JPS6017204B2 - Method for producing active energy beam-curable resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an active energy ray-curable resin composition, and more particularly, the present invention is comprised of a vinyl polymer curable by active energy rays and a solvent, and which contains substantially 100% of the composition. % can be a film-forming component.

BACKGROUND ART In recent years, technologies related to curing processes using active energy rays such as electron beams, Y-rays, and ultraviolet rays have attracted much attention in the coating field, and research and development thereof has been actively conducted. The paint used in the above-mentioned curing process is, for example, a varnish-type active energy ray-curable resin composition, which is blended with pigments, fillers, and other additives. has a carbon-carbon double bond (i.e., Q8-ethylenically unsaturated group) in part of its molecular structure, and when irradiated with active energy rays, a radical crosslinking reaction occurs, forming a hardened coating film with strong ruts. do. The advantage of such paints is that, unlike thermosetting paints, they do not require heating and form a hardened coating in a short time; It is strongly desired that all components be converted into a coating film by active energy rays without containing any compounds. However, under such circumstances, many of the above active energy ray-curable resin compositions, especially addition (co-)
Polymerized resin varnishes use non-curing compounds such as xylol and butyl acetate as polymerization solvents during their manufacture, so in order to turn them into paints and apply them to the curing process, the resulting varnish must be After making it into a paint as it is and applying it to the object to be coated, the solvent in the undried paint film is removed by setting or heating means, and then active energy rays are irradiated, or the resulting varnish is first heated under reduced pressure. The current method is to use vinyl monomer as a diluting solvent to remove the solvent, then form a paint, apply it as described above, and immediately irradiate it with active energy rays.

However, although it is thought that such a method can form a cured coating film that does not contain solvents that have an adverse effect on coating performance, in reality it is not fully satisfactory, or there are process-related and other problems. Problems may occur. For example, in method (2), the introduction of a setting process or a heating process can have negative effects (it is originally advantageous in terms of the process to irradiate active energy rays immediately after coating the object to be coated). In this case, a considerable amount of time is required, and in the case of heating, high-temperature conditions are required, and as a result, the advantages of the curing process, such as short curing time and no need for heating, are lost. Furthermore, in method (2), it is very difficult to remove the solvent from the varnish.

That is, as the solvent is removed, the viscosity of the varnish increases rapidly, which not only makes operations such as Nada Azusa difficult, but also causes local heating, which causes the Q,8-ethylene unsaturated groups in the resin to become radicals due to the heat. It is often seen that a crosslinking reaction occurs, resulting in unwanted gelation, and it is impossible to completely remove the solvent in the varnish. Therefore, in order to compensate for the drawbacks of the above-mentioned varnish-type active energy ray-curable resin composition, the present inventors used a polyol having two or more hydroxyl groups in the molecule as a polymerization solvent. A polymer solution is prepared, and then one carboxylic acid anhydride group (CO
)20) A resin obtained by adding a saturated or Q,B-ethylenically unsaturated compound having 20) and then adding a saturated or Q,P-ethylenically unsaturated compound having one epoxy group in the molecule. He devised an ionizing radiation-curable resin composition containing the following (see Mochiko Sho 49-47254).

However, it is necessary to add a small amount of solvent (hydrocarbon type or ester type) to dissolve the polymerization initiator, to improve compatibility with the resulting polymer, to adjust the viscosity, etc. However, it has not yet been possible to make 100% of the coating-forming component. The object of the present invention is to fully reflect the advantages of the curing process, to avoid problems such as gelation during manufacturing, and to reduce substantially ZloO% of the composition.
An object of the present invention is to provide a method for producing a varnish-type active energy ray-curable resin composition which can be used as a film-forming component. As a result of intensive research to achieve this objective, the present inventors have found that, without removing the polymerization solvent, which is essential for the production of varnish, from the system, the solvent can also be radicalized by irradiation with active energy rays. If a Q8-ethyleneically unsaturated group that causes a crosslinking reaction is added, it will efficiently become the above-mentioned film-forming component, and the addition of such an unsaturated group will make the compound having the unsaturated group a functional compound that can react with each other. Focusing on the fact that this can be achieved by reacting through groups,
First, a resin varnish consisting of a mixed system of a vinyl polymer having a reactive functional group and a non-polymerizable compound having a reactive functional group as a polymerization solvent is produced, and then the polymer components and polymerization solvent in the varnish are mixed. It has been found that the desired photocurable resin composition can be obtained by imparting the above-mentioned unsaturated groups to both components.

The present invention was completed based on the above findings, and its gist is that a mixed system of a vinyl polymer having a reactive functional group and a non-polymerizable compound having a reactive functional group as a solvent thereof, reacting a Q,8-ethylenically unsaturated compound having a functional group capable of reacting with a reactive functional group in the system;
A method for producing an active energy ray-curable resin composition, characterized in that the active energy ray-curable resin composition is obtained by introducing a Q,8-ethylene unsaturated group into the above-mentioned pinyl polymer and non-polymerizable compound. .

Here, the term "reactive functional group" does not cause radical polymerization per se, but can easily cause a reaction, and specifically refers to a hydroxyl group, a carboxyl group, a glycidyl group, etc. In the present invention, the mixed system of the above-mentioned vinyl polymer having a reactive functional group and a non-polymerizable compound having a reactive functional group as a solvent can be prepared as follows. It is obtained by solution polymerizing a vinyl monomer having the following in the presence of a non-polymerizable compound having a reactive functional group as a polymerization solvent and, if necessary, reacting it with a specific compound,
Furthermore, those in which the initially reactive functional group in the mixed system is modified into another reactive functional group are also included, if necessary.

Therefore, the "non-polymerizable compound" of the mixed system also includes a compound into which a Q,8-ethylenically unsaturated group is introduced by employing an unsaturated compound during the above reaction or modification. do. Hereinafter, specific methods for producing such a mixed system will be listed. '1-A vinyl monomer having a reactive functional group alone or a combination thereof with another vinyl monomer is used as a polymerization solvent for a non-polymerized polymer having one reactive functional group different from the above-mentioned reactive functional group. solution polymerization in the presence of a reactive functional compound or a mixture of this and a non-polymerizable compound having one functional group identical to the reactive functional group of the above vinyl monomer, and then to the resulting polymerized system, has a functional group that can react with either of the different (two types) of reactive functional groups present in A method of reacting selected saturated and/or unsaturated compounds.

As the above-mentioned vinyl monomer having a reactive functional group, ordinary ones may be adopted, and when specifically classified according to the type of the functional group, the following ones (■) to (■) can be mentioned. One type selected from the group or a mixture of two or more types selected from those having the same functional group may be used.

@When the reactive functional group is a hydroxyl group: (methacrylic acid (herein, (meth)acrylic means acrylic or methacryl; the same applies hereinafter)) hydroxyalkyl esters ((meth)acrylic acid 2-hydroxyl group) chill, 2-hydroxypropyl (meth)acrylate, etc.),
Halogenated derivatives of the above esters (3-chloro-2-hydroxypropyl acrylate, etc.), methylolated derivatives of (meth)acrylamide (N-methylol(meth)acrylamide, etc.), unsaturated alcohols (allyl alcohol ), saturated monoglycidyl compounds (tertiary glycidyl nonanoate, etc.) and Q,B-ethylene unsaturated carboxylic acids ((meth)acrylic acid, maleic acid, itaconic acid, monoalkyl maleate, mono itaconic acid), reaction products between Q,6-ethylenically unsaturated monoglycidyl compounds (glycidyl (meth)acrylate, etc.) and saturated carboxylic acids (formic acid, acetic acid, etc.), etc.

■When the reactive functional group is a carpoxyl group: Q,B-ethylenically unsaturated carboxylic acids, (meth)acrylic acid hydroxyalkyl esters and dicarboxylic acid anhydrides (hexahydrophthalic anhydride, succinic anhydride, etc.) is the reaction product of polycarboxylic acid anhydride (such as trimellitic anhydride), Q,8-ethylenically unsaturated dicarboxylic acid anhydride (such as itaconic anhydride, maleic anhydride) and saturated monohydroxy compounds (butanol, propanol, etc.) ) reaction products, etc.

@When the reactive functional group is a glycidyl group: Glycidyl esters of Q,8-ethylenically unsaturated carboxylic acids (glycidyl (meth)acrylate, etc.), glycidyl ethers of the above-mentioned hydroxyl group-containing vinyl monomers (allyl glycidyl ether, metaallyl glycidyl ether, glycidyl ether of 2-hydroxyethyl (meth)acrylate, etc.), etc.

Examples of the above other pinyl monomers used in combination as necessary include (meth)acrylic acid alkyl esters (methyl (meth)acrylate, ethyl (meth)acrylate, (
(butyl meth)acrylate, uryl (meth)acrylate, etc.), hydrocarbon-based pinyl monomers (styrene, vinyltoluene, etc.), and vinyl monomers that do not have reactive functional groups, and those that pose a problem during copolymerization. Examples include pinyl monomers having a functional group such as an amino group within a limited range, and one or a mixture of two or more of these may be used.

The non-polymerizable compound having one reactive functional group used as the polymerization solvent generally has an average molecular weight of 3.
00 or less or those that are liquid at room temperature are suitable, and specifically categorized by the type of functional group, the following (■ ~
■).

Note that if a polymer with a molecular weight exceeding 300 is used, the solution viscosity at the end of the polymerization reaction will be very high.
Not only would subsequent operations be difficult, but a considerable amount of volatile solvent or vinyl monomer for dilution must be added in order to keep the viscosity at an appropriate level, including when forming a coating, which sufficiently achieved the intended purpose of the present invention. It also means that it will not be done. ■When the reactive functional group is a hydroxyl group: Alkyl alcohols (methanol,
Ethanol, n-propanol, isopropanol, n
), ketone alcohols (diacetone alcohol, etc.), ether alcohols (ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, etc.), saturated monoglycidyl compounds (butyl glycidyl ether, etc.) , phenyl glycidyl ether, etc.) and saturated monocarboxylic acids (acetic acid, propionic acid, etc.).

■When the reactive functional group is a carpoxyl group: Saturated monocarboxylic acids (acetic acid, propionic acid, butyric acid, saturated fatty acids, etc.), saturated monohydroxy compounds (ethanol, ethylene glycol monobutyl ether, etc.) and Q,8-dicarboxylic anhydride reaction products with substances (hexahydrophthalic anhydride, succinic anhydride, etc.).

■When the reactive functional group is a glycidyl group: Saturated monoglycidyl compounds (epichlorohydrin, butyl glycidyl ether, phenyl glycidyl ether, dibromocresyl glycidyl ether, styrene oxide, epoxy resin (product manufactured by Shell) ``Cardura E''), Q-olefin oxide, orthophenyl vinyl glycidyl ether, etc.).

Select one type of non-polymerizable compound from each of these groups (■ to blood), depending on the intended use of the resin composition, from among those having a functional group different from the reactive functional group of the vinyl monomer used. Alternatively, a mixture of two or more types may be used.

The amount of the polymerization solvent to be used is approximately 10 parts by weight of the vinyl monomers (including the vinyl monomers having the above-mentioned reactive functional groups and other vinyl monomers if necessary). , the same applies hereafter), 20 to 12 foundations, preferably 4
It may be selected within the range of 0 to 80 parts. If the amount used is less than 2 parts, the resulting mixed system will have an extremely high viscosity, making it difficult to manufacture and handle. There is a risk that the takaazusa efficiency during the step of introducing unsaturated groups may decrease and gelation may occur due to local heating, and if the number of anchors exceeds 12,
Although the mixed system with low viscosity can be obtained, on the other hand, the cured film of the desired resin composition becomes brittle and requires a large amount of energy for curing. The above solution polymerization may be carried out according to usual conditions, for example, the above-mentioned vinyl monomer group and a polymerization initiator (azobisisobutyronitrile, 2,2'- azobis-(2,4-dimethylvaleronitrile), etc.), or a mixture of a polymerization solvent and a polymerization initiator is added dropwise to the vinyl monomer group set at the polymerization temperature, and then, if necessary, It can be aged at high temperature or at elevated temperature.

The polymerization temperature may be generally 45 to 130 qo, and the polymerization time may be generally 1 to 6 hours. In this way, a mixed system (polymer solution) of a vinyl polymer and a non-polymerizable compound in which two different types of reactive functional groups are present is obtained.

The number of reactive functional groups possessed by the pinyl polymer in this mixed system varies depending on the number of reactive functional groups of the non-polymerizable compound and the amount used, but generally 0.1 to 6 per 1000 molecular weight, preferably 0.1 to 6 reactive functional groups per 1000 molecular weight. It is desirable that the number is set in a range of 0.5 to 3. The number of such reactive functional groups is 0
．． If it is less than 1, there will be a shortage of Q,P-ethylene unsaturated groups introduced, resulting in poor curability, and if it exceeds 6, the viscosity of the desired resin composition will be high, making it difficult to handle. At the same time, the physical performance of the cured film tends to deteriorate. The saturated or unsaturated compound to be reacted with the polymerization system obtained after the solution polymerization is one whose functional group satisfies the above requirements in combination with the two reactive functional groups in the polymerization system, Specific combinations thereof and reactive functional groups generated and remaining are as follows. The above saturated or unsaturated compounds include:
When the functional group is a carboxylic anhydride group: Q,8-ethylenically unsaturated dicarboxylic anhydride (maleic anhydride, itaconic anhydride, etc.), saturated dicarboxylic anhydride (hexahydrophthalic anhydride, phthalic anhydride, succinic anhydride, etc.) acids, etc.)
, tricarboxylic anhydride (methylcyclohexenetricarboxylic anhydride, trimellitic anhydride, etc.), when the functional group is a glycidyl group: Glycidyl esters of Q,8-ethylenically unsaturated carboxylic acids ((meth)acrylic glycidyl ethers of Q,8-ethylenically unsaturated carboxylic acids (allyl glycidyl ether, metaallyl glycidyl ether, etc.)
, 8-ethylenically unsaturated monoglycidyl compounds, saturated monoglycidyl compounds (epichlorohydrin, butylglycidyl ether, phenylglycidyl ether, styrene oxide, "Cardilla E", Q-olefin oxide, orthophenyl) phenolglycidyl ether, etc.), and when the functional group is a carboxyl group: (meth)acrylic acid, hydroxyl group-containing vinyl monomers (2-hydroxyethyl (meth)acrylate, furyl alcohol, etc.) ) and Q,8-dicarboxylic anhydride (hexahydrophthalic anhydride, succinic anhydride, itaconic anhydride, maleic anhydride, etc.), Q,8-ethylenically unsaturated dicarboxylic anhydride (itaconic anhydride,
maleic anhydride) and saturated monohydroxy compounds (such as maleic anhydride) and saturated monohydroxy compounds (
butanol, propanol, etc.)
, 8-ethylene unsaturated monocarboxy compounds, unsaturated fatty acids (linseed oil fatty acids, tall oil fatty acids, etc.),
Saturated monocarboxylic acids (acetic acid, propionic acid, butyric acid, coconut acid, palm kernel oil, etc.), saturated monohydroxy compounds (ethanol, ethylene glycol monoethyl ether, etc.) and Q,8-dicarboxylic acid. Examples include saturated monocarboxy compounds such as reaction products with anhydrides (hexahydrophthalic anhydride, bran water succinic acid, etc.).

By reacting equimolar numbers of such saturated and/or unsaturated compounds, the mixed system of a vinyl polymer and a non-polymerizable compound in which the same reactive functional group (carboxyl group or hydroxyl group) is present can be obtained.

The mixed system obtained as described above may be directly subjected to the next step of introducing an 8-ethylene unsaturated group, but
If necessary, a saturated and/or unsaturated compound having a glycidyl group or a carboxylic acid anhydride is reacted under normal conditions to modify the reactive functional group in the above mixed system into another reactive functional group (carboxyl group→ hydroxyl group, hydroxyl group → carboxyl group).

Through such modification, the cured film performance and viscosity of the desired resin composition can be adjusted over a wide range. Incidentally, among the above-mentioned saturated or unsaturated compounds, the unsaturated compound may be appropriately selected from among the Q,8-ethylenically unsaturated compounds used in the next step. Specific examples of the above saturated compounds include, for example, when the functionality is carboxylic anhydride: saturated polycarboxylic anhydride (hexahydrophthalic anhydride,
(trimellitic anhydride, etc.), and when the functional group is glycidyl, saturated monoglycidyl compounds (epichlorohydrin, tylglycidyl ether, "Cardilla E", etc.) can be mentioned. {2} A pinyl monomer having a reactive functional group alone or a combination of this and other vinyl monomers is used as a polymerization solvent, and a non-vinyl monomer having one reactive functional group different from the above reactive functional group is used as a polymerization solvent. A method of solution polymerization in the presence of a polymerizable compound or a mixture of this and a non-polymerizable compound having one functional group identical to the reactive functional group of the vinyl monomer.

In the solution polymerization, the types of vinyl monomers and other vinyl monomers having reactive functional groups and non-polymerizable compounds used as polymerization solvents are those listed in '1) above. It is sufficient to appropriately select those whose reactive functional groups do not easily react with each other and combine them as described above.
The amount of polymerization solvent used and the polymerization conditions may also be the same as (1)'.

By such solution polymerization, for example, a mixed system of a vinyl polymer and a non-polymerizable compound in which two types of reactive functional groups, a hydroxyl group and another reactive functional group (specifically, a carboxyl group or a glycidyl group) are present, can be obtained. This is directly subjected to the next step of introducing a Q,8-ethylenically unsaturated group. The number of reactive functional groups possessed by the vinyl polymer in such a mixed system varies depending on the number of reactive functional groups of the non-polymerizable compound and the amount used, but generally it is 0 per 1000 molecular weight as in the case of '1} above. .1 to 6, preferably 0
．． It is desirable that the number is set in a range of 5 to 3. '
3'(i) A non-polymerizable compound having one glycidyl group or a vinyl monomer having a hydroxyl group alone or a combination thereof with a vinyl monomer having no reactive functional group as a polymerization solvent. Solution polymerization is carried out in the presence of a mixture of this and a non-polymerizable compound having one or more hydroxyl groups, and then the resulting polymerization system contains a saturated compound having a carboxylic anhydride group that reacts with the hydroxyl group of the resulting polymer /or an unsaturated compound is reacted to generate a carboxyl group, and at the same time, this carboxyl group reacts with the glycidyl group of the non-polymerizable compound to form a hydroxyl group, and one of the non-polymerizable compounds that is a polymerization solvent is added to the polymer. or (ii) using a vinyl monomer having a glycidyl group alone or in combination with a vinyl monomer having no reactive functional group as a polymerization solvent having one hydroxyl group. Solution polymerization is carried out in the presence of a non-polymerizable compound or a mixture of this and a non-polymerizable compound having one or more glycidyl groups, and then a carboxylic acid that reacts with the hydroxyl group of the non-polymerizable compound is added to the resulting polymerization system. A saturated and/or unsaturated compound having an acid anhydride group is reacted to form a carboxyl group, and at the same time, this carboxyl group reacts with the glycidyl group of the resulting polymer to form a hydroxyl group. method of introducing some of the sex compounds.

In the solution polymerization of (i or (ii)), a vinyl monomer having a hydroxyl group or a glycidyl group and a vinyl monomer having no reactive functional group are employed, and a glycidyl group or a vinyl monomer as a polymerization solvent is used. The type of non-polymerizable compound having one hydroxyl group may be appropriately selected from those listed in ``1'' above and combined as described above, and the polymerization conditions may also be in accordance with ``1''. .

In addition, among the polymerization solvents used as necessary, examples of non-polymerizable compounds having two or more hydroxyl groups or glycidyl groups include saturated polyhydroxy compounds (
Ethylene glycol, tripropylene glycol, polypropylene glycol, neobentyl glycol, 1,
6-hexanediol, glycerin, trimethylolethane, trimethylolpropane, bentaeri slit, etc.), and saturated polyglycidyl compounds (ethylene glycol glycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol di Glycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1
, 6-hexanediol diglycidyl ether, neobentyl glycol diglycidyl ether, 3,4-epoxy 6-methylcyclohexylmethyl-3,4-epoxy 6-methylcyclohexane carpoxylate, dicyclobentadiene dioxide, vinylcyclohexene dioxide , dibentene dioxide, phthalate diglycidyl ester, adipate diglycidyl ester, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, epoxidized natural oils and fats, other polyvalent epoxy resins, etc.), and each group One or a mixture of two or more selected from these may be used. The amount of the polymerization solvent to be used in the solution polymerization may be selected within the range of 20 to 14 parts, preferably 40 to 10 parts, based on 100 parts of the total amount of vinyl monomers normally used.

If it deviates from this range, a scandal similar to the previous case of '1' will occur. Furthermore, in order to introduce a part of the polymerization solvent, the amount of polymerization solvent used is adjusted so that the number of moles of glycidyl groups or hydroxyl groups in the polymerization solvent is in excess of the hydroxyl groups or glycidyl groups of the vinyl monomer. All you have to do is decide. Through such solution polymerization, a polymerization system of a vinyl polymer and a non-polymerizable compound in which hydroxyl groups and glycidyl groups are present is obtained, and the number of hydroxyl groups or glycidyl groups possessed by the vinyl polymer in the polymerization system is determined by the non-polymerizable compound. Although it varies depending on the number and amount of hydroxyl groups in the compound, it is generally 0.1 to 6, preferably 0.5 to 3, per 1000 molecular weight as in the case of '1-' above. It is desirable to set it within the range of .

Examples of saturated or unsaturated compounds having a carboxylic anhydride group that react with the hydroxyl group in the polymerization system include Q,8-dicarboxylic anhydride (phthalic anhydride, succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride). , tetrabromophthalic anhydride, tetrachlorophthalic anhydride, hettic anhydride, imic anhydride, maleic anhydride, etc.), and tricarboxylic anhydride (trimellitic anhydride, methylcyclohexenetricarboxylic anhydride, etc.) These can be used alone or in a mixture of two or more.

By reacting the above-mentioned saturated and/or unsaturated compounds in an appropriate ratio, the carboxylic acid anhydride group thereof reacts with the hydroxyl group in the polymerization system as described above to become a free carboxyl group, and at the same time, the group is removed from the polymerization system. reacts with the glycidyl groups present in the molecule to generate free hydroxyl groups. Therefore, depending on the composition of the carboxylic acid anhydride group, hydroxyl group, and glycidyl group involved in the reaction, the types of reactive functional groups that survive after the reaction are determined, for example, hydroxyl group alone, carboxyl group alone, glycidyl group and hydroxyl group, carboxyl group. and a hydroxyl group, or a carboxyl group and a carboxylic acid anhydride group. Specifically, for example, if the functional group contained in the vinyl polymer in (ii) above is a glycidyl group, and the functional group contained in the polymerization solvent is a hydroxyl group or a hydroxyl group and a glycidyl group, the number of moles of the blended composition The combination of changes and surviving reactive functional groups is as follows: change in the number of moles in the blended composition → surviving reactive functional group carboxylic acid anhydride stalk < glycidyl group → glycidyl group and hydroxyl group, carboxylic acid anhydride stalk = Glycidyl group → hydroxyl group alone,
Glycidyl group < Carboxylic anhydride stem < Hydroxyl group → Hydroxyl group and carboxyl group, Glycidyl group 10 Hydroxyl group = Carboxylic acid anhydride stem → Carboxyl group alone, Glycidyl group 10 Hydroxyl group < Carboxylic acid anhydride group → Carboxyl group and carboxylic acid anhydride Base.

The same thing can be said even if the functional group contained in the vinyl polymer mentioned above is a hydroxyl group and the functional group contained in the polymerization solvent is a glycidyl group or a glycidyl group and a hydroxyl group.

As described above, the mixed system in which one or two types of reactive functional groups are present is obtained, and this is used as it is in the next step Q.
Although it may be subjected to the step of introducing an 8-ethylenically unsaturated group, if necessary, as in the case of [1' above, a carboxyl group,
The two reactive functional groups may be converted into one reactive functional group by reaction with a saturated and/or unsaturated compound having a carboxylic acid anhydride, a glycidyl group, or a hydroxyl group.

The specific combinations are as follows. Among the above saturated or unsaturated compounds, examples of saturated compounds having a hydroxyl group include saturated monohydroxy compounds (butanol, ethylene glycol monoethyl ether, diacetone alcohol, etc.) and saturated polyhydroxy compounds (ethylene glycol, (polypropylene glycol, glycerin, bentaerythritate, etc.), and for unsaturated compounds having a hydroxyl group and saturated or unsaturated compounds having other functional groups, Q,8-ethylenically unsaturated compounds used in the next step, respectively. and the saturated compounds used in '1} above.

In the present invention, a Q,8-ethylenically unsaturated group having a functional group is used to introduce a Q,8-ethylenically unsaturated group into the mixed vinyl polymer obtained in m to (3} above and the polymerization solvent. As the compound, one having an appropriate functional group may be employed depending on the type of reactive functional group present in the mixed system, and this is subjected to the reaction in one or two steps.

The combination of both functional groups is as follows. A typical example of introducing a Q,8-ethylenically unsaturated group in the above two-step process is the case where it is applied to the mixed system obtained in the above-mentioned production example [21]. A Q,3-ethylene unsaturated compound having an isocyanate group that reacts with a hydroxyl group in the system is reacted, and then a Q,8-ethylene having a glycidyl group or a carboxyl group is reacted with a carboxyl group or glycidyl group remaining in the mixed system. What is necessary is to react a sexually unsaturated compound.

Examples of the above-mentioned Q,8-ethylenically unsaturated compounds having an isocyanate group include diisocyanate compounds (
isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, lysine diisocyanate, etc.), one of the isocyanate groups is replaced with a Q,8-ethylenically unsaturated monohydroxy compound (2-hydroxyethyl (meth)acrylate, allyl alcohol). , reaction products of (meth)acrylic acid and glycidyl (meth)acrylate) or Q,8-ethylenically unsaturated amino compounds (monomethylaminoethyl (meth)acrylate, monoethylamino(meth)acrylate, etc.) Examples include those substituted with ethyl (ethyl, etc.).

Examples of the Q,3-ethylenically unsaturated compound having a carboxylic anhydride group include Q,B-ethylenically unsaturated dicarboxylic anhydrides such as itaconic anhydride and maleic anhydride. Examples of the above-mentioned glycidyl group-containing Q,8-ethylenically unsaturated compounds include glycidyl esters of Q,8-ethylenically unsaturated carboxylic acids (
glycidyl (meth)acrylate, etc.) and glycidyl ethers of hydroxyl group-containing vinyl monomers (allyl glycidyl ether, methallyl glycidyl ether,
(glycidyl ether of 2-hydroxyethyl (meth)acrylate, etc.).

Examples of the Q,8-ethylenically unsaturated compounds having a carboxyl group include Q,8-ethylenically unsaturated monocarboxylic acids [(meth)acrylic acid, maleic acid monoalkyl ester, itaconic acid monoalkyl ester, etc. q,B-ethylenically unsaturated hydroxy compound (2-hydroxyethyl (meth)acrylate, allyl alcohol, reaction product of (meth)acrylic acid and glycidyl (meth)acrylate, etc.) and Q,8-dicarboxylic anhydride Reaction products with substances (hexahydrothermal phthalic acid, succinic anhydride, itaconic anhydride, maleic anhydride, etc.), o, quethylenically unsaturated dicarboxylic acid anhydrides (itaconic anhydride, maleic anhydride, etc.) and saturated monomers. Examples include reaction products with hydroxy compounds (butanol, ethylene glycomonoethyl ether, etc.) and unsaturated fatty acids (linseed oil fatty acid, tall oil fatty acid, etc.).

Examples of the above-mentioned Q,8-ethylenically unsaturated compounds having a hydroxyl group include hydroxyalkyl (meth)acrylate esters (2-hydroxyethyl (meth)acrylate, etc.), halogenated derivatives of the above-mentioned esters (
3-chloro-2-hydroxypropyl (meth)acrylate, etc.), unsaturated alcohols (allyl alcohol, etc.), saturated monoglycidyl compounds (glycidyl tertiary nonanoate, etc.) and Q,6-ethylenically unsaturated carboxylic acids (( (meth)acrylic acid, etc.), and Q
, 8-ethylenically unsaturated glycidyl compounds ((meth)
glycidyl acrylate) and monocarboxylic compounds (such as glycidyl acrylate) and monocarboxylic compounds (such as glycidyl acrylate).
(acetic acid, (meth)acrylic acid, etc.).

The reaction to introduce this Q,P-ethylene unsaturated group is
The reaction may be carried out within a range where the reactive functional group of the mixed system and the functional group of the Q,8-ethylenically unsaturated compound can advantageously undergo an addition reaction. For example, if the mixed system requires a reaction catalyst (such as triethylamine). In its presence, an equimolar amount of the 8-ethylenically unsaturated compound may be added and the reaction may be carried out at 40 to 120°C for 1 to 8 hours.

In this way, the target active energy ray-curable resin composition (that is, the polymer component and solvent component constituting the composition are both endowed with Q,8-ethylenically unsaturated groups, and these are (contributes to active energy ray curing and becomes a film-forming component). In addition, as long as all of the constituent components of the resin composition can retain Q,8-ethylene unsaturated groups, it is possible to stop various reactions midway through, and it is also possible to improve curability and cure. For the purpose of improving coating performance, etc., the reaction may be repeated with another Q,8-ethylenically unsaturated compound via the reactive functional group generated after the reaction. That is, through such repetition, more Q,3-ethylene unsaturated groups are introduced. According to the method of the present invention having the above configuration, substantially 100% of the constituent components of the resulting active energy ray-curable resin composition undergo a radical crosslinking reaction upon irradiation with active energy rays to form a cured film. However, volatile components can be substantially eliminated from the coating.

In addition, the method of the present invention can omit the conventional process of removing the polymerization solvent, which is a great advantage in manufacturing on an industrial scale, and has improved the outlook for the production of active energy ray-curable resin compositions. It can be said to be open. In order to make the above resin composition into a paint, it may be used as an active energy ray-curable paint as it is, and if necessary, it may be added with oligomers, vinyl monomers, pigments, etc. that can be cured by active energy rays. Add an agent (among active energy rays, when using ultraviolet irradiation, it is necessary to add a photosensitizer such as an anthraquinone compound, penzoin or its derivatives due to the energy intensity), etc., and disperse and mix using a conventional method to activate the active energy ray. It may also be used as an energy ray curable paint.

Such a paint can form a completely cured film with almost no volatile components even if it is irradiated with active energy rays immediately after being applied to metal, wood, plastic, etc., and is a paint with substantially 100% non-volatile content. It can be said. Next, the present invention will be specifically explained with reference to Examples.

In the examples, "part" and "1%" mean "part by weight" and "% by weight." Example 1 Put 40 liters of butanol into a reaction container and heat to a temperature of 1.
A mixed solution consisting of 37 parts of methyl methacrylate, 50 parts of n-butyl acrylate, 172 parts of methacrylic acid, 2 parts of azobisisobutyronitrile, and 1 part of dodecyl mercaptan was added to this for 2 hours. and then maintained at the same temperature for 4 hours to obtain a hydroxyl group- and carboxyl group-containing vinyl copolymer solution E.

Next, this solution E was cooled and maintained at 90 qo, and then maleic anhydride 53 base was added thereto and heated to react at 110°C for 2 hours, cooled again to 90°C, and then glycidyl methacrylate 1051 A mixture of 1 part of hydroquinone and 1 part of hydroquinone was added dropwise over a period of 1 hour, and stirring was continued for 3 hours using a small amount of triethylamine as a catalyst to obtain an active energy ray-curable resin composition. Example 2 In a reaction vessel, 50 parts of "Cardura E" (trade name, manufactured by Epoxy Resin Shell Co., Ltd.), 30 parts of methyl methacrylate, 25 parts of lauryl acrylate, 255 parts of ethyl acrylate, and 2-hydroxyacrylic acid were added. Add 195 parts of chilli, heat and maintain the temperature at 100°C, and add 10 parts of epoxy resin (Cardura 8) to which 25 parts of azobisisobutyronitrile and 15 parts of dodecyl mercaptan are dissolved. ．． It is added dropwise immediately and maintained for 4 hours to obtain a glycidyl group- and hydroxyl group-containing vinyl copolymer solution F.

Next, this solution F was kept cooled to 90°C, and a mixture of 176 parts of acrylic acid and 0.5 parts of hydroquinone was added dropwise thereto over 1 hour, and then heated to 100°C.
After adding 590 parts of tetrano-hydrophthalic anhydride and continuing the reaction for 4 hours, a mixture of 50 parts of glycidyl acrylate and 1 part of hydroquinone was added and the reaction was continued for 4 hours. A curable resin composition is obtained.

Example 3 72 Etsuro acrylic acid, 116 Ikkuni glycidyl acrylate, and 2 parts of hydroquinone were placed in a reaction vessel, and the reaction was continued for 4 hours while heating and maintaining the temperature at 100 qo to prepare Q,8-ethylenically unsaturated monohydroxy compound G.
get.

Put isophorone diisocyanate 222 into another reaction vessel, heat and maintain the temperature at 40:00, add part of the above compound C205 dropwise over 2 hours, and then react at the same temperature for 4 hours. Continue to obtain a q,8-ethylenically unsaturated monoisocyanate compound.

Furthermore, 60 parts of ethylene glycol monoethyl ether was placed in another reaction vessel, heated and maintained at a temperature of 60 qo,
To this, 14 parts of glycidyl methacrylate, 50 parts of ethyl acrylate, 3 parts of styrene, 2,2'-azobis-(2,4-dimethylvaleronitrile) (trade name "V-65" manufactured by Wako Pure Chemical Industries, Ltd.) 2 A mixed solution consisting of one part of lauryl mercaptan and one part of lauryl mercaptan was added dropwise over a period of 2 hours, and the reaction was continued for 3 hours at the same temperature, and then the temperature was raised to 80 qo and reacted for 1 hour. A combined solution 1 is obtained.

Next, a mixture of 86 parts of methacrylic acid and 0.1 part of hydroquinone monomethyl ether was added dropwise to this solution 1 at the same temperature over a period of 1 hour, and then the temperature was raised to 100 qC and 3.
After continuing the reaction for an hour, the mixture was cooled to 4,000 ml, and 3,600 parts of the above compound was added dropwise over 2 hours, followed by reaction for 4 hours to obtain an active energy ray-curable resin composition.

Example 4 600 parts of palm kernel oil fatty acid was placed in a reaction vessel, heated and maintained at a temperature of 100°C, and 195 parts of 2-hydroxyethyl acrylate, 50 parts of cyclohexyl acrylate, 20 parts of methyl methacrylate, A mixed solution consisting of 105 parts of styrene, 25 parts of azobisisobutyronitrile, and 1 part of lauryl mercaptan was added dropwise over a period of 2 hours, and the reaction was then continued at the same temperature for 4 hours to produce a vinyl copolymer containing carboxyl and hydroxyl groups. Obtain a solution.

Next, 360 parts of phenylglycidyl ether was added to this solution at the same temperature and reacted for 3 hours, and then cooled to 400 ml. 183 anchor portions were added dropwise over a period of 2 hours, and the reaction was then continued at the same temperature for 4 hours to obtain an active energy ray-curable resin composition. Example 5 The hydroxyl group- and carboxyl group-containing copolymer solution E147 obtained in Example 1 was placed in a reaction vessel, heated and maintained at a temperature of 100 qo, and 128 parts of glycidyl acrylate and 114 parts of allyl glycidyl cable were added to the reaction vessel. A mixture of 0.2 parts of glycidyl methacrylate and 0.2 parts of hydroquinone was added dropwise over 1 hour, and the reaction was continued for 4 hours at the same temperature, then 112 parts of tetrahydrophthalic anhydride was added and reacted for 2 hours, and then 105 parts of glycidyl methacrylate was added. 1 and reacted for 4 hours to obtain an active energy ray-curable resin composition.

Example 6 60 parts of coconut oil fatty acid and 116 parts of diacetone alcohol were placed in a reaction vessel, heated and maintained at a temperature of 60°C, and 13 parts of 2-hydroxyethyl methacrylate,
From 30 parts of methyl methacrylate, 40 parts of ethyl acrylate, 17 parts of styrene, 25 parts of 2,2'-azobis-(2,4-dimethylvaleronitrile) ("V-65") and 1 part of lauryl mer-butane. The mixed solution was added dropwise over a period of 2 hours, and the reaction was continued for 3 hours at the same temperature, and then the temperature was raised to 80°C and the reaction was continued for an additional 2 hours to form a solution of a vinyl copolymer containing hydroxyl and carboxyl groups. obtain.

Next, 105 parts of methylcyclohexenetricarboxylic anhydride, 147 parts of maleic anhydride, and 2 parts of hydroquinone monomethyl ether were added to this solution, and after reacting at 10°C for 5 hours, 755 parts of glycidyl methacrylate was added to this solution.
1 hour, and then reacted at the same temperature for 4 hours to obtain an active energy ray-curable resin composition. Example 7 60 parts of epoxy resin "Cardura E") and 20 parts of ethylene glycol monoethyl ether were placed in a reaction vessel, heated and maintained at a temperature of 110°C, and 174 parts of 2-hydroxyethyl acrylate, Ethyl acrylate 40
2. A mixed solution consisting of anchor, 30 parts of methyl methacrylate, 20 parts of styrene, and 15 parts of dodecyl mercaptan. The mixture is added dropwise over an hour, and the reaction is continued at the same temperature for 3 hours to obtain a solution of a vinyl copolymer containing hydroxyl groups and glycidyl groups.

Next, this solution was kept cooled at a temperature of 100q0, a mixture of 176 parts of acrylic acid and 0.7 parts of hydroquinone was added dropwise to it over 0.5 hours, and then heated to a temperature of 115 q0.
The mixture was kept at 0:00 pm, reacted for 4 hours, cooled to 40°C, and then 289 parts of the Q,8-ethylenically unsaturated monoisocyanate compound obtained in Example 3 was added dropwise over a period of 2 hours. ,
Next, the reaction is continued for 4 hours at the same temperature to obtain an active energy ray-curable resin composition.

The characteristics of the active energy ray-curable resin compositions obtained in Examples 1 to 7 above and the volatile content of the cured film when the compositions were irradiated with active energy rays are shown in Table 1.

Table 1 r Viscosity in the table: Gardner bubble viscometer (25°C) non-volatile content (%)
: 3 to 5 days of the resin composition was collected in a non-volatile content measuring dish, and 10
Residue rate when heated at 0qC for 3 hours.

Curing method: EBC (electron beam irradiation): 30 eV, 3 hours
A regular ad irradiation with accelerated electron beam. UVC (ultraviolet irradiation)
: Using a 2kW, 30W/arc lamp, irradiation was performed for 3 minutes at a distance of 2% (2% by weight of penzoyl isopropyl ether was added as a photosensitizer).

) Volatile content in the coating (%): #
Each resin composition was coated using a base bar coater, immediately irradiated with active energy rays, and then the coated weight was measured. Next, this coated steel plate was placed in an 8-piston vacuum dryer and dried under reduced pressure for 6 hours to determine the weight loss rate. Example 8 222 parts of isophorone diisocyanate was placed in a reaction vessel, heated and maintained at a temperature of 4000°C, and a mixture of 1276 parts of 2-hydroxyethyl acrylate and 2 parts of dibutyltin dilaurate as a catalyst was added thereto. The dropwise addition takes about 2 hours so as not to exceed the temperature of 50 oo, and the reaction is then continued for 2 hours to obtain 3-ethylenically unsaturated monoisocyanate compound J.

Put 40 parts of butanol into another reaction vessel, heat and maintain the temperature at 60q0, add 108 parts of acrylic acid, 40 parts of ethyl acrylate, 30 parts of methyl methacrylate, 192 parts of styrene, 2,2' - A mixed solution consisting of 3 parts of azobis-(2,4-dimethylvaleronitrile) ("V-65") and 15 parts of dodicyl mercaptan was added dropwise over about 2 hours, and after being maintained for 2 hours, the temperature was raised to 80°C. The reaction was continued for 2 hours to obtain a vinyl copolymer solution containing hydroxy groups and carboxyl groups.

Next, after cooling and maintaining this solution at 40°C, the above compound J210 anchor part was added dropwise to it so as not to exceed the temperature of 50°C, and then the temperature was maintained at the same temperature for 2 hours, and then the temperature was raised to 70°C. After continuing the reaction for 2 hours, 192 parts of glycidyl acrylate and 0.4 parts of hydroquinone were added, and 9 parts of glycidyl acrylate and 0.4 parts of hydroquinone were added.
The mixture was heated to a temperature of 100.degree. C. and reacted for 4 hours in the presence of a certain amount of triethylamine to obtain an active energy ray-curable resin composition.

Example 9 60 parts of coconut oil and fat acid and 146 parts of succinic acid monoethyl ester were placed in a reaction vessel, heated and maintained at a temperature of 60:00, and 26 parts of 2-hydroxyethyl methacrylate was added to the reactor.
A mixed solution consisting of 41 parts of ethyl acrylate, 33 parts of methyl methacrylate, 25 parts of 2,2-azopis-(2,4-dimethylvaleronitrile) ("V-65") and 15 parts of dodecylmercaptan was prepared. The mixture was added dropwise over about 2 hours, and then the reaction was continued at the same temperature for 2 hours, and then the temperature was raised to 80°C and the reaction was continued for 2 hours to obtain a solution of a vinyl copolymer containing hydroxyl and carboxyl groups.

Next, after cooling and maintaining this solution at 40 oo, the Q,8-ethylenically unsaturated monoisocyanate compound J77 base group obtained in Example 8 was added dropwise thereto so as not to exceed the temperature of 50 oo, and for 2 hours. After holding, the mixture was further reacted at 70 qo, and then 490 parts of glycidyl acrylate and 1 part of hydroquinone monomethyl ether were added, the temperature was raised to 9,000 °C, and the mixture was reacted for 4 hours to obtain an active energy ray-curable resin composition.

Example 10 142 parts of glycidyl methacrylate, 1 part of triethylamine, and hydride are placed in a reaction vessel.

2.1 parts of quinone was added, heated and maintained at a temperature of 100q0, 720 parts of acrylic acid was added dropwise over about 1 hour, and then 3. The reaction continues for an hour to obtain Q,8-ethylenically unsaturated monohydroxy compound K. In another reaction vessel, 1740 parts of tolylene diisocyanate and 200 parts of the above compound K were placed, heated and maintained at a temperature of 4000°C, and a mixture of 150 parts of the above compound K and 2.1 parts of sibutyltin dilaurate was added to the reactor at a temperature of 5. The mixture was added dropwise so as not to exceed 0, and after being maintained for 2 hours, the reaction was further continued at 70 qo for 2 hours to obtain Q,8-ethylenically unsaturated monoisocyanate compound L.

In addition, add epoxy resin Cardura E to another reaction vessel.
Add 2-hydroxyethyl methacrylate, 435 parts of methyl methacrylate, 19 parts of lauryl methacrylate, 31 parts of n-butyl acrylate, and azo. About 1.5 parts of a mixed solution of 25 parts of pisobutyronitrile and 1 part of lauryl mercaptan was added. The mixture was added dropwise for an hour, and then the reaction was continued at the same temperature for 3 hours to obtain a solution of a vinyl copolymer containing hydroxyl groups and glycidyl groups.

Next, after cooling and maintaining this solution at 40 qo, 200 parts of the above compound L was added dropwise thereto without exceeding the temperature of 50°C, and after the solution was maintained for 2 hours, the reaction was further carried out at 70 qo for 2 hours, and then 235 parts of acrylic acid and Hydroquinone 0.
Add 15 parts and raise the temperature to 100°C. 3. An active energy ray-curable resin composition is obtained by a time-consuming reaction. Example
11 Add 5.8 parts of Cardura E') 90 base material and triethylamine with epoxy resin to a reaction container, and heat to a temperature of 1.
A mixture of 265 parts of acrylic acid and 0.25 parts of hydroquinone was added dropwise thereto over about 1 hour, and the reaction was then continued at the same temperature for 3.5 hours to form a Compound M is obtained.

In a separate reaction vessel, 130 parts of butyl glycidyl ether, 70 parts of epoxy resin Gucardilla E) and 74 parts of piptanol were added, heated and maintained at a temperature of 10. A mixed solution consisting of 232 parts of 2-hydroxyethyl acrylate, 32 parts of methyl methacrylate, 116 parts of styrene, 30 parts of ethyl acrylate, 3 parts of azobisisobutyronitrile, and 15 parts of lauryl mercaptan was added to about 1. The solution was added dropwise over an hour, and the reaction was continued for 3 hours at the same temperature to obtain a glycidyl group- and hydroxyl group-containing pinyl copolymer solution.

Next, after cooling and maintaining this solution at 40°C, 1556 parts of the Q,8-ethylenically unsaturated monoisocyanate compound L obtained in Example 10 was added dropwise thereto so as not to exceed the temperature of 50°C. After holding for 2 hours, the reaction is further continued at 70°C for 2 hours.

Next, 281 parts of acrylic acid was added to this, the temperature was raised to 90 qo, and the reaction was continued for 4 hours.Furthermore, 400 parts of tetrahydrophthalic anhydride and 256 parts of glycidyl acrylate were added, and the reaction was continued for 6 hours at the same temperature to determine the activation energy. A line-curable resin composition is obtained. The characteristics of the active energy ray-curable resin compositions obtained in Examples 8 to 11 above and the volatile content of the cured film when the compositions were irradiated with active energy rays are shown in Table 2.

Table 2 Example 12 Ethylene glycol monoethyl ether 22 was added to the reaction vessel.
Add 5 parts and 37 parts of butanol and heat to a temperature of 6.
Glycidyl methacrylate 426
36 parts of ethyl acrylate, 24 parts of n-butyl acrylate, 40 parts of methyl methacrylate, 29 parts of 2,2'-azobis-(2,4-dimethylvaleronitrile) ("V-65"), and dodecyl A mixed solution consisting of 21 parts of mercaptan was added dropwise over about 2 hours, maintained at the same temperature for 2 hours, and then further heated to 80q0 and reacted for 2 hours to obtain a glycidyl group- and hydroxyl group-containing vinyl copolymer solution.

Next, add tetrahydrophthalic anhydride 7 to this solution at the same temperature.
6 was added, and the temperature was raised to 12°C to react for 5 hours. After introducing a part of the polymerization solvent into the side chain of the copolymer via tetrahydrophthalic acid, 28% glycidyl methacrylate was added.
4 parts of dibutyltin dilaurate and 0.4 parts of hydroquinone were added to convert free carpoxyl groups into hydroxyl groups (reacted for 3 hours, then cooled and maintained at a temperature of 40°C, and then added with 2.2 parts of dibutyltin dilaurate and 456 parts of glycerol dimethacrylate). was added, and furthermore, xylylene diisocyanate 94 was added dropwise so that the temperature did not exceed 50:00 pm, and the reaction was continued for 2 hours to obtain an active energy ray-curable resin composition.

Example 13 50 parts of butanol, 26 parts of butyl glycidyl ether and 45 parts of 1,6-hexanediol diglycidyl ether were placed in a reaction vessel and heated to a temperature of 100oC.
A mixed solution consisting of 284 parts of glycidyl acrylate, 50 parts of lauryl methacrylate, 25 parts of methyl methacrylate, 25 parts of styrene, 32 parts of azobisisobutyronitrile, and 2 parts of dodecylmercaptan was added to this. About i. The solution was added dropwise over a period of time, maintained at the same temperature for 2 hours, and further reacted at 120 quartz for 1 hour to obtain a glycidyl group- and hydroxyl group-containing vinyl copolymer solution.

Next, this solution was kept cooled to 90°C, then 67% of maleic anhydride and 0.2 parts of hydroquinone were added thereto, and the temperature was raised to 10,000°C and reacted for 4 hours to form a copolymer side chain via maleic anhydride. After introducing butanol,
A mixture of 7 parts of acrylic acid and 0.1 part of hydroquinone was added dropwise over 0.5 hours, and then Q,8-ethylenically unsaturated groups were introduced into the remaining glycidyl groups at the same temperature (reaction was allowed to take place for about 3 hours). , an active energy ray-curable resin composition is obtained.

Example 14 Butyl glycidyl ether 26 in the reaction vessel
Add Ikari Kaku and 14 parts of epichlorohydrin, heat and maintain at a temperature of 100 qC, add 116 parts of 2-hydroxyethyl acrylate, 45 parts of 2-ethylhexyl acrylate, 203 parts of methyl methacrylate, and methacrylate. Dimethylaminoethyl acid 1st, styrene 2nd
About 1.2 parts of a mixed solution consisting of 21 parts of azobisisobutyronitrile, 15 parts of lauryl mercaptan, and 15 parts of lauryl mercaptan was added. It took an hour to drip, and after keeping it at the same temperature for 2 hours, it was further heated to 120
00 for 2 hours to obtain a glycidyl group- and hydroxyl group-containing vinyl copolymer solution.

Next, after cooling and maintaining this solution at 90 qo, 96 parts of trimellitic anhydride and 4 parts of maleic anhydride were added thereto, and the temperature was raised to 10 qo and reacted for 5 hours to infuse these acids into the side chains of the copolymer. After introducing part of the polymerization solvent via the anhydrides, 91 parts of methacrylic acid, 14 parts of linseed oil fatty acids and hydride.

After adding 0.1 part of quinone and reacting for another 3 hours to convert the functional groups present in the system into hydroxyl groups, 315 parts of maleic anhydride and 41 parts of glycidyl acrylate were added and reacted for 4 hours to determine the activation energy. A line-curable resin composition is obtained. Example 15 50 anchor parts of epoxy resin (Cardura E) in the reaction vessel,
Phenylglycidyl ether 525 parts, butanol 11
1 part and 106 parts of diethylene glycol were heated and maintained at a temperature of 6,500, and to this were added 288 parts of 2-hydroxypropyl methacrylate, 20 parts of methyl methacrylate, 50 parts of lauryl methacrylate, 30 parts of styrene, and 30 parts of styrene. A Namiai solution consisting of 1 part of 2,2'-azobis-(2,4-dimethylvaleronitrile) ("V-65") and 13 parts of lauryl mercaptan was added dropwise over about 2 hours, and 1 part of the solution was added at the same temperature.
After the temperature was maintained for a certain period of time, the temperature was further raised to 80o0 and maintained for 2 hours to obtain a vinyl copolymer solution containing hydroxyl groups and glycidyl groups.

Next, 616 parts of itaconic anhydride and 0.6 parts of hydroquinone monomethyl ether were added to this solution at the same temperature.
4. Raise the temperature to 100oo. After a part of the polymerization solvent was introduced into the side chain of the copolymer, it was cooled and maintained at 40 qo. 78 parts of isophorone diisocyanate was added thereto and reacted for about 3 parts, and then glycerol dimethac IJ-
A mixture of 69 parts of isocyanate and 1.5 parts of dibutyltin dilaurate was added dropwise at a temperature not exceeding 50°C, and the temperature was maintained for 2 hours. The reaction was further continued at 70qo until free isocyanate disappeared, and cured with active energy rays. A synthetic resin composition is obtained.

Example 16 Add Cardura E to the reaction vessel using epoxy resin.
) 245 parts, ethylene glycomonoethyl ether 2
Add 25 parts of 2-hydroxyethyl acrylate and 148 parts of butanol, heat and maintain at a temperature of 10,000, add 58 parts of 2-hydroxyethyl acrylate, 60 parts of ethyl acrylate, 40 parts of methyl methacrylate, and azobisisobutyronitrile. A mixed solution consisting of 1 part of anchor and 15 parts of dodecyl mercaptan is prepared in 1. The mixture was added dropwise over an hour and kept at the same temperature for 2 hours to obtain a solution of a vinyl copolymer containing hydroxyl groups and glycidyl groups.

Next, 588 parts of maleic anhydride and 0.5 parts of hydroquinone were added to this solution at the same temperature and reacted for 4 hours to introduce a part of the polymerization solvent into the side chains of the copolymer. Seventy grams of glycidyl acid was added to the mixture, and the mixture was reacted for about 2 hours using a small amount of tricotylamine as a catalyst to obtain an active energy ray-curable resin composition.

Table 3 shows the characteristics of the active energy ray-curable resin compositions obtained in Examples 12 to 16 and the volatile content of the cured film when the compositions were irradiated with active energy rays.

As is clear from the results in Table 3 and above and Tables 1 to 3 in Examples 1 to 16, the active energy ray-curable resin composition obtained by the method of the present invention has a non-volatile content of substantially 100%.
It is possible to consider the percentage, and it is recognized that the desired effect will be achieved.

Claims (1)

[Scope of Claims] 1. In a mixed system of a vinyl polymer having a reactive functional group and a non-polymerizable compound having a reactive functional group as its solvent, a functional group capable of reacting with the reactive functional group in the system is added. An active energy ray-curable resin composition is obtained by reacting an α,β-ethylenically unsaturated compound having a group and introducing an α,β-ethylenically unsaturated group into the above-mentioned vinyl polymer and non-polymerizable compound. In this case, the mixed system of the vinyl polymer and the non-polymerizable compound uses a vinyl monomer having a reactive functional group as a polymerization solvent, and a non-polymerizable polymer having one reactive functional group different from the above-mentioned reactive functional group. or the same functional group as the reactive functional group possessed by this and the above vinyl monomer.
solution polymerization in the presence of a mixture with a non-polymerizable compound, and then the resulting mixed system has a functional group capable of reacting with either one of the different types of reactive functional groups present in the system, It is characterized in that it is obtained by reacting saturated and/or unsaturated compounds selected so that the reactive functional group produced as a result of the reaction is the same as the remaining reactive functional group. A method for producing an active energy ray-curable resin composition. 2 The functional group of the vinyl monomer is a carbosigyl group, the functional group of the non-polymerizable compound is a hydroxyl group, and the functional group of the saturated and/or unsaturated compound is a carboxylic acid anhydride group (-(C
The method according to item 1 above, wherein in O)_2O), the generated reactive functional group and the remaining reactive functional group are carboxyl groups, and the functional group of the α,β-ethylenically unsaturated compound is a glycidyl group. 3 The functional group of the vinyl monomer is a glycidyl group, the functional group of a non-polymerizable compound is a hydroxyl group, and the functional group of a saturated and/or unsaturated compound is a carboxyl group, and the reactive functional group generated and the remaining reaction 2. The method according to item 1 above, wherein the functional group is a hydroxyl group and the functional group of the α,β-ethylenically unsaturated compound is an isocyanate group. 4 The functional group of the vinyl monomer is a hydroxyl group, the functional group of a non-polymerizable compound is a carboxyl group, and the functional group of a saturated and/or unsaturated compound is a glycidyl group. 2. The method according to item 1 above, wherein the functional group is a hydroxyl group, and the functional group of the α,β-ethylenically unsaturated compound is an isocyanate group. 5 The functional group of the vinyl monomer is a hydyloxyl group, the functional group of a non-polymerizable compound is a carboxyl group and a hydyloxyl group, and the functional group of a saturated and/or unsaturated compound is a carboxylic anhydride group (-(CO)_2O) The method according to item 1 above, wherein the reactive functional group produced and the reactive functional group remaining are carboxyl groups, and the functional group of the α,β-ethylenically unsaturated compound is a glycidyl group. 6 The functional group of the vinyl monomer is a hydroxyl group, the functional group of a non-polymerizable compound is a glycidyl group and a hydroxyl group, and the functional group of a saturated and/or unsaturated compound is a carboxyl group, and the reactive functional group and 2. The method of item 1 above, wherein the remaining reactive functional group is a hydroxyl group and the functional group of the α,β-ethylenically unsaturated compound is an isocyanate group. 7 A mixed system of vinyl polymer and non-polymerizable compound is
A vinyl monomer having a reactive functional group is used as a polymerization solvent with a non-polymerizable compound having one reactive functional group different from the above-mentioned reactive functional group, or with this and a reactive functional group possessed by the above-mentioned vinyl monomer. Solution polymerization is carried out in the presence of a mixture with a non-polymerizable compound having one same functional group, and then a functional group that can react with one of the different reactive functional groups present in the polymerized system is added. A saturated and/or unsaturated compound a selected such that the reactive functional group produced as a result of the reaction is the same as the remaining reactive functional group is reacted with 8. The method according to item 1 above, which is obtained by reacting a saturated and/or unsaturated compound b having a functional group capable of reacting with a reactive functional group to generate another reactive functional group. The functional group of the vinyl monomer is a hydroxyl group, the functional group of the non-polymerizable compound is a glycidyl group, and the functional group of the saturated and/or unsaturated compound a is a carboxyl group, resulting in reactive functional groups and residual reactions. the reactive functional group is a hydroxyl group, the functional group of the saturated and/or unsaturated compound b is a carboxylic acid anhydride group (-(CO)_2O), another reactive functional group is a carboxyl group, and α,β-ethylene The seventh above, wherein the functional group of the sexually unsaturated compound is a glycidyl group.
The method described in section. 9 The functional group of the vinyl monomer is a carboxyl group, the functional group of the non-polymerizable material is a hydroxyl group, and the functional group of the saturated and/or unsaturated compound a is a glycidyl group, and the reactive functional group to be generated and the remaining the reactive functional group is a hydroxyl group, and/or the functional group of the unsaturated compound b is a carboxylic acid anhydride group (-(CO)_2O), another reactive functional group is a carboxyl group, and α,β-ethylene 2. The method according to item 1 above, wherein the functional group of the sexually unsaturated compound is a glycidyl group. 10 A non-polymerizable compound in which the mixed system of a vinyl polymer and a non-polymerizable compound uses a vinyl monomer having a reactive functional group as a polymerization solvent and has one reactive functional group different from the above-mentioned reactive functional group. Or one obtained by solution polymerization in the presence of a mixture of this and a non-polymerizable compound having one functional group identical to the reactive functional group of the vinyl monomer (however, vinyl monomer or non-polymerizable compound (the reactive functional group of the compound is a hydroxyl group) and has an isocyanate group that reacts with the hydroxyl group in the above mixed system as the α,β-ethylenically unsaturated compound, and then the above-mentioned 2. The method according to item 1 above, wherein a substance having a functional group capable of reacting with a remaining reactive functional group other than a hydroxyl group is reacted. 11 The functional group of the vinyl monomer is a glycidyl group, the functional group of the non-polymerizable compound is a hydroxyl group, and the functional group of the α,β-ethylenically unsaturated compound to be reacted next, although it has an isocyanate group, is a glycidyl group. The method according to item 10 above. 12 The functional group of the vinyl monomer is a hydroxyl group, the functional group of the non-polymerizable compound is a carboxyl group, and the functional group of the α,β-ethylenically unsaturated compound to be reacted next is a glycidyl group although it has an isoanate group. The method according to item 10 above. 13 The functional group of the vinyl monomer is a hydroxyl group, the functional group of the non-polymerizable compound is a glycidyl group, and the functional group of the α,β-ethylenically unsaturated compound to be reacted next, which has an isocyanate group, is a carboxyl group. The method according to item 10 above. 14 The functional group of the vinyl monomer is a hydroxyl group, the functional group of the non-polymerizable compound is a glycidyl group and a hydroxyl group, and the functional group of the α,β-ethylenically unsaturated compound to be reacted next, although it has an isoanate group. 11. The method according to item 10 above, wherein is a carboxyl group. 15 In the mixed system of vinyl polymer and non-polymerizable compound, a vinyl monomer having a hydroxyl group is used as a polymerization solvent, or a non-polymerizable compound having one glycidyl group or this and one or two hydroxyl groups is used as a polymerization solvent. Solution polymerization is carried out in the presence of a mixture with a non-polymerizable compound having the above, and then the resulting polymerization system is saturated and/or A saturated compound is reacted to generate a carboxyl group, and at the same time, this carboxyl group is reacted with the glycidyl group of the non-polymerizable compound to form a hydroxyl group, and a part of the non-polymerizable compound is introduced into the polymer. 2. The method according to item 1 above, wherein 16 The mixed system of a vinyl polymer and a non-polymerizable compound consists of a vinyl monomer having a glycidyl group, a non-polymerizable compound having one hydroxyl group, or this and one or two glycidyl groups as a polymerization solvent. Solution polymerization is carried out in the presence of a mixture with a copolymerizable compound having the above, and then the resulting polymerization system contains a saturated and/or Or, it can be obtained by reacting an unsaturated compound to produce a carboxyl group, and at the same time, this carboxyl group reacts with the glycidyl group of the resulting polymer to form a hydroxyl group, and by introducing a part of the non-polymerizable compound into the polymer. The method according to item 1 above. 17. The method according to any one of items 1 to 16 above, wherein a vinyl monomer having a reactive functional group is copolymerized with a pinyl monomer having no reactive functional group during solution polymerization.