JP2763775B2 - Active energy ray-curable unsaturated resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an active energy ray-curable unsaturated resin composition.

(Conventional technology and its problems) Conventionally, various types of active energy ray-curable unsaturated resin compositions have already been developed, and these are widely used in the fields of coating, composite materials, electronic components and the like. Attempts have been made to develop resin compositions mainly composed of vinyl resins as one of those active energy ray-curable unsaturated resin compositions. Currently, as a composition mainly composed of a vinyl resin composition, a composition obtained by reacting a high acid value vinyl resin with an aliphatic epoxy group-containing vinyl compound is known, but a coating formed from the composition is Adhesion and water resistance to an object to be coated are inferior, and properties which are sufficiently satisfactory for practical use have not yet been achieved.

(Means for Solving the Problems) The present invention has made intensive studies to solve the above-mentioned problems, and as a result, as an active energy ray-curable unsaturated resin composition, an acid group-containing acrylic resin and an alicyclic resin Use an organic liquid obtained by diluting a reaction product of an epoxy group-containing unsaturated compound or a reaction product of an alicyclic epoxy group-containing unsaturated resin and an acid group-containing unsaturated compound with an organic solvent and a polymerizable vinyl monomer. The inventors have found that all of the above problems can be solved, and have completed the present invention.

Thus, the present invention includes an acid-containing acrylic resin obtained by polymerizing an ethylenically unsaturated acid as an essential component, and an ester bond formed by a ring-opening addition reaction between an epoxy group and a carboxyl group. An active energy ray-curable unsaturated resin composition obtained by blending an organic solvent and / or a polymerizable vinyl monomer with a reaction product with an unsaturated alicyclic epoxy group-containing unsaturated compound,
And an alicyclic epoxy group obtained by polymerizing an alicyclic epoxy group-containing unsaturated compound containing no ester bond formed by a ring-opening addition reaction between an epoxy group and a carboxyl group as an essential monomer component The present invention provides an active energy ray-curable unsaturated resin composition obtained by blending an organic solvent and / or a polymerizable vinyl monomer with a reaction product of a resin-containing resin and an acid group-containing unsaturated compound.

The acid group-containing acrylic resin used in the composition of the present invention,
An ethylenically unsaturated acid such as (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, or (anhydrous) maleic acid is an essential component, and an ester of (meth) acrylic acid is added thereto. [For example, 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,
amide-based unsaturated compounds [for example, (meth) acrylamide, diacetone acrylamide, N-methylolacrylamide, N-butoxymethylacrylamide, etc.]; polyolefin-based compounds [for example, butadiene, isoprene, chloroprene, etc.]
And one or more other monomers selected from [for example, (meth) acrylonitrile, methyl isopropenyl ketone, vinyl acetate, veoba monomer (shell chemical product), vinyl propionate, vinyl pivalate, etc.]. Other generally known copolymers can be used.

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

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 one molecule. Specifically, for example, the following general formula [In each formula, R ₁ represents a hydrogen atom or a methyl group. R ₂ represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms. R ₃
Represents a divalent hydrocarbon group having 1 to 10 carbon atoms. l is 0-10
Indicates an integer. ] Etc. can be mentioned.

In the above, ₂ having 1 to 6 carbon atoms represented by R 2
As the monovalent aliphatic saturated hydrocarbon group, a linear or branched alkylene group such as methylene, ethylene, propylene,
Examples thereof include a tetramethylene, ethylethylene, pentamethylene, and hexamethylene groups. Examples of the divalent hydrocarbon group having 1 to 10 carbon atoms represented by R ₃ include methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, polymethylene, phenylene, Can be mentioned.

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

A method for producing a resin containing an unsaturated group using the above-mentioned acid group-containing acrylic resin and an alicyclic epoxy group-containing unsaturated compound includes, for example, a solution of an acid group-containing acrylic resin in an inert organic solvent (for example, an alcohol-based resin). , Esters, aromatic hydrocarbons, aliphatic hydrocarbons, etc.) and an alicyclic epoxy group-containing unsaturated compound under the reaction conditions of about 20 to 120 ° C and about 1 to 5 hours. It can be done by doing.

The resin containing an unsaturated group thus obtained has a molecular weight of
0.2 to 4.0 unsaturated groups per 1000, preferably 0.7 to 3.5
In the range. When the number of unsaturated groups is less than 0.2, the curability of the coating film becomes insufficient, and the adhesion to the object to be coated and the water resistance are poor, while the number of unsaturated groups is 4.
If the number is more than 0, the composition may be thickened or gelled during the addition reaction with the acid group-containing acrylic resin, and if the composition is stored for a long period of time, it may be undesirably thickened or gelled.

The resin may have a number average molecular weight in the range of 1,000 to 100,000, preferably 3,000 to 70,000.
If the molecular weight is less than 1,000, the water resistance of the coating is inferior, while if the molecular weight is more than 100,000, the viscosity becomes high and handling becomes inconvenient, and the film-enhancing property also deteriorates, and the coating with poor adhesion to the water-resistant coated object is poor. Is not preferred.

Further, the resin may have a resin acid value preferably in the range of 300 or less. If the acid value is larger than 300, the water resistance of the coating is inferior, which is not preferable.

In the composition of the present invention, instead of the reaction product of the acid group-containing acrylic resin and the alicyclic epoxy group-containing unsaturated compound, the alicyclic epoxy group-containing vinyl resin and the acid group-containing unsaturated compound Reactants can also be used.

As the alicyclic epoxy group-containing resin, the alicyclic epoxy group-containing unsaturated monomer represented by the general formulas (I) to (IX) is used as an essential monomer component, and the acid group-containing acrylic resin is added thereto. The same monomer as used in the resin [eg (meth)
Acrylic acid esters, vinyl aromatic compounds, other monomers, etc.] and one or more monomers selected from the group.

The acid group-containing unsaturated compound is a compound having one unsaturated group and an acid group in one molecule, and is reacted with the alicyclic epoxy group-containing resin to form an unsaturated group in the resin. Is introduced. Specifically, for example, (meth) acrylic acid, 2-carboxyethyl (meth) acrylate,
Preferred are ethylenically unsaturated acids such as 2-carboxypropyl (meth) acrylate and (anhydride) maleic acid.

The method for producing a resin having an unsaturated group using the alicyclic epoxy group-containing resin and the acid group-containing unsaturated compound includes, for example, a solution of the alicyclic epoxy group-containing resin in an inert organic solvent and an acid group-containing unsaturated resin. About 20 to 110 ° C, about 1 to 1
The reaction can be carried out under a reaction condition of 7 hours.

The resin containing an unsaturated group thus obtained has a number of unsaturated groups of from 0.2 to 4.0, preferably from 0.7 to 3.5, and a number average molecular weight of from 1,000 to 100,00 per 1,000 molecular weight in the same manner as described above.
It can have 0, preferably in the range of 3,000 to 70,000.

In the active energy ray-curable unsaturated resin composition used in the present invention, conventionally known polymerizable vinyl monomers and polymerizable prepolymers can be appropriately blended according to the use and required coating film performance. .

Specific examples of the polymerizable vinyl monomer include, for example, monovalent vinyl monomers [eg, esters of (meth) acrylic acid, vinyl aromatic compounds, amide unsaturated compounds, and polyolefins used in the high-acid-value acrylic resin. Monomers such as system compounds and other monomers; adducts of hydroxyl group-containing monomers with monoisocyanates (eg, butyl isocyanate and phenyl isocyanate); aziridine group-containing monomers and phosphorus-containing vinyl monomers. ] And polyvalent vinyl monomers [for example, a reaction product of a polyhydric alcohol and a (meth) acrylate (for example, butanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, etc.), a polyalkylene glycol and (meth)
Reaction products with acrylic acid esters (for example, diethylene glycol diacrylate, propylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, etc.), reaction products of caprolactone-modified polyhydric alcohol with (meth) acrylic acid esters, phosphorus-containing And divinyl monomers. ].

Specific examples of the polymerizable prepolymer include, for example, a polymerizable unsaturated group-containing resin that can be made water-soluble [eg, a resin in which a hydroxyalkyl (meth) acrylate is introduced into a carboxyl group-containing polyol via a polyisocyanate compound]. And a polymerizable unsaturated group-containing resin [for example, (meth) acrylate of polyester polyol, (meth) acrylate of polyether polyol, (meth) acrylate of acrylic polyol, polyepoxy and (meth) acrylic acid. And a resin in which a hydroxyalkyl (meth) acrylate is introduced into an adduct and a polyol via a polyisocyanate compound.

The polymerizable vinyl monomer and the 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, if necessary, pigments and dyes to such an extent that the curability of active energy rays is not impaired.

The composition of the present invention is a paint, a printing ink, a photoresist,
Particularly useful for solder resists, printing 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 material, plastic, metal (zinc,
For example, natural roll coaters, reverse roll coaters, gravure roll coaters, screen printing machines, curtain coaters, air sprays, airless sprays, bar coaters, knife coaters, spin coaters, brushes, etc. The coating is performed using a coating machine such as a dip coating machine, and then the coating is irradiated with an electron beam or an ultraviolet active energy ray to cure the coating. The above coating thickness is 2000μ in dry film thickness
m, preferably in the range of 1 to 1000 μm. Film thickness
If it is more than 2000 μm, the curability inside the coating film is inferior, so that it is not preferable.

Examples of electron beam accelerators that emit active energy rays include Cockcroft type, Cockcroft-Walton type, Van de Graf type, Resonant transformer type, Transformer type,
Examples include an insulating core transformer type, a dynamitron type, a linear filament type, a broad beam type, an area beam type, a cathode electrode type, and a high frequency type. The irradiation dose of the electron beam is not particularly limited as long as it gives a dose necessary for curing the coating film. Generally, the irradiation dose is about 100 to 2000 KeV and about 0.5 to 20 megarads (Mrad). The atmosphere for irradiating the electron beam is preferably performed in an inert gas.

Examples of the irradiation source of the ultraviolet ray for emitting the active energy ray include a mercury lamp, a high-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, and sunlight. The atmosphere for irradiating ultraviolet rays is preferably irradiated in air or in an inert gas. When the irradiation atmosphere is air, it is particularly preferable to use a high-pressure mercury lamp as the irradiation source. Also,
Irradiation conditions vary depending on the amount of photopolymerization initiator absorbed, but 3000
It is carried out within a few minutes, usually from 1 second to 20 minutes, using a light beam having a wavelength of 波長 4500 °.

When the coating composition of the present invention is cured with ultraviolet light, a photopolymerization initiator is added to the coating composition, and typical examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin n.
-Propyl ether, benzoin n-butyl ether,
Benzophenone, P-methylbenzophenone, Michler's ketone, acetophenone, 2-chlorothioxanthone,
Examples include anthraquinone, chloroanthraquinone, 2-methylanthraquinone, phenyl disulfide 2-nitrofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, and tetramethylthiuram disulfide. These photopolymerization initiators can be used alone or in combination of two or more.
The amount of the photopolymerization initiator is preferably in the range of about 0.1 to 10% by weight based on the active energy ray-curable paint. Further, for the purpose of accelerating the photopolymerization reaction by the above photopolymerization initiator, a photopolymerization accelerator can be used in combination with the above photopolymerization initiator, and typical examples thereof include triethylamine and triethanolamine. And tertiary amines such as 2-dimethylaminoethanol, alkylphosphines represented by triphenylphosphine, and thiols represented by β-thioglycol.

(Function and Effect) The composition of the present invention is particularly useful in 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 resin. The addition reaction between the derived alicyclic epoxy group and the acid group derived from the acid group-containing unsaturated compound easily reacts due to the high reactivity of the ring-opening polymerization reaction of the epoxy group, and the active energy ray curing in the resin Possible unsaturated groups can be introduced. In addition, the coating formed from the composition has a relatively large steric hindrance in the chemical bond generated by the chemical reaction between the acid group of the acrylic resin and the alicyclic epoxy group, so that a hydrolysis promoting substance (for example, water, It is chemically stable against seawater, etc., and thus exhibits remarkable curing with excellent durability such as water resistance.

(Examples) Hereinafter, the present invention will be described more specifically with reference to examples.

Synthesis example 1 of unsaturated resin 30 parts by weight of styrene, 35 parts by weight of butyl acrylate, 35 parts by weight of acrylic acid and azobisisobutyronitrile 3
The mixed solution consisting of parts by weight is
The mixture was added dropwise over 3 hours to 50 parts by weight of n-butanol and 40 parts by weight of methyl isobutyl ketone in a reaction vessel maintained at a temperature of ° C. After the dropping, the mixture is aged for 1 hour, and a mixed solution comprising 1 part by weight of azobisdimethyl valeronitrile and 10 parts by weight of methyl isobutyl ketone is added dropwise for 1 hour, and the mixture is aged for 5 hours to obtain a high acid value acrylic resin (acid value). 260) A solution was obtained. Then add the following compound to this solution 98 parts by weight and hydroquinone monomethyl ether 0.14
Add an unsaturated resin (acid value: about 20, number of unsaturated groups: 1.98 / molecular weight)
1000, a number average molecular weight of about 17,000) solution was obtained.

Synthesis Example 2 of Unsaturated Resin The following compound was added to 204 parts by weight of the acid group-containing acrylic resin solution of Synthesis Example 1. Was added thereto, and the mixture was reacted at 80 ° C. for 5 hours while blowing air to obtain a solution of an unsaturated resin (acid value: 1, number of unsaturated groups: 2.25 / molecular weight: 1000, number average molecular weight: about 18,000).

Synthesis Example 3 of unsaturated resin 40 parts by weight of butyl methacrylate, butyl acrylate
A mixture of 35 parts by weight, 25 parts by weight of acrylic acid and 1 part by weight of azobisisobutyronitrile was treated with n-butanol 9 in a reaction vessel maintained at 110 ° C. under a nitrogen gas atmosphere.
It was added dropwise to 0 parts by weight over 3 hours. After the dropwise addition, the mixture was aged for 1 hour, and a mixed solution composed of 1 part by weight of azobisdimethyl valeronitrile and 10 parts by weight of methyl isobutyl ketone was added dropwise for 1 hour, and the mixture was aged for 5 hours to obtain a high acid value acrylic resin (acid value). 184) A solution was obtained. Then add the following compound to this solution 62 parts by weight and 0.12 parts by weight of hydroquinone were added, and the mixture was reacted at 80 ° C. for 5 hours while blowing air to obtain a solution of an unsaturated resin (acid value: 0, number of unsaturated groups: 2.07 / molecular weight: 1,000, number average molecular weight: about 30,000). .

Synthesis example 4 of unsaturated resin 20 parts by weight of methyl methacrylate, 20 parts by weight of styrene,
Butyl cellosolve in a reaction vessel in which a mixed system consisting of 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 was maintained at 105 ° C. under a nitrogen gas atmosphere. It was dropped into 60 parts by weight over 3 hours. After the dropping, the mixture is aged for 1 hour, and a mixed solution composed of 1 part by weight of azobisdimethylpareronitrile and 7 parts by weight of butyl cellosolve is added dropwise for 1 hour. 150) A solution was obtained. Then add the following compound to this solution 25 parts by weight and 0.06 parts by weight of hydroquinone were added, and the mixture was reacted at 80 ° C. for 5 hours while blowing in air to obtain a solution of an unsaturated resin (acid value: 60, number of unsaturated groups: 1.1 / molecular weight: 1,000, number average molecular weight: 10,000).

Synthesis example 5 of unsaturated resin 25 parts by weight of styrene, 23 parts by weight of butyl acrylate, A mixture of 52 parts by weight and 3 parts by weight of t-butylperoxy-2-ethylhexanoate was kept in a reaction vessel kept at 110 ° C. under a nitrogen gas atmosphere.
The mixture was added dropwise to 70 parts by weight of methyl isobutyl ketone over 3 hours. After the dropwise addition, the mixture was aged for 1 hour, and a mixed solution consisting of 1 part by weight of t-butylperoxy-2-ethylhexanoate and 10 parts by weight of methyl isobutyl ketone was added dropwise for 1 hour. A cyclic epoxy group-containing acrylic resin solution was obtained. Then add acrylic acid 16 to this solution
The mixture was reacted at 80 ° C. for 7 hours while blowing air thereinto to obtain a solution of an unsaturated resin (having an unsaturated group number of 1.85 / molecular weight of 1,000 and a number average molecular weight of about 18,000).

Synthesis example 6 of unsaturated resin 40 parts by weight of butyl methacrylate, butyl acrylate
24 parts by weight, A mixture of 36 parts by weight and 2 parts by weight of t-butyl peroxy-2-ethylhexanoate was treated with isobutyl acetate 90 in a reaction vessel maintained at 110 ° C. under a nitrogen gas atmosphere.
The solution was added dropwise over 3 hours to parts by weight. After the dropwise addition, the mixture was aged for 1 hour, and a mixed solution consisting of 1 part by weight of t-butylperoxy 2-ethylhexanoate and 10 parts by weight of isobutyl acetate was added.
It was added dropwise over a period of time and aged for 7 hours to obtain an alicyclic epoxy group-containing acrylic resin solution.

Next, 14 parts by weight of acrylic acid and hydroquinone were added to this solution.
Add 0.12 parts by weight and react at 80 ° C for 5 hours while blowing air into the unsaturated resin (1.66 units of unsaturated group / 1000 molecular weight,
(Number average molecular weight 25,000) solution was obtained.

Synthesis Example 1 of Comparative Resin 30 parts by weight of styrene, 40 parts by weight of butyl acrylate, 30 parts by weight of acrylic acid and azobisisobutyronitrile 3
From a weight part, the mixed solution was dropped in 50 parts by weight of n-butanol and 40 parts by weight of methyl isobutyl ketone in a reaction vessel kept at 120 ° C. under a nitrogen gas atmosphere over 3 hours.
After the dropwise addition, the mixture was aged for 1 hour, and a mixed solution comprising 1 part by weight of azobisdimethyl valeronitrile and 10 parts by weight of cellosolve was added to 1 part.
It was added dropwise over a period of time and aged for 5 hours to obtain a high acid value acrylic resin (acid value 222) solution. Next, 56 parts by weight of glycidyl methacrylate, 0.13 parts by weight of hydroquinone, and 0.6 parts by weight of tetraethylammonium bromide are added, and the mixture is reacted at 120 ° C. for 8 hours while blowing air into the unsaturated resin (acid value 5, acid number 5, unsaturated group number 2.5 / molecular weight 1000, A number average molecular weight of about 15,000) was obtained.

Example 1 10 parts by weight of α-hydroxyisobutylphenone was added to 300 parts by weight of the solution of Synthesis Example 1 of an unsaturated resin, and the solution was coated on an aluminum plate with a bar coater.
After drying for 5 minutes, the film was cured by UV irradiation for 5 seconds with a 120 W / cm high pressure mercury lamp. This coating thickness was about 20 μm. Also,
The adhesion and water resistance of this coating film were examined.

Example 2 To 300 parts by weight of the solution of Synthesis Example 1 of an unsaturated resin, 100 parts by weight of a vinyl monomer ARONIX M5700 (manufactured by Toa Gosei Co., Ltd .; the same applies hereinafter) and 20 parts by weight of tripropylene glycol diacrylate were added. After heating to 100 ° C., the pressure was reduced while blowing in air to remove n-butanol and methyl isobutyl ketone in the solution. Further, 16 parts by weight of α-hydroxyisobutylphenone was added. This composition was coated on an aluminum plate with a bar coater, and 120 W / c
Irradiated with a high pressure mercury lamp for 5 seconds to cure. This coating thickness was 20 μm. The adhesion and water resistance of this coating film were examined.

Example 3 106 parts by weight of 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 the unsaturated resin, and the solvent was removed in the same manner as in Example 2. 17 parts by weight of α-hydroxyisobutylphenone were 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 Synthetic Example 5 of an unsaturated resin, this solution was coated on an aluminum plate with a bar coater and dried at 80 ° C. for 15 minutes. UV irradiation for 2 seconds with a 120 W / cm high pressure mercury lamp to cure. This coating thickness was about 20 μm. The adhesion and water resistance of this coating film were examined.

Example 5 To 220 parts by weight of the solution of Synthesis Example 5 of an unsaturated resin, 60 parts by weight of a vinyl monomer Aronix M5700 and 12 parts by weight of tripropylene glycol diacrylate were added and heated to 100 ° C., and the pressure was reduced while blowing air. , N-butanol and methyl isobutyl ketone in the solution were removed. Further, 10 parts by weight of α-hydroxyisobutylphenone was added. This composition was coated on an aluminum plate with a bar coater and irradiated with a 12 W / cm high-pressure mercury lamp for 2 seconds to cure. This coating thickness was 20 μm. The adhesion and water resistance of this coating film were examined.

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

Comparative Example 2 Aronix M was added to 260 parts by weight of the solution of Comparative Resin Synthesis Example 1.
80 parts by weight of 5700 and 16 parts by weight of tripropylene glycol diacrylate were added, and the solvent was removed in the same manner as in Example 2. Then, 13 parts by weight of α-hydroxyisobutylphenone was added. Further, it was cured in the same manner as in Example 2.

Table 1 summarizes the results of the coating film tests of Examples 1 to 5 and Comparative Examples 1 and 2.

1) Adhesion: According to the test method of JIS D-0202, cut 100 test pieces at intervals of 1mm into test pieces and peel off with cellophane adhesive tape. And the original number of cells (10
0) was expressed as the denominator.

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

Example 6 To 264 parts by weight of the solution of Synthesis Example 3 of an unsaturated resin, 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. ° C, and then the pressure was reduced while blowing air into the solution,
The butanol solvent was removed. Further, 62 parts by weight of titanium white was added and dispersed by a ball mill to prepare a white paint.
This paint was applied on a gypsum board having a thickness of 1.5 cm using a curtain coater, and then irradiated with an electron beam of 7 Mrad to cure the coating film to form a gypsum tile. The coating thickness is about 100 μm. Adhesion to gypsum was good, and the appearance and adhesion were evaluated for 3 months after sticking to the wall.

Example 7 198 parts by weight of the solution of Synthesis Example 4 of an unsaturated resin, 20 parts by weight of a phenol novolak epoxy resin (epoxy equivalent: 173), 5 parts by weight of α-hydroxyisobutylphenone, and 0.5 part by weight of phthalocyanine green were kneaded with three rolls. . This composition was used as a solder resist ink for printed wiring boards. Next, the ink is applied on a copper through-hole printed wiring board by a screen printing method, and is heated at 70 ° C.
After drying for 10 minutes (film thickness 15-20μ), adhere the film on which the required pattern is drawn to 800mJ with a 3KW ultra-high pressure mercury lamp.
/ cm ² . Further, the unexposed portion was removed with a 1% sodium carbonate solution, and then heated at 140 ° C. for 30 minutes to obtain a solder resist film. This resist film is
Excellent heat resistance such as solder plating resistance and chemical resistance to acids and alkalis.

Example 8 To 217 parts by weight of the solution of Synthesis Example 6 of the unsaturated resin, 40 parts by weight of tripropylene glycol diacrylate, 40 parts by weight of 1,6-hexanediol diacrylate, and 30 parts by weight of trimethylolpropane triacrylate were added, and 100 ° C. Then, the pressure was reduced while blowing in air to remove isobutyl acetate in the solution. 55 parts by weight of titanium white was added and dispersed by a ball mill to prepare a white paint. This paint was used in Example 4
A white gypsum tile was prepared by irradiating with an electron beam in the same manner as described above.
The gypsum was adhered to a wall and evaluated for appearance and adhesion for 3 months.

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Claims (2)

(57) [Claims] 1. An ester bond formed by a ring-opening addition reaction between an acid group-containing acrylic resin obtained by polymerizing an ethylenically unsaturated acid as an essential component and an epoxy group and a carboxyl group. An active energy ray-curable unsaturated resin composition obtained by mixing an organic solvent and / or a polymerizable vinyl monomer with a reaction product with an alicyclic epoxy group-containing unsaturated compound. 2. An oil obtained by polymerizing an alicyclic epoxy group-containing unsaturated compound containing no ester bond formed by a ring-opening addition reaction between an epoxy group and a carboxyl group as an essential monomer component. An active energy ray-curable unsaturated resin composition obtained by mixing an organic solvent and / or a polymerizable vinyl monomer with a reaction product of a cyclic epoxy group-containing resin and an acid group-containing unsaturated compound.