JPH0726079B2 - Adhesive composition - Google Patents

Description

The present invention relates to a novel fluorine-containing epoxy resin and a novel adhesive composition containing a fluorine-containing epoxy (meth) acrylate resin.

[Conventional technology]

With the development of optical communication, there is an increasing demand for organic materials suitable for molding lenses and prisms and laminating optical members. In particular, optical adhesives used for bonding optical members have (1) a low refractive index to match the refractive index with optical members such as glass, etc. (2) Do not apply high temperature to the surrounding materials during bonding work. Therefore, it is required to cure at low temperature.

Until now, epoxy resin compositions have been mainly used for the above applications. Since the refractive index of the bisphenol A type epoxy resin that is usually used is too high (1.55 to 1.58), a fluorine substituent is introduced into the bisphenol A type epoxy resin,
An adhesive composition having a lowered refractive index is disclosed in Japanese Patent Application No. 58-217794.

[Problems to be Solved by the Invention]

However, these conventional products have a high refractive index (1.51 to 1.5
8), there is a drawback that the loss due to reflection at the interface with the optical member such as quartz (refractive index 1.46) is large. Also,
The return light due to the reflection at this interface has a drawback that it makes the operation of the laser diode light source of the optical communication line unstable.

An object of the present invention is to provide an adhesive composition excellent in water resistance, heat resistance, adhesive strength and the like, which solves the drawback of the conventional epoxy resin having a high refractive index.

[Means for Solving the Problems]

When the present invention is generally provided, the first invention of the present invention relates to an adhesive composition, which is represented by the following general formula I: (Where M is n represents 0 or any positive number),
It is characterized by containing a photopolymerization initiator or a curing agent.

The second invention of the present invention relates to another adhesive composition, which is represented by the following general formula II: (Where M is n is 0 or an arbitrary positive number, Y is a compound represented by H or CH ₃ group), and a polymerization initiator.

The composition of the present invention has, as other components, for example, a conventional epoxy resin, an epoxy (meth) acrylate resin,
In addition to various acrylate resins such as urethane acrylate and butadiene acrylate or modified products thereof, a diluent, a curing (initiator) agent, a coupling agent and the like may be contained.

The content of the fluorine-containing compound represented by the general formula I or II in the adhesive composition is such that the refractive index is reduced, water resistance, heat resistance,
From the standpoint of increasing the adhesive strength, the amount is preferably 1% by weight or more, and if the amount is less than this, the curing is inferior.

Examples of the epoxy compound represented by the above general formula I of the present invention include compounds having the structures shown below and mixtures thereof.

(In the above formula, n is 0 or a positive number) Further, examples of the epoxy acrylate compound represented by the above general formula II of the present invention include compounds having the structures shown below and mixtures thereof.

(Wherein n is 0 or a positive number) n of the epoxy compound represented by the general formula I and the epoxy acrylate compound represented by the general formula II of the present invention.
With respect to the value of 0, since a compound having a large value of n becomes solid and it becomes difficult to apply an adhesive or the like,
It is preferably 4.

The epoxy compound represented by the general formula I of the present invention can be obtained by reacting a corresponding glycol with epichlorohydrin and a dehydrochlorination agent, for example, by the method described in JP-A-64-85949. Can be obtained.

In addition, the epoxy (meth) acrylate represented by the general formula II of the present invention can be obtained by reacting the epoxy compound represented by the general formula I with acrylic acid or methacrylic acid, for example, by the method described in the above publication. Can be obtained.

In the adhesive composition of the present invention, examples of the epoxy resin used by mixing with the epoxy compound represented by the formula I include an epoxy resin represented by the following structural formula: (However, n is 0 or a positive number) Besides, novolak epoxy, o-cresol novolak epoxy, epoxidized polybutadiene and the like can be used.

As the curing agent, for example, a curing agent used in conventional epoxy resins such as polyamine, polyol, and acid anhydride can be used.

Specific examples of polyamines include diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), dipropylenetriamine (DPTA), bis (hexamethylene) triamine, 1,3,6
-Trisaminomethylcyclohexane (TMAH), trimethylhexamethylenediamine (TMD), polyether polyamines, diethylaminopropylamine (DEAP
A), menthanediamine (MDA), isophoronediamine (IPD), bis (4-amino-3-methylcyclohexyl) methane, N-aminoethylpiperazine (AEP), metaxylylenediamine (MXDA), metaphenylenediamine ( MPDA), diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [5.5] undecane (ATU), cyanoethylated Examples thereof include polyamines.

Furthermore, in addition to these, a polyamidoamine produced mainly by condensation of dimer acid and polyamine can be used. Examples of the polyamidoamine are trade name Thomaid [Fuji Kasei Kogyo Co., Ltd.], trade name Versamide [Henkel Shiramizu Co., Ltd.], trade name Ratukamide [Dainippon Ink & Chemicals Co., Ltd.], trade name Polymide Examples include Sanyo Chemical Industry Co., Ltd., trade name EPOMIK [Mitsui Petrochemical Industry Co., Ltd.], and trade name Sunmide [Sanwa Chemical Industry Co., Ltd.].

Specific examples of the polyol include phenol novolak,
Examples thereof include o-cresol novolac, polyvinylphenol, and brominated products thereof, 2,2-bis (4'-oxyphenyl) propane, and 2,2-bis (4'-oxyphenyl) perfluoropropane.

Specific examples of the acid anhydride include phthalic acid, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid anhydrides, maleic acid, succinic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid anhydrides, and methylnaphthic acid. , Dodecenylsuccinic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, methylcyclohexenetetracarboxylic acid anhydrides, chlorendic acid, tetrabromophthalic acid anhydrides, and the like.

As the thermosetting catalyst, imidazoles, Lewis acids, and other thermosetting catalysts used in conventional epoxy resins can be used.

Specific examples of the imidazoles include 2-methylimidazole (2MZ) and 2-ethyl-4-methylimidazole (2E4
MZ), 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole (2PZ), 1
-Benzyl-2-methylimidazole (1B2MZ), 1-
Cyanoethyl-2-methylimidazole (2MZCM), 1
-Cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ.CN), 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium・ Trimeritate (2PZ ・ CNS),
2-Methylimidazolium isocyanurate, 2-phenylimidazolium isocyanurate, 2,4-diamino-6- [2-methylimidazolyl- (1)]-ethyl-s-triazine (2MZ-2ZINE), 2, 4-diamino-6
-[2-Ethyl-4-methylimidazolyl- (1)]-
Examples thereof include ethyl-s-triazine (2E4MZ-AZINE) and 2-phenyl-4,5-dihydroxymethylimidazole (2PHZ).

Specific examples of Lewis acids include boron trifluoride (BF ₃ ), zinc chloride (ZnCl ₂ ), tin tetrachloride (SnCl ₄ ), aluminum chloride (AlCl ₃ ), phosphorus pentafluoride (PF ₅ ), pentafluoride Examples include arsenic (AsF ₅ ), antimony pentafluoride (SbF ₅ ), etc. These are generally used as amine complexes.

As the photocuring catalyst, a known compound such as a diazonium salt, a sulfonium salt, an iodonium salt, or a selenium salt, which is known to be effective for an epoxy resin, can be arbitrarily selected and used.

Diazonium salt has the general formula ^{_{A: Ar-N 2 + X}} - ... can be expressed by (A). Examples of Ar include ortho, meta, para nitrophenyl, methoxyphenyl, and 2,5.
A group such as -dichlorophenyl, p- (N-morpholino) phenyl, 2,5-diethoxy-4- (p-trimercapto) phenyl can be shown. X ⁻ represents an anion, and can be, for example, BF ₄ ⁻ , FeCl ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ^−, or the like.

Examples of the sulfonium salt include bis [4- (diphenylsulfonio) phenyl] sulfido-bis-hexafluorophosphate, bis- [4- (diphenylsulfonio) phenyl] sulfido-bis-hexafluoroantimonate and the like. In addition, Japanese Patent Publication No. 59-42688, No. 15
The compounds described on page 24, line 24 to page 18, line 1 can be used. Examples of the iodonium salt include di (4-ter-butylphenyl) iodonium hexafluorophosphate, di- (4-ter-butylphenyl) iodonium hexafluoroantimonate and the like, as well as JP-B No. 59-42688, page 11, page 28. 1st from line 1
The compounds described on page 2, line 30 can be used.

Examples of the selenium salt include triphenyl selenium hexafluoroantimonate, 4-ter-butylphenyl diphenyl tetrafluoroborate, and 2,3-dimethylphenyl diphenyl hexafluoroantimonate.

As the diluent, butyl glycidyl ether, alkyl monoglycidyl ether having 2 to 25 carbon atoms such as 2-ethylhexyl glycidyl ether, butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether,
Dodecanediol diglycidyl ether, pentaerythritol polyglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, phenyl glycidyl ether, resorcin diglycidyl ether, p-ter-butylphenyl glycidyl ether, allyl glycidyl ether, tetrafluoro Propyl glycidyl ether, octafluoropentyl glycidyl ether, dodecafluorooctyl diglycidyl ether, styrene oxide, limonene diepoxide, limonene monoxide, α-pinene epoxide, β-pinene epoxide, cyclohexene epoxide, cyclooctene epoxide, vinyl cyclohexene dioxide, etc. In addition to, a compound represented by the following structural formula can be used .

As the coupling agent (epoxy type), carbon functional silane coupling such as γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. Agents.

Known compounds known as reactive oligomers or prepolymers having at least one carbon-carbon double bond in the molecule when mixed with the epoxy (meth) acrylate compound represented by the formula II in the adhesive composition of the present invention. It is also possible to use. Examples of such compounds include (1) ethylenically unsaturated polyesters obtained by condensation oligomerization of polybasic carboxylic acid with polyhydric alcohol and ethylenically unsaturated monocarboxylic acid (2) polyvalent Compounds obtained by adding ethylenically unsaturated monocarboxylic acid to epoxy compound (3) Ethylenically unsaturated monocarboxylic acid esters of polyether polyol (4) Polyethylenic unsaturated compound of ethylenically unsaturated monocarboxylic acid Examples thereof include ethylenically unsaturated polyurethanes obtained by adding hydroxyalkyl esters, diallyl phthalate prepolymers, diallyl isophthalate prepolymers and diallyl terephthalate prepolymers.

Specific examples of the above (1) include an oligoester (meth) acrylate obtained by condensation oligomerization with maleic anhydride, propylene glycol, and (meth) acrylic acid.

Specific examples of (2) include epoxy (meth) acrylate obtained by adding (meth) acrylic acid to bisphenol A diglycidyl ether, and epoxy (meth) acrylate obtained by adding (meth) acrylic acid to hydrogenated bisphenol A epoxide. Can be mentioned.

Specific examples of (3) include polyethylene glycol di (meth) acrylate and polytetraethylene glycol di (meth) acrylate.

Specific examples of (4) include urethane (meth) acrylate obtained by reacting 2-hydroxyethyl (meth) acrylate with polyurethane obtained by reacting ethylene glycol with excess diisocyanate and having isocyanate groups at both ends. Can be mentioned.

Examples of the curing initiator include (a) 2,2′-azobisisobutyronitrile and 2,2′-
Azobis (2,4-dimethylvaleronitrile), (1-phenylethyl) azodiphenylmethane, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile),
Dimethyl-2,2'-azobisisobutyrate, 2,2'-azobis (2-methylbutyronitrile), 1,1-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyrate Ronitrile, 2,2'-azobis (2,4,4-trimethylpentane), 2-phenylazo-
2,4-Dimethyl-4-methoxyvaleronitrile, 2,2'-
Azo compounds such as azobis (2-methylpropane), diacyl peroxides such as benzoyl peroxide and p-chlorobenzoyl peroxide, ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, tert-butyl perbenzoate, tert.
-Butyl peroxy-2-ethylhexoate and other peresters, tert-butyl hydroperoxide, cumene hydroperoxide and other hydroperoxides,
Thermal polymerization initiators such as dialkyl peroxides such as di-tert-butyl peroxide, di-sec-butyl peroxide and dicumyl peroxide, and thermal polymerization initiators such as diaryl peroxides (b) 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, benzophenone,
Examples thereof include photopolymerization initiators such as methyl o-benzoylbenzoate, benzoin isobutyl ether, 2-chlorothioxanthone, and 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one.

As the reactive diluent, styrene, 1,6-hexanediol di (meth) acrylate, isobornyl (meth) acrylate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, butylene glycol dimethacrylate, 2-hydroxyethyl methacrylate, 2- Hydroxypropyl methacrylate, lauryl acrylate, modified dicyclopentynyl acrylate, glycidyl methacrylate, tetrahydrofurfuryl acrylate, 1,3-butylene glycol dimethacrylate, and a carbon-carbon double bond as shown in the structural formula below. Compounds.

It is also possible to incorporate a coupling agent such as trimethoxysilylpropyl (meth) acrylate.

〔Example〕

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

Example 1 The following formula Epoxy resin (abbreviated as CHEP) and the following formula Polyamine polyamine (PEPA) which is a polyamine type curing agent as an epoxy resin (abbreviated as DPEP) shown in, a boron trifluoride monoethylamine complex (BMA) which is a heat curing catalyst, and trif which is a photocuring catalyst. PF ₆ enyl sulfonium ^- refractive index of the cured product in the case of adding salt (TPS), adhesive strength, glass transition temperature (Tg), the result of investigation for hot-water resistance are shown in Table 1.

Here, the refractive index was a value at 20 ° C. at the sodium D-line wavelength (589.3 μm), and ▲ n ²⁰ _D ▼ was determined by an Atsube refractometer. For the adhesive strength, the adhesive test piece made of BK7 glass shown in FIG. 1 was used, and the shear adhesive strength at 23 ° C. was obtained. The tensile strength was 5 mm / min. Tg was determined by DSC. The first
1 is a schematic cross-sectional view of an adhesion test piece using a BK7 glass plate, FIG. 1-2 is a schematic plan view thereof, and reference numeral 1 is BK7.
A glass plate and 2 mean an adhesive and an adhesive portion. The unit of numerical values in the figure is mm.

Regarding the heat resistance, the glass test piece shown in FIG. 2 was used, and the time until peeling occurred on the test piece when immersed in hot water at 80 ° C. was determined. FIG. 2-1 is a schematic cross-sectional view of a hot water resistant test piece using a glass plate, FIG. 2-2 is a schematic plan view thereof, reference numeral 3 means a slide glass, 4 means an adhesive and an adhesive portion. . The unit of the numerical values in the figure is mm.

The curing conditions were 65 ° C. and 6 hours when polyether polyamine was used as a curing agent. In the case of boron trifluoride monoethylamine, the temperature was 120 ° C. for 3 hours, and in the case of the triphenylsulfonium salt, it was cured by heating at 60 ° C. with ultraviolet irradiation of 100 mJ / cm ² using an ultrahigh pressure mercury lamp.

The abbreviations and structures of the compounds used as diluents are shown below: The abbreviations and structures of the compounds used as comparative examples are shown below: AFEP Epicote 828 In Table 1, when CHEP and DPEP were used, the cured product had a lower refractive index than the comparative example, and the silica glass (n ²⁰ _D ▼
= 1.46) and the like, the refractive index matching property with an optical member having a low refractive index is significantly improved. Further, it is clear that the adhesive strength also has a sufficiently large value, and a bonding composition excellent in hot water resistance can be obtained.

Example 2 The refractive index, adhesive strength, Tg, and hot water resistance when an adhesive composition containing an epoxy (meth) acrylate resin was cured by irradiation with ultraviolet rays of 100 mJ / cm ² were examined in the same manner as in Example 1. did. Table 2 shows the abbreviations and structures of the epoxy (meth) acrylate resins used.

The abbreviations and chemical structures of the diluents used are shown below: Benzoin isobutyl ether (BB
E) was used.

The results are shown in Table 3.

From Table 3, the examples have a smaller refractive index than the comparative examples, and the refractive index matching property with the low-refractive-index optical members used for optical parts and the like is improved. In addition, the adhesive strength, hot water resistance, and Tg also have good values, which indicates that they are useful as an adhesive composition having a low refractive index.

Example 3 FIG. 4 shows the result of measurement of the return loss when the epoxy resin composition and the epoxy (meth) acrylate resin composition of the present invention were applied to the optical fiber connection part shown in FIG. 3 at a wavelength of 1.3 μm. Show. FIG. 3 is a schematic view of a return loss measurement test piece, where symbol 5 is an optical fiber, 6 is a protective tube, and 7 is an adhesive and an adhesive portion. Fig. 4 shows the refractive index (▲ n ²⁰ _D ▼, horizontal axis) and return loss (dB, vertical axis).
It is a graph which shows the relationship with. The control of the refractive index of the composition was performed using various compositions of Examples 1 and 2 and Comparative Example 2
This was done by mixing the seed resins.

By using the composition of the present invention, the return loss is -35.
It can be set to less than or equal to dB, and it can be seen that the refractive index matching property with the quartz fiber is significantly improved.

Reference example 1 103 g (0.1 mol) of epoxy resin and acrylic acid 1
8.0 g (0.25 mol) was added to 100 ml of toluene, 1 g of trimethylbenzylammonium chloride and 0.1 g of p-methoxyphenol were further added, and the mixture was heated to reflux with stirring. After 14 hours, heating was stopped and the mixture was cooled to room temperature. The reaction solution was washed with saturated saline until the aqueous layer showed no acidity, dried over anhydrous sodium sulfate, added with 0.1 g of p-methoxyphenol, and heated to 80 to 90 ° C under a pressure of 1 to 2 mmHg. The solvent was heated to remove the solvent, and 98 g of a compound (abbreviated as compound B) in which n was 0.1, Y was H and Z was C ₃ F ₁₇ in the general formula II was obtained as a viscous liquid.

IR (liquid film, cm ^-1 ) 3400 OH, 2900 CH, CH ₂ , 1722 C = O, 1635 C = C, 1402 C = C Reference Example 2 In Reference Example 1, methacrylic acid 2 was used instead of acrylic acid.
Using the same procedure as in Reference Example 1 except that 1.5 g was used, the general formula II
In, 93 g of a compound in which n is 0.1, Y is CH ₃ , and Z is C ₃ F ₁₇ is obtained.

IR (liquid film, cm ^-1 ) 3400 OH, 2900 CH, CH ₂ , 1725 C = O, 1640 C = C 1404 C = C Example 4 The following formula (Epoxy equivalent 514, Refractive index 1.391) Epoxy resin (abbreviated as Compound A) as a curing agent, polyamine type curing agent, polyether polyamine (PEPA), and thermosetting catalyst, boron trifluoride monoethylamine complex Table 4 shows the results of examining the refractive index, adhesive strength, glass transition temperature (Tg), and hot water resistance of the cured product when (BMA) was added.

Here, the refractive index, adhesive strength, Tg, and hot water resistance were determined in the same manner as in Example 1.

The curing conditions were 65 ° C. and 6 hours when polyether polyamine was used as a curing agent. In the case of boron trifluoride monoethylamine, the temperature was 120 ° C. for 3 hours.

Reference Example 3 An adhesive composition containing an epoxy acrylate resin was used.
Refractive index when cured by UV irradiation of 0 mJ / cm ² ,
The adhesive strength, Tg, and hot water resistance were examined in the same manner. The epoxy acrylate resin used is compound B.

Benzoin isobutyl ether (BB
E) was used.

The results are shown in Table 5.

[Advantages of the Invention] The adhesive composition of the present invention has a low refractive index, good refractive index matching with an optical member such as quartz, and excellent water resistance, heat resistance, and adhesive strength. It is useful as an optical adhesive or the like for optical parts used in.

[Brief description of drawings]

Figure 1-1 is a schematic cross-sectional view of an adhesive test piece using a BK7 glass plate, Figure 1-2 is a schematic plan view thereof, and Figure 2-1 is a cross-sectional view of a hot water resistant test piece using a glass plate. Schematic, second
2 is a schematic plan view thereof, FIG. 3 is a schematic view of a test piece for measuring return loss, and FIG. 4 is a graph showing the refractive index dependence of return loss. 1: BK7 glass plate, 2, 4, 7: adhesive and adhesive part, 3: slide glass, 5: optical fiber, 6: protective tube

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Norio Murata 1-1-6 Uchisaiwaicho, Chiyoda-ku, Tokyo Nihon Telegraph and Telephone Corporation (72) Motonobu Kubo 4-13-13 Kumanocho, Toyonaka City, Osaka Prefecture No. 1 (72) Inventor Yoshiki Shimizu 72 Ichinoi, Akame-cho, Nabari-shi, Mie (72) Inventor Hideo Kobayashi 2-21-21 Ichitsuya, Settsu-shi, Osaka (56) Reference JP-A-58-67708 ( JP, A) JP 58-206674 (JP, A) JP 60-110775 (JP, A) JP 61-47717 (JP, A) JP 62-220516 (JP, A) JP Sho 63-309 (JP, A)

Claims (2)

[Claims] 1. The following general formula I: (Where M is n represents 0 or any positive number),
An adhesive composition comprising a photopolymerization initiator or a curing agent. 2. The following general formula II: (Where M is An adhesive composition, characterized in that n is 0 or any positive number, Y is a compound represented by H or CH ₃ group), and a polymerization initiator.