JP2761092B2 - Two-part curable resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention provides a method of irradiating light (radiation, far ultraviolet ray, ultraviolet ray, visible light ray) to immediately or temporarily harden,
The present invention relates to a two-part mixed type curable resin composition which can be fully cured while being kept at room temperature.

[Related Art] Due to the speed of curing, ultraviolet curable resins are used in various applications such as adhesives, potting materials, paints, and inks. However, there is a drawback that curing shrinkage is large and adhesion to a substrate is poor compared to epoxy resins and urethane resins. Further, since the portion not exposed to light remains as an uncured portion, the use is restricted.

Therefore, resins that are temporarily cured by ultraviolet light and completely cured by other factors have been studied in the past, and are disclosed in JP-A-63-2078.
As disclosed in Japanese Patent Publication No. 12, a UV / heat combined low moisture absorption resin is being developed. This is a system containing an acryloyl group, an epoxy group and a carboxyl group in the system, and is cured by polymerization of the acryloyl group during photocuring, and the epoxy group and the carboxyl group are bonded during thermal curing. This cures. But,
In this system, since heating is required when the epoxy group and the carboxyl group are bonded, it cannot be applied to a heat-sensitive substrate.

Also, by adding a catalyst that opens the epoxy group to the resin containing an epoxy group and an acryloyl group in the system immediately before use, polymerization of the acryloyl group occurs in photocuring, and epoxy groups or epoxy groups in thermal curing or room temperature curing. There are also commercially available products that cure by the combination of a group and a hydroxyl group contained in the system. However, this system is unsuitable for automatic mixing because the amount of catalyst added to the base agent is extremely small and the viscosities of both are greatly different.

In JP-A-1-85268, an adhesive composition which is cured by ultraviolet light and moisture has been developed. However, this system has the disadvantages that it is not possible to cure a thick film to which moisture cannot reach, and that carbon dioxide gas tends to be bubbled because of the use of isocyanate.

Japanese Patent Application Laid-Open No. 63-230705 discloses that a photopolymerizable resin is added to a acryloyl group-containing photosensitive resin by adding a thermopolymerizable peroxide. There is a problem that the heat is large, the adhesion to the substrate is deteriorated by the influence of the shrinkage of the polymerization of the acryloyl group itself, and the surface is left sticky due to the inhibition of surface hardening due to the inhibition of the polymerization of oxygen.

[Problems to be Solved by the Invention] As described above, the conventional resin composition can be temporarily cured by light, can be completely cured at room temperature, is suitable for thick film curing by potting and the like, and is particularly suitable for automated production. It is not possible to obtain a good surface curability that can exert its effects in a line.

The present invention eliminates all of these disadvantages, becomes solid upon irradiation with light, and becomes a tough cured product at room temperature. In addition, thick film curability, surface curability, adhesion to substrates, environmental resistance, and electrical insulation It is an object of the present invention to provide a two-pack type curable resin composition which is excellent in water resistance and can be automatically mixed and applied.

[Means for Solving the Problems] The present invention provides (A) an epoxy acrylate in which a part of an epoxy group in the molecule is acrylic-modified, a urethane acrylate having at least two acryloyl groups in the molecule, and a bisphenol-type epoxy oligomer. And a base liquid containing a photopolymerization initiator as a main component, and (B) 3,9-bis (3-aminopropyl) -2,4,8,10-
The present invention relates to a two-part curable resin composition comprising a curing agent liquid containing tetraspiro [5,5] undecane or a modified product thereof as a main component.

[Functions / Examples] The two-component mixed type curable resin composition of the present invention comprises the following main component liquid and curing agent liquid.

The main agent liquid contains, as main components, an epoxy acrylate in which a part of epoxy groups in the molecule is acrylic-modified, a urethane acrylate having at least two acryloyl groups in the molecule, a bisphenol-type epoxy oligomer, and a photopolymerization initiator.

The epoxy acrylate is a component blended as a photopolymerization component.

The molecular weight of the epoxy acrylate is preferably from 200 to 5,000, more preferably from 250 to 4,000. If the molecular weight is less than 200, the resin will have a large shrinkage upon curing and the adhesion to the substrate will be reduced, and further the plasticity of the resin itself will be lost, so that the toughness will be reduced. And the epoxy equivalent increases, so that the amount added to the base material is significantly restricted, and as the molecular weight increases, the compatibility with the curing agent decreases and curing tends to be hindered.

The acrylic modification rate (esterification rate) of the epoxy acrylate is preferably from 0.3 to 0.8, and more preferably from 0.35 to 0.75. If the esterification ratio exceeds 0.8, the toughness of the resin composition decreases, and if it is less than 0.3, the photopolymerizability decreases, which is not practical.

Examples of such epoxy acrylates include bisphenol A type partially esterified epoxy acrylates (for example, 630X-150, manufactured by Showa Polymer Co., Ltd.),
Modified bifunctional bisphenol epoxy oligomers such as bisphenol F-type partially esterified epoxy acrylate and bisphenol AD-type partially esterified epoxy acrylate are preferred. Incidentally, a polyfunctional novolak system is not suitable because it adversely affects the adhesion. Further, the epoxy acrylate is preferably modified with ethylene oxide, propylene oxide, epichlorohydrin, urethane or the like to provide flexibility, or a Br-added type to impart flame retardancy. These may be used alone or in combination of two or more.

The mixing ratio of the epoxy acrylate is 8 to 75 in the base liquid.
% (% By weight, hereinafter the same), more preferably 10 to 50%. If the amount of epoxy acrylate is too small, no curing to the toughness of the resin is observed, and if the amount is too large, the toughness in the photocured state is reduced.

Urethane acrylate is further compounded as a photopolymerizable component in the base liquid in order to increase the sensitivity at the time of photocuring and to improve the toughness of the photocured product.

Urethane acrylate is a bifunctional or trifunctional compound having a molecular weight of 500 to 20,000, preferably 700 to 10,000.
Are more preferred. When the molecular weight is less than 500, the strength of the photocured film formed at the time of photocuring is low, and when it exceeds 2,000, the compatibility with the curing agent is reduced and the photocuring speed tends to be reduced.

Specific examples of such urethane acrylate include:
For example, Chemlink 9503, 9504, 9505 (all made by Satmer), Alonix M-1200, M-1100 (all,
Toa Gosei Chemical Industry Co., Ltd.), NK ester U-108-A
(Manufactured by Shin-Nakamura Chemical Co., Ltd.), XP-4200B, XP-7000B,
XP-2700, XP-3000B, XP-2000B, XP-10 (all manufactured by Nihon Synthetic Chemical Industry Co., Ltd.), Ebecryl-204, 205 and 21
0, 220, 230, 254, 264, 265, 270, 320
(Above, manufactured by UCB), Art Resin UN-5200, UN-110
0, UN-6060, UN-9000, UN-1255, UN-250
0, UN-2355TM, SH-500, SH-380GA, SH-983
2 (above, manufactured by Negami Industry Co., Ltd.) and Beam Set 502H (manufactured by Arakawa Chemical Industry Co., Ltd.). These may be used alone or in combination of two or more.

The mixing ratio of the urethane acrylate is 5 to 50 in the base solution.
%, More preferably 7 to 40%. The ratio is 5
When the amount is less than 50%, the sensitivity at the time of photocuring is increased, and the toughness of the photocured product is hardly obtained. The effect tends to be weak. The effects of increasing the sensitivity and improving the toughness are important in handling in a light-cured state.

In order to adjust the viscosity and improve the curing speed by light, a polyfunctional acrylate-based reactive diluent having a molecular weight of 100 to 2,000 may be added to the main solution.

Specific examples of the reactive diluent include dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, alkyl-modified dipentaerythritol pentaacrylate (Kayarad D-310 manufactured by Nippon Kayaku Co., Ltd.), alkyl-modified Dipentaerythritol tetraacrylate (Kayarad D-320 manufactured by Nippon Kayaku Co., Ltd.), caprolactone-modified dipentaerythritol hexaacrylate (DPCA-20, DPCA-30, DPCA-60, DPCA manufactured by Nippon Kayaku Co., Ltd.) −12
0), ditrimethylolpropane tetraacrylate,
Examples include pentaerythritol triacrylate, pentaerythritol tetraacrylate, and trimethylolpropane triacrylate. Of course, acrylates may be used instead of methacrylates.

If the mixing ratio of the reactive diluent is too large, the toughness of the resin is impaired.

A bisphenol-type epoxy oligomer is further added to the base liquid to improve adhesion and toughness.

Bisphenol type epoxy oligomer has a molecular weight of 300
-3000 is preferable, and 500-2000 is more preferable. If the molecular weight is less than 300, the cured product becomes brittle, and the adhesion to the base material is reduced.If the molecular weight is more than 3000, the epoxy equivalent of the system becomes large, so that the mixing ratio with the curing agent becomes unbalanced, and the Workability tends to decrease because the viscosity also increases.

 Further, the epoxy equivalent is preferably from 150 to 1,000.

Specific examples of such epoxy oligomers include, for example, bisphenol A epoxy oligomer, bisphenol F epoxy oligomer, bisphenol AD epoxy oligomer, and the like, and are selected according to the viscosity of the base liquid.

The mixing ratio of the bisphenol-type epoxy oligomer is
The content is preferably 20 to 85%, more preferably 30 to 80% in the main solution. If the proportion is less than 20%, the cured product tends not to have sufficient heat resistance and toughness, and if it exceeds 85%, the photocurability tends to decrease.

If necessary, a urethane-modified epoxy oligomer may be added to the base liquid in place of part (about 20% or less) of the bisphenol-type epoxy oligomer in order to impart flexibility to the resin. Examples include EPU-6, EPU-6A, EPU-11, and EPU-6 manufactured by Asahi Denka Kogyo Co., Ltd.
PU-15, EPU-73, EPU-17 and the like.

As the photopolymerization disclosure agent to be blended in the main solution, those suitable for thick film curing are preferable. Specific examples of such a photopolymerization initiator include, for example, diethoxyacetophenone, benzoin ethyl ether, benzoyl isopropyl ether, benzyl dimethyl ketal, camphorquinone,
2-methyl-1- [4- (methylthio) phenyl] -2
-Morpholinopropane-1, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane and the like.

The mixing ratio of the photopolymerization initiator is preferably from 2 to 10%, more preferably from 2.5 to 5%, in the main solution. If the ratio is less than 2%, the photocuring sensitivity tends to decrease, and if it exceeds 10%, the photocured film thickness becomes thin, and the adhesion, moisture resistance and heat resistance of the cured product tend to decrease.

Further, an epoxy resin diluent such as an aliphatic diglycidyl ether may be used in order to obtain a low viscosity base solution. When an epoxy resin diluent is used, its blending ratio is preferably 20% or less in the base solution from the viewpoint of toughness, heat resistance and adhesion to a substrate of the cured product.

In addition, a coupling agent, a thickener, a leveling agent, a coloring agent, a filler, and the like may be blended in the base liquid according to the application.

The viscosity of the base solution is usually adjusted to about 400 to 10,000 cps (35 ° C.).

The curing agent liquid used in the present invention contains 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [5,5] undecane (hereinafter referred to as ATU) or a modified product thereof as a main component. Is what you do.

Because ATU is an aliphatic compound, it has good UV transmission and, in comparison to other aliphatic epoxy curing agents,
The cured product can have excellent heat resistance and toughness. In addition, since this compound forms a crystal at normal temperature, it is usually sold after being modified, and such a modified product may be used as it is in the present invention. Examples of the modified product include Epomate series manufactured by Yuka Shell Epoxy Co., Ltd.

The mixing ratio of ATU and modified ATU is 50 to 100% in the curing agent liquid.
Is preferable, and 55 to 100% is more preferable. The ratio is 50
If it is less than 10%, a cured product utilizing the characteristics of the ATU cannot be obtained, and crack resistance is reduced particularly due to thermal shock.

The curing agent liquid may contain other curing agent components,
As such a curing agent component, a proamide having a large active hydrogen equivalent, a polyetherdiamine, or a modified product thereof is suitable. Since polyether diamine has a low viscosity, it can be thickened by reacting it with a bisphenol-type epoxy oligomer. However, these are effective in controlling the reaction rate and the active hydrogen equivalent, but when used in large amounts, they reduce the toughness and moisture resistance of the cured product. Therefore, the mixing ratio is preferably 50% or less in the curing agent liquid.

In addition, the curing agent liquid has a coupling agent according to the application,
A thickener, an antifoaming agent, a leveling agent, a coloring agent, a filler, and the like may be added.

The viscosity of the curing agent liquid is usually adjusted to about 400 to 10,000 cps (35 ° C.).

The two-part curable resin composition of the present invention comprises the above-mentioned base liquid and curing agent liquid, and is used by being mixed immediately before use.

The mixing ratio between the main agent liquid and the curing agent liquid is preferably such that the epoxy equivalent / active hydrogen equivalent is in the range of 0.8 / 1 to 1 / 0.8. The weight ratio of the base liquid / hardener liquid is preferably in the range of 1/4 to 4/1, and 1/1
Is preferable, but usually the mixing ratio of the curing agent is smaller.

The mixing method is not particularly limited, and for example, an automatic mixing / discharging machine can be used, or measurement mixing and discharging can be performed by a person.

When using an automatic mixing and discharging machine, the difference between the viscosities of the two liquids is preferably small in order to achieve uniform mixing.
It is preferable that the mixing ratio of the two liquids is not extremely different. However, in the resin composition of the present invention, the viscosities of the base liquid and the curing agent liquid can be easily adjusted, and the amounts used can be kept from being largely different. Therefore, a resin composition suitable for automatic application can be obtained.

The resin composition of the present invention can be preliminarily cured by irradiating light to temporarily cure the resin composition, and left at room temperature or under heating conditions, and can be gradually cured, even with potting having a thickness of about 1 cm. A cured product that can be completely cured and has excellent surface curability, adhesion to a substrate, and electrical insulation is obtained.

Next, the present invention will be described more specifically with reference to examples, but these are merely examples, and the present invention is not limited to these.

Example 1 23.8 g of Lipoxy 630X-150 (50% acrylated bis-A type epoxy acrylate manufactured by Showa Polymer Co., Ltd.), EP-490
1 (bisphenol F type epoxy resin manufactured by Asahi Denka Kogyo Co., Ltd.) 47.6 g, SH-380GA (trifunctional urethane acrylate manufactured by Negami Kogyo Co., Ltd.) 9.5 g, glycyrol ED-503 (Asahi Denka Kogyo Co., Ltd.) 9.5 g, Alonix M-320 (propylene oxide dimer-modified trimethylolpropane triacrylate manufactured by Toa Gosei Chemical Industry Co., Ltd.) and 4.8 g of diethoxyacetophenone (DEAP) were mixed at 80 ° C. And stirred while warming. After the mixture becomes clear, return to room temperature and the viscosity is about 700 cps
(35 ° C.) was obtained. This is referred to as a main agent liquid 1.

On the other hand, a solution obtained by adding 3.1 g of EP-4901 to 11.9 g of EH-280 (polyether diamine manufactured by Asahi Denka Kogyo Co., Ltd.) was reacted under a nitrogen atmosphere at 120 ° C. for 4 hours while stirring, and then allowed to reach room temperature. I put it back. The viscosity of the obtained liquid was about 750 cps (35 ° C.). 35.0 g of Epomate B002 (ATU-modified epoxy curing agent manufactured by Yuka Shell Epoxy Co., Ltd.) was added thereto, and the mixture was stirred until the whole became uniform to obtain a curing agent liquid having a viscosity of 960 cps (35 ° C.). This is referred to as a curing agent liquid 1.

The main agent liquid 1 and the curing agent liquid 1 are cast at a ratio of 2: 1 (weight ratio) into a polyester FRP petri dish having a diameter of 9 cm and a depth of 10 mm using a two-liquid mixing / discharging apparatus (manufactured by Naka Liquid Control Co., Ltd.). When irradiated with a 250 W ultra-high pressure mercury lamp at an irradiation intensity of 50 mW / cm ² for 14 seconds, it was cured to a depth of about 4 mm from the surface. When this petri dish was left at 20 ° C. for 12 hours, it was completely cured to the bottom. The obtained cured product was in good contact with the petri dish wall surface. The petri dish was immersed in red ink, and the pressure was reduced by a vacuum pump, but no seepage at the interface was observed.

The Shore D hardness of the cured product was 21, and the Shore D hardness of the cured product cured without irradiation with UV was 19. Since there is little difference in hardness between the obtained cured product and the same cured product except that UV irradiation was not performed, it is considered that the physical properties are mostly due to the epoxy / amine component. .

Also, use a potted petri dish at -20 ° C for 1hr / +
After 300 cycles of a heat shock test at 80 ° C for 1 hour, the sample was further exposed to a humidity test at 60 ° C and 95% Rh for 30 days, but the appearance and the hardness and electrical resistance did not change. Was.

Example 2 Lipoxy 630X-150 24.7 g, EP-4901 49.4 g, SH-380
GA 12.3 g, EPU-6 (urethane-modified epoxy oligomer manufactured by Asahi Denka Kogyo KK) 9.9 g, SH-380GA 12.3 g, DEAP
3.7 g and 0.005 g of a silicone-based antifoaming agent were mixed and stirred while warming to 80 ° C. After the mixture became transparent, it was returned to room temperature to obtain a resin composition having a viscosity of about 2460 cps (35 ° C.).
This is referred to as a base liquid 2.

On the other hand, a solution obtained by adding 3.5 g of EP-4901 to 11.5 g of EH-280 was reacted under a nitrogen atmosphere at 120 ° C. for 4 hours while stirring, and then returned to room temperature. The viscosity of the obtained liquid is about 1800 cps (3
5 ° C). Add 35.0 g of Epomate B002 to this,
Stir until the whole becomes uniform to obtain a viscosity of about 1870 cps (35
° C). This is referred to as a curing agent liquid 2.

The diameter of the main agent liquid 2 and the curing agent liquid 2 is determined using a two-liquid mixing and discharging device (manufactured by Naka Liquid Control Co., Ltd.) at a ratio of 2: 1.
Cast into a 9 cm, 10 mm deep Polyether FRP Petri dish, 250 W
Irradiation with an ultra-high pressure mercury lamp at an irradiation intensity of 50 mW / cm ² for 14 seconds hardened to a depth of about 5 mm from the surface. When this petri dish was left at 20 ° C. for 12 hours, it was completely cured to the bottom. The obtained cured product was in good contact with the petri dish wall surface. The petri dish was immersed in red ink, and the pressure was reduced by a vacuum pump, but no seepage at the interface was observed.

The Shore D hardness of the UV-irradiated surface of the cured product was 22, and the Shore D hardness of the cured product cured without UV irradiation was 21.5.
Since the difference in hardness between the obtained cured product and the cured product cured in the same manner except that UV irradiation was not performed is small,
It is considered that the physical properties are mostly due to the epoxy / amine component.

Also, use a potted petri dish at -20 ° C for 1hr / +
After 300 cycles of a heat shock test at 80 ° C for 1 hour, the sample was further exposed to a humidity test at 60 ° C and 95% Rh for 30 days, but the appearance and the hardness and electrical resistance did not change. Was.

Example 3 24.7 g of lipoxy 630X-150, 49.4 g of EP-4901, 7.41 g of beam set 502H (urethane acrylate manufactured by Arakawa Chemical Industries, Ltd.), 4.94 g of glycylol ED-503, 4.94 g of dipentaerythritol hexaacrylate (DEHA) g, DEAP
3.7 g and 0.005 g of a silicone-based antifoaming agent were mixed and stirred while warming to 80 ° C. After the resin in the inside became transparent, the temperature was returned to room temperature to obtain a resin composition having a viscosity of about 1900 cps (35 ° C.).
This is referred to as a main agent liquid 3.

On the other hand, a solution obtained by adding 3.5 g of EP-4901 to 11.5 g of EH-280 was reacted under a nitrogen atmosphere at 120 ° C. for 4 hours while stirring, and then returned to room temperature. The viscosity of the obtained liquid is about 1350 cps (3
5 ° C). Add 35.0 g of Epomate B002 to this,
Stir until the whole becomes uniform to obtain a viscosity of about 1350 cps (35
° C). This is referred to as a curing agent liquid 3.

The diameter of the main agent liquid 3 and the curing agent liquid 3 is determined using a two-liquid mixing and discharging device (manufactured by Naka Liquid Control Co., Ltd.) at a ratio of 2: 1.
Cast into a 9 cm, 10 mm deep Polyether FRP Petri dish, 250 W
Irradiation with an ultra-high pressure mercury lamp at an irradiation intensity of 50 mW / cm ² for 14 seconds hardened to a depth of about 4 mm from the surface. When this petri dish was left at 20 ° C. for 12 hours, it was completely cured to the bottom. The obtained cured product adhered well to the petri dish wall surface, and the Shore D hardness of the UV-irradiated surface of the cured product was 20.5, and the Shore D hardness of the cured product cured without UV irradiation was 19.5. Since the difference in hardness between the obtained cured product and the cured product cured in the same manner except that no UV irradiation was performed is slight, it is considered that the physical properties are mostly attributed to the epoxy / amine component.

Also, use a potted petri dish at -20 ° C for 1hr / +
After 300 cycles of a heat shock test at 80 ° C for 1 hour, it was further exposed to the conditions of a humidity test at 60 ° C and 95% Rh for 30 days, but the appearance, the hardness, and the electrical resistance did not change. .

[Effect of the Invention] The two-part curable resin composition of the present invention can be applied by automatic mixing and coating, can be temporarily cured by light irradiation, can be completely cured by standing at room temperature, and the cured product is a substrate Adhesion with
This has the effect of being excellent in environmental resistance and electrical insulation.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // G03F 7/027 513 G03F 7/027 513 515 515 (72) Inventor Satoshi Yanagiura 8-1-1 Honcho Tsukaguchi, Amagasaki City, Hyogo Prefecture No. Mitsubishi Materials Corporation Materials Research Laboratory (72) Inventor Yasushi Yamamoto 8-1-1 Tsukaguchi Honcho, Amagasaki City, Hyogo Prefecture Mitsubishi Electric Corporation Materials Research Laboratory (56) References JP-A-63-207812 (JP, A) JP-A-49-30465 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08G 59/20-59/56 C08F 299/00-299/08 C08F 2/44-2 / 50 G03E 7/027

Claims (1)

(57) [Claims] 1. A main component comprising (A) an epoxy acrylate in which a part of the epoxy group in the molecule is acrylic-modified, a urethane acrylate having at least two acryloyl groups in the molecule, a bisphenol-type epoxy oligomer, and a photopolymerization initiator. (B) 3,9-bis (3-aminopropyl) -2,4,8,10-
A two-part curable resin composition comprising a curing agent liquid containing tetraspiro [5,5] undecane or a modified product thereof as a main component.