JP6062120B2 - Curable composition, cured product, method of using curable composition, and optical device - Google Patents

Description

  The present invention relates to a curable composition from which a cured product having excellent peel resistance and heat resistance and high adhesive strength is obtained, a cured product obtained by curing the composition, and the composition as an adhesive for optical elements. Or it is related with the method used as a sealing material for optical elements, and an optical device.

Conventionally, the curable composition has been variously improved according to the application, and has been widely used in industry as a raw material for optical parts and molded articles, an adhesive, a coating agent, and the like.
In addition, the curable composition has attracted attention as a composition for optical element fixing materials such as an optical element adhesive and an optical element sealing material when producing an optical element sealing body.

  Examples of the optical element include various lasers such as a semiconductor laser (LD), light emitting elements such as a light emitting diode (LED), a light receiving element, a composite optical element, and an optical integrated circuit. In recent years, blue and white light optical elements having a shorter peak emission wavelength have been developed and widely used. Such a light emitting element with a short peak wavelength of light emission has been dramatically increased in brightness, and accordingly, the amount of heat generated by the optical element tends to be further increased.

  However, with the recent increase in brightness of optical elements, the cured product of the composition for optical element fixing materials is exposed to higher energy light or higher temperature heat generated from the optical element for a long time, and deteriorates and peels off. Or a problem that the adhesive strength is reduced.

In order to solve this problem, in Patent Documents 1 to 3, a composition for an optical element fixing material containing a polysilsesquioxane compound as a main component is disclosed in Patent Document 4, and a hydrolyzate / polycondensate of a silane compound is disclosed in Patent Document 4. A member for a semiconductor light emitting device to be used has been proposed.
However, even for cured products such as compositions and members described in Patent Documents 1 to 4, it may be difficult to obtain peeling resistance and heat resistance while maintaining sufficient adhesive force.
Therefore, development of the curable composition which is excellent in peeling resistance and heat resistance, and can obtain the hardened | cured material which has high adhesive force is earnestly desired.

JP 2004-359933 A JP 2005-263869 A JP 2006-328231 A JP 2007-112975 (US2009008673A1)

  The present invention has been made in view of the situation of such prior art, and is a curable composition from which a cured product having excellent peel resistance (delamination resistance), heat resistance, and high adhesive strength can be obtained, It is an object to provide a cured product obtained by curing a composition, a method of using the composition as an optical element adhesive or an optical element sealing material, and an optical device.

  As a result of intensive studies to solve the above problems, the present inventors have determined that a composition containing a specific silane compound polymer, fine particles, and a silane coupling agent in a specific ratio as described below is resistant to peeling. The present invention has been completed by finding that the cured product has excellent properties and heat resistance and has high adhesive strength.

  Thus, according to the present invention, the following [1] to [7] curable composition, [8], [9] cured product, [10], [11] curable composition, and [12] Optical devices are provided.

[1] A curable composition having the following components (A) to (E), wherein the component (A) and the component (B) are mixed in a mass ratio of the component (A) and the component (B) [( A) component: (B) component] = 100: 0.3-100: 20 The ratio is contained, and the curable composition characterized by the above-mentioned.
(A) The following formula (a)

(In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms. A plurality of R ¹ may be the same or different. Z is a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms. Or represents a halogen atom, s represents a positive integer, and t and u each independently represents 0 or a positive integer.)
The silane compound polymer (B) represented by the formula (B) Fine particles having an average primary particle diameter of more than 0.04 μm and 8 μm or less (C) A silane coupling agent having a nitrogen atom in the molecule (D) having an acid anhydride structure in the molecule Silane coupling agent (E) Silane coupling agent having a sulfur atom-containing functional group in the molecule

[2] The curable composition according to [1], wherein the component (B) is at least one fine particle selected from silica, silicone, and a metal oxide whose surface is coated with silicone.
[3] The curable composition according to [1], wherein the component (A) has a mass average molecular weight of 800 to 50,000.
[4] The curable composition according to [1], further containing a diluent.
[5] The total amount of the component (A), the component (B), the component (C), the component (D), and the component (E) is 50 with respect to the total components excluding the diluent of the curable composition. It is -100 mass%, The curable composition as described in [1] characterized by the above-mentioned.
[6] The curable composition according to any one of claims 1 to 5, wherein a solid content concentration of the curable composition is 50 to 100% by mass.
[7] The curable composition according to [1], which is a composition for an optical element fixing material.

[8] A cured product obtained by curing the curable composition according to [1].
[9] The cured product according to [8], which is an optical element fixing material.

[10] A method of using the curable composition according to [1] as an adhesive for an optical element fixing material.
[11] A method of using the curable composition according to the above [1] as a sealing material for an optical element fixing material.
[12] An optical device obtained by using the curable composition according to [1] as an adhesive for an optical element fixing material or an encapsulant for an optical element fixing material.

According to the curable composition of this invention, the hardened | cured material which is excellent in peeling resistance and heat resistance, and has high adhesive force can be obtained.
The curable composition of this invention can be used when forming an optical element fixing material, and can be used especially suitably as an adhesive for optical elements and a sealing material for optical elements.
The cured product of the present invention is excellent in peeling resistance and heat resistance and has high adhesive strength in fixing an optical element.

  Hereinafter, the present invention will be described in detail by dividing it into 1) a curable composition, 2) a cured product, 3) a method for using the curable composition, and 4) an optical device.

1) Curable composition The curable composition of this invention is a curable composition which has the following (A)-(E) component, Comprising: (A) component and (B) component, (A) component And (B) component in a mass ratio of [(A) component: (B) component] = 100: 0.3 to 100: 20.

(A) Silane compound polymer represented by the following formula (a) The component (A) used in the present invention is a silane compound polymer represented by the following formula (a).

(B) Fine particles having an average primary particle diameter of more than 0.04 μm and 8 μm or less (C) A silane coupling agent having a nitrogen atom in the molecule (D) A silane coupling agent having an acid anhydride structure in the molecule (E) Silane coupling agent having a sulfur atom-containing functional group in the molecule

(A) Component (A) component used for the curable composition of this invention is the silane compound polymer represented by said Formula (a) (henceforth "silane compound polymer (A)"). It is.

In the formula (a), R ¹ represents an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, n- A hexyl group, n-octyl group, n-nonyl group, etc. are mentioned. Among these, a C1-C6 alkyl group is preferable and a C1-C3 alkyl group is more preferable.

Z represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom. Examples of the alkoxy group having 1 to 10 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, t-butoxy group, pentyloxy group, hexyloxy group and octyloxy group. Examples of the halogen atom include a chlorine atom and a bromine atom.
Among these, Z is preferably a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms.
s represents a positive integer, and t and u each independently represent 0 or a positive integer.
A plurality of R ¹ may be all the same or different. The plurality of Z may be all the same or different.

The manufacturing method of a silane compound polymer (A) is not specifically limited. For example, the silane compound polymer (A) can be produced by condensing the silane compound (1) represented by the formula (1): R ¹ Si (OR ² ) _x (X ¹ ) _3-x. . Here, “condensation” is used in a broad concept including hydrolysis and polycondensation reactions.

In formula (1), R ¹ represents the same meaning as described above. R ² represents an alkyl group having 1 to 10 carbon atoms, X ¹ represents a halogen atom, and x represents an integer of 0 to 3.

Examples of the alkyl group having 1 to 10 carbon atoms of R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, and a t-butyl group.
Examples of the halogen atom for X ¹ include a chlorine atom and a bromine atom.
When x is 2 or more, OR ² may be the same or different. When (3-x) is 2 or more, X ¹ may be the same or different.

  Specific examples of the silane compound (1) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, Alkyl trialkoxy such as n-propyltripropoxysilane, n-propyltributoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, isooctyltriethoxysilane Silane compounds;

  Methylchlorodimethoxysilane, methylchlorodiethoxysilane, methyldichloromethoxysilane, methylbromodimethoxysilane, ethylchlorodimethoxysilane, ethylchlorodiethoxysilane, ethyldichloromethoxysilane, ethylbromodimethoxysilane, n-propylchlorodimethoxysilane, n Alkylhalogenoalkoxysilane compounds such as propyldichloromethoxysilane, n-butylchlorodimethoxysilane, n-butyldichloromethoxysilane;

Methyltrichlorosilane, methyltribromosilane, ethyltritrichlorosilane, ethyltribromosilane, n-propyltrichlorosilane, n-propyltribromosilane, n-butyltrichlorosilane, isobutyltrichlorosilane, n-pentyltrichlorosilane, n-hexyl And alkyltrihalogenosilane compounds such as trichlorosilane and isooctyltrichlorosilane;
A silane compound (1) can be used individually by 1 type or in combination of 2 or more types.

  Among these, as the silane compound (1), an alkyltrialkoxysilane compound is preferable because a curable composition capable of obtaining a cured product superior in adhesiveness can be obtained.

  A method for condensing the silane compound (1) is not particularly limited, and a method of adding a predetermined amount of catalyst to the silane compound (1) in a solvent or without a solvent and stirring at a predetermined temperature may be mentioned. It is done.

The catalyst used may be either an acid catalyst or a base catalyst.
Also, an acid catalyst and a base catalyst can be used in combination. For example, after performing a condensation reaction of a silane compound in the presence of an acid catalyst, a basic catalyst may be added to the reaction solution to make it basic, and the condensation reaction may be further performed under basic conditions.
Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, acetic acid, and trifluoroacetic acid; It is done.

  Examples of the base catalyst include ammonia (water), trimethylamine, triethylamine, lithium diisopropylamide, lithium bis (trimethylsilyl) amide, pyridine, 1,8-diazabicyclo [5.4.0] -7-undecene, aniline, picoline, 1, Organic bases such as 4-diazabicyclo [2.2.2] octane and imidazole; organic salt hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium t Metal alkoxides such as butoxide; metal hydrides such as sodium hydride and calcium hydride; metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide; gold such as sodium carbonate, potassium carbonate and magnesium carbonate Carbonates; and the like are; sodium bicarbonate, metal bicarbonates such as potassium bicarbonate.

  The usage-amount of a catalyst is 0.1 mol%-10 mol% normally with respect to the total molar amount of a silane compound, Preferably it is the range of 1 mol%-5 mol%.

  When a solvent is used, it can be appropriately selected according to the type of silane compound. For example, water; aromatic hydrocarbons such as benzene, toluene and xylene; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate and methyl propionate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone And alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, s-butyl alcohol, t-butyl alcohol; These solvents can be used alone or in combination of two or more.

  The amount of the solvent used is 0.1 to 10 liters, preferably 0.1 to 2 liters per mol of the total molar amount of the silane compound.

  The temperature at which the silane compound is condensed (reacted) is usually in the temperature range from 0 ° C. to the boiling point of the solvent used, preferably in the range of 20 ° C. to 100 ° C. If the reaction temperature is too low, the progress of the condensation reaction may be insufficient. On the other hand, if the reaction temperature is too high, it is difficult to suppress gelation. The reaction is usually completed in 30 minutes to 20 hours.

  After completion of the reaction, when an acid catalyst is used, an alkaline aqueous solution such as sodium hydrogen carbonate is added to the reaction solution. When a base catalyst is used, the reaction solution is added with an acid such as hydrochloric acid. The target silane compound polymer can be obtained by performing summation and removing the salt produced by filtration or washing with water.

When the silane compound polymer (A) is produced by the above method, the portion of the silane compound (1) that is not dehydrated and / or dealcoholized in the OR ² or X ¹ is in the silane compound polymer (A). Remain. That is, when the remaining OR ² or X ¹ is 1, in the formula (a), (CHR ¹ X ⁰ -D-SiZO _2/2 ) remains, and the remaining OR ² or X ¹ is 2 In the formula (a), it remains as (CHR ¹ X ⁰ -D-SiZ ₂ O _1/2 ).

The silane compound polymer (A) may be a homopolymer (R ¹ is a type of polymer) or a copolymer (R ¹ is a polymer of two or more types).
When the silane compound polymer (A) is a copolymer, the silane compound polymer (A) is any copolymer such as a random copolymer, a block copolymer, a graft copolymer, and an alternating copolymer. However, a random copolymer is preferable from the viewpoint of ease of production and the like.
The structure of the silane compound polymer (A) may be any of a ladder structure, a double decker structure, a cage structure, a partially cleaved cage structure, a cyclic structure, and a random structure.

The mass average molecular weight (Mw) of the silane compound polymer (A) is usually in the range of 800 to 50,000, preferably 3,000 to 30,000, more preferably 5,000 to 15,000. By being in the said range, the hardened | cured material which is excellent in the handleability of a composition, and excellent in adhesiveness and heat resistance is obtained.
The mass average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, as standard polystyrene conversion values by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent (the same applies below). .)

  The molecular weight distribution (Mw / Mn) of the silane compound polymer (A) is not particularly limited, but is usually 1.0 to 10.0, preferably 1.1 to 6.0. By being in the said range, the hardened | cured material which is excellent in adhesiveness and heat resistance is obtained.

  A silane compound polymer (A) can be used individually by 1 type or in combination of 2 or more types.

(B) component The curable composition of this invention contains the microparticles | fine-particles whose average primary particle diameter exceeds 0.04 micrometer and is 8 micrometers or less as (B) component.
The fine particles are not particularly limited, and may be fine particles made of an inorganic material or fine particles made of an organic material. The constituents of fine particles made of inorganic materials include metals; metal oxides; minerals; metal carbonates such as calcium carbonate and magnesium carbonate; metal sulfates such as calcium sulfate and barium sulfate; metal hydroxides such as aluminum hydroxide; Examples thereof include metal silicates such as aluminum silicate, calcium silicate and magnesium silicate; silica; silicone; metal oxide whose surface is coated with silicone; Examples of the constituent component of the fine particles made of an organic material include acrylic beads.
Two or more kinds of these fine particles may be used in combination.

  Here, the metal refers to Group 1 (excluding H), Group 2-11, Group 12 (excluding Hg), Group 13 (excluding B), Group 14 (excluding C and Si) in the periodic table, An element belonging to Group 15 (excluding N, P, As and Sb) or Group 16 (excluding O, S, Se, Te and Po).

Silica may be any of dry silica, wet silica, and organically modified silica, and may be a mixture of two or more of these.
Silicone means an artificial polymer compound having a main skeleton with a siloxane bond. For example, dimethyl polysiloxane, diphenyl polysiloxane, methylphenyl polysiloxane and the like can be mentioned.

  Examples of the metal oxide include titanium oxide, alumina, boehmite, chromium oxide, nickel oxide, copper oxide, titanium oxide, zirconium oxide, indium oxide, zinc oxide, and composite oxides thereof. The metal oxide fine particles include sol particles composed of these metal oxides.

Examples of minerals include smectite and bentonite.
Examples of the smectite include montmorillonite, beidellite, hectorite, saponite, stevensite, nontronite, and soconite.

  Among these, in the present invention, since the object of the present invention is easily expressed, silica, silicone, or metal oxide fine particles whose surface is coated with silicone is preferable, and silica and silicone are more preferable.

  The shape of the fine particles may be any of a spherical shape, a chain shape, a needle shape, a plate shape, a piece shape, a rod shape, a fiber shape, and the like, but a spherical shape is preferable. Here, the spherical shape means a substantially spherical shape including a polyhedron shape that can be approximated to a spherical shape, a spheroidal shape, an oval shape, a confetti shape, an eyebrow shape, and the like.

The average primary particle diameter of the fine particles is more than 0.04 μm and not more than 8 μm. When it is larger than 0.04 μm, the effect of adding fine particles can be obtained. The dispersibility of the curable composition obtained as it is 8 micrometers or less becomes a favorable thing.
The average primary particle diameter is more preferably 0.06 to 7 μm, further preferably 0.3 to 6 μm, and particularly preferably 1 to 4 μm from the viewpoint of achieving both peel resistance and dispersibility.
In the present invention, the average primary particle size is determined by measuring the particle size distribution by a laser scattering method using a laser diffraction / scattering particle size distribution measuring device (for example, product name “LA-920” manufactured by Horiba, Ltd.). Says what is required.

  The amount of component (B) used is usually such that the proportion of component (A) and component (B) used is the mass ratio of component (A) to component (B) (component (A): component (B)). The amount is 100: 0.3 to 100: 20, preferably 100: 0.5 to 100: 15, and more preferably 100: 0.8 to 100: 12. When the amount of the component (B) used is less than the above range, it is difficult to obtain the intended peeling resistance effect, and when it is more than the above range, the adhesive strength decreases, which is not preferable.

(C) Component The curable composition of this invention contains the silane coupling agent which has a nitrogen atom in a molecule | numerator (henceforth a "silane coupling agent (C)") as (C) component. .

  The silane coupling agent (C) is not particularly limited as long as it is a silane coupling agent having a nitrogen atom in the molecule. Examples thereof include trialkoxysilane compounds represented by the following formula (c-1), dialkoxyalkylsilane compounds or dialkoxyarylsilane compounds represented by the formula (c-2), and the like.

In the above formula, R ^a represents an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, or a t-butoxy group. A plurality of R ^a may be the same or different.
R ^b represents an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or a t-butyl group; or a phenyl group, a 4-chlorophenyl group, a 4- An aryl group having a substituent or not having a substituent, such as a methylphenyl group;

R ^c represents a ^C 1-10 organic group having a nitrogen atom. R ^c may further be bonded to a group containing another silicon atom.
Specific examples of the organic group having 1 to 10 carbon atoms of R ^c include N-2- (aminoethyl) -3-aminopropyl group, 3-aminopropyl group, N- (1,3-dimethyl-butylidene) amino. A propyl group, 3-ureidopropyltriethoxysilane, N-phenyl-aminopropyl group, etc. are mentioned.

Among the compounds represented by the formula (c-1) or (c-2), the compound in the case where R ^c is an organic group bonded to another group containing a silicon atom includes an isocyanurate skeleton. And an isocyanurate-based silane coupling agent bonded to another silicon atom, and an urea-based silane coupling agent bonded to another silicon atom via a urea skeleton.

Among these, as the silane coupling agent (C), an isocyanurate-based silane coupling agent and a urea-based silane coupling agent are preferable from the viewpoint of obtaining a cured product having higher adhesive force. Further, those having 4 or more alkoxy groups bonded to silicon atoms are preferred.
Having 4 or more alkoxy groups bonded to silicon atoms means that the total count of alkoxy groups bonded to the same silicon atom and alkoxy groups bonded to different silicon atoms is 4 or more.

  The isocyanurate-based silane coupling agent having 4 or more alkoxy groups bonded to silicon atoms is a urea-based silane cup in which the compound represented by the following formula (c-3) has 4 or more alkoxy groups bonded to silicon atoms. Examples of the ring agent include compounds represented by the following formula (c-4).

Wherein, R ^a are as defined above.
t1 to t5 each independently represents an integer of 1 to 10, preferably an integer of 1 to 6, and particularly preferably 3.

Specific examples of the compound represented by the formula (c-3) include 1,3,5-N-tris (3-trimethoxysilylpropyl) isocyanurate, 1,3,5, -N-tris (3- Triethoxysilylpropyl) isocyanurate, 1,3,5, -N-tris (3-trii-propoxysilylpropyl) isocyanurate, 1,3,5, -N-tris (3-tributoxysilylpropyl) isocyanate 1,3,5-N-tris [(tri (C1-6) alkoxy) silyl (C1-10) alkyl] isocyanurate such as nurate;
1,3,5, -N-tris (3-ditoxymethylsilylpropyl) isocyanurate, 1,3,5, N-tris (3-dimethoxyethylsilylpropyl) isocyanurate, 1,3,5,- N-tris (3-dimethoxy i-propylsilylpropyl) isocyanurate, 1,3,5, -N-tris (3-dimethoxy n-propylsilylpropyl) isocyanurate, 1,3,5, -N-tris ( 3-dimethoxyphenylsilylpropyl) isocyanurate, 1,3,5, -N-tris (3-diethoxymethylsilylpropyl) isocyanurate, 1,3,5, -N-tris (3-diethoxyethylsilylpropyl) ) Isocyanurate, 1,3,5, -N-tris (3-diethoxy i-propylsilylpropyl) isocyanurate, 1,3 , -N-tris (3-diethoxyn-propylsilylpropyl) isocyanurate, 1,3,5, -N-tris (3-diethoxyphenylsilylpropyl) isocyanurate, 1,3,5, -N-tris (3-dii-propoxymethylsilylpropyl) isocyanurate, 1,3,5, -N-tris (3-dii-propoxyethylsilylpropyl) isocyanurate, 1,3,5, -N-tris (3 -Di-propoxy i-propylsilylpropyl) isocyanurate, 1,3,5, -N-tris (3-dii-propoxy n-propylsilylpropyl) isocyanurate, 1,3,5, -N-tris (3-Dii-propoxyphenylsilylpropyl) isocyanurate, 1,3,5, -N-tris (3-dibutoxymethylsilylpropyl) Sosocyanurate, 1,3,5, -N-tris (3-dibutoxyethylsilylpropyl) isocyanurate, 1,3,5, -N-tris (3-dibutoxy i-propylsilylpropyl) isocyanurate, 1,3 1,3,5-N such as 1,5, -N-tris (3-dibutoxy n-propylsilylpropyl) isocyanurate, 1,3,5, -N-tris (3-dibutoxyphenylsilylpropyl) isocyanurate -Tris [(di (C1-6) alkoxy) silyl (C1-10) alkyl] isocyanurate;

Specific examples of the compound represented by the formula (c-4) include N, N′-bis (3-trimethoxysilylpropyl) urea, N, N′-bis (3-triethoxysilylpropyl) urea, N N, N′-bis (3-tripropoxysilylpropyl) urea, N, N′-bis (3-tributoxysilylpropyl) urea, N, N′-bis (2-trimethoxysilylethyl) urea, N′-bis [(tri (C1-6) alkoxysilyl) (C1-10) alkyl] urea;
N, N′-bis (3-dimethoxymethylsilylpropyl) urea, N, N′-bis (3-dimethoxyethylsilylpropyl) urea, N, N′-bis (3-diethoxymethylsilylpropyl) urea, etc. N, N′-bis [(di (C1-6) alkoxy (C1-6) alkylsilyl (C1-10) alkyl) urea;
N, N′-bis [(di (C 1-6)) such as N, N′-bis (3-dimethoxyphenylsilylpropyl) urea, N, N′-bis (3-diethoxyphenylsilylpropyl) urea Alkoxy (6 to 20 carbon atoms) arylsilyl (1 to 10 carbon atoms) alkyl) urea; and the like.

These can be used alone or in combination of two or more.
Among these, as component (C) of the present invention, 1,3,5-N-tris (3-trimethoxysilylpropyl) isocyanurate, 1,3,5-N-tris (3-triethoxysilylpropyl) ) Isocyanurate (hereinafter referred to as “isocyanurate compound”), N, N′-bis (3-trimethoxysilylpropyl) urea, N, N′-bis (3-triethoxysilylpropyl) urea (hereinafter referred to as “ It is preferable to use a combination of an isocyanurate compound and a urea compound.

  When the isocyanurate compound and the urea compound are used in combination, the use ratio of both is preferably 100: 1 to 100: 200 in terms of mass ratio of (isocyanurate compound) and (urea compound).

In addition, it is preferable that it is 35 mass parts or less with respect to 100 mass parts of said (A) component, and, as for the usage-amount of an isocyanurate compound, it is more preferable that it is 25 mass parts or less. The same applies when the isocyanurate compound is used alone or in combination with the urea compound.
Moreover, it is preferable that it is 20 mass parts or less with respect to 100 mass parts of said (A) component, and, as for the usage-amount of a urea compound, it is more preferable that it is 15 mass parts or less. The same applies when the urea compound is used alone or in combination with the isocyanurate compound.

In the curable composition of the present invention, the component (A) and the component (C) are mixed at a mass ratio of the component (A) to the component (C) (component (A): component (C)) 100: 0. It is preferable to contain in the ratio of 3-100: 40, It is more preferable to contain in the ratio of 100: 1-100: 30, It is further more preferable to contain in the ratio of 100: 3-100: 25.
By using the component (A) and the component (C) at such a ratio, it is possible to obtain a curable composition from which a cured product having excellent heat resistance and high adhesive strength can be obtained.

(D) Component In the curable composition of the present invention, as the component (D), a silane coupling agent having an acid anhydride structure in the molecule (hereinafter sometimes referred to as “silane coupling agent (D)”). including.

The silane coupling agent (D) is an organosilicon compound having both a group (Q) having an acid anhydride structure and a hydrolyzable group (R ^e ) in one molecule. Specifically, it is a compound represented by the following formula (d).

In the formula, Q represents an acid anhydride structure, R ^d represents an alkyl group having 1 to 6 carbon atoms, or a phenyl group having or not having a substituent, and R ^e having 1 to 1 carbon atoms. 6 represents an alkoxy group or a halogen atom, i and k represent an integer of 1 to 3, j represents an integer of 0 to 2, and i + j + k = 4. When j is 2, R ^d may be the same or different. when k is 2 or 3, among a plurality of R ^e may be different from each be the same. When i is 2 or 3, a plurality of Qs may be the same or different.
Q is the following formula

(Wherein, h represents an integer of 0 to 10) and the like, and the group represented by (Q1) is particularly preferable.
In formula (d), examples of the alkoxy group having 1 to 6 carbon atoms represented by R ^e include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a t-butoxy group.
Examples of the halogen atom include a chlorine atom and a bromine atom.

Examples of the alkyl group having 1 to 6 carbon atoms of R ^d include the same groups as those exemplified as the alkyl group having 1 to 6 carbon atoms represented by R ^1. Examples of the phenyl group that does not include the same groups as those exemplified for R ² above.
Especially, as a compound represented by Formula (d), following formula (d-1)

(In the formula, R ^e , h, i, j, and k represent the same meaning as described above.)
The compound represented by these is preferable. In the formula, h is preferably 2 to 8, more preferably 2 or 3, and particularly preferably 3.

Specific examples of the silane coupling agent represented by the formula (d-1) include 2- (trimethoxysilyl) ethyl succinic anhydride, 2- (triethoxysilyl) ethyl succinic anhydride, 3- (trimethoxy Tri (carbon number 1-6) alkoxysilyl (carbon number 2-8) alkyl succinic anhydrides such as (silyl) propyl succinic anhydride, 3- (triethoxysilyl) propyl succinic anhydride;
Di (C 1-6) alkoxymethylsilyl (C 2-8) alkyl succinic anhydride, such as 2- (dimethoxymethylsilyl) ethyl succinic anhydride;
(C1-C6) alkoxydimethylsilyl (C2-C8) alkyl succinic anhydride, such as 2- (methoxydimethylsilyl) ethyl succinic anhydride;

Trihalogenosilyl (2-8 carbon atoms) alkyl succinic anhydride, such as 2- (trichlorosilyl) ethyl succinic anhydride, 2- (tribromosilyl) ethyl succinic anhydride;
Dihalogenomethylsilyl (2 to 8 carbon atoms) alkyl succinic anhydride, such as 2- (dichloromethylsilyl) ethyl succinic anhydride;
And halogenodimethylsilyl (2 to 8 carbon atoms) alkyl succinic anhydrides such as 2- (chlorodimethylsilyl) ethyl succinic anhydride.

Among these, tri (carbon number 1-6) alkoxysilyl (carbon number 2-8) alkyl succinic anhydride is preferable, 3- (trimethoxysilyl) propyl succinic anhydride, 3- (triethoxysilyl) propyl succinic anhydride Acid is particularly preferred.
(D) A component can be used individually by 1 type or in combination of 2 or more types.

In the curable composition of the present invention, the component (A) and the component (D) are mixed at a mass ratio of the component (A) to the component (D) (component (A): component (D)) 100: 0. It is preferable to contain in the ratio of 01-100: 30, and it is more preferable to contain in the ratio of 100: 0.1-100: 10.
By using the component (A) and the component (D) at such a ratio, the cured product of the curable composition of the present invention has excellent heat resistance, adhesiveness, and peel resistance.

(E) Component The curable composition of the present invention may be referred to as a silane coupling agent having a sulfur atom-containing functional group in the molecule (hereinafter referred to as “silane coupling agent (E)”) as the component (E). .)including.

As the silane coupling agent (E), thiol group (—SH); acylthio group (—S—CO—R ′); sulfide group (—S—); disulfide group (—S—S—) are included in the molecule. There is no particular limitation as long as it is a silane coupling agent having a sulfur atom-containing functional group such as a polysulfide group such as a tetrasulfide group (—S—S—S—S—) [— (S) _n —];

  As the silane coupling agent (E), a silane coupling agent represented by any one of the following formulas (e-1) to (e-4), other silane coupling agents having a sulfur atom-containing functional group, these And the like.

[Wherein Y ¹ and Y ² each independently represent an alkoxy group having 1 to 10 carbon atoms, and A ¹ and A ² each independently represent a carbon having a substituent or no substituent. A divalent hydrocarbon group having 1 to 20 carbon atoms is represented, and R ′ represents a monovalent organic group having 1 to 20 carbon atoms. v represents an integer of 1 to 4. Y ¹ and Y ² may be the same as or different from each other. ]

Examples of the alkoxy group having 1 to 10 carbon atoms of Y ¹ and Y ² include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an s-butoxy group, an isobutoxy group, and a t-butoxy group. Etc.
Y ¹ and Y ² are more preferably an alkoxy group having 1 to 6 carbon atoms.

Of A ^{1, A 2,} having a substituent, or a divalent hydrocarbon group having 1 to 20 carbon atoms having no substituent, an alkylene group having 1 to 20 carbon atoms, alkenylene of 2 to 20 carbon atoms Group, C2-C20 alkynylene group, C6-C20 arylene group, C7-C20 divalent group comprising a combination of (alkylene group, alkenylene group, or alkynylene group) and arylene group, etc. Is mentioned.

Examples of the alkylene group having 1 to 20 carbon atoms include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.
Examples of the alkenylene group having 2 to 20 carbon atoms include vinylene group, propenylene group, butenylene group, pentenylene group and the like.
Examples of the alkynylene group having 2 to 20 carbon atoms include an ethynylene group and a propynylene group.
Examples of the arylene group having 6 to 20 carbon atoms include an o-phenylene group, an m-phenylene group, a p-phenylene group, and a 2,6-naphthylene group.

  Substituents which these alkylene groups having 1 to 20 carbon atoms, alkenylene groups having 2 to 20 carbon atoms, and alkynylene groups having 2 to 20 carbon atoms may have are halogen atoms such as fluorine atoms and chlorine atoms. An alkoxy group such as a methoxy group or an ethoxy group; an alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group;

Examples of the substituent of the arylene group having 6 to 20 carbon atoms include cyano group; nitro group; halogen atom such as fluorine atom, chlorine atom and bromine atom; alkyl group such as methyl group and ethyl group; methoxy group, ethoxy group and the like And the like.
These substituents may be bonded at arbitrary positions in groups such as an alkylene group, an alkenylene group, an alkynylene group, and an arylene group, and a plurality of them may be bonded in the same or different manner.

  As a divalent group consisting of a combination of a substituted or non-substituted group (alkylene group, alkenylene group or alkynylene group) and a substituted or non-substituted arylene group , At least one of the above-mentioned substituents or no substituents (an alkylene group, an alkenylene group, or an alkynylene group) and at least one of the arylene groups having the above-mentioned substituents or no substituents. Examples include groups bonded in series. Specific examples include groups represented by the following formula.

Among these, as A ¹ and A ² , an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group is preferable.

R ′ is not particularly limited as long as —CO—R ′ can function as a protecting group. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n -An alkyl group such as an octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, and an n-dodecyl group; a phenyl group having a substituent or not having a substituent; and the like.
Examples of the substituent of the phenyl group having a substituent of R ′ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n- And alkyl groups such as pentyl group and n-hexyl group; halogen atoms such as fluorine atom, chlorine atom and bromine atom; alkoxy groups such as methoxy group and ethoxy group;
R ′ is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms.
v represents an integer of 1 to 4, preferably 1, 2 or 4, more preferably 2 or 4.

  Examples of the silane coupling agent represented by the formula (e-1) include mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, mercaptomethyltripropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, Examples include mercaptoalkyltrialkoxysilanes such as 2-mercaptoethyltripropoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropyltripropoxysilane.

  Examples of the silane coupling agent represented by the formula (e-2) include 2-hexanoylthioethyltrimethoxysilane, 2-hexanoylthioethyltriethoxysilane, 2-octanoylthioethyltrimethoxysilane, and 2-octanoy. Ruthioethyltriethoxysilane, 2-decanoylthioethyltrimethoxysilane, 2-decanoylthioethyltriethoxysilane, 3-hexanoylthiopropyltrimethoxysilane, 3-hexanoylthiopropyltriethoxysilane, 3-octanoy Alkanoylthioalkyltrialkoxysilane compounds such as ruthiopropyltrimethoxysilane, 3-octanoylthiopropyltriethoxysilane, 3-decanoylthiopropyltrimethoxysilane, and 3-decanoylthiopropyltriethoxysilane It is.

  Examples of the silane coupling agent represented by the formula (e-3) include 2-trimethoxysilylethylsulfanyltrimethoxysilane, 2-trimethoxysilylethylsulfanyltriethoxysilane, 2-triethoxysilylethylsulfanyltrimethoxysilane, 2 -Triethoxysilylethylsulfanyltriethoxysilane, 3-trimethoxysilylpropylsulfanyltrimethoxysilane, 3-trimethoxysilylpropylsulfanyltriethoxysilane, 3-triethoxysilylpropylsulfanyltrimethoxysilane, 3-triethoxysilylpropylsulfanyl Examples include triethoxysilane.

  Examples of the silane coupling agent represented by the formula (e-4) include bis (2-trimethoxysilylethyl) disulfide, bis (2-triethoxysilylethyl) disulfide, bis (3-trimethoxysilylpropyl) disulfide, bis Disulfide compounds such as (3-triethoxysilylpropyl) disulfide, bis (4-trimethoxysilylbutyl) disulfide, bis (4-triethoxysilylbutyl) disulfide; bis (2-triethoxysilylethyl) tetrasulfide, bis ( And tetrasulfide compounds such as 3-trimethoxysilylpropyl) tetrasulfide and bis (3-triethoxysilylpropyl) tetrasulfide;

  Other silane coupling agents having a sulfur atom-containing functional group include 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, Thiocarbamoyl group-containing silane coupling agents such as 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide and 2-trimethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide; 3-trimethoxysilylpropyl Benzothiazolyl group-containing silane coupling agents such as benzothiazolyl tetrasulfide and 3-triethoxysilylpropylbenzothiazolyl tetrasulfide; 3-triethoxysilylpropyl (meth) acrylate monosulfur I de, 3-trimethoxysilylpropyl (meth) acrylate monosulfide, etc. (meth) acrylate group-containing silane coupling agent [ "(meth) acrylate" means acrylate or methacrylate. ]; Polysulfide group-containing silane coupling agents such as bis (3-triethoxysilylpropyl) polysulfide, bis (2-triethoxysilylpropyl) polysulfide, and bis (4-triethoxysilylbutyl) polysulfide;

  Oligomers are partial hydrolysis products of these compounds and have a molecular weight of usually 300-3000.

Among these, as the component (E), a silane coupling agent represented by the formula (e-1) or the formula (e-3) and an oligomer thereof are preferable, and 2-mercaptoethyltrimethoxysilane, 2- Y ^{1 in} formula (e-1) such as mercaptoethyltriethoxysilane, 2-mercaptoethyltripropoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltripropoxysilane, and the like. A silane coupling agent in which is an alkoxy group having 1 to 10 carbon atoms; 2-trimethoxysilylethylsulfanyltrimethoxysilane, 2-trimethoxysilylethylsulfanyltriethoxysilane, 2-triethoxysilylethylsulfanyltrimethethoxysilane, 2 -Triethoxy Rylethylsulfanyltriethoxysilane, 3-trimethoxysilylpropylsulfanyltrimethoxysilane, 3-trimethoxysilylpropylsulfanyltriethoxysilane, 3-triethoxysilylpropylsulfanyltrimethoxysilane, 3-triethoxysilylpropylsulfanyltriethoxysilane A silane coupling agent in which Y ¹ and Y ² are an alkoxy group having 1 to 10 carbon atoms in the formula (e-3); and oligomers thereof are more preferable, 3-mercaptopropyltrimethoxysilane, 3 -Trimethoxysilylpropylsulfanyltriethoxysilane and oligomers thereof are more preferred.
A silane coupling agent (E) can be used individually by 1 type or in combination of 2 or more types.

  The amount of component (E) used is preferably the mercapto equivalent [the number of moles of mercapto group per 1 g of curable composition (or the number of moles converted to mercapto group, the same applies hereinafter)]. 0.001 to 1.00 mmol / g, more preferably 0.005 to 0.80 mmol / g, and particularly preferably 0.015 to 0.60 mmol / g. The mercapto equivalent can be measured and determined by a known method.

The content ratio (mass ratio) of the (A) component and the (E) component is [(A) component]: [(E) component] = 100: 0.1 to 100: 50, preferably 100: 0.3. It is -100: 30, Especially preferably, it is 100: 0.4-100: 25.
The hardened | cured material of the curable composition containing (A) component and (E) component in such a ratio becomes excellent in peeling resistance and heat resistance, and has high adhesive force. When the content ratio of the component (E) is less than the above range, the object of the present invention cannot be achieved, and when it is large, the obtained cured product may be colored and the adhesive strength at high temperature may be lowered.

  In this invention, it is preferable that the sum total of the mass of said (A) component-(E) component is 60 mass% or more of all the compositions, and it is more preferable that it is 70 mass% or more.

(F) Diluent The curable composition of the present invention preferably further contains a diluent for the purpose of imparting fluidity.
As the diluent, for example, diethylene glycol monobutyl ether acetate, glycerin diglycidyl ether, butanediol diglycidyl ether, diglycidyl aniline, neopentyl glycol glycidyl ether, cyclohexane dimethanol diglycidyl ether, alkylene diglycidyl ether, polyglycol diglycidyl ether , Polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, 4-vinylcyclohexene monooxide, vinylcyclohexene dioxide, methylated vinylcyclohexene dioxide, and the like.
These diluents can be used alone or in combination of two or more.
The amount of the diluent used is preferably such that the solid content concentration of the curable composition of the present invention is 50 to 100% by mass, more preferably 60 to 90% by mass, and 70 to 85% by mass. Is more preferable.
Moreover, when the curable composition of this invention contains a diluent, the total amount of (A) component, (B) component, (C) component, (D) component, and (E) component is curable composition. It is preferable that it is 50-100 mass% with respect to the whole component except the diluent of a thing, and it is more preferable that it is 60-100 mass%. The total amount of the component (A), the component (B), the component (C), the component (D), and the component (E) is within the above range, so that the curable composition of the present invention has heat resistance and Excellent adhesion.

(G) Other components The curable composition of the present invention may further contain other components in the above-described component within a range not impairing the object of the present invention.
Examples of other components include an antioxidant, an ultraviolet absorber, and a light stabilizer.

  Antioxidants are added to prevent oxidative degradation during heating. Examples of the antioxidant include phosphorus antioxidants, phenolic antioxidants, sulfur antioxidants and the like.

  Examples of phosphorus antioxidants include phosphites and oxaphosphaphenanthrene oxides. Examples of phenolic antioxidants include monophenols, bisphenols, and high-molecular phenols. Examples of the sulfur-based antioxidant include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, and the like.

  These antioxidants can be used alone or in combination of two or more. The usage-amount of antioxidant is 10 mass% or less normally with respect to (A) component.

The ultraviolet absorber is added for the purpose of improving the light resistance of the resulting cured product.
Examples of the ultraviolet absorber include salicylic acids, benzophenones, benzotriazoles, hindered amines and the like.
An ultraviolet absorber can be used individually by 1 type or in combination of 2 or more types.
The usage-amount of a ultraviolet absorber is 10 mass% or less normally with respect to (A) component.

The light stabilizer is added for the purpose of improving the light resistance of the resulting cured product.
Examples of the light stabilizer include poly [{6- (1,1,3,3, -tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6 , 6-tetramethyl-4-piperidine) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidine) imino}] and the like.
These light stabilizers can be used alone or in combination of two or more.
The total amount of these other components (excluding the diluent) is usually 20% by mass or less based on the component (A).

  In the curable composition of the present invention, for example, the components (A) to (E) and, if desired, the components (F) and (G) are blended at a predetermined ratio, and mixed and defoamed by a known method. Can be obtained.

According to the curable composition of the present invention obtained as described above, a cured product having excellent peel resistance and heat resistance and high adhesive strength can be obtained.
Therefore, the curable composition of the present invention is suitably used as a raw material for optical parts and molded articles, an adhesive, a coating agent, and the like. In particular, since the problem relating to deterioration of the optical element fixing material accompanying the increase in luminance of the optical element can be solved, the curable composition of the present invention can be suitably used as an optical element fixing composition. .

2) Cured product The second of the present invention is a cured product obtained by curing the curable composition of the present invention.
Heat curing is mentioned as a method of hardening the curable composition of this invention. The heating temperature for curing is usually 100 to 200 ° C., and the heating time is usually 10 minutes to 20 hours, preferably 30 minutes to 10 hours.

The hardened | cured material of this invention has high adhesive force, and is excellent in peeling resistance and heat resistance.
Therefore, the hardened | cured material of this invention can solve the problem regarding deterioration accompanying the increase in the brightness of an optical element, and can be used suitably as an optical element fixing material. For example, it is suitably used as a raw material for optical parts and molded articles, an adhesive, a coating agent, and the like.

It can be confirmed as follows, for example, that the cured product obtained by heating the curable composition of the present invention is excellent in peel resistance.
After applying the curable composition to the LED lead frame, the sapphire chip is pressure-bonded and cured by heat treatment at 170 ° C. for 2 hours, and then the sealing material is poured into the cup and heated at 150 ° C. for 1 hour. Process to obtain a cured specimen. This test piece was exposed to an environment of 85 ° C. and 85% RH for 168 hours, then pre-heated at 160 ° C. and treated by IR reflow with a maximum temperature of 260 ° C. for 1 minute, and then a heat cycle tester The test is allowed to stand at −40 ° C. and + 100 ° C. for 30 minutes, and one cycle is performed for 300 cycles. Thereafter, the sealing material is removed, and it is examined whether or not the elements are peeled off together. In the cured product of the present invention, the probability of peeling is usually 45% or less, more preferably 25% or less.

It can be confirmed that the cured product obtained by curing the curable composition of the present invention has a high adhesive force, for example, by measuring the adhesive force as follows. That is, the curable composition is applied to the mirror surface of the silicon chip, the application surface is placed on the adherend,
Crimp and heat treat to cure. This is left for 30 seconds on a measurement stage of a bond tester that has been heated to a predetermined temperature (for example, 23 ° C., 100 ° C.) in advance, and is horizontal (sheared) with respect to the adhesive surface from a position 50 μm high from the adherend. Direction) and measure the adhesive force between the test piece and the adherend.
The adhesive strength of the cured product is preferably 60 N / 2 mm □ or more at 23 ° C., more preferably 80 N / 2 mm □ or more, and particularly preferably 100 N / 2 mm □ or more. The adhesive strength of the cured product is preferably 40 N / 2 mm □ or more at 100 ° C., more preferably 50 N / 2 mm □ or more, and particularly preferably 60 N / 2 mm □ or more.

3) Method of using curable composition The third aspect of the present invention is a method of using the curable composition of the present invention as a composition for an optical element fixing material such as an optical element adhesive or an optical element sealing material. It is.
Examples of optical elements include light emitting elements such as LEDs and LDs, light receiving elements, composite optical elements, and optical integrated circuits.

<Adhesive for optical elements>
The curable composition of this invention can be used conveniently as an adhesive agent for optical elements.
As a method of using the curable composition of the present invention as an adhesive for optical elements, the composition is applied to one or both adhesive surfaces of a material to be bonded (such as an optical element and its substrate), followed by pressure bonding. Then, the method of making it heat-cure and adhere | attach the materials made into the object of adhesion | attachment firmly is mentioned.

  Main substrate materials for bonding optical elements include glass such as soda lime glass and heat-resistant hard glass; ceramics; sapphire; iron, copper, aluminum, gold, silver, platinum, chromium, titanium, and these metals Metals such as stainless steel (SUS302, SUS304, SUS304L, SUS309, etc.); polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyether Synthetic resins such as ether ketone, polyether sulfone, polyphenylene sulfide, polyether imide, polyimide, polyamide, acrylic resin, norbornene resin, cycloolefin resin, glass epoxy resin, etc. And the like.

  The heating temperature at the time of heat curing is usually 100 to 200 ° C., although it depends on the curable composition used. The heating time is usually 10 minutes to 20 hours, preferably 30 minutes to 10 hours.

<Encapsulant for optical element>
The curable composition of this invention can be used suitably as a sealing material of an optical element sealing body.
As a method of using the curable composition of the present invention as an encapsulant for optical elements, for example, the composition is molded into a desired shape to obtain a molded body containing the optical element, and then heated. The method etc. which manufacture an optical element sealing body by making it harden | cure are mentioned.
The method for molding the curable composition of the present invention into a desired shape is not particularly limited, and a known molding method such as a normal transfer molding method or a casting method can be employed.

  Although the heating temperature at the time of heat-curing depends on the curable composition to be used, it is usually 100 to 200 ° C. The heating time is usually 10 minutes to 20 hours, preferably 30 minutes to 10 hours.

  Since the obtained optical element sealing body uses the curable composition of the present invention, it has excellent peel resistance and heat resistance, and has high adhesive strength.

4) Optical device A fourth aspect of the present invention is an optical device using the curable composition of the present invention as an adhesive for optical element fixing materials or a sealing material for optical element fixing materials.
Examples of optical elements include light emitting elements such as LEDs and LDs, light receiving elements, composite optical elements, and optical integrated circuits.
The optical device of the present invention is obtained by fixing the optical element using the curable composition of the present invention as an adhesive or sealing material for fixing the optical element. For this reason, the optical element is fixed with a high adhesive force and has excellent durability.

  EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to the following Example. Unless otherwise specified, “%” and “parts” are based on mass.

(Mass average molecular weight measurement)
The mass average molecular weight (Mw) and number average molecular weight (Mn) of the silane compound polymer obtained in the following production examples were standard polystyrene equivalent values, and were measured using the following apparatus and conditions.
Device name: HLC-8220GPC, manufactured by Tosoh Corporation Column: TSKgelGMHXL, TSKgelGMMHXL, and TSKgel2000HXL sequentially connected Solvent: Tetrahydrofuran Injection volume: 80 μl
Measurement temperature: 40 ° C
Flow rate: 1 ml / min Detector: Differential refractometer

(Measurement of IR spectrum)
The IR spectrum of the silane compound polymer obtained in the production example was measured using a Fourier transform infrared spectrophotometer (Spectrum 100, manufactured by Perkin Elmer).

(Production Example 1)
After charging 71.37 g (400 mmol) of methyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBE-13) in a 300 ml eggplant-shaped flask, 0.10 g of 35% hydrochloric acid (silane) was added to 21.6 ml of distilled water. An aqueous solution in which 0.25 mol% of the total amount of the compound was dissolved was added with stirring. The whole volume was stirred at 30 ° C. for 2 hours, then heated to 70 ° C. and stirred for 5 hours, and then 140 g of propyl acetate was added. The mixture was stirred. To this, 0.12 g of 28% ammonia water (0.5 mol% based on the total amount of silane compounds) was added with stirring, and the whole volume was heated to 70 ° C. and further stirred for 3 hours. Purified water was added to the reaction solution, liquid separation was performed, and this operation was repeated until the pH of the aqueous layer became 7. The organic layer was concentrated with an evaporator, and the concentrate was vacuum-dried to obtain 55.7 g of a silane compound polymer (A1). The weight average molecular weight of this _{(M W)} is 7800, the molecular weight distribution (PDI) was 4.52.
IR spectrum data of the silane compound polymer (A1) are shown below.
Si—CH ₃ : 1272 cm ⁻¹ , 1409 cm ⁻¹ , Si—O: 1132 cm ⁻¹

Example 1
To 100 parts (parts by mass, the same shall apply hereinafter) of the silane compound polymer (A1) obtained in Production Example 1,
As the component (B), 3 parts of silicone fine particles having an average primary particle diameter of 0.8 μm (manufactured by Nikko Rica Corporation: MSP-SN08, referred to as “(B2)” in Table 1 below),
As component (C), 10 parts of 1,3,5-N-tris [3- (trimethoxysilyl) propyl] isocyanurate (referred to as “(C1)” in Table 1 below),
As the component (D), 1 part of 3- (trimethoxysilyl) propyl succinic anhydride (referred to as “(D1)” in Table 1 below),
As component (E), 0.5 part of 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-803, in Table 1 below, referred to as “(E1)”), and
Diethylenecricol monobutyl ether acetate was added so that the solid content was 80%, and the entire volume was thoroughly mixed and defoamed to obtain curable composition 1.

(Examples 2-27, Comparative Examples 1-4)
In Example 1, the type of component (B), the amount used (part), the amount used (C), the amount used (D) of component (part), the type of component (E), the amount used (part) are shown in Table 1 below. The curable compositions 2 to 27 of Examples 2 to 27 and the curable compositions 1r to 4r of Comparative Examples 1 to 4 were obtained in the same manner as in Example 1 except that the curable compositions 1 to 4r of Comparative Examples 1 to 4 were obtained.
In the following table, types of component (B): B1 to B4, B9, types of component (E): E1 to E3 represent the following.

B1: Silicone fine particles (average primary particle size: 0.5 μm), manufactured by Nikko Rica Co., Ltd., MSP-SN05
B2: Silicone fine particles (average primary particle size: 0.8 μm), manufactured by Nikko Rica Co., Ltd., MSP-SN08
B3: Silicone fine particles (average primary particle size: 2 μm), Momentive Performance Mate Reals Japan GK, Tospearl 120
B4: Silicone fine particles (average primary particle size: 4.5 μm), manufactured by Momentive Performance Materials Japan, Tospearl 145
B9: Silica-based fine particles (average primary particle size: 0.07 μm), manufactured by Tokuyama Corporation, Silfil NSS-5N

E1: 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-803, mercapto equivalent (number of moles of mercapto group per 1 g of E1): 5.10 mmol / g)
E2: 3-trimethoxysilylpropylsulfanyltriethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., X-12-1056ES, mercapto equivalent (number of moles of mercapto group per 1 g of E2): 2.79 mmol / g]
E3: oligomer [molecular weight: 700, manufactured by Shin-Etsu Chemical Co., Ltd., X-41-1810, mercapto equivalent (number of moles of mercapto group per 1 g of E3): 2.22 mmol / g]

For the cured products of the curable compositions 1-27 and 1r-4r obtained in Examples 1-27 and Comparative Examples 1-4, the adhesive strength was measured and the peel resistance was evaluated as follows. .
The measurement results and evaluation are shown in Table 1 below.

(Measurement of adhesive strength)
Each of the curable compositions 1-27, 1r-4r is applied to a mirror surface of a 2 mm square silicon chip so that the thickness is about 2 μm, and the coated surface is placed on an adherend (silver-plated copper plate). Placed and crimped. Then, it heat-processed at 170 degreeC for 2 hours, it was made to harden | cure, and the adherend with a test piece was obtained. The test piece-attached adherend is left for 30 seconds on a measurement stage of a bond tester (series 4000, manufactured by Daisy) heated in advance to a predetermined temperature (23 ° C., 100 ° C.), and has a height of 50 μm from the adherend. From the position, stress was applied in a horizontal direction (shear direction) to the bonding surface at a speed of 200 μm / s, and the bonding strength (N / 2 mm □) between the test piece and the adherend at 23 ° C. and 100 ° C. was measured. .

(Peel resistance test)
On the LED lead frame (Enomoto, product name: 5050 D / G PKG LEADFRAME), the curable compositions 1-27 and 1r-4r are applied to about 0.4 mmφ, and then a 0.5 mm square sapphire chip is applied. Crimped. Then, after curing by heat treatment at 170 ° C. for 2 hours, a sealing material (manufactured by Shin-Etsu Chemical Co., Ltd., product name: EG6301) is poured into the cup, and heat treatment is performed at 150 ° C. for 1 hour to obtain a test piece. It was.
This test piece is exposed to an environment of 85 ° C. and 85% RH for 168 hours, and then subjected to IR reflow (reflow furnace: manufactured by Sagami Riko Co., Ltd., product name “ WL-15-20DNX type "). Thereafter, 300 cycles were carried out, with one cycle being a test that was allowed to stand at −40 ° C. and + 100 ° C. for 30 minutes each in a thermal cycle tester. Then, operation which removes a sealing material was performed, and it was investigated whether the element peeled together in that case. This test was performed 12 times for each curable composition.
In Table 1 below, the number of times the elements are peeled off is counted. If the peeling occurrence rate is 25% or less, “A”, if it is greater than 25% and less than 50%, “B”, if greater than 50%, “C”. "
In the following table, the right column of (E) indicates the mercapto equivalent (number of moles of mercapto group per 1 g of curable composition) (mmol / g) with respect to the curable composition.

It can be seen from Table 1 that all of the cured products of the curable compositions 1 to 27 of Examples 1 to 27 have an evaluation of peel resistance of A and are excellent in peel resistance. Also, the adhesive strength is all 122 N / 2 mm □ or more at 23 ° C. and 77 N / 2 mm □ or more at 100 ° C., indicating that the adhesive strength and heat resistance are also excellent.
On the other hand, the cured products 1r to 4r of the curable compositions of Comparative Examples 1 to 4 all have a peel resistance evaluation of C, indicating that the peel resistance is poor. The adhesive strength is 98 N / 2 mm □ or less at 23 ° C. and 34 N / 2 mm □ or less at 100 ° C., indicating that the adhesive strength and heat resistance are poor.

Claims (12)

A curable composition having the following components (A) to (E), wherein the component (A) and the component (B) are mixed in a mass ratio of the component (A) and the component (B) [(A) component : (B) component] = 100: 0.3 to 100: 20, and the component (A) and the component (C) are mixed in a mass ratio of the component (A) and the component (C). A) component: (C) component] = 100: 0.3 to 100: 40 in a ratio of (A) component and (D) component in a mass ratio of (A) component and (D) component. , [(A) component: (D) component] = 100: 0.01 to 100: 30, the (A) component and the (E) component are combined into the (A) component and the (E) component. A curable composition, which is contained in a mass ratio of [(A) component: (E) component] = 100: 0.1 to 100: 50 .
(A) The following formula (a)

(In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms. A plurality of R ¹ may be the same or different. Z is a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms. Or represents a halogen atom, s represents a positive integer, and t and u each independently represents 0 or a positive integer.)
The silane compound polymer (B) represented by the formula (B) Fine particles having an average primary particle diameter of more than 0.04 μm and 8 μm or less (C) A silane coupling agent having a nitrogen atom in the molecule (D) having an acid anhydride structure in the molecule Silane coupling agent (E) Silane coupling agent having a sulfur atom-containing functional group in the molecule   The curable composition according to claim 1, wherein the component (B) is at least one fine particle selected from silica, silicone, and a metal oxide whose surface is coated with silicone.   The curable composition of Claim 1 whose mass mean molecular weights of the said (A) component are 800-50,000.   Furthermore, the curable composition of Claim 1 containing a diluent.   The total amount of the component (A), the component (B), the component (C), the component (D), and the component (E) is 50 to 100 mass with respect to the entire component excluding the diluent of the curable composition. The curable composition according to claim 1, wherein the curable composition is%.   The curable composition according to claim 1, wherein a solid content concentration of the curable composition is 50 to 100% by mass.   The curable composition according to claim 1, which is a composition for an optical element fixing material.   Hardened | cured material formed by hardening | curing the curable composition of Claim 1.   The cured product according to claim 8, which is an optical element fixing material.   The method which uses the curable composition of Claim 1 as an adhesive agent for optical element fixing materials.   The method which uses the curable composition of Claim 1 as a sealing material for optical element fixing materials.   The optical device which used the curable composition of Claim 1 as an adhesive agent for optical element fixing materials, or a sealing material for optical element fixing materials.