JP2691625B2 - Two-component mixed curable resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention provides a two-component mixed curable resin which is instantly cured by light rays or ultraviolet rays and slowly cured at room temperature or by heating.

[Prior Art] UV curable resin is used for adhesives, because of its fast curing speed.
It is used in various applications such as potting materials, paints and inks. However, the curing shrinkage was larger than that of epoxy and urethane resins, and the adhesion to the substrate was poor. In addition, the places not exposed to light remain as uncured portions, which limits the use.

Resins that cure due to ultraviolet rays and other factors have been studied in the past, and Toyobo Co., Ltd. has invented the novel UV / heat combined low hygroscopic resin disclosed in JP-A-63-207812. This contains an acrylic group, an epoxy group, and a carboxyl group in the system, which cures when the acrylic group polymerizes during photocuring, and cures when the epoxy group and the carboxyl group bond during thermal curing. Is. However, this system cannot be applied to a heat-sensitive substrate because heating is required when the epoxy group and the acrylic group are bonded.

In addition, a catalyst that opens the epoxy group immediately before use is added to a resin containing an epoxy group and an acrylic group in the system, polymerization of the acrylic group occurs in photocuring, and epoxy groups or epoxy groups are combined with each other in heat curing or room temperature curing. There are also commercially available products that cure by binding the hydroxyl groups contained in the system. However, in this system, the amount of the catalyst added to the main agent was remarkably small, and the viscosities of the two were significantly different, so that it was unsuitable for automatic mixing.

Chemitech Co., Ltd. has invented an adhesive composition which is cured by ultraviolet rays and moisture in Japanese Patent Laid-Open No. 01-85268. However, this system has a drawback in that it cannot cure a thick film that moisture cannot reach, and since it uses isocyanate, carbon dioxide gas easily forms bubbles and foams.

Toyobo Co., Ltd. discloses in JP-A-63-230705 that a heat-polymerizable peroxide is further added to a photosensitive resin containing an acrylic group,
Although it has thermal polymerizability, the heat of polymerization in the case of thick film curing is large, and the adhesion to the substrate is poor due to the shrinkage of the polymerization of the acrylic group itself. , The surface remained sticky.

[Problems to be Solved by the Invention] As described above, the conventional resin composition is capable of photo-curing and room-temperature curing and is suitable for thick film curing such as potting and automatic coating,
In addition, a resin having good surface curability cannot be obtained. The present invention compensates for all of these drawbacks, and can be cured under both light and room temperature, and has excellent thick film curability, surface curability, and adhesion to a substrate. A cured resin is provided.

[Means for Solving the Problems] The two-component mixed curable resin composition of the present invention comprises an organic compound having an epoxy group and an acrylic unsaturated group in one molecule, to which a photopolymerization initiator is added. The main agent liquid and the hardener liquid containing at least one of a light-transmitting aliphatic amine epoxy resin and a mercapto epoxy resin having room temperature curability and UV transparency are used, and these are mixed and cured.

[Function] The two-component mixed type curable resin composition according to the present invention is cured by light, ultraviolet rays, normal temperature or heating.

[Examples] A two-liquid type curable resin composition according to the present invention comprises two liquids, a main liquid and a hardener liquid, which are mixed at a constant ratio immediately before use and then irradiated with light or ultraviolet rays to form a resin. Let it harden,
Even a portion that has not been cured due to the inaccessibility of light or ultraviolet rays is gradually cured by leaving it at room temperature or under heating conditions. By the way, the main agent liquid according to the present invention is mainly composed of an organic compound having a molecular weight of 300 to 5000 having both an epoxy group and an acrylic unsaturated group in the molecule, and specifically, a bisphenol A type partially esterified epoxy acrylate. (For example, Showa Highpolymer Co., Ltd. 630X-15
0), bisphenol F-type partially esterified epoxy acrylate and bisphenol AD-type partially esterified epoxy acrylate are preferable, and those modified with ethylene oxide, propylene oxide, epichlorohydrin, urethane to give the acrylate flexibility. A Br addition type is also preferable for imparting flame retardancy.

And the ratio of these acrylic groups and epoxy groups (esterification rate) is preferably 0.3 to 0.8, and the compounding ratio is
30% to 85% by weight is preferred.

Further, by adding urethane diacrylate having a molecular weight of 800 to 20000 to 5% to 50% of the total amount of the main component liquid according to the present invention, the toughness of the photo-cured portion is increased and the occurrence of cracks due to curing shrinkage is prevented. The adhesion with the material can be improved. Chemilink 9503, 9504, 9505 (above Satomer), Aronix M-1200, M-1100 (above Toa Gosei Co., Ltd.), NK Ester U-108-A (Shin Nakamura Chemical Co., Ltd.), XP- 4200B, XP-2700, XP-3000B, XP-2000
B, XP-10 (Nippon Gosei Co., Ltd.), Ebecryl-204, 20
5, Same 210, Same 220, Same 230, Same 254, Same 264, Same 265, Same 27
0, same 320 (above UCB), art resin UN-5200, same UN-1
100, same UN-6060, same UN-9000, same UN-1255, same UN-2500,
When at least one of UN-1255TM, SH-500 and SH-9832 was used, the above effects were observed.

In addition, it is necessary to add a reactive diluent with a molecular weight of 100 to 2000 in order to adjust the viscosity and improve the curing speed, and in order to improve room temperature curability, add a polyfunctional epoxy monomer and improve photocuring sensitivity. It is effective to add a trifunctional or higher functional acrylate monomer. The addition of glycidyl acrylate having both an epoxy group and an acrylic unsaturated group is effective for improving the curability of both. The amount of the reactive diluent added is preferably 5 to 65% of the total amount of the main agent liquid.

A photopolymerization initiator is added to the main component liquid in order to impart photosensitivity to ultraviolet ray or visible light to the two-component mixed curable resin according to the present invention.
Those that can be exposed to light of m or more are preferable, and those having a light-sensitive wavelength that is too short can cure only the surface of the resin. Further, the peroxide-based photopolymerization initiator that causes a reaction with the amine component of the curing agent is not preferable unless the two liquids are used up immediately because the gelation proceeds immediately after the two liquids are mixed. It is unsuitable for automatic mixing and coating machines that require a pot life of more than a minute. As a photopolymerization initiator capable of curing a thick film with a relatively long pot life after mixing the two liquids, benzoin isobutyl ether, benzoin propyl ether, 4-benzoyl-4'-methyldisulfide, benzyl dimethyl ketal, 1 -(4-Isopropylphenyl) -2-hydroxy-2methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl]
-2-Morhoinopropanone-1, 1-phenyl-1,
2-Propanedion-2- (O-ethoxycarbonyl)
It is preferable to use at least one of oxime, camphorquinone, a benzophenone / Michler's ketone mixture and a benzophenone / 4,4'-bis (diethylamino) -benzophenone mixture.

Further, a coupling agent, a thickener, a defoaming agent, a leveling agent, and a coloring agent may be added to the main agent liquid depending on the use.

On the other hand, the curing agent is preferably an aliphatic amine type or a mercaptan type from the viewpoints of room temperature curability and ultraviolet ray transparency. When an aromatic amine is used, it is difficult to cure with light, and
It did not cure even if left at room temperature for 3 days after mixing with the main agent liquid. Further, even aliphatic amines having a poor light transmission property are not preferable because they impair the photocurability. Further, when a mercaptan-based curing agent is used, a resin that is excellent in photocurability and hardens quickly even at room temperature can be obtained, but on the other hand, the usable time after mixing is short and it is not suitable for use in an automatic mixing and discharging machine. ,
Suitable for manual work. If it is desired to accelerate the curing rate at room temperature, heating at 40 ° C to 150 ° C is effective.

When using an automatic mixing / discharging machine, it is preferable that the difference in viscosity between the two liquids is small. Therefore, by blending two or more kinds of curing agents or by reacting the curing agent with an organic compound having an epoxy group in advance, By using after viscous, it is possible to bring the viscosity of the main agent liquid and the curing agent liquid close to each other, and obtain a material suitable for automatic coating.

Next, specific examples of the two-component mixed curable resin according to the present invention will be shown, but these are merely examples, and the present invention is not limited thereto.

[Example 1] Lipoxy 630X-150 (Showa Highpolymer Co., Ltd., 50% acrylated bis A type epoxy acrylate) 30 g, Chemilink-9
503 (Satomer, urethane acrylate) 6g, glycidyl methacrylate 6g, glycyrrole ED-505 (Asahi Denka Co., Ltd., trifunctional epoxy monomer) 4g, Aronix M-
320 (Toagosei Co., Ltd., propylene oxide dimer modified trimethylolpropane triacrylate) 4g, 2
-Methyl-1- [4- (methylthio) phenyl] -2-
Add 11.9 g of morpholino propane to a 10 ml beaker, 80
Stir while warming to ℃. When the resin inside becomes transparent, it is returned to room temperature to obtain a resin composition having a viscosity of about 1600 cps (20 ° C). This is referred to as a main agent liquid 1. Next, Hardener 261 (Asahi Denka Co., Ltd., both ends amine oligomer ester compound)
A solution obtained by adding 8 g of glycyrrole ED-505 to 40 g is reacted under a nitrogen atmosphere at 120 ° C. for 4 hours while stirring. The viscosity of the obtained liquid was about 1800 cps (20 ° C). This is referred to as a curing agent liquid 1.

Using a two-liquid mixing and discharging device (manufactured by Naka Liquid Control Co., Ltd.) at a ratio of 3: 1, the above-mentioned main agent liquid 1 and curing agent liquid 1 were cast into a polyester FRP petri dish having a diameter of 9 cm and a depth of 10 mm, and the amount was over 250 W When irradiated with a 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. Furthermore, when this petri dish was left at 20 ° C. for 12 hours, it completely hardened to the bottom. The obtained two-component mixed type curable resin composition was in good contact with the wall surface of the petri dish and could not be taken out manually. This cured resin composition had different physical properties between the photocured portion and the room temperature cured portion. The photocured portion had Tg of 58 ° C. and Shore D hardness of 95, whereas the room temperature cured portion had Tg of 16 ° C. and Shore D hardness of 42. The photo-cured portion in the upper layer portion has excellent moisture resistance and has a property of being hard to be deformed by a strong external force. On the other hand, the room temperature cured portion in the lower layer portion serves to relieve internal stress due to curing shrinkage, and further has excellent adhesion to the substrate and heat shock resistance.

It took 42 minutes at 25 ° C. until the viscosity of the mixture of the main agent liquid 1 and the hardening agent liquid 1 became twice as high as the initial mixing (3300 cps).

[Example 2] Lipoxy 630X-15030g, XP-2000B (Nippon Gosei Co., Ltd.,
Urethane acrylate) 4g, glycidyl methacrylate
6 g, Aronix M-325 (Toagosei Co., Ltd., caprolactone-modified tris (acryloxyethyl) isocyanurate) 4 g, glycyrrole 505 3 g, and benzyl dimethyl ketal 1.9 g are put in a 100 ml beaker and stirred while warming to 80 ° C. When the resin inside becomes transparent, the viscosity will be approx.
A resin composition of 2000 cps (20 ° C) is obtained. This is referred to as a base liquid 2. Next, QX-40 (Okaka Shell Epoxy Co., Ltd.)
A mercaptan-based epoxy curing agent is referred to as a curing agent liquid 2.

The main agent liquid 2 and the curing agent liquid 2 are rapidly mixed at a ratio of 2: 1 and cast into the petri dish used in Example 1. Then, when it was irradiated with the light source used in Example 1 for 4 seconds, it was cured to a depth of 7.5 mm from the surface. When it was allowed to stand at 20 ° C for 2 hours, it was completely cured to the bottom. In the case of the two-component mixed type curable resin composition in this case, the difference in the physical properties between the photo-cured part and the room-temperature cured part is slight, the boundary is not clear, and the surface hardness exceeds Shore D100. And Tg was 68 ° C. Furthermore, in this case, the thickening action started immediately after mixing, and almost no fluidization occurred after 3 minutes.

Although the coupling agent, the thickening agent, the leveling agent, the defoaming agent, and the coloring agent are not added in the above-mentioned examples, they may be added as necessary.

[Effect of the Invention] Since the two-component mixed curable resin composition according to the present invention is constituted as described above, it has an effect that it can be cured by light or ultraviolet rays, room temperature or heating.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location G03F 7/032 501 G03F 7/032 501

Claims (1)

(57) [Claims] 1. A base compound solution and an ordinary temperature curable composition comprising an organic compound having both an acrylic unsaturated group and an epoxy group in one molecule, to which a photopolymerization initiator sensitive to light of 250 nm or more is added. It is composed of a curing agent liquid composed of at least one kind of a light-transmitting aliphatic amine epoxy resin or mercapto epoxy resin having ultraviolet transparency, and by mixing these base liquids and curing agent liquids with light or ultraviolet rays, Alternatively, a two-component mixed type curable resin composition that is cured at room temperature or in a heating atmosphere.