TW201247768A

TW201247768A - Curable resin composition

Info

Publication number: TW201247768A
Application number: TW101118124A
Authority: TW
Inventors: Toshinobu Fujimura; Yasunobu Tagami; Kazuhiro Koda
Original assignee: Nof Corp
Priority date: 2011-05-31
Filing date: 2012-05-22
Publication date: 2012-12-01
Also published as: TWI481658B; JP2012246463A; KR101521044B1; CN102958974B; KR20140021678A; WO2012164869A1; JP5828225B2; CN102958974A

Abstract

Provided is a curable resin composition that adheres well to an inorganic substrate. Said curable resin composition contains the following: a multifunctional thiol compound (A) having a molecular weight of 200 to 2,000; a multifunctional epoxy resin (B) having a molecular weight of 200 to 50,000 and an epoxy equivalent of 80 to 6,000 g/mol; a thioether-containing alkoxysilane derivative (C) having a specific structure; and an amine compound (D) having a molecular weight of 90 to 700. The weight of component (A) is 0.05 to 30 times the weight of component (B). The curable resin composition contains 0.5 to 50 weight parts of component (C) and 0.01 to 50 weight parts of component (D) per 100 total weight parts of components (A) and (B).

Description

201247768 六、發明說明：【發明所屬之技術領域】本發明涉及對玻璃、氧化銦錫（1丁〇)、鋁等無機基材黏附性優異的固化性樹脂組合物。【先前技術】目前，將各種塗料塗布於玻璃等無機基材時’為了提高黏附性，常在環氧樹脂組合物中添加矽烷偶聯劑（例如專利文獻丨）。另外，作為現有的環氧樹脂固化劑了^吏用硫醇化合物，作為活化環氧基與硫醇意之間反應的催化劑，可使用胺之類的鹼性物質（例如非專利文獻丨）。並且，眾所周知硫醇化合物與具有多個雙鍵的多官能輯的混合物，可以形成絲來進行固^的固化性樹脂組合物（例如專利文獻2)。現有技術文獻專利文獻專利文獻1 :日本特開平7-300491號公報專利文獻2 :日本特開平6-306172號公報非專利文獻非專利文獻1:環氧樹脂綜述，第丨卷，基礎篇〗，P2G4_2G5 脂技術協會編。 ^ 【發明内容】本發明所要解決的技術問題但疋’如專利文獻}所述的技術中，# 於熱固性樹脂中。另外，黏附性改善效果也不能說是充分，例:要 • 2晴添加鈦、料鹽或她旨、聚氨咖旨物著力助劑所需求的黏附性。這種情況下，加人這些附著力^ 力助編s σ 1序人數’而且還存在著f要選定不損傷塗料特性的附著助劑種類、嚴密測試最佳添加量等問題。 201247768 另一方面，如非專利文獻1所述的以硫醇化合物為固化劑的固化性組合物的固化膜，對有機物的黏附性優異。但是，對玻璃、ITO、鋁等無機物的黏附性不夠充分。尤其，以硫醇化合物為固化劑的固化性組合物的固化膜耐水性差，因此如果在高溫高濕下暴露的話存在著黏附性大大下降的問題。另外，如專利文獻2所述的混合了硫醇化合物和多官能聚烯的光固性的固化性树月曰組合物，所得到的固化物對無機物的黏附性也不夠充分。並且，以硫醇化合物為固化劑的固化性組合物，如果以胺為催化劑，即使在室溫下也能進行固化’因_此在望得到一種可用時間（在使用的環境下可使用的時間）長的固化組合物。因此，本發明是鑒於上述情況而完成的，其目的是提供一種對玻璃、氧化銦錫（ΙΊΌ)、鋁等無機基材的黏附性優異的固化性樹脂組合物。解決技術問題的手段本發明人為了解決上述問題，進行了深入研究，結果發現，代替現有的矽烷偶聯劑或硫醇化合物，含有特定的含硫醚的烷氧基矽烷衍生物為有效成分的固化性樹脂組合物，對無機基材具有優異的黏附性，進而完成了本發明。即’本發明為含有下述（A)、（B)、（c)及⑴）成分的固化性樹脂組合物，所述（A)成分為分子量為200〜2000的多官能硫醇化合物，所述（B) 成分為分子量為200〜50000且環氧當量為8〇〜6〇〇〇g/mo丨的多官能環氧樹脂，所述（C)成分為以下述通式（1)或通式（2)所示的含硫醚的烷氧基石夕院衍生物’所述（D)成分為分子量為90〜700的胺類化合物。並且，所述（A)成分與（B)成分的重量比（A) / (B)為〇.〇5〜30，以所述（A) 成分與所述（B)成分的總重量為100重量份計，混入0.5〜50重量份的所述（C)成分、〇.〇卜50重量份的所述（D)成分。[Technical Field] The present invention relates to a curable resin composition which is excellent in adhesion to an inorganic substrate such as glass, indium tin oxide (1 butyl hydride) or aluminum. [Prior Art] When various coating materials are applied to an inorganic substrate such as glass, in order to improve adhesion, a decane coupling agent is often added to the epoxy resin composition (for example, Patent Document). Further, as a conventional epoxy resin curing agent, a thiol compound is used, and as a catalyst for activating the reaction between an epoxy group and a thiol, an alkaline substance such as an amine can be used (for example, Non-Patent Document No.). Further, a curable resin composition in which a mixture of a thiol compound and a polyfunctional group having a plurality of double bonds is formed and can be formed into a wire is known (for example, Patent Document 2). CITATION LIST Patent Literature Patent Literature 1: JP-A-H07-300491, JP-A-H06-306172, JP-A No. 6-306172, Non-Patent Document Non-Patent Document 1: Epoxy Resin Review, Volume I, Basics, Edited by P2G4_2G5 Fat Technology Association. [Disclosure] The technical problem to be solved by the present invention is as described in the patent document, in the thermosetting resin. In addition, the effect of improving the adhesion cannot be said to be sufficient. For example, it is necessary to add titanium, salt, or the adhesion required by the granules. In this case, the addition of these adhesion forces helps to s s σ 1 sequence number', and there are also problems such as selecting the type of adhesion aid that does not damage the coating properties, and strictly testing the optimum addition amount. On the other hand, the cured film of the curable composition containing a thiol compound as a curing agent as described in Non-Patent Document 1 is excellent in adhesion to an organic substance. However, the adhesion to inorganic substances such as glass, ITO, and aluminum is insufficient. In particular, since the cured film of the curable composition containing a thiol compound as a curing agent has poor water resistance, there is a problem that the adhesion is greatly lowered if exposed to high temperature and high humidity. Further, in the photocurable curable dendrimer composition in which a thiol compound and a polyfunctional polyolefin are mixed as described in Patent Document 2, the obtained cured product is insufficient in adhesion to an inorganic substance. Further, when the curable composition containing a thiol compound as a curing agent can be cured even at room temperature by using an amine as a catalyst, it is expected to obtain a usable time (a time usable in an environment of use). Long curing composition. In view of the above, it is an object of the present invention to provide a curable resin composition which is excellent in adhesion to an inorganic substrate such as glass, indium tin oxide or aluminum. Means for Solving the Problems In order to solve the above problems, the present inventors conducted intensive studies and found that, in place of the conventional decane coupling agent or thiol compound, a specific thioether-containing alkoxydecane derivative is contained as an active ingredient. The curable resin composition has excellent adhesion to an inorganic substrate, and the present invention has been completed. That is, the present invention is a curable resin composition containing the following components (A), (B), (c), and (1)), wherein the component (A) is a polyfunctional thiol compound having a molecular weight of 200 to 2,000. The component (B) is a polyfunctional epoxy resin having a molecular weight of 200 to 50,000 and an epoxy equivalent of 8 to 6 〇〇〇g/mo, and the component (C) is a compound of the following formula (1) or The thioether-containing alkoxystone derivative represented by the formula (2) The component (D) is an amine compound having a molecular weight of 90 to 700. Further, the weight ratio (A) / (B) of the component (A) to the component (B) is 〇. 5 to 30, and the total weight of the component (A) and the component (B) is 100. To the parts by weight, 0.5 to 50 parts by weight of the component (C), and 50 parts by weight of the component (D) are mixed.

S 201247768S 201247768

其中，a為1〜4的整數’ b為〇〜3的整數，c為〇或i，a+b+c=4 ; m為 1 或 2 ; R1 為-CHrCH(CH3)·、- c(CH3)2-、-CH2-CH2-或-CH(CH3)-中任意一種所示的二價基團，R2為曱基或乙基；化學式2Wherein, a is an integer of 1 to 4 'b is an integer of 〇~3, c is 〇 or i, a+b+c=4; m is 1 or 2; R1 is -CHrCH(CH3)·, -c( CH3) a divalent group represented by any one of 2-, -CH2-CH2- or -CH(CH3)-, R2 is a fluorenyl group or an ethyl group;

其中’ a’為1〜3的整數，b’為0〜2的整數，c，為〇或i，a，+b，+c，=3 ; a，，為0〜3的整數’ b”為〇〜2的整數，c”為〇或1，a，，+b，，+c，，=3 ; m為！或2 ; R1為媽谓卿·、-C(CH3)r、-CHrCH24CH(CH3).中任意—種所示的二價基團，R2為曱基或乙基；像這樣，作為附著力助劑，以特定的含硫醚的烷氧基矽烷衍生物（c) 為有效成分，均衡加入（A)〜（D)成分，對無機基材能夠表現出優異的點附性。另外在本發明中，當量是指為了形成lm〇l某化學物質的官能團個數時所需的化學物質的重量，可以通過（分子量）/ 〇分子中官能團的個數）求得。另外，在聚合物的情況下，“分子量，，表示重均分子量。本發明的固化性樹脂組合物，除了所述的（A)〜（D)成分之外，還可以含有下述（E)成分。不含（E)成分的所述本發明的固化性樹脂組合物為熱固性，但如果向其中添加（E)成分，則能夠給予固化性樹脂組合物光固性或光熱兩級固性，可以根據操作環境或使用目的等選擇固化反應。具體地說， 201247768 作為（E)成分，也可以含有分子量為2〇〇〜5〇〇〇〇且（曱基）丙烯酸酯當量為 80〜6000g/mo丨的多官能（甲基）丙烯酸醋化合物。以所述（A)成分和所述 (B)成分的總重量為1〇〇重量份計，可以混入2〜3〇〇重量份該成分。另外’在本發明中，‘‘（曱基）丙烯酸酯，，表示包括丙烯酸酯和甲基丙烯酸酯兩者的總稱》作為所述胺類化合物（D)，優選使用以下述通式（3)所示的咪唑化合物。因此，儘管固化性樹脂組合物在35°c以下的使用、儲存溫度範圍内難以進行固化反應，可用時間延長，但其可以在6〇〇c下進行固化反應，因此可兼teLSJ夺間、儲存穩定性與低溫固化兩方面^__ 化學式3Where 'a' is an integer from 1 to 3, b' is an integer from 0 to 2, c is 〇 or i, a, +b, +c, =3; a, is an integer 'b' from 0 to 3 For an integer of 〇~2, c" is 〇 or 1, a,, +b,, +c,, =3; m is! Or 2; R1 is a divalent group represented by any of the formulas -, -C(CH3)r, -CHrCH24CH(CH3). R2 is a thiol group or an ethyl group; as such, as an adhesion aid The specific thioether-containing alkoxydecane derivative (c) is used as an active ingredient, and the components (A) to (D) are added in a balanced manner to exhibit excellent adhesion to an inorganic substrate. Further, in the present invention, the equivalent means the weight of the chemical substance required for forming the number of functional groups of a chemical substance of lm〇l, and can be determined by (molecular weight) / the number of functional groups in the molecule. In addition, in the case of a polymer, the molecular weight is a weight average molecular weight. The curable resin composition of the present invention may contain the following (E) in addition to the components (A) to (D) described above. The curable resin composition of the present invention which does not contain the component (E) is thermosetting, but when the component (E) is added thereto, the curable resin composition can be imparted with photocurability or photothermal property. The curing reaction can be selected depending on the operating environment, the purpose of use, etc. Specifically, as the component (E), 201247768 may also have a molecular weight of 2 〇〇 5 5 〇〇〇〇 and a (fluorenyl) acrylate equivalent weight of 80 6,000 6000 g / A polyfunctional (meth)acrylic acid vinegar compound of mo丨. The component may be mixed in an amount of 2 to 3 parts by weight based on the total weight of the component (A) and the component (B). Further, 'in the present invention, ''(fluorenyl) acrylate, denotes a general term including both acrylate and methacrylate." As the amine compound (D), it is preferred to use the following formula (3) The imidazole compound shown. Therefore, The tube curable resin composition is difficult to carry out a curing reaction in a use temperature and a storage temperature range of 35 ° C or less, and the usable time is prolonged. However, it can be subjected to a curing reaction at 6 〇〇 c, so that it can simultaneously have a teLSJ and storage stability. Both with low temperature curing ^__ Chemical Formula 3

• ♦ · < 3 ) 其中，R為氰基、碳原子數1〜10的烴基、以2,3_二氨基三嗪取代的碳原子數1〜10的烴基、碳原子數卜4的院氧基或氮原子，r4、r6、r7為碳原子數1〜20的烴基、碳原子數丨〜4的烷氧基或氫原子當R4〜R7鍵合形成環的情況下為碳原子數2〜8的烴基。、另外，作為所述多官能硫醇化合物（A)，優選使用下述通式（4)所示的多官能硫醇化合物。 ’、化學式4♦ · < 3 ) wherein R is a cyano group, a hydrocarbon group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 10 carbon atoms substituted with 2,3-diaminotriazine, and a number of carbon atoms An oxy group or a nitrogen atom, wherein r4, r6, and r7 are a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having a carbon number of 丨4 or a hydrogen atom; and when R4 to R7 are bonded to each other to form a ring, the number of carbon atoms is 2 ~8 hydrocarbon groups. Further, as the polyfunctional thiol compound (A), a polyfunctional thiol compound represented by the following formula (4) is preferably used. ', chemical formula 4

其中’ n為2〜5的整數，P為2〜10的整數，R8為碳原子數2〜30的烴基酸二)、碳原子數2〜4〇的由越氧（_〇_)與烴基構成的基團（α2)、異氛聰果=裒（α3)或由異氰脲酸酯環與烴基構成的基團（α4)中的任一種。如疋每類多官能硫醇化合物，則固化性樹脂組合物的儲存穩定性優異。Wherein 'n is an integer of 2 to 5, P is an integer of 2 to 10, R8 is a hydrocarbyl acid having 2 to 30 carbon atoms; and an oxygen (2〇4) and a hydrocarbon group having 2 to 4 carbon atoms. Any of the constituent groups (α2), heterosexual fruit = 裒 (α3) or a group composed of an isocyanurate ring and a hydrocarbon group (α4). The curable resin composition is excellent in storage stability of each type of polyfunctional thiol compound.

S 201247768 另外，作為所述多官能環氧樹脂（B)，優選使用縮水甘油醚型環氧樹月曰或縮水甘油醋型環氧樹脂。這類多官能環氧樹脂，室溫下的反應性緩慢，更能延長可用時間。另外，在本發明中表示數值範圍的‘‘00〜XX”，其概念是包括下限值 (〇〇 )及上限值（“XX”）。即，明確表示〇〇以上χχ以下。發明效果根據本發明’通過以特定的含硫醚的烷氧基矽烷衍生物（C)為有效成分’並均衡魏為必要成分的（A)〜⑼，無需像現有的使用魏偶聯劑的情況那樣添加其他既暮^^濟丨，並且抑制成為附著力促進劑的有放成金 (C)的添加量，同時可獲得優異的黏附性。另外，在現有的使用硫醇化合物的情況下對玻璃、氧化銦錫、等無機基彻請性不夠充分，而本發明組合物對玻璃、氧化銦錫、鋁等無機基材黏附性優異，可作為至今未有的新穎的固化性樹脂組合物。另外’本發明的固化性樹脂組合物，由於可用時間（使用環境下的可使用時間）比較長，因此操作性也良好，儲存穩定性也優異。並且，使其熱固化時，與現有技術相比可以使其在低溫短時間内m化。g卩，在室溫下難以固化，當熱固化時，即使於6〇ΐ左右的低溫下反應性（固化性）也優異。另外，可提高使本發明的固化性樹脂組合物固化後的固化膜的強韌性、耐水性、耐熱性、柔軟性及均一性等。因此，在無機基材上形成固化臈後，即使暴露於像高溫多濕條件下（例如12〇(；c><100RH%x9〇小時左右）這樣的苛刻環境中，也能夠維持充分的黏附性。【實施方式】以下，對本發明進行詳細說明。本發明的固化性樹脂組合物是以下述 (A)、（B)、（C)及（D)成分為必要成分，根據需要還可以含有（E)成分的固化性樹脂組合物。 <多官能硫醇化合物（（A)成分）> 本發明的固化性樹脂組合物中的多官能硫醇化合物（A)是指具有兩個 7 201247768 以上硫醇基（-SH基）的有機化合物。多官能硫醇化合物的分子量為 200〜2000，優選300〜1800，更加優選350〜1600。即使分子量小於200，關於黏附性也沒有問題，但是多官能硫醇化合物的揮發性高，具有臭味增強的傾向。另一方面，如果分子量大於2000，相對於後述的多官能環氧樹脂 (B)的溶解性降低，對無機基材的黏附性可能下降。作為多官能硫醇化合物（A)’可以例舉如下述通式（4)所示的多官能硫醇化合物。另外，多官能硫醇化合物（A)，即可以僅單獨使用一種，也可以兩種以上混合使用。化學式5S 201247768 Further, as the polyfunctional epoxy resin (B), a glycidyl ether type epoxy resin or a glycidol type epoxy resin is preferably used. Such multifunctional epoxy resins are slow to react at room temperature and extend the useful life. Further, in the present invention, the term ''00 to XX'' of the numerical range is included, and the concept includes the lower limit value (〇〇) and the upper limit value ("XX"). According to the present invention, by using the specific thioether-containing alkoxydecane derivative (C) as an active ingredient' and balancing Wei as an essential component (A) to (9), it is not necessary to add other as in the case of using a conventional coupling agent. The addition amount of the gold (C) which is an adhesion promoter is suppressed, and excellent adhesion is obtained at the same time. In addition, in the case of using a thiol compound, glass, indium oxide is used. The inorganic base is less than sufficient, and the composition of the present invention is excellent in adhesion to an inorganic substrate such as glass, indium tin oxide or aluminum, and can be used as a novel curable resin composition which has not been hitherto. The curable resin composition is long in operability due to the usable time (the usable time in the use environment), and is excellent in storage stability. Moreover, when it is thermally cured, it is related to the prior art. The ratio can be made to be m in a short time at a low temperature. It is difficult to cure at room temperature, and when it is thermally cured, it is excellent in reactivity (curability) even at a low temperature of about 6 Torr. The cured film after curing of the curable resin composition of the present invention has toughness, water resistance, heat resistance, flexibility, uniformity, etc. Therefore, even after forming a cured crucible on an inorganic substrate, it is exposed to conditions such as high temperature and humidity. In the harsh environment such as 12 〇 (; c >< 100 RH % x 9 hrs or so), sufficient adhesion can be maintained. [Embodiment] Hereinafter, the present invention will be described in detail. The curable resin of the present invention. The composition is a curable resin composition containing the component (A), (B), (C), and (D) as an essential component and, if necessary, the component (E). <Multifunctional thiol compound (( A) Component) The polyfunctional thiol compound (A) in the curable resin composition of the present invention means an organic compound having two thiol groups (-SH groups) of 7 201247768 or more. Molecular weight is 200~2000 Preferably, it is 300 to 1800, more preferably 350 to 1600. Even if the molecular weight is less than 200, there is no problem in adhesion, but the polyfunctional thiol compound has high volatility and tends to enhance odor. On the other hand, if the molecular weight is more than 2000 The solubility in the polyfunctional epoxy resin (B) to be described later is lowered, and the adhesion to the inorganic substrate may be lowered. The polyfunctional thiol compound (A)' may be exemplified by the following formula (4). Further, the polyfunctional thiol compound (A) may be used alone or in combination of two or more.

其中，η為2〜5的整數’ p為2〜10的整數，R8為碳原子數2〜30的烴基 (αΐ)、碳原子數2〜40的由醚氧（-0-)與烴基構成的基團（α2)、異氰脲酸酯環（α3)或由異氰脲酸酯環與烴基構成的基團（α4)中的任一種。在上述通式（4)中’即使是η=1的化合物也沒有大問題，可以使用，但是得到的多官能硫醇化合物反應性較高，因此含有該化合物的固化性樹脂組合物的儲存穩定性多少存在變差的傾向。與其相對，如果是n=2〜5範圍内的化合物，儲存穩定性優異，同時在6〇°C左右的低溫中，可以短時間内使其固化。另外，隨著η數值的增大，所得到的多官能硫醇化合物的反應性降低，含有該化合物的固化性樹脂組合物的熱固化時的固化時間具有變長的傾向。因此，在上述通式（4)所示的化合物中，最優選11=2的化合物。如果η=2，多官能硫醇化合物的反應性對儲存穩定性和縮短熱固化時的固化時間這兩者均最佳。可以通過下述通式（5)所示的巯基羧酸與下述通式所示的多官能醇的酯化反應得到上述通式（4)所示的多官能硫醇化合物。Wherein, η is an integer of 2 to 5', p is an integer of 2 to 10, R8 is a hydrocarbon group having 2 to 30 carbon atoms (αΐ), and 2 to 40 carbon atoms are composed of ether oxygen (-0-) and a hydrocarbon group. Any of the group (α2), the isocyanurate ring (α3) or the group (α4) composed of an isocyanurate ring and a hydrocarbon group. In the above formula (4), even a compound having η = 1 can be used without any major problem, but the obtained polyfunctional thiol compound has high reactivity, and therefore the storage of the curable resin composition containing the compound is stable. There is a tendency for sex to deteriorate. On the other hand, in the case of a compound in the range of n = 2 to 5, the storage stability is excellent, and at a low temperature of about 6 ° C, it can be cured in a short time. In addition, as the value of η increases, the reactivity of the obtained polyfunctional thiol compound decreases, and the curing time of the curable resin composition containing the compound tends to become longer at the time of thermal curing. Therefore, among the compounds represented by the above formula (4), a compound of 11 = 2 is most preferable. If η = 2, the reactivity of the polyfunctional thiol compound is optimal for both storage stability and shortening of curing time upon heat curing. The polyfunctional thiol compound represented by the above formula (4) can be obtained by an esterification reaction of a mercaptocarboxylic acid represented by the following formula (5) with a polyfunctional alcohol represented by the following formula.

S 201247768 化學式6S 201247768 Chemical Formula 6

CnH2n HS’ 、COOH · 其中，n為1〜5的整數。化學式7 R8~(-〇H ) p ...(6) 其中，p為2〜10的整數，R8為碳原子數為2〜30的烴基（α1)、碳原子數2〜40的由醚氧(-〇-)與烴基構成的基團（α2)、異氰脲酸酯環（α3)或由異亂腺酸醋環與煙基構成的基團（α4)中的任一種。在上述通式（6)所示的化合物中，優選由ρ為2〜4且r8為碳原子數 2〜20的烴基構成的基團的化合物（αυ )、ρ為2〜6且rS為碳原子數2〜3〇的由醚氧（-0-)和烴基構成的基團的化合物（必丨）或卩為3且R8為由異氰脲酸酯環與碳原子數1〜3的烴基構成的基團的化合物（α4_υ。這是因為，如果是這樣的化合物，則與多官能環氧樹脂（Β)的溶解性高。作為（cd-1) ’可以例舉如碳原子數2〜2〇的烷撐二醇、甘油、季戊四醇或三經甲基丙烧等。作物2_丨)可以例舉如聚乙二醇、聚丙二醇、二季戍四醇等。作為(α4-1) ’可以例舉如三（2_經基乙基）異氛腺酸醋等。 <多官能環氧樹脂（（B)成分）> c本發明賴化性樹驗合物中的多官能環氧樹脂⑻轉有兩個以上 %氧基（喊乙烧環）的有機化合物。多官能環氧樹脂的分子量為 200〜5_〇 ’優選細〜48_，更加優選·〜4_。即使分子量小於· 會造成對域紐，賴軸分的鱗性降低，可能 Γ5!〇〇!"θΤ?#^ 80"000g/mo11 ^ 過多，未與多官能硫醇化合物⑷單位體積内的環氧基 %基反應的¥氧基大量剩餘，因此 201247768 由固化性樹馳合物構成_化膜_性可能下降，在暴露於高溫多濕環境的情況τ_性可訂降y -方面，如果魏t量大於麵g/m〇丨環氧基濃度顯著降低’因此射官能猶化合物（A)的麵基的反應效率降低，固化性樹脂組合物構成_化膜_性可能下降，縣露於高溫多渴環境的情況下黏附性可能下降。作為多官能環氧樹脂（Β) ’可以例舉如縮水甘油_環氧樹脂、縮水甘油醋型魏齡、縮水甘油胺型魏樹脂或㈣氧化物氧化含雙鍵化合物的雙_制的氧倾魏顧等4巾，由於在室訂敝應性緩慢及可用時間延長，水甘油_魏_旨魏树賴姐氳樹脂。尤其是縮水甘油_環氧樹脂，由於沒有可與多官能硫醇化合物⑷ 反應的官關’可以不依賴反應條件制均__化性樹脂組合物甚至固化膜。另外，多官能環氧樹脂（B)可以僅單獨使用一種，也可以兩種以上混合使用。 <縮水甘油醚型環氧樹脂> 作為縮水甘賴型環氧樹脂，優選環氧氣丙院與下述通式⑺所示化合物之間的反應產物。化學式8 R9-f〇H )q . . .(7) 其中，q為2〜3的整數，R9為碳原子數2〜2〇〇的烴基碳原子數 2〜300的由醚氧（_〇_)與烴基構成的基團異氰脲酸酯環（阳）、異氰脲酸酯環與烴基構成的基團（β4)。在上述通式（7)所示的化合物中，因為與其他成分的溶解性高，因此優選q為2〜20且R9為由碳原子數2〜15〇的烴基構成的基團的化合物（βΜ) 或q為2〜2〇且r9為碳原子數2〜15〇的由烴基與醚氧（_〇_)構成的基團的化合物（β2-1 )。作為（βΜ )可以例舉如碳原子數2〜1〇的烷撐二醇' 甘油、李戊四醇、三羥曱基丙烷、笨酚酚醛、雙酚Α等。作為（β2-1)可以例舉如聚乙二醇、聚丙二醇或二季戊四醇等。上述環氧氣丙烷與通式（7)所示的化合物間的反應如下，使環氧氣丙 201247768CnH2n HS' , COOH · wherein n is an integer of 1 to 5. Chemical formula 7 R8~(-〇H ) p (6) wherein p is an integer of 2 to 10, R 8 is a hydrocarbon group having 2 to 30 carbon atoms (α1), and an ether having 2 to 40 carbon atoms Any one of a group consisting of oxygen (-〇-) and a hydrocarbon group (α2), an isocyanurate ring (α3), or a group consisting of a heterogeneous sulphuric acid ring and a smoky group (α4). In the compound represented by the above formula (6), a compound (αυ) having a group of ρ of 2 to 4 and r 8 of a hydrocarbon group of 2 to 20 carbon atoms is preferable, and ρ is 2 to 6 and rS is carbon. a compound having a group of 2 to 3 Å having an oxygen group (-0-) and a hydrocarbon group (required) or hydrazine is 3 and R 8 is an isocyanurate ring and a hydrocarbon group having 1 to 3 carbon atoms. The compound (α4_υ) of the constituent group is because, in the case of such a compound, the solubility with the polyfunctional epoxy resin is high. As (cd-1) ', for example, a carbon number of 2 is exemplified. 2〇 alkylene glycol, glycerin, pentaerythritol or trimethyl methacrylate, etc. The crop 2_丨) may, for example, be polyethylene glycol, polypropylene glycol or diquaternary tetraol. The (α4-1) ' can be exemplified by tris(2-cytoethyl)isophthalic acid vinegar or the like. <Polyfunctional epoxy resin ((B) component)> c The polyfunctional epoxy resin (8) in the lysing tree complex of the present invention is converted to an organic compound having two or more % oxy groups (called ethene ring) . The molecular weight of the polyfunctional epoxy resin is 200 to 5 Å Å, preferably 〜 48 Å, more preferably 〜 4 。. Even if the molecular weight is less than ·, it will cause a decrease in the squamousness of the domain, and it may be Γ5!〇〇!"θΤ?#^ 80"000g/mo11 ^ Too much, not with the polyfunctional thiol compound (4) within the unit volume The epoxy group has a large amount of oxy group remaining in the epoxy group, so 201247768 is composed of a curable tree-like compound. The film may be degraded, and in the case of exposure to a high-temperature and high-humidity environment, τ_ability may be reduced to y-, If the amount of Wei t is larger than the surface g/m 〇丨 the epoxy group concentration is significantly lowered', the reaction efficiency of the surface group of the fluorescing functional compound (A) is lowered, and the composition of the curable resin composition may decrease. Adhesion may decrease in hot and thirsty environments. The polyfunctional epoxy resin (Β) can be exemplified by glycidol-epoxy resin, glycidol-type vinegar-type Weiling, glycidylamine-type Wei resin or (iv) oxide-oxidized double-bonded compound. Wei Gu and other 4 towels, due to the slowness of the room and the prolonged time available, water glycerin _ Wei _ Wei Wei Lai sister 氲 resin. In particular, the glycidyl-epoxy resin can be made into a uniform resin film or even a cured film without depending on the reaction conditions because it has no reactivity with the polyfunctional thiol compound (4). Further, the polyfunctional epoxy resin (B) may be used alone or in combination of two or more. <Glycidyl ether type epoxy resin> As the water-reducing type epoxy resin, a reaction product between the epoxy gas and the compound represented by the following formula (7) is preferable. Chemical Formula 8 R9-f〇H ) q . . . (7) wherein q is an integer of 2 to 3, and R 9 is a hydrocarbon group having 2 to 2 carbon atoms and having 2 to 300 carbon atoms by ether oxygen (_〇) _) a group composed of a hydrocarbyl group isocyanurate ring (cation), an isocyanurate ring and a hydrocarbon group (β4). In the compound represented by the above formula (7), since it has high solubility with other components, a compound in which q is 2 to 20 and R9 is a group composed of a hydrocarbon group having 2 to 15 carbon atoms is preferable (βΜ) Or a compound (β2-1) wherein q is 2 to 2 Å and r9 is a group of a hydrocarbon group and an ether oxygen (_〇_) having a carbon number of 2 to 15 Å. The (βΜ) may, for example, be an alkylene glycol having a carbon number of 2 to 1 Å, glycerin, pentaerythritol, trihydroxydecylpropane, phenol novolac, bisphenol oxime or the like. The (β2-1) may, for example, be polyethylene glycol, polypropylene glycol or dipentaerythritol. The reaction between the above epoxidized gas propane and the compound represented by the general formula (7) is as follows, and the epoxy propylene is made 2012.

J = 反應後得到的環氧躺的部分魏細環聚合得到的環所示的結構化學式9 裒^丙淀與通式⑺所示的化合物的反應產物，具有如下述通式（8)J = a ring obtained by the polymerization of a portion of the epoxy ring obtained by the reaction. The structure shown by the formula 9 is a reaction product of the compound represented by the formula (7) having the following formula (8)

其中q為2 30的整數，R9為碳原子數2〜200的烴基（βΐ )、碳原子數2 3⑻的由喊氧（_〇_)與烴基構成的基團（印）、異氰腺酸醋環（阳）或由異氰脲酸酯環與烴基形成的基團（料）。 <縮水甘油酯型環氧樹脂> ，水甘油S旨型環氧樹脂’是將（甲基）丙烯酸縮水甘油§旨等具有環氧基的單體，單獨或與碳原子數4〜25的（甲基）丙烯酸院基醋共聚得到的重均分子量Α 3_〜2〇_的聚合物’或者是環氧氣丙院與下述通式⑼所示的化合物的反應產物等。化學式10 R10~(-cooh ) r ...(9) 其中’r為2〜8的整數，R10為碳原子數2〜20的烴基（β5)、碳原子數 2〜30的由醚氧（_〇_)與烴基構成的基團（ρ6)、異氰脲酸酯環（β7)或異氰脲酸酯環與烴基構成的基團（β8)中的任一種。、環氧氯丙烧與通式（9)所示化合物間的反應如下，使環氧氣丙烷與通式（9)所示化合物峨基域反應制得氣醇，以氫氧化鱗域使制得的氣醇關環’制得縮水甘油g旨型環氧樹脂。另外，也可以使錢縮水甘油醋型環氧樹脂的部分環氧基開環聚合制得的環氧樹脂。 201247768 在上述通式（9)所示的化合物中，優選r為2〜4且R1。為碳原子數2〜10 的由烴基構成的基團的化合物（β5_1)或r為2〜6且rIq為碳原子數2〜3〇的由氧（-〇-)與經基構成的基團的化合物（β6_ι )或圹為3且r1〇為由異氰脲酸酯環與烴基構成的基團的化合物這是因為其溶解性高。作為（β5-〗），可以例舉如氫化鄰苯二曱酸或偏苯三酸等。作為（阼-丨），可以例舉如季戊四醇與偏苯三酸酐的反應產物。作為（β8-1 )，可以例舉如 1，3,5-三（2-羧乙基）異氰脲酸醋等。 %氧氣丙烷與通式（9)所示化合物的反應產物，具有下述通式（1〇) 所示結構。_ 化學式11Wherein q is an integer of 2 30, R9 is a hydrocarbon group having 2 to 200 carbon atoms (βΐ), a group having 2 to 3 (8) carbon atoms and a hydrocarbon group (imprint), and isocyanuric acid An vinegar ring (yang) or a group formed from an isocyanurate ring and a hydrocarbon group. <Glycidyl Ester Type Epoxy Resin>, Glycidyl S-Type Epoxy Resin' is a monomer having an epoxy group such as glycidyl (meth)acrylate, alone or in combination with carbon atoms 4 to 25. The polymer having a weight average molecular weight of ( 3_~2〇_ obtained by copolymerization of (meth)acrylic acid-based vinegar or a reaction product of a compound represented by the following formula (9). Chemical Formula 10 R10~(-cooh) r (9) wherein 'r is an integer of 2 to 8, R10 is a hydrocarbon group having 2 to 20 carbon atoms (β5), and an oxygen group having 2 to 30 carbon atoms ( _〇_) Any one of a group consisting of a hydrocarbon group (ρ6), an isocyanurate ring (β7) or an isocyanurate ring and a hydrocarbon group (β8). The reaction between the epichlorohydrin and the compound of the formula (9) is as follows. The epoxide is reacted with the sulfhydryl group of the compound represented by the formula (9) to obtain an alcohol, which is obtained by oxidizing the scale. The alcohol-gas ring is made of glycidol g-type epoxy resin. Further, an epoxy resin obtained by ring-opening polymerization of a partial epoxy group of a glycidol type epoxy resin may be used. 201247768 In the compound represented by the above formula (9), it is preferred that r is 2 to 4 and R1. a compound (β5_1) having a group of 2 to 10 carbon atoms and a group of 2 to 6 and rIq having 2 to 3 carbon atoms and having a group consisting of oxygen (-〇-) and a radical The compound (β6_ι) or the compound in which ruthenium is 3 and r1〇 is a group composed of an isocyanurate ring and a hydrocarbon group is because of its high solubility. As (β5-), for example, hydrogenated phthalic acid or trimellitic acid can be exemplified. As (阼-丨), a reaction product such as pentaerythritol and trimellitic anhydride can be exemplified. The (β8-1) may, for example, be 1,3,5-tris(2-carboxyethyl)isocyanuric acid vinegar or the like. The reaction product of % oxygen propane with a compound of the formula (9) has a structure represented by the following formula (1). _ Chemical formula 11

其中’ r為2〜8的整數’ R1C為碳原子數2〜2〇的烴基⑻）、碳原子數 2〜3~0的由醚氧（_〇_)與烴基構成的基團（ρ6)、異氰脲酸酯環（(37)或由異氰脲酸酯環與烴基構成的基團（β8)中的任一種。 <含硫醚的烷氧基矽烷衍生物（C)成分> 含硫醚的烷氧基矽烷衍生物（c)’是固化本發明的固化性樹脂組合物時，為了提尚對無機基材的黏附性而添加的附著力促進劑。該含硫醚的烷氧基矽院衍生物（C)，具有硫醚基，以二硫鍵與由多官能硫醇化合物（Α) 和多官能環氧樹脂（Β)交聯反應生成的硫醚基發生化學鍵合。此時，由於含硫醚的烷氧基矽烷衍生物（C)與多官能硫醇化合物的相溶性高且反應效率高，因此得到的附著力促進效果高。並且，含硫醚的烷氧基矽烷衍生物（C)具有烷氧矽基，可以與由多官能硫醇化合物（Α)和多官能環氧樹脂（Β)反應生成的羥基反應。結果，所得到的樹脂固化物交聯密度提高，形成強韌的具有高耐水性的交聯體（固化物> 另外，含硫醚的烷氧基矽烷衍生物（C)的烷氧矽基，可以與無機基材發生化學鍵合，能夠大幅度提高與無機基材間的附著力。Wherein 'r is an integer of 2 to 8', R1C is a hydrocarbon group (8) having 2 to 2 carbon atoms, and a group consisting of ether oxygen (_〇_) and a hydrocarbon group (ρ6) having 2 to 3 to 0 carbon atoms. Any one of an isocyanurate ring ((37) or a group consisting of an isocyanurate ring and a hydrocarbon group (β8). < Sulfide-containing alkoxydecane derivative (C) component &gt The thioether-containing alkoxydecane derivative (c)' is an adhesion promoter added to cure the adhesion to the inorganic substrate when the curable resin composition of the present invention is cured. The alkoxy oxime derivative (C) has a thioether group and is chemically bonded to a thioether group formed by crosslinking a polyfunctional thiol compound (Α) and a polyfunctional epoxy resin (Β) by a disulfide bond. In this case, since the thioether-containing alkoxydecane derivative (C) has high compatibility with the polyfunctional thiol compound and high reaction efficiency, the obtained adhesion promoting effect is high. Further, the thioether-containing alkoxylate. The decane derivative (C) has an alkoxy group which can react with a hydroxyl group formed by reacting a polyfunctional thiol compound (Α) with a polyfunctional epoxy resin (Β). As a result, the obtained resin cured product has a higher crosslinking density, and forms a tough crosslinked body having high water resistance (cured product). Further, the alkoxy group of the thioether-containing alkoxydecane derivative (C) The sulfhydryl group can be chemically bonded to the inorganic substrate, and the adhesion to the inorganic substrate can be greatly improved.

S 12 201247768 本發明的固化性樹脂組合物中的含硫醚的烷氧基矽烷衍生物（c)是下述通式（1)或通式（2)所示的化合物。另外，含硫醚的烷氧基矽烷衍生物（C)可以僅單獨使用一種，也可以兩種以上混合使用。化學式12S 12 201247768 The thioether-containing alkoxydecane derivative (c) in the curable resin composition of the present invention is a compound represented by the following formula (1) or (2). Further, the thioether-containing alkoxydecane derivative (C) may be used alone or in combination of two or more. Chemical formula 12

其中，a為1〜4的整數’ b為〇〜3的整數，c為0或1，a+b+c=4 ; m為 1 或 2 ; R1 為-CH2-CH(CH3)- ' -C(CH3)r、-CH2-CH2-或-CH(CH3)-中任意一種所示的二價基團，R2為甲基或乙基；化學式13Wherein, a is an integer of 1 to 4 'b is an integer of 〇~3, c is 0 or 1, a+b+c=4; m is 1 or 2; R1 is -CH2-CH(CH3)-' - a divalent group represented by any one of C(CH3)r, -CH2-CH2- or -CH(CH3)-, R2 is a methyl group or an ethyl group;

其中’ a’為1~3的整數，b，為〇〜2的整數，c’為〇或卜a，+b，+c，=3 ; a” 為〇〜3的整數，b”為〇〜2的整數，c”為〇或卜a，，+b，，+c，，=3 ; m為1或2 ; R1 為-ch2-ch(ch3)-、-c(ch3)2-、-CH2-CH2-或-CH(CH3)-中任意-種所示的一價基團，R2為甲基或乙基；上述通式（1)所示的含硫醚的烷氧基矽烷衍生物分子量低，與 %氧樹脂的相溶性高，因此適宜在想要提高固化物的強韌性時使用。另外，通式（2)所示的含硫醚的烷氧基矽烷衍生物（c),在更少量添加的條件下，適宜在想要得到高黏附性的情況下使用。在上述通式（1)中，b不為〇的含硫醚的烷氧基矽烷衍生物（c)，由於還具有硫醇基，因此可以與多官能環氧樹脂（B)反應。因此，能夠進〆步提高交聯密度，可以得到強韌的固化物。同樣，在上述通式⑵中，b， 13 201247768 或b”不為〇的含硫醚的烷氧基矽烷衍生物（c)，由於還具有硫醇基，因此可以與多官能環氧樹脂（B)反應。因此，能夠進一步提高交聯密度，可以得到強韌的固化物。本發明的固化性樹脂組合物中的含硫醚的烷氧基矽烷衍生物（C)，可以通過（11)所示的含烷氧矽基的化合物（X)，與通式（12)或通式（13) 所示的多官能硫醇化合物（γ)反應制得。化學式14 -0r2 (1 1〉 Γ 心2 — 其中，R2為曱基或乙基，R11為氫原子或曱基。化學式15Where 'a' is an integer from 1 to 3, b is an integer from 〇 to 2, c' is 〇 or a, +b, +c, =3; a" is an integer from 〇 to 3, b" is 〇 An integer of ~2, c" is 〇 or 卜 a,, +b,, +c,, =3; m is 1 or 2; R1 is -ch2-ch(ch3)-, -c(ch3)2-, a monovalent group represented by any one of -CH2-CH2- or -CH(CH3)-, R2 is a methyl group or an ethyl group; and a thioether-containing alkoxydecane derivative represented by the above formula (1) Since the molecular weight is low and the compatibility with the % oxygen resin is high, it is preferably used when it is desired to increase the toughness of the cured product. Further, the sulfide-containing alkoxydecane derivative represented by the formula (2) (c) In the case of a smaller amount of addition, it is suitably used in the case where high adhesion is desired. In the above formula (1), b is not a hydrazine-containing alkoxydecane derivative (c), Since it also has a thiol group, it can react with the polyfunctional epoxy resin (B). Therefore, the crosslinking density can be increased step by step, and a tough cured product can be obtained. Similarly, in the above formula (2), b, 13 201247768 or b" is not a thiol-containing alkoxydecane derivative (c) Since it also has a thiol group, it can react with the polyfunctional epoxy resin (B). Therefore, the crosslinking density can be further increased, and a tough cured product can be obtained. The thioether-containing alkoxydecane derivative (C) in the curable resin composition of the present invention may be obtained by the alkoxyfluorenyl group-containing compound (X) represented by (11), and the formula (12) or The polyfunctional thiol compound (γ) represented by the formula (13) is obtained by a reaction. Chemical Formula 14 -0r2 (1 1> Γ 2 - wherein R 2 is a fluorenyl group or an ethyl group, and R 11 is a hydrogen atom or a fluorenyl group.

其中’m為1或2’d為3或4，e為〇或1，d+e=4。化學式16Where 'm is 1 or 2'd is 3 or 4, and e is 〇 or 1, d+e=4. Chemical formula 16

其中’ m為1或2 ’ d，為2或3，e，為〇或1，d，+e，=3，d”為2或3，e” 為〇或 1，d，’+ e，，=3。作為上述通式（11)所示的含院氡⑦基的化合物（χ)’可以例舉如3_ 甲基丙烯酿氧基丙基三甲氧基魏、3_丙烯醯氧基丙基三甲氧基魏、3_ 甲基丙稀醯氧基丙基三乙氧基魏、3_丙稀醯氧基丙基三甲氧基石夕院。作為上述通式（丨2)麻的彡官驗醇化合物⑺，可以例舉如三經曱基丙垸三（3·祕丙酸g旨）或季細醇四（3·龜丙_)。作為上述通 201247768 式（13)所示的多官能硫醇化合物，可以例舉如雙三羥曱基丙烷六（3_巯基丙酸酯）或雙季戊四醇六（3-酼基丙酸酯）。另外，在通式（12)或通式（13) 中，在使用m23的化合物的情況下，在得到的含硫醚的烷氧基矽烷衍生物中’疏水性且非極性的烴基數增加，從而使硫醚基對基材的取向性減弱，難以得到黏附性。含烷氧矽基的化合物（X)與多官能硫醇化合物（γ)，優選在催化劑或自由基引發劑的存在下反應。如果添加催化劑或自由基引發劑，能夠在更短時間内且更高效率地使其發生反應。作為Jtih劑，優選為胺類的鹼性催化劑，可以使且值胺、仲胺或叔胺類’或者使用咪唑類化合物。例如作為伯胺可例舉甲胺、乙胺、丙胺、丁胺、乙二胺等；作為仲胺可例舉二曱胺、二乙胺、二丙胺、甲基乙基胺、二苯基胺等；作為叔胺可例舉三甲胺、三乙胺、三丙胺、三苯基胺、丨，8_ 二氮雜雙環(5,4,0)-十一碳-7-烯、2,4,6-三（二曱胺基曱基）苯酚等。作為咪唑類化合’例如可例舉1-曱基咪唑、1，2-二甲基咪唑、丨，4_二曱基_2_乙基咪唾、1-苯基咪唑等的咪唑同系物；卜甲基氧甲基咪唑、i_甲基_2_氧乙基味 °坐專氧炫•基诉生物，1-甲基-4(5)-石肖基咪°坐、1，2-二甲基-5(4)-氨基味。坐等硝基及氨基衍生物；苯並咪唑、1-曱基苯並咪唑、1_甲基_2_苄基苯並咪唑等。作為自由基引發劑優選過氧化物或偶氮化合物。作為過氧化物，例如可例舉過乳化一本曱醯、過氧化-2-乙基己酸叔丁酷、過氧化十二醯、叔丁基過氧化氲專。作為偶氣化合物，例如可例舉偶氮二異丁腈及2,2，_偶氮雙 (2-曱基丁腈）等。 & 作為含硫醚的烷氧基矽烷衍生物（C)的製備方法，在以上的溫度下就能夠使其反應，但是為了在短時間内（例如5小時以内）使其反應，更優選添加胺類專驗性催化劑或自由基引發劑，在6〇〜8〇。〇下使其反應。在含硫謎的烧氧基石夕烧衍生物的製備方法中，即使無溶劑也能夠使反應進行，但疋若在低溫下使其反應的情況下或想要降低黏度的情況下，也可以添加溶劑使其反應。此時優選不與烷氧矽基、雙鍵、硫醇基反應的溶劑’優選例如醇類、酮類、酯類或芳香族類。 15 201247768 作為不與烷氧矽基、雙鍵、硫醇基反應的醇類，優選相對於反應溫度具有適當沸點的醇類，尤其優選沸點為50〜180。(：的醇類。其原因是在沸點比上述範圍更低的情況下，難以在工業化情況下生產；比上述溫度更高的情況下’在需要除去溶劑時難以蒸餾溶劑。作為不與烷氧矽基、雙鍵、硫醇基反應的酮類，優選相對於反應溫度具有適當沸點的酮類，尤其優選沸點為50〜180。(：的酮類。其原因是在沸點比上述範圍更低的情況下，難以在工業化情況下生產；比上述溫度更高的情況下，在需要除去溶劑時難以蒸德溶劑。例如有曱基乙基酮、甲基異丁基酮等。 ___ 、作為不與烷氧矽基、雙鍵、硫醇基反應的酯類，優選相對於反應溫度具有適當沸點的酯類，尤其優選沸點為50〜180。(：的酯類。其原因是在沸點比上述範圍更低的情況下，難以在工業化情況下生產；比上述溫度更高的情況下’在需要除去溶劑時難以蒸飽溶劑。例如有醋酸乙酯、醋酸甲酯、醋酸丁酯、醋酸甲氧基丁酯、醋酸乙二醇***、醋酸戊酯、醋酸正丙酯、醋酸異丙酯等。 <胺類化合物（D)成分> 本發明的固化性樹脂組合物中的胺類化合物，是用於促進（催化）硫醇基與環氧基間的反應而添加的。作為胺類化合物（D)，可以例舉如分子量為90〜700、優選1〇〇〜690、尤其優選11〇〜680的單官能胺或具有多個氨基的多元胺。如果胺類化合物（D)的分子量不足90，則胺的揮發性較高，不僅具有臭氣或孔隙等缺陷’而且由於加熱固化時胺的濃度降低難以進行交聯反應，導致黏附性下降。如果胺類化合物（D)的分子量超過7〇〇，則容易導致耐水性下降黏附性易下降。作為單官能胺類，可以例舉如伯胺、仲胺或叔胺。作為多元胺，可以例舉如伯胺、仲胺、叔胺、複合胺。複合胺是指具有伯胺基、仲胺基、叔胺基中兩種以上的胺。作為這些複合胺’可以例舉如咪唑啉化合物、咪唑化合物、 N取代弧嗪化合物、N，N-二甲基尿素衍生物等。另外，胺類化合物（D)可以僅單獨使用一種，也可以兩種以上混合使用。Where 'm is 1 or 2' d, is 2 or 3, e, is 〇 or 1, d, +e, = 3, d" is 2 or 3, and e" is 〇 or 1, d, '+ e, , = 3. The compound (χ) of the formula 7 represented by the above formula (11) can be exemplified by 3-methacryloxypropyltrimethoxywei and 3-propyleneoxypropyltrimethoxy. Wei, 3_ methyl propyl methoxy propyl triethoxy wei, 3 propylene methoxy propyl trimethoxy shixiyuan. The quinone alcohol-compounding compound (7) of the above formula (丨2) can be exemplified by triterpene phthalocyanine (3), or quaternary alcohol 4 (3 turmeric). The polyfunctional thiol compound represented by the formula (13) in the above-mentioned 201247768 may, for example, be bistrihydroxydecylpropane hexa(3- mercaptopropionate) or dipentaerythritol hexa(3-mercaptopropionate). Further, in the general formula (12) or the general formula (13), in the case of using the compound of m23, the number of hydrophobic and non-polar hydrocarbon groups in the obtained thioether-containing alkoxydecane derivative increases. Thereby, the orientation of the thioether group to the substrate is weakened, and it is difficult to obtain adhesion. The alkoxyfluorenyl group-containing compound (X) is reacted with a polyfunctional thiol compound (?), preferably in the presence of a catalyst or a radical initiator. If a catalyst or a radical initiator is added, it can be reacted in a shorter time and more efficiently. As the Jtih agent, an amine-based basic catalyst is preferable, and an amine, a secondary amine or a tertiary amine can be used, or an imidazole compound can be used. For example, a primary amine may, for example, be methylamine, ethylamine, propylamine, butylamine or ethylenediamine; and as the secondary amine, diamine, diethylamine, dipropylamine, methylethylamine or diphenylamine may be exemplified. And the tertiary amine may, for example, be trimethylamine, triethylamine, tripropylamine, triphenylamine, hydrazine, 8-diazabicyclo(5,4,0)-undec-7-ene, 2,4, 6-tris(diamidoguanyl) phenol and the like. Examples of the imidazole compounding include, for example, imidazolium homologues such as 1-mercaptoimidazole, 1,2-dimethylimidazole, anthracene, 4-dimercapto-2-ethylsulfate, and 1-phenylimidazole; Methyl oxymethylimidazole, i_methyl 2 _ oxyethyl taste ° sit oxygen oxygen • 基 base bio, 1-methyl-4 (5) - Shi Xiaojiimi ° sit, 1,2-dimethyl - 5(4)-Amino taste. Wait for the nitro group and the amino derivative; benzimidazole, 1-mercaptobenzimidazole, 1-methyl-2-benzylbenzimidazole, and the like. As the radical initiator, a peroxide or an azo compound is preferred. The peroxide may, for example, be emulsified by one hydrazine, tert-butyl peroxy-2-ethylhexanoate, decyl peroxide, or tert-butyl peroxide. The azo compound may, for example, be azobisisobutyronitrile or 2,2,-azobis(2-mercaptobutyronitrile). & As a method for producing the sulfide-containing alkoxydecane derivative (C), the reaction can be carried out at the above temperature, but in order to cause the reaction to be carried out in a short time (for example, within 5 hours), it is more preferable to add Amine-specific catalysts or free radical initiators are available in 6〇~8〇. Let it react under the armpit. In the method for producing a sulfur-containing enriched alkoxylate derivative, the reaction can be carried out without a solvent, but if the reaction is carried out at a low temperature or if the viscosity is desired to be lowered, it may be added. The solvent is allowed to react. In this case, the solvent which does not react with the alkoxy group, the double bond or the thiol group is preferably, for example, an alcohol, a ketone, an ester or an aromatic. 15 201247768 The alcohol which does not react with an alkoxy group, a double bond, or a thiol group is preferably an alcohol having an appropriate boiling point with respect to the reaction temperature, and particularly preferably has a boiling point of 50 to 180. (: alcohols. The reason is that it is difficult to produce in the case of industrialization in the case where the boiling point is lower than the above range; in the case of higher than the above temperature, it is difficult to distill the solvent when it is necessary to remove the solvent. The ketone group which reacts with a mercapto group, a double bond or a thiol group is preferably a ketone having an appropriate boiling point with respect to the reaction temperature, and particularly preferably a ketone having a boiling point of from 50 to 180. The reason is that the boiling point is lower than the above range. In the case of industrialization, it is difficult to produce in the case of industrialization; when it is higher than the above temperature, it is difficult to evaporate the solvent when it is necessary to remove the solvent. For example, mercaptoethyl ketone, methyl isobutyl ketone, etc. ___ The ester which reacts with an alkoxyfluorenyl group, a double bond, or a thiol group is preferably an ester having an appropriate boiling point with respect to the reaction temperature, and particularly preferably an ester having a boiling point of 50 to 180. The ester is derived from the above boiling point. In the case of a lower range, it is difficult to produce in the case of industrialization; when the temperature is higher than the above temperature, it is difficult to evaporate the solvent when it is necessary to remove the solvent. For example, ethyl acetate, methyl acetate, butyl acetate, Acid methoxybutyl ester, ethylene glycol ethyl acetate, amyl acetate, n-propyl acetate, isopropyl acetate, etc. <Amine compound (D) component> Amine in the curable resin composition of the present invention The compound is added for promoting (catalyzing) a reaction between a thiol group and an epoxy group. As the amine compound (D), for example, a molecular weight of 90 to 700, preferably 1 to 690, particularly A monofunctional amine of 11 〇 to 680 or a polyamine having a plurality of amino groups is preferred. If the molecular weight of the amine compound (D) is less than 90, the volatility of the amine is high, not only has defects such as odor or pores but also due to heating When the concentration of the amine is lowered, it is difficult to carry out the crosslinking reaction, and the adhesion is lowered. When the molecular weight of the amine compound (D) exceeds 7 Å, the water resistance is liable to lower and the adhesion is liable to lower. As the monofunctional amine, for example, The primary amine may, for example, be a primary amine, a secondary amine, a tertiary amine or a complex amine. The composite amine means two of a primary amino group, a secondary amino group and a tertiary amine group. The above amines as these complex amines For example, an imidazoline compound, an imidazole compound, an N-substituted arcazine compound, an N,N-dimethylurea derivative, etc. may be used. The amine compound (D) may be used alone or in combination of two or more. .

S 16 201247768 另外，為了調整催化活性’胺類化合物（D)可以預先與有機酸形成鹽° 作為預先與胺類化合物（D)反應的有機酸，可以例舉如碳原子數1〜20反分子中具有1〜5個羧基的硬脂酸或2-乙基己酸等脂肪族羧酸、碳原子數 1〜20且分子中具有1〜10個羧基的均苯四曱酸、偏苯三酸、安息香酸等芳香族羧酸或異氰脲酸。另外’為了調整催化活性，胺類化合物（D)還可以在與多官能環氧樹脂（B)形成加成物後混入。 <咪唑化合物> 在胺類化合物（D)中，咪唑化合物最適於兼得儲存穩定性和低溫下的 ''〜·固-化性。另外，還可以使用以苯酚樹脂-塗复的3卡唑化合物。該咪唑化合物為以下述通式（3)表示的化合物。化學式17S 16 201247768 In addition, in order to adjust the catalytic activity, the amine compound (D) may be formed into a salt with an organic acid in advance. As an organic acid which is previously reacted with the amine compound (D), for example, an antimolecular molecule having 1 to 20 carbon atoms may be mentioned. An aliphatic carboxylic acid such as stearic acid or 2-ethylhexanoic acid having 1 to 5 carboxyl groups, pyromellitic acid having 1 to 20 carbon atoms and having 1 to 10 carboxyl groups in the molecule, and trimellitic acid An aromatic carboxylic acid or isocyanuric acid such as benzoic acid. Further, in order to adjust the catalytic activity, the amine compound (D) may be mixed after forming an adduct with the polyfunctional epoxy resin (B). <Imidazole compound> In the amine compound (D), the imidazole compound is most suitable for both storage stability and ''solidification' at low temperatures. Further, a 3 carbazole compound coated with a phenol resin can also be used. This imidazole compound is a compound represented by the following formula (3). Chemical formula 17

其中，R3為氰基、碳原子數1〜1〇的烴基、以2,3_二氨基三嗪取代的碳原子數1〜10的烴基、碳原子數丨〜4的烷氧基或氫原子，R4、R6、R7為碳原子數1〜20的烴基、碳原子數1〜4的烷氧基或氫原子，當R4〜R7鍵合形成環的情況下為碳原子數為2〜8的烴基。具體地說，可例舉2-甲基咪唑、2-十一烷基咪唑、2_十七烷基咪唑、2_ 笨基°米°坐、1，2-二甲基咪唑、2-苯基-4-曱基咪唑、节基_2_曱基咪唑、丨_节 2-笨基咪唑、2_乙基_4_甲基咪唑、ι_ (2_氰基乙基）_2_曱基咪唑、ι_ (2_ 氰基乙基）-2-十—烷基咪唑、1- (2-氰基乙基）-2-乙基-4-曱基咪唑、1_ (2-氛基乙基）-2-苯基味唑、1_(2_氰基乙基）_2_乙基斗曱基咪嗤、2,3二氮]Η· 吡咯並（l，2-a)苯並咪唾、2,4_二氨基_6_ (2_甲基咪嗤·（〖））_乙基_s三嗪、 2,4-一氣基-6- (2’-十一烷基咪唾_ (1，））乙基·s_三嗪、2,4二氨基_6_ (2，_ 乙基_4’曱基咪唑-(1，))-乙基-s-三嗪、2-苯基-4,5-二羥基甲基咪唑、2_苯基-4-曱基-5-經基甲基咪唑。 201247768 <多官能（曱基）丙烯酸酯化合物（（E)成分）〉本發明的固化性樹脂組合物中如果有多官能硫醇化合物（A)、多官能 %氧樹脂（B)及胺類化合物（D)，則可以通過熱進行固化。另一方面，在想要賦予本發明的固化性樹脂組合物光固性或光熱兩級固化性的情況下，則可以添加多官能（甲基）丙烯酸酯化合物（E)。眾所周知’在熱或光的激發下，硫醇與雙鍵發生加成反應。因此，多 S旎硫醇化合物（A)與含多官能雙鍵的化合物的混合物，可形成固化性樹脂組合物。在本發明中，在上述雙鍵令，優選具有兩個以上丙烯醯氧基或甲紅#醯氧基的化合物的多官能（曱基）丙赃^旨化合物⑻。在眾多的含雙鍵的化合物中，選擇多官能（甲基）丙烯酸酯的理由是，在室溫下與本發明的固化性樹脂組合物中的多官能硫醇化合物難以反應’能設疋長可用時間，在與多官能硫醇化合物（A)反應時，可以形成強韌的固化物；難以通過麵化合物⑼催化财官能猶化合物（A)的反應，並且不與多官能環氧樹脂（B)反應等。作為該多官能（甲基）丙烯酸酯（E)，可以例舉優選如下述通式（】4) 所示的化合物。另外，多官能（甲基）丙烯酸酯（E)可以僅單獨使用一種，也可以兩種以上混合使用。化學式18Wherein R3 is a cyano group, a hydrocarbon group having 1 to 1 carbon atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with 2,3-diaminotriazine, an alkoxy group having a carbon number of 丨4 or a hydrogen atom; R4, R6 and R7 are a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a hydrogen atom, and when R4 to R7 are bonded to each other to form a ring, the number of carbon atoms is 2 to 8. Hydrocarbyl group. Specifically, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-stupyl, 1,2-dimethylimidazole, 2-phenyl -4-mercaptoimidazole, nodal group 2_mercaptoimidazole, 丨-section 2-styl imidazole, 2-ethyl 4-methylimidazole, ι_(2-cyanoethyl)_2-mercaptoimidazole , ι_(2_Cyanoethyl)-2-decamethylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-indolyl imidazole, 1-(2-aminoethyl)- 2-phenyl oxazole, 1-(2-cyanoethyl)_2-ethyl hydrazine, 2,3 diaza]pyridinium, pyrrolo(l,2-a)benzopyrene, 2, 4_Diamino_6_(2_Methylammonium·())_Ethyl_s triazine, 2,4-one gas group-6- (2'-undecyl imino-salt (1,) Ethyl·s_triazine, 2,4 diamino-6-(2,-ethyl-4-4'nonyl imidazole-(1,))-ethyl-s-triazine, 2-phenyl-4, 5-Dihydroxymethylimidazole, 2-phenyl-4-indolyl-5-tramethylmethylimidazole. 201247768 <Polyfunctional (fluorenyl) acrylate compound (component (E))> If the polyfunctional thiol compound (A), the polyfunctional oxy-resin (B), and the amine are present in the curable resin composition of the present invention Compound (D) can be cured by heat. On the other hand, when it is desired to impart curable or photothermal two-stage curability to the curable resin composition of the present invention, a polyfunctional (meth) acrylate compound (E) can be added. It is well known that thiol undergoes an addition reaction with a double bond under the excitation of heat or light. Therefore, a mixture of a polysulfonyl thiol compound (A) and a compound having a polyfunctional double bond can form a curable resin composition. In the present invention, the above-mentioned double bond is preferably a polyfunctional (fluorenyl) propyl compound (8) having a compound of two or more acryloxy groups or a red group. Among the many compounds containing a double bond, the reason why the polyfunctional (meth) acrylate is selected is that it is difficult to react with the polyfunctional thiol compound in the curable resin composition of the present invention at room temperature. The available time, when reacted with the polyfunctional thiol compound (A), can form a tough cured product; it is difficult to catalyze the reaction of the functional compound (A) by the surface compound (9), and does not react with the multifunctional epoxy resin (B) ) Reaction, etc. The polyfunctional (meth) acrylate (E) is preferably a compound represented by the following formula (4). Further, the polyfunctional (meth) acrylate (E) may be used alone or in combination of two or more. Chemical formula 18

其中，s為2〜30的整數’ R12為碳原子數2〜2〇〇的烴基（ε1)、碳原子數 2〜300的由醚氧（·〇_)與烴基構成的基團⑹、異氛腺酸醋環⑹或由異氰脲酸酯環與烴構成的基團（ε4)，Rn為氫原子或曱基。另外’作為多官能（甲基）丙晞g“旨⑻，可適宜使用聚合物類的化合物。作為聚合物類的多官能（曱基）丙烯酸酯（E)，可以例舉如：在（甲基）丙稀酸縮水甘油S旨等具有環氧基的（甲基）丙炼酸_化合物的均聚物或共聚物中，使如（曱基）丙稀酸等具有可與環氧基反應的基_ (曱基) 201247768 旨化合物的均聚物或共聚物中，使如2-甲基丙烯酸2· 2酸基乙“具材触基反應的基_ (甲基）㈣義化合物反應制付的聚合物；在（甲基）丙_等具有麟的（曱基）丙騎醋化合物的均聚物或共聚物中’使如（甲基）丙稀酸縮水甘油轉具有可舰基反應的（甲基）丙稀酸SI化合物反應制得的聚合物等。多官能（甲基）丙烯酸醋化合物⑻的分子量為2〇〇〜5〇〇〇〇，優選 220〜40_’更加優選24()〜3_。多官能（甲基）丙稀酸醋化合物⑻ 的分子量即使小於200，J_附性也沒有問題，但是存在揮發性變高d 味變強的傾向。另-转，如果纽5Q_，姆於其他成分的溶解性可能下降。另外’多官能（曱基）丙稀酸酿⑻的（甲基）丙稀酸醋當量為 ^6_g/md ’優選8〇〜侧’更加優選85〜麵。如果（甲基）丙稀酸醋當量小於80 g/mo卜則單位體積β (曱基）丙稀酿氧基過多，未與多官能硫醇化合物（Α)的硫醇基反應的（曱基）丙雜氧基大量剩餘，因此由固化性樹脂組合物構成的固化膜_性可能下降，在高溫多濕條件下暴露的情况下，黏附性可能下降。另一方面，如果（曱基）丙烤義當量大於_〇 g/mol，則（甲基）丙烯醯氧基濃度顯著降低，因此與多官能硫醇化合物的硫醇基的反應效率下降，可能轉致㈣化性樹駄合物構成的固化膜的韌性下降，在高溫多濕環境下暴露時黏附性下降。 <組成比（均衡配比）> 本發明的固化性樹脂組合物，混入多官能硫醇化合物（A)與多官能環氧樹脂（B) ’使其重量比（A) /⑻為〇〇5〜3〇。該處，“（A) /⑻，，是指以多官能環氧樹脂⑻的重量除多官能硫醇化合物⑷的重量。最佳的（A) / (B)值’因固化性樹脂組合物所要求的特性、多官能硫醇化合物（A)或多官能環氧樹脂以及根據情況添加的多官能（甲基）丙烯酸0曰化合物（E)的結構不同而不同。固化性樹脂組合物固化後的特性，嚴格受固化性樹脂組合物單位重量中的（硫醇基數）/(環氧基數+(甲基）丙 201247768 ί 物/ (環㈣）比）嶋響。例如，硫醇/ (環 =另方範軸’易形絲密交聯，且容㈣成強_固化物。另一方面，如果硫醇/(環氧+稀）比為(Μ以上不足0.5或2 〇以下超 =5時，能夠得到柔軟的黏性固化物。如果硫醇/(環㈣）比不足或超過2.G時，難以凝膠化，有黏附性下降的趨勢。另外’本發明的固化性樹脂組合物，以多官能硫醇化合物⑷和多官能環氧樹脂⑻的總重量（Α+Β)為觸重量份計，加入〇5〜％重量份含硫_院氧基魏衍生物（C)’優選加人G 5〜45重量份。相對於（Α补 (C)成分的配比量不足〇.5 _身，難以得到優異的黏附性，如果超過— 5〇重量份，固化物的《密度降低，_性下降，因此黏附性可能下降。另外’本發明的固化性樹脂組合物，以多官能硫醇化合物（a)和多官能環氧樹脂⑻的總重量（A+B)為觸重量份計，加入有_〜％重量份的麵化合物（D) ’優選加入0_01〜45重量份。相對於（a+b)，⑼成分的配比量不足G.G1時，由於需要時間進行硫醇基與環氧基的反應因此導致固化不良’如果超過5〇重量份時’則交聯密度可能降低，黏附性可能下降。另外，在本發明的固化性樹脂組合物中也混入多官能（甲基）丙烯酸酯化合物（E)的情況下，以多官能硫醇化合物（A)和多官能環氧樹脂（b) 的總重量（A+B)為100重量份計，加入有2〜3〇〇重量份多官能（甲基）丙烯酸酯化合物（E) ’優選加入2〜250重量份。相對於（A+B)，成分的配比量不足2時，難以賦予其光固性，如果超過3〇〇重量份，具有黏附性下降的傾向。 <固化性樹脂組合物> 如果多官能硫醇化合物（A)的硫醇基與多官能環氧樹脂（b)的環氧基反應’則生成硫醚基或經基。含硫醚的烧氧基石夕烧（C)也具有硫喊武，以二硫鍵同上述硫醇基與環氧基反應生成的硫醚基交聯。另外，含硫峻的烧氧基石夕院化合物（C)也同時具有烧氧石夕基，同上述硫醇基和環氧基反應、生成的羥基交聯。結果，可以形成緊密的交聯體。使本發明的固化性樹脂^ 201247768 組合物固化後的固化物’因為形成了緊密的交聯體，因此耐熱性、強韋刀性及耐水性等提高。並且’其是以硫醚基或二硫鍵交聯形成的固化物，因此也富有柔韌性，從而具有高黏附性。並且’含硫醚的烷氧基矽烧化合物（c)，也同時具有三烷氧矽基’因此尤其能夠與玻璃之類的無機基材形成化學鍵’進而本發明的固化性樹脂組合物對無機基材的黏附性顯著提高。另外’在本發明的固化性樹脂組合物中，視需要添加的多官能（甲基）丙烯酸醋化合物（E)的（曱基）丙烯醯基和多官能硫醇化合物（a)的硫醇基也在光的激發下反應。因此，多官能硫醇化合物（A)與多官能環氧樹多官能（甲基）丙烯酸醋化合物丄^混合物，是用光和熱兩級固化的固化性樹脂。並且，可以通過控制各自的組成成分量’來控制光固化及熱固化的程度。目前’多種硫醇化合物被用作固化劑（用於使環氧樹脂或（甲基）丙烯酸酯化合物等主劑固化而添加的化合物另外，眾所周知，在硫醇基與 %氧基，或硫醇基與（曱基）丙稀酿基的任一反應中，胺等驗性物質具有降低反應活化能（催化）的效果。另外’本發明的固化性樹脂組合物’為了反應體系均一、容易塗布等，也可以用有機溶劑稀釋後使用。作為該有機溶劑，可以例舉如醇類溶劑、芳香族烴類溶劑、醚類溶劑、酯類溶劑及醚酯類溶劑、酮類溶劑、磷酸酯類溶劑。相對於100重量份固化性樹脂組合物，這些有機溶劑的配比量^ 選控制為少於10000重量份，但是基本上在形成固化膜時溶劑已揮發，因此不會對固化膜的物理性質造成大影響。但是，以具有可與硫醇基、環氧基或（甲基）丙烯醯基反應的官能團的化合物及胺類化合物用作溶劑時，有可能會損害本發明的效果。另外，為了調節黏度，本發明的固化性樹脂組合物也可以混入二氧化 =粉末等黏度調節劑。相對於1001量份固化性樹脂組合物，這些黏度調 :劑的配比量優選小於300重量份^如果黏度調節劑的配比量超過⑽重量份，黏附性可能會下降。另外，本發明的固化性樹脂組合物也可以添加通常的塗料或黏結劑中 21 201247768 可以例舉如用於使塗布表面平滑的丨的銘鹽、用於提高光反應性的光自由基引相對於100重量份固化性樹脂組合物，這重量份。如果這些添加劑的配比量超過80 使用的各種添加劑。作為這些添加劑，表面活性劑、用於延長可用時間的鋁鹽發劑、光生域基、光生酸劑等。相對於些添加劑的配比量優選小於80重量份重量份，黏附性可能會下降。實施例下面例舉實施例及比較例對本發明進行更具體的說明，但是本發明並不限定於此。本實施例及比較例中所用的試劑如下所示。另外，Mw表示重均分子量。 _ __ <多官能硫醇化合物（A成分）> (A-l、Mw : 372) 化學式19Wherein, s is an integer of 2 to 30', R12 is a hydrocarbon group (?1) having 2 to 2 carbon atoms, and a group (6) composed of an ether oxygen (??) and a hydrocarbon group having 2 to 300 carbon atoms; An alanine ring (6) or a group composed of an isocyanurate ring and a hydrocarbon (?4), and Rn is a hydrogen atom or a sulfhydryl group. Further, as the polyfunctional (meth)propene g (8), a polymer compound can be suitably used. As the polymer-based polyfunctional (fluorenyl) acrylate (E), for example, a homopolymer or a copolymer of a (meth) succinic acid compound having an epoxy group, such as (mercapto)acrylic acid or the like having a reactivity with an epoxy group In the homopolymer or copolymer of the compound, a reaction such as a 2-(meth)(tetra)-synthesis compound having a 2-methacrylic acid 2/2 acid group a polymer that is used in a homopolymer or copolymer of (meth)propionate or the like having a ruthenium (meth) acetate compound A polymer obtained by reacting a (meth)acrylic acid SI compound or the like. The polyfunctional (meth)acrylic acid vinegar compound (8) has a molecular weight of 2 Å to 5 Å, preferably 220 to 40 Å, and more preferably 24 () to 3 _. When the molecular weight of the polyfunctional (meth)acrylic acid vinegar compound (8) is less than 200, there is no problem in J_adhesiveness, but there is a tendency that the volatility becomes high and the d taste becomes strong. Another-turn, if New 5Q_, the solubility of other ingredients may decrease. Further, the (meth)acrylic acid vinegar equivalent of 'polyfunctional (fluorenyl)acrylic acid (8) is ^6_g/md', preferably 8 Å to Å, more preferably 85 Å. If the (meth)acrylic acid vinegar equivalent is less than 80 g/mo, the unit volume of β (mercapto) propylene is too much, and does not react with the thiol group of the polyfunctional thiol compound (Α). Since a large amount of the propenyloxy group remains, the cured film composed of the curable resin composition may be degraded, and when exposed under high temperature and high humidity conditions, the adhesion may be lowered. On the other hand, if the (fluorenyl) propionate equivalent is more than _〇g/mol, the (meth) propylene decyloxy group concentration is remarkably lowered, and thus the reaction efficiency with the thiol group of the polyfunctional thiol compound is lowered, possibly The toughness of the cured film composed of the (four) chemical tree chelates is lowered, and the adhesion is lowered when exposed to a high temperature and high humidity environment. <Composition ratio (equal ratio)> The curable resin composition of the present invention is mixed with a polyfunctional thiol compound (A) and a polyfunctional epoxy resin (B) to have a weight ratio (A) / (8) of 〇〇 5~3〇. Here, "(A) / (8)," means the weight of the polyfunctional thiol compound (4) is divided by the weight of the polyfunctional epoxy resin (8). The optimum (A) / (B) value is due to the curable resin composition The required characteristics, the structure of the polyfunctional thiol compound (A) or the polyfunctional epoxy resin, and the polyfunctional (meth)acrylic acid oxime compound (E) added as the case may be different. After the curable resin composition is cured The characteristics are strictly controlled by the number of (thiol groups) / (number of epoxy groups + (meth) C. 201247768 ί / (ring (tetra))) per unit weight of the curable resin composition. For example, thiol / (ring = The other side of the axis is easy to cross-link, and the volume (4) is strong _ hardened. On the other hand, if the thiol / (epoxy + lean) ratio is (Μ less than 0.5 or less than 2 超 super = 5 When the thiol/(cyclo(tetra)) ratio is less than or exceeds 2.G, it is difficult to gel and the adhesiveness tends to decrease. Further, the curable resin composition of the present invention , based on the total weight (Α+Β) of the polyfunctional thiol compound (4) and the multifunctional epoxy resin (8), 5 to % by weight of sulfur-containing oxalate derivative (C)' is preferably added in an amount of 5 to 45 parts by weight of G. The amount of the compound (C) is less than 〇.5 _ body, It is difficult to obtain excellent adhesion, and if it exceeds 5% by weight, the density of the cured product is lowered, and the _ property is lowered, so the adhesion may be lowered. Further, the curable resin composition of the present invention is a polyfunctional thiol compound ( a) and the total weight (A+B) of the polyfunctional epoxy resin (8) is in parts by weight, and ～~% by weight of the surface compound (D) is added. Preferably, 0 to 01 to 45 parts by weight are added. b) When the compounding amount of the component (9) is less than G.G1, it takes time to carry out the reaction of the thiol group with the epoxy group, thereby causing poor curing. If it exceeds 5 parts by weight, the crosslinking density may be lowered, and the adhesion may be lowered. In the case where the polyfunctional (meth) acrylate compound (E) is also mixed in the curable resin composition of the present invention, the polyfunctional thiol compound (A) and the polyfunctional epoxy resin (b) are used. The total weight (A + B) is 100 parts by weight, and the weight is 2 to 3 inches. The polyfunctional (meth) acrylate compound (E) ' is preferably added in an amount of 2 to 250 parts by weight. When the compounding amount of the component is less than 2 with respect to (A+B), it is difficult to impart photosetting property if it exceeds 3 Å. In the case of parts by weight, the adhesiveness tends to decrease. <Curable resin composition> If the thiol group of the polyfunctional thiol compound (A) reacts with the epoxy group of the polyfunctional epoxy resin (b), sulfur is formed. Ether group or mercapto group. The thioether-containing alkoxylated sulphur (C) also has a sulfur-sulfur, cross-linking with a thioether group formed by reacting a disulfide bond with the above thiol group and an epoxy group. The sulphur-burning oxet compound (C) also has a oxysyl group, which is crosslinked with the above-mentioned thiol group and epoxy group to form a hydroxyl group. As a result, a close crosslinked body can be formed. Since the cured product after curing of the curable resin of the present invention ^ 201247768 is formed into a compact crosslinked body, heat resistance, strong knife resistance, water resistance and the like are improved. And it is a cured product formed by crosslinking with a thioether group or a disulfide bond, and thus is also flexible and thus has high adhesion. Further, the 'sulfur ether-containing alkoxy sulphur compound (c) also has a trialkoxy fluorenyl group. Therefore, it is particularly capable of forming a chemical bond with an inorganic substrate such as glass. Further, the curable resin composition of the present invention is inorganic. The adhesion of the substrate is remarkably improved. Further, in the curable resin composition of the present invention, the (mercapto)acrylonitrile group of the polyfunctional (meth)acrylic acid vinegar compound (E) and the thiol group of the polyfunctional thiol compound (a) are optionally added. It also reacts under the excitation of light. Therefore, the polyfunctional thiol compound (A) and the polyfunctional epoxy resin polyfunctional (meth)acrylic acid vinegar compound are a curable resin which is cured by light and heat. Further, the degree of photocuring and heat curing can be controlled by controlling the respective component amounts '. At present, various thiol compounds are used as curing agents (compounds for curing a main component such as an epoxy resin or a (meth) acrylate compound. Further, it is known that a thiol group and a oxy group, or a thiol. In any reaction between a group and a (fluorenyl) propylene group, an amine or the like has an effect of lowering the activation energy (catalysis) of the reaction. Further, the 'curable resin composition of the present invention' is uniform and easy to coat for the reaction system. The organic solvent may be diluted with an organic solvent, and examples of the organic solvent include alcohol solvents, aromatic hydrocarbon solvents, ether solvents, ester solvents, and ether ester solvents, ketone solvents, and phosphate esters. The solvent is used in an amount of less than 10,000 parts by weight based on 100 parts by weight of the curable resin composition, but the solvent is volatilized substantially at the time of forming the cured film, and thus the physical properties of the cured film are not The nature has a large effect. However, when a compound having a functional group reactive with a thiol group, an epoxy group or a (meth) propylene group and an amine compound are used as a solvent, there is In addition, in order to adjust the viscosity, the curable resin composition of the present invention may be mixed with a viscosity adjusting agent such as a dioxide = powder, and the viscosity adjusting agent may be added to the 1001 part by weight of the curable resin composition. The amount of the compounding agent is preferably less than 300 parts by weight. If the amount of the viscosity adjusting agent exceeds (10) parts by weight, the adhesion may be lowered. Further, the curable resin composition of the present invention may be added to a usual coating or binder 21 201247768 For example, a salt of ruthenium for smoothing a coated surface, a photoradical for promoting photoreactivity, and 100 parts by weight of a curable resin composition may be exemplified. If the ratio of these additives exceeds 80 various additives used as these additives, surfactants, aluminum salt hair extensions for prolonging the usable time, photogenic domains, photoacid generators, etc., preferably in an amount of less than 80 parts by weight relative to the additives, Adhesiveness may decrease. EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples and comparative examples, but the present invention is not The reagents used in the examples and the comparative examples are as follows. Further, Mw represents a weight average molecular weight. _ __ <Multifunctional thiol compound (component A)> (A-1, Mw: 372) Chemical formula 19

(A-2、Mw : 399) 化學式20(A-2, Mw: 399) Chemical formula 20

(A-3、Mw : 526) 化學式21(A-3, Mw: 526) Chemical Formula 21

(A-4、Mw : 488) 化學式22(A-4, Mw: 488) Chemical Formula 22

S 22 201247768 〇 οS 22 201247768 〇 ο

(Α-6、Mw : 416) 化學式24 ο(Α-6, Mw: 416) Chemical Formula 24

(Α-7、Mw : 785 ) 化學式25(Α-7, Mw: 785) Chemical formula 25

(Α-8、Mw : 1584) 化學式26 23 201247768(Α-8, Mw: 1584) Chemical formula 26 23 201247768

<多官能環氧樹脂（B成分）> (B-l、Mw : 220、環氧當量：110) 化學式27<Multifunctional epoxy resin (component B)> (B-1, Mw: 220, epoxy equivalent: 110) Chemical formula 27

(B-2、Mw : 360、環氧當量：90) 化學式28(B-2, Mw: 360, epoxy equivalent: 90) Chemical formula 28

(B-3、Mw : 350、環氧當量：175) 化學式29 (B-4、Mw : 5500、環氧當量：3000) 化學式30(B-3, Mw: 350, epoxy equivalent: 175) Chemical formula 29 (B-4, Mw: 5500, epoxy equivalent: 3000) Chemical formula 30

η平均為15。The average η is 15.

S 24 201247768 (B-5、Mw : 1500、環氧當量：186) 化學式31S 24 201247768 (B-5, Mw: 1500, epoxy equivalent: 186) Chemical formula 31

η平均為7。 (Β-6、Mw : 220、環氧當量：110) 化學式32The average η is 7. (Β-6, Mw: 220, epoxy equivalent: 110) Chemical formula 32

O_hO_0^7 (B-7、Mw : 18000、環氧當量：250) 曱基丙烯酸縮水甘油酯與甲基丙烯酸環己酯的共聚物（以己烷對 50wt%曱基異丁基酮溶液再沉澱的白色固體）。 (B-8、Mw : 45000、環氧當量：250) 曱基丙烯酸縮水甘油酯與甲基丙烯酸環己酯的共聚物（以己烷對 50wt°/。曱基異丁基酮溶液再沉澱的白色固體）。 <含硫醚的烷氧基矽烷衍生物（C成分）> (C-1) 化學式33 25 201247768 Y^S、 ,0O_hO_0^7 (B-7, Mw: 18000, epoxy equivalent: 250) Copolymer of glycidyl methacrylate and cyclohexyl methacrylate (reprecipitated with hexane to 50 wt% decyl isobutyl ketone solution) White solid). (B-8, Mw: 45000, epoxy equivalent: 250) Copolymer of glycidyl methacrylate and cyclohexyl methacrylate (reprecipitated with hexane to 50 wt% / decyl isobutyl ketone solution) White solid). <Sulfur ether-containing alkoxydecane derivative (component C)> (C-1) Chemical formula 33 25 201247768 Y^S, ,0

00

s、人 JD、^^Si(OCH3h O O (C-2) 化學式34 (H傳i /，γ〇Ύ~0γ^\ 〇v^\/Si(OCH3)3 (H3CO)3Sis, person JD, ^^Si(OCH3h O O (C-2) Chemical Formula 34 (H-transmit i /, γ〇Ύ~0γ^\ 〇v^\/Si(OCH3)3 (H3CO)3Si

O s-^r0 Vn 〇 oO s-^r0 Vn 〇 o

〇、/\^Si(OCH3)3 o〇, /\^Si(OCH3)3 o

(C-3) 化學式35 (HaCOJaSiv^-s^O(C-3) Chemical Formula 35 (HaCOJaSiv^-s^O

Y^S Ο I (HaCOJaSi^^^OY^S Ο I (HaCOJaSi^^^O

oo

SS

0、 o0, o

,SH,SH

一 SH o o (C-4) 化學式36 (HaCOhSix^-^oA SH o o (C-4) Chemical Formula 36 (HaCOhSix^-^o

HSHS

O O 〇、O O 〇,

,SH,SH

,SH 0 (C-5) 化學式37, SH 0 (C-5) Chemical Formula 37

(C2H5〇)3Si^^^O (CjHsO^Si^^s^O(C2H5〇)3Si^^^O (CjHsO^Si^^s^O

° \ /0 〇、/\/Si(OC2H5h 、s° \ /0 〇, /\/Si(OC2H5h, s

〇、/\^Si(OC2H5)3 (C-6) 化學式38 s 26 0〇, /\^Si(OC2H5)3 (C-6) Chemical Formula 38 s 26 0

ZUIZH·/ /UOZUIZH·/ /UO

% I% I

Si(OCH3)3 化學式39 (H3CO)3Si (H3CO)3Si 一（C，-i)化學式40Si(OCH3)3 Chemical formula 39 (H3CO)3Si(H3CO)3Si-(C,-i) Formula 40

(H3CO)3Si (C’-2)化學式41 (C2H50)3Siv 一^i(OCH3)3) 〇 / O^S^〇^cAc^〇^S^O^Si(OC2H5)3j (C，、3) 化學式42 (〇2Η5〇)3δί、(H3CO)3Si (C'-2) Chemical Formula 41 (C2H50)3Siv I^i(OCH3)3) 〇/ O^S^〇^cAc^〇^S^O^Si(OC2H5)3j (C, 3 ) Chemical formula 42 (〇2Η5〇) 3δί,

Vs^° -〇yW〇丫 (c，、4) 27 201247768 化學式43Vs^° -〇yW〇丫 (c, 4) 27 201247768 Formula 43

(C’-5) 化學式44(C’-5) Chemical Formula 44

(H3CO)3Si^^O(H3CO)3Si^^O

Ο.Hey.

HSHS

<胺類化合物（D成分）> (D-l、Mw : 136) 化學式45<Amine compound (D component)> (D-l, Mw: 136) Chemical formula 45

(D-2) 1，8-二氮雜雙環（5,4,0)十一碳-7-烯與硬脂酸的1:1當量反應物 (D-3、Mw : 680) 化學式46 (OCH2CH(CH3))n1NH2 ^ ^-(OCH2CH(CH3))n2NH2 、OCH2CH(CH3)>n3NH2 nl、n2、n3為1〜5的整數，平均3.5的混合物。 (D，-卜 Mw : 110) 化學式47 c2h5(D-2) 1:1 equivalent of 1,8-diazabicyclo(5,4,0)undec-7-ene and stearic acid (D-3, Mw: 680) Chemical Formula 46 ( OCH2CH(CH3))n1NH2^^-(OCH2CH(CH3))n2NH2, OCH2CH(CH3)>n3NH2 nl, n2, n3 are an integer of 1 to 5, an average of 3.5 mixtures. (D,-Bu Mw : 110) Chemical formula 47 c2h5

HN^N (D，-2、Mw : 144) s 28 201247768 化學式48HN^N (D, -2, Mw : 144) s 28 201247768 Formula 48

W (D，-3、Mw : 163) 化學式49 c2h5 ν〇(η2〇2ΧνΛν Η — (D，-4、Mw : 219) 化學式50 H3N ch3 >=卜 h3n 〜N^N w (D，-5) 化學式51W (D, -3, Mw : 163) Chemical formula 49 c2h5 ν〇(η2〇2ΧνΛν Η — (D,-4, Mw : 219) Chemical formula 50 H3N ch3 >=Bu h3n 〜N^N w (D,- 5) Chemical Formula 51

\=J\=J

HOOC\^w^COOHHOOC\^w^COOH

TTTT

HOOC/^jSi^COOH 2-苯基咪唑與均苯四甲酸的鹽 (D，-6、Mw : 158) 化學式52HOOC/^jSi^COOH 2-Phenyl imidazole and pyromellitic acid salt (D, -6, Mw: 158) Chemical formula 52

(D，-7、Mw : 306) 29 201247768 化學式53 C17H35 人 \=/ <多官能（甲基）丙烯酸酯化合物（E成分）> (E-l、Mw : 246、雙鍵當量：123) 化學式54(D, -7, Mw: 306) 29 201247768 Chemical Formula 53 C17H35 Person \=/ <Polyfunctional (meth) acrylate compound (E component)> (El, Mw : 246, double bond equivalent: 123) Chemical formula 54

(E-2、Mw : 352、雙鍵當量：88) 化學式55 〇 Ο(E-2, Mw: 352, double bond equivalent: 88) Chemical formula 55 〇 Ο

化學式56Chemical formula 56

(E-4、Mw : 5000、雙鍵當量：3000) 化學式57(E-4, Mw: 5000, double bond equivalent: 3000) Chemical formula 57

η平均為13 (Ε-5、Mw : 1200、雙鍵當量：180)The average η is 13 (Ε-5, Mw: 1200, double bond equivalent: 180)

S 30 201247768 化學式58S 30 201247768 Chemical Formula 58

化學式59 )=°Chemical formula 59 )=°

V=5〇 (E-7、Mw : 22000、雙鍵當量：320) 以D-3為催化劑，甲基丙烯酸縮水甘油酯與甲基丙烯酸環己酯的共聚物等摩爾加成曱基丙烯酸的聚合物（以己烷對5〇wt%甲基異丁基酮溶液再沉殿的白色固體）。 <其他試劑> (F-1、与A成分) 化學式60 0V=5〇(E-7, Mw: 22000, double bond equivalent: 320) Using D-3 as a catalyst, a copolymer of glycidyl methacrylate and cyclohexyl methacrylate is equimolarly added to methacrylic acid. The polymer (white solid with hexane in a 5 wt% methyl isobutyl ketone solution). <Other reagents> (F-1, and component A) Chemical formula 60 0

31 201247768 (F-2、与C成分）化學式61 ^Y〇vv^^Si(〇CH3)3 Ο 如表1、2所示，以均衡配比分別混入（Α)〜⑻成分，以刮刀授掉至均勻。對攪拌後的樣本進行下述評價，其結果如表丨、2所示。 <黏附性評價> 以棒式塗布機在無域玻璃（ΟΑ-10 '曰本電氣硝子公司生產、厚度 0.7mm)及鋁板（Α5052Ρ、日本Testpane丨公司生產、厚度―上塗布各實施例及比較例至厚度為1〇〇μηι ’於14〇t下加熱丨小時，在各基材上得到固化膜。在121 〇100RH%x90小時的條件下處理得到固化膜的基材，然後以JIS K5600-5-6所規定的塗膜機械性質-黏附性（橫切法）試驗方法進行评價。完全無剝離記為◎、剝離占整體面積1成以下記為〇、除此之外記為 X。表中黏附性1為無域玻璃基材上的結果，黏附性2為鋁板基材上的結果。 <確認光固性> 以棒式塗布機在無域玻璃上塗布各實施例及比較例至厚度為1〇〇μηι，以尚壓水銀燈照射500mJ/cm2 (換算為i射線）的光。以刮刀抑制照射了的塗膜時，刮刀上未沾附塗布液的情況記為〇。 <確認儲存穩定性（保藏穩定性）> 以下述黏度計測定各實施例及比較例剛混合後的黏度。將各實施例及比較例在30°C下加熱12小時後，再測定黏度。以混合後的黏度除加熱後的黏度得到的增黏率為1.0〜1.8的記為〜]0的記為〇、除此之外的記為\。機種：東機產業（株）制（R型黏度計）、溫度：25。〇。31 201247768 (F-2, and C components) Chemical formula 61 ^Y〇vv^^Si(〇CH3)3 Ο As shown in Tables 1 and 2, the components (Α)~(8) are mixed in a balanced ratio and scraped Dropped evenly. The sample after stirring was subjected to the following evaluation, and the results are shown in Table 丨 and 2. <Adhesion evaluation> Each of the examples was coated with a bar coater in a non-domain glass (manufactured by ΟΑ-10 '曰本电硝子公司, thickness 0.7 mm) and an aluminum plate (Α5052Ρ, manufactured by Japan Testpane Co., Ltd., thickness) And a comparative example to a thickness of 1 〇〇μηι 'heated at 14 〇t for a few hours to obtain a cured film on each substrate. The substrate of the cured film was treated under conditions of 121 〇 100 RH% x 90 hours, and then JIS was obtained. The mechanical properties of the coating film specified by K5600-5-6-adhesiveness (cross-cutting method) were evaluated. The total non-peeling was recorded as ◎, and the peeling accounted for 1% or less of the total area as 〇, otherwise marked as X. The adhesion 1 in the table is the result on the non-domain glass substrate, and the adhesion 2 is the result on the aluminum plate substrate. <Confirmation of photo-curability> Coating each of the examples on a non-domain glass by a bar coater In the comparative example, the thickness was 1 〇〇μηι, and the light was irradiated at 500 mJ/cm 2 (in terms of i-ray) with a mercury lamp. When the coating film was irradiated with a doctor blade, the coating liquid on the blade was not marked as 〇. <Confirm storage stability (preservation stability)> The viscosity of each of the examples and the comparative examples immediately after mixing was measured. Each of the examples and the comparative examples was heated at 30 ° C for 12 hours, and then the viscosity was measured. The viscosity after mixing was removed by the viscosity after heating. The value of the value of 1.0 to 1.8 is ], and the other is 〇, and the other is marked as \. Model: Toki Sangyo Co., Ltd. (R-type viscometer), temperature: 25.

S 32 201247768 i< it較两 1 C3 1 i 1 o o*j CNJ 〇 «r> oi CO 100.0 s csj ir> <y> c-> l 〇 1 25.97 1 X X ◎ 上 ,.Α-3 <〇 CM te> Cs4 ri m «ρ m s C3 IO GO <c> 100.0 CM 丄 oo in CM Q P-- Oi es< ο X ο τ 1 CO CP P： Ol ffl s era g 寸 100.0 VO i 卜· Σ <〇 CO ο X X Ο 1 實旌ί?ΰ 工 τ <〇 CM 5 T CD o CSJ CSJ o oo 1〇〇P I 0.76 | CMI csj 5 D'-5 1 CM r-* ◎ ◎ ◎ CT3 -Α-5 s 卜 IO ΓΟ in CQ 1 1500 1 CO GO IO c4 (〇 1 100.0 I s o I C.-3 I s ..P'±-..-. 03 S o ◎ ◎ ◎ CVJ ? < oo oo 0¾ l〇丨 B-4 1 '5500 1 3000 1 i 100.0 1 CD o C，-2 I oq D-3 1 n to CO eo If) ◎ ◎ ◎ Τ < CD l〇 n*· m 1 18000 I s CV «r> 1 100.0 1 s i CNl o 3 1 3.45 1 ◎ ◎ ◎ ο τ 1 Α-7 1 in GD 卜 l〇 <〇 l s o l〇 CSJ n i 100.0 1 CO s C'-5 I 〇> o O ! 25.97 1 ◎ ◎ ◎ 〇> < CO CM 9 \ B-6 1 § o oo s I 100.0 1 f5 s CM 5 tr> bk 1 〇 ◎ ◎ ©> CO ΙΓ> s Γ-- irt ΓΟ in ώ I 1500 I i in csl <〇 1 100.0 I o CO ύ s C\| 1 D'-4 1 σ> s <s ◎ ◎ Γγ· k oo TO σ» to CD I 5500 I 1 3000 1 〇» I 100.0 I s o Ρ«» ώ 2 1 D'-3 1 CO <〇 S ir> ◎ ◎ ◎ <ρ < CO ΙΛ rp ffl 丨18000」 o ir> «Μ l〇穿 I 100.0 1 u> cn· CO ύ iO 7 Ch ΙΛ 3 ◎ ◎ ◎ ΙΟ Γρ < in eo l a o m 奐 1 mo 1 g «vi I 05 I cn o i o 1 25.97 1 ◎ ◎ ◎ 了 «ρ < CO esi LO eg cd iO CO CD s cr> JO CO to 1 100.0 1 rr csl ώ cn in ID·?」 CM g ◎ ◎ Ο ? esi < &> σ> n ce r·^ CSJ ffl s o s OJ 100.0 I eo ώ 卜 ώ (O eo S O ◎ ◎ 〇 V cn < CO CN| 〇 53.2 ΓΟ m s r> v> 46.8 100.0 CM ύ o U*3 Oi Δ 5m CM s ◎ ◎ ο 丁 CM < σ> σ) c-> cp p· CNJ m s c〇 s C«i esi 100.0 iti 寸 CO ώ 卜· 〇 <〇 n o ◎ ◎ ο 實旌尻·比餃Κ φτ Φ iiSi 製 Φ nn E^. 璐 Φ φτ| ¥ 黏吃/生： ife: 游穏定性 A成分 B成分 ffl < % C成分 D成分 1 33 201247768 t:: u -t λ <r> < «ο CM ΙΓ> 0 TO e>i CD S CO s LO 〇 S C3 1 1 Ω «0 〇2 8 〇 ur» ill <0 S L〇 σ> o to 1 X 〇〇 i.'-' m 忑 (O < s 0 s I s § 8 S g 〇 s s ai T 0 c» CM 〇 es| tr> s <X> 10 Ul 1 g C> 1 ◎ ◎ ◎ o ie> Z <〇 (NJ m 0 <0 s Oi 〇 0 穿 <=! § s? 了 o 〇 cp i CO <0 s 5 II 0 1 〇 i 〇 s 1 ® @ 0 5： C 〇> 〇> CO tr> & «ρ CD I s CNJ \r> 〇 s a r^* ¢0 0 S CSJ eja c> g uS C\i J； CO 0 s •w^ Ο s ◎ ◎ ◎ 0 r〇 Λ 〇〇 i Γ— ώ s ro s <〇 rvi 0 s s CNJ OJ ώ r-*. 0 Q an CO r-‘ <M ill Oi ir> CO s 0 3 1 ◎ ◎ 〇 CNI Σ <〇 < €D 〇*> <0 cr> %r> ω 1 <£> 〇〇 CO 0 寒写 o CO 卜 Q CO cr> LO CO LIJ CO rr> CO CO CO LO 1 ◎ ◎ ◎ 〇 Ϊ ^r <C 〇〇 «Ν cn m l〇 GO s o s O) L〇 ώ 〇> €1=» 2 00 10 s PJ«- til i s CO 1 ◎ ◎ ◎ 0 〇 I < 卜 C> s 了 m § o 8 S 0 0 2 s aS ώ 〇 s T CM to g <b 宁 UJ 1 s 〇 1 ◎ ◎ ◎ 0 ΟΪ eg cp <C CO 0 s ώ 〇 0 0 0 s s r- ύ 0 § CJ> Ck CO to g 耷 1 I § CO 0 s 1 ◎ ◎ ◎ 0 CO CVJ CM < «·> ΙΓΪ 00 «Ο m 震 ^r S CSJ U~3 0 g s CO ώ c=> i/S CNI CNI 0 ? G tr> 01 z 荽 CM 舀 0 g* 0 s ◎ ◎ ◎ 0 r- 1 CSJ CO i jo- C>l m § s «Ο uS Csl s s oi ΙΟ 6 r*~ n-^ T 0 0 s r~~ CVJ lIj K CO s 0 5 i ◎ ◎ ◎ 〇 CO esj T < CO ir> V CD I 罢 «Ο c*i 0 3 s R τ ο to C-3 P*- 0 <0 〇> 1C CJ3 UJ <〇 CO s CO 会 Csl 1 ◎ ◎ ◎ 〇 L〇 CsJ T < CO CSI Ο» ώ 荽 to 00 <=? s Τ'— CT> 2 05 «0 T a CO ir> s Γ^- UJ i CSJ s CO LO c6 1 ◎ ◎ ◎ 〇 T CM ep < <〇 CSJ ir> S <VJ ώ i s 〇 tg> s LT> CO iO Σ <〇 r〇 «Ο g cp UJ S l〇 s cq in 1 ◎ 0 〇 fJ3 CV cm < a> 〇> o 〇> 5 Σ 0 LO IA 0 g 〇〇 CO ώ CO o«i r〇 i g <0 σ> oo rj- ill § a s <*3 5 1 ◎ ◎ 〇 0 esi CM CO < <〇 CM l〇 <P s? CjJ CD s s 〇 s 0. s ir> 00 ώ \r> ά 40 ΓΟ s CO UJ <〇 s 00 s 1 ◎ ◎ 〇 0 J, CSI < CO s 〇 3 □Q § 0 10 0 s cp 0 00 cp a § K od r- 山〇 1 CVI s c*> s I ◎ ◎ 〇 0 k·' ：w s ¢1 Φ s Φ*) <k w iiflt tiN 每 « -H 赕棚 S W Φ « 剕丨 « φΐ 钿 ill ife a -Jl| k iM ••HI m !H· 萆 φ3 餐 αι CD i 03 s UJ ώ Ul ，己 «5τ! B ii 34 201247768 從表1及表2的結果可知，全部實施例均具有高的黏附性。另外，可確認在實施例2-1〜2-16中，因添加了（E)成分，能夠賦予光固性。另外，可明確在實施例1-5〜1-14、2-5〜2-16中，將胺類限定為咪唑化合物，從而提高了儲存穩定性（保藏穩定性）。另一方面，如各比較例所示，不含有本發明中必要成分（A)〜（D)中的任一種或為不同的材料，不能得到對無機基材優異的黏附性。【圖式簡單說明】【主要元件符號說明】 35S 32 201247768 i< it is more than two 1 C3 1 i 1 oo*j CNJ 〇«r> oi CO 100.0 s csj ir><y>c-> l 〇1 25.97 1 XX ◎ 上,.Α-3 &lt ;〇CM te> Cs4 ri m «ρ ms C3 IO GO <c> 100.0 CM 丄oo in CM Q P-- Oi es< ο X ο τ 1 CO CP P: Ol ffl s era g inch 100.0 VO i · Σ <〇CO ο XX Ο 1 实旌ί?ΰ工τ <〇CM 5 T CD o CSJ CSJ o oo 1〇〇PI 0.76 | CMI csj 5 D'-5 1 CM r-* ◎ ◎ ◎ CT3 -Α-5 s IO ΓΟ in CQ 1 1500 1 CO GO IO c4 (〇1 100.0 I so I C.-3 I s ..P'±-..-. 03 S o ◎ ◎ ◎ CVJ ? <; oo oo 03⁄4 l〇丨B-4 1 '5500 1 3000 1 i 100.0 1 CD o C,-2 I oq D-3 1 n to CO eo If) ◎ ◎ ◎ Τ < CD l〇n*· m 1 18000 I s CV «r> 1 100.0 1 si CNl o 3 1 3.45 1 ◎ ◎ ◎ ο τ 1 Α -7 1 in GD 卜 l〇<〇lsol〇CSJ ni 100.0 1 CO s C'-5 I 〇 > o O ! 25.97 1 ◎ ◎ ◎ 〇 >< CO CM 9 \ B-6 1 § o oo s I 100.0 1 f5 s CM 5 tr> bk 1 〇 ◎ ◎ ©> CO ΙΓ> s Γ- - irt ΓΟ in ώ I 1500 I i in Csl <〇1 100.0 I o CO ύ s C\| 1 D'-4 1 σ> s <s ◎ ◎ Γγ· k oo TO σ» to CD I 5500 I 1 3000 1 〇» I 100.0 I so Ρ «» ώ 2 1 D'-3 1 CO <〇S ir> ◎ ◎ ◎ <ρ < CO ΙΛ rp ffl 丨18000" o ir> «Μ l〇穿I 100.0 1 u> cn· CO ύ iO 7 Ch ΙΛ 3 ◎ ◎ ◎ ΙΟ Γρ < in eo laom 奂 1 mo 1 g «vi I 05 I cn oio 1 25.97 1 ◎ ◎ ◎ «ρ < CO esi LO eg cd iO CO CD s cr> JO CO To 1 100.0 1 rr csl ώ cn in ID·?" CM g ◎ ◎ Ο ? esi <&>σ> n ce r·^ CSJ ffl sos OJ 100.0 I eo ώ ώ (O eo SO ◎ ◎ 〇 V cn < CO CN| 〇53.2 ΓΟ ms r>v> 46.8 100.0 CM ύ o U*3 Oi Δ 5m CM s ◎ ◎ ο CM <σ> σ) c-> cp p· CNJ msc〇s C«i esi 100.0 iti 寸 ώ · · 〇〇 ◎ ◎ 实旌尻比比 φ φ φ φ ii φ Φ φ ^ ^ ^ ^ ^ ^ ^ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ A component B component ffl < % C component D component 1 33 201247768 t:: u -t λ <r>< ο CM ΙΓ> 0 TO e>i CD S CO s LO 〇S C3 1 1 Ω «0 〇2 8 〇ur» ill <0 SL〇σ> o to 1 X 〇〇i.'-' m 忑( O < s 0 s I s § 8 S g 〇ss ai T 0 c» CM 〇es| tr> s <X> 10 Ul 1 g C> 1 ◎ ◎ ◎ o ie> Z <〇(NJ m 0 <0 s Oi 〇0 wear<=! § s? o 〇cp i CO <0 s 5 II 0 1 〇i 〇s 1 ® @ 0 5: C 〇>〇> CO tr>& «ρ CD I s CNJ \r> 〇sar^* ¢0 0 S CSJ eja c> g uS C\i J; CO 0 s •w^ Ο s ◎ ◎ ◎ 0 r〇Λ 〇〇i Γ— s s ro s <〇rvi 0 ss CNJ OJ ώ r-*. 0 Q an CO r-' <M ill Oi ir> CO s 0 3 1 ◎ ◎ 〇CNI Σ <〇< €D 〇* ><0cr>%r> ω 1 <£> 〇〇CO 0 寒写 o CO 卜Q CO cr> LO CO LIJ CO rr> CO CO CO LO 1 ◎ ◎ ◎ 〇Ϊ ^r < C 〇〇«Ν cn ml〇GO sos O) L〇ώ 〇> €1=» 2 00 10 s PJ«- til is CO 1 ◎ ◎ ◎ 0 〇I <卜C> s m § o 8 S 0 0 2 s aS ώ 〇s T CM to g <b Ning UJ 1 s 〇 1 ◎ ◎ ◎ 0 ΟΪ eg cp <C CO 0 s ώ 〇0 0 0 ss r- ύ 0 § CJ> Ck CO to g 耷1 I § CO 0 s 1 ◎ ◎ ◎ 0 CO CVJ CM <«·> ΙΓΪ 00 «Ο m 震^r S CSJ U~3 0 gs CO ώ c=> i/S CNI CNI 0 ? G tr> 01 z 荽CM 舀0 g* 0 s ◎ ◎ ◎ 0 r- 1 CSJ CO i jo- C>lm § s «Ο uS Csl ss oi ΙΟ 6 r*~ n-^ T 0 0 sr~~ CVJ lIj K CO s 0 5 i ◎ ◎ ◎ 〇CO esj T < CO ir> V CD I Ο«Ο c*i 0 3 s R τ ο to C-3 P*- 0 <0 〇> 1C CJ3 UJ <〇CO s CO will Csl 1 ◎ ◎ ◎ 〇L〇CsJ T < CO CSI Ο» ώ 荽to 00 <=? s Τ'- CT> 2 05 «0 T a CO ir> s Γ^- UJ i CSJ s CO LO c6 1 ◎ ◎ ◎ 〇T CM ep << 〇CSJ ir> S <VJ ώ is 〇tg> s LT> CO iO Σ <〇r〇«Ο g cp UJ S l〇s cq in 1 ◎ 0 〇fJ3 CV cm <a>〇> o 〇> 5 Σ 0 LO IA 0 g 〇〇CO ώ CO o«ir〇ig <0 σ> oo rj- ill § as <*3 5 1 ◎ ◎ 〇0 esi CM CO <<〇CML〇<P s? CjJ CD ss 〇s 0. s ir> 00 ώ \r> ά 40 ΓΟ s CO UJ <〇s 00 s 1 ◎ ◎ 〇0 J, CSI < CO s 〇3 □Q § 0 10 0 s cp 0 00 cp a § K od r- Hawthorn 1 CVI sc*> s I ◎ ◎ 〇0 k·' :ws ¢1 Φ s Φ*) <kw iiflt tiN Every « -H shed SW Φ « 剕丨« φΐ 钿ill ife a -Jl| k iM ••HI m !H· 萆φ3 Meal αι CD i 03 s UJ ώ Ul , ««τ! B ii 34 201247768 From the results of Tables 1 and 2, all the examples have high adhesion. Further, in Examples 2-1 to 2-16, it was confirmed that the (E) component was added, and the photocurability was able to be imparted. Further, it is clear that in the examples 1-5 to 1-14 and 2-5 to 2-16, the amines are limited to the imidazole compound, thereby improving storage stability (preservation stability). On the other hand, as shown in each comparative example, any one of the essential components (A) to (D) in the present invention or a different material is not contained, and excellent adhesion to an inorganic substrate cannot be obtained. [Simple description of the diagram] [Explanation of main component symbols] 35

Claims

201247768 七、申請專利範圍： 1. 一種固化性樹脂組合物，其特徵在於，含有下述（A)、（B)、（C)&(D) 成分，所述（A)成分為分子量為2〇〇〜2〇〇〇的多官能硫醇化合物；所述（B)成分為分子量為2〇〇〜50000且環氧當量為80〜6000g/mol的多官能環氧樹脂；所述（C)成分為以下述通式或通式（2)所示的含硫醚的烷氧基矽烷衍生物；所述（D)成分倉分子量為9〇〜700的胺類化合物；-- 所述（A)成分與（B)成分的重量比（a) / (B)為0.05〜30 ; 以所述（A)成分與所述（B)成分的總重量為1〇〇重量份計，混入〇.5〜50 重量份的所述（C)成分、0.01〜50重量份的所述（D)成分；化學式1201247768 VII. Patent Application Range: 1. A curable resin composition comprising the following components (A), (B), (C) and (D), wherein the component (A) has a molecular weight of a polyfunctional thiol compound having a molecular weight of from 2 Å to 50,000 and an epoxy equivalent of from 80 to 6000 g/mol; The component is a thioether-containing alkoxydecane derivative represented by the following formula or formula (2); and the component (D) has an amine compound having a molecular weight of 9 〇 to 700; The weight ratio (a) / (B) of the component A) to the component (B) is 0.05 to 30; and the mixture of the component (A) and the component (B) is 1 part by weight based on the total weight of the component (B). .5 to 50 parts by weight of the component (C), 0.01 to 50 parts by weight of the component (D);

其中，a為1〜4的整數，b為0〜3的整數，c為0或1，a+b+c=4 ; m為 1 或 2 ; R1 為 _CHrCH(CH3)·、_ c(CH3)2-、-CH2-CHr4-CH(CH3)-中任意一種所示的二價基團，R2為甲基或乙基；化學式2Wherein a is an integer from 1 to 4, b is an integer from 0 to 3, c is 0 or 1, a+b+c=4; m is 1 or 2; R1 is _CHrCH(CH3)·, _c( CH3) a divalent group represented by any one of 2-, -CH2-CHr4-CH(CH3)-, R2 is a methyl group or an ethyl group;

其中，a’為1〜3的整數，b，為〇~2的整數，c，為〇或卜a，+b，+c，=3 ; a，為0〜3的整數，b”為〇〜2的整數，c”為0或卜a’，+b，，+c，，=3 ; m為i 36 s 201247768 或 2 ; R1 為-CH2-CH(CH3)-、- C(CH3)2-、-CH2-CH2-或-CH(CH3)-中任意一種所禾的二價基團，R2為甲基或乙基。 2. 根據申請專利範圍第1項所述的固化性樹脂組合物，其特徵在於，還混有（E)成分，作為（E)成分為分子量200〜50000且（甲基）丙烯酸酯當量為80〜6000g/mol的多官能（甲基）丙烯酸酯化合物；以所述（A) 成分和所述（B)成分的總重量為1〇〇重量份計，混入2〜300重量份該（E) 成分。 3. 根據申請專利範圍第1項或第2項所述的固化性樹脂組合物，其特徵在於，所述胺類化全1(D)為下述通式（3)所示的咪唑化合物丄___ 化學式3Wherein, a' is an integer of 1 to 3, b is an integer of 〇~2, c is 〇 or a, +b, +c, =3; a, an integer of 0 to 3, b" is 〇 An integer of ~2, c" is 0 or a', +b,, +c,, =3; m is i 36 s 201247768 or 2; R1 is -CH2-CH(CH3)-, - C(CH3) a divalent group of any one of 2-, -CH2-CH2- or -CH(CH3)-, and R2 is a methyl group or an ethyl group. 2. The curable resin composition according to the first aspect of the invention, characterized in that the component (E) is further mixed, and the (E) component has a molecular weight of 200 to 50,000 and a (meth) acrylate equivalent of 80. ～6000 g/mol of a polyfunctional (meth) acrylate compound; mixing 2 to 300 parts by weight of the (E) component based on the total weight of the component (A) and the component (B) ingredient. 3. The curable resin composition according to the first aspect or the second aspect of the invention, wherein the amine-based all 1 (D) is an imidazole compound represented by the following formula (3). ___ Chemical Formula 3

其中，R5為氰基、碳原子數1〜1〇的烴基、以2,3_二氨基三嗪取代的碳原子數1〜10的煙基、碳原子數丨〜4的烷氧基或氫原子，R4、R6、y為碳原子數1〜20的烴基、碳原子數丨〜4的烷氧基或氫原子，當R4〜R7鍵合形成的情况下為碳原子數2〜8的煙基。化合物；化學式4 4.根據申請專利範圍第U項中任一所述的固化性樹脂組合物其特徵在於’所述多官能硫醇化合物（A)為下述通式⑷所示的多官能 λ Ρ Δ-jL· · 口 rWherein R5 is a cyano group, a hydrocarbon group having 1 to 1 carbon atom, a ketone group having 1 to 10 carbon atoms substituted with 2,3-diaminotriazine, an alkoxy group having 碳4 or 4 or a hydrogen atom; The atom, R4, R6, and y are a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having a carbon number of 丨4 or a hydrogen atom, and a carbon atom having 2 to 8 carbon atoms when R4 to R7 are bonded to each other. base. The curable resin composition according to any one of the above claims, wherein the polyfunctional thiol compound (A) is a polyfunctional λ represented by the following formula (4). Δ Δ-jL· · mouth r

’ ρ為2〜10的整數，R8為碳原子數2〜3〇的烴基（αι )、 &氧與烴基構成的基團（α2)、異氰脲酸酯環（α3) 中的任一種。 ^中，η為2〜5的整數，？為2〜1〇的整數，R8為碳原子卖 ^原子〜4G灿喊無基構賴基IS U2)、J s'由異__環與烴基構成的基團（α4)中的任 37 201247768 5.根據申請專利範圍第1〜4項中任一所述固化性樹脂組合物，其特徵在於，所述多官能環氧樹脂（B)為縮水甘油醚型環氧樹脂或縮水甘油酯型環氧樹脂。 S 38 201247768 四、指定代表圖： (一）本案指定代表圖為： (二）本代表圖之元件符號簡單說明：五、本案若有化學式時，請揭示最能顯示發明特徵的化學式：'ρ is an integer of 2 to 10, and R8 is a hydrocarbon group (αι) having 2 to 3 carbon atoms, a group (α2) composed of oxygen and a hydrocarbon group, and an isocyanurate ring (α3). . In ^, η is an integer of 2~5,? An integer of 2 to 1 ,, R8 is a carbon atom to sell ^ atom ~ 4G can be shouted without a base lyion IS U2), J s ' is composed of a hetero-_ ring and a hydrocarbon group (α4) in any of the groups 37 201247768 The curable resin composition according to any one of claims 1 to 4, wherein the polyfunctional epoxy resin (B) is a glycidyl ether type epoxy resin or a glycidyl ester type ring. Oxygen resin. S 38 201247768 IV. Designated representative map: (1) The representative representative of the case is as follows: (2) The symbol of the symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention:

S 2S 2