JPH01289820A - Actinic radiation-curable unsaturated resin composition - Google Patents

Abstract

PURPOSE:To obtain the title compsn. having excellent adhesiveness to a substrate to be coated and water resistance by compounding a reaction product of an acrylic resin contg. acid groups and an unsatd. compd. contg. an alicyclic epoxy group with a diluent consisting of an org. solvent or a polymerizable vinyl monomer. CONSTITUTION:The title compsn. is prepd. by compounding a reaction product of an acrylic resin contg. acid groups [e.g., a copolymer of (meth)acrylic acid with methyl (meth)acrylate] and an unsatd. compd. contg. an alicyclic epoxy group [e.g., a compd. of formula I or II (wherein R1 is H or CH3 and R2 is a 1-6C divalent aliph. satd. hydrocarbon group etc.)] with a diluent consisting of an org. solvent and/or a polymerizable vinyl monomer. A coating film formed of this compsn. is chemically stable to a substance accelerating hydrolysis (e.g., water or sea water) and exhibits an excellent effect on the durability such as water resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to an active energy ray-curable unsaturated resin composition.

(Prior art and its problems) Various active energy ray-curable unsaturated resin compositions have been developed and are widely used in the fields of coatings, composite materials, electronic parts, etc.; Attempts have been made to develop a resin composition based on vinyl resin as one of these active energy ray-curable unsaturated resin compositions. Currently, as a composition mainly composed of vinyl resin compositions,
A product obtained by reacting a high acid value vinyl resin with an aliphatic epoxy group-containing vinyl compound is known, but the coating formed from this composition has poor adhesion and water resistance to the coated object, and still remains. It has not yet shown sufficient properties for practical use.

(Means for Solving the Problems) As a result of intensive research in order to solve the above-mentioned problems, the present invention has developed an active energy ray-curable unsaturated resin composition containing acid group-containing acrylic resin and alicyclic resin. A reaction product with an epoxy group-containing unsaturated compound, or a reaction product between an alicyclic epoxy group-containing unsaturated resin and an acid group-containing unsaturated compound,
It has been discovered that all of the above-mentioned problems can be solved by using an organic liquid diluted with an organic solvent and a polymerizable vinyl nitrate, and the present invention has been completed.

That is, the present invention provides a composition and a resin comprising a reaction product of an acid group-containing acrylic resin and an alicyclic epoxy group-containing unsaturated compound, mixed with an organic solvent and/or a diluent of a polymerizable vinyl hexamer. The present invention relates to an active energy ray-curable unsaturated resin composition prepared by blending an organic solvent and/or a polymerizable vinyl monomer diluent with a reaction product of a cyclic epoxy group-containing unsaturated resin and an acid group-containing unsaturated compound.

The acid group-containing acrylic resin used in the composition of the present invention is
Ethylenically unsaturated acids such as (meth)acrylic acid, 2-carboxyethyl (meth)acrylate, 2-carboxypropyl (meth)acrylate, and (anhydrous) maleic acid are essential components, and esters of (meth)acrylic acid are used as essential components. [e.g. methyl (meth)acrylate, ethyl (meth)
acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, etc.]; Vinyl aromatic compound [
For example, styrene, α-methylstyrene, vinyltoluene, P-chlorostyrene, etc.]; Amide-based unsaturated compounds [For example, (meth)acrylamide, diaseptacrylamide, N-methylolacrylamide, N-butoxymethylacrylamide, etc.]; Polyolefin-based compounds [e.g. butadiene, isoprene, chloroprone, etc.] and others [e.g. (meth)acrylonitrile,
Commonly known copolymers are used, which are copolymerized with one or more monomers selected from methyl isopropenyl ketone, vinyl acetate, beoba monomer (Shell Chemical Products), vinyl propionate, vinyl pivalate, etc. can.

The above-mentioned acid group-containing acrylic resin can be prepared by introducing an unsaturated group into the resin by reacting a part of the acid groups derived from the resin with an epoxy group derived from an alicyclic epoxy group-containing unsaturated compound. However, since it is necessary to introduce into the resin an unsaturated group necessary for curing with active energy rays,
The acid value of the resin is 15 or more, preferably in the range of 40 to 500.

The alicyclic epoxy group-containing unsaturated compound used in the composition of the present invention is a compound having one radically polymerizable unsaturated group and an alicyclic epoxy group in the molecule. Specifically, for example, the following general formula % formula % [In each general formula, R represents a hydrogen atom or a methyl group, R
2 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms; eR3 represents a divalent hydrocarbon group having 1 to 10 carbon atoms; 0 represents an integer from 0 to 10; be able to.

In the above, 2 having 1 to 6 carbon atoms represented by R2
As a valent aliphatic saturated hydrocarbon group.

Straight-chain or branched alkylene groups such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene groups and the like can be mentioned. Examples of the divalent hydrocarbon group having 1 to 10 carbon atoms represented by R3 include methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, polymethylene, and phenyle.

In addition to the above-mentioned alicyclic epoxy group-containing unsaturated compounds, aliphatic epoxy group-containing unsaturated compounds such as glycidyl (meth)acrylate, glycidyl β-methyl (meth)acrylate, allyl glycidyl ether, etc. It can be used in combination with the epoxy group-containing unsaturated compound in an amount of 90% by weight or less based on the total amount.

The method for producing a resin containing an unsaturated group using the acid group-containing acrylic resin and the alicyclic epoxy group-containing unsaturated compound is, for example, a solution of the acid group-containing acrylic resin in an inert organic solvent (for example, an alcohol-based , ester type, aromatic hydrocarbon type, aliphatic hydrocarbon type, etc.) and the alicyclic epoxy group-containing unsaturated compound at about 20 to 120°C.
This can be carried out by reacting under reaction conditions for about 1 to 5 hours.

The thus obtained unsaturated group-containing resin has a molecular weight of 1
The number of unsaturated groups per 000 ranges from 0.2 to 4.0, preferably from 0.7 to 3.5. If the number of unsaturated groups is less than 0.2, the curability of the coating will be insufficient, resulting in poor adhesion to the coated object, water resistance, etc. On the other hand, if the number of unsaturated groups is more than 4.0, acid resistant This is not preferable because there is a risk of thickening or gelling during the addition reaction with the group-containing acrylic resin, and if the composition is stored for a long period of time, there is a risk of thickening or gelling.

Further, the resin has a number average molecular weight of 1,000 to ioo,
ooo, preferably in the range of 3.000 to 70.000.If the molecular weight is less than 1.000, the water resistance of the coating will be poor;
If it is larger, the viscosity becomes high, making it inconvenient to handle, and the film has poor film-thickening properties, resulting in a film with poor adhesion to water-resistant objects, which is not preferable.

Further, the resin preferably has a resin acid value in the range of 300 or less. When the acid value is greater than 300,
This is not preferred because the water resistance of the film is poor.

The composition of the present invention contains, in addition to the reaction product of the acid group-containing acrylic resin and the alicyclic epoxy group-containing unsaturated compound, a reaction product of the alicyclic epoxy group-containing vinyl resin and the acid group-containing unsaturated compound. Can be mentioned.

As the alicyclic epoxy group-containing unsaturated resin, the alicyclic epoxy group-containing unsaturated monomers represented by the general formulas (I) to (XV) are used as essential monomer components, and the acid group-containing One or more monomers selected from the same monomers as used in acrylic resins [for example, (meth)acrylic acid esters, vinyl aromatic compounds, and other monomers, etc.] Examples include copolymers obtained by polymerization reaction.

An unsaturated compound containing an acid group is a compound having one unsaturated group and an acid group in one molecule, and is reacted with the above-mentioned alicyclic epoxy group-containing unsaturated resin to form an unsaturated compound in the resin. This is to introduce a saturated group.

Specifically, ethylenically unsaturated acids such as (meth)acrylic acid, 2-hydroxyethyl (meth)acrylate, 2-carboxypropyl (meth)acrylate, and (anhydrous) maleic acid are preferably mentioned.

A method for producing an unsaturated group-containing resin using the above-mentioned alicyclic epoxy group-containing unsaturated resin and acid group-containing unsaturated compound includes, for example, using a solution of an alicyclic epoxy group-containing unsaturated resin in an inert organic solvent. about 20 to 11 acid group-containing unsaturated compounds
This can be carried out by reacting at 0° C. for about 1 to 7 hours.

The thus obtained unsaturated group-containing resin has a number of unsaturated groups in the range of 0.2 to 4.0, preferably 0.7 to 3.5 per 1000 molecular weight, and a number average molecular weight of 1. 000 to 100,000, preferably 3,000 to
70.000.

The active energy ray-curable unsaturated resin composition used in the present invention may contain conventionally known polymerizable vinyl monomers and polymerizable prepolymers as appropriate depending on the intended use and required coating performance. .

Specifically, as the polymerizable vinyl mop.

For example, monovalent vinyl monomers [for example, esters of (meth)acrylic acid used in the above-mentioned high acid value acrylic resins, vinyl aromatic compounds, amide unsaturated compounds, polyolefin compounds, and other monomers]: hydroxyl groups Containing monomers and monoisocyanates (e.g. butyl isocyanate).

(phenylisocyanate, etc.); examples include aziridine group-containing monomers and phosphorus-containing vinyl monomers. polyvinyl heptamers [e.g., reaction products of polyhydric alcohols and (meth)acrylic esters (e.g., butanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, etc.), polyalkylene glycols and (meth) ) Reaction products with acrylic esters (e.g. diethylene glycol diacrylate, propylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, etc.), reaction products with caprolactone-modified polyhydric alcohols and (meth)acrylic esters, Examples include phosphorus vinyl monomer. ].

Specifically, the polymerizable prepolymer includes 1, for example, a polymerizable unsaturated group-containing resin that can be water-based [for example, a resin in which hydroxyalkyl (meth)acrylate is introduced into a carboxyl group-containing polyol via a polyisocyanate compound, etc.] and polymerizable unsaturated group-containing resins [for example, (meth)acrylic esters of polyester polyols, (meth)acrylic esters of polyether polyols, and (meth)acrylic esters of acrylic polyols.

Examples include adducts of polyepoxy and (meth)acrylic acid, and resins J in which hydroxyalkyl (meth)acrylate is introduced into polyol via a polyincyanate compound.

The above-mentioned polymerizable vinyl monomer and polymerizable propolymer can be blended in an amount of 100 parts by weight or less, preferably 50 parts by weight or less, based on 100 parts by weight of the resin solid content of the active energy ray-curable resin composition.

Further, the composition of the present invention may contain pigments, dyes, etc., if necessary, to the extent that they do not inhibit the curability of active energy rays.

The composition of the present invention is particularly useful in paints, printing inks, photoresists, solder resists, printing plate materials, adhesives, pressure-sensitive adhesives, and the like.

The method of forming a film using the composition of the present invention includes, for example, wood, paper, inorganic materials, plastics, metals (zinc, iron,
For example, natural roll coater, reverse roll coater, gravure roll coater, screen printing 4! Coating is performed using a coating machine such as a curtain coater, air spray, airless spray, bar coater, knife coater, spin coater, brush, or dip coater, and then the object is irradiated with electron beams or ultraviolet active energy rays. This can be done to cure the coating. The above coating film thickness is 2000 in dry film thickness.
- below, preferably in the range of 1 to 1ooo-. If the film thickness is more than 2,000 mm, the hardening properties inside the film will be poor, which is not preferable.

Examples of electron beam accelerators that emit active energy rays include Kotskucroft type, Kotscroft-Walton type, Pan de Graaf type, resonant transformer type, transformer type, insulated core transformer type, dynamidron type, and linear filament type. type, broad beam type, area beam type, cathode electrode type, high frequency type, etc. The amount of electron beam irradiation is not particularly limited as long as it provides the dose necessary to cure the coating, but generally it is about 100 to 2000 KeV and about 0.5 to 2000 KeV.
A dose of 20 megarads (Mrad) is applied. The atmosphere in which the electron beam is irradiated is preferably an inert gas.

Examples of the ultraviolet irradiation source that emits active energy rays include a mercury lamp, a high-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, and sunlight. The atmosphere in which ultraviolet rays are irradiated is preferably air or an inert gas. Furthermore, when the irradiation atmosphere is air, it is particularly preferable to use a high-pressure mercury lamp as the irradiation source, and the irradiation conditions vary depending on the absorption amount of the photopolymerization initiator.
Within a few minutes using a light beam with a wavelength of 0 to 4500,
This is usually carried out for a period of 1 second to 20 minutes.

In addition, when the coating composition of the present invention is cured with ultraviolet rays, a photopolymerization initiator is added to the coating composition, typical examples of which include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin n −
Propyl ether, pentuin n-butyl ether, benzophenone, P-methylbenzophenone, Michler's ketone, acetophenone, 2-chlorothioxanthone, anthraquinone, chloroanthraquinone, 2-methylanthraquinone, phenyl disulfide 2-nitrofluthalene, butyroin, Examples include anisoin ethyl ether, azobisisobutyronitrile, and tetramethylthiuram disulfide. These photoinitiators are 1
One species or a combination of two or more species can be used.

Also, the amount of photopolymerization initiator to be blended is approximately 0.1 to 101f for the active energy ray-cured paint! It is preferable to mix it in the range of , amount %. Further, in order to promote the photopolymerization reaction by the photopolymerization initiator, a photopolymerization accelerator can be used in combination with the photopolymerization initiator, typical examples of which include triethylamine, triethanolamine, etc. , tertiary amines such as 2-dimethylaminoethanol, alkyl phosphines such as triphenylphosphine, and thiols such as β-thioglycol.

(Actions and Effects) The composition of the present invention is characterized in particular by an addition reaction between an alicyclic epoxy group derived from an alicyclic epoxy group-unsaturated compound and an acid group derived from an acrylic resin, and an alicyclic epoxy group-containing unsaturated compound. The addition reaction between the alicyclic epoxy group derived from the resin and the acid group derived from the acid group-containing unsaturated compound occurs easily due to the high reactivity of the ring-opening polymerization reaction of the epoxy group, and active energy is generated in the resin. Linearly curable unsaturated groups can be introduced.

In addition, the film formed from the composition is coated with hydrolysis accelerators (e.g. water, Because it is chemically stable against seawater (e.g., seawater), it has remarkable effects such as excellent durability such as water resistance.

(Examples) The present invention will be explained in more detail below using five examples.

Synthesis example 1 of unsaturated resin: 30 parts by weight of styrene, 35 parts by weight of butyl acrylate,
5 parts by weight of n-butanol in a reaction vessel in which a mixed solution consisting of 35 parts by weight of acrylic acid and 3 parts by weight of azobisisobutyronitrile was maintained at 110°C under a nitrogen gas atmosphere.
Q heavy ffj (parts) was added dropwise to 40 parts by weight of methyl isobutyl ketone over 3 hours.

After dropping, it was aged for 1 hour, and a mixed solution consisting of 1 part by weight of azobisdimethylvaleronitrile and 10 parts by weight of methyl isobutyl ketone was added dropwise over 1 hour. 260) After obtaining a solution, 98 parts by weight of the following compound and 0.1 parts by weight of hydroquinone monomethyl
4- Add the weight part of Teru and blow air to it at 80°C.
Reaction was carried out for 5 hours to form an unsaturated resin (acid value: 20, number of unsaturated groups: 1.98/molecular weight: 1ooo).

A solution with a number average molecular weight of 17,000 was obtained.

Synthesis Example 2 of Unsaturated Resin 0.15 parts by weight of the following compound hydroquinone was added to 204 parts by weight of the acid group-containing acrylic resin solution of Synthesis Example 1, and air was blown into the solution. Value 1, number of unsaturated groups 2.25/molecular weight 10
00. A solution with a number average molecular weight of about 18,000 was obtained.

Synthesis Example 3 of Unsaturated Resin A mixed solution consisting of 1 part of butyl methacrylate (4Ofi), 35 parts by weight of butyl acrylate, 25 parts by weight of acrylic acid, and 1 part by weight of azobisin butyronitrile was heated to 110''C under a nitrogen gas atmosphere. n- in the reaction vessel holding
After adding 0 drops to 90 parts by weight of butanol over 3 hours, it was aged for 1 hour, and azobisdimethylvaleronitrile 1
A mixed solution consisting of parts by weight and methyl isobutyl ketone 1023 (i parts) was added dropwise over 1 hour and further aged for 5 hours to obtain a high acid value acrylic resin (acid value 184) solution.
Next, 62 parts by weight of the following compound and 1 part of hydroquinone O, 121 fL were added to this solution, and the mixture was reacted at 80°C for 5 hours while blowing air to produce an unsaturated resin (acid value O1, number of unsaturated groups 2.07/molecular weight 1000, A solution with a number average molecular weight of 30.000 was obtained.

Synthesis Example 4 of Unsaturated Resin 20 parts by weight of methyl methacrylate, 20 parts by weight of styrene, 25 parts by weight of methyl acrylate.

15 parts by weight of 2-hydroxyethyl methacrylate, 20 parts by weight of acrylic acid and 5 parts by weight of azobisisobutyronitrile
A mixed system consisting of 10 parts by weight was heated under a nitrogen gas atmosphere.
It was added dropwise over 3 hours to 60 parts by weight of butyl cellosolve in a reaction vessel kept at 5°C.After the addition, the solution was aged for 1 hour.
A mixed solution consisting of 1 part by weight of azobisdimethylvaleronitrile and 7 parts by weight of butyl cellosolve was added dropwise over 1 hour, and further aged for 5 hours to obtain a high acid value acrylic resin (acid value 150) solution. To this solution, 25 parts by weight of the following compound and 1 part of hydroquinone 0.06i were added and reacted at 80"C for 5 hours while blowing air to produce an unsaturated resin (acid value 60, number of unsaturated groups 1.1/molecular weight 10
00, number average molecular weight 10.000) solution was obtained.

Synthesis Example 5 of Unsaturated Resin 25 parts by weight of styrene, 23 parts by weight of butyl acrylate and 3 parts of E-butylperoxy 2-ethylhexanoate!
l! 1 part of the mixed solution in a nitrogen gas atmosphere
20 parts by weight of n-butanol and 701 parts of methyl isobutyl ketone were added dropwise over 3 hours to 20 parts by weight of n-butanol and 701 parts of methyl isobutyl ketone in a reaction vessel kept at 10°C. After the addition, the mixture was aged for 1 hour, and 1 ml of 1 J part of t-butyl peroxy 2-ethylhexanoate was added. A mixed solution consisting of 10 parts by weight of Then, 0.12 parts by weight of hydroquinone was added and reacted at 80°C for 7 hours while blowing air.
A solution with a number average molecular weight of 18.000 was obtained.

Synthesis Example 6 of Unsaturated Resin A mixed solution consisting of 4 parts by weight of butyl methacrylate, 36 parts by weight of butyl acrylic acid, and 2 parts by weight of t-butylperoxy 2-ethylhexoate was heated under a nitrogen gas atmosphere.
It was added dropwise over 3 hours to 90 parts by weight of isobutyl acetate in a reaction vessel maintained at lO'o, and after the dropwise addition, it was aged for 1 hour to obtain t-butyl peroxy 2-ethylhexanoate.
1 part by weight, 10 parts by weight of isobutyl acetate
The mixture was added dropwise over a period of time, and further aged for 7 hours to obtain an alicyclic epoxy group-containing acrylic resin solution.

Next, 1433 parts of acrylic acid and 0.12 parts of hydroquinone were added to this solution, and the mixture was heated to 80°C while blowing air.
After 5 hours of reaction, unsaturated resin (number of unsaturated groups: 1.66/
A solution with a molecular weight of too much and a number average molecular weight of 25.000 was obtained.

Comparative resin synthesis example 1 Styrene 30fE parts, butyl acrylate 4Offi
50 parts by weight of n-butanol in a reaction vessel in which a mixture of 30 parts by weight of acrylic acid and 3 parts by weight of azobisisobutyronitrile was maintained at 120°C under a nitrogen gas atmosphere.
part by weight, was added dropwise over 3 hours into 40 parts by weight of methyl isobutyl ketone.After the dropwise addition, it was aged for 1 hour, and a mixed solution consisting of 1 part by weight of azobisdimethylvaleronitrile and 10 parts by weight of cellosolve was added dropwise over 1 hour. Then, 56 parts by weight of zero-order glycidyl methacrylate, 0.13 parts by weight of hydroquinone, and 0.6 parts by weight of tetraethylammonium bromide were added to obtain a high acid value acrylic resin (acid value 222) solution by aging for 5 hours, and air was added. 12 while blowing
React at 0°C for 8 hours to obtain an unsaturated resin (acid value 5, number of unsaturated groups 2.5/molecular weight 1000, number average molecular weight 15,00
0) A solution was obtained.

Example 1 After adding 712,710 parts by weight of α-hydroxyisobutyl to 300 parts by weight of the solution of Synthesis Example 1 of unsaturated resin, this solution was coated on an aluminum plate with a bar coater and heated at 80°C.
After drying for 15 minutes, UV irradiation was performed for 5 seconds using a 1 20 W/am high-pressure mercury lamp for curing. This coating thickness is approximately 2
Also, the adhesion and water resistance of this coating film were examined.

Example 2 Add 300 parts by weight of the solution of Synthesis Example 1 of unsaturated resin to vinyl monomer Aronix M5700 (manufactured by Toagosei ■, trade name,
After adding 100 parts by weight of tripropylene glycol diacrylate and 20 parts by weight of tripropylene glycol diacrylate and heating to 100°C, the pressure was reduced while blowing air to remove n-butanol and methyl isobutyl ketone from the solution. Furthermore, α
-16 parts by weight of hydroxyisobutylphenone were added. This composition was applied onto an aluminum plate using a bar coater, and irradiated with a 120 W/cm high-pressure mercury lamp for 5 seconds to cure it. The coating thickness was 20%. The adhesion and water resistance of this coating film were examined.

Example 3 106 parts by weight of the vinyl monomer Aronix M5700 and 22 parts by weight of tripropylene glycol diacrylate were added to 312 parts by weight of the solution of Synthesis Example 2 of unsaturated resin, and the solvent was removed in the same manner as in Example 2. 17 parts by weight of α-hydroxyisobutylphenone was added. Further, it was cured in the same manner as in Example 2.

Example 4 After adding 6 parts by weight of α-hydroxyisobutylphenone to 220 parts by weight of the solution of Synthesis Example 5 of unsaturated resin, this solution was coated on an aluminum plate with a bar coater and heated at 80°C.
After drying for 5 minutes, it was cured by UV irradiation for 2 seconds using a 120 W/cm high pressure mercury lamp. The coating thickness was approximately 20 mm. The adhesion and water resistance of this coating were examined.

Example 5 To 220 parts by weight of the solution of Synthesis Example 5 of unsaturated resin, 60 parts by weight of vinyl monomer Aronix M5700 and 12 parts by weight of tripropylene glycol diacrylate were added to give 100 parts by weight.
After heating to °C, the pressure was reduced while blowing air to remove n-butanol and methyl isobutyl ketone from the solution. Furthermore, 727,710 parts by weight of α-hydroxyisobutyl was added. This composition was applied onto an aluminum plate using a bar coater, and irradiated with a 12 W/cm high pressure mercury lamp for 2 seconds to cure it. The coating thickness was 20ttm.

The adhesion and water resistance of this coating film were examined.

Comparative Example 1 After adding 8 parts by weight of α-hydroxyisobutylphenone to 260 parts by weight of the solution of Comparative Resin Synthesis Example 1, the same test as in Example 1 was conducted.

Comparative Example 2 80 parts by weight of Aronix M5700 and 16 parts by weight of tripropylene glycol diacrylate were added to 260 parts by weight of the solution of Comparative Resin Synthesis Example 1, and the solvent was removed in the same manner as in Example 2, followed by α-hydroxyisobutylphenone. 13
parts by weight were added.

Further, it was cured in the same manner as in Example 2.

The coating film test results of Examples 1 to 3 and Comparative Example 1 are summarized in Table 1.

1) Adhesion: According to the test method of JIS D-0202, make ioom cross-cuts on the test piece at 1 mm intervals, then peel with cellophane adhesive tape, and calculate the number of squares without peeling as a numerator. , the original number of squares (100) is expressed as the denominator.

2) Adhesion after immersion in water After the coated plate was immersed in warm water at 50°C for one day, the moisture on the surface was wiped off, and after being left at room temperature for 1 hour, the same test as in 1) was conducted.

Example 6 50 parts by weight of tripropylene glycol diacrylate, 50 parts by weight of 1,6 hexanediol diacrylate, and 50 parts by weight of trimethylolpropane triacrylate were added to 264 parts by weight of the solution of Synthesis Example 3 of unsaturated resin. In addition, 10
After heating to 0°C, the pressure was reduced while blowing air to remove the n-butanol solvent in the solution. Furthermore, 62 parts by weight of titanium white was added and dispersed in a ball mill to produce a white paint. Apply this paint to a thickness of 1 coat using a curtain coater.
．． After painting on 5cm Cerakola board.

The coating was cured by irradiating it with a 7 megarad electron beam to create Ceracola tiles. The coating thickness is approximately ioo.m. Adhesion to Ceracola was good, and as a result of evaluating the appearance and adhesion after sticking it to a wall for 3 months, it was as good as at the beginning.

Example 7 198 parts by weight of the solution of Synthesis Example 4 of unsaturated resin, 20 parts by weight of phenol novolak epoxy resin (epoxy equivalent: 173), 5 parts by weight of α-hydroxyisobutylphenone,
0.5 parts by weight of phthalocyanine green was kneaded using three rolls. This composition was used as a solder resist ink for printed wiring boards. Next, the ink is applied onto a copper through-hole printed wiring board using a screen printing method,
After drying at 70 °C for io minutes (film thickness 15-20 l),
Closely attach the film with the necessary pattern drawn on it, 3KW
A light intensity of 800 mJ/Cm2 was irradiated with an ultra-high pressure mercury lamp. Furthermore, after removing the unexposed areas with a 1% sodium carbonate solution, a solder resist film was obtained by heating at 140° C. for 30 minutes. This resist film had excellent heat resistance such as solder sticking resistance, and chemical resistance to acids and alkalis.

Example 8 40 parts by weight of tripropylene glycol diacrylate, 40 parts by weight of 1.6 hexanediyl diacrylate, and 30 parts by weight of trimethylolpropane triacrylate were added to 217 parts by weight of the solution of Synthesis Example 6 of unsaturated resin to make 100 parts by weight.
After heating to a temperature of 100 ml, the pressure was reduced while blowing air to remove isobutyl acetate from the solution. 55 parts by weight of titanium white was added and dispersed in a ball mill to prepare a white paint. White Ceracola tiles were made by irradiation with electron beams.The Ceracola tiles were pasted on a wall and evaluated for appearance and adhesion for 3 months, and as a result, they were as good as the initial stage.

Claims (1)

[Claims] 1. An active energy ray obtained by blending an organic solvent and/or a polymerizable vinyl monomer diluent with a reaction product of an acid group-containing acrylic resin and an alicyclic epoxy group-containing unsaturated compound. Curable unsaturated resin composition. 2. An active energy ray-curable unsaturated resin composition obtained by blending an organic solvent and/or a polymerizable vinyl monomer diluent with a reaction product of an alicyclic epoxy group-containing unsaturated resin and an acid group-containing unsaturated compound. thing.