WO2015030116A1

WO2015030116A1 - Polyene-polythiol composition

Info

Publication number: WO2015030116A1
Application number: PCT/JP2014/072579
Authority: WO
Inventors: 貴子星野; 慶次後藤
Original assignee: 電気化学工業株式会社
Priority date: 2013-08-30
Filing date: 2014-08-28
Publication date: 2015-03-05
Also published as: TWI652312B; JPWO2015030116A1; JP6407153B2; TW201518418A

Abstract

Provided is a polyene-polythiol composition having excellent storage stability. The composition comprises: (A) a silsesquioxane derivative having at least two carbon-carbon unsaturated bonds per molecule and having a random structure; (B) a polythiol; (C) a photo-radical polymerization initiator; and (D) a dialkyl phosphite.

Description

Polyene-polythiol composition

The present invention relates to a polyene-polythiol-based composition, for example, a polyene-polythiol-based resin composition. The present invention relates to an adhesive comprising a polyene-polythiol composition, a coating agent (coating agent), and a molding material, for example. The present invention relates to an adhesive body bonded using the composition, a coated body coated with the composition, a cured body, and an optical component. Here, “poly” indicates polyfunctionality of bifunctionality or higher.

In recent years, resin compositions that are cured by irradiation with actinic rays such as ultraviolet rays or heat have been used in various fields such as adhesives and coating agents. As one of such resin compositions, a resin composition containing polyene and polythiol as main components is known (Patent Document 1).

The polyene-polythiol-based resin composition has excellent transparency in the visible light region (380 to 780 nm), adhesiveness, and surface curability under air (hereinafter referred to as surface curability). As adhesives and molding materials for transparent plastics and the like, they are used in various fields such as optical parts and electronic parts.

However, the conventional polyene-polythiol-based resin has a problem in that the resin composition is yellowed and exposed to transparency when exposed to a high temperature exceeding 200 ° C. such as solder reflow. Therefore, a resin composition satisfying excellent heat resistance has been desired.

Silsesquioxane derivatives are one of the materials that have recently attracted attention as resin compositions having excellent heat resistance and light resistance. A radical reaction type or addition reaction type silsesquioxane derivative, a copolymer, a resin and a method for producing them are disclosed that react with light or heat (Patent Document 2). A resin composition, a varnish, a molded body, an adhesive, an adhesive sheet, a sealing material, a nanoimprinting composition, and the like using the above-described properties are disclosed (Patent Document 3).

Patent Document 3 shows that a polyene-polythiol-based resin assembly composition using a silsesquioxane derivative has transparency, adhesiveness, and heat resistance. An adhesive using the above characteristics, a sealing agent for liquid crystal sealing, a cured film, and the like are disclosed.

Patent Document 4 contains (A) (meth) acryloyl group-containing silicone compound, (B) thiol compound, (C) photopolymerizable monomer, and (D) photoradical polymerization initiator, and (A) to (D ) Component (A) is 10 wt% or more and 80 wt% or less, component (B) is 1 wt% or more and 80 wt% or less, (C) component is 10 wt% or more and 80 wt% or less, In addition, a polyene / polythiol-based photosensitive resin composition characterized in that the component (D) is 0.1 wt% or more and 5 wt% or less is disclosed.

Patent Document 5 is characterized by containing a condensate obtained by hydrolysis and condensation of an alkoxysilane containing an alkoxysilane having a carbon-carbon double bond, and a compound having a secondary thiol group. An ultraviolet curable resin composition is disclosed.

Patent Document 6 contains a repeating unit derived from a (meth) acrylic acid ester having a trialkoxysilyl group, and an alkali-soluble copolymer having an ethylenic carbon-carbon double bond in the molecule. Disclosed is a photosensitive composition comprising a silsesquioxane-containing compound obtained by co-condensing a good trialkoxysilane compound, metal fine particles and / or metal oxide fine particles, and a photopolymerization initiator. ing.

Japanese Patent Laid-Open No. 03-243626 JP 2004-143449 A JP 2010-168452 A JP 2011-202128 A JP 2008-184514 A JP 2008-298880 A

However, Patent Document 2 does not describe an application such as an adhesive. In addition, the silsesquioxane derivatives of Patent Documents 2 to 4 are of a cage type. The resin composition using the cage-type silsesquioxane derivative has a problem that it does not dissolve in the polyene-polythiol resin composition. Patent Document 5 exemplifies triphenylphosphine and triphenyl phosphite as the phosphorus compound, but does not describe dialkyl phosphite. Patent Document 6 exemplifies ethyl phosphite and diphenyl phosphite as the phosphoric acid compound, but does not describe dialkyl phosphite. Patent Document 6 does not describe polythiol.

The present invention relates to (A) a silsesquioxane derivative having two or more carbon-carbon unsaturated bonds per molecule and having a random structure, (B) polythiol, (C) photoradical polymerization initiator (D) A composition containing dialkyl phosphite.

Moreover, according to this invention, the composition whose (A) is a silsesquioxane derivative represented by following General formula [1] is provided.
General formula [1]

(In the formula, R ₀ has one or more functional groups selected from a (meth) acryloyl group, a vinyl group, a vinyl ether group, an allyl group, and an allyl ether group. R ₀ may be the same or different. Some of the (meth) acryloyl group, vinyl group, vinyl ether group, allyl group and allyl ether group are alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and alkyl halides having 1 to 6 carbon atoms. And may be substituted with a group, a phenyl group or a halogen, m represents the degree of polymerization.)

Moreover, according to this invention, the composition whose (D) is dialkyl phosphite represented by following General formula [3] is provided.
General formula [3]

(In the formula, R ₁ and R ₂ are each an alkyl group. R ₁ and R ₂ may be the same group or different groups.)

According to the present invention, there is also provided a composition wherein (D) is a dialkyl phosphite having a branched or straight chain alkyl group having 1 to 18 carbon atoms. Moreover, according to this invention, the composition whose (D) is 1 or more types in the group which consists of dimethyl phosphite and diethyl phosphite is provided. According to the present invention, there is further provided a composition containing a compound having a carbon-carbon unsaturated bond other than (E) a silsesquioxane derivative. Moreover, according to this invention, the composition whose (E) is an allyl compound is provided. Moreover, according to this invention, the composition which contains (F) antioxidant further is provided to the said composition. Moreover, according to this invention, the composition which contains the (G) adhesiveness imparting agent further to the said composition is provided. Moreover, according to this invention, the said composition is further provided with the composition containing (H) nitroso compound. Moreover, according to this invention, the adhesive agent consisting of the said composition is provided. Moreover, according to this invention, the adhesive body formed by adhere | attaching using the said adhesive agent is provided. Moreover, according to this invention, the coating agent which consists of the said composition is provided. Moreover, according to this invention, the coating body formed by coat | covering using the said coating agent is provided. Moreover, according to this invention, the laminated body by which the membrane | film | coat by the said coating agent was formed in the single side | surface or both surfaces of a base material is provided. Moreover, according to this invention, the laminated body whose said base material is a glass material is provided. Moreover, according to this invention, the hardening body which consists of the said composition is provided. Moreover, according to this invention, the optical waveguide formed by laminating | stacking the layer which consists of the said hardening body, and the layer which has a higher refractive index than this layer is provided. Moreover, according to this invention, the optical component containing the said composition is provided.

The present invention has storage stability. In addition, the present invention has, for example, heat resistance, light resistance, transparency, fast curability, or adhesiveness.

Hereinafter, embodiments of the present invention will be described in detail. In the present specification, A to B mean A to B. A resin composition is illustrated and demonstrated as a composition of this embodiment.

(A) Polyene The (A) polyene of this embodiment is a silsesquioxane derivative (A) having two or more carbon-carbon unsaturated bonds per molecule and having a random structure. As the polyene (A) of this embodiment, a silsesquioxane derivative represented by the following general formula [1] is preferable. (A) Polyene of this embodiment is used as a main component with the polythiol mentioned later.

General formula [1]

In this embodiment, the silsesquioxane derivative preferably used has a functional group having a carbon-carbon unsaturated bond such as a (meth) acryloyl group, a vinyl group, a vinyl ether group, an allyl group, and an allyl ether group in the molecule. Silsesquioxane compound. As the carbon-carbon unsaturated bond, a (meth) acryloyl group is preferable. The average number of functional groups in one molecule is preferably 2 to 50, more preferably 3 to 10. The average number of functional groups in one molecule is any of 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50. Or a range of any two values.

It is known that the silsesquioxane derivative of the present embodiment can be obtained in a ladder type structure or a random type structure depending on the conditions of cohydrolysis and cocondensation of alkoxysilane. The derivative has, for example, a structure represented by the following general formula [2].

General formula [2]

(In the formula, R ₀ has one or more functional groups selected from (meth) acryloyl group, vinyl group, vinyl ether group, allyl group and allyl ether group. R ₀ may be the same or different. ) A part of acryloyl group, vinyl group, vinyl ether group, allyl group and allyl ether group are alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and halogenated alkyl groups having 1 to 6 carbon atoms. , Phenyl group, or halogen may be substituted.)

The silsesquioxane derivative of the present embodiment is mainly composed of a silsesquioxane derivative having a random structure. However, the silsesquioxane derivative having a cage structure (cage type) is within the range that does not impair the object of the present embodiment. An oxane derivative or a silsesquioxane derivative having a ladder structure may be contained. Specifically, the silsesquioxane derivative of this embodiment preferably contains 10% by mass or more of a random structure, and particularly preferably contains 20% by mass or more. It may contain 100% by mass of a random structure. If this random structure is 10% by mass or more, the adhesiveness is excellent. From another viewpoint, the silsesquioxane derivative of the present embodiment preferably includes a cage-type (cage-type) structure or a ladder-type structure by 90% by mass or less. preferable. The silsesquioxane derivative of the present embodiment is a cage-type (cage-type) structure or a ladder-type structure silsesquioxane derivative of 0% to less than 50% by mass, 45% by mass or less, 40% by mass or less, and 30% by mass. Hereinafter, it may be contained by 20% by mass or less and 10% by mass or less. As a measuring method of the content rate of the random type structure, cage type (cage type) structure or ladder type structure of the silsesquioxane derivative of the present embodiment, for example, the GPC measurement results and mass spectrometry after liquid chromatography separation ( LC-MS) measurement results and ¹ H-NMR measurement results are compared for calculation. The content of the random structure of the silsesquioxane derivative of this embodiment is 10% by mass, 20% by mass, 30% by mass, 40% by mass, 50% by mass, 60% by mass, 70% by mass, and 80% by mass. %, 90% by mass, or 100% by mass or more, and may be within the range of any two values.

The molecular weight of the silsesquioxane derivative is preferably 100 to 100,000, more preferably 500 to 60,000. When the molecular weight is 100 or more, excellent heat resistance can be obtained, and when the molecular weight is 100,000 or less, the viscosity of the adhesive does not become too high, and the workability and moldability are not impaired and stored. There is no problem with stability. The molecular weight of the silsesquioxane derivative is 100, 200, 300, 400, 500, 600, 700, 800, 900, 1,000, 2,000, 3,000, 4,000, 5,000, 6 , 000, 7,000, 8,000, 9,000, 10,000, 20,000, 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000 , 100,000, or any two values.

The molecular weight of the oligomer refers to the weight average molecular weight calculated as the average molecular weight per molecule. In the examples of this embodiment, the weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) is used.

In the silsesquioxane derivative of the present embodiment, the number of grams of the silsesquioxane derivative per equivalent of the ethylenically unsaturated group (for example, when the ethylenically unsaturated group is a (meth) acrylic group, (meth) Acrylic group equivalent) is preferably 50 to 300 g / eq, more preferably 100 to 200 g / eq. The ethylenically unsaturated group refers to one or more functional groups selected from a (meth) acryloyl group, a vinyl group, a vinyl ether group, an allyl group, and an allyl ether group. In addition, the gram number of the silsesquioxane derivative per 1 equivalent of ethylenically unsaturated groups is 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190. , 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300 g / eq, or any two values.

(B) Polythiol The (B) polythiol of this embodiment has two or more thiol groups per molecule.

The average molecular weight of the polythiol of this embodiment is preferably 50 to 15,000. The polythiol of this embodiment is used as a main component together with the aforementioned polyene. Preferred polythiols include mercapto group-substituted alkyl compounds such as dimercaptobutane and trimercaptohexane, mercapto group-substituted allyl compounds such as dimercaptobenzene, polyhydric alcohol esters such as thioglycolic acid and thiopropionic acid, and alkylenes of polyhydric alcohols. Examples include a reaction product of an oxide adduct and hydrogen sulfide.

Examples of the polythiol of the present embodiment include tris [(3-mercaptopropionyloxy) -ethyl] isocyanurate, trimethylolpropane-tris- (β-thiopropionate), tris-2-hydroxyethyl-isocyanurate, tris- β-mercaptopropionate, pentaerythritol tetrakis (β-thiopropionate), 1,8-dimercapto-3,6-dioxaoctane, 1,8-dimercapto-3,6-disulfide octane, triazine thiol, and more Includes polythiols of silsesquioxane derivatives. The polythiol of this embodiment is not particularly limited, and may be a single thiol or a mixture of two or more. Among these, one or more members selected from the group consisting of trimethylolpropane-tris- (β-thiopropionate) and tris [(3-mercaptopropionyloxy) -ethyl] isocyanurate are preferable, and trimethylolpropane is preferable. -Tris- (β-thiopropionate) is more preferred.

The mass ratio of the silsesquioxane derivative of (A) of this embodiment to the polythiol of (B) is preferably 5 to 95:95 to 5 when the total of (A) and (B) is 100, ~ 90: 85-10 is more preferred, and 35-85: 65-15 is most preferred. The mass ratio is 5:95, 10:90, 15:85, 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50:50, 55:45. , 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10, within the range of 95: 5 or any two values Also good.

About (C) radical photopolymerization initiator Furthermore, it is preferable that the resin composition of this embodiment contains (C) radical photopolymerization initiator.

The (C) photoradical polymerization initiator of this embodiment is not particularly limited as long as it is a compound that absorbs light and generates a radical capable of initiating polymerization. Examples of the photo radical polymerization initiator of this embodiment include benzoin derivatives such as benzyl, benzoin, benzoin benzoic acid, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether, benzophenone derivatives such as benzophenone and 4-phenylbenzophenone, 2,2 Alkyl acetophenone derivatives such as -dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxyacetophenone, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 1- (4-isopropylphenyl) -2-hydroxy -2-Methylpropan-1-one, 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1 - Α-hydroxyacetophenone derivatives such as phenyl-propan-1-one, bisdiethylaminobenzophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2- Α-aminoalkylacetophenone derivatives such as dimethylamino-1- (4-morpholinophenyl) -1-butanone-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethyl) And acylphosphine oxide derivatives such as benzoyl) -phenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide. The radical photopolymerization initiator of the present embodiment is not particularly limited, and may be a single type or a mixture of two or more types. Among these, one or more members selected from the group consisting of alkylacetophenone derivatives and α-hydroxyacetophenone derivatives are preferable, and alkylacetophenone derivatives are more preferable. Of the alkyl acetophenone derivatives, 2,2-dimethoxy-1,2-diphenylethane-1-one is preferred. Of the α-hydroxyacetophenone derivatives, 2-hydroxy-2-methyl-1-phenyl-propan-1-one is preferred.

The radical photopolymerization initiator of this embodiment can be mixed with polyene or polythiol in advance.

The amount of the (C) radical photopolymerization initiator used in this embodiment is 0.01 with respect to a total of 100 parts by mass of the component (A), the component (B), and the component (E) used as necessary. Is preferably 10 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass. If it is 0.01 mass part or more, sufficient sclerosis | hardenability can be obtained, and if it is 10 mass parts or less, visible light transparency will not be impaired. In addition, this usage-amount is 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2. 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 parts by mass May be within the range of any value or any two values.

(D) Furthermore, about the dialkyl phosphite, it is preferable that the resin composition of this embodiment contains (D) dialkyl phosphite.

(D) dialkyl phosphite of this embodiment has two alkyl groups per molecule. The dialkyl phosphite has, for example, a structure represented by the following general formula [3].

General formula [3]

The alkyl group is preferably a branched or straight chain alkyl group having 1 to 18 carbon atoms, more preferably a branched or straight chain alkyl group having 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms. Most preferred are branched or straight chain alkyl groups having carbon atoms, and even more preferred are branched or straight chain alkyl groups having 1 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group including a 2-ethylhexyl group and an n-octyl group, a lauryl group, and an oleyl group. As the alkyl group, a hydrocarbon group is preferable. Among dialkyl phosphites, one or more members selected from the group consisting of dimethyl phosphite, diethyl phosphite, di (2-ethylhexyl) phosphite, dilauryl phosphite and dioleyl phosphite are preferred. One or more members of the group consisting of dimethyl phosphate and diethyl phosphite are more preferred, and diethyl phosphite is most preferred.
The amount of (D) dialkyl phosphite used in the present embodiment is 0.01 to 100 parts by mass with respect to 100 parts by mass in total of the component (A), the component (B), and the component (E) used as necessary. 10 parts by mass is preferable, and 0.05 to 5 parts by mass is more preferable. If it is 0.01 mass part or more, sufficient storage stability can be obtained, and if it is 10 mass parts or less, curability will not be impaired. In addition, this usage-amount is 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2. 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 parts by mass May be within the range of any value or any two values.

(E) Other compound having carbon-carbon unsaturated bond The resin composition of the present embodiment further contains (E) a compound having a carbon-carbon unsaturated bond other than the silsesquioxane derivative. Can do.

(E) The compound having a carbon-carbon unsaturated bond other than the silsesquioxane derivative is not particularly defined, but even if it is a monofunctional compound having one carbon-carbon unsaturated bond, carbon -It may be a bifunctional or higher functional compound having two or more carbon unsaturated bonds.

The viscosity of the compound having a carbon-carbon unsaturated bond other than the (E) silsesquioxane derivative of this embodiment is preferably 1000 mPa · s or less, and 500 mPa · s or less in terms of adjusting the viscosity of the composition. Is more preferable, and 100 mPa · s or less is most preferable.

The molecular weight of the compound having a carbon-carbon unsaturated bond other than the (E) silsesquioxane derivative of this embodiment is preferably 1000 or less, more preferably 100 to 800, in terms of adjusting the viscosity of the composition. 100 to 500 is most preferred. The carbon-carbon unsaturated bond particularly refers to a carbon-carbon double bond.

The compound having a carbon-carbon unsaturated bond other than the (E) silsesquioxane derivative of the present embodiment is not particularly limited, but 2-ethylhexyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, butanediol mono (meth) acrylate, Butyl (meth) acrylate, ethylene oxide modified (hereinafter referred to as “EO”) cresol (meth) acrylate, dipropylene glycol (meth) acrylate, ethoxylated phenyl (meth) acrylate, ethyl (meth) acrylate, iso Chill (meth) acrylate, isooctyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, lauryl (meth) acrylate, Nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, octyl (meth) acrylate, phenoxyethyl (meth) acrylate, 1,9-nonanediol di (meth) acrylate, propylene oxide (hereinafter “PO”) Neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) Acrylate, tris ((meth) acryloxyethyl) isocyanurate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate , Pentaerythritol tetra (meth) acrylate, trimethylolethane trivinyl ether, hexanediol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, triethylene glycol diethylene vinyl ether, ethylene glycol dipropylene vinyl ether, triethylene glycol diethylene vinyl ether, diallyl Phthalate, diallyl male , Triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, tetraallyloxyethane, trimethylolpropane diallyl, trimethylolpropane triallyl and the like. Of these, allyl compounds having an allyl group are preferred. Examples of the allyl compound include diallyl phthalate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, tetraallyloxyethane, trimethylolpropane diallyl, trimethylolpropane triallyl and the like. Among allyl group compounds, one or more members selected from the group consisting of triallyl isocyanurate and diallyl maleate are preferable. The compound having a carbon-carbon unsaturated bond other than the (E) silsesquioxane derivative of this embodiment preferably excludes the (G) adhesion-imparting agent described later.

The amount of the compound having a carbon-carbon unsaturated bond other than the (E) silsesquioxane derivative of this embodiment is low in viscosity, so that the workability is improved and the adhesiveness is improved. A total of 100 parts by mass of A), component (B), and component (E) is preferably 60 parts by mass or less, more preferably 2 to 50 parts by mass, most preferably 5 to 30 parts by mass, and 7 to 15 parts by mass. Is even more preferred.

(F) Antioxidant It is preferable that the resin composition of the present embodiment further contains (E) an antioxidant because excellent heat resistance and storage stability can be obtained.

(F) Antioxidant is an antioxidant substance added in order to suppress the oxidation of the component in a product. The antioxidant is not particularly limited, but triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythrityl tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2′- Methylene bis (6-tert-butyl-p-cresol), isooctyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2′-methylene bis (4-methyl-6-tert- Butylphenol), 2,2,4,4-tetramethyl-21-oxo-7-oxa .20-diazadispiro [5.1.1.12] -henicosane-20-propionic acid dodecyl ester and 2,2,4,4-tetramethyl-21-oxo-7-oxa-3.20-diazadispiro [5. 1.11.2] -Henicosane-20-propionic acid tetradecyl ester mixture, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, bis (2 , 2,6,6-tetramethyl-4-piperidyl) sebacate and other hindered amines, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4, Phosphorus compounds such as 8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine, dilauryl 3,3′-thio Sulfur compounds such as dipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, pentaerythrityl tetrakis (3-laurylthiopropionate), 2-mercaptobenzimidazole Is mentioned. In these, a phenol type compound and / or a hindered amine compound are preferable, and a phenol type compound is more preferable.
Among the phenolic compounds, the group consisting of isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and 2,2′-methylenebis (4-methyl-6-tert-butylphenol) One or more of them are preferable, and isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and 2,2′-methylenebis (4-methyl-6-tert-butylphenol) are used in combination. It is more preferable. When isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and 2,2′-methylenebis (4-methyl-6-tert-butylphenol) are used in combination, the mixing ratio is isooctyl. In a total of 100 parts by mass of -3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and 2,2′-methylenebis (4-methyl-6-tert-butylphenol), isooctyl-3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate: 2,2′-methylenebis (4-methyl-6-tert-butylphenol) = 1: 99 to 99: 1 is preferred, and 5:95 to 97 : 3 is more preferable, and 85:15 to 95: 5 is most preferable.

The amount of the antioxidant (F) used in this embodiment is 0.001 to 3 with respect to 100 parts by mass in total of the component (A), the component (B), and the component (E) used as necessary. Part by mass is preferable, and 0.01 to 2 parts by mass is more preferable. If it is 0.001 part by mass or more, durability and storage stability are sufficient, and if it is 3 parts by mass or less, reliable adhesiveness is obtained, and there is no possibility of becoming uncured.

The mass ratio of the polyene and the polythiol in the present embodiment is preferably 98: 2 to 2:98 when the total of the polyene and the polythiol is 100 in terms of obtaining good heat resistance and adhesion, and 90:10 to 10:90 is more preferable. In particular, it is most preferable when the double bond in the polyene and the thiol group in the polythiol have a chemical equivalent. The chemical equivalent here means that (number of moles of polyene / number of double bonds of polyene molecule) and (number of moles of polythiol / number of SH groups of polythiol molecule) are equal. Here, polyene refers to component (A) and component (E), and polythiol refers to component (B).

(G) Adhesion imparting agent In the present embodiment, (F) an adhesion imparting agent may be used to improve adhesion. Examples of the adhesion promoter include 3-glycidoxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane, γ- (meth) acryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltri Ethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, hydroxyethyl (meta Acrylate Phosphate esters, (2-hydroxyethyl) (meth) acrylic acid phosphate, (meth) acrylate Roxio carboxyethyl acid phosphate, and (meth) acrylate Roxio carboxyethyl acid phosphate Tomono ethylamine half salt and the like. Among these, at least one member selected from the group consisting of γ- (meth) acryloxypropyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane is preferable.

(G) The amount of the adhesion-imparting agent used is 0.001 to 10 parts by mass with respect to 100 parts by mass in total of the component (A), the component (B), and the component (E) used as necessary. Preferably, 0.01 to 5 parts by mass is more preferable. If it is 0.001 part by mass or more, the adhesiveness is sufficient, and if it is 10 parts by mass or less, reliable adhesiveness is obtained.

(H) Nitroso Compound In this embodiment, (H) a nitroso compound may be used to improve storage stability.

As the nitroso compound, N-nitrosoarylhydroxylamine salts are preferred. N-nitrosoarylhydroxylamine salts include ammonium salt, sodium salt, potassium salt, magnesium salt, strontium salt, aluminum salt, copper salt, zinc salt, cerium salt, iron salt, nickel salt of N-nitrosophenyl hydroxylamine And cobalt salts. Among these, one or more members selected from the group consisting of N-nitrosophenyl hydroxylamine aluminum salt and N-nitrosophenyl hydroxylamine ammonium salt are preferable, and N-nitrosophenyl hydroxylamine aluminum salt is more preferable.

(H) The amount of the nitroso compound used is preferably 0.0001 to 1 part by mass with respect to 100 parts by mass in total of the component (A), the component (B), and the component (E) used as necessary. 0.001 to 0.1 parts by mass is more preferable. If it is 0.0001 part by mass or more, the storage stability is improved, and if it is 1 part by mass or less, the curability is not impaired.

The resin composition of the present embodiment is a range that does not impair the intended effect, and if necessary, a thermal radical polymerization initiator, a curing accelerator, a filler, a colorant, a thixotropic agent, a plasticizer, a surfactant, Additives such as lubricants and antistatic agents can be added.

The resin composition of this embodiment can be used as an adhesive or a coating agent. As a base material to be bonded or coated with the adhesive or coating agent of the present embodiment or a base material to form a molded body with the adhesive or coating agent of the present invention, halogenated materials such as glass materials, potassium bromide, calcium fluoride, etc. Single crystal ceramics such as mineral, sapphire, acrylic resin, polycarbonate resin, polystyrene resin, polyester resin, polyethylene terephthalate resin, polyvinyl chloride resin, polyethylene resin, polypropylene resin, fluorine resin, cellulose resin, diethylene glycol bisallyl carbonate resin, styrene Butadiene copolymer, (meth) acrylic acid methyl-styrene copolymer, silicone resin, polycycloolefin resin, (meth) acrylonitrile-butadiene-styrene copolymer resin, poly (meth) acrylic ester resin, poly Tan resin, polyphenyl sulfide resin, liquid crystal polymer, epoxy resin, resin material such as resin reinforced with glass fiber or carbon fiber, semiconductor material such as silicon, germanium, gallium, indium, zinc oxide, titanium oxide, metal layer, Examples of the above-mentioned semiconductor materials on which resin layers and ceramic layers are deposited, plated, and sputtered, and metal materials such as iron, stainless steel, aluminum, zinc, magnesium, copper, brass, phosphor bronze, silver, gold, and platinum. . All or part of the substrate is composed of these materials. When a glass material is used as the substrate, the resin composition of the present embodiment has a great effect. The glass material is preferably selected from soda glass such as soda lime glass, quartz glass, lead glass, borosilicate glass, and alkali-free glass, and more preferably borosilicate glass.
In this embodiment, the laminated body formed in the one or both surfaces of the base material may be sufficient as the film | membrane by an adhesive agent or a coating material.
The resin composition of this embodiment can be used as an optical component. Examples of the optical component include a lens and a prism.

The resin composition of the present embodiment can be cured by active energy rays such as light and ultraviolet rays. An optical member using the resin composition of the present embodiment can also be bonded by active energy rays.

For curing, coating or bonding with active energy rays, halogen lamp, metal halide lamp, high power metal halide lamp (containing indium etc.), low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, xenon lamp, xenon excimer lamp, xenon An irradiation device using a flash lamp or the like as a light source can be applied, and laser light, electron beam (EUV), or the like can also be applied.

The above apparatus can irradiate condensed light by a direct irradiation, a reflecting mirror, or the like, and collect and irradiate with a fiber or the like. A low wavelength cut filter, a heat ray cut filter, a cold mirror, or the like can also be used.

This embodiment has an effect of being excellent in, for example, heat resistance, light resistance, transparency, fast curability, adhesiveness, and storage stability. The present invention can provide an adhesive body, a cured body, a molded body, an optical component, and an optical waveguide.

An optical waveguide confines light by creating a part with a slightly higher refractive index than the surroundings on the surface of the substrate or just below the substrate surface, and controls light propagation, branching, reflection, refraction, amplification, attenuation, etc. Electronic components that perform multiplexing / demultiplexing and switching. This invention can provide an optical waveguide by laminating | stacking the layer which consists of a hardening body of the resin composition of this invention, and the layer which has a higher refractive index than this layer.

Specific examples of specific components of the optical waveguide include optical multiplexing circuits, frequency filters, optical switches, and optical interconnection components used in the fields of communication and optical information processing.

As described above, the embodiments of the present invention have been described with reference to the drawings. However, these are exemplifications of the present invention, and various configurations other than the above can be adopted.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

<Examples 1 to 16 and Comparative Examples 1 to 3>
Resin compositions were prepared by mixing the components shown in Tables 1 and 2 in the composition shown in the table. The following compounds were selected for each component listed in Tables 1-2.

(A) Silsesquioxane derivative having two or more carbon-carbon unsaturated bonds per molecule and having a random structure (a-1) manufactured by Toagosei Co., Ltd .: polyacryloyloxypropyl polyorganosilsesqui Oxane (AC-SQ TA-100) (weight average molecular weight 1,200 to 4,000 in terms of polystyrene by GPC, acryl group equivalent 165 g / eq
(A-2) Toagosei Co., Ltd .: polymethacryloyloxypropyl polyorganosilsesquioxane (MAC-SQ TM-100) (weight average molecular weight in terms of polystyrene by GPC 1,000 to 2,500, methacryl group equivalent 179 g) / Eq
(B) Polythiol (b-1) manufactured by Sakai Chemical Industry Co., Ltd .: trimethylolpropane-tris- (β-thiopropionate) (TP)
(B-2) SC Organic Chemical Company: Tris [(3-mercaptopropionyloxy) -ethyl] isocyanurate (TEMPIC)
(E) Compound having carbon-carbon unsaturated bond other than silsesquioxane derivative (e-1) Nippon Kasei Co., Ltd .: triallyl isocyanurate (TAIC)
(E-2) Kurokin Kasei Co., Ltd .: diallyl maleate (DAM)
(C) Photo radical polymerization initiator (c-1) manufactured by BASF: 2,2-dimethoxy-1,2-diphenylethane-1-one (IRGACURE651)
(C-2) manufactured by BASF: 2-hydroxy-2-methyl-1-phenyl-propan-1-one (DAROCUR 1173)
(D) Dialkyl phosphite (d-1) Wako Pure Chemical Industries: Diethyl phosphite (d-2) Tokyo Chemical Industry: Dimethyl phosphite (d-3) Johoku Chemical Co., Ltd .: Phosphorous Di (2-ethylhexyl) acid (JPE-208)
(D-4) Johoku Chemical Industry Co., Ltd .: Dilauryl phosphite (JP-212)
(D-5) Johoku Chemical Industry Co., Ltd .: Dioleyl phosphite (JP-260)
(F) Antioxidant (f-1) manufactured by BASF: isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (IRGANOX1135)
(F-2) manufactured by Sumitomo Chemical Co., Ltd .: 2,2′-methylenebis (4-methyl-6-tert-butylphenol) (Sumilyzer MDP-S)
(G) Adhesion imparting agent (g-1) manufactured by Momentive: γ-methacryloxypropyltrimethoxysilane (A-174)
(G-2) Shin-Etsu Chemical Co., Ltd .: 3-glycidoxypropyltrimethoxysilane (KBM-403)
(H) Nitroso compound (h-1) Wako Pure Chemical Industries, Ltd .: N-nitrosophenylhydroxylamine aluminum salt (Q-1301)
(H-2) Wako Pure Chemical Industries, Ltd .: N-nitrosophenylhydroxylamine ammonium salt (Q-1300)
(I) Silsesquioxane derivative polyene having a cage structure (i-1) manufactured by Toagosei Co., Ltd .: Octa [(3-methacryloxypropyl) dimethylsiloxy] silsesquioxane] (Q-8) (molecular weight 2027)
(J) Phosphorus compound (j-1) Commercial product: Triphenyl phosphite

The following performance evaluation was performed on the compositions obtained in the above Examples and Comparative Examples, and the results are shown in Tables 1 and 2.

(Adhesive curing conditions)
For the evaluation, an adhesion test specimen was prepared according to the procedure described below.

Curing method Curing was performed under the condition of an integrated light amount of 3000 mJ / cm ² at a wavelength of 365 nm by a curing apparatus manufactured by HOYA using an ultrahigh pressure mercury lamp.

(1) The viscosity of the viscosity composition was measured using an E-type viscometer under the conditions of a temperature of 25 ° C. and a rotation speed of 20 rpm.

(2) Light transmittance (transparency evaluation, after UV curing)
As a test piece, a test piece was prepared by curing a resin composition having a shape of 20 mmφ × 200 μmt on a BK7 glass (borosilicate glass, 30 mmφ × 3 mmt) substrate under the curing conditions described above. The light transmittance was measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-2550), and the transmittance at wavelengths of 400 nm and 600 nm was measured. The evaluation results are shown in Tables 1 and 2.

(3) Heat resistance test (after light transmittance, heat resistance test)
A test piece was prepared by curing a resin composition having a shape of 20 mmφ × 200 μmt on a BK7 glass (30 mmφ × 3 mmt) substrate as a test piece under the curing conditions described above. This test piece was exposed to an atmosphere of 260 ° C. for 40 seconds. Using a spectrophotometer (manufactured by Shimadzu Corporation, UV-2550), the transmittance of the test piece after the exposure was measured, and the transmittance at wavelengths of 400 nm and 600 nm was measured. The evaluation results are shown in Tables 1 and 2.

(4) Light resistance test (after light transmittance, light resistance test)
A test piece was prepared by curing a resin composition having a shape of 20 mmφ × 200 μmt on a BK7 glass (30 mmφ × 3 mmt) substrate as a test piece under the curing conditions described above. This test piece was exposed for 80 hours under light of 365 nm light with an illuminance of 7 mW / cm ² using a high-pressure mercury lamp (Toshier 400 HC-0411, manufactured by Toshiba Corporation). Using a spectrophotometer (manufactured by Shimadzu Corporation, UV-2550), the transmittance of the test piece after the exposure was measured, and the transmittance at wavelengths of 400 nm and 600 nm was measured. The evaluation results are shown in Tables 1 and 2.

(5) Tensile shear bond strength (adhesiveness)
It measured according to JIS K 6850. Specifically, using Tempax (trademark) glass (25 mm × 25 mm × 2.0 mm) as an adherend, the bonded portion was 8 mm in diameter, and two Tempax glasses were made with the produced resin composition. Bonding was performed, and the resin composition was cured under the curing conditions described above to prepare a tensile shear bond strength test piece. The produced test piece was measured for tensile shear bond strength at a tensile speed of 10 mm / min in an environment of a temperature of 23 ° C. and a humidity of 50% using a tensile tester. The evaluation results are shown in Tables 1 and 2.

(6) Storage stability test (storage stability evaluation)
After the initial viscosity (V ₀ ) of the composition was measured, a curing acceleration test was conducted in a high-temperature environment at 40 ° C. in a state where it was put in a container and covered (sealed system), and the viscosity of the composition after 4 weeks ( V ₄₎ were measured. The _formula was determined viscosity change rate according to _V 4 / V _0. Those having a viscosity change rate of 2 or less were judged to have good storage stability (storage stability).

From Tables 1 and 2, the following was confirmed. The resin composition of this example is excellent in storage stability, heat resistance, light resistance, transparency, and adhesiveness. However, in Example 1 and Examples 9 to 10, since the (H) nitroso compound was not used, the storage stability was slightly low.
The number of carbon atoms in the alkyl group of the dialkyl phosphite is preferably from 1 to 18 alkyl groups, more preferably from 1 to 12 alkyl groups, from the viewpoints of adhesion and storage stability. The group was most preferred, 1-2 alkyl groups were even more preferred, and the ethyl group was even more preferred (Comparison between Example 2 and Examples 13-16).
However, in Examples 11 to 12, since (G) an adhesion-imparting agent was used, the adhesiveness was large. When (D) dialkyl phosphite of this example is not used, storage stability cannot be obtained (Comparative Example 1). When triphenyl phosphite is used, storage stability and adhesion cannot be obtained (Comparative Example 2). When a cage-type silsesquioxane derivative is used, it does not dissolve in the resin composition and the effect of this example cannot be obtained (Comparative Example 3). When (B) polythiol of this example is not used, heat resistance and adhesion cannot be obtained (Comparative Example 4).

The present invention provides a polyene-polythiol-based composition having excellent storage stability. The present invention also provides a polyene-polythiol-based composition excellent in, for example, heat resistance, light resistance, transparency, fast curability, adhesion, and storage stability. The adhesive, coating agent, and molding material of the present invention exhibit remarkable effects in various fields such as optical waveguide layers, optical components, and electronic components.

Claims

(A) Silsesquioxane derivative having two or more carbon-carbon unsaturated bonds per molecule and having a random structure, (B) polythiol, (C) photoradical polymerization initiator, (D) A composition containing a dialkyl phosphite.
The composition according to claim 1, wherein (A) is a silsesquioxane derivative represented by the following general formula [1].
General formula [1]

(In the formula, R 0 has one or more functional groups selected from a (meth) acryloyl group, a vinyl group, a vinyl ether group, an allyl group, and an allyl ether group. R 0 may be the same or different. Some of the (meth) acryloyl group, vinyl group, vinyl ether group, allyl group and allyl ether group are alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and alkyl halides having 1 to 6 carbon atoms. And may be substituted with a group, a phenyl group or a halogen, m represents the degree of polymerization.)
3. The composition according to claim 1, wherein (D) is a dialkyl phosphite represented by the following general formula [3].
General formula [3]

(In the formula, R 1 and R 2 are each an alkyl group. R 1 and R 2 may be the same group or different groups.)
The composition according to any one of claims 1 to 3, wherein (D) is a dialkyl phosphite having a branched or straight-chain alkyl group having 1 to 18 carbon atoms.
The composition according to claim 1, wherein (D) is one or more members selected from the group consisting of dimethyl phosphite and diethyl phosphite.
The composition according to any one of claims 1 to 5, further comprising (E) a compound having a carbon-carbon unsaturated bond other than the silsesquioxane derivative.
The composition according to claim 6, wherein (E) is an allyl compound.
The composition according to any one of claims 1 to 7, further comprising (F) an antioxidant.
The composition according to any one of claims 1 to 8, further comprising (G) an adhesion-imparting agent.
The composition according to any one of claims 1 to 9, further comprising (H) a nitroso compound.
An adhesive comprising the composition according to any one of claims 1 to 10.
The adhesive body formed by adhere | attaching using the adhesive agent of Claim 11.
A coating comprising the composition according to any one of claims 1 to 10.
A covering formed by coating with the coating agent according to claim 13.
The laminated body in which the membrane | film | coat by the coating agent of Claim 13 was formed in the single side | surface or both surfaces of a base material.
The laminate according to claim 15, wherein the substrate is a glass material.
A cured body comprising the composition according to any one of claims 1 to 10.
An optical waveguide formed by laminating a layer made of the cured body according to claim 17 and a layer having a higher refractive index than this layer.
An optical component comprising the composition according to any one of claims 1 to 10.