JPH1069081A - Composition for alkali-soluble resist - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure superior water resistance and durability by adding an org. solvent and/or a polymerizable vinyl monomer as a diluent to a reactional product of acid group-contg. acrylic resin with an alicyclic epoxy group-contg. unsatd. compd. SOLUTION: A reactional product of acid group-contg. acrylic resin with an alicyclic epoxy group-contg. unsatd, compd. or a reactional product of an alicyclic epoxy group-contg. unsatd. resin with an acid group-contg. umsatd. compd. is diluted with an org. solvent and/or a polymerizable vinyl monomer and the resultant org. liq. is used. Alicyclic epoxy groups originating in the alicyclic epoxy group-contg. unsatd. compd. and acid groups originating in the acid group-contg. acrylic resin or alicyclic epoxy group originating in the alicyclic epoxy group-contg. unsatd. resin and acid groups originating in the acid group-contg. unsatd. compd. readily take part in addition reaction because of high reactivity of the epoxy groups to ring opening polymn. reaction and unsatd. groups curable with active energy beams can be introduced into the resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to the use of an active energy ray-curable unsaturated resin composition in an alkali-soluble resist composition.

[0002]

2. Description of the Related Art Conventionally, various active energy ray-curable unsaturated resin compositions have been developed.
These are widely used in the fields of coatings, composite materials, electronic components, etc. Recently, as one of those active energy ray-curable unsaturated resin compositions, the development of resin compositions mainly composed of vinyl resin has been developed. Attempted. 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.

[0003]

Means for Solving the Problems According to the present invention, as a result of diligent research for solving the above-mentioned problems, an active energy ray-curable unsaturated resin composition is obtained by using 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.

That is, the present invention provides a composition comprising an organic solvent and / or a diluent of a polymerizable vinyl monomer mixed with a reaction product of an acid group-containing acrylic resin and an alicyclic epoxy group-containing unsaturated compound. The present invention relates to an active energy ray-curable unsaturated resin composition obtained by mixing an organic solvent and / or a diluent of a polymerizable vinyl monomer with a reaction product of an alicyclic 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 includes ethylene such as (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, and (anhydrous) maleic acid. And an unsaturated ester of (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth). ) Acrylate, stearyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, etc.]; vinyl aromatic compounds [for example, styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene, etc.]; amides Unsaturated compounds [for example ( Data) acrylamide, diacetone acrylamide, N- methylol acrylamide, N
-Butoxymethylacrylamide and the like]; polyolefin-based compounds [for example, butadiene, isoprene, chloroprene and the like] and others [for example, (meth) acrylonitrile, methyl isopropenyl ketone, vinyl acetate, beoba monomer (shell chemical product), vinyl propionate,
Vinyl pivalate, etc.] and generally known copolymers obtained by copolymerizing one or more monomers selected from the group consisting of vinyl pivalate and the like.

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

The unsaturated compound containing an alicyclic epoxy group 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

[0008]

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[0009]

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[0010]

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[In each formula, R ₁ represents a hydrogen atom or a methyl group. R ₂ represents a divalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms. R ₃ represents a divalent hydrocarbon group having 1 to 10 carbon atoms. l shows the integer of 0-10. ] Etc. can be mentioned.

In the above, as the divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms represented by R ₂ , a linear or branched alkylene group such as methylene, ethylene,
Examples include propylene, 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,

[0013]

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And the like.

In addition to the above-mentioned unsaturated compounds having an alicyclic epoxy group, unsaturated compounds having an aliphatic epoxy group such as glycidyl (meth) acrylate, glycidyl β-methyl (meth) acrylate and allyl glycidyl ether may be used. 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 alicyclic 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 at about 20 to 120 ° C.
The reaction can be carried out under a reaction condition of about 1 to 5 hours.

The resin containing an unsaturated group thus obtained has a number of unsaturated groups of from 0.2 to 4.0 per 1,000 molecular weight,
Preferably, it can have from 0.7 to 3.5. If the number of unsaturated groups is less than 0.2, the curability of the film becomes insufficient, and the adhesion to the object to be coated and the water resistance are poor. On the other hand, if the number of unsaturated groups is more than 4.0, acid During the addition reaction with the group-containing acrylic resin, the composition may thicken or gel during the addition reaction, and when the composition is stored for a long period of time, the composition may thicken or gel, which is not preferable.

The resin has a number average molecular weight of 1,000.
0-100,000, preferably 3,000-70,00
It can have in the range of 0. If the molecular weight is less than 1,000, the water resistance of the coating is poor, while the molecular weight is less than 10
If it is larger than 000, the viscosity becomes high, handling becomes inconvenient, and the film-thickness deteriorates, resulting in a film having poor adhesion to a water-resistant coated object, which is not preferable.

Further, the resin preferably has a resin acid value of 3
It can have in the range of 00 or less. If the acid value is larger than 300, the water resistance of the coating film is inferior.

In the composition of the present invention, an alicyclic epoxy group-containing vinyl resin and an acid group-containing unsaturated resin are used in place of the reaction product of the acid group-containing acrylic resin and the alicyclic epoxy group-containing unsaturated compound. Reaction products with saturated compounds can also be used.

As the alicyclic epoxy group-containing unsaturated resin, an alicyclic epoxy group-containing unsaturated monomer represented by any of the above general formulas (I) to (XV) is used as an essential monomer component. One or more monomers selected from the same monomers as used in the acid group-containing acrylic resin [eg, (meth) acrylic acid esters, vinyl aromatic compounds and other monomers] And a copolymer obtained by a copolymerization reaction of

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 unsaturated resin to form a resin. An unsaturated group is introduced therein. Specifically, for example, ethylenically unsaturated acids such as (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, and (anhydride) maleic acid are preferably exemplified.

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

The resin having an unsaturated group thus obtained has a number of unsaturated groups of 0.1 to 1,000 per 1,000 in the same manner as described above.
2 to 4.0, preferably 0.7 to 3.5 and a number average molecular weight of 1,000 to 100,000, preferably 3,
It can have in the range of 000-70,000.

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

Specific examples of the polymerizable vinyl monomer include, for example, monovalent vinyl monomers [eg, esters of (meth) acrylic acid, vinyl aromatic compounds, and amide unsaturated monomers used in the high acid value acrylic resin. Monomers such as compounds, polyolefin compounds and other monomers;
Adducts of hydroxyl group-containing monomers with monoisocyanates (eg, butyl isocyanate, phenyl isocyanate, etc.); aziridine group-containing monomers, phosphorus-containing vinyl monomers, and the like. ] 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) Reactants with acrylic esters (eg,
Diethylene glycol diacrylate, propylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, etc.), a reaction product of a caprolactone-modified polyhydric alcohol and a (meth) acrylate, a phosphorus-containing divinyl monomer, and the like. ].

Specific examples of the polymerizable prepolymer include, for example, a polymerizable unsaturated group-containing resin which can be converted to an aqueous solution [eg, a hydroxyalkyl (meth) acrylate is introduced into a carboxyl group-containing polyol via a polyisocyanate compound]. Resin and the like] 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) Resins in which hydroxyalkyl (meth) acrylate is introduced into an adduct with acrylic acid 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.

The composition of the present invention may further 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 particularly useful for paints, printing inks, photoresists, solder resists, printing materials, adhesives, pressure-sensitive adhesives and the like.

The method for forming a coating film using the composition of the present invention can be performed, for example, on a substrate such as wood, paper, inorganic material, plastic, metal (zinc, iron, copper, aluminum, etc.) by using a natural roll coater, a reverse roll coater or the like. Coating is performed using a coating machine such as a roll coater, a gravure roll coater, a screen printing machine, a curtain coater, an air spray, an airless spray, a bar coater, a knife coater, a spin coater, a brush, and a dip coating machine. The coating film can be cured by irradiating with a ray or an active energy ray of ultraviolet rays. The coating film thickness is 2,000 μm or less, preferably 1 to 1000 μm, as a dry film thickness. When the film thickness is more than 2000 μm, the curability inside the film is inferior.

Examples of electron beam accelerators for emitting active energy rays include Cockcroft type, Cockcroft-Walton type, Van de Graaf type, resonance transformer type,
Examples include a transformer type, 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 amount of the electron beam is not particularly limited as long as it gives a dose necessary for curing the coating film, but is generally about 100 to 2000 Ke.
Irradiate with V a dose of 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 ultraviolet rays for emitting 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 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. Irradiation conditions vary depending on the absorption amount of the photopolymerization initiator, but irradiation is performed within a few minutes using a light beam having a wavelength of 3000 to 4500 °, usually in a range of 1 second to 20 minutes.

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 and benzoin ethyl ether. ,
Benzoin n-propyl ether, benzoin n-butyl ether, benzophenone, P-methylbenzophenone, Michler's ketone, acetophenone, 2-chlorothioxanthone, anthraquinone, chloroanthraquinone,
2-methylanthraquinone, phenyl disulfide 2-
Nitrofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide and the like can be mentioned. These photopolymerization initiators can be used alone or in combination of two or more. The photopolymerization initiator is preferably compounded in an amount 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.

[0034]

The composition of the present invention is particularly useful in an addition reaction between an alicyclic epoxy group derived from an unsaturated compound of an alicyclic epoxy group and an acid group derived from an acrylic resin, and an unsaturated reaction containing an alicyclic epoxy group. The addition reaction between the alicyclic epoxy group derived from the resin 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,
An active energy ray-curable unsaturated group can be introduced into the resin. 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 and the like, and has a remarkable effect with excellent durability such as water resistance.

[0035]

EXAMPLES The present invention will be described more specifically with reference to the following examples.

Synthesis Example 1 of Unsaturated Resin 30 parts by weight of styrene, 35 parts by weight of butyl acrylate,
A mixture of 35 parts by weight of acrylic acid and 3 parts by weight of azobisisobutyronitrile was charged to 50 parts by weight of n-butanol and 40 parts by weight of methyl isobutyl ketone in a reaction vessel kept at 110 ° C. under a nitrogen gas atmosphere for 3 hours. It dripped over. After dropping, the mixture was aged for 1 hour, and 1 part by weight of azobisdimethylvaleronitrile and 1 part of methyl isobutyl ketone were added.
A mixture of 0 parts by weight was added dropwise over 1 hour, and the mixture was aged for 5 hours to obtain a high acid value acrylic resin (acid value 260) solution. Then add the following compound to this solution

[0037]

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98 parts by weight and 0.14 parts by weight of hydroquinone monomethyl ether were added and reacted at 80 ° C. for 5 hours while blowing air into the unsaturated resin (acid value: about 20, number of unsaturated groups: 1.98 units / molecular weight: 1,000, number: An average molecular weight of about 17,000) 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

[0040]

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The mixture was reacted at 80 ° C. for 5 hours while blowing air into the unsaturated resin (acid number 1, unsaturated group number 2.25).
(Number / molecular weight: 1,000, number average molecular weight: about 18,000) solution was obtained.

Synthesis Example 3 of Unsaturated Resin A mixture of 40 parts by weight of butyl methacrylate, 35 parts by weight of butyl acrylate, 25 parts by weight of acrylic acid and 1 part by weight of azobisisobutyronitrile was heated to 110 ° C. in a nitrogen gas atmosphere. It was dropped into 90 parts by weight of n-butanol in the held reaction vessel over 3 hours. After dripping, 1
After aging for 1 hour, 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, and the mixture was aged for 5 hours to obtain a high acid value acrylic resin (acid value: 184) solution. Obtained. Then add the following compound to this solution

[0043]

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62 parts by weight and hydroquinone 0.12
The mixture was reacted at 80 ° C. for 5 hours while blowing air into the unsaturated resin (acid value: 0, unsaturated group number: 2.07 /
A solution having a molecular weight of 1,000 and a number average molecular weight of about 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 Was added dropwise over 3 hours to 60 parts by weight of butyl cellosolve in a reaction vessel maintained at 105 ° C. under a nitrogen gas atmosphere. After the dropping, the mixture is aged for 1 hour, a mixed solution comprising 1 part by weight of azobisdimethyl valeronitrile and 7 parts by weight of butyl cellosolve is added dropwise for 1 hour, and further aged for 5 hours to obtain a high acid value acrylic resin (acid value 150). ) A solution was obtained. Then add the following compound to this solution

[0046]

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25 parts by weight and hydroquinone 0.06
The reaction was carried out at 80 ° C. for 5 hours while blowing air into the unsaturated resin (acid value: 60, number of unsaturated groups: 1.1 /
A solution having a molecular weight of 1,000 and a number average molecular weight of 10,000) was obtained.

Synthesis Example 5 of Unsaturated Resin 25 parts by weight of styrene, 23 parts by weight of butyl acrylate,

[0049]

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52 parts by weight and t-butylperoxy 2
20 parts by weight of n-butanol and 7 parts of methyl isobutyl ketone in a reaction vessel maintained at 110 ° C. in a nitrogen gas atmosphere containing a mixture of 3 parts by weight of ethyl ethyl enoate
It was added dropwise to 0 parts by weight over 3 hours. After dropping, 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, and the mixture was further aged for 7 hours to obtain a fat. A cyclic epoxy group-containing acrylic resin solution was obtained. Next, 16 parts by weight of acrylic acid and 0.12 parts by weight of hydroquinone were added to the solution, and air was blown into the solution at 80.degree.
The mixture was reacted for an hour 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, 24 parts by weight of butyl acrylate,

[0052]

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36 parts by weight and t-butylperoxy 2
A mixed solution consisting of 2 parts by weight of -ethylhexanoate was dropped into 90 parts by weight of isobutyl acetate in a reaction vessel kept at 110 ° C over 3 hours under a nitrogen gas atmosphere. 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 dropwise over 1 hour, and aged for 7 hours to obtain an alicyclic ring. An acrylic resin solution having the formula epoxy group was obtained.

Next, 14 parts by weight of acrylic acid and 0.12 parts by weight of hydroquinone were added to this solution and reacted at 80 ° C. for 5 hours while blowing air into the unsaturated resin (1.66 units of unsaturated group / molecular weight of 1,000, Average molecular weight 25,000
0) A solution was obtained.

Synthesis Example 1 of Comparative Resin 30 parts by weight of styrene, 40 parts by weight of butyl acrylate,
A mixture was prepared from 30 parts by weight of acrylic acid and 3 parts by weight of azobisisobutyronitrile under nitrogen atmosphere.
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 0 ° C. After the dropping, the mixture is aged for 1 hour, a mixed solution composed of 1 part by weight of azobisdimethyl valeronitrile and 10 parts by weight of cellosolve is added dropwise for 1 hour, and the mixture is further aged for 5 hours to obtain a high acid value acrylic resin (acid value 222). A solution was obtained. Next, 56 parts by weight of glycidyl methacrylate, 0.13 parts by weight of hydroquinone and 0.6 parts by weight of tetraethylammonium bromide were added, and the mixture was blown at 120 ° C. while blowing air.
After reacting for 8 hours, the unsaturated resin (acid number 5, unsaturated group number 2.
5 / molecular weight 1000, number average molecular weight about 15,000)
A solution was obtained.

EXAMPLE 1 10 parts by weight of .alpha.-hydroxyisobutylphenone were added to 300 parts by weight of the solution of Synthesis Example 1 of the unsaturated resin, and the solution was coated on an aluminum plate with a bar coater.
After drying for 15 minutes, UV irradiation was performed with a 120 W / cm high-pressure mercury lamp for 5 seconds to cure. This coating thickness is about 20μm
Met. Further, the adhesion and water resistance of this coating film were examined.

Example 2 100 parts by weight of a vinyl monomer ARONIX M5700 (trade name, manufactured by Toa Gosei Co., Ltd., the same applies hereinafter), and 20 parts by weight of tripropylene glycol diacrylate were added to 300 parts by weight of the solution of Synthesis Example 1 of an unsaturated resin. After heating to 100 ° C. and adding air, 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 irradiated with a 120 W / cm high-pressure mercury lamp for 5 seconds.
Cured. This coating thickness was 20 μm. The adhesion and water resistance of this coating film were examined.

Example 3 To 312 parts by weight of the solution of Synthesis Example 2 of an unsaturated resin, 106 parts by weight of vinyl monomer Aronix M5700 and 22 parts by weight of tripropylene glycol diacrylate were added, and the solvent was added in the same manner as in Example 2. After removal, 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 the unsaturated resin, this solution was coated on an aluminum plate with a bar coater,
After drying for 5 minutes, UV irradiation was performed 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.

[0060] 60 parts by weight of vinyl monomer, Aronix M5700 solution 220 parts by weight Synthesis Example 5 Example 5 unsaturated resin, by adding 12 parts by weight of tripropylene glycol diacrylate 100
After heating to ° C., the pressure was reduced while blowing in air to remove n-butanol and methyl isobutyl ketone in the solution. 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 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 Synthetic Example 1 of Comparative Resin, and the solvent was removed in the same manner as in Example 2. Hydroxyisobutylphenone 13
Parts by weight were 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.

[0064]

[Table 1]

1) Adhesion: According to the test method of JIS D-0202, 100 test pieces were cut into a test piece at intervals of 1 mm, and then peeled with a cellophane adhesive tape to obtain a square having no peeling. The number was used as a numerator, and the number of original cells (100) was used as a denominator.

2) Adhesion after water immersion The coated plate was immersed in warm water at 50 ° C. for one day, water was removed from the surface, and left at room temperature for one hour.

[0067]Example 6 To 264 parts by weight of the solution of Synthesis Example 3 of the unsaturated resin,
50 parts by weight of lenglycol diacrylate, 1,6 hex
50 parts by weight of sundiol diacrylate, trimethylo
Add 50 parts by weight of lupropane triacrylate and add 10 parts by weight.
After heating to 0 ° C, the pressure was reduced while blowing air into the solution.
The n-butanol solvent in was removed. In addition, titanium white
Add 62 parts by weight, disperse with a ball mill and apply white paint.
Produced. Thick this paint using a curtain coater
After painting on 1.5cm gypsum board, 7M
Girder tiles are irradiated with electron beams to cure the coating film and gypsum tile.
made. The coating thickness is about 100 μm. With gypsum
Adhesion is good.
As a result of evaluating the adhesion, it was good as in the initial stage. Example 7 198 parts by weight of the solution of Synthesis Example 4 of an unsaturated resin, phenol
Novolak epoxy resin (epoxy equivalent 173) 20 weight
Parts, α-hydroxyisobutylphenone 5 parts by weight,
Kneading 0.5 parts by weight of tarocyanine green with three rolls
did. This composition is used as a solder resist for printed wiring boards.
Used as ink. Next, apply the ink to a copper
On a printed circuit board by screen printing
After drying at 15 ° C for 10 minutes (film thickness 15-20μ),
3KW ultra-high pressure with the film on which the pattern is drawn
800mJ / cm with mercury lamp^TwoWas irradiated. Further
After removing the unexposed area with a 1% sodium carbonate solution,
Solder resist by heating at 40 ° C for 30 minutes
A membrane was obtained. This resist film is resistant to solder plating, etc.
Excellent heat resistance, 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. Ten
After heating to 0 ° C., 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 irradiated with an electron beam in the same manner as in Example 4 to produce a white gypsum tile. The gypsum was adhered to a wall and evaluated for appearance and adhesion for 3 months.

Claims (2)

[Claims] 1. A reaction product of an acid group-containing acrylic resin and an alicyclic epoxy group-containing unsaturated compound, an organic solvent and / or a polymerizable vinyl monomer, a photopolymerization initiator, and if necessary, a dye. An alkali-soluble resist composition comprising: 2. A reaction product of an alicyclic epoxy group-containing unsaturated resin and an acid group-containing unsaturated compound contains an organic solvent and / or a polymerizable vinyl monomer, a photopolymerization initiator, and if necessary, a dye. An alkali-soluble resist composition comprising: