JPS62517A - Sealant for optical element - Google Patents

Abstract

PURPOSE:A sealant for optical elements having high moisture resistance, high heat resistance, excellent mechanical properties and molding workability and is reliably used as a sealant for electronic and electrical components, comprising a specified epoxy resin and a curing agent. CONSTITUTION:An epoxy resin of formula I [wherein R<1> is an organic compound residue having l active hydrogen groups, n1, n2 and nl are each 0-100 and their sum is 1-100, l is 1-100, A is a substituted oxycyclohexane skeleton of formula II (wherein X is any one of the groups of formulas III-V, and R2 is H, alkyl, carboalkyl or carboaryl and contains at least one group of formula III), obtained by epoxidizing a polycyclohexene oxide polymer, obtained by polymerizing 4-vinylcyclohexene-1-oxide by ring opening by using an active hydrogen-containing organic compound as an initiator, with a peroxide is mixed with a curing agent (e.g., diethylenetriamine) and, optionally, a filler, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a sealant for optical devices that has excellent moisture resistance, heat resistance, and mechanical properties.

[Prior art]

Semiconductor devices that handle light, that is, optical devices, include light-emitting diodes, optical sensors, and light-emitting devices for optical communications.

There are light-receiving elements, etc., but as a resin that requires transparency to completely seal these elements and parts, it has a high light transmittance,
It must also have good properties such as heat resistance, electrical properties, and moisture resistance, and epoxy resin compositions are most commonly used in terms of reliability and cost.

[Problem that the invention seeks to solve]

Glycidyl ether type resins made by reacting polyhydric alcohols such as bisphenol A, bisphenol F, novolak resin, and hydrogenated bisphenol F with epichlorohydrin are suitable as epoxy resins for soil use that have high transmittance in the entire visible light wavelength range. There are also so-called alicyclic epoxy resins produced by epoxidizing internal olefins.

However, using glycidyl ether of novolak resin7
The cured product had high heat resistance but poor hue, while the cured product using other glycidyl ether type epoxy resins did not have sufficient heat resistance. Additionally, glycidyl ether type epoxy resins generally contain several 1100 chlorine atoms.
Since it contains pp, there are problems such as free chlorine ions corroding internal wiring, etc., and the cured product becoming discolored over time.

On the other hand, alicyclic epoxy resins essentially do not contain chlorine and are superior to glycidyl ether type epoxy resins in terms of heat resistance, transparency, and electrical properties, but water resistance can sometimes be a problem. .

The present invention has been made in view of the above drawbacks.

The purpose is to provide an encapsulant for optical devices that has moisture resistance and heat resistance, as well as excellent mechanical properties.

As a result of intensive research to achieve the above object, the present inventors have found that the encapsulant for optical devices described below has superior moisture resistance and heat resistance compared to conventional ones, and has excellent mechanical properties. He discovered that the compound was suitable as an encapsulant for optical devices and completed the present invention.

[Structure of the invention]

That is, the present invention provides [(a) an epoxy resin represented by the general formula chain (b)
A sealing agent for optical devices characterized by containing a curing agent as an essential component.

However, R1 is an organic compound residue having t active hydrogens.

"r * nl"・ntn Oalso1l-1001Z)J
l number, the sum of which is from 1 to 100.

t represents an integer from 1 to 1000.

A is an oxycyclohexane skeleton having a substituent,
It is expressed by the following formula.

R1 is represented by at least formula (I) and contains one or more of H, an alkyl group, a carboalkyl group, or a carboalkyl group.

In the epoxy resin represented by formula (I) of the present invention,
R3 is an organic substance residue having active hydrogen, and its precursor organic substance having active hydrogen includes alcohols, phenols, and carboxylic acids.

Examples include abans and thiols.

The alcohol may be a monohydric alcohol or a polyhydric alcohol.

For example, methanol, ethanol, propatool.

Aliphatic alcohols such as butanol, pentanol, hexanol, octatool, aromatic alcohols such as benzyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, diglopylene glycol, 1.3-butanediol, 1.4 butanediol, bentanediol, 1.6 hexanediol, neopentyl glycol, oxypivalic acid neopentyl glycol ester, cyclohexane')ll) -l.

Glycerin, jigvaseline. Polyglycerin, trimethylolpropane, trimethylolethane.

Examples include polyhydric alcohols such as pentaerythritol and dipentaerythritol.

Phenols include phenol, resol, catechol, and pyrogallol. Hydroquinone.

Hydroquinone monomethyl ether, bisphenol A
, bisphenol F, 4,4'-dihydroxybenzophenone, bisphenol S, phenol resin, cresol novolak resin, etc.

Carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, fatty acids from animal and vegetable oils, fumaric acid, maleic acid, adipic acid, dodecanoic acid, trimellitic acid, pyromellitic acid,
Examples include polyacrylic acid, phthalic acid, isophthalic acid, and terephthalic acid. Also included are compounds having both a hydroxyl group and a carboxylic acid, such as lactic acid, citric acid, and quincaproic acid.

Examples of abans include methylamine and ethylamine.

Propylamine, butylamine, pentylamine.

Hexylamine, nclohexylamine, octylamine, dodecylamine, 4,4'-cyabafudiphenylmethane. Examples include inphorone diamine, toluene diamine, hexamethylene diamine, xylene diamine, diethylene triamine, triethylene tetramine, and ethanolamine.

Examples of thiols include mercapto compounds such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, and phenyl mercaptan, mercaptopropionic acid or polyhydric alcohol ester of mercaptopropionic acid, ff
Examples include ethylene glycol dimethylcabutoprobionic acid ester, trimethylolpropane trimercabutoprobionic acid ester, and bentaerythritol benthamercabutoprobionic acid ester.

Furthermore, other compounds having active hydrogen include polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, cellulose, cellulose acetate, cellulose acetate butyrate, hydroxyethyl cellulose,
Acrylic polyol resin, styrene allyl alcohol copolymer ILL styrene-maleic acid copolymer resin, alkyd resin.

Polyester polyol resin, polyester carbon*
fM resin, polycaprolactone polyol resin.

Examples include polypropylene polyol and polyetramethylene glycol.

(9) The compound having active hydrogen may have an unsaturated double bond in its skeleton, and specifically, allyl alcohol, acrylic acid, methacrylic acid, 3-cyclohexenemethanol, tetra Dorophthalic acid, etc. The unsaturated double bonds of these compounds may also have an epoxidized structure.

nl j nfi...n in general formula (1)
t is 0 or an integer from 1 to 100, but if it is 100 or more, the resin will have a high melting point and will be difficult to handle, making it practically unusable.

t is an integer from 1 to 100.

Among the substituents X of A in formula (I), CHO island is the main thing.

Specifically, the novel epoxy resin represented by the formula α) of the present invention is prepared by using an organic compound having active hydrogen as an initiator iCL, 4
- Polyether resin obtained by ring-opening polymerization of vinylcyclohexene-1-oxide, that is, produced by epoxidizing a polycyclohexene oxide polymer having a vinyl group side chain with an oxidizing agent such as peracid. can do.

4-Vinylcyclohexene-1-oxide is obtained by partially epoxidizing vinylcyclohexene obtained by a dimerization reaction of butadiene with peracetic acid.

It is preferable to use a catalyst when polymerizing 4-vinylcyclohexene-1-oxide in the presence of active hydrogen.

Catalysts include amines such as methylamine, ethylamine, propylamine, and piperazine; organic basic acids such as pyridines and ibadazole; organic acids such as formic acid, acetic acid, and propionic acid; and inorganic acids such as sulfuric acid and hydrochloric acid. , alkali metal alcoholades such as sodium methylate, KOH, N
Alkali such as aOH, BFI, ZnCl2.
Examples include Lewis acids such as AtC14 and 5n04 or their complexes, and organometallic compounds such as triethyl7A/i and diethylzinc.

These catalysts can be used in an amount of 0.01-10%, preferably 0.1-5% based on the reactants. The reaction temperature is -70 to 200°C, preferably -30°C to 10°C.
It is 0°C.

The reaction can also be carried out using a solvent. It is not possible to use solvents that contain active hydrogen.

In other words, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, benzene, toluene,
Aromatic solvents such as xylene, ethers, aliphatic hydrocarbons, esters, etc. can be used.

Now, the polycyclohexene oxide polymer synthesized in this way and having a vinyl group side chain is epoxidized to produce the novel epoxy resin of the present invention (formula (1) +2) using peracids and hydroperoxides.

Either can be used.

Peracids include performic acid, peracetic acid, and perbenzoic acid.

Trifluoroperacetic acid and the like can be used.

Among these, peracetic acid is a particularly preferred epoxidizing agent because it is industrially available at low cost and has high stability.

Hydrogen peroxide and tert-butyl hydroperoxide are examples of hydrocarbons A.

Cumene peroxide etc. can be used.

A catalyst can be used during epoxidation if necessary. For example, in the case of a peracid, an alkali such as soda carbonate or an acid such as sulfuric acid may be used as a catalyst. In the case of hydroperoxides, the catalytic effect can be obtained by using a mixture of tungstic acid and caustic soda with hydrogen peroxide, an organic acid with hydrogen peroxide, or molybdenum hexacarbonyl with tert-butyl hydroperoxide. .

The epoxidation reaction is carried out by adjusting the presence or absence of a solvent and the reaction temperature depending on the equipment and physical properties of the raw materials.

Depending on the conditions of the epoxidation reaction, a side reaction occurs with the substituent in the raw material or the epoxidizing agent at the same time as the olefin bond is epoxidized, resulting in a modified phosphorus substituent, which is included in the target compound. The ratio of the three substituents in the target compound (the ratio of the three substituents) is determined by the type of epoxidizing agent, the molar ratio of the epoxidizing agent to the olefin bond, and the reaction conditions.

For example, when the epoxidizing agent is peracetic acid, the modified substituent has the structure shown below, which is mainly generated from the epoxy group produced by the acid and the acetic acid produced as a by-product.

The target compound can be removed from the reaction phase liquid by conventional chemical industrial means such as concentration.

Further, the epoxy resin used in the present invention can be used in combination with other epoxy resins as long as the properties of the sole are not impaired. Here, other epoxy resins may be any commonly used epoxy resins, but if kept, epoxy dilutions such as Ebibis type epoxy, bisphenol F epoxy, novolac epoxy, alicyclic type epoxy, styrene oxide, butyl glycidyl ether, etc. Contains agents.

The curing agent used in the present invention may be any curing agent used for known epoxy resins, as long as it does not impair the performance of the parts after sealing, such as amines, boriabad resins, acid anhydrides, etc.
Contains cationic catalysts such as polymercaptan resins, novolac resins, dicyandiamide, and boron trisulfide C)7mine complexes.

Here, the amines include the following.

Diethylenetriamine, triethylenetetramine, menthenethiaban, metaxylylenediamine.

Aliphatic polyamines such as bis(4-amino-3-methylchlorohequinyl)methane, adducts of the aliphatic polyamines and known epoxy compounds, reactants with acrylonitrile, and reactants with ketones.

Methanene diamine, cyabafudiphenylmethane.

Aromatic polyamines such as diaminodiphenylsulfone and diaminodiphenylsulfide, and adducts of the aromatic polyabane and known epoxy compounds.

Tris (dimethylamine methyl) phenol.

2nd and 37th compounds such as piperidine, imidazole and their rust conductors, and their salts.

Boriabad resins include fatty acids and dimer acids.

Includes reactants of fatty acids such as trimer acids and aliphatic polyamines.

Acid anhydrides include the following:

Phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl anhydride Acid anhydrides such as nadic acid, cono-phosphate anhydride, dodecenylsuccinic anhydride, cono-phosphate anhydride, and mixtures of the above-mentioned acid anhydrides.

Novolak resins include phenol or phenolic cresol, a low molecular weight resinous product made by condensing a mixture of dihydroxybenzenes with formaldehyde.

Amine complexes of boron trifluoride include monoethylamine, hiberidine, aniline, and butyl amine.

Complexes of low molecular weight amine compounds such as dibutylamine, cyclohexylabane, dicyclohexylamine, tributylamine, and triethanolamine and boron trifluoride are included.

Another hardening agent is boron tetrafluoride.

There are salts such as diazonium salts, iodonium salts, bromonium salts, and sulfinium salts of super strong acids such as phosphorus hexafluoride and arsenic hexafluoride. Among these curing agents, aliphatic polyamines and aromatic polyamines.

Boriabad resin and polymercaptan resin can be used as a mixture in any ratio, and can be used alone or at hardness rate k.
fJI4! ! For this purpose, all curing accelerators can be used together. Here, as the hardening accelerator, the second and third
7-bans can be used.

The acid anhydride can be used as it is, but a curing catalyst and a curing accelerator can also be used together for the purpose of adjusting the curing rate and improving the physical properties of the cured product.

Here, the curing catalyst is the secondary and tertiary amines, and the tin octylate curing accelerator is water.

Ethanol, Gropanol, Ingropanol.

alcohols such as cyclohexyltonol and ethylene glycol; carboxylic acids such as acetic acid, phlopionic acid, succinic acid, and hexahydrophthalic acid; and amines containing active hydrogen such as ethylenecyabane and diethylene) .

The novolak resin can be used alone or in combination with a curing catalyst for the purpose of adjusting the curing rate. Here, the curing catalysts are the aforementioned secondary and tertiary amines.

Dicyanthate can be used alone or in combination with a curing catalyst for the purpose of adjusting the curing rate. Here, the curing catalysts are the aforementioned secondary and tertiary amines.

The amine complex of boron trifluoride can be used alone or in combination with a curing rate regulator for the purpose of adjusting the curing rate.

Any curing rate regulator may be used as long as it can be used in conventional epoxy resins, but specific examples include carboxylic acids, amines, metal acetylacetone complexes, titanium, tin, etc. These include organometallic compounds of metals, glycols, organoboron compounds, etc.

Although there are the above-mentioned curing agents that can be used in the sealant of the present invention, acid anhydride-based curing agents are preferred.

The sealant of the present invention includes an epoxy resin represented by formula (1) and a curing agent for epoxy resin as essential components.

Fillers, coupling agents, and mold release agents as required.

Flame retardants, dyes and pigments, etc. can be used together.

As a general method for preparing the sealant of the present invention as a complete molding material, for example, when preparing a solid sealant,
After selecting the epoxy resin, curing agent, etc. in a predetermined composition ratio and thoroughly mixing the raw material composition with a mixer etc., it is further melted and mixed by heating rolls, or mixed by a kneader etc., and then cooled and solidified. A molding material can be obtained by crushing the material into an appropriate size.

When using a liquid sealant, a predetermined amount of epoxy resin, curing agent, etc. can be mixed such that k<xa-, etc., to obtain a -liquid or two-liquid molding material.

When the sealant prepared in this way is used for optical devices such as light emitting diodes, optical sensors, light emitting devices for optical communication, and light receiving devices, there are various well-known molding methods as a sealing method. For example, low pressure transfer molding method, injection molding method, compression molding method, casting method, etc.
It is applicable to almost all encapsulation techniques.

(Effects of the Invention) The sealant of the present invention has high moisture resistance, high heat resistance, excellent mechanical properties, and good moldability, so it can be used for sealing electronic and electrical parts, etc. sufficient reliability can be obtained.

(Example) The present invention will be further explained in detail with reference to Examples below.

Synthesis Example 1 Allyl alcohol 58f (1 mol), 4-vinylcyclohexene-1-oxide 868f (7 mol) and BF, etherate 4.7f'k were mixed at 60°C, and gas chromatography analysis revealed that 4-vinyl The reaction was carried out until the conversion of cyclohexene-1-O-inside was 98% or higher. Nigel acetate was added to the resulting crude reaction solution and washed with water, and then the ethyl acetate layer was concentrated to obtain a viscous liquid.

In the infrared absorption spectrum of the product, there was no absorption due to the epoxy group at 9810.850 cm, which was observed in the raw material, and absorption due to ether bonds was present at 1080 and 1150 cm. Gas chromatography analysis Although the allyl alcohol in the product is a trace amount, the infrared absorption spectrum shows an absorption of OH group at 3450 cm-'', which confirms that this compound has the structure shown by the following formula. Compound 49299 was dissolved in ethyl acetate and charged into a reactor, and a solution of 395 ft of peracetic acid in ethyl acetate was added dropwise over 2 F#. During this time, the reaction temperature was 40℃
I kept it. After the addition of peracetic acid, the mixture was further aged at 40°C for 6 hours.

Add ethyl acetate to the reaction crude solution and add sodium carbonate □
Wash with alkaline water containing 416Pt, followed by distilled water.
Thoroughly washed with □.

The ethyl acetate layer was concentrated to obtain a viscous clear liquid.
□This compound has an oxirane oxygen content of 9.27%.
: In the infrared absorption spectrum, a characteristic absorption due to the epoxy group □ was observed at 1260 cm-''.Furthermore, an absorption by the residual vinyl group [L] was observed at 1640 cm-'', and as in Example 1, this Compound 4921 and peracetic acid 395? The following reaction was carried out to obtain a viscous transparent liquid.

This compound had an oxirane oxygen content of 9.27%, and in its infrared absorption spectrum, a characteristic absorption attributed to the epoxy group was observed at 260 cm-''. Furthermore, an absorption due to the residual vinyl group was observed at 1640 cm-1. , 3450cm-
' Ic OH group, 1730 cvt-" K O-
Since absorption by CO- group is observed, this compound has the general formula (I
) structure (R, nigericidyl group or allyl group.

n=average 7. Contains a group in which a portion of acetic acid is added to an epoxy group].

Synthesis Example 2 In the same manner as in Example 1, 186.3 ri of trimethylol chloride and 4-vinylcyclohexene-1-oxide were reacted to obtain a viscous liquid product.

In the infrared absorption spectrum of the product, there is no absorption by the epoxy group at 7j 8] 0,850 cm-'' seen in the raw material, 1080.1150 (7
)-1 has an absorption caused by an ether bond, and NMR analysis confirmed that this compound has a structure represented by the following formula.

Furthermore, as in Example-1, this compound 573t and peracetic acid 387'? A viscous transparent liquid was obtained.

This compound had an oxirane oxygen content of 9.031, and a characteristic absorption due to the epoxy group was observed at 1 260 cnt in the infrared absorption spectrum.
-' shows absorption due to residual vinyl groups, 345
O, H group at 0, O- at 1730
Since absorption by CO- group is observed, this compound has the general formula (I
) (2) structure n (Rt: trimethylolpropane residue L=3.nl·n,·n3 = average 5.contains tl-1 part of a group in which acetic acid is added to an epoxy group).

Examples 1 and 2 The products of Synthesis Examples 1 and 2 were treated by using 4-methylhexahydrophthalic anhydride (Rikazid Mu-700.% Nippon Rika ■) as a curing agent and penzyldimethylabane as a curing catalyst. Compound according to the following formulation, and at 80℃ approx.
After melting and mixing for a minute, the mixture was degassed under reduced pressure and cured by pouring to obtain a cured product. Curing is done in an oven at 100°C.
Pre-curing was carried out for an hour, and post-curing was further carried out at 160° C. for 6 hours.

The appearance, hardness and heat distortion temperature of the obtained hardened material are shown in Table 1.

Here, the heat distortion temperature and hardness were measured in accordance with JIS-6911.

Mixing prescription Epoxy resin 1.0 equivalent MH-700
0. g equivalent benzyldimethylamine (based on the formulation) 0.5% by weight Comparative Example 1 Bisphenol A diglycidyl ether (Epicor) 828. The same formulation as in Example 1 was used to formulate the epoxy resin.

Mixing was carried out at room temperature, and after degassing under reduced pressure, curing was carried out in the same manner as in Example. Appearance of the obtained cured product.

The hardness and heat distortion temperature are as shown in Table 1. Comparative Example 2 Cresol novolak epoxy resin (Evotod YDCN-702, Tobu Kasei) was used as the epoxy resin, and the same formulation as in Example was used.

Next, mixing, defoaming, casting and curing were performed in the same manner as in Example 1. The appearance, hardness, and heat distortion temperature of the obtained homocured product are as shown in Table 1.

Table 1 As is clear from Table 1, the photoresist sealant of the present invention has excellent transparency and excellent heat resistance and mechanical properties.

Claims (1)

[Claims] (a) Epoxy resin represented by general formula (I) (b)
A sealant for optical devices characterized by containing a curing agent as an essential component. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ However, R_1 is an organic compound residue with 1 active hydrogen. n_1, n_2... n_l is 0 or 1 to 100
is an integer whose sum is from 1 to 100. l represents an integer from 1 to 100. A is an oxycyclohexane skeleton having a substituent,
It is expressed by the following formula. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ X is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ R_2 is any one of H, an alkyl group, a carboalkyl group, a carboaryl group, but ▲ A mathematical formula, a chemical formula, There are tables, etc. ▼ Contains at least one or more of the following in the resin represented by formula (I).