JPH03210324A - Two-liquid curing resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

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

[Prior Art] Ultraviolet curing resins are used in a variety of applications such as adhesives, botting materials, paints, and inks because of their fast curing speed. However, compared to epoxy and urethane resins, curing shrinkage was large and the adhesion to the substrate was poor.

Furthermore, areas that are not exposed to light remain as uncured areas, which limits its application.

Resins that harden due to ultraviolet rays and other factors have been researched for some time, and Toyobo Co., Ltd.
We have invented a new low moisture absorption resin that can be used in conjunction with UV/heat, as seen in the publication No. This has acrylic groups, epoxy groups,
It contains a carboxyl group and is cured by polymerization of the acrylic group during photocuring, and is cured by bonding between the epoxy group and the carboxyl group during heat curing. However, this system requires heating when the epoxy group and acrylic group bond, so it could not be applied to base materials that are sensitive to heat.

In addition, a catalyst that opens the epoxy groups is added to the resin containing epoxy groups and acrylic groups in the system immediately before use, and the acrylic groups polymerize in photocuring, and the epoxy groups polymerize with each other or with each other in thermocuring or room temperature curing. There are commercially available products that cure by bonding the hydroxyl groups contained in the system, but in this system, the amount of catalyst added to the main ingredient is extremely small, and the viscosity of the two is also greatly different, so it is difficult to mix automatically. It was inappropriate.

Chemical Co., Ltd. has invented an adhesive composition that cures with ultraviolet rays and moisture in Japanese Patent Application Laid-Open No. 01-852687.
However, this system has the disadvantage that it cannot cure thick films that cannot be reached by moisture, and because it uses isocyanate, carbon dioxide gas tends to form bubbles and foam.

In JP-A-63-230705, Toyobo Co., Ltd. adds a thermally polymerizable peroxide to a photosensitive resin containing an acrylic group to impart thermal polymerizability, but polymerization in the case of thick film curing is difficult. The adhesion to the substrate was poor due to the large amount of heat and the contraction of the polymerization itself of the acrylic group, and the surface remained sticky due to inhibition of surface hardening due to inhibition of polymerization by oxygen.

[Problems to be Solved by the Invention] As described above, it is possible to obtain a resin with conventional resin compositions that is capable of photocuring and room temperature curing, is suitable for thick film curing such as botting, and automatic coating, and has good surface curing properties. I can't. The present invention compensates for all of these drawbacks by creating a two-component mixed type that can be cured both by light and at room temperature, has excellent thick film curing properties, surface curing properties, and adhesion to substrates, and can be automatically mixed and applied. It provides a cured resin.

[Means for Solving the Problems] The two-component mixed curable resin composition of the present invention is made of an organic compound having an epoxy group and an acrylic unsaturated group in one molecule, and a photopolymerization initiator added thereto. The main agent liquid is mixed with a curing agent liquid consisting of at least one of a translucent aliphatic amine-based epoxy resin or a mercapto-based epoxy resin that is curable at room temperature and transparent to ultraviolet rays.

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

Pretext flow side] The two-component mixed curable resin composition according to the present invention comprises a base liquid,
Consisting of two liquid hardeners, the resin is mixed at a certain ratio just before use, and then exposed to light or ultraviolet light to cure the resin. Even areas that are not cured because the light or ultraviolet light does not reach can be cured at room temperature or heated. By leaving it under certain conditions, it gradually hardens. By the way, the main liquid according to the present invention is
Organic compounds with a molecular weight of 300 to 5000 that have both an epoxy group and an acrylic unsaturated group in the molecule are mainly used, and specifically, bisphenol A type partially esterified epoxy acrylate (for example, Showa Kobunshi Co., Ltd. 630X)
-150), bisphenol F type partially esterified epoxy acrylate, and bisphenol AD type partially esterified epoxy acrylate are preferable, and in order to impart flexibility to the above acrylate, ethylene oxide,
Also preferred are those modified with propylene oxide, epichlorohydrin, urethane, and those modified with Br to impart flame retardancy.

The ratio of these acrylic groups to epoxy groups (esterification rate) is preferably 0.3 to 0.8, and the blending ratio is preferably 30% to 85% by weight of the entire base liquid.

Furthermore, by adding urethane diacrylate having a molecular weight of 800 to 20,000 to the base resin solution in an amount of 5 to 50% of the total weight of the base resin solution, the toughness of the photocurable part is increased, the occurrence of cracks due to curing shrinkage is prevented, and the base material The adhesion to the material can be improved. Chemilink 9503, 950
4, 9505 (Satmar Corporation), Aronix M-
1200, M-1100 (Toagosei Co., Ltd.), N
K ester U~108-A (Shin Nakamura Chemical Co., Ltd.),
xp-4200B, XP-7000B,
P-2700, XP-3000B, XP-2000
B, XP-10 (Nippon Gosei Co., Ltd.), E becr
yl-204, yl-205. 21O1 220, 23
0, 254, 264, 265, 270. 32
0 (all manufactured by UCB), Art Resin UN-5200
, UN-1100, UN-6060, UN-
9000, UN-1255, UN-2500
, UN-1255TM, 5H-500, 5H-9
When at least one type of 832 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 to adjust the viscosity and improve the curing speed, and to improve room temperature curability, it is necessary to add a polyfunctional epoxy monomer and to improve the photocuring sensitivity. It is effective to add an acrylate monomer having trifunctional or higher functionality. Furthermore, addition of a substance having both an epoxy group and an acrylic unsaturated group, such as glycidyl acrylate, is effective in improving the curing properties of both.

The amount of these reactive diluents added is 5 to 50% of the total base liquid.
65% is preferred.

In order to impart photosensitivity to ultraviolet rays or visible light to the two-component mixed cured resin according to the present invention, a photopolymerization initiator is added to the main resin.
It is preferable to use a material that can be sensitive to light of nm or more, and a material whose sensitive wavelength is too short can only cure the surface of the resin. In addition, peroxide-based photopolymerization initiators that cause reactions with the amine component of the curing agent will cause gelation to proceed immediately after mixing the two liquids, so they are not preferred unless the two liquids are mixed and used immediately. It is unsuitable for automatic mixing and coating machines that require a pot life of more than 1 minute. Photopolymerization initiators that have a relatively long pot life after mixing two liquids and are capable of thick film curing include benzoin isobutyl niter, benzoin propyl ether, 4-benzoyl-4'-methyl disulfide, benzyl dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2methylpropane-1-
on, 2-methyl-1-(4-(methylthio)phenyl-2-morphoinopropanone-1,1-phenyl-1
, 2-propanedione-2-(0-ethoxycarbonyl)oxime, camphorquinone, a benzophenone/Michler's ketone mixture, and a benzophenone/4,4'-bis(diethylamino)-benzophenone mixture.

Further, a coupling agent, a thickener, an antifoaming agent, a novelting agent, and a coloring agent may be added to the main liquid depending on the purpose.

On the other hand, the curing agent is preferably an aliphatic amine type or a mercaptan type from the viewpoint of room temperature curability and ultraviolet transmittance. When an aromatic amine was used, it was difficult to cure with light, and it did not cure even after being left at room temperature for 3 days after being mixed with the main solution. Also, among aliphatic amines, types with poor light transmittance are not preferred because they impair photocurability. Furthermore, when using a mercaptan-based curing agent, it is possible to obtain a resin that has excellent photocurability and hardens quickly even at room temperature, but on the other hand, the pot life after mixing is short, making it unsuitable for use with automatic mixing and dispensing machines. but,
Suitable for manual work. Moreover, when it is desired to accelerate the curing speed at room temperature, heating at 40°C to 150°C is effective.

Note that when using an automatic mixing and dispensing machine, it is preferable that the difference in viscosity between the two liquids be small, so blend two or more types of curing agents or react the curing agent with an organic compound having an epoxy group in advance to increase the amount of viscosity. By using the resin after it has been allowed to thicken, the viscosities of the base liquid and the curing agent liquid can be made close to each other, making it possible to obtain a product suitable for automatic application.

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

Pretext flow side 1 Coriboxy 630X-1,50 (Showa Kobunshi Co., Ltd., 5
0% acrylated bis A type epoxy acrylate 30g,
Chemilink-9503 (Satomar Co., Ltd., urethane acrylate) 6 g, glycidyl methacrylate axis, glycyol ED-505 (Asahi Denka Co., Ltd., trifunctional epoxy monomer) 4 g, Aronix M-320 (Toagosei Co., Ltd.)
propylene oxide dimer modified trimethylolpropane triacrylate) 4g, 2-methyl-1-(4-
(Methylthio)phenyl-2-morpholinopropane-
Put 11.9 g into a 100i beaker and stir while warming to 80°C. When the resin inside becomes transparent, return it to room temperature to obtain a resin composition with a viscosity of about 1600 cps (20°C). This is referred to as base liquid 1. Next, Hardener 261 (
A solution prepared by adding 5058 g of glycyol ED-50 to 40 g of a double-terminated amine oligomer ester compound (manufactured by Asahi Denka Co., Ltd.) is reacted at 120° C. for 4 hours under a nitrogen atmosphere with stirring. The viscosity of the obtained liquid is approximately 1800 cps (20°C)
Met. This will be referred to as curing agent liquid 1.

The above main agent liquid 1 and curing agent liquid 1 were poured into a polyester FRP petri dish with a diameter of 9 cm and a depth of 10 mm using a two-liquid mixing bath device (manufactured by Nakaliquid Control Co., Ltd.) at a ratio of 3=1, and the mixture was heated at 250 W. 50mW/cf with ultra-high pressure mercury lamp
When irradiated for 14 seconds at an irradiation intensity of f12, it was cured to a depth of about 4 mm from the surface. 20 more of this petri dish
When it was left to stand at ℃ for 12 hours, it was completely cured to the bottom.

The obtained two-component mixed cured resin composition adhered well to the wall surface of the petri dish and could not be taken out by inputting.

This cured resin composition has different physical properties in the photocured part and the room temperature cured part, and the photocured part has a T g of 58°C and a shore D hardness of 9.
5, the room-temperature cured portion had a T g of 16°C and a shore D hardness of 42. The photocured portion in the upper layer has excellent moisture resistance and is resistant to deformation by strong external forces. On the other hand, the room-temperature curing portion in the lower layer helps relieve internal stress caused by curing shrinkage, and also has excellent adhesion to the base material and heat shock resistance.

It took 42 minutes at 25° C. for the viscosity of the mixture of base liquid 1 and curing agent liquid 1 to become twice as high as that at the beginning of mixing (3300 cps).

[Example 2] Lipoxy 630X-15030g, XP-20
00B (Nippon Gosei Co., Ltd., urethane acrylate) 4
g, glycidyl methacrylate 6g, Aronix M-3
25 (Toagosei Co., Ltd., caprolactone-modified tris(acryloxyethyl)isocyanurate) 4 g, glycyol 5053 g, benzyl dimethyl ketal 1.9 g
Pour into a 00ml beaker and stir while warming to 80℃. Once the resin inside becomes transparent, return it to room temperature and the viscosity will be about 2.
000 cps (20°C) of the resin composition is obtained. This will be referred to as base liquid 2. Next, add QX-40 (Yuka Shell Epoxy Co., Ltd.), a mercaptan-based epoxy hardener to the hardener solution 2.
shall be.

The base material liquid 2 and hardening agent liquid 2 were quickly mixed at a ratio of 2:1, and the mixture was poured into the shear 1 used in Example 1. Next, when irradiated for 4 seconds with the light source used in Example 1, 7.5
It was cured to a depth of mm. When it was further left at 20°C for 2 hours, it was completely cured down to the bottom. In this case, in the case of a two-component mixed curable resin composition, the difference in physical properties between the photo-cured part and the room-temperature cured part is slight, the boundary between them is not clear, and the surface hardness exceeds Shore D100. The temperature was 68°C. Furthermore, in this case, the thickening effect started immediately after mixing, and after 3 minutes, there was almost no flow.

In the above examples, a coupling agent, a thickener, a leveling agent, an antifoaming agent, and a coloring agent are not added, but they may be added if necessary.

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

Claims (1)

[Claims] A base liquid consisting of an organic compound that has both an acrylic unsaturated group and an epoxy group in one molecule, and a photopolymerization initiator that is sensitive to light of 250 nm or more, and has room temperature curability and UV transparency. It consists of a curing agent liquid consisting of at least one type of light-transparent aliphatic amine-based epoxy resin or mercapto-based epoxy resin, and by mixing these main resin and curing agent liquid, it can be cured with light or ultraviolet rays, or at room temperature or in a heated atmosphere. A two-component mixed curing resin composition that is cured under the conditions.