JPH04149443A - Two pack mixing type hardenable resin composition - Google Patents

Abstract

PURPOSE:To temporarily harden by photoirradiation, to completely harden by leaving to stand at ordinary temperature, and to improve adhesion with a base material, environmental resistance, and electric insulation by forming a composition with a specific main agent liquid and a specific hardening agent liquid. CONSTITUTION:This composition is formed by a main agent liquid, having such main ingredients as epoxy acrylete, part of whose epoxy group in a molecule is acrylic-denatured, urethane acrylate having at least two acryloyl groups in a molecule, bisphenol type epoxy oligomer, and a photopolymerization initiator, and a hardening agent liquid, having such main ingredients as 3, 9-bis (3- aminopropyl)-2, 4, 8, 10-tetraspiro [5, 5] undecane or its denatured substance. Thus, the composition becomes solid by photoirradiation and becomes a tough hardened substance at ordinary temperature. Further, thick film hardenability, surface hardenability, adhesion with a base material, environmental resistance, and electric insulation are improved, and automatic intermixing application is made possible.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention is directed to the use of light (radiation, far ultraviolet rays, ultraviolet rays, visible light
After irradiating s) and temporarily curing it immediately or in a short time,
The present invention relates to a two-component tabletop curable resin composition that can be main-cured while being maintained at room temperature.

[Prior Art] Ultraviolet curing resins are used in a variety of applications such as adhesives, potting materials, paints, and inks because of their speed of curing. However, it has drawbacks such as greater curing shrinkage than epoxy resins and urethane resins, and poor adhesion to substrates. Furthermore, the areas that are not exposed to light remain as uncured areas, which limits its uses.

Therefore, resins that are temporarily cured by ultraviolet rays and completely cured by other factors have been researched for some time.
As disclosed in HllZ Publication, low moisture absorption resins that can be used in combination with UV and heat are being developed. This system contains acryloyl groups, epoxy groups, and carboxyl groups. During photocuring, the acryloyl groups polymerize and harden, and during heat curing, the epoxy groups and carboxyl groups bond. This hardens the material.

However, this system requires heating when the epoxy group and carboxyl group are bonded, so it cannot be applied to base materials that are sensitive to heat.

In addition, by adding a catalyst that opens the epoxy groups to a resin containing epoxy groups and acryloyl groups in the system immediately before use, the acryloyl groups polymerize in photocuring, and the epoxy groups or epoxy groups in thermocuring or room temperature curing occur. There are also commercially available products that cure by bonding the group with the hydroxyl group contained in the system. However, in this system, the amount of catalyst added to the main component is extremely small, and the viscosities of the two are also significantly different, making it unsuitable for automatic mixing.

Unexamined Japanese Patent Publication No. 1. In Japanese Patent No. 85288, an adhesive composition that is cured by ultraviolet rays and moisture is developed. However, this system has the drawbacks that it is not possible to cure a thick film that cannot be reached by moisture, and because it uses isocyanate, carbon dioxide gas tends to form bubbles and foam.

JP-A No. 63-230705 discloses that thermal polymerizability can be imparted by adding a thermally polymerizable peroxide to a photosensitive resin containing an acryloyl group; however, in the case of thick film curing, polymerization There are problems in that the heat is large, the adhesion to the substrate is poor due to the shrinkage of the polymerization itself of the acryloyl group, and the surface remains sticky due to inhibition of surface hardening due to inhibition of polymerization by oxygen.

[Problems to be solved by the invention] As described above, conventional resin compositions are temporarily cured by light,
It can be completely cured at room temperature, is suitable for thick film curing by botting, etc., and automatic coating, and cannot be made to have good surface hardening properties, especially in automated production lines.

The present invention eliminates all of these drawbacks, becomes solid when irradiated with light, becomes a tough cured product at room temperature, and has properties such as thick film hardening, surface hardening, adhesion to substrates, environmental resistance, and electrical insulation. It is an object of the present invention to provide a two-component mixed curable resin composition that has excellent properties and can be automatically mixed and coated.

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

[Function/Example] The two-component mixed curable resin composition of the present invention consists of a base liquid and a curing agent liquid as shown below.

The main component liquid mainly includes epoxy acrylate in which some of the epoxy groups in the molecule are modified with acrylic, 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 that is blended as a photopolymerization component.

The molecular weight of the epoxy acrylate is preferably 200 to 5,000, more preferably 250 to 4,000. If the molecular weight is less than 200, the curing shrinkage of the resin will be large, resulting in a decrease in adhesion to the substrate, and the resin itself will lose its plasticity, resulting in a decrease in toughness. If it exceeds 5000, the epoxy acrylate itself will become highly viscous or solid. Furthermore, since the epoxy equivalent weight increases, the amount added to the base resin is severely restricted, and as the molecular weight increases, the compatibility with the curing agent also decreases, which tends to hinder curing.

The acrylic modification rate (esterification rate) of epoxy acrylate is preferably 0.3 to 0.8, and OJ5 to 0.75.
is even more preferable. If the esterification rate exceeds 0.8, the toughness of the resin composition will decrease, and if it is less than 0.3, the photopolymerizability will decrease, which is not practical.

Examples of such epoxy acrylates include bisphenol A type partially esterified epoxy acrylate (for example, 630X-150 manufactured by Showa Kobunshi Fin),
Modified bifunctional bisphenol type epoxy oligomers such as bisphenol F type partially esterified epoxy acrylate and bisphenol AD type partially esterified epoxy acrylate are preferred. Note that polyfunctional novolacs are not suitable because they have an adverse effect on adhesion. Furthermore, in order to impart flexibility to the epoxy acrylate, ethylene oxide, propylene oxide,
Those modified with epichlorohydrin, urethane, etc.
A Br-added type is also preferred in order to impart flame retardancy.

These may be used alone or in combination of two or more.

The blending ratio of epoxy acrylate is 8 to 75 in the base liquid.
% (weight %, hereinafter the same), more preferably 10 to 50%. If the amount of epoxy acrylate is too small, there will be no effect on the toughness of the resin, and if it is too large, the toughness in the photocured state will decrease.

Urethane acrylate is further blended into the base liquid as a photopolymerization component in order to increase the sensitivity during photocuring and improve the toughness of the photocured product.

Urethane acrylate is a bifunctional or trifunctional compound, preferably having a molecular weight of 500 to 20,000, 7
00 to 10,000 is more preferable. If the molecular weight is less than 500, the strength of the photocured film formed during photocuring will be weak. If it exceeds 20,000, the compatibility with the curing agent will decrease and the photocuring rate will tend to decrease.

Specific examples of such urethane acrylates include Chemilink 9503, Chemilink 9504, Chemilink 9505 (
(manufactured by Satmar), Aronixt 1200, M-
1100 (manufactured by Toagosei Chemical Co., Ltd.), NK Ester U-108-A (manufactured by Shin-Nakamura Chemical Co., Ltd.), XP-
4200B, XP-7000BSXP-2700, XP
-3000B, XP-2000BSXP-10 (manufactured by Nippon Gosei Kagaku Kogyo ■), Ebecryl-204
, 205, 210, 220, 230, 254
, 2B4, 265, 270, 320 (above, U
CB), Art Resin IIN-5200, UN-
1,100, 0N-6060, 0N-9000, 1N-1255, UN-2500, UN-125
5TM, SR-500, 5R-380G^, 5
H-9832 (manufactured by Negami Kogyo Co., Ltd.), beam set 5
Examples include 02H (manufactured by Arayo Kagaku Kogyo ■). These may be used alone or in combination of two or more.

The blending ratio of urethane acrylate is 5 to 50 in the base liquid.
% is preferable, and 7 to 40% is more preferable.

If the ratio is less than 5%, the sensitivity will increase during photocuring and the toughness of the photocured product will be improved. If it exceeds 50%, the adhesion to the substrate will decrease, and the area irradiated with light will remain at room temperature. Even after curing, the toughness-improving effect tends to be weak. This effect of increasing sensitivity and improving toughness is important when handling in a photocured state.

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

Specific examples of the reactive diluent include dipentaerythritol hexaacrylate, diventaerythritol monohydroxybentaacrylate, alkyl-modified dipentaerythritol pentaacrylate (Kayarad D-310 manufactured by Nippon Kakami Co., Ltd.), alkyl Modified dipentaerythritol tetraacrylate (Kayarad D-320 manufactured by Nippon Kayaku ■), caprolactone modified dipentaerythritol hexaacrylate (DPCA-20, DPCA-30, DPCA-80, D manufactured by Nippon Kayaku ■)
PCA-120), ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and trimethylolpropane triacrylate. Naturally, methacrylate can be used instead of acrylate.

If the proportion of the reactive diluent is too large, the toughness of the resin will be impaired, so the proportion of the reactive diluent in the base liquid is preferably 20% or less.

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

The molecular weight of bisphenol type epoxy oligomer is 30
0 to 3000 is preferable, and 500 to 2000 is more preferable. If the molecular weight is less than 300, the cured product will become brittle and the adhesion to the base material will decrease. If it exceeds 3,000, the epoxy equivalent of the system will increase, resulting in an imbalance in the mixing ratio with the curing agent, and furthermore, the system will deteriorate. Since the viscosity also increases, workability tends to decrease.

Further, the epoxy equivalent is preferably 150 to 1000.

Specific examples of such epoxy oligomers include bisphenol A type epoxy oligomers, bisphenol F type epoxy oligomers, bisphenol AD type epoxy oligomers, etc., and are selected depending on the viscosity of the base liquid.

The blending ratio of the bisphenol type epoxy oligomer is preferably 20 to 85%, more preferably 30 to 80%, in the base liquid. When the ratio is less than 20%, the cured product tends not to have sufficient heat resistance and toughness, and when it exceeds 85%, photocurability tends to decrease.

In addition, in order to impart flexibility to the resin, some bisphenol-type epoxy oligomers (
(approximately 20% or less), a urethane-modified epoxy oligomer may be blended instead, and specific examples thereof include EPU-6, EPU-6A, and EP manufactured by Asahi Denka Kogyo Kan Co., Ltd.
tJ-11, EPU-15, EPU-73, EPU-1
7 etc.

The photopolymerization initiator to be added to the base liquid is preferably one suitable for thick film curing. Specific examples of such photopolymerization initiators include jetoxyacetophenone, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, camphorquinone,
-Methyl-1-[4-(methylthio)phenyl2-
Examples include morpholinopropane-1,2-hydroxy-2-methyl-niphenylpropan-1-one and 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane.

The proportion of the photopolymerization initiator in the base liquid is preferably 2 to 10%, more preferably 2.5 to 5%. When the ratio is less than 2%, the sensitivity of photocuring tends to decrease, and when it exceeds 10%, the photocured film thickness becomes thinner, and the adhesion, moisture resistance, and
Heat resistance tends to decrease.

Furthermore, an epoxy resin diluent such as aliphatic diglycidyl ethers may be used to obtain a base liquid with low viscosity. When using an epoxy resin diluent, it is preferable that the proportion thereof in the main resin solution is 20% or less from the viewpoints of toughness, heat resistance, and adhesion of the cured product to the base material.

Further, a coupling agent, a thickener, a leveling agent, a coloring agent, a filler, etc. may be added to the main liquid according to the purpose.

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

The curing agent liquid used in the present invention is 3.9-bis(3-aminopropyl)-2,4,Ill, 10-tetraspiro[5
, 5-undecane (hereinafter referred to as ATU) or a modified product thereof as a main component.

Since ATU is an aliphatic compound, it has good UV transmittance, and compared to other aliphatic epoxy curing agents,
The heat resistance and toughness of the cured product can be improved. Since this compound forms crystals at room temperature, it is usually sold after being modified, and such a modified product may be used as is in the present invention.

Examples of such modified products include the Epomate series manufactured by Yuka Shell Epoxy (2).

The blending ratio of ATU and ATLI modified products is 50% in the curing agent solution.
-100% is preferable, and 55-100% is more preferable. If the ratio is less than 50%, a cured product that takes advantage of the characteristics of ATLI cannot be obtained, and the crack resistance particularly due to thermal shock decreases.

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

Further, a coupling agent, a thickener, an antifoaming agent, a leveling agent, a coloring agent, a filler, etc. may be added to the curing agent liquid depending on the purpose.

The viscosity of the curing agent liquid is usually 400 to 10,000 cps (3
5℃).

The two-component mixed curable resin composition of the present invention is composed of the base liquid and the curing agent liquid, and is used by mixing them immediately before use.

The mixing ratio of the base resin 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 110.8. In terms of weight ratio, the range of base liquid/curing agent liquid is preferably 1/4 to 4/1, and the closer it is to 1/1, the more preferable it is, but usually the blending ratio of the curing agent is smaller.

There are no particular limitations on the mixing method; for example, an automatic mixing and discharging machine may be used, or manual mixing and dispensing may be carried out.

When using an automatic mixing and dispensing machine, it is preferable that the difference in viscosity between the two liquids be small in order to mix them uniformly, and it is also preferable that the mixing ratio of the two liquids not be extremely different. In the resin composition of the invention, the viscosity of the base liquid and the curing agent liquid can be easily adjusted and the amounts used can be kept from making a large difference, so that the resin composition can be suitable for automatic coating.

The resin composition of the present invention can be temporarily cured by irradiating it with light, and then can be fully cured gradually by leaving it at room temperature or under heating conditions, and can be used even in pottings with a thickness of about 100 yen (100 yen). It can be completely cured, resulting in a cured product with excellent surface hardening properties, adhesion to substrates, and electrical insulation.

EXAMPLES Next, the present invention will be explained in more detail 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 830X-150 (50% acrylated bis A type epoxy acrylate manufactured by Showa Kobunshi Naka Co., Ltd.).

EP-4901 (bisphenol F type epoxy resin manufactured by Asahi Denka Kogyo ■) 47.6 g 1 SH-380G^ (trifunctional urethane acrylate manufactured by Nedo Kogyo ■) 9.5 g, glycyol ED-503 (2 manufactured by Asahi Denka Kogyo ■) functional epoxy monomer) 9.5 g, Aronixt 320 (propylene oxide dimer modified trimethylolpropane triacrylate manufactured by Toagosei Kagaku Kogyo Kan) 4.8 g
and 4.8 g of jetoxyacetophenone (DEAP)
were mixed and stirred while warming to 80°C. After the mixture becomes transparent, return it to room temperature and the viscosity will be about 700Cps (3
5° C.) was obtained. This is referred to as base liquid 1.

On the other hand, a solution in which 1 g of EP-49013 was added to EH-28 [1 (polyether diamine manufactured by Asahi Denka Kogyo ■) N, 9r was reacted at 120°C for 4 hours under a nitrogen atmosphere with stirring. Returned to room temperature. The viscosity of the resulting liquid was approximately 750 cps (35°C). Add Epomate BOO2 (ATO modified epoxy curing agent manufactured by Yuka Shell Epoxy) to this. 35. A curing agent solution having a viscosity of 960 cps (35° C.) was obtained by adding Og and stirring until the whole was uniform.

This is referred to as hardening agent liquid 1.

Using a two-liquid mixing and discharging device (manufactured by Nakaliquid Control ■), pour base agent liquid 1 and curing agent liquid 1 at a ratio of 2=1 (weight ratio) into a polyester PRP petri dish with a diameter of 9cI, 111cm, and a depth of 10mm. 50 rise w/c with super high pressure mercury lamp
When irradiated for 14 seconds at an irradiation intensity of I#, it was cured to a depth of about 4 mm from the surface. In addition, 2 of these petri dishes
When it was left at 0°C for 12 hours, it was completely cured to the bottom. The obtained cured product adhered well to the wall of the Petri dish.
Although the petri dish was immersed in red ink and the pressure was reduced using a vacuum pump, no seepage was observed at the interface.

The shore D hardness of the cured product was 21, and the shore D hardness of the cured product cured without UV irradiation was 19.

Since there was only a slight difference in hardness between the obtained cured product and a cured product cured in the same manner except without UV irradiation, it is thought that the physical properties were mostly due to the epoxy/amine component.

In addition, using a potted Petri dish, heat at -20°C for 1 hour.
r/ After 300 cycles of heat shock test at +80°C lhr, it was further exposed to 30 days of humidity test at 60°C and 95% Rh, but the appearance was as expected.
No change in hardness or electrical resistance was observed.

Example 2 Lipokine 830X-15024, 7g, EP-19
0149.4g.

5) 1-380G^12.3 g, EPU-6 (urethane-modified epoxy oligomer manufactured by Asahi Denka Kogyo ■) 9.
9 g, 5H-380GAI2.8g5DEAP
3.7 g and 0.005 g of silicone antifoaming agent were mixed and stirred while warming to 80°C.

After the mixture becomes clear, bring it back to room temperature and the viscosity is about 246.
A resin composition of 0 cps (35°C) was obtained. This will be referred to as base liquid 2.

On the other hand, EP-49013,5 to EH-28011,5g
120℃ under a nitrogen atmosphere while stirring the solution to which g was added.
After reacting for 4 hours, the temperature was returned to room temperature. The viscosity of the resulting liquid was approximately 1800 eps (35°C). To this was added 285° Og of Epomate BOO, and the mixture was stirred until the whole was homogeneous to obtain a curing agent liquid with a viscosity of about 1870 cps (35° C.). This will be referred to as hardening agent liquid 2.

Using a two-liquid mixing and discharging device (manufactured by Nakaliquid Control ■) to mix base agent liquid 2 and curing agent liquid 2 at a ratio of 2:1,
The mold was poured into a polyester F"RP Petri dish with a depth of 10 mm, and irradiated with a 250 W ultra-high pressure mercury lamp at an irradiation intensity of 50 + aW/c- for 14 seconds, and the mold was cured to a depth of about 5 + am from the surface. 12 at °C
When I left it for a while, it completely hardened down to the bottom.

The resulting cured product adhered well to the wall of the Petri dish, and no seepage was observed at the interface, probably because the Petri dish was immersed in the red ink and the pressure was reduced using a vacuum pump.

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 there was only a slight difference in hardness between the obtained cured product and a cured product cured in the same manner except that t+V irradiation was not performed, it is thought that the physical properties were mostly due to the epoxy/amine component.

In addition, using a potted Petri dish, heat at -20°C for 1 hour.
After conducting 300 cycles of heat shock test at r/+80℃lhr, it was further exposed to a humidity test at 60℃ and 95% Rh for 30 days, but the appearance was as expected, and no changes in hardness or electrical resistance were observed. I couldn't.

Example 3 Lipoxy [180X-15024, 7g, EP-49
0149.4g.

Beam Set 502) 1 (urethane acrylate manufactured by Arayo Kagaku Kogyo ■>7.41g, glycyol ED-50
34.94g, dipentaerythritol hexaacrylate (DEHA) 4.94g 5DEAP 3.7g and silicone antifoaming agent 0.005g were mixed, 80
The mixture was stirred while warming to ℃. After the resin inside became transparent, it was returned to room temperature to obtain a resin composition with a viscosity of about 1900 eps (35° C.). This will be referred to as base liquid 3.

On the other hand, E) I-28011, 5g EP-49013,
120 g in a nitrogen atmosphere while stirring the solution to which 5 g was added.
After reacting at ℃ for 4 hours, the temperature was returned to room temperature. The viscosity of the resulting liquid was approximately 1350 cps (35°C). Epomate BOO235.Og was added to this and stirred until the whole was homogeneous to obtain a curing agent liquid with a viscosity of about 1350 cps (35° C.). This will be referred to as hardening agent liquid 3.

The base agent liquid 3 and the curing agent liquid 3 were poured into a polyester FRP Petri dish with a diameter of 9 parts and a depth of lhm using a two-liquid mixing and discharging device (manufactured by Naka Liquid Control ■) at a ratio of 2=1.
1 at an irradiation intensity of 50 mW/c- with a 250 V ultra-high pressure mercury lamp.
When irradiated for 4 seconds, it was cured to a depth of approximately 4 mm from the surface. Furthermore, when this petri dish was left to stand at 20° C. for 12 hours, it was completely hardened down to the bottom.

The obtained cured product adhered well to the wall surface of the petri dish, 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.
Met. Since there was only a slight difference in hardness between the obtained cured product and a cured product cured in the same manner except without UV irradiation, it is thought that the physical properties were mostly due to the epoxy/amine component.

In addition, using a bottling Petri dish,
/ After 300 cycles of heat shock test at +80℃lhr, further humidity test 3 at 60℃95%Rh
Although exposed under conditions of 0 days, the appearance, hardness,
No change in electrical resistance was observed.

[Effects of the Invention] The two-component mixed curable resin composition of the present invention can be automatically mixed and applied, is temporarily cured by light irradiation, and can be completely cured by being left at room temperature, and the cured product can be cured easily on the substrate. This has the effect of providing excellent adhesion with other materials, environmental resistance, and electrical insulation.

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Claims (1)

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