JP2007291313A - Ultraviolet light curable resin composition, cured material of the same and various article derived from the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ultraviolet light curable resin composition cured easily by the ultraviolet light, enabling the thick film curing since it has a low shrinkage and realizing a cured material satisfying various characteristics such as heat resistance, chemical resistance, surface hardness, etc., and the cured material obtained from the composition. <P>SOLUTION: This ultraviolet light curable resin composition is characterized by containing (A) a condensate obtained by hydrolyzing and condensing (a1) a thiol group-containing alkoxy silanes expressed by general formula (1): R<SP>1</SP>Si(OR<SP>2</SP>)<SB>3</SB>---(1) [wherein, R<SP>1</SP>is a 1-8C hydrocarbon having at least one thiol group or an aromatic hydrocarbon group having at least one thiol group; R<SP>2</SP>is H, a 1-8C hydrocarbon group or an aromatic hydrocarbon group] and (B) a compound having a carbon carbon double bond. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an ultraviolet curable resin composition, a cured product obtained by ultraviolet curing the composition, and various articles derived therefrom.

  A compound having a carbon-carbon double bond such as an acryl group, a methacryl group, an allyl group, or a vinyl group can be polymerized by an active energy ray in the presence of a polymerization initiator, and thus various active energy ray curable resin compositions. Used in various fields. However, coating with a thin film causes polymerization inhibition due to oxygen at the time of curing, resulting in insufficient curing, making it difficult to obtain the desired performance, and due to large curing shrinkage, warping and cracking are likely to occur, making it suitable for thick film curing. There are problems such as not.

  In contrast, the reaction between the compound having a carbon-carbon double bond and the compound having a thiol group (ene-thiol reaction) proceeds by ultraviolet irradiation regardless of the presence or absence of a polymerization initiator, and inhibits reaction by oxygen. There are advantages such as not receiving and small shrinkage in curing. Regarding a curing method and a cured product using this reaction, use of an unsaturated thiol compound having a carbon-carbon double bond and a thiol group in one molecule (see, for example, Patent Document 1), carbon- A resin composition composed of a compound having a plurality of carbon double bonds and a compound having a plurality of thiol groups (for example, see Patent Documents 2 to 5) has been proposed.

  On the other hand, as a means of further improving the characteristics of organic materials, by combining inorganic materials with organic materials, so-called organic materials that have been imparted with the characteristics of inorganic materials such as high heat resistance, chemical resistance, and high surface hardness. -Inorganic hybrid technology has attracted attention in recent years. Regarding the ultraviolet curable resin composition using the ene-thiol reaction, a composition comprising a silicone having a carbon-carbon double bond and a silicone having a thiol group (see, for example, Patent Documents 6 to 9) is known. Yes. However, in the methods described in Patent Documents 6 to 9, since the inorganic component to be used is silicone (a rubber state at room temperature), sufficient heat resistance and surface hardness cannot be obtained.

JP 49-51333 A JP-A-49-54491 JP 50-27836 A JP-A-53-134096 JP 2003-295431 A Japanese Patent Laid-Open No. 56-110731 Japanese Patent Laid-Open No. 60-110552 Japanese Patent Laid-Open No. 05-320511 US Patent Application Publication No. 2004/209972

  The present invention is a cured product utilizing an ene-thiol reaction, which is easily cured by ultraviolet rays, can be cured with a thick film due to low shrinkage, and has various properties such as heat resistance, chemical resistance, and surface hardness. It aims at providing the ultraviolet curable resin composition for implement | achieving the cured | curing material which can satisfy | fill a characteristic, and providing the cured | curing material obtained from the said composition.

  As a result of intensive studies to solve the above problems, the present inventors have found that a composition comprising a hydrolysis condensate of a thiol group-containing alkoxysilane and a compound having a carbon-carbon double bond, and an ultraviolet cured product thereof. It has been found that the above problems can be solved, and the present invention has been completed.

That is, the present invention relates to the general formula (1):
R ¹ Si (OR ² ) ₃ (1)
(In the formula, R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms having at least one thiol group, or an aromatic hydrocarbon group having at least one thiol group, and R ² represents a hydrogen atom, having 1 to 1 carbon atoms. 8 represents a hydrocarbon group or an aromatic hydrocarbon group.) A condensate (A) obtained by hydrolysis and condensation of a thiol group-containing alkoxysilane (a1) (hereinafter referred to as component (A)) And a compound (B) having a carbon-carbon double bond (hereinafter referred to as component (B)) as essential components. The present invention also relates to a cured product obtained by curing the composition with ultraviolet rays. The present invention further relates to various articles derived therefrom.

  According to the present invention, there is provided an ultraviolet curable resin composition that can provide a cured product having improved properties such as heat resistance, chemical resistance, and surface hardness while utilizing ultraviolet curable by an ene-thiol reaction. it can. Further, the cured product of the present invention obtained from the ultraviolet curable resin composition comprises a coating agent (light guide plate, polarizing plate, liquid crystal panel, EL panel, PDP panel, OHP film, optical fiber, color filter, optical disk substrate, lens, liquid crystal Cell plastic substrates or prisms), adhesives (liquid crystal panels, EL panels, PDP panels, color filters, optical disk substrates, etc.), sealing materials (light emitting elements, light receiving elements, photoelectric conversion elements, or optical transmission) This is useful for applications such as related parts).

Component (A) used in the present invention has the general formula (1):
R ¹ Si (OR ² ) ₃ (1)
(In the formula, R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms having at least one thiol group, or an aromatic hydrocarbon group having at least one thiol group, and R ² represents a hydrogen atom, having 1 to 1 carbon atoms. 8 is a compound obtained by hydrolysis and condensation of a thiol group-containing alkoxysilane (a1) represented by 8). Specific examples of the thiol group-containing alkoxysilanes (a1) (hereinafter referred to as component (a1)) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltripropoxysilane, 3- Mercaptopropyltributoxysilane, 1,4-dimercapto-2- (trimethoxysilyl) butane, 1,4-dimercapto-2- (triethoxysilyl) butane, 1,4-dimercapto-2- (tripropoxysilyl) butane 1,4-dimercapto-2- (tributoxysilyl) butane, 2-mercaptomethyl-3-mercaptopropyltrimethoxysilane, 2-mercaptomethyl-3-mercaptopropyltriethoxysilane, 2-mercaptomethyl-3-mercapto Propyl tripropoxy Silane, 2-mercaptomethyl-3-mercaptopropyltributoxysilane, 1,2-dimercaptoethyltrimethoxysilane, 1,2-dimercaptoethyltriethoxysilane, 1,2-dimercaptoethyltripropoxysilane, 1, Examples include 2-dimercaptoethyltributoxysilane, and the exemplified compounds can be used alone or in appropriate combination. Among the exemplified compounds, 3-mercaptopropyltrimethoxysilane is particularly preferable because of high reactivity of hydrolysis reaction and easy availability.

  In addition to component (a1), trialkylalkoxysilanes such as trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxy Dialkyl dialkoxysilanes such as silane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, methyltrimethoxysilane Methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, Alkyltrialkoxysilanes such as rutriethoxysilane, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, etc. Metal alkoxides (a2) (hereinafter referred to as component (a2)) such as tetraalkoxyzirconiums such as tetraalkoxytitaniums, tetraethoxyzirconium, tetrapropoxyzirconium, and tetrabutoxyzirconium can be used. The component (a2) can be used either alone or in combination of two or more. Of these, the crosslink density of the component (A) can be adjusted by using trialkylalkoxysilanes, dialkyldialkoxysilanes, and tetraalkoxysilanes. By using alkyltrialkoxysilanes, the amount of thiol groups contained in component (A) can be adjusted. By using tetraalkoxytitanium or tetraalkoxyzirconium, the refractive index of the finally obtained ultraviolet cured product can be increased.

  When component (a1) and component (a2) are used in combination, [number of moles of thiol group contained in component (a1)] / [total number of moles of component (a1) and component (a2)] (molar ratio: 1 The average number of thiol groups contained per molecule is preferably 0.2 or more. If it is less than 0.2, the number of thiol groups contained in the resulting component (A) is reduced, so that the ultraviolet curability is lowered and the effect of improving the physical properties such as hardness of the cured product is insufficient. Tend to be. [Total number of moles of each alkoxy group contained in component (a1) and component (a2)] / [Total number of moles of component (a1) and component (a2)] (molar ratio: alkoxy contained per molecule) The average number of groups) is preferably 2.5 or more and 3.5 or less, and more preferably 2.7 or more and 3.2 or less. When it is less than 2.5, the crosslinking density of the obtained component (A) is low, and the heat resistance of the cured product tends to decrease. Moreover, when it exceeds 3.5, when manufacturing a component (A), it exists in the tendency which becomes easy to gelatinize.

  Component (A) used in the present invention can be obtained by condensing component (a1) alone or in combination with component (a2), condensing them after hydrolysis. By the hydrolysis reaction, the alkoxy group contained in component (a1) or component (a2) becomes a hydroxyl group, and alcohol is by-produced. The amount of water required for the hydrolysis reaction is [number of moles of water used in hydrolysis reaction] / [total number of moles of each alkoxy group contained in component (a1) and component (a2)] (molar ratio). 4 or more and 10 or less, preferably 1. When it is less than 0.4, there is an alkoxy group remaining without being hydrolyzed in the component (A), which is not preferable. On the other hand, if it exceeds 10, the amount of water to be removed in the subsequent condensation reaction (dehydration reaction) increases, which is economically disadvantageous.

  In addition, when the component (a2) is used in combination with a tetraalkoxytitanium, a tetraalkoxyzirconium or the like, particularly a metal alkoxide having a high hydrolyzability and condensation reactivity, the hydrolysis and condensation reaction proceeds rapidly, and the system May gel. In this case, gelation can be avoided by adding the component (a2) after the hydrolysis reaction of the component (a1) has been completed and all water has been consumed.

  The catalyst used for the hydrolysis reaction is not particularly limited, and a conventionally known hydrolysis catalyst can be arbitrarily used. Of these, formic acid is preferred because it has high catalytic activity and also functions as a catalyst for the subsequent condensation reaction. The amount of formic acid added is preferably 0.1 to 25 parts by weight, and more preferably 1 to 10 parts by weight with respect to 100 parts by weight as the total of component (a1) and component (a2). When the amount is more than 25 parts by weight, the stability of the resulting ultraviolet curable resin composition tends to be lowered, and the amount of removal increases even if formic acid can be removed in a subsequent step. On the other hand, when the amount is less than 0.1 parts by weight, the reaction does not substantially proceed or the reaction time tends to be long. Although reaction temperature and time can be arbitrarily set according to the reactivity of a component (a1) or a component (a2), it is about 0-100 degreeC normally, Preferably it is about 20-60 degreeC, 1 minute-about 2 hours. The hydrolysis reaction can be performed in the presence or absence of a solvent. The type of the solvent is not particularly limited, and one or more arbitrary solvents can be selected and used, but it is preferable to use the same solvent as that used in the condensation reaction described later. When the reactivity of component (a1) or component (a2) is low, it is preferable to carry out without solvent.

  The hydrolysis reaction is carried out by the above method, but the [number of moles of hydroxyl group formed by hydrolysis] / [total number of moles of each alkoxy group contained in component (a1) and component (a2)] (molar ratio) is 0. It is preferable to make it progress so that it may become 0.5 or more, and it is still more preferable to adjust to 0.8 or more. The condensation reaction following the hydrolysis reaction proceeds not only between the hydroxyl groups generated by hydrolysis but also between the hydroxyl groups and the remaining alkoxy groups, so that at least half (molar ratio is 0.5 or more) is hydrolyzed. Just do it.

  In the condensation reaction, water is by-produced between the hydroxyl groups, and alcohol is by-produced between the hydroxyl groups and the alkoxy group to vitrify. A conventionally known dehydration condensation catalyst can be arbitrarily used for the condensation reaction. As described above, formic acid is preferable because it has high catalytic activity and can be used as a catalyst for hydrolysis reaction. The reaction temperature and time can be arbitrarily set according to the reactivity of the component (a1) or component (a2), but are usually about 40 to 150 ° C., preferably 60 to 100 ° C., about 30 minutes to 12 hours. .

  Condensation reaction is carried out by the above method. [Total number of moles of unreacted hydroxyl group and unreacted alkoxy group] / [Total number of moles of alkoxy groups contained in component (a1) and component (a2)] (molar ratio ) Is preferably 0.3 or less, and more preferably 0.2 or less. If it exceeds 0.3, the unreacted hydroxyl group and alkoxy group undergo a condensation reaction during storage of the UV curable resin composition to gel, the condensation reaction occurs after curing, volatile matter occurs, and cracks occur, This is not preferable because it tends to impair the performance of the cured product.

  The condensation reaction is preferably performed by diluting the solvent so that the concentration of component (a1) (or both when component (a2) is used in combination) is about 2 to 80% by weight. It is more preferable. It is preferable to use a solvent having a boiling point higher than that of water and alcohol generated by the condensation reaction because these can be distilled off from the reaction system. When the concentration is less than 2% by weight, the component (A) contained in the obtained ultraviolet curable resin composition is decreased, which is not preferable. When it exceeds 80% by weight, gelation occurs during the reaction, or the molecular weight of the component (A) to be generated becomes excessively high, and the storage stability of the resulting ultraviolet curable resin composition tends to deteriorate. As the solvent, one or more arbitrary solvents can be selected and used. It is preferable to use a solvent having a boiling point higher than that of water and alcohol produced by the condensation reaction because these can be distilled off from the reaction system. Component (B) can also be used as part of the solvent.

  It is preferable to remove the catalyst used after completion of the condensation reaction because the stability of the finally obtained ultraviolet curable resin composition is improved. The removal method can be appropriately selected from various known methods depending on the catalyst used. For example, when formic acid is used, it can be easily removed by a method such as heating to above the boiling point or depressurization after completion of the condensation reaction, and formic acid is also preferred in this respect.

  The component (B) used in the present invention is not particularly limited, and a conventionally known compound having a carbon-carbon double bond can be appropriately used. Examples of the functional group related to the carbon-carbon double bond include a vinyl group, an acrylic group, a methacryl group, and an allyl group.

  The carbon-carbon double bond of component (B) reacts with the thiol group of component (A) (ene-thiol reaction), but the reaction mechanism differs depending on the presence or absence of a polymerization initiator.

  When no polymerization initiator is used, this reaction is considered to be based on the following reaction mechanism [reaction formula (1)].

（式中、Ｒ_aは成分（Ａ）のチオール基以外の残基を、Ｒ_bは成分（Ｂ）の炭素−炭素２重結合以外の残基をそれぞれ示す。）。すなわち、炭素−炭素２重結合１個に対してチオール基１個が付加する反応である。

(In the formula, R _a represents a residue other than the thiol group of component (A), and R _b represents a residue other than the carbon-carbon double bond of component (B)). That is, it is a reaction in which one thiol group is added to one carbon-carbon double bond.

  On the other hand, in the case of using a polymerization initiator, in addition to the addition reaction of the above reaction formula (1), this reaction includes the following chain radical reaction process [reaction formulas (2) to (5)], and The reaction proceeds with the side reaction shown in the reaction formula (6).

（該式中、Ｉは重合開始剤を示す。）。すなわち、反応式（２）：重合開始剤より紫外線によってラジカルが生成する段階、反応式（３）：成分（Ａ）のチオール基の水素が引き抜かれ、チイルラジカルが生成する段階、反応式（４）：成分（Ａ）に生成したチイルラジカルが成分（Ｂ）の炭素−炭素２重結合と反応、炭素ラジカルが生成する段階、反応式（５）：炭素ラジカルが成分（Ａ）のチオール基の水素を引き抜き、チイルラジカルが再生する段階を経由する。

(In the formula, I represents a polymerization initiator). That is, reaction formula (2): a stage in which radicals are generated by ultraviolet rays from a polymerization initiator, reaction formula (3): stage in which hydrogen of the thiol group of component (A) is withdrawn, and thiyl radical is generated, reaction formula (4) : Reaction of the thiyl radical generated in component (A) with the carbon-carbon double bond of component (B), formation of a carbon radical, reaction formula (5): carbon radical converts hydrogen of thiol group of component (A) It goes through a stage where it is extracted and the thiyl radical is regenerated.

である。 The side reaction is

It is.

  Reaction formula (6): The carbon radical produced | generated by reaction formula (4) reacts with the carbon-carbon double bond of a component (B), and when a carbon radical reproduce | regenerates, the polymerization reaction of components (B) will also be simultaneous. Occur.

  As described above, when a polymerization initiator is not used, the thiol group in component (A) and the carbon-carbon double bond in component (B) react at 1: 1 (molar ratio), but polymerization occurs. When an initiator is used, the reaction will be 1: 1 or more.

  From the above viewpoint, the proportion of components (A) and (B) used in preparing the ultraviolet curable resin composition of the present invention is appropriately determined depending on the presence or absence of a polymerization initiator. When the polymerization initiator is not used, specifically, [number of moles of thiol group contained in component (A)] / [number of moles of carbon-carbon double bond contained in component (B)] (molar ratio) ) Is preferably 0.9 to 1.1, more preferably 1.0. If it is less than 0.9, carbon-carbon double bonds remain even after UV curing, and the weather resistance tends to be lowered. Moreover, when it exceeds 1.1, a thiol group may remain | survive and a malodor may be generated by the decomposition | disassembly.

  On the other hand, when using a polymerization initiator, specifically, [number of moles of thiol group contained in component (A)] / [number of moles of carbon-carbon double bond contained in component (B)] (mole The ratio is preferably 0.01 to 1.1. When the amount is less than 0.01, the amount of the component (A) used is too small, so that the desired effect of the present invention tends to be hardly obtained. Furthermore, the carbon-carbon double bond tends to remain, and the weather resistance of the cured product tends to be lowered. Moreover, when it exceeds 1.1, a thiol group may remain | survive and a malodor may be generated by the decomposition | disassembly.

  In addition, in order to avoid the disadvantage that the functional groups having a carbon-carbon double bond are polymerized with each other in preference to the reaction between the functional group having a carbon-carbon double bond and the thiol group, the component (B) Among them, the functional group is preferably an allyl group. The compounds containing one allyl group include cinnamic acid, monoallyl cyanurate, monoallyl isocyanurate, pentaerythritol monoallyl ether, trimethylolpropane monoallyl ether, glycerin monoallyl ether, bisphenol A monoallyl ether, bisphenol. Examples thereof include F monoallyl ether, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, and tripropylene glycol monoallyl ether. Compounds containing two allyl groups include diallyl phthalate, diallyl isophthalate, diallyl cyanurate, diallyl isocyanurate, pentaerythritol diallyl ether, trimethylolpropane diallyl ether, glyceryl diallyl ether, bisphenol A diallyl ether, bisphenol F diallyl ether Ethylene glycol diallyl ether, diethylene glycol diallyl ether, triethylene glycol diallyl ether, propylene glycol diallyl ether, dipropylene glycol diallyl ether, tripropylene glycol diallyl ether, and the like. Examples of the compound containing three or more allyl groups include triallyl isocyanurate, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, trimethylolpropane triallyl ether, and the like. These compounds can be used either alone or in combination. Among these, triallyl isocyanurate, diallyl phthalate, and pentaerythritol triallyl ether are particularly preferable.

  Moreover, as a component (B), a thing with a higher molecular weight than the said compound can be used. The ultraviolet curable resin composition using a high molecular weight product tends to improve the flexibility of the resulting cured product. Examples of the high molecular weight compound include a copolymer composed of methylallylsiloxane and dimethylsiloxane, a copolymer composed of epichlorohydrin and allylglycidyl ether (Daiso Co., Ltd .: trade name “Epichromer”, Nippon Zeon Co., Ltd .: Commodity Name "Gechron"), allyl group-terminated polyisobutylene polymer (Kaneka Co., Ltd .: trade name "Epion") and the like. These compounds can be used alone or in combination of two or more.

  When using component (B), [number of moles of carbon-carbon double bonds contained in component (B)] / [number of moles of component (B)] (molar ratio: carbon-carbon contained per molecule) The average number of double bonds is preferably 2 or more. When it is less than 2, since the curability of the ultraviolet curable resin composition is lowered and the cross-linking density of the obtained cured product is lowered, physical properties such as heat resistance and surface hardness of the cured product tend to be lowered.

  It does not specifically limit as a polymerization initiator which can be used when preparing the ultraviolet curable resin composition of this invention, A conventionally well-known photocation initiator, photoradical initiator, etc. can be selected arbitrarily. Examples of the photocation initiator include sulfonium salts, iodonium salts, metallocene compounds, benzoin tosylate, and the like, which are compounds that generate an acid upon irradiation with ultraviolet rays. Examples of such commercially available products include Cyracure UVI-6970 and UVI. -6974, UVI-6990 (all trade names manufactured by Union Carbide, Inc.), Irgacure 264 (Ciba Specialty Chemicals), CIT-1682 (manufactured by Nippon Soda Co., Ltd.), and the like. The usage-amount of a photocationic polymerization initiator is normally about 10 weight part or less with respect to 100 weight part of this composition, Preferably it is 1-5 weight part. Examples of the photo radical initiator include Darocur 1173, Irgacure 651, Irgacure 184, Irgacure 907 (all trade names of Ciba Specialty Chemicals), benzophenone, and the like, and about 15 parts by weight or less with respect to 100 parts by weight of the composition. The amount is preferably 1 to 15 parts by weight. When there is a concern about a decrease in the weather resistance of the resulting cured product, it is better not to use a photoinitiator or a photosensitizer, especially when used for an optical member that requires high weather resistance and transparency. .

  Moreover, in order to improve the stability of an ultraviolet curable resin composition more, the compound which suppresses ene-thiol reaction can be mix | blended. Examples of such compounds include phosphorus compounds such as triphenylphosphine and triphenyl phosphite; p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2, 6-di-tert-butyl-p-cresol, 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol) Radical), N-nitrosophenylhydroxylamine aluminum salt, diphenylnitrosamine and other radical polymerization inhibitors; benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol, diaza Tertiary amines such as bicycloundecene; 2-methylimidazole, 2- Examples include imidazoles such as ethyl-4-methylimidazole, 2-ethylhexylimidazole, 2-undecylimidazole, and 1-cyanoethyl-2-methylimidazole.

  Among the phosphorus compounds, triphenyl phosphite is preferable because it has a high inhibitory effect on the ene-thiol reaction, is liquid at room temperature, and is easy to handle. The amount of the compound to be blended in the ultraviolet curable resin composition is preferably about 0.1 to 10 parts by weight with respect to 100 parts by weight of the composition. When the amount is less than 0.1 parts by weight, the effect of suppressing the ene-thiol reaction is insufficient, and when the amount exceeds 10 parts by weight, the remaining amount in the obtained cured product is increased and the physical properties of the cured product are deteriorated. Tend.

  Of the radical polymerization inhibitors, nitrosophenylhydroxylamine aluminum salt is preferable because it has a high inhibitory effect on the ene-thiol reaction even in a small amount and is excellent in the color tone of the resulting cured product. The amount of the compound to be blended in the ultraviolet curable resin composition is preferably about 0.0001 to 0.1 parts by weight with respect to 100 parts by weight of the composition. When the amount is less than 0.0001 part by weight, the effect of suppressing the ene-thiol reaction is insufficient, and when it exceeds 0.1 part by weight, the ultraviolet curability tends to be lowered.

  Of the tertiary amines, benzyldimethylamine is preferable because it has a high inhibitory effect on the ene-thiol reaction even in a small amount and is liquid at room temperature and easy to handle. The amount of the compound to be blended in the ultraviolet curable resin composition is preferably about 0.001 to 5 parts by weight with respect to 100 parts by weight of the composition. When the amount is less than 0.001 part by weight, the effect of suppressing the ene-thiol reaction is insufficient. When the amount exceeds 5 parts by weight, an unreacted hydroxyl group and alkoxy group in the component (A) undergo a condensation reaction. This is not preferable because it tends to gel.

  The concentrations of the active ingredients (A) and (B) of the ultraviolet curable resin composition can be appropriately determined according to the application, and a solvent can be blended as necessary. A conventionally well-known thing can be arbitrarily used as a solvent. When the ultraviolet curable resin composition is used as a coating agent, it may be diluted with a solvent to obtain a desired viscosity. Further, when the ultraviolet curable resin composition is cured to a thick film of 1 mm or more, or when used as an adhesive, the total concentration of the components (A) and (B) is preferably 90% by weight or more, More preferably, it is 95% by weight or more. The total concentration may be calculated from the concentration of the components (A) and (B) and the amount of the solvent added at the time of charging the ultraviolet curable resin composition, or the solvent contained in the ultraviolet curable resin composition. It can also be obtained by heating for about 2 hours above the boiling point of and by changing the weight before and after heating. In the application, if it is less than 90% by weight, the physical properties of the cured product tend to be lowered due to foaming during curing and molding, or solvent remaining in the cured product. In addition, since the solvent is indispensably used during the synthesis of component (A), when used in the application, the solvent should be volatilized after the reaction so that the nonvolatile content is 90% by weight or more. Good. Moreover, after preparing an ultraviolet curable resin composition, the used solvent can be volatilized and the total density | concentration of an active ingredient (A) and (B) can also be raised.

  Although the essential component of the ultraviolet curable resin composition of this invention consists of the component (A) obtained as mentioned above and a component (B), as another aspect of this invention, it is a component (a1). ) And the optional component (a2) in the presence of formic acid, followed by a condensation reaction in the presence of the solvent and component (B). Conditions such as reaction temperature, reaction time, and solvent type are all the same as in the case of the component (A).

  The ultraviolet curable resin composition may contain the component (a1) and / or a hydrolyzate thereof (excluding the condensate) [hereinafter also referred to as component (C)] depending on the application. . As the component (C), the component (a1) used in the synthesis of the component (A) can be used as it is, or a hydrolyzate thereof can be used in combination. When the ultraviolet curable resin composition containing the component (C) is used as a coating agent for inorganic substrates such as glass and metal, there is an advantage that the adhesion can be further improved. It is preferable that the compounding quantity of a component (C) is 0.1-20 weight part with respect to 100 weight part of this composition. When the amount is less than 0.1 part by weight, the effect of improving the adhesion of the ultraviolet curable resin composition to the inorganic substrate tends to be insufficient. On the other hand, when the amount exceeds 20 parts by weight, the amount of volatile components when the component (C) undergoes hydrolysis and condensation increases, so that the ultraviolet curable resin composition can be cured thick or the resulting cured product is brittle. There is a tendency to become. As such a component (C), 3-mercaptopropyltrimethoxysilane is particularly preferable in terms of the effect of improving adhesion.

  Moreover, an epoxy group-containing compound (D) (hereinafter referred to as component (D)) can be blended in the ultraviolet curable resin composition depending on the application. As the component (D), a conventionally known compound having an epoxy group can be used. When the ultraviolet curable resin composition containing the component (D) is used as a coating agent for an organic substrate such as plastic, there is an advantage that the adhesion can be further improved. Component (D) reacts with the thiol group of component (A), is incorporated into the cured product by chemical bonding, and has an advantage of suppressing physical properties such as heat resistance of the cured product. In the case of a compound having two or more epoxy groups, the crosslinking density with the component (A) is increased, and the decrease in physical properties is minimized. The compounding amount of the component (D) is about 0.1 to 20 parts by weight with respect to 100 parts by weight of the ultraviolet curable resin composition, and [number of moles of thiol groups contained in the component (A)] / [ The total (molar ratio) of the number of moles of carbon-carbon double bonds contained in component (B) and the number of moles of epoxy groups contained in component (D) is about 0.9 to 1.1. It is preferable to mix | blend with, More preferably, it is 1.0. If it is less than 0.1 part by weight, the effect of improving the adhesion to the organic substrate tends to be insufficient. Moreover, when it exceeds 20 weight part, there exists a tendency for the storage stability of an ultraviolet curable resin composition to fall, or for ultraviolet curable to fall. Among the components (D), the bisphenol A type epoxy resin is particularly preferable because it contains two epoxy groups and is easily available.

  In addition, the ultraviolet curable resin composition includes a metal alkoxide as the component (a2) and / or a hydrolyzate thereof (excluding the condensate) (E) [hereinafter also referred to as a component, depending on the application. (E)] can be blended. As the component (E), the metal alkoxides used in the synthesis of the component (A) can be used as they are, their hydrolysates can be used, or these can be used in combination. By using the ultraviolet curable resin composition containing the component (E), the refractive index of the obtained cured product can be adjusted. When the ultraviolet curable resin composition is used as a coating agent having a high refractive index, alkoxytitaniums and alkoxyzirconiums are suitable as the component (E). It is preferable that the compounding quantity of a component (E) is about 0.1-20 weight part with respect to 100 weight part of ultraviolet curable resin compositions. If it is less than 0.1 part by weight, the refractive index improving effect tends to be insufficient. When the amount exceeds 20 parts by weight, the amount of volatile components when the component (E) undergoes hydrolysis or condensation reaction increases, so that the ultraviolet curable resin composition foams during curing, warpage or cracks occur. The resulting cured product tends to be brittle.

  Furthermore, the ultraviolet curable resin composition has a plasticizer, a weather resistance agent, an antioxidant, a heat stabilizer, a lubricant, and an antistatic agent within the range that does not impair the effects of the present invention. , Whitening agents, colorants, conductive agents, mold release agents, surface treatment agents, viscosity modifiers, fillers, and the like may be blended.

In order to prepare a desired cured product using the ultraviolet curable resin composition thus obtained, when the composition is coated on a predetermined substrate or filled in a predetermined mold and contains a solvent, What is necessary is just to irradiate an ultraviolet-ray after volatilizing this solvent. The method for volatilizing the solvent may be appropriately determined according to the type, amount, film thickness, etc. of the solvent, but it is heated to about 40 to 150 ° C., preferably 60 to 100 ° C., for 5 seconds to 2 at normal pressure or reduced pressure. The condition is about time. The irradiation amount of ultraviolet rays may be appropriately determined according to the type and film thickness of the ultraviolet curable resin composition, but may be irradiated so that the integrated light amount is about 50 to 10,000 mJ / cm ² . Moreover, when coating or filling with a thick film, it is preferable to improve photocurability by adding a photoreaction initiator or a photosensitizer to the composition as described above.

  Moreover, the physical property of hardened | cured material can be improved further by further heating the hardened | cured material obtained by ultraviolet irradiation. The heating method may be appropriately determined, but the heating is performed at about 40 to 300 ° C., preferably 100 to 250 ° C., and the conditions are about 1 minute to 6 hours.

(Application to coating agent)
A coating layer can be obtained by coating an ultraviolet curable resin composition on a desired substrate and curing the composition with ultraviolet rays. As the substrate, various known materials such as inorganic substrates such as glass, iron, aluminum, copper, and ITO, and organic substrates such as PE, PP, PET, PEN, PMMA, PSt, PC, and ABS are appropriately selected. Can be used. When coating on an inorganic base material, when the adhesion is insufficient, it is preferable to use the component (C) in combination as described above. Moreover, when coating to an organic base material, when adhesiveness is insufficient, it is preferable to use a component (D) together as mentioned above. Also, the coating property can be improved to some extent by diluting the ultraviolet curable resin composition with a solvent. Light guide plate, polarizing plate, liquid crystal panel, EL panel, PDP panel, OHP film, optical fiber, color filter, optical disk substrate, lens, liquid crystal cell by coating and curing UV curing resin composition as described above A coating layer can be formed on plastic substrates, prisms and the like.

  Moreover, when the refractive index of the cured film obtained from an ultraviolet curable resin composition is higher than a base material, an antireflection effect can be provided. When the component (A) is produced, the component (a2) is used in combination with the component (a1), or as described above, the metal alkoxide is used as the component (E) to obtain the ultraviolet curable resin composition. The refractive index of the cured film can be improved. Therefore, anti-reflection effect is applied to the coating layer applied to the light guide plate, polarizing plate, liquid crystal panel, EL panel, PDP panel, OHP film, optical fiber, color filter, optical disk substrate, lens, plastic substrate for liquid crystal cell, prism. In the case of imparting, it is preferable to add an appropriate amount of the component to the ultraviolet curable resin composition.

(Application to adhesive)
An intended adhesive layer can be obtained by interposing an ultraviolet curable resin composition between predetermined substrates and then curing the composition with ultraviolet light. As the substrate, the same materials as those used when forming the coating layer can be used. However, in order to cure the adhesive layer with ultraviolet rays, at least one surface needs to transmit ultraviolet rays. In order to prevent foaming of the adhesive layer, the volatile content in the ultraviolet curable resin composition is less than 10%, preferably less than 5%, as described above, or the volatile content is removed before bonding. Is preferred. Adhesives with a transparent adhesive layer can be obtained by adhering with the ultraviolet curable resin composition as described above, which is suitable for producing liquid crystal panels, EL panels, PDP panels, color filters, optical disk substrates and the like. is there.

(Application to sealing material)
A molding material sealed with a transparent cured product can be obtained by applying a thick film of the ultraviolet curable resin composition or pouring the ultraviolet curable resin composition into a predetermined mold, followed by curing with ultraviolet rays. Such a material is particularly suitable for use in optical parts such as a light emitting element, a light receiving element, a photoelectric conversion element, and an optical transmission related part. When preparing the molded cured product, as described above, a suitable amount of a photocuring catalyst or a photosensitizer is blended in the composition, or the volatile content in the composition is less than 10%, Preferably it is less than 5%.

(Application to transparent substrate)
A transparent substrate can be obtained by impregnating a glass cloth (base material) with an ultraviolet curable resin composition and curing it with ultraviolet rays. Various known glass cloths can be appropriately selected and used. As the glass cloth, various fabrics obtained from various known glass fibers (strands composed of E glass, C glass, ECR glass, etc., yarn, roving, etc.) can be used. It is particularly preferable because it is inexpensive and has excellent availability. The method for impregnating the glass cloth with the ultraviolet curable resin composition is not particularly limited, and various known methods can be employed, and a coating method may be employed. Further, in order to make the transparent substrate obtained colorless and transparent, it is preferable that the difference in refractive index between the cured product obtained from the ultraviolet curable resin composition and the glass cloth is within 0.05, within 0.01 More preferably, it is more preferable that they are the same. Moreover, the impregnation property to a glass cloth can also be improved more by carrying out solvent dilution of the ultraviolet curable resin composition. In addition, the usage-amount of the ultraviolet curable resin composition with respect to a glass cloth can be suitably determined according to the use of the transparent substrate obtained, and is normally 20-500 weight part per 100 weight part of glass cloth. Moreover, the thickness of the transparent substrate obtained can also be suitably determined according to this use, and is normally set to 20 μm to 1 mm. A transparent substrate obtained by impregnating a glass cloth with the ultraviolet curable resin composition as described above and curing it with ultraviolet rays is excellent in transparency and heat resistance. Therefore, a light guide plate, a polarizing plate, a liquid crystal panel, an EL panel, and a PDP. It is suitable for producing a coating layer on a panel, a color filter, an optical disk substrate, a liquid crystal cell plastic substrate, and the like.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In each example, parts and% are based on weight unless otherwise specified.

Production Example 1 (Production of condensate (A-1))
In a reactor equipped with a stirrer, a condenser, a water separator, a thermometer, and a nitrogen inlet, 190 parts of 3-mercaptopropyltrimethoxysilane (manufactured by Toray Dow Corning Co., Ltd .: trade name “SH-6062”), 52.3 parts of ion-exchanged water ([number of moles of water used for hydrolysis reaction] / [number of moles of alkoxy groups contained in component (a1)] (molar ratio) = 1.0), 95% formic acid 9.5 The portion was charged and hydrolyzed at room temperature for 30 minutes. During the reaction, the temperature rose by a maximum of 22 ° C. due to exotherm. After the reaction, 287.36 parts of propylene glycol monomethyl ether acetate (manufactured by Nippon Emulsifier Co., Ltd .: trade name “MFG-AC”) was charged and heated. When the temperature was raised to 82 ° C., methanol generated by hydrolysis began to be distilled off. The temperature was raised to 105 ° C. over 30 minutes, and water generated by the condensation reaction was distilled off. The reaction was further carried out at 105 ° C. for 1 hour and 30 minutes, and then the pressure was reduced at 70 ° C. to 150 mmHg, and a part of the remaining methanol, water, formic acid, and propylene glycol monomethyl ether acetate was distilled off to obtain a condensate (A -1) 385.2g was obtained. [Mole number of unreacted hydroxyl group and alkoxy group] / [Mole number of alkoxy group contained in component (a1)] (molar ratio) was 0.15, and the concentration was 32.0%. Moreover, the thiol equivalent of the condensate (A-1) was 398 g / eq.

Production Example 2 (Production of condensate (A-2))
In the same reactor as in Production Example 1, 190 parts of 3-mercaptopropyltrimethoxysilane, 52.3 parts of ion-exchanged water ([number of moles of water used for hydrolysis reaction] / [alkoxy group contained in component (a1)) Number of moles] (molar ratio) = 1.0), and 9.5 parts of 95% formic acid were charged and hydrolyzed at room temperature for 30 minutes. During the reaction, the temperature rose by a maximum of 22 ° C. due to exotherm. After the reaction, 287.36 parts of toluene was charged and heated. When the temperature was raised to 72 ° C., part of methanol and toluene generated by hydrolysis began to be distilled off. The temperature was raised to 75 ° C. over 20 minutes, and water was distilled off by condensation reaction. After further reacting at 75 ° C. for 1 hour, the pressure was reduced at 70 ° C. to 150 mmHg to distill off the remaining methanol, water and formic acid. Dilution with 200.99 parts of methanol gave 525.11 parts of condensate (A-2). [Mole number of unreacted hydroxyl group and alkoxy group] / [Mole number of alkoxy group contained in component (a1)] (molar ratio) was 0.14, and the concentration was 23.5%. Moreover, the thiol equivalent of the condensate (A-2) was 398 g / eq.

Production Example 3 (Production of condensate (A-3))
In the same reactor as in Production Example 1, 190 parts of 3-mercaptopropyltrimethoxysilane, 52.30 parts of ion-exchanged water ([number of moles of water used for hydrolysis reaction] / [alkoxy group contained in component (a1)) Number of moles] (molar ratio) = 1.0), and 9.50 parts of 95% formic acid were charged and hydrolyzed at room temperature for 30 minutes. During the reaction, the temperature rose by a maximum of 22 ° C. due to exotherm. After the reaction, 287.36 parts of diethylene glycol dimethyl ether was charged and heated. When the temperature was raised to 75 ° C., methanol generated by hydrolysis began to be distilled off. After further reacting at 75 ° C. for 30 minutes, the pressure was reduced at 70 ° C. to 150 mmHg, and the remaining methanol, water and formic acid were distilled off to obtain 389.44 parts of condensate (A-3). [Mole number of unreacted hydroxyl group and alkoxy group] / [Mole number of alkoxy group contained in component (a1)] (molar ratio) was 0.14, and the concentration was 31.6%. Moreover, the thiol equivalent of the condensate (A-3) was 402 g / eq.

Production Example 4 (Production of condensate (A-4))
In the same reactor as in Production Example 1, 15.0 parts of 3-mercaptopropyltrimethoxysilane, 5.05 parts of phenyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) (of the thiol group contained in [component (a1)) Number of moles] / [total number of moles of component (a1) and component (a2)] = 0.75, [total number of moles of each alkoxy group contained in component (a1) and component (a2)] / [component (a1) ) And component (a2) total number of moles] = 3), 5.51 parts of ion-exchanged water ([number of moles of water used for hydrolysis reaction] / [each alkoxy contained in component (a1) and component (a2)) Total number of moles of groups] (molar ratio) = 1.0), and 1.00 part of 95% formic acid was charged and hydrolyzed at room temperature for 30 minutes. During the reaction, the temperature rose by a maximum of 20 ° C. due to exotherm. After the reaction, 19.52 parts of propylene glycol monomethyl ether acetate was charged and heated. When the temperature was raised to 82 ° C., methanol generated by hydrolysis began to be distilled off. The temperature was raised to 105 ° C. over 30 minutes, and the water was distilled off by condensation reaction. Furthermore, after making it react at 105 degreeC for 1 hour and 30 minutes, 25.13 parts of condensates (A-4) are obtained by depressurizing 70 degreeC-150 mmHg, and distilling off remaining methanol, water, and formic acid. It was. [Mole number of unreacted hydroxyl group and alkoxy group] / [total mole number of each alkoxy group contained in component (a1) and component (a2)] (molar ratio) is 0.12, and the concentration is 51.8%. there were. Moreover, the thiol equivalent of the condensate (A-4) was 329 g / eq.

Production Example 5 (Production of condensate (A-5))
In the same reactor as in Production Example 1, 18.0 parts of 3-mercaptopropyltrimethoxysilane, 2.24 parts of diphenyldimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) (moles of thiol groups contained in [component (a1)) Number] / [total number of moles of component (a1) and component (a2)] = 0.91, [total number of moles of each alkoxy group contained in component (a1) and component (a2)] / [component (a1) And the total number of moles of component (a2)] = 2.9), 5.29 parts of ion-exchanged water ([number of moles of water used for hydrolysis reaction] / [component (a1) and component (a2)) Total number of moles of alkoxy groups] (molar ratio) = 1.0) and 0.90 part of 95% formic acid were charged and subjected to a hydrolysis reaction at room temperature for 30 minutes. During the reaction, the temperature rose by a maximum of 20 ° C. due to exotherm. After the reaction, 20.23 parts of propylene glycol monomethyl ether acetate was charged and heated. When the temperature was raised to 82 ° C., methanol generated by hydrolysis began to be distilled off. The temperature was raised to 105 ° C. over 30 minutes, and the water was distilled off by condensation reaction. Furthermore, after making it react at 105 degreeC for 1 hour and 30 minutes, 29.0 parts of condensates (A-5) are obtained by depressurizing 70 degreeC-150 mmHg, and distilling off remaining methanol, water, and formic acid. It was. [Mole number of unreacted hydroxyl group and alkoxy group] / [Total mole number of each alkoxy group contained in component (a1) and component (a2)] (molar ratio) is 0.10, and the concentration is 46.5%. there were. Moreover, the thiol equivalent of the condensate (A-5) was 316 g / eq.

Production Example 6 (Production of condensate (A-6))
In the same reactor as in Production Example 1, 12.0 parts of 3-mercaptopropyltrimethoxysilane and 3.60 parts of ion exchange water ([number of moles of water used in hydrolysis reaction] / [component (a1)) The number of moles of alkoxy groups] (molar ratio) = 1.0) and 0.67 part of 95% formic acid were charged and subjected to a hydrolysis reaction at room temperature for 30 minutes. During the reaction, the temperature rose by a maximum of 20 ° C. due to exotherm. After the reaction, 1.39 parts of tetrabutyl titanate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 20.25 parts of diethylene glycol dimethyl ether were charged and heated. The temperature was raised to 75 ° C., and a condensation reaction was performed for 30 minutes. [[Mole number of thiol group contained in component (a1)] / [Total number of moles of component (a1) and component (a2)] = 0.94, [Included in component (a1) and component (a2) The total number of moles of each alkoxy group] / [total number of moles of component (a1) and component (a2)] = 3.1. The pressure was further reduced at 70 ° C. to 150 mmHg for 1 hour, and the remaining methanol, water and formic acid were distilled off to obtain 29.39 parts of the condensate (A-6). [Mole number of unreacted hydroxyl group and alkoxy group] / [Mole number of alkoxy group contained in component (a1)] (molar ratio) was 0.17, and the concentration was 27.8%. Moreover, the thiol equivalent of the condensate (A-6) was 481 g / eq.

Production Example 7 (Production of condensate (A-7))
In the same reactor as in Production Example 1, 180 parts of 3-mercaptopropyltrimethoxysilane and 49.55 parts of ion-exchanged water ([number of moles of water used for hydrolysis reaction] / [alkoxy group contained in component (a1)) Number of moles] (molar ratio) = 1.0), and 9.00 parts of 95% formic acid were charged, followed by hydrolysis at room temperature for 30 minutes. During the reaction, the temperature rose by a maximum of 22 ° C. due to exotherm. After the reaction, 272.23 parts of toluene was charged and heated. When the temperature was raised to 72 ° C., part of methanol and toluene generated by hydrolysis began to be distilled off. The temperature was raised to 75 ° C. over 20 minutes, and water was distilled off by condensation reaction. After further reacting at 75 ° C. for 1 hour, the pressure was reduced at 70 ° C. to 150 mmHg to distill off the remaining methanol, water and formic acid. Further, the pressure was reduced at 70 ° C. to 5 mmHg, and toluene was distilled off to obtain 124.49 parts of the condensate (A-7). [Mole number of unreacted hydroxyl group and alkoxy group] / [Mole number of alkoxy group contained in component (a1)] (molar ratio) was 0.16, and the concentration was 93.7%. Moreover, the thiol equivalent of the condensate (A-7) was 136 g / eq.

Production Example 8 (Production of condensate (A-8))
In the same reactor as in Production Example 1, 15.0 parts of 3-mercaptopropyltrimethoxysilane, 5.05 parts of phenyltrimethoxysilane ([number of moles of thiol group contained in component (a1)] / [component (a1 ) And the total number of moles of component (a2)] = 0.75, [total number of moles of each alkoxy group contained in component (a1) and component (a2)] / [total of component (a1) and component (a2) Number of moles] = 3), 5.51 parts of ion-exchanged water ([number of moles of water used for hydrolysis reaction] / [total number of moles of each alkoxy group contained in component (a1) and component (a2)]) Ratio) = 1.0), and 1.00 part of 95% formic acid was charged and hydrolyzed at room temperature for 30 minutes. During the reaction, the temperature rose by a maximum of 20 ° C. due to exotherm. After the reaction, 19.52 parts of toluene was charged and heated. When the temperature was raised to 72 ° C., part of methanol and toluene generated by hydrolysis began to be distilled off. The temperature was raised to 75 ° C. over 20 minutes, and water was distilled off by condensation reaction. After further reacting at 75 ° C. for 1 hour, the pressure was reduced at 70 ° C. to 150 mmHg to distill off the remaining methanol, water and formic acid. Further, the pressure was reduced at 70 ° C. to 5 mmHg, and toluene was distilled off to obtain 13.84 parts of condensate (A-8). [Number of moles of unreacted hydroxyl group and alkoxy group] / [total number of moles of each alkoxy group contained in component (a1) and component (a2)] (molar ratio) is 0.16, and the concentration is 94.0%. there were. Moreover, the thiol equivalent of the condensate (A-8) was 181 g / eq.

Production Example 9 (Production of condensate (A-9))
In the same reactor as in Production Example 1, 18.0 parts of 3-mercaptopropyltrimethoxysilane, 2.24 parts of diphenyldimethoxysilane ([number of moles of thiol group contained in component (a1)] / [component (a1)) And the total number of moles of component (a2)] = 0.91, [total number of moles of each alkoxy group contained in component (a1) and component (a2)] / [total number of moles of component (a1) and component (a2) Number] = 2.9), 5.29 parts of ion-exchanged water ([number of moles of water used for hydrolysis reaction] / [total number of moles of each alkoxy group contained in component (a1) and component (a2)]) (Molar ratio) = 1.0), 0.90 part of 95% formic acid was charged, followed by hydrolysis at room temperature for 30 minutes. During the reaction, the temperature rose by a maximum of 20 ° C. due to exotherm. After the reaction, 20.23 parts of toluene was charged and heated. When the temperature was raised to 72 ° C., part of methanol and toluene generated by hydrolysis began to be distilled off. The temperature was raised to 75 ° C. over 20 minutes, and water was distilled off by condensation reaction. After further reacting at 75 ° C. for 1 hour, the pressure was reduced at 70 ° C. to 150 mmHg to distill off the remaining methanol, water and formic acid. Further, the pressure was reduced at 70 ° C. to 5 mmHg, and toluene was distilled off to obtain 14.41 parts of the condensate (A-9). [Mole number of unreacted hydroxyl group and alkoxy group] / [total mole number of each alkoxy group contained in component (a1) and component (a2)] (molar ratio) is 0.16, and the concentration is 93.6%. there were. Moreover, the thiol equivalent of the condensate (A-9) was 157 g / eq.

Examples 1 to 20 (Production of UV curable resin composition)
For 10 parts of the condensate (A-1) obtained in Production Example 1, triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd .: trade name “Tyke”, [carbon-carbon double contained in component (B) Number of moles of bond] / [number of moles of component (B)] = 3) 2.09 parts ([number of moles of thiol group contained in component (A)] / [carbon-carbon contained in component (B) 2 The number of moles of heavy bonds] (molar ratio) = 1.0) and 0.20 part of triphenyl phosphite (manufactured by Tokyo Chemical Industry Co., Ltd.) were arranged to obtain an ultraviolet curable resin composition (F-1). . Similarly, it was set as the ultraviolet curable resin composition (F-2 to F-20) according to the following table using the condensate (A-1 to 9) obtained in Production Examples 1 to 9.

  In the table, DAP: diallyl phthalate (manufactured by Daiso Co., Ltd .: trade name “Daiso Dup Monomer”, [number of moles of carbon-carbon double bonds contained in component (B)] / [number of moles of component (B)] = 2), P-30M: Pentaerythritol triallyl ether (Daiso Co., Ltd. product name: “Neoallyl P-30M”, [number of moles of carbon-carbon double bonds contained in component (B)] / [component Number of moles of (B)] = 3), SH-6062: 3-mercaptopropyltrimethoxysilane (trade name, manufactured by Toray Dow Corning Co., Ltd.), SR-8EG: polyethylene glycol diglycidyl ether (Sakamoto Pharmaceutical Co., Ltd.) ) Made: trade name, epoxy equivalent 285 g / eq), Epicoat 828: bisphenol A type liquid epoxy resin (trade name, epoxy produced by Japan Epoxy Resin Co., Ltd.) The amount 189g / eq), Q-1301: shows the N- nitrosophenylhydroxylamine aluminum salt (Wako Pure Chemical Industries, Ltd., trade name).

Example 21 (Production of UV curable resin composition)
In the same reactor as in Production Example 1, 25.0 parts of 3-mercaptopropyltrimethoxysilane, 8.42 parts of phenyltrimethoxysilane, 9.18 parts of ion-exchanged water ([number of moles of water used for hydrolysis reaction] / [Total number of moles of each alkoxy group contained in component (a1) and component (a2)] (molar ratio) = 1.0), 1.67 parts of 95% formic acid are charged and subjected to a hydrolysis reaction at room temperature for 30 minutes. It was. During the reaction, the temperature rose by a maximum of 26 ° C. due to exotherm. After the reaction, 50.54 parts of toluene was charged and heated. When the temperature was raised to 72 ° C., part of methanol and toluene generated by hydrolysis began to be distilled off. The temperature was raised to 75 ° C. over 1 hour, and the water was distilled off by condensation reaction. After adding 10.58 g of triallyl isocyanurate, the pressure was reduced at 70 ° C. to 150 mmHg to distill off the remaining methanol, water and formic acid. Furthermore, it reduced pressure at 70 degreeC-5mmHg, and 33.97 parts of ultraviolet curable resin compositions (E-19) were obtained by distilling toluene off. [Number of moles of unreacted hydroxyl group and alkoxy group] / [total number of moles of alkoxy groups contained in component (a1) and component (a2)] (molar ratio) is 0.14, and the concentration is 95.0%. Met.

Example 22 (Production of UV curable resin composition)
In the same reactor as in Production Example 1, 25.0 g of 3-mercaptopropyltrimethoxysilane, 8.42 parts of phenyltrimethoxysilane, 9.18 parts of ion-exchanged water ([number of moles of water used for hydrolysis reaction] / [Total number of moles of each alkoxy group contained in the component (a1) and the component (a2)] (molar ratio) = 1.0), 1.67 parts of 95% formic acid were charged, followed by hydrolysis at room temperature for 30 minutes. . During the reaction, the temperature rose by a maximum of 26 ° C. due to exotherm. After the reaction, 50.54 parts of toluene was charged and heated. When the temperature was raised to 72 ° C., part of methanol and toluene generated by hydrolysis began to be distilled off. The temperature was raised to 75 ° C. over 1 hour, and the water was distilled off by condensation reaction. After 15.68 parts of diallyl phthalate was added thereto, the pressure was reduced at 70 ° C. to 150 mmHg to distill off the remaining methanol, water and formic acid. Furthermore, it reduced pressure at 70 degreeC-5mmHg, and 39.65 parts of ultraviolet curable resin compositions (E-20) were obtained by distilling toluene off. [Mole number of unreacted hydroxyl group and alkoxy group] / [total mole number of each alkoxy group contained in component (a1) and component (a2)] (molar ratio) is 0.14, and the concentration is 94.2%. there were.

Example 23 (Production of UV curable resin composition)
In the same reactor as in Production Example 1, 25.0 parts of 3-mercaptopropyltrimethoxysilane, 8.42 parts of phenyltrimethoxysilane, 9.18 parts of ion-exchanged water, [number of moles of water used for hydrolysis reaction] / [Total number of moles of each alkoxy group contained in component (a1) and component (a2)] (molar ratio) = 1.0), 1.67 parts of 95% formic acid are charged and subjected to a hydrolysis reaction at room temperature for 30 minutes. It was. During the reaction, the temperature rose by a maximum of 26 ° C. due to exotherm. After the reaction, 50.54 parts of toluene was charged and heated. When the temperature was raised to 72 ° C., part of methanol and toluene generated by hydrolysis began to be distilled off. The temperature was raised to 75 ° C. over 1 hour, and the water was distilled off by condensation reaction. To this was added 10.88 parts of pentaerythritol triallyl ether, and the pressure was reduced at 70 ° C. to 150 mmHg to distill off the remaining methanol, water and formic acid. Furthermore, it reduced pressure at 70 degreeC-5mmHg, and distilled off toluene, and obtained 34.69 parts of ultraviolet curable resin compositions (E-21). [Number of moles of unreacted hydroxyl group and alkoxy group] / [total number of moles of each alkoxy group contained in component (a1) and component (a2)] (molar ratio) is 0.14, and the concentration is 93.9%. there were.

Comparative Example 1 (Production of UV curable resin composition)
Dipentaerythritol hexaacrylate (manufactured by Arakawa Chemical Industries, Ltd .: trade name “Beamset-700”) was used as it was.

Comparative Example 2 (Production of UV curable resin composition)
To 10 parts of dipentaerythritol hexaacrylate, 0.5 part of a photo radical initiator (manufactured by Ciba Specialty Chemicals Co., Ltd .: trade name “Irgacure Irg-184”) was blended to prepare an ultraviolet curable resin composition.

Comparative Example 3 (Production of UV curable resin composition)
For 10 parts of pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Sakai Chemical Industry Co., Ltd .: trade name “PEMP”), 6.20 parts of triallyl isocyanurate and 0.20 part of triphenyl phosphite It mix | blended and it was set as the ultraviolet curable resin composition.

Comparative Example 4 (Production of UV curable resin composition)
To 10 parts of pentaerythritol tetrakis (3-mercaptopropionate), 10.08 parts of diallyl phthalate and 0.20 part of triphenyl phosphite were blended to obtain an ultraviolet curable resin composition.

Comparative Example 5 (Production of UV curable resin composition)
To 99 parts of pentaerythritol tetrakis (3-mercaptopropionate), 6.99 parts of pentaerythritol triacrylate and 0.20 part of triphenyl phosphite were blended to obtain an ultraviolet curable resin composition.

Comparative Example 6 (Production of thermosetting composition)
A comparative thermosetting composition was synthesized according to Example 3 of JP-A-2005-290286. Specifically, 8 parts of bisphenol A glycidyl ether (manufactured by Japan Epoxy Resin Co., Ltd., trade name “Epicoat 828”, epoxy equivalent 190 g / eq) was dissolved in 8 parts of tetrahydrofuran to obtain a resin solution. Next, 18 parts of phenyltrimethoxysilane, 8 parts of 3-glycidoxypropyltriethoxysilane, 8 parts of a 10% by weight aqueous solution of formic acid, and 49 parts of tetrahydrofuran were refluxed at 60 ° C. for 3 hours with stirring, and a thermosetting agent (Asahi) 1 part of Denka Kogyo Co., Ltd., trade name “ADEKA OPTON CP-66”) and 16 parts of the resin solution were added to obtain a thermosetting composition.

(Curability of composition)
The ultraviolet curable resin compositions obtained in Examples 1 to 8 and 14 to 18 were coated on a steel plate so that the film thickness after curing was about 15 μm, and the solvent was dried at 120 ° C. for 30 minutes. After drying, using an ultraviolet irradiation device (USHIO INC., Trade name “UV-152”), ultraviolet light was irradiated with a 365 nm ultraviolet detector so that the integrated light amount was 200 mJ / cm ² . Similarly, the ultraviolet curable resin compositions obtained in Examples 9 to 13, 19 to 23, and Comparative Examples 1 to 5 were also coated so that the film thickness after curing was about 15 μm, and an ultraviolet irradiation device (USHIO INC. Ltd.: using trade name "UV-152"), integrated light quantity at 365nm UV detector was irradiated with ultraviolet rays so as to be 200 mJ / cm ^2. The thermosetting composition obtained in Comparative Example 6 was coated so that the film thickness after curing was about 15 μm, and the solvent was dried at 60 ° C. for 30 minutes. Subsequently, thermosetting was performed at 120 ° C. for 3 hours and at 150 ° C. for 1 hour. The curability of the obtained cured product was evaluated by a pencil hardness test according to a general test method of JIS K-5401.

  As is clear from Table 2, the ultraviolet curable resin composition of Comparative Example 1 was not cured at all, and the ultraviolet curable resin composition of Comparative Example 2 was insufficiently cured. That is, it can be seen that curing by general radical polymerization cannot be performed without an initiator, and even if a curing agent is added, the thick film does not cure. On the other hand, the ultraviolet curable resin compositions of Examples 1 to 21 and Comparative Examples 3 to 5 are cured without any problem, and the curing system using the ene-thiol reaction is ultraviolet curable without an initiator. It can be seen that the curing system of the present invention has the same curability as that of the conventional organic-organic system. Moreover, since the surface hardness is high in the hardened | cured material of Examples 1-21 cured using the same component (B) compared with the hardened | cured material of Comparative Examples 3-5, the ultraviolet curable resin composition of this invention Is recognized as suitable as a hard coating agent.

(Stability of UV curable resin composition)
The ultraviolet curable resin compositions obtained in Examples 9, 19, and 20 were taken in brown bottles and allowed to stand at room temperature, and the stability of the ultraviolet curable resin composition was evaluated by the number of days until gelation.

  As is clear from Tables 2 and 3, the ultraviolet curable resin compositions of Examples 19 and 20 have the same curability as the ultraviolet curable resin composition of Example 9, and the stability is greatly improved. You can see that For this reason, in applications where stability is particularly required when it is made into one solution, it is stable by adding a tertiary amine such as benzyldimethylamine and a radical polymerization inhibitor such as N-nitrosophenylhydroxylamine aluminum salt. Can be improved.

(Weather resistance of cured film)
The ultraviolet curable resin compositions obtained in Examples 8 to 10 and Comparative Examples 2 to 5 were coated on a glass plate so that the film thickness after curing was about 5 μm, and using the above ultraviolet irradiation apparatus, Ultraviolet rays were irradiated with an ultraviolet detector so that the integrated light amount was 200 mJ / cm ² . The obtained cured product was further irradiated with ultraviolet rays so that the integrated light amount was 20000 mJ / cm ^2, and the degree of coloring after irradiation was visually evaluated. The evaluation criteria are as follows.
○: Almost not colored Δ: Slightly colored (slightly yellow) ×: Darkly colored (brown)

  As is apparent from Table 4, the cured product of Comparative Example 2 is colored brown, and the cured products of Comparative Examples 3 to 5 are slightly colored yellow. On the other hand, the cured products of Examples 8 to 10 are hardly colored, and it can be seen that the cured product of the present invention is superior in weather resistance compared to conventional organic-organic systems.

(Adhesion to inorganic materials)
The ultraviolet curable resin compositions obtained in Examples 9 and 14 were coated on various inorganic substrates so as to have a film thickness of about 15 μm after curing, and using the aforementioned ultraviolet irradiation device, the integrated light intensity was measured with a 365 nm ultraviolet detector. Was irradiated with ultraviolet rays so as to be 500 mJ / cm ² . About the obtained hardened | cured material, it evaluated by the gobang eyes cellophane tape peeling test by the general test method of JISK-5400.

  As is clear from Table 2 and Table 5, the cured product of Example 14 in which the component (C) was blended had the same curability as that of the cured product of Example 9, and adhered to the inorganic substrate. It can be seen that the performance is greatly improved. From this, the ultraviolet curable resin composition of Example 14 is applied to a light guide plate, a polarizing plate, a liquid crystal panel, an EL panel, a PDP panel, an optical fiber, a color filter, an optical disk substrate, a lens, a prism and the like made of an inorganic base material. It is recognized that it is suitable as an adhesive for coating agents, liquid crystal panels made of inorganic substrates, EL panels, PDP panels, color filters, and optical disk substrates.

(Adhesion to organic materials)
The ultraviolet curable resin compositions obtained in Examples 9, 16, and 17 were coated on various inorganic substrates so as to have a film thickness of about 15 μm after curing, and using the above ultraviolet irradiation device, a 365 nm ultraviolet detector. Ultraviolet rays were irradiated so that the integrated light amount was 500 mJ / cm ² . About the obtained hardened | cured material, it evaluated by the gobang eyes cellophane tape peeling test by the general test method of JISK-5400.

  As is clear from Tables 2 and 6, the cured products of Examples 16 and 17 in which the component (D) is arranged have a slightly lower surface hardness than the cured product of Example 9, but the organic base material is obtained. It can be seen that the adhesion is greatly improved. From this, the ultraviolet curable resin compositions of Examples 16 and 17 are light guide plates, polarizing plates, liquid crystal panels, EL panels, PDP panels, OHP films, optical fibers, color filters, optical disk substrates, lenses made of organic substrates. It is recognized that it is suitable as a coating agent for plastic substrates for liquid crystal cells, prisms, etc., and as an adhesive for liquid crystal panels, EL panels, PDP panels, color filters, and optical disk substrates made of organic base materials.

(Refractive index)
The ultraviolet curable resin composition obtained in Examples 8, 9, 15, 18 and Comparative Example 3 was diluted with propylene glycol monomethyl ether acetate so that the nonvolatile content was 30% by weight, and then cured on a silicon substrate. The film thickness after coating was about 50 nm, and the solvent was dried at 120 ° C. for 15 minutes. After drying, using the above-described ultraviolet irradiation device, ultraviolet rays were irradiated with a 365 nm ultraviolet detector so that the integrated light amount was 200 mJ / cm ² . Moreover, after diluting the thermosetting composition obtained in Comparative Example 6 with propylene glycol monomethyl ether acetate so that the non-volatile content is 30% by weight, the film thickness after curing on the silicon substrate is about 50 nm. Coated and solvent dried at 60 ° C. for 10 minutes. Subsequently, it was thermally cured at 120 ° C. for 30 minutes. About the obtained hardened | cured material, the refractive index was measured using the ellipsometer (Nippon Vacuum Technology Co., Ltd. product name: "ESM-1").

  As apparent from Table 7, the cured product of Example 8 in which titanate was arranged as component (a2) and the cured product of Example 15 in which titanate was arranged as component (E) were compared with the cured product of Example 9. It can be seen that the refractive index is improved. Accordingly, the ultraviolet curable resin compositions of Examples 8 and 15 were a light guide plate, a polarizing plate, a liquid crystal panel, an EL panel, a PDP panel, an OHP film, an optical fiber, a color filter, an optical disk substrate, a lens, and a plastic for a liquid crystal cell. It is recognized that it is suitable as a coating agent for antireflection films such as substrates and prisms.

(Production of transparent substrate)
Commercially available glass cloth (clipper glass cloth micro B, film thickness) so that (weight of glass cloth) / (weight of composition) becomes 100/200 after curing the compositions obtained in Example 18 and Comparative Example 3. The substrate having a thickness of 80 μm is obtained by impregnating 28 μm with a refractive index of 1.54) and irradiating the ultraviolet light with the 365 nm ultraviolet detector so that the integrated light quantity becomes 2000 mJ / cm ² using the above-mentioned ultraviolet irradiation device. It was. Further, the glass cloth was impregnated with the composition obtained in Comparative Example 6, the solvent was stripped off with a dryer at 60 ° C., heated at 120 ° C. for 3 hours, and press molded at 150 ° C. for 1 hour to increase the thickness. A substrate having a thickness of 80 μm was obtained. The appearance of the obtained substrate was visually evaluated. The evaluation criteria are as follows.
O: Almost transparent Δ: Translucent x: Opaque Further, the flexibility of the substrate was evaluated by the radius of curvature at which a crack occurred when the substrate was bent.

  As is clear from Table 8, the substrate obtained in Comparative Example 3 was translucent, whereas the substrates obtained in Example 18 and Comparative Example 6 were almost transparent. The substrate of Comparative Example 6 cracked when the radius of curvature was 5 cm or less, whereas the substrates of Example 18 and Comparative Example 3 did not crack even when bent so that the radius of curvature was 1 cm or less. . From the above-mentioned various test results, the substrate of Example 18 is superior to the substrates of Comparative Example 3 and Comparative Example 6 in various physical properties, and as a base material for flexible liquid crystal panels, EL panels, PDP panels, color filters, etc. It is recognized that it is more suitable to use.

(Adhesiveness)
The ultraviolet curable resin compositions obtained in Example 9 and Comparative Examples 2 and 3 were coated on a steel plate so that the film thickness after curing was about 5 μm, and the lid was covered with a polycarbonate plate having a thickness of 2 mm or a glass plate having a thickness of 2 mm. Then, using the above-described ultraviolet irradiation device, ultraviolet light was irradiated so that the integrated light amount was 1000 mJ / cm ² when the 365 nm ultraviolet detector did not have a lid. About the obtained hardened | cured material, sclerosis | hardenability was evaluated by the pencil hardness test by the general test method of JISK-5401.

  As is clear from Table 9, the ultraviolet curable resin composition of Comparative Example 2 was not cured at all, whereas the UV curable resin compositions of Comparative Example 3 and Example 9 were cured without problems. From the above various test results, the cured product of Example 9 is superior in physical properties to the cured product of Comparative Example 3, and is used as an adhesive for liquid crystal panels, EL panels, PDP panels, color filters, and optical disk substrates. Is more suitable.

(Heat-resistant)
The ultraviolet curable resin composition obtained in Example 9 and Comparative Example 3 was poured into an aluminum cup so that the film thickness after curing was about 1 mm, and the integrated light amount was measured with a 365 nm ultraviolet detector using the above ultraviolet irradiation device. There was irradiated with ultraviolet rays so as to be 5000 mJ / cm ^2. The resulting cured product was heated with a dryer at 200 ° C. for 30 minutes. The cured product is cut into 5 mm × 25 mm, and dynamic storage elasticity is measured using a viscoelasticity measuring device (manufactured by Seiko Instruments Inc., trade name “DMS6100”, measurement condition: frequency 1 Hz, slope 3 ° C./min). The heat resistance was evaluated by measuring the rate. The measurement results are shown in FIG. As is apparent from FIG. 1, in Example 9, Tg is improved as compared with Comparative Example 3, and it is recognized that there is little decrease in elastic modulus even at high temperatures and excellent heat resistance.

The correlation of the temperature and dynamic storage elastic modulus about the hardened | cured material obtained from the composition of Example 9 and Comparative Example 3 is illustrated.

Claims (24)

General formula (1):
R ¹ Si (OR ² ) ₃ (1)
(In the formula, R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms having at least one thiol group, or an aromatic hydrocarbon group having at least one thiol group, and R ² represents a hydrogen atom, having 1 to 1 carbon atoms. And a condensate (A) obtained by hydrolyzing and condensing a thiol group-containing alkoxysilane (a1) represented by 8) or a carbon-carbon double bond. The ultraviolet curable resin composition characterized by containing the compound (B) which has this. The ultraviolet curable resin composition according to claim 1, wherein the condensate (A) is obtained by hydrolyzing the alkoxysilane (a1) in the presence of formic acid and then performing a condensation reaction in the presence of a solvent. . General formula (1):
R ¹ Si (OR ² ) ₃ (1)
(In the formula, R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms having at least one thiol group, or an aromatic hydrocarbon group having at least one thiol group, and R ² represents a hydrogen atom, having 1 to 1 carbon atoms. And a thiol group-containing alkoxysilane (a1) represented by formula (8) is hydrolyzed in the presence of formic acid, and then a solvent and a compound having a carbon-carbon double bond An ultraviolet curable resin composition obtained by a condensation reaction in the presence of (B). The ultraviolet curable resin composition in any one of Claims 1-3 in which a condensate (A) contains the metal alkoxide (a2) which does not have a thiol group as the structural component. The ultraviolet curable resin composition according to claim 1, wherein the alkoxysilane (a1) is 3-mercaptopropyltrimethoxysilane. The ultraviolet curable resin composition according to any one of claims 1 to 5, wherein the compound (B) is an allyl group-containing compound. Furthermore, the ultraviolet curable resin composition in any one of Claims 1-6 containing alkoxysilane (a1) and / or its hydrolyzate (however, a condensate is not included) (C). The ultraviolet curable resin composition according to claim 7, wherein the component (C) is 3-mercaptopropyltrimethoxysilane and / or a hydrolyzate thereof (however, a condensate is not included). Furthermore, the ultraviolet curable resin composition in any one of Claims 1-8 containing an epoxy group containing compound (D). The ultraviolet curable resin composition according to claim 9, wherein the epoxy group-containing compound (D) has two or more epoxy groups per molecule. Furthermore, the ultraviolet curable resin composition in any one of Claims 1-10 containing metal alkoxide (a2) and / or its hydrolyzate (however, a condensate is not included) (E). The ultraviolet curable resin composition according to claim 11, wherein the component (E) is at least one selected from the group consisting of alkoxysilanes, alkoxytitaniums, and alkoxyzirconiums. The ultraviolet curable resin composition according to claim 1, wherein the nonvolatile content is 90% by weight or more. Furthermore, the ultraviolet curable resin composition in any one of Claims 1-13 containing the compound which suppresses ene-thiol reaction. A cured product obtained by ultraviolet curing the ultraviolet curable resin composition according to claim 1. A coated article comprising a coating layer obtained by ultraviolet-curing the ultraviolet-curable resin composition according to claim 1 on a substrate. The coated article according to claim 16, wherein the coating layer is formed so as to have a refractive index higher than that of the substrate. 18. The coated article according to claim 17, which is suitable for use as a light guide plate, a polarizing plate, a liquid crystal panel, an EL panel, a PDP panel, an OHP film, an optical fiber, a color filter, an optical disk substrate, a lens, a plastic substrate for a liquid crystal cell, or a prism. A multilayer structure obtained by applying the ultraviolet curable resin composition according to any one of claims 1 to 14 to an adherend, adhering this to another member, and then ultraviolet curing. The multilayer structure according to claim 19, which is suitable for a liquid crystal panel, an EL panel, a PDP panel, a color filter, or an optical disk substrate. A sealed article obtained by ultraviolet curing using the ultraviolet curable resin composition according to claim 1 as a sealing material. The sealed article according to claim 21, which is suitable for use as a light emitting element, a light receiving element, a photoelectric conversion element, or an optical transmission related part. A transparent substrate obtained by impregnating a glass cloth with the ultraviolet curable resin composition according to any one of claims 1 to 14, followed by ultraviolet curing. The transparent substrate according to claim 23, which is suitable for use as a light guide plate, a polarizing plate, a liquid crystal panel, an EL panel, a PDP panel, a color filter, an optical disk substrate, or a plastic substrate for a liquid crystal cell.

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