JP2013067732A - Cationic curing type resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cationic curing type resin composition excellent in normal state strength as well as durable strength; and an optical device assembled using the cationic curing type resin composition.SOLUTION: There are provided: (1) a cationic curing type resin composition including an epoxy resin (component A), a reactive diluent (component B), a cation polymerization initiator (component C), a filler (component D), and a silane coupling agent (component E), where the component D includes a urethane resin filler (component D1); and (2) an optical device assembled using the cationic curing type resin composition described in (1).

Description

  The present invention relates to a cationic curable resin composition.

For precision optical devices such as optical lenses, optical pickups, light detection sensors, and displays such as personal computers, adhesives for optical devices (hereinafter, for optical devices) are used to fix or cover the components of each device. (Also referred to as an adhesive) is used (for example, Patent Document 1).
As an optical device adhesive, Patent Document 2 discloses a cured product from the viewpoint of not distorting the objective lens when the optical device adhesive is cured when fixing the objective lens of the optical pickup with the optical device adhesive. A cationic curable resin composition having a certain hardness (softness) is disclosed, and Patent Document 3 discloses a viewpoint of preventing light leakage of a backlight, preventing intrusion of external light, etc. as a sealing agent for a liquid crystal display. To a suitable photocurable resin composition are disclosed.

JP 2002-251776 A JP 2011-080044 A JP 2010-126630 A

"Epoxy resin handbook", 236 pages, December 25, 1987, first edition issued

However, in recent years, precision optical devices, which are becoming smaller and higher in performance, are used in high-temperature and high-humidity environments due to the miniaturization of component parts and the high integration of optical devices. Even in the case where the adhesive is used for precision optical devices, the adhesive for optical devices used for precision optical devices is only strong in the indoor environment after curing (hereinafter also referred to as normal strength). In addition, durability under a high temperature and high humidity environment (hereinafter referred to as durability strength) is also required.
Furthermore, in addition to precision and small size, such as an optical pickup, optical devices that require productivity from the viewpoint of cost are required to be cured in a short time (hereinafter also referred to as curability).

  It is an object of the present invention to provide a cationic curable resin composition having excellent durability as well as normal strength and an optical device assembled using the cationic curable resin composition.

The present invention
(1) Cationic curable resin composition containing epoxy resin (component A), reactive diluent (component B), cationic polymerization initiator (component C), filler (component D) and silane coupling agent (component E) A thing,
The present invention relates to a cationic curable resin composition in which the component D includes a urethane resin filler (component D1), and (2) an optical device assembled using the cationic curable resin composition described in (1).

  ADVANTAGE OF THE INVENTION According to this invention, the optical apparatus assembled using the cationic curable resin composition which is excellent in durability strength with normal state strength, and this cationic curable resin composition can be provided.

The top view of a punch test. Sectional drawing of a punch test.

The cationic curable resin composition of the present invention (hereinafter also referred to as a cationic curable resin composition)
A cationic curable resin composition containing an epoxy resin (component A), a reactive diluent (component B), a cationic polymerization initiator (component C), a filler (component D) and a silane coupling agent (component E). And
The component D includes a urethane resin filler (component D1).

(Component A)
Component A in the cationic curable resin composition is an epoxy resin, which has no inhibition of curing by oxygen and has a high thermal elastic modulus as compared with an acrylic resin (Non-Patent Document 1). From the viewpoint that the optical component does not move with a certain accuracy from a predetermined position when the component is fixed to the housing (hereinafter also referred to as a fixing accuracy), it is preferable as an adhesive for an optical device.

  Component A is bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac from the viewpoint of securing fixing accuracy in addition to normal strength and durability strength. Type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, polybutadiene type epoxy resin, polyisoprene type epoxy resin, alicyclic epoxy resin and aliphatic epoxy resin The above epoxy resins are preferred.

  Phenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin are impurities (from the viewpoint of ensuring the curability of the cationic curable resin composition in the presence of component C and the low halogen content. For example, it is preferable to use those purified to remove epichlorohydrin used in the synthesis, halogen-containing intermediates not ring-closed to the epoxy group, and the like. Examples of the purification of the phenol type epoxy resin include purification by distillation, purification by chromatography using silica gel, alumina, etc., purification by hydrolyzing a covalently bonded halogen with an alkaline aqueous solution such as an aqueous sodium hydroxide solution, etc. Is mentioned. As a purified product of bisphenol A type epoxy resin, EXA-8067 manufactured by DIC Corporation can be used.

  In addition, it is preferable that the halogen content is 500 ppm or less in the cationic curable resin composition from the viewpoint of reducing electric corrosion (electrolytic corrosion) and protecting the global environment. When EXA-8067 from DIC is used as component A, low halogenation can also be achieved.

As the alicyclic epoxy resin, an alicyclic epoxy resin having a molecular weight of 300 or more is preferable from the viewpoint of securing fixing accuracy.
Vinylcyclohexene monooxide 1,2-epoxy-4-vinylcyclohexane (for example, CEL2000 manufactured by Daicel Chemical Industries),
1,2: 8,9 diepoxy limonene (for example, CEL3000 manufactured by Daicel Chemical Industries),
3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate (for example, CEL2021P manufactured by Daicel Chemical Industries),
1,2-epoxy-4- (2-oxiranyl) cyclosoxane adduct of 2,2-bis (hydroxymethyl) -1-butanol (for example, EHPE3150 manufactured by Daicel Chemical Industries),
One or more epoxy resins selected from the group consisting of 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate and hydrogenated biphenyl type alicyclic epoxy resins are preferred.

  As the aliphatic epoxy resin, an alicyclic epoxy resin having a molecular weight of 300 or more is preferable from the viewpoint of securing fixing accuracy. Ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether , Neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolpropane diglycidyl ether and polyethylene glycol diglycidyl ether One or more epoxy resins selected from are preferred.

As the component A, from the viewpoint of securing fixing accuracy, a bisphenol A type epoxy resin (for example, Epicron 850 or Epicron 860 manufactured by DIC) and a hydrogenated bisphenol A type epoxy resin (for example, YX8034 manufactured by JER) are more used. Preferably
Bisphenol A epoxy resin (Epiclon 860 manufactured by DIC) is more preferable.

(Component B)
The cationic curable resin composition contains component B which is a reactive diluent from the viewpoint of ensuring normal strength and curability and from the viewpoint of adjusting the liquid properties centered on viscosity to improve application workability and the like. .
Component B is an alicyclic epoxy resin (preferably having a molecular weight of less than 300), aliphatic from the viewpoint of securing normal strength and curability, reducing viscosity to improve coating workability, and reducing shrinkage. Those containing a cationizable functional group such as an epoxy resin (preferably having a molecular weight of less than 300), an oxetane compound and a vinyl compound are preferred, and an oxetane compound is more preferred.

  As oxetane compounds, 3-ethyl-3-hydroxymethyloxetane (OXA), 1,4-bis [{(3-ethyl-3-oxetanyl) methoxy} methyl] benzene (XDO), 3-ethyl-3- (phenoxy) Methyl) oxetane (OXT-211 (POX)), 2-ethylhexyloxetane (OXT-212 (EHOX)), xylylene bisoxetane (OXT-121 (XDO)), bis (3-ethyl-3-oxetanylmethyl) ether (OXT-221 (DOX)), 3-ethyl-[{(3-triethoxysilylpropoxy) methyl) oxetane, oxetanylsilsesquioxane, phenol novolac oxetane, and the like. The number in parentheses indicates the product number of Toagosei Co., Ltd. Each oxetane compound may be used alone or in combination of two or more.

(Component C)
Component C in the cationic curable resin composition is a polymerization initiator and acts as a photoacid generator. From the viewpoint of curability in addition to normal strength and durability, Lewis acid or Bronsted is preferably irradiated by energy rays. A compound that generates an acid, and a sulfonium salt and / or an iodonium salt is preferable.

As a sulfonium salt, in addition to normal strength and durability strength, from the viewpoint of curability,
Triphenylsulfonium hexafluorophosphate,
Triphenylsulfonium hexafluoroantimonate,
Triphenylsulfonium tetrakis (pentafluorophenyl) borate,
4,4′-bis [diphenylsulfonio] diphenyl sulfide bishexafluorophosphate,
4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenyl sulfide bishexafluoroantimonate,
4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenyl sulfide bishexafluorophosphate,
7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoroantimonate,
7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone tetrakis (pentafluorophenyl) borate,
4-phenylcarbonyl-4′-diphenylsulfonio-diphenyl sulfide hexafluorophosphate,
4- (p-tert-butylphenylcarbonyl) -4′-diphenylsulfonio-diphenyl sulfide hexafluoroantimonate,
4- (p-tert-butylphenylcarbonyl) -4′-di (p-toluyl) sulfonio-diphenyl sulfide tetrakis (pentafluorophenyl) borate and the like are preferable.
As commercially available sulfonium salt cationic polymerization initiators, Asahi Denka Co., Ltd. SP-170, SP-172, SP-150, SP-152, San Apro Co. CPI-210S, etc. are preferable, and Asahi Denka Co., Ltd. SP- 170, SP-172, or CPI-210S manufactured by Sun Apro is more preferable.
These salts may be used alone or in combination of two or more.

As an iodonium salt, in addition to normal strength and durability strength, from the viewpoint of curability,
Diphenyliodonium tetrakis (pentafluorophenyl) borate,
Diphenyliodonium hexafluorophosphate,
Diphenyliodonium hexafluoroantimonate,
Di (4-nonylphenyl) iodonium hexafluorophosphate and the like are preferable.
As a commercially available iodonium salt-based cationic polymerization initiator, PI2074 manufactured by Rhodia is preferable.
These salts may be used alone or in combination of two or more.

(Components D and D1)
Component D in the cationic curable resin composition is a filler that essentially includes component D1 that is a urethane resin filler.
Conventionally, fillers have been used for optical device adhesives for the purpose of reducing the curing shrinkage during curing, but in the present invention, from the viewpoint of achieving both normal strength and durable strength, a cationic curing type. When the structure of the resin composition is designed, it has been found that when the component D1 and the silane coupling agent described below coexist in the filler, both the normal strength and the durability strength can be achieved extremely well.

Component D1 is obtained, for example, by mixing a raw material resin that is a polyisocyanate prepolymer, a functional agent, and a bleed modifier to form a mixture, and then subjecting the raw material resin to suspension polymerization or suspension crosslinking. The polyisocyanate prepolymer refers to a reaction product of isocyanate or diisocyanate and polyol having a reactive isocyanate group at the terminal. In terms of content, the polyol may be polyester, polyether, or acrylic polyol.
A preferable production method of the component D1 is disclosed in, for example, Japanese Patent Application Laid-Open No. 2002-173410.

From the viewpoint of coexistence of normal strength and durability strength of the cationic curable resin composition,
The oil absorption amount of component D1 is preferably 50 to 200 ml / 100 g, more preferably 60 to 185, and further preferably 65 to 150 ml / 100 g, more preferably from the viewpoint of curability. It is 65-120 ml / 100g, More preferably, it is 65-100 ml / 100g, More preferably, it is 65-90 ml / 100g.

Oil absorption is based on JISK5101-13-2 (2004), oil is changed to toluene in boiled sea urchin, and the sample amount of a sample is 40g.
(I) Take 40 g of sample in the center of the measurement plate, and gradually drop toluene into the center of the sample in an amount corresponding to 4 or 5 drops of oil as it is boiled at a time. Mix well with a knife and check the liquidity.
(Ii) In the above (i), when the liquid property is confirmed, if there is no fluidity as a whole, the dropping and kneading of toluene and the confirmation of the liquid property are repeated.
(Iii) In the above (i) or (ii), if liquidity is confirmed, if it is fluid, it is left as it is for 1 hour to confirm the liquidity.
(Iv) In the above (iii), if the liquidity is confirmed after standing for 1 hour and the whole is not fluid, dripping and kneading of the toluene in (i) above, and confirmation of the liquidity in (iii) above, Repeat for a long time and check the liquidity.
(V) In the above (iii) or (iv), if the liquid property after being allowed to stand for 1 hour is confirmed, if the whole is fluid, it is determined as an end point.

The content of the component D1 in the component D is from the viewpoint of compatibility between normal strength and durability strength.
Preferably it is 10-100 weight%, More preferably, it is 70-100 weight%, More preferably, it is 80-100 weight%, More preferably, it is 90-100 weight%.

  When component D is composed of component D1 and a filler suitable for curability different from component D1 (component D2), the cation curable resin composition has a good curability in addition to the compatibility between normal strength and durability strength. It can be secured.

Component D2 is preferably an organic filler from the viewpoint of imparting good curability to the cationic curable resin composition,
Preferably, at least one organic filler selected from the group consisting of acrylic fillers, styrene fillers, acrylic / styrene copolymer fillers, fluorine resin fillers, polyethylene fillers, polypropylene fillers, and silicone fillers,
More preferably, at least one organic filler selected from the group consisting of acrylic / styrene copolymer fillers, polyethylene fillers, and polypropylene fillers,
Acrylic / styrene copolymer filler is more preferred.

From the viewpoint of the normal strength, durability strength and curability of the cationic curable resin composition,
In the total amount of components D1 and D2, the content of component D1 is preferably 50 to 100% by weight, more preferably 70 to 100% by weight, still more preferably 80 to 100% by weight, and still more preferably Is 90 to 100% by weight, more preferably 100% by weight (the components D1 and D2 in the component D have a suitable composition as the cationic curable resin composition of the first embodiment) Also called a thing).

  The cationic curable resin composition of the first aspect is, for example, an LD (laser diode), a photodetector (PD: photodetector), an optical component such as a lens or a prism, or an optical module on which an optical component such as a lens is mounted. Since the optical device can be quickly fixed with high fixing accuracy, it is useful as an adhesive for an optical device for assembly. In addition, it can be used for fixing optical components such as mirrors and suspension wires.

From the viewpoint of the normal strength, durability strength and curability of the cationic curable resin composition,
The content of component D1 in the total amount of components D1 and D2 is preferably 10% by weight or more and less than 50% by weight, more preferably 15 to 45% by weight, still more preferably 20 to 40% by weight. More preferably, it is 25 to 35% by weight (the cation curable resin composition in which the components D1 and D2 in the component D have these compositions is also referred to as the cation curable resin composition of the second embodiment).

  The cationic curable resin composition of the second aspect is, for example, an optical pickup device described in paragraph 0023 of Patent Document 1, Japanese Patent Application Laid-Open No. 2007-35238, Japanese Patent Application Laid-Open No. 2007-31006, and an inclination of an actuator by a skew screw. It can be suitably used for fixing after adjusting the.

From the viewpoint that the cationic curable resin composition of the first aspect has both durability strength and curability, and the cationic curable resin composition of the second aspect has both normal strength, durability strength and curability,
In component D, the total amount of components D1 and D2 is preferably 50 to 100% by weight, more preferably 60 to 100% by weight, still more preferably 70 to 100% by weight, still more preferably 80 to It is 100% by weight, more preferably 90 to 100% by weight, and still more preferably 100% by weight.

From the viewpoint that the cationic curable resin composition has both durable strength and curability,
The average particle size of component D is preferably 0.5 to 150 μm, more preferably 1 to 100 μm, still more preferably 5 to 60 μm, still more preferably 10 to 40 μm, still more preferably 15 to 35 μm.
In addition, the average particle diameter of the component D is measured by a laser diffraction / scattering type particle size distribution measuring device manufactured by HORIBA (for example, Partica LA-950V2 manufactured by HORIBA).

(Component E)
Component E in the cationic curable resin composition is a silane coupling agent, from the viewpoint of coexistence of normal strength and durability strength of the cationic curable resin composition,
Tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane, dimethoxydiisopropoxysilane, diethoxydiisopropoxysilane, diethoxydibutoxysilane ;
Trialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltriethoxysilane, ethyltributoxysilane, cyclohexyltriethoxysilane, phenyltriisopropoxysilane; and dimethyldimethoxysilane, dimethyldi Consists of dialkoxysilanes such as ethoxysilane, diethyldiethoxysilane, diethyldibutoxysilane, phenylethyldiethoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane At least one silane coupling agent selected from the group is preferred,
Methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltriethoxysilane, ethyltributoxysilane, cyclohexyltriethoxysilane, phenyltriisopropoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxy More preferably, at least one trialkoxysilane-based silane coupling agent selected from the group consisting of silane and 3-methacryloxypropyltrimethoxysilane,
3-Glycidoxypropyltrimethoxysilane is more preferred.

(Other ingredients)
The cationic curable resin composition is necessary for diluting each component individually in advance when producing the photosensitizer (component F) and the cationic curable resin composition within the scope of the effects of the present invention. Other components such as reactive or non-reactive diluents can be included. However, the reactive diluent necessary to dilute each component individually in advance is included in component B.

As component F which is a photosensitizer, from the viewpoint of curability of the cationic curable resin composition, for example, carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, light And reducing dyes.
Specifically, as component F,
Benzoin derivatives such as benzoin methyl ether, benzoin isopropyl ether, α, α-dimethoxy-α-phenylacetophenone;
Benzophenone derivatives such as benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4′-bis (diethylamino) benzophenone;
Thioxanthone derivatives such as 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone;
Anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone; acridone derivatives such as N-methylacridone and N-butylacridone;
In addition, α, α-diethoxyacetophenone, benzyl, fluorenone, xanthone, uranyl compound and the like can be mentioned. These photosensitizers may be used alone or in combination of two or more.
A preferred photosensitizer is 2,4-diethylthioxanthone (Nippon Kayaku DETX-S).

(Cationically curable resin composition)
The cationic curable resin composition can be prepared by adding each component to a blending tank, and preferably mixing and stirring at a temperature of 50 to 80 ° C. In this case, Component C may be added after being dissolved or dispersed in a solvent such as Component E or 4-butyrolactone.

From the viewpoint of coexistence of normal strength and durability strength of the cationic curable resin composition,
The content of component D in the total amount of components A and D is preferably 10 to 70% by weight, more preferably 20 to 60% by weight, still more preferably 30 to 60% by weight, still more preferably 40 to 60% by weight. And
The content of component C is preferably 1 to 20 parts by weight, more preferably 2 to 15 parts by weight, still more preferably 4 to 10 parts by weight, and even more preferably 6 to 9 parts by weight with respect to 100 parts by weight of component A. Yes,
The content of component E is preferably 0.5 to 10 parts by weight, more preferably 1 to 8 parts by weight, still more preferably 1.5 to 6 parts by weight, based on 100 parts by weight of components A and C in total. More preferably, it is 2 to 5 parts by weight, and further preferably 2 to 4 parts by weight.

From the viewpoint of securing normal strength and curability, and from the viewpoint of improving the workability by adjusting the liquidity centered on the viscosity,
The content of component B is preferably 5 to 100 parts by weight, more preferably 5 to 85 parts by weight, still more preferably 5 to 70 parts by weight, and still more preferably 5 to 100 parts by weight of the total of components A and D. It is -55 weight part, More preferably, it is 10-45 weight part, More preferably, it is 15-35 weight part.

From the viewpoint of coexistence of durability strength and curability, or parallel strength of normal strength, durability strength and curability,
The total content of components A to E is preferably 80 to 100% by weight, more preferably 85 to 100% by weight, still more preferably 90 to 100% by weight, and more preferably 95 to 95% in the cationic curable resin composition. It is 100% by weight, more preferably 98 to 100% by weight, still more preferably 99 to 100% by weight, and still more preferably 99.5 to 100% by weight.

When component F is included, the content thereof is preferably 0.1 to 70 parts by weight, more preferably 0.2 to 50 parts by weight, still more preferably 0.3 to 35 parts by weight with respect to 100 parts by weight of component C. More preferably, it is 1-30 parts by weight, more preferably 1.5-20 parts by weight, and still more preferably 1.6-17 parts by weight.
When iodonium salt-based PI 2074 is used as component C, the use of photosensitizer DETX-S is preferred,
When sulfonium salt-based CPI-210S is used as Component C, the curability is excellent without adding a photosensitizer.

Each composition of Examples 4-6 and Comparative Examples 1-3 was manufactured using the following raw materials.
(1) Component A (epoxy resin)
Bisphenol A type epoxy resin (EPICLON860 manufactured by DIC)
Hydrogenated bisphenol A epoxy resin (YX-8034 manufactured by JER)

(2) Component B
3-ethyl-3- (phenoxymethyl) oxetane (OXT-211 (POX) manufactured by Toagosei Co., Ltd.)
Xylylenebisoxetane (OXT-121 (XDO) manufactured by Toagosei Co., Ltd.)

(3) Component C (cationic polymerization initiator)
Rhodia PI2074

(4) Component D1 (Component D) (urethane resin filler)
Negami Kogyo P-400T (average particle size 16.5 μm)
C-300 manufactured by Negami Kogyo Co., Ltd. (average particle size 21.0 μm)
GS350T manufactured by Negami Kogyo Co., Ltd. (average particle size 20.0 μm)

(5) Component D2 (Component D)
Acrylic-styrene copolymer resin filler (GS350T manufactured by Negami Kogyo Co., Ltd. (average particle size 20.0 μm))
Acrylic-styrene copolymer resin filler (BS350TM manufactured by Negami Kogyo Co., Ltd. (average particle size 29.4 μm))
In Table 1, “acryl-styrene” is represented as “Ac-St”.

(6) Component E (silane coupling agent)
KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.

  Based on the formulation shown in Table 1, 3 g of component 2020 PI2074 is dissolved in 3 g of component E KBM-403, and component A, component C component E solution, component D, and component B (total 126 g) are added. , Added to the mixing tank (NO.300 (manufactured by Kinki container), capacity 300 ml, made of polyethylene), stirred at 50 ° C. with a stirrer (RW28 (manufactured by IKA), 600 rpm) until it became transparent The cationic curable resin compositions of Examples 1 to 6 of the present invention and the compositions of Comparative Examples 1 to 3 were prepared.

[Evaluation conditions]
Normal strength and durability strength after curing of the compositions of Examples 4 to 6 and Comparative Examples 1 to 3 were measured.

(1) Normal strength Width × length × thickness = 25 mm × 50 mm × 2 mm A5052P grade aluminum plate with a width × length × thickness = 10 mm × 10 mm × 2 mm polyphenylene sulfide resin (FZ3805- manufactured by DIC) A1) (hereinafter also referred to as PPS pieces), and the compositions of Examples 4 to 6 and Comparative Examples 1 to 3 were placed on both sides of the PPS pieces perpendicular to the length direction of the aluminum plate. 003 cm3 points are attached. Point attachment was performed by injecting from a syringe controlled by air using a digital dispenser ML-5000XII (manufactured by Musashi Engineering Co., Ltd.) (FIG. 1).
Next, the spot-attached composition was irradiated with energy of 500 mW / cm ² × 10 s with a high-pressure mercury lamp LC8 (manufactured by Hamamatsu Photonics), and the spot-attached composition was cured to obtain a sample for a punch test.
The maximum compressive strength (hereinafter referred to as “push-out test”) when the punching test is performed on the center part of the surface side of the aluminum plate without the PPS piece, between the PPS piece and the aluminum plate bonded with the cured composition of the punching test sample. (Also called punching strength) was measured (FIG. 2). The punching was performed by using a uniaxial compression tester (tensile compression tester Technograph TG-10 kN, manufactured by Minebea Co., Ltd.), and applying a cylinder having a diameter of 3 mm to the center at a compression rate of 10 mm / min.
The punching strength immediately after curing the pointed composition is
In the case of 20N or more, the normal strength is ○,
When the strength is 10 or more and less than 20, the normal strength is Δ,
When the intensity is less than 10, the normal strength is ×
It was evaluated that.

(2) Durability Strength After the punch test sample is stored at 65 ° C. and 95% RH for 100 hours, the bonded portion of the PPS piece and the aluminum plate that are bonded with the cured composition is visually observed. At the interface between the PPS piece of the adhesive part and the cured composition,
When there is no uki or peeling, durability strength is ○,
Durability is ×
It was evaluated that.

(3) Curability The curability of each composition of Examples 4 to 6 and Comparative Examples 1 to 3 was tested.
Curability is determined by applying a UV irradiation machine made by Hamamatsu Photonics after applying each composition to a thickness of 1 mm.
500 mW / cm ² (365 nm) was irradiated for 2.5 seconds, 5 seconds, 10 seconds, 15 seconds, 20 seconds or 30 seconds, and the cured state was confirmed by finger touch. By touching
◎ when solidified by irradiation with energy of 1500 mJ / cm ² or less,
The case where it solidifies by irradiation of energy of 3000-4500mJ / cm < ² >,
△, even when irradiated with energy exceeding 4500 mJ / cm ² ,
The case where it was liquid even when irradiated with energy exceeding 4500 mJ / cm ^{2 was} evaluated as x.

  The above results are summarized in Table 1.

Table 1 shows the evaluation results of curability, normal strength and durability.
It is considered that the cation curable resin compositions of Examples 1 to 3 cannot have a normal state strength in the range of irradiation energy tried in Examples 4 to 6.
However, the cation curable resin compositions of Examples 1 to 3 are solidified by irradiating energy so that the normal strength becomes ◯, for example, increasing the illuminance or extending the irradiation time. When the results of Examples 4 to 6 and Comparative Examples 1 to 3 described later are seen, if the energy is irradiated and solidified so that the normal strength becomes ◯, the durability strength becomes ◯, that is, It is expected that normal strength and durability strength are compatible.
In the cationic curable resin compositions of Examples 4 to 6, the curability, normal strength, and durability strength are all “good”, and these properties are arranged side by side.
Each of the compositions of Comparative Examples 1 to 3 has an endurance strength of x, and the normal state strength and the endurance strength are not compatible.

1: Aluminum plate 2: PPS piece 3: Composition of Examples 4 to 6 or Comparative Examples 1 to 4: Cylinder punching direction during a punching test

Claims (10)

A cationic curable resin composition containing an epoxy resin (component A), a reactive diluent (component B), a cationic polymerization initiator (component C), a filler (component D) and a silane coupling agent (component E). And
The cationic curable resin composition in which the component D includes a urethane resin filler (component D1).   The cationic curable resin composition according to claim 1, wherein the oil absorption amount of the component D1 is 50 to 200 ml / 100 g.   The cationic curable resin composition according to claim 1 or 2, wherein the content of the component D1 is 10 to 100% by weight in the component D.   The cation curable resin composition according to any one of claims 1 to 3, wherein a content of the component D is 10 to 70% by weight in a total amount of the component A and the component D.   5. The cation-curable resin composition according to claim 1, wherein the content of the component E is 1 to 10 parts by weight with respect to a total of 100 parts by weight of the component A and the component D.   The cation curable resin composition according to any one of claims 1 to 5, wherein the content of component B is 5 to 100 parts by weight with respect to 100 parts by weight of components A and C in total.   The cationic curable resin composition according to claim 1, which is an adhesive for optical devices for assembling an optical device.   The cationic curable resin composition according to claim 7, wherein the optical device is an optical pickup device.   An optical device assembled using the cationic curable resin composition according to claim 7.   The optical pick-up apparatus assembled using the cationic curable resin composition of Claim 8.

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