JP3071046B2 - Two-part curable resin composition and method of using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a two-part curable resin composition and a method for using the same. For more information,
For example, it can be cured temporarily by irradiating light such as radiation, far-ultraviolet light, ultraviolet light, or visible light, immediately or in a short time, and then left at room temperature for full curing. The present invention relates to a two-component curable resin composition useful for applications such as adhesives and adhesives, and a method for using the same.

[0002]

2. Description of the Related Art UV-curable resins are used in various applications such as adhesives, potting materials, paints, and inks because of their speed of curing. However, the ultraviolet curable resin has a disadvantage that the curing shrinkage is large as compared with the epoxy resin and the urethane resin, and the adhesion to the base material is poor. In addition, the heat generated during curing due to the reaction heat is large,
It may damage parts and the like. In addition, shadows that are hardly exposed to light, such as the back side of the component, remain as uncured portions, which limits applications.

Therefore, a resin which is temporarily cured by ultraviolet rays and completely cured by other factors has been studied, and as disclosed in JP-A-63-207812, combined use of ultraviolet rays (UV) and heat has been studied. Development of low moisture absorption resin is underway. The resin contains an acrylic group, an epoxy group and a carboxyl group in the system, and is temporarily cured by polymerization of the acrylic group during photocuring, and epoxy group during thermal curing. And a carboxyl group are combined to cure. However, this system requires heating in order to bond the epoxy group and the carboxyl group, and cannot be applied to a substrate that is weak to heat.

Further, by adding a catalyst for opening the epoxy group immediately before use to a resin containing an epoxy group and an acrylic group or a cinnamoyl group in the system, polymerization of the acrylic group occurs by photocuring, and heat curing or room temperature In the case of curing, those in which epoxy groups are bonded to each other or the epoxy group and a hydroxyl group contained in the system are combined and cured are commercially available. However, in this system, the amount of the catalyst added to the main agent is extremely small, and the viscosities of both are greatly different.

Japanese Patent Application Laid-Open No. 1-85268 discloses that
An adhesive composition that cures with ultraviolet light and moisture is disclosed. However, this system has the drawbacks that a thick film having a thickness to which moisture cannot reach cannot be cured, and that carbon dioxide gas is easily foamed as bubbles due to the use of isocyanate.

Further, Japanese Patent Application Laid-Open No. 63-230705 discloses that a photopolymerizable resin is added to a photosensitive resin containing an acryl group by adding a thermally decomposable peroxide to impart thermal polymerizability. In the case of film curing, the heat of polymerization is large, the adhesion to the substrate deteriorates due to the shrinkage due to the polymerization of the acrylic group, and the surface curability deteriorates because the polymerization is easily inhibited by oxygen. The cured product remains and causes stickiness and corrosion.

The present inventors have conducted intensive studies to improve these drawbacks and have proposed a two-part mixed type cured resin composition as described below (Japanese Patent Laid-Open No. 3-210324, Japanese Patent Application No. 2-273785, Japanese Patent Application No. 2-2
73784).

[0008] The two-component mixed type resin composition proposed in JP-A-3-210324 has both a (meth) acrylic group and an epoxy group in one molecule, and has a molecular weight of 250 nm.
A main agent liquid comprising an organic compound to which a photopolymerization initiator sensitive to the above light is added, and a curing comprising at least one of an aliphatic amine epoxy curing agent and a mercapto epoxy curing agent having room temperature curability and ultraviolet transmittance. A two-part mixed type cured resin composition comprising a base liquid and a pre-cured composition prepared by mixing the main liquid and the curing agent liquid with light or ultraviolet light, and then completely left at room temperature or heated. It is a curable resin composition that can be cured.

[0009] The composition ameliorates a number of disadvantages which have heretofore been problematic. A resin having both a (meth) acrylic group and an epoxy group in one molecule (hereinafter referred to as a half (meth) acrylated epoxy resin) is an effective component for improving the toughness of a cured resin. It is more expensive than other resins and has poor storage stability. Further, since the half (meth) acrylated epoxy resin has poor ultraviolet transmittance and has only one photopolymerizable functional group, it is not suitable for curing a thick film by ultraviolet rays.

The two-component curable resin composition proposed in Japanese Patent Application No. 2-273785 is a main component liquid containing an acrylic oligomer, an epoxy oligomer and a photopolymerization initiator as main components, and an aromatic resin. A curable resin composition comprising a non-amine compound as a curing agent liquid, wherein at least one of the photopolymerization initiators is a peroxide-based photopolymerization initiator; and an acrylic oligomer, It is a curable resin composition containing a main component liquid containing an epoxy oligomer, a photopolymerization initiator and a peroxide as main components, and a non-aromatic amine compound as a curing agent liquid.

The above composition is also prepared by mixing a base liquid and a hardener liquid.
It is a composition that can be temporarily cured by light, etc., and then completely cured at room temperature, but has poor storage stability because it contains a peroxide in the system.When blending a resin composition, it is heated to lower the viscosity. There is a problem that you can not do.

Further, a two-part curable resin composition proposed in Japanese Patent Application No. 2-273784 is an epoxy acrylate in which a part of epoxy groups in the molecule is acrylic-modified, and at least two epoxy acrylates in the molecule are used. Base liquid mainly containing urethane acrylate having an acryloyl group, a bisphenol-type epoxy oligomer and a photopolymerization initiator, and 3,9-bis (3-aminopropyl) -2,
A curable resin composition comprising a curing agent liquid containing 4,8,10-tetraoxaspiro [5.5] undecane or a modified product thereof as a main component.

The above composition is also a curable composition which can be temporarily cured by light irradiation after mixing and then fully cured by keeping it at room temperature. However, the storage stability of the acrylic-modified epoxy acrylate is poor. Therefore, there is a problem that the entire storage period is only three months at room temperature.

[0014]

As described above, the conventional resin composition can be cured by light, can be completely cured at room temperature, has excellent storage stability, and can cure thick films such as potting. A resin composition that satisfies all conditions of being suitable for automatic mixing and discharging, particularly having good surface curability and being inexpensive enough to exert its effects in an automated mass production line. There is no problem.

[0015]

SUMMARY OF THE INVENTION The present invention solves all of these drawbacks, temporarily cures by irradiation of ultraviolet light for several seconds to several tens of seconds, and furthermore, when left at room temperature, forms a tough cured product. Curability, surface curability, adhesion to substrate,
It is an object of the present invention to provide a two-part curable resin composition that is excellent in environmental resistance and electrical insulation, is inexpensive, and can be automatically mixed and discharged.

The present invention relates to (A) a urethane (meth) acrylate having at least three (meth) acryl groups in a molecule, a glycol-based or glycerol-based dimethacrylate, a bisphenol-type epoxy resin, and a compound represented by the general formula (I):

[0017]

Embedded image (Wherein R represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms) and / or a compound represented by the formula (I)
I):

[0018]

Embedded image And (B) 3,9-bis (3-aminopropyl) -2,4,
The present invention relates to a two-part curable resin composition comprising a curing agent liquid containing 8,10-tetraoxaspiro [5.5] undecane and / or a modified product thereof as a main component.

[0019]

According to the present invention, tri- or more functional urethane (meth) acrylate and glycol-based or glycerol-based dimethacrylate are used as photo-curing components in the curable resin composition. CH
₃₎ By using ₂ CO- or HC (OC ₂ H ₅₎ compounds containing ₂ CO-, it is possible to increase the film thickness capable of photocuring, good thick photocurable surface curability with high sensitivity A membrane can be provided. The urethane (meth) acrylate has the effect of expressing the strength of the photocurable film, and the glycol or glycerol dimethacrylate has the effect of promoting photocuring sensitivity and thick film curing.

The primary or secondary amine in the curable resin composition is completely cured by reacting with the epoxy group in the base solution at room temperature to form a tough film.

The base liquid and the curing agent liquid in the curable resin composition of the present invention are suitable for automatic mixing and discharging, because their viscosity can be easily adjusted and the mixing ratio can be easily adjusted.

[0022]

EXAMPLES Urethane (meth) having at least three (meth) acryl groups in the molecule as one of the four main components of the base liquid of the two-component curable resin composition of the present invention.
Acrylate is used.

The urethane (meth) acrylate is 1
A compound having three or more, preferably 3 to 6, of either or both an acryl group and a methacryl group in the molecule.

Since the urethane (meth) acrylate has at least three (meth) acryl groups, the gelation rate upon light irradiation is high. In addition, the urethane (meta)
Since acrylate has a urethane bond, it has an effect of imparting toughness to the photocured film.

The molecular weight of the urethane (meth) acrylate is preferably from 400 to 6000, more preferably from 500 to 3,000.

Since urethane (meth) acrylate has a molecular weight of 400 to 6000, it has good compatibility with other components and relatively low viscosity.

The urethane (meth) acrylate is preferably incorporated in the base solution in an amount of 2 to 25% (% by weight, the same applies hereinafter), and if it is less than 2%, the photocurable film becomes brittle and cracks easily occur. %, The quality of the photocured film is improved, but the toughness of the cured product at room temperature is low, and the adhesion to the substrate, heat resistance, and moisture resistance are reduced.

Specific examples of the urethane (meth) acrylate include, for example,

[0029]

Embedded image And so on. Examples of the urethane (meth) acrylate that is commercially available as a commercial product include Art Resin UN-380-1G and UN-
3320HA, UN-3320HB, UN-3320H
C (above, manufactured by Negami Industry Co., Ltd.), NK ester U-4H
A, NK ester U-4H, NK ester U-6HA,
NK ester U-6H (above, Shin-Nakamura Chemical Co., Ltd.)
UA-101H (corresponding to the compound of the formula (III)), UA-101I (corresponding to the compound of the formula (IV)),
UA-101T (corresponding to the compound of the formula (V)) (all manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like.

Glycol or glycerol-based dimethacrylate (hereinafter, referred to as "glycerol-based dimethacrylate") is a second component of the four components, which are the main components of the base liquid of the two-component curable resin composition of the present invention.
Dimethacrylate) is used.

The dimethacrylate has two methacryl groups at both ends of the main chain,

[0032]

Embedded image Is a compound containing at least one unit of any one of the above.

In the present invention, since the dimethacrylate is used, the photocuring sensitivity of the curable resin composition increases, and the photocurable film thickness increases.

Further, since the dimethacrylate has two methacryl groups, it has a high gelation rate and cures deeply.

The molecular weight of the dimethacrylate is 190 to 600, more preferably 190 to 400, in view of the gelation rate.
Is preferred.

The mixing ratio of the dimethacrylate is preferably 2 to 25%, more preferably 2 to 10% of the base solution. If the compounding ratio is less than 2%, there is no effect on the photosensitivity of the composition or the increase in the cured film thickness. small,
A tendency to hinder handling occurs.

Further, the weight ratio (percentage) of dimethacrylate to urethane (meth) acrylate is set at 1 from the viewpoint of the balance between the curing speed, the curing depth, and the toughness of the photocured film.
0-120% is preferred.

Specific examples of the glycol-based or glycerol-based dimethacrylate include, for example,

[0039]

Embedded image And so on.

A bisphenol-type epoxy resin is used as the third component among the four components which are the main components of the main component liquid of the two-component curable resin composition of the present invention.

The bisphenol type epoxy resin has the general formula (XIII):

[0042]

Embedded image It is a compound represented by these.

The bisphenol-type epoxy resin having the above structure reacts with the diamine as a curing agent when left at room temperature to form a cured product as a whole, and is an important component that determines the physical properties of the cured product in the final state. is there.

As the bisphenol type epoxy resin, those having good adhesion of the cured product to the substrate, toughness, high heat resistance, high humidity resistance, and low curing shrinkage are preferable.

The bisphenol-type epoxy resin preferably has a molecular weight of 300 to 3,000, and more preferably 500 to 2,000.
Is more preferred. 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, and the mixing balance with the curing agent becomes poor. Further, the workability tends to decrease because the viscosity of the system also increases.

The epoxy equivalent is preferably from 150 to 1,000 in consideration of the mixing balance between the base liquid and the curing agent.

The mixing ratio of the bisphenol type epoxy resin is preferably from 50 to 95%, more preferably from 30 to 85% in the base solution.
Is more preferred. If the compounding ratio is less than 50%, the cured product tends to have insufficient heat resistance and toughness, and if it exceeds 95%, the photocurability tends to decrease.

The weight ratio (percentage) of the total amount of the urethane (meth) acrylate and dimethacrylate in the base solution to the bisphenol-type epoxy resin is determined by the adhesiveness of the cured product to the substrate, heat resistance, moisture resistance, and toughness. From the point of 5
~ 50% is preferred.

Specific examples of such epoxy resins include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol AD type epoxy resin.
02, 807, 808, 815, 819, 825, 82
8, 834, 1001, 1002 (all manufactured by Yuka Shell Epoxy Co., Ltd.), Adeka Resin EP-4100, EP
-4200, EP-4300, EP-4400, EP-
4520, EP-4340, EP-4900, EP-4
901 (all manufactured by Asahi Denka Kogyo KK) and the like. When the epoxy resin is actually used, the epoxy resin is selected from the epoxy resins according to the viscosity of the base liquid and the epoxy equivalent.

Of the four components that are the main components of the main component liquid of the two-component curable resin composition of the present invention, components other than the above three components are represented by the following general formula (I):

[0051]

Embedded image Wherein R represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, and / or a compound represented by the formula (I
I):

[0052]

Embedded image Is used as a photopolymerization initiator.

These polymerization initiators have HOC in the molecule.
Since it has (CH ₃ ) ₂ CO— or HC (OC ₂ H ₅ ) ₂ CO—, the ultraviolet light absorption of the polymerization initiator itself is small, and especially, it is kept low after irradiation. It has a characteristic of being relatively long at 450 nm, and is suitable for hardening a thick film because light having a wavelength effective for cleavage is transmitted deeply.

Thioxanthone and Michler's ketone / benzophenone mixed systems are known for curing thick films.
These have strong UV absorption of their own, so
Although it is suitable for curing of a certain thickness, it is not suitable for curing of 1 mm or more.

The mixing ratio of the photopolymerization initiator is 0.1
-10% is preferable, and 0.3-3% is more preferable.
If the compounding ratio is less than 0.1%, the photocuring sensitivity tends to decrease, and if it exceeds 10%, it becomes difficult to cure the thick film due to the ultraviolet absorption of the photopolymerization initiator itself, and low molecular weight compounds are contained in the system. The heat resistance, moisture resistance, and mechanical strength of the cured product tend to decrease due to the increase.

The weight ratio (percentage) of the photopolymerization initiator with respect to the total amount of the main component liquid and the curing agent liquid is 0.00 from the viewpoint of the gelation rate, the gelation depth, and the crosslink density during photocuring.
7-10% is preferred.

Specific examples of the compound represented by the general formula (I) in the photopolymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocur 1173 manufactured by Merck). , 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one (Darocur 1116 manufactured by Merck), 1- (4-
Dodecylphenyl) -2-hydroxy-2-methylpropan-1-one (Darocur 953 manufactured by Merck) and the like. These photopolymerization initiators may be used alone or as a mixture of two or more.

The base liquid of the two-part curable resin composition may contain other components, if necessary, in addition to the main components.

First, if necessary, a urethane-modified epoxy resin is blended at a rate of about 60% or less in place of a part of the bisphenol-type epoxy resin in order to impart flexibility to the resin, if necessary. Is also good. In this case, the urethane-modified epoxy resin is calculated as a bisphenol-type epoxy resin. Specific examples of the urethane-modified epoxy resin include, for example, EPU-6 manufactured by Asahi Denka Kogyo Co., Ltd.
EPU-6A, EPU-15, EPU-73, EPU-
17 and the like.

Further, an epoxy resin diluent such as an aliphatic diglycidyl ether may be blended 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 viewpoints of toughness, heat resistance and adhesion to the substrate of the cured product.

Further, a coupling agent, a thickener, a leveling agent, a filler, a flame retardant and the like may be blended in the base liquid according to the use.

As a main component of the curing agent liquid of the two-part curable resin composition of the present invention, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5.
5] Undecane (hereinafter ATU) and / or its modified products are used.

This compound is mixed with the epoxy resin after about 2 minutes.
It reacts with an epoxy group in 3 hours to form a crosslinked and cured product.

ATU is a compound having a spiro ring, which is an alicyclic ring, in its skeleton, so that it has a good ultraviolet transmittance and has a higher heat resistance and toughness as compared with other aliphatic epoxy curing agents. Can be excellent. In addition, since this compound forms a crystal at room temperature, it is usually sold after being modified by blending with other curing agents or diluents.
In the present invention, such a modified product may be used as it is.
As the modified product, for example, Yuka Shell Epoxy Co., Ltd.
B001, B002,
C002, N001, N002, QX2 and the like.

The mixing ratio of the ATU and / or the modified ATU is preferably 50 to 100% in the curing agent liquid. Although the optimum value varies depending on the setting of the viscosity, the mixing ratio and the pot life, it is preferable that the number is as large as possible in consideration of only the physical properties of the cured product. If the ratio is less than 50%, a cured product utilizing the characteristics of ATU cannot be obtained, and crack resistance due to a thermal shock tends to decrease.

The curing agent liquid of the two-part mixed curable resin composition of the present invention may contain other components, if necessary, in addition to the ATU.

First, another curing agent component may be added to the curing agent liquid in order to adjust the viscosity, the mixing ratio and the pot life. As the curing agent component, polyamide or polyetherdiamine having a relatively large active hydrogen equivalent and a modified product thereof are preferable. Polyether diamine has a slow reaction time with epoxy, so it has a pot life delay effect, but on the other hand, because of its low viscosity, it is used by reacting with a bisphenol-type epoxy resin to increase the viscosity and increase the active hydrogen equivalent. . These are effective in adjusting 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.

Further, a coupling agent, a thickening agent, an antifoaming agent, a leveling agent, a filler, and the like may be blended in the curing agent liquid according to the use.

When the main component liquid comprising the above components and the curing agent liquid are mixed, the mixing ratio is determined by weight in terms of mixing accuracy when mixing with an automatic mixer and ease of mixing in a short time. Usually, it is preferably adjusted to be in the range of 3: 1 to 1: 2, and it is preferable to adjust the difference in viscosity between the two to within ± 35% so as to facilitate uniform mixing. The epoxy equivalent of the main component and the active hydrogen equivalent of the curing agent are 14:10 to 10:10.
It is preferable to mix them in a ratio of 10:12.

Next, a method of using the two-part curable resin composition of the present invention will be described. The method of using the composition is a method in which after mixing the two-part curable resin composition, the composition is temporarily cured by irradiation with light, and then fully cured at room temperature.

First, the base liquid and the curing agent liquid in the two-part mixture type composition are mixed.

As described above, the mixing ratio of the main agent and the curing agent is as follows:
It is usually preferable to adjust the weight ratio in the range of 3: 1 to 1: 2.

The mixing method is not particularly limited. For example, an automatic mixing / discharging device can be used, or a person can perform metered mixing and discharging. However, when an automatic mixing and discharging device is used, a dynamic mixer type is more preferable than a static mixer type.

When an automatic mixing and discharging machine is used, the difference in viscosity between the two liquids is 30% or less or 10
It is preferable that the two liquids are as small as 00 cps or less, and it is preferable that the two liquids are mixed at a ratio of at most 1: 3 so as not to be extremely different. In the resin composition of the present invention, the viscosity of the base liquid and the curing agent liquid can be easily adjusted, and the mixing ratio can be prevented from being largely different, so that the resin composition suitable for automatic coating can be obtained.

Next, the mixed curable resin composition is temporarily cured by light irradiation.

The term "temporary curing" means that the composition is cured in a short time at least until it does not flow and is not deformed even if it is tilted or inverted.

The temporary curing can be performed using radiation such as ultraviolet rays, far ultraviolet rays, visible rays, electron beams, X-rays and γ-rays.

When pre-curing using ultraviolet light, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and an ultraviolet fluorescent lamp are generally used. Suitable for coating, metal halide lamps are suitable for potting and molding because they provide high photocuring sensitivity and a thick cured film.

In the case of temporary curing with a metal halide lamp, the conventional epoxy + acrylic system could only cure light up to 5 mm.
Is possible. The pre-cured material does not flow even if it is tilted or inverted, and does not deform, and can directly proceed to the next step in the production line.

Further, the resin composition of the present invention is preliminarily cured by irradiating light as described above, and thereafter, is completely cured by being left at room temperature.

The above-mentioned main curing refers to hardness, which can withstand practical use,
It refers to the state where environmental resistance and adhesion are obtained. In the case of the present invention, after being temporarily cured, it is allowed to stand at room temperature to obtain 12 to 2
It can be completely cured in about 4 hours,
A cured product excellent in surface curability, adhesion to a substrate, and electrical insulation is obtained.

Therefore, the cured product of the present invention is most suitable for insulation and protection of electronic circuit boards and electronic parts and adhesives.

Further, it goes without saying that complete curing can be performed by performing the main curing under heating conditions in the curing process.

In the case of curing by heating, the temperature is preferably 120 ° C. or lower, and if it is higher than that, the adhesion is reduced. However, annealing at 80 to 120 ° C. after curing at room temperature is effective for improving adhesion.

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 Epicoat 8 manufactured by Yuka Shell Epoxy Co., Ltd. as a bisphenol A type epoxy resin
28 650 g, EPU-6 199 g manufactured by Asahi Denka Kogyo KK as urethane-modified epoxy resin, NK manufactured by Shin-Nakamura Chemical Co., Ltd. as urethane (meth) acrylate
74 g of ester U-6H, 49 g of NK ester 3G manufactured by Shin-Nakamura Chemical Industry Co., Ltd. as dimethacrylate (methacrylic reactive diluent), 2-hydroxy-2-methyl-1-phenylpropan-1-one (Merck) 10 g of Darocure 1173) and 1 g of KP-330 manufactured by Shin-Etsu Chemical Co., Ltd. as a defoaming agent are mixed under a light-shielded environment until the whole becomes uniform, and a viscosity of about 1900 cps (3
5 ° C.).

Next, 115 g of EH-280 manufactured by Asahi Denka Kogyo Co., Ltd. was used as polyetherdiamine and EP-49 manufactured by Asahi Denka Kogyo Co., Ltd. was used as a bisphenol epoxy resin.
The liquid to which 1035 g had been added was stirred in a nitrogen atmosphere at 120 ° C. for 4 hours, reacted, and then returned to room temperature. The viscosity of the obtained liquid was about 2100 cps (35 ° C.). To this, 350 g of Epomate B002 manufactured by Yuka Shell Epoxy Co., Ltd. and 0.5 g of KP-330 manufactured by Shin-Etsu Chemical Co., Ltd. were added as ATU modified epoxy curing agents, and the mixture was stirred until the whole became uniform, and the viscosity became 2000 cps. (35 ° C)
Was obtained. This is referred to as a curing agent liquid 1.

The main agent liquid 1 and the curing agent liquid 1 are mixed by using a two-liquid mixing and discharging device (manufactured by Naka Liquid Control Co., Ltd.)
Mix at a ratio of 1 (weight ratio), diameter 9cm, depth 20m
m PBT / glass 25% Petri dish, 1.5k
When irradiation was performed with a w metal halide lamp at an irradiation intensity of 50 mW / cm ² for about 10 seconds, the resin was cured to a depth of 10 mm from the surface. (However, it could be cured to a depth of 15 mm from the surface by irradiating for 25 seconds.) The cured film was taken out of the petri dish with tweezers, washed with acetone, and measured with a caliper.

The cured product was a hard gel, but the uncured liquid inside did not leak even if the petri dish was tilted or inverted until it was completely cured. Furthermore, this petri dish is kept at
, And was completely cured to the bottom. The obtained cured product was in good contact with the petri dish, and the petri dish was immersed in the red ink, and the pressure was reduced by a vacuum pump, but no permeation was observed at the interface.

Shore D of the cured product cured by the above process
The hardness was 21 even when cured without irradiating UV. Shore D hardness was measured according to JIS K 7215.

As described above, since the hardness of the cured product is not so different depending on the presence or absence of the UV curing, the physical properties are almost the same as those of the epoxy resin.
It is thought to be due to the diamine component. Into a Petri dish of the same specifications, cast an orifice washer with a diameter of 30 mm and cast the same. Under the same conditions as in the above process, five light-cured and room temperature-cured samples were prepared.
A heat shock test was performed at 20 ° C. for 60 minutes for 300 cycles, and further exposed to a humidity test at 80 ° C. and 95% RH for 30 days, but no crack was found in the cured product.

Further, a cured product sample having a diameter of 30 mm and a thickness of 20 mm was prepared under the same conditions and subjected to the same heat shock test and humidity test to measure the resin hardness and the electrical resistance. Was 21 after the test, and the electrical resistance was 10 ⁵ before the test.
MΩ or more, and after the test, 10 ⁵ MΩ or more, no change was observed. In addition, the electrical resistance measured the pin angle resistance of the sample hardened by inserting a pin of 2 mm square in advance. At this time, the pin interval was 10 mm, and the film thickness was 20 mm.

Further, the main agent liquid 1 and the curing agent liquid 1
After storage at 0 ° C. for 6 months in the dark, no change such as thickening was observed, and no change was observed in the cured product.

Example 2 As a bisphenol type epoxy resin, EP-4901650 manufactured by Asahi Denka Kogyo KK
g, As a urethane-modified epoxy resin, Asahi Denka Kogyo Co., Ltd.
6199g manufactured by Shin-Nakamura Chemical Co., Ltd. as urethane (meth) acrylate
H 74 g, NK ester 3 manufactured by Shin-Nakamura Chemical Co., Ltd. as dimethacrylate (methacrylic reactive diluent)
G 49 g, 1- (4-isopropylphenyl) -2-
10 g of hydroxy-2-methylpropan-1-one (Darocur 1116 manufactured by Merck) and 1 g of KP-330 manufactured by Shin-Etsu Chemical Co., Ltd. as an antifoaming agent were mixed under a light-shielded environment until the whole was uniform, A main solution 2 having a viscosity of 1200 cps was obtained.

Next, 115 g of EH-280 manufactured by Asahi Denka Kogyo Co., Ltd. was used as polyetherdiamine and EP-4 manufactured by Asahi Denka Kogyo Co., Ltd. was used as a bisphenol type epoxy resin.
The solution to which 31Og of 910 was added was stirred in a nitrogen atmosphere at 120 ° C for 4 hours, reacted, and then returned to room temperature. The viscosity of the obtained liquid was about 750 cps (35 ° C.). To this was added 350 g of Epomate B002 (manufactured by Yuka Shell Epoxy Co., Ltd.) as an ATU-modified epoxy curing agent, and the mixture was stirred until the whole became uniform to obtain a viscosity of 960 cps (35 ° C.).
Was obtained. This is referred to as a curing agent liquid 2.

The main component liquid 2 and the curing agent liquid 2 were mixed at a ratio of 2: 1.2 (weight ratio) using a two-liquid mixing / discharging apparatus (manufactured by Naka Liquid Control Co., Ltd.), and had a diameter of 9 cm and a depth of 9 cm. 2
Pour into 0 mm PBT / glass 25% Petri dish;
Irradiation with a 5 kW metal halide lamp at an irradiation intensity of 50 mW / cm ² for about 10 seconds hardened to a depth of 8 mm from the surface. The cured product was a solid gel, but the uncured liquid inside did not leak even if the petri dish was tilted or inverted for a long time. Further, this petri dish was placed at 20 ° C for 12 hours.
After standing for a time, it was completely cured to the bottom. The obtained cured product was in good contact with the petri dish, and the petri dish was immersed in the red ink, and the pressure was reduced by a vacuum pump, but no permeation was observed at the interface.

Shore D of the cured product cured by the above process
The hardness was 21 even when cured without irradiating UV.

As described above, since the hardness of the cured product is not so different depending on the presence or absence of UV curing, the physical properties are almost the same as those of the epoxy resin.
It is thought to be due to the diamine component. Into a Petri dish of the same specifications, cast an orifice washer with a diameter of 30 mm and cast the same. Under the same conditions as in the above process, five light-cured and room temperature-cured samples were prepared.
A heat shock test was performed at 20 ° C. for 60 minutes for 300 cycles, and further exposed to a humidity test at 80 ° C. and 95% RH for 30 days, but no crack was found in the cured product.

A cured product sample having a diameter of 30 mm and a thickness of 20 mm was prepared under the same conditions and subjected to the same heat shock test and humidity test to measure the resin hardness and electric resistance. Was 21 after the test, and the electrical resistance was 10 ⁵ before the test.
MΩ or more, and after the test, 10 ⁵ MΩ or more, no change was observed. Further, the main agent liquid 2 and the curing agent liquid 2 were stored at 50 ° C. for 3 months in a dark place, but no change such as thickening was observed.
No change in the cured product was observed.

Example 3 As a bisphenol type epoxy resin, EP-4901600 manufactured by Asahi Denka Kogyo KK
g, Yuko Shell Epoxy Co., Ltd. Epicoat 1001
50 g, EPU-6 199 g manufactured by Asahi Denka Kogyo Co., Ltd. as urethane-modified epoxy resin, 74 g NK ester U-6H manufactured by Shin-Nakamura Chemical Co., Ltd. as urethane (meth) acrylate, dimethacrylate (methacrylic reactive diluent) 49 g of NK ester 1G manufactured by Shin-Nakamura Chemical Co., Ltd., 1- (4-isopropylphenyl)
12 g of 2-hydroxy-2-methylpropan-1-one (Darocur 1116 manufactured by Merck) and 1 g of KP-330 manufactured by Shin-Etsu Chemical Co., Ltd. as a defoaming agent at 70 ° C. in a light-shielded environment at 70 ° C. After the mixture was returned to room temperature, a base solution 3 having a viscosity of 1600 cps (35 ° C.) was obtained.

The main component liquid 3 and the curing agent liquid 1 obtained in Example 1 were
Two-liquid mixing and discharging device (Naka Liquid Control Co., Ltd.)
Using a ratio of 2: 1 (weight ratio) to a PBT / glass 25% petri dish with a diameter of 9 cm and a depth of 20 mm.
50mW / cm ² with 1.5kw metal halide lamp
Irradiation for about 10 seconds at an irradiation intensity of 10
mm to a depth of mm. The cured product is a solid gel,
The uncured liquid inside did not leak even if the petri dish was tilted or inverted for a long time. Furthermore, this petri dish is kept at 20 ° C for 1 hour.
After standing for 2 hours, it was completely cured to the bottom. The obtained cured product was in good contact with the petri dish, and the petri dish was immersed in the red ink and the pressure was reduced by a vacuum pump, but no permeation was observed at the interface.

Shore D of the cured product cured by the above process
The hardness was 20, and was 20 even when cured without irradiating UV. As described above, since the hardness of the cured product is not so different depending on the presence or absence of the UV curing, it is considered that the physical properties are almost caused by the epoxy resin / diamine component. Into a Petri dish of the same specifications, an orifice washer with a diameter of 30 mm was cast and cast. Under the same conditions as in the above process, five light-cured and room temperature-cured samples were prepared.
300 cycles of a heat shock test at 60 ° C. for 60 minutes, and further performed under the conditions of a humidity resistance test at 80 ° C. and 95% RH.
Exposure was performed on day 0, and no cracks were found in the cured product.

Further, a cured product sample having a diameter of 30 mm and a thickness of 20 mm was prepared under the same conditions and subjected to the same heat shock test and humidity test to measure the resin hardness and the electrical resistance. 20 after the test
And the, for the electrical resistance, before the test is 10 ⁵ MΩ or more, after the test there was no change and 10 ⁵ MΩ or more.
The main solution 3 and the curing agent solution 1 were stored at 50 ° C. for 3 months in a dark place, but no change such as thickening was observed, and no change was observed in the cured product.

[0104]

The two-part curable resin composition of the present invention is inexpensive and suitable for automatic mixing and coating. It is temporarily cured by light irradiation and can be completely cured by leaving it at room temperature to obtain a thick film. Excellent curability and surface curability. Moreover, the cured product has excellent adhesion to the substrate, environmental resistance, and electrical insulation.

Further, the characteristics of the cured resin composition can be sufficiently exhibited by the method of using the curable composition of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI H05K 3/28 H05K 3/28 D (72) Inventor Satoshi Yanagiura 1-1-1, Tsukaguchi-Honmachi, Amagasaki-shi Mitsubishi Electric Corporation Materials Inside the Device Laboratory (72) Yasushi Yamamoto 8-1-1 Honcho Tsukaguchi, Amagasaki-shi Mitsubishi Electric Corporation Inside the Materials Device Laboratory (72) Inventor Fumiaki Baba 8-1-1 Honcho Tsukaguchi, Amagasaki-shi Mitsubishi Electric Corporation (56) References JP-A-4-149443 (JP, A) JP-A-5-53317 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F 7 / 027 C08F 2/44-2/50 G03F 7/028 G03F 7/004 H05K 3/28

Claims (2)

(57) [Claims] 1. A urethane (meth) acrylate having at least three (meth) acryl groups in a molecule, a glycol-based or glycerol-based dimethacrylate, a bisphenol-type epoxy resin, and a compound represented by the general formula (I): 1) (Wherein R represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms) and / or a compound represented by the formula (I)
I): embedded image And (B) 3,9-bis (3-aminopropyl) -2,4,
A two-part curable resin composition comprising a curing agent liquid containing 8,10-tetraoxaspiro [5.5] undecane and / or a modified product thereof as a main component. 2. After the two-part curable resin composition according to claim 1 is mixed, the composition is preliminarily cured by irradiation with light and further main-cured at room temperature or by heating.
A method for using the liquid mixture type curable resin composition.