時之容易性、隱蔽性、作業性等更優異者。上述OD值更佳為2以上。 再者，上述濕氣硬化型樹脂組成物之硬化物之OD值可使用光學密度計而測定。The moisture-curable resin composition of the present invention preferably has an optical density (OD value) of 1 or more in a cured product having a thickness of 500 μm. When the above OD value is 1 or more, the moisture-curable resin composition of the present invention is more excellent in easiness of confirming the bonded state, concealability, workability, and the like. The above-mentioned OD value is more preferably 2 or more. In addition, the OD value of the hardened|cured material of the said moisture hardening type resin composition can be measured using an optical density meter.

作為使用本發明之濕氣硬化型樹脂組成物較佳地接著之被接著體，可列舉：金屬、玻璃、塑膠等各種被接著體。 作為上述被接著體之形狀，例如可列舉：膜狀、片狀、板狀、面板狀、盤狀、桿（棒狀體）狀、箱體狀、殼體狀等。Various types of adherends such as metal, glass, and plastic can be mentioned as the adherend to which the moisture-curable resin composition of the present invention is preferably bonded. As a shape of the said to-be-adhered body, film shape, sheet shape, plate shape, panel shape, disk shape, rod (rod shape), box shape, case shape, etc. are mentioned, for example.

作為上述金屬，例如可列舉：鋼鐵、不鏽鋼、鋁、銅、鎳、鉻或其合金等。As said metal, steel, stainless steel, aluminum, copper, nickel, chromium, or alloys thereof etc. are mentioned, for example.

作為上述玻璃，例如可列舉：鹼玻璃、無鹼玻璃、石英玻璃等。As said glass, an alkali glass, an alkali-free glass, a quartz glass etc. are mentioned, for example.

作為上述塑膠，例如可列舉：聚烯烴系樹脂、聚醯胺系樹脂、芳香族聚酯系樹脂、聚腈系樹脂、聚甲基丙烯酸酯系樹脂、聚乙烯系樹脂、聚碳酸酯等。 作為上述聚烯烴系樹脂，例如可列舉：高密度聚乙烯、超高分子量聚乙烯、同排聚丙烯、對排聚丙烯、乙烯丙烯共聚物樹脂等。 作為上述聚醯胺系樹脂，例如可列舉：尼龍6（N6）、尼龍66（N66）、尼龍46（N46）、尼龍11（N11）、尼龍12（N12）、尼龍610（N610）、尼龍612（N612）、尼龍6/66共聚物（N6/66）、尼龍6/66/610共聚物（N6/66/610）、尼龍MXD6（MXD6）、尼龍6T、尼龍6/6T共聚物、尼龍66/PP共聚物、尼龍66/PPS共聚物等。 作為上述芳香族聚酯系樹脂，例如可列舉：聚對苯二甲酸丁二酯（PBT）、聚對苯二甲酸乙二酯（PET）、聚間苯二甲酸乙二酯（PEI）、PET/PEI共聚物、聚芳酯（PAR）、聚萘二甲酸丁二酯（PBN）、液晶聚酯、聚氧伸烷基二醯亞胺二酸/聚對苯二甲酸丁二酯共聚物等。 作為上述聚腈系樹脂，例如可列舉：聚丙烯腈（PAN）、聚甲基丙烯腈、丙烯腈/苯乙烯共聚物（AS）、甲基丙烯腈/苯乙烯共聚物、甲基丙烯腈/苯乙烯/丁二烯共聚物等。 作為上述聚甲基丙烯酸酯系樹脂，例如可列舉：聚甲基丙烯酸甲酯（P MMA）、聚甲基丙烯酸乙酯等。 作為上述聚乙烯系樹脂，例如可列舉：乙烯/乙酸乙烯酯共聚物（EVA）、聚乙烯醇（PVA）、乙烯醇/乙烯共聚物（EVOH）、聚偏二氯乙烯（PVDC）、聚氯乙烯（PVC）、氯乙烯/偏二氯乙烯共聚物、偏二氯乙烯/甲基丙烯酸酯共聚物等。Examples of the plastics include polyolefin resins, polyamide resins, aromatic polyester resins, polynitrile resins, polymethacrylate resins, polyethylene resins, and polycarbonate. Examples of the polyolefin-based resin include high-density polyethylene, ultrahigh-molecular-weight polyethylene, parallel polypropylene, parallel polypropylene, and ethylene-propylene copolymer resins. Examples of the polyamide-based resin include nylon 6 (N6), nylon 66 (N66), nylon 46 (N46), nylon 11 (N11), nylon 12 (N12), nylon 610 (N610), and nylon 612. (N612), nylon 6/66 copolymer (N6/66), nylon 6/66/610 copolymer (N6/66/610), nylon MXD6 (MXD6), nylon 6T, nylon 6/6T copolymer, nylon 66 /PP copolymer, nylon 66/PPS copolymer, etc. Examples of the aromatic polyester-based resins include polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), PET /PEI copolymer, polyarylate (PAR), polybutylene naphthalate (PBN), liquid crystal polyester, polyoxyalkylene diimide diacid/polybutylene terephthalate copolymer, etc. . Examples of the polynitrile-based resins include: polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile/styrene copolymer (AS), methacrylonitrile/styrene copolymer, methacrylonitrile/ Styrene/butadiene copolymer, etc. As said polymethacrylate resin, polymethylmethacrylate (PMMA), polyethylmethacrylate, etc. are mentioned, for example. Examples of the above-mentioned polyethylene-based resins include ethylene/vinyl acetate copolymer (EVA), polyvinyl alcohol (PVA), vinyl alcohol/ethylene copolymer (EVOH), polyvinylidene chloride (PVDC), polyvinyl chloride Vinyl (PVC), vinyl chloride/vinylidene chloride copolymer, vinylidene chloride/methacrylate copolymer, etc.

又，作為上述被接著體，亦可列舉：於表面具有金屬鍍覆層之複合材料，作為該複合材料之鍍覆之基底材，例如可列舉：上述之金屬、玻璃、塑膠等。 進而，作為上述被接著體，亦可列舉：對金屬表面藉由鈍態化處理而形成鈍態皮膜之材料，作為該鈍態化處理，例如可列舉：加熱處理、陽極氧化處理等。尤其於國際鋁合金名為6000號之材質之鋁合金等情形時，藉由進行硫酸法耐酸鋁處理或磷酸法耐酸鋁處理作為上述鈍態化處理，而可提高接著性。In addition, as the above-mentioned adherend, a composite material having a metal plating layer on the surface can also be mentioned, and as a base material for plating of the composite material, for example, the above-mentioned metal, glass, plastic, etc. can be mentioned. Furthermore, as said to-be-adhered body, the material which formed the passivation film on the metal surface by passivation process is mentioned, and as this passivation process, heat treatment, anodic oxidation process, etc. are mentioned, for example. Especially in the case of the aluminum alloy of the international aluminum alloy name No. 6000, the adhesion can be improved by performing the sulfuric acid anodized aluminum treatment or the phosphoric acid anodized aluminum treatment as the above-mentioned passivation treatment.

作為使用本發明之濕氣硬化型樹脂組成物而將被接著體接著之方法，例如可列舉：具有以下之步驟之方法等。 即，首先，進行於第1構件塗佈本發明之濕氣硬化型樹脂組成物之步驟。繼而，進行經由濕氣硬化型樹脂組成物而將上述第1構件與第2構件貼合之步驟（貼合步驟）。上述貼合步驟後，進行藉由本發明之濕氣硬化型樹脂組成物中之濕氣硬化型樹脂之濕氣硬化而將上述第1構件與上述第2構件接著之步驟（濕氣硬化步驟）之方法等。又，較佳為於本發明之濕氣硬化型樹脂組成物含有光聚合性化合物之情形時，進行於上述第1構件塗佈本發明之濕氣硬化型樹脂組成物後，對本發明之濕氣硬化型樹脂組成物照射光，使本發明之濕氣硬化型樹脂組成物中之光聚合性化合物硬化之步驟（光硬化步驟）。於該情形時，較佳為包括於上述貼合步驟後照射光之步驟。藉由包括於上述貼合步驟後照射光之步驟，可提高與被接著體之剛接著後之接著性（初期接著性）。於上述第1構件及/或上述第2構件為使光穿透之材質之情形時，較佳為穿過使光穿透之上述第1構件及/或上述第2構件而照射光。又，於上述第1構件及/或上述第2構件為不易使光穿透之材質之情形時，較佳為於上述第1構件與上述第2構件經由上述濕氣硬化型樹脂組成物所接著之結構體之側面即濕氣硬化型樹脂組成物所露出之部分照射光。As a method of adhering an adherend using the moisture-curable resin composition of the present invention, for example, a method including the following steps may be mentioned. That is, first, a step of applying the moisture-curable resin composition of the present invention to the first member is performed. Next, a step of bonding the above-mentioned first member and second member via the moisture-curable resin composition (bonding step) is performed. After the above bonding step, the step of joining the first member and the second member by moisture curing of the moisture curable resin in the moisture curable resin composition of the present invention (moisture curing step) is performed. method etc. Also, when the moisture-curable resin composition of the present invention contains a photopolymerizable compound, it is preferable to apply the moisture-curable resin composition of the present invention to the above-mentioned first member, and to remove the moisture of the present invention. The curable resin composition is irradiated with light to cure the photopolymerizable compound in the moisture-curable resin composition of the present invention (photocuring step). In this case, it is preferable to include a step of irradiating light after the above-mentioned bonding step. By including the step of irradiating light after the bonding step, the adhesiveness (initial adhesiveness) immediately after bonding with the adherend can be improved. When the first member and/or the second member are made of a light-transmitting material, it is preferable to irradiate light through the first member and/or the second member through which light passes. Also, when the first member and/or the second member are made of a material that does not easily transmit light, it is preferable that the first member and the second member are bonded via the moisture-curable resin composition. The side of the structure, that is, the exposed portion of the moisture-curable resin composition, is irradiated with light.

本發明之濕氣硬化型樹脂組成物可較佳地用於電子零件用接著劑或顯示元件用接著劑。使用本發明之濕氣硬化型樹脂組成物而成之電子零件用接著劑、及使用本發明之濕氣硬化型樹脂組成物而成之顯示元件用接著劑亦分別為本發明之一種。 [發明之效果]The moisture-curable resin composition of the present invention can be preferably used as an adhesive for electronic parts or an adhesive for display elements. Adhesives for electronic components using the moisture-curable resin composition of the present invention and adhesives for display devices using the moisture-curable resin composition of the present invention are also a type of the present invention. [Effect of Invention]

根據本發明，可提供一種著色性及硬化性優異，且可抑制褪色之濕氣硬化型樹脂組成物。又，根據本發明，可提供一種使用該濕氣硬化型樹脂組成物而成之電子零件用接著劑及顯示元件用接著劑。According to the present invention, it is possible to provide a moisture-curable resin composition which is excellent in colorability and curability, and which can suppress discoloration. Moreover, according to this invention, the adhesive agent for electronic parts and the adhesive agent for display elements which use this moisture hardening type resin composition can be provided.

以下，列舉實施例更詳細地說明本發明，但本發明並不僅限定於該等實施例。Hereinafter, although an Example is given and this invention is demonstrated in more detail, this invention is not limited only to these Examples.

（合成例1（濕氣硬化型胺酯樹脂A之製作）） 將作為多元醇化合物之100重量份之聚四亞甲基醚二醇（三菱化學公司製造之「PTMG-2000」）、與0.01重量份之二丁基二月桂酸錫加入至500 mL容量之可分離式燒瓶，於真空下（20 mmHg以下）、於100℃攪拌30分鐘，進行混合。其後，設為常壓，添加作為聚異氰酸酯化合物之二苯基甲烷二異氰酸酯（日曹商事公司製造之「Pure MDI」）26.5重量份，於80℃攪拌3小時而反應，獲得濕氣硬化型胺酯樹脂A（重量平均分子量2700）。(Synthesis Example 1 (Preparation of Moisture Curing Type Urethane Resin A)) Polytetramethylene ether glycol ("PTMG-2000" manufactured by Mitsubishi Chemical Corporation) and 0.01 Dibutyltin dilaurate in parts by weight was added to a separable flask with a capacity of 500 mL, and stirred at 100° C. for 30 minutes under vacuum (below 20 mmHg) for mixing. Thereafter, set to normal pressure, add 26.5 parts by weight of diphenylmethane diisocyanate ("Pure MDI" manufactured by Nisso Shoji Co., Ltd.) as a polyisocyanate compound, and react with stirring at 80°C for 3 hours to obtain a moisture hardening type Urethane resin A (weight average molecular weight 2700).

（合成例2（濕氣硬化型胺酯樹脂B之製作）） 將作為多元醇化合物之100重量份之聚丙二醇（AGC公司製造之「EXCENOL 2020」）、與0.01重量份之二丁基二月桂酸錫放入至500 mL容量之可分離式燒瓶中，於真空下（20 mmHg以下）、於100℃攪拌30分鐘並混合。其後，設為常壓，添加作為聚異氰酸酯化合物之二苯基甲烷二異氰酸酯（日曹商事公司製造之「Pure MDI」）26.5重量份，於80℃攪拌3小時而反應，獲得濕氣硬化型胺酯樹脂B（重量平均分子量2900）。(Synthesis example 2 (production of moisture-curing urethane resin B)) 100 parts by weight of polypropylene glycol ("EXCENOL 2020" manufactured by AGC Corporation) as a polyol compound, and 0.01 part by weight of dibutyl dilauryl Put the stannic acid into a separable flask with a capacity of 500 mL, stir and mix at 100°C for 30 minutes under vacuum (below 20 mmHg). Thereafter, set to normal pressure, add 26.5 parts by weight of diphenylmethane diisocyanate ("Pure MDI" manufactured by Nisso Shoji Co., Ltd.) as a polyisocyanate compound, and react with stirring at 80°C for 3 hours to obtain a moisture hardening type Urethane resin B (weight average molecular weight 2900).

（合成例3（濕氣硬化型胺酯樹脂C之製作）） 於放入有與合成例1同樣地所獲得之濕氣硬化型胺酯樹脂A 100重量份之反應容器中，添加3-巰基丙基三甲氧基矽烷（信越化學工業公司製造之「KBM-803」）9.8重量份。其後，於80℃攪拌1小時而混合，獲得於分子末端具有異氰酸基與三甲氧基矽烷基之濕氣硬化型胺酯樹脂C（重量平均分子量3100）。(Synthesis Example 3 (Preparation of Moisture Curing Urethane Resin C)) In a reaction vessel containing 100 parts by weight of the moisture curing urethane resin A obtained in the same manner as in Synthesis Example 1, 3-mercapto Propyltrimethoxysilane (“KBM-803” manufactured by Shin-Etsu Chemical Co., Ltd.) 9.8 parts by weight. Thereafter, they were stirred and mixed at 80° C. for 1 hour to obtain a moisture-curing urethane resin C (weight average molecular weight: 3100) having an isocyanate group and a trimethoxysilyl group at the molecular terminal.

（實施例1〜10、比較例1、2） 根據表1中所記載之摻合比，將各材料藉由行星式攪拌裝置（Thinky公司製造之「去泡攪拌太郎」）進行攪拌後，藉由陶瓷三輥研磨機而均勻地混合，獲得實施例1〜10、比較例1、2之濕氣硬化型樹脂組成物。(Examples 1 to 10, Comparative Examples 1 and 2) According to the blending ratio recorded in Table 1, each material was stirred by a planetary stirring device ("Foaming Stirring Taro" manufactured by Thinky Company), and then Mix uniformly by a ceramic three-roll mill to obtain the moisture-curable resin compositions of Examples 1-10 and Comparative Examples 1 and 2.

＜評價＞ 對實施例及比較例中所獲得之各濕氣硬化型樹脂組成物進行以下之評價。將結果示於表1。<Evaluation> The following evaluations were performed on each of the moisture-curable resin compositions obtained in Examples and Comparative Examples. The results are shown in Table 1.

（著色性） 將實施例及比較例中所獲得之各濕氣硬化型樹脂組成物塗佈於表面具有500 μm厚度之鐵氟龍（註冊商標）小片作為間隙劑之載玻片上。於其上進而重疊另一載玻片，使用UV-LED（波長365 nm），照射3000 mJ/cm2 之紫外線，放置一晚，藉此進行濕氣硬化，獲得厚度500 μm之著色性試片。針對所獲得之著色性試片，使用光學密度計（X-rite公司製造之「光譜儀」）測定光學密度（OD值）。 將OD值為1.5以上之情形設為「〇」，將1以上且未達1.5之情形設為「△」，將未達1之情形設為「×」，評價著色性。(Colorability) Each of the moisture-curable resin compositions obtained in Examples and Comparative Examples was coated on a glass slide having a Teflon (registered trademark) chip having a thickness of 500 μm on the surface as a spacer. Overlay another glass slide on it, use UV-LED (wavelength 365 nm), irradiate 3000 mJ/cm 2 of ultraviolet rays, and let it stand overnight to perform moisture hardening to obtain a coloring test piece with a thickness of 500 μm . The optical density (OD value) of the obtained coloring test piece was measured using an optical densitometer (“spectrometer” manufactured by X-rite Corporation). When the OD value was 1.5 or more, it was made "O", when it was 1 or more and less than 1.5, it was made "△", and when it was less than 1, it was made "x", and the coloring property was evaluated.

（接著性） 使用滴塗裝置，將實施例及比較例中所獲得之各濕氣硬化型樹脂組成物以約1 mm之寬度塗佈於聚碳酸酯基板上。關於實施例9、10中所獲得之各濕氣硬化型樹脂組成物，將作為間隙劑之100 μm厚度之鐵氟龍（註冊商標）小片藉由攪拌裝置均勻地分散後，塗佈於聚碳酸酯基板上。繼而，藉由使用UV-LED（波長365 nm），照射紫外線3000 mJ/cm2 ，使濕氣硬化型樹脂組成物光硬化後，重疊另一聚碳酸酯基板，放置20 g之砝碼，放置一晚，藉此進行濕氣硬化，獲得接著性評價用樣品。 圖1中顯示自上方觀察接著性評價用樣品之情形之模式圖（圖1（a））、及顯示自橫向觀察接著性評價用樣品之情形之模式圖（圖1（b））。 將所獲得之各接著性評價用樣品放入至85℃、85RH%之恆溫恆濕烘箱，相對於地面吊掛100 g之砝碼，靜置24小時。 將24小時靜置後之偏移為1 mm以下之情形設為「〇」，將超過1 mm且3 mm以下之情形設為「△」，將超過3 mm之情形設為「×」，評價濕氣硬化型樹脂組成物之接著性。(Adhesiveness) Each of the moisture-curable resin compositions obtained in Examples and Comparative Examples was coated on a polycarbonate substrate in a width of about 1 mm using a dispensing device. For each of the moisture-curable resin compositions obtained in Examples 9 and 10, Teflon (registered trademark) flakes with a thickness of 100 μm as a spacer were uniformly dispersed by a stirring device, and then coated on polycarbonate on the ester substrate. Next, by using UV-LED (wavelength 365 nm) to irradiate ultraviolet rays of 3000 mJ/cm 2 to light-cure the moisture-curable resin composition, another polycarbonate substrate was stacked, a 20-g weight was placed, and the Moisture hardening was carried out by this overnight, and the sample for adhesiveness evaluation was obtained. Fig. 1 shows a schematic view of the sample for adhesive evaluation viewed from above (Fig. 1(a)), and a schematic view showing the sample for adhesive evaluation viewed from the lateral direction (Fig. 1(b)). Put the obtained adhesive evaluation samples into a constant temperature and humidity oven at 85°C and 85RH%, hang a 100 g weight on the ground, and let it stand for 24 hours. The case where the deviation after 24 hours of standing still was 1 mm or less was regarded as "〇", the case of exceeding 1 mm and less than 3 mm was designated as "△", and the case of exceeding 3 mm was designated as "×", and evaluated Adhesiveness of moisture curable resin composition.

（褪色防止性） 將實施例及比較例中所獲得之各濕氣硬化型樹脂組成物塗佈於表面具有500 μm厚度之鐵氟龍（註冊商標）小片作為間隙劑之載玻片上。於其上進而重疊另一載玻片，使用UV-LED（波長365 nm），照射3000 mJ/cm2 之紫外線，放置一晚，藉此進行濕氣硬化，獲得厚度500 μm之試片。針對所獲得之試片，使用光學密度計（X-rite公司製造之「光譜儀」）測定光學密度（OD值）A。繼而，將各試片於60℃、90%RH環境下放置72小時後，使用光學密度計測定光學密度（OD值）B。 將A－B＜0.2之情形設為「〇」，將0.2≦A－B＜0.5之情形設為「△」，將0.5≦A－B之情形設為「×」，評價褪色防止性。(Prevention of discoloration) Each moisture-curable resin composition obtained in Examples and Comparative Examples was coated on a glass slide having a Teflon (registered trademark) chip having a thickness of 500 μm on the surface as a spacer. Overlay another glass slide on it, and use UV-LED (wavelength 365 nm) to irradiate 3000 mJ/cm 2 of ultraviolet light, and leave it overnight to perform moisture hardening to obtain a test piece with a thickness of 500 μm. The optical density (OD value) A of the obtained test piece was measured using an optical densitometer (“spectrometer” manufactured by X-rite Corporation). Next, after leaving each test piece in an environment of 60° C. and 90% RH for 72 hours, the optical density (OD value) B was measured using an optical densitometer. The case of AB<0.2 was made "O", the case of 0.2≦AB<0.5 was made "△", and the case of 0.5≦AB was made "×", and the anti-fading property was evaluated.

[表1]

Figure 107127963-A0304-0001
[產業上之可利用性][Table 1]
Figure 107127963-A0304-0001
 [Industrial availability]

根據本發明，可提供一種著色性及硬化性優異，且可抑制褪色之濕氣硬化型樹脂組成物。又，根據本發明，可提供一種使用該濕氣硬化型樹脂組成物而成之電子零件用接著劑及顯示元件用接著劑。According to the present invention, it is possible to provide a moisture-curable resin composition which is excellent in colorability and curability, and which can suppress discoloration. Moreover, according to this invention, the adhesive agent for electronic parts and the adhesive agent for display elements which use this moisture hardening type resin composition can be provided.

1‧‧‧聚碳酸酯基板2‧‧‧濕氣硬化型樹脂組成物1‧‧‧Polycarbonate Substrate 2‧‧‧Moisture Curing Resin Composition

圖1中，（a）係表示自上方觀察接著性評價用樣品之情形之模式圖，（b）係表示自橫向觀察接著性評價用樣品之情形之模式圖。In FIG. 1 , (a) is a schematic diagram showing a state of observing the sample for adhesiveness evaluation from above, and (b) is a schematic diagram showing the state of observing the state of the sample for adhesiveness evaluation from the side.

1‧‧‧聚碳酸酯基板 1‧‧‧Polycarbonate substrate

2‧‧‧濕氣硬化型樹脂組成物 2‧‧‧Moisture curable resin composition

Claims (13)

一種濕氣硬化型樹脂組成物，其含有濕氣硬化型樹脂與感光性著色劑，上述濕氣硬化型樹脂係具有異氰酸基之濕氣硬化型胺酯樹脂及含有水解性矽烷基之樹脂之至少任一種，且著色後之上述感光性著色劑與上述濕氣硬化型樹脂反應。 A moisture-curable resin composition comprising a moisture-curable resin and a photosensitive colorant, wherein the moisture-curable resin is a moisture-curable urethane resin having an isocyanate group and a resin containing a hydrolyzable silyl group At least one of them, and the colored photosensitive colorant reacts with the moisture-curable resin. 如請求項1所述之濕氣硬化型樹脂組成物，其含有無色染料(leuco dye)作為上述感光性著色劑。 The moisture curable resin composition according to claim 1, which contains a leuco dye as the photosensitive colorant. 如請求項1或2所述之濕氣硬化型樹脂組成物，其含有下述式(1)所表示之化合物作為上述感光性著色劑：
Figure 107127963-A0305-02-0038-1
 式(1)中，R1及R2係氫原子、碳數1以上且8以下之烷基、苯基、或3-三氟甲基苯基，可分別相同，亦可不同；式(1)中，R3係氫原子、或碳數1以上且3以下之烷基。 The moisture-curing resin composition according to claim 1 or 2, which contains a compound represented by the following formula (1) as the photosensitive colorant:
Figure 107127963-A0305-02-0038-1
 In formula (1), R 1 and R 2 are hydrogen atoms, alkyl groups with a carbon number of 1 or more and 8 or less, phenyl, or 3-trifluoromethylphenyl, which may be the same or different; the formula (1 ), R 3 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 如請求項1或2所述之濕氣硬化型樹脂組成物，其中，上述感光性著色劑之含量相對於上述濕氣硬化型樹脂100重量份，為0.1重量份以上且10重量份以下。 The moisture-curable resin composition according to claim 1 or 2, wherein the content of the photosensitive colorant is 0.1 to 10 parts by weight relative to 100 parts by weight of the moisture-curable resin. 如請求項1或2所述之濕氣硬化型樹脂組成物，其中，上述濕氣 硬化型樹脂係具有異氰酸基之濕氣硬化型胺酯樹脂。 The moisture-curable resin composition according to claim 1 or 2, wherein the moisture Curing resin is a moisture-curing urethane resin with isocyanate groups. 如請求項1或2所述之濕氣硬化型樹脂組成物，其含有光聚合性化合物。 The moisture-curable resin composition according to claim 1 or 2, which contains a photopolymerizable compound. 如請求項6所述之濕氣硬化型樹脂組成物，其中，上述感光性著色劑之含量相對於上述光聚合性化合物與上述濕氣硬化型樹脂之合計100重量份，為0.1重量份以上且10重量份以下。 The moisture-curable resin composition according to claim 6, wherein the content of the photosensitive colorant is 0.1 parts by weight or more based on 100 parts by weight of the total of the photopolymerizable compound and the moisture-curable resin. 10 parts by weight or less. 如請求項1或2所述之濕氣硬化型樹脂組成物，其含有光酸產生劑。 The moisture curable resin composition according to claim 1 or 2, which contains a photoacid generator. 如請求項1或2所述之濕氣硬化型樹脂組成物，其含有敏化劑。 The moisture curable resin composition according to claim 1 or 2, which contains a sensitizer. 如請求項1或2所述之濕氣硬化型樹脂組成物，其含有非感光性著色劑。 The moisture-curable resin composition according to claim 1 or 2, which contains a non-photosensitive colorant. 如請求項1或2所述之濕氣硬化型樹脂組成物，其中，厚度500μm之硬化物之光學密度為1以上。 The moisture curable resin composition according to claim 1 or 2, wherein the optical density of the cured product having a thickness of 500 μm is 1 or more. 一種電子零件用接著劑，其係使用請求項1、2、3、4、5、6、7、8、9、10或11所述之濕氣硬化型樹脂組成物而成。 An adhesive for electronic parts, which is formed by using the moisture-curing resin composition described in claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11. 一種顯示元件用接著劑，其係使用請求項1、2、3、4、5、6、7、8、9、10或11所述之濕氣硬化型樹脂組成物而成。 An adhesive for display elements, which is formed by using the moisture-curing resin composition described in claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11.
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