TW201247768A - Curable resin composition - Google Patents

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

[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 201247768

Wherein, 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;

Where '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 ) 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

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 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 &gt;&lt; 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.

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 Chemical Formula 6

CnH2n 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. &lt;Polyfunctional epoxy resin ((B) component)&gt; 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!&quot;θΤ?#^ 80&quot;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. &lt;Glycidyl ether type epoxy resin&gt; 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 = 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)

Wherein 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. &lt;Glycidyl Ester Type Epoxy Resin&gt;, 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

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). &lt; 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 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

Wherein, 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;

Where '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.

Where 'm is 1 or 2'd is 3 or 4, and e is 〇 or 1, d+e=4. Chemical formula 16

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). &amp; 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. &lt;Amine compound (D) component&gt; 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 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). &lt;Imidazole compound&gt; 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

Wherein 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 &lt;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

Wherein, 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. &lt;Composition ratio (equal ratio)&gt; 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. &lt;Curable resin composition&gt; 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. _ __ &lt;Multifunctional thiol compound (component A)&gt; (A-1, Mw: 372) Chemical formula 19

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

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

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

S 22 201247768 〇 ο

(Α-6, Mw: 416) Chemical Formula 24

(Α-7, Mw: 785) Chemical formula 25

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

&lt;Multifunctional epoxy resin (component B)&gt; (B-1, Mw: 220, epoxy equivalent: 110) Chemical formula 27

(B-2, Mw: 360, epoxy equivalent: 90) Chemical formula 28

(B-3, Mw: 350, epoxy equivalent: 175) Chemical formula 29 (B-4, Mw: 5500, epoxy equivalent: 3000) Chemical formula 30

The average η is 15.

S 24 201247768 (B-5, Mw: 1500, epoxy equivalent: 186) Chemical formula 31

The average η is 7. (Β-6, Mw: 220, epoxy equivalent: 110) Chemical formula 32

O_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). &lt;Sulfur ether-containing alkoxydecane derivative (component C)&gt; (C-1) Chemical formula 33 25 201247768 Y^S, ,0

0

0

s, 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 o

〇, /\^Si(OCH3)3 o

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

Y^S Ο I (HaCOJaSi^^^O

o

S

0, o

,SH

A SH o o (C-4) Chemical Formula 36 (HaCOhSix^-^o

HS

O O 〇,

,SH

, SH 0 (C-5) Chemical Formula 37

(C2H5〇)3Si^^^O (CjHsO^Si^^s^O

° \ /0 〇, /\/Si(OC2H5h, s

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

ZUIZH·/ /UO

% I

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

(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 Formula 43

(C’-5) Chemical Formula 44

(H3CO)3Si^^O

Hey.

HS

&lt;Amine compound (D component)&gt; (D-l, Mw: 136) Chemical formula 45

(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)&gt;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 Formula 48

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

\=J

HOOC\^w^COOH

TT

HOOC/^jSi^COOH 2-Phenyl imidazole and pyromellitic acid salt (D, -6, Mw: 158) Chemical formula 52

(D, -7, Mw: 306) 29 201247768 Chemical Formula 53 C17H35 Person \=/ &lt;Polyfunctional (meth) acrylate compound (E component)&gt; (El, Mw : 246, double bond equivalent: 123) Chemical formula 54

(E-2, Mw: 352, double bond equivalent: 88) Chemical formula 55 〇 Ο

Chemical formula 56

(E-4, Mw: 5000, double bond equivalent: 3000) Chemical formula 57

The average η is 13 (Ε-5, Mw: 1200, double bond equivalent: 180)

S 30 201247768 Chemical Formula 58

Chemical formula 59 )=°

V=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). &lt;Other reagents&gt; (F-1, and component A) Chemical formula 60 0

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. &lt;Adhesion evaluation&gt; 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. &lt;Confirmation of photo-curability&gt; 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. &lt;Confirm storage stability (preservation stability)&gt; 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&lt; it is more than two 1 C3 1 i 1 oo*j CNJ 〇«r&gt; oi CO 100.0 s csj ir&gt;&lt;y&gt;c-&gt; l 〇1 25.97 1 XX ◎ 上,.Α-3 &lt ;〇CM te&gt; Cs4 ri m «ρ ms C3 IO GO &lt;c&gt; 100.0 CM 丄oo in CM Q P-- Oi es&lt; ο X ο τ 1 CO CP P: Ol ffl s era g inch 100.0 VO i · Σ &lt;〇CO ο XX Ο 1 实旌ί?ΰ工τ &lt;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 ? &lt;; 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 &lt; CD l〇n*· m 1 18000 I s CV «r&gt; 1 100.0 1 si CNl o 3 1 3.45 1 ◎ ◎ ◎ ο τ 1 Α -7 1 in GD 卜 l〇&lt;〇lsol〇CSJ ni 100.0 1 CO s C'-5 I 〇 &gt; o O ! 25.97 1 ◎ ◎ ◎ 〇 &gt;&lt; CO CM 9 \ B-6 1 § o oo s I 100.0 1 f5 s CM 5 tr&gt; bk 1 〇 ◎ ◎ ©&gt; CO ΙΓ&gt; s Γ- - irt ΓΟ in ώ I 1500 I i in Csl &lt;〇1 100.0 I o CO ύ s C\| 1 D'-4 1 σ&gt; s &lt;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 &lt;〇S ir&gt; ◎ ◎ ◎ &lt;ρ &lt; CO ΙΛ rp ffl 丨18000" o ir&gt; «Μ l〇穿I 100.0 1 u&gt; cn· CO ύ iO 7 Ch ΙΛ 3 ◎ ◎ ◎ ΙΟ Γρ &lt; in eo laom 奂 1 mo 1 g «vi I 05 I cn oio 1 25.97 1 ◎ ◎ ◎ «ρ &lt; 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 &lt;&&gt;σ&gt; n ce r·^ CSJ ffl sos OJ 100.0 I eo ώ ώ (O eo SO ◎ ◎ 〇 V cn &lt; CO CN| 〇53.2 ΓΟ ms r&gt;v&gt; 46.8 100.0 CM ύ o U*3 Oi Δ 5m CM s ◎ ◎ ο CM &lt;σ&gt; σ) c-&gt; 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 &lt; % C component D component 1 33 201247768 t:: u -t λ &lt;r&gt;&lt; ο CM ΙΓ&gt; 0 TO e&gt;i CD S CO s LO 〇S C3 1 1 Ω «0 〇2 8 〇ur» ill &lt;0 SL〇σ&gt; o to 1 X 〇〇i.'-' m 忑( O &lt; s 0 s I s § 8 S g 〇ss ai T 0 c» CM 〇es| tr&gt; s &lt;X&gt; 10 Ul 1 g C&gt; 1 ◎ ◎ ◎ o ie&gt; Z &lt;〇(NJ m 0 &lt;0 s Oi 〇0 wear&lt;=! § s? o 〇cp i CO &lt;0 s 5 II 0 1 〇i 〇s 1 ® @ 0 5: C 〇&gt;〇&gt; CO tr&gt;& «ρ CD I s CNJ \r&gt; 〇sar^* ¢0 0 S CSJ eja c&gt; g uS C\i J; CO 0 s •w^ Ο s ◎ ◎ ◎ 0 r〇Λ 〇〇i Γ— s s ro s &lt;〇rvi 0 ss CNJ OJ ώ r-*. 0 Q an CO r-' &lt;M ill Oi ir&gt; CO s 0 3 1 ◎ ◎ 〇CNI Σ &lt;〇&lt; €D 〇* &gt;&lt;0cr&gt;%r&gt; ω 1 &lt;£&gt; 〇〇CO 0 寒写 o CO 卜Q CO cr&gt; LO CO LIJ CO rr&gt; CO CO CO LO 1 ◎ ◎ ◎ 〇Ϊ ^r &lt; C 〇〇«Ν cn ml〇GO sos O) L〇ώ 〇&gt; €1=» 2 00 10 s PJ«- til is CO 1 ◎ ◎ ◎ 0 〇I &lt;卜C&gt; s m § o 8 S 0 0 2 s aS ώ 〇s T CM to g &lt;b Ning UJ 1 s 〇 1 ◎ ◎ ◎ 0 ΟΪ eg cp &lt;C CO 0 s ώ 〇0 0 0 ss r- ύ 0 § CJ&gt; Ck CO to g 耷1 I § CO 0 s 1 ◎ ◎ ◎ 0 CO CVJ CM &lt;«·&gt; ΙΓΪ 00 «Ο m 震^r S CSJ U~3 0 gs CO ώ c=&gt; i/S CNI CNI 0 ? G tr&gt; 01 z 荽CM 舀0 g* 0 s ◎ ◎ ◎ 0 r- 1 CSJ CO i jo- C&gt;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 &lt; CO ir&gt; V CD I Ο«Ο c*i 0 3 s R τ ο to C-3 P*- 0 &lt;0 〇&gt; 1C CJ3 UJ &lt;〇CO s CO will Csl 1 ◎ ◎ ◎ 〇L〇CsJ T &lt; CO CSI Ο» ώ 荽to 00 &lt;=? s Τ'- CT&gt; 2 05 «0 T a CO ir> s Γ^- UJ i CSJ s CO LO c6 1 ◎ ◎ ◎ 〇T CM ep &lt;&lt; 〇CSJ ir&gt; S &lt;VJ ώ is 〇tg&gt; s LT&gt; CO iO Σ &lt;〇r〇«Ο g cp UJ S l〇s cq in 1 ◎ 0 〇fJ3 CV cm &lt;a&gt;〇&gt; o 〇&gt; 5 Σ 0 LO IA 0 g 〇〇CO ώ CO o«ir〇ig &lt;0 σ&gt; oo rj- ill § as &lt;*3 5 1 ◎ ◎ 〇0 esi CM CO &lt;&lt;〇CML〇&lt;P s? CjJ CD ss 〇s 0. s ir&gt; 00 ώ \r&gt; ά 40 ΓΟ s CO UJ &lt;〇s 00 s 1 ◎ ◎ 〇0 J, CSI &lt; CO s 〇3 □Q § 0 10 0 s cp 0 00 cp a § K od r- Hawthorn 1 CVI sc*&gt; s I ◎ ◎ 〇0 k·' :ws ¢1 Φ s Φ*) &lt;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 (1)

201247768 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); Wherein 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; Wherein, 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 Wherein 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 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 2