JP7547725B2 - Water-peelable curable composition - Google Patents

Description

The present invention relates to a water-removable curable composition, and preferably to a water-removable active energy ray-curable composition, and belongs to these technical fields.
In this specification, "acryloyl group and/or methacryloyl group" is referred to as "(meth)acryloyl group", "acrylate and/or methacrylate" is referred to as "(meth)acrylate", and "acrylic acid and/or methacrylic acid" is referred to as "(meth)acrylic acid".
In addition, the compound having an ethylenically unsaturated group is referred to as the "curable component" in the composition, and the other components are referred to as the "non-curable components".

Hot melt adhesives such as wax and rosin have been used to cut various precision parts such as oscillators, lenses, prisms, capacitors, package parts, and magnets made from materials such as crystal, quartz, optical glass, ceramics, stainless steel, ferrite, and aluminum, as well as to temporarily fix parts during polishing.
However, this type of adhesive requires high temperature work at about 150°C during bonding and removal, and then cleaning with an alkaline solvent or halogen-based organic solvent. Therefore, the temporary fixing and removal operations require skill and are dangerous, and also lead to a deterioration of the working environment and environmental pollution.

In order to solve the above-mentioned drawbacks, an active energy ray-curable adhesive composition for temporary fixing has been proposed, in which workpieces are temporarily fixed with an adhesive that is cured by active energy rays and can be peeled off with some kind of peeling medium when removing.
For example, Patent Document 1 discloses a temporary fixing adhesive composition containing N,N-diethyl(meth)acrylamide and a photopolymerization initiator.
Furthermore, Patent Document 2 discloses a temporary fixing adhesive composition containing a compound selected from N,N-dimethylacrylamide, N-vinylcaprolactam, acryloylmorpholine, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycerol (meth)acrylate, and alkylene glycol mono(meth)acrylate, and a radical polymerization initiator.
Furthermore, Patent Document 3 discloses an adhesive composition for temporary fixing, which contains a compound having two or more acrylic groups in the molecule, which has no urethane bond and has at least one bond selected from an ester bond and an ether bond in its main skeleton, at least one type selected from diethylacrylamide and dimethylacrylamide, water, and a photopolymerization initiator.

However, when hot water is used as a stripping medium, the compositions described in Patent Documents 1 and 2 require a very long stripping time, which is problematic and makes them impractical.
Furthermore, the composition described in Patent Document 3 has a short peel time, but has a low initial peel strength, and has problems such as peeling of the substrate during temporary fixing.

JP 2011-148842 A JP 2003-313510 A International Publication No. 2015/056632 Pamphlet

The inventors of the present invention have conducted extensive research to find a water-peelable curable composition that has such excellent adhesive strength to the substrate that it will not peel off even when the substrate (workpiece) is processed after adhesion, and the cured product can be easily peeled off in water after processing of the substrate.

Means for Solving the Problems The present inventors have discovered that, in order to solve the above problems, a composition containing a polyfunctional (meth)acrylate produced from a plant-derived alcohol and having both a hydroxyl group and an ether group in the molecule has high adhesive strength to a substrate (part to be processed) and therefore excellent processability, and further, the cured product thereof has excellent peelability when immersed in water after processing of the substrate, thereby completing the present invention.
The present invention will be described in detail below.

The composition of the present invention provides a cured product that has high adhesion to a substrate (a part to be processed) and therefore has excellent processability, and also has excellent peelability when immersed in water after processing of the substrate.
Therefore, the composition of the present invention can be preferably used in various applications requiring temporary fixation, and more preferably can be used as a water-strippable active energy ray-curable composition.

FIG. 1 is a side view for explaining the evaluation method in the examples.

The present invention relates to a water-peelable curable composition comprising component (A): a (meth)acrylate of an alkylene oxide adduct of an alditol (excluding glycerol), the cured product of which has peelability in water at 20 to 100°C.
In the following description, "alditol (excluding glycerol)" may be simply referred to as "alditol".
The component (A), the water-peelable curable composition, and applications will be described below.

1. Component (A) Component (A) is a (meth)acrylate of an alkylene oxide adduct of an alditol (excluding glycerol).
In the present invention, an alkylene oxide adduct of alditol (hereinafter referred to as "AZ-RO") is used as the raw material compound of component (A), provided that glycerol is not included as the alditol in the present invention.

1-1. AZ-RO
As the alditol which is the raw material compound of AZ-RO, various compounds can be used.
Specific examples of alditols include erythritol, threitol, ribitol, arabinitol, xylitol, allitol, sorbitol, mannitol, iditol, galactitol, and talitol, and it is preferable to use the D-form, which is easily available.
Among these compounds, erythritol, xylitol, sorbitol (D-glycitol), and mannitol are preferred because they are industrially easily available and the desired (meth)acrylates can be easily produced from them, and it is preferable to use the D-form, which is easily available.
These compounds are derived from plants and have a low environmental impact.
As the alditol, these compounds can be used alone or in combination of two or more kinds.
Of these compounds, sorbitol is preferred as the alditol.

Examples of the alkylene oxide unit in AZ-RO include ethylene oxide, propylene oxide, tetramethylene oxide, and mixed units of these alkylene oxides. Among these, ethylene oxide is preferred because the resulting (meth)acrylate has excellent curing properties.
Regarding the number of moles of alkylene oxide added in AZ-RO, a compound having a large number of moles added is preferred because it is generally easy to handle and can reduce inhibition of radical polymerization in the presence of oxygen.
The number of moles of alkylene oxide added in AZ-RO is preferably 1-20, and more preferably 2-15.
By making the number of moles of alkylene oxide added 1 or more, the compound dissolves only in hydrophilic solvents such as water and alcohol, and is difficult to dissolve in compounds having one (meth)acryloyl group in the transesterification reaction, or in organic solvents, thereby preventing the transesterification reaction from proceeding with difficulty, and when the obtained (meth)acrylate is used as a curable composition, it is possible to prevent a significant decrease in compatibility with other components. On the other hand, by making the number of moles of alkylene oxide added 20 or less, it is possible to provide a cured product with high heat resistance when the obtained (meth)acrylate is used as a curable composition.

The component (A) is produced by (meth)acrylating AZ-RO.
Examples of methods for producing the component (A) include a method in which AZ-RO is subjected to a transesterification reaction with a compound having one (meth)acryloyl group [hereinafter referred to as a "monofunctional (meth)acrylate"] in the presence of a transesterification catalyst, and a method in which AZ-RO is subjected to a dehydration esterification reaction with (meth)acrylic acid in the presence of an acid catalyst, and the transesterification reaction is preferred.

1-2. Preferred form of component (A) Component (A) is preferably a mixture of reaction products containing (meth)acrylates obtained by transesterification of AZ-RO and monofunctional (meth)acrylates. Component (A) is a mixture of (meth)acrylates and by-products having different numbers of (meth)acryloyl groups.

Examples of the alkylene oxide unit in the component (A) include ethylene oxide, propylene oxide, tetramethylene oxide, and mixed units of these alkylene oxides, with ethylene oxide being preferred in terms of excellent curability.
Regarding the number of moles of alkylene oxide added in the component (A), compounds having a large number of moles added are generally preferred because they are easier to handle and can reduce inhibition of radical polymerization in the presence of oxygen.
The number of moles of alkylene oxide added in the component (A) is preferably 1 to 20, and more preferably 2 to 15.
By making the number of moles of alkylene oxide added 1 or more, the compound dissolves only in hydrophilic solvents such as water and alcohol, and is difficult to dissolve in monofunctional (meth)acrylates and organic solvents in the transesterification reaction, which prevents the transesterification reaction from proceeding easily, and when the resulting (meth)acrylate is used as a curable composition, it is possible to prevent a significant decrease in compatibility with other components. On the other hand, by making the number of moles of alkylene oxide added 20 or less, it is possible to improve the heat resistance of the cured product when the resulting (meth)acrylate is used as a curable composition.

As the component (A), a hydrophilic compound is preferable, and a water-soluble compound is more preferable.
The hydrophilic or water-soluble (A) component makes the curable composition hydrophilic or water-soluble, and the resulting cured product is also hydrophilic or water-soluble. By utilizing this property, the curable composition containing the (A) component can be used for various applications, and the cured product is also hydrophilic or water-soluble and has excellent releasability from the processed part.
In the present invention, "hydrophilic" or "water-soluble" means that the solubility of component (A) in distilled water at a temperature of 22°C is 10% or more.
The solubility is defined by the following formula, and means that when distilled water and component (A) are mixed and allowed to stand, the mixture is in a homogeneous liquid state without turbidity or layer separation.
(A) Solubility (%) of component in distilled water
= parts by weight of distilled water / (parts by weight of distilled water + parts by weight of component (A)) x 100
In the present invention, component (A) having a (meth)acryloyl group is obtained by subjecting the hydroxyl group of AZ-RO, which is a raw material compound of component (A), to an ester exchange reaction. By suppressing the (meth)acrylate conversion rate of the hydroxyl group to less than 50% and leaving the hydroxyl group, component (A) can exhibit extremely high solubility in water.

Moreover, as component (A), a mixture having a hydroxyl value of 100 to 400 mgKOH/g is preferred, and a hydroxyl value of 150 to 300 mgKOH/g is more preferred. By making the hydroxyl value 100 mgKOH/g or more, the release properties of the composition containing component (A) can be improved, and by making the hydroxyl value 400 mgKOH/g or less, the photocurability of the composition can be improved.
In the present invention, the hydroxyl value means a value obtained by adding a mixture of acetic anhydride and pyridine to a sample, heating the sample in a warm bath at 92°C for 1 hour, adding a small amount of water and heating the sample in a warm bath at 92°C for 10 minutes, allowing the sample to cool, and then titrating the acid with an ethanol solution of potassium hydroxide using a phenolphthalein solution as an indicator.

The compound represented by the following general formula (5) is preferred as component (A).

[In formula (5), R ¹⁴ to R ¹⁶ each independently represent a divalent aliphatic hydrocarbon group having 2 to 4 carbon atoms, and when there are a plurality of R ¹⁴ to R ¹⁶ , they may be the same or different. X ¹ to X ³ each independently represent a hydrogen atom or a (meth)acryloyl group. a, b, and c each independently represent a positive number, and are not all 0 at the same time, satisfying 0<(a+nb+c)≦80. n represents an integer of 2 to 4.]

R ¹⁴ to R ¹⁶ are divalent aliphatic hydrocarbon groups having 2 to 4 carbon atoms. Examples of the aliphatic hydrocarbon groups include linear aliphatic hydrocarbon groups and branched aliphatic hydrocarbon groups.
Specific examples of the straight-chain aliphatic hydrocarbon group include an ethylene group, a 1,3-propylene group (a trimethylene group), and a 1,4-butylene group (a tetramethylene group).
Specific examples of branched aliphatic hydrocarbon groups include a 1,2-propylene group (isopropylene group) and a 1,1-dimethylethylene group (isobutylene group).
Of these functional groups, R ¹⁴ to R ¹⁶ are preferably ethylene groups.

In formula (5), n, which means the alditol skeleton structure, is an integer of 2 to 4.
a, b and c mean the number of moles of oxyalkylene units present in the hydroxyl group of the alditol, each of which is a positive number and which cannot all be 0 at the same time.
a+nb+c means the total number of moles of oxyalkylene units present in the alditol molecule (the average number of moles of alkylene oxide added relative to the total number of alditol molecules). a+nb+c satisfies the following formula.
0<(a+nb+c)≦80
The lower limit of a+nb+c is preferably 1 or more. It is more preferable that a+nb+c is 2≦(a+nb+c)≦10. By setting it in this range, synthesis is easy and it is advantageous in terms of economy, and the compatibility with other components is good, so that the degree of freedom in compounding design is high, and a composition with excellent curability can be obtained.

From the viewpoints of reactivity during the ester exchange reaction and the rapid curing of component (A), it is preferable that the (meth)acrylate is an acrylate.

1-3. Method for Producing Component (A) As a method for producing component (A), as described above, a method in which AZ-RO is subjected to a transesterification reaction with a monofunctional (meth)acrylate in the presence of a transesterification catalyst is preferred.
Furthermore, the method for producing the component (A) is preferably a method in which AZ-RO is subjected to a transesterification reaction with a monofunctional (meth)acrylate in the presence of catalysts X and Y described below.
Catalyst X: one or more compounds selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure, or a salt or complex thereof, an amidine, or a salt or complex thereof, a compound having a pyridine ring, or a salt or complex thereof, and a phosphine, or a salt or complex thereof.
Catalyst Y: A compound containing zinc.
A preferred method for producing the component (A) will now be described.

1-3-1. AZ-RO
AZ-RO is as described above in detail.

1-3-2. Monofunctional (meth)acrylate The monofunctional (meth)acrylate used as the raw material of component (A) is a compound having one (meth)acryloyl group in the molecule, and examples thereof include the compound represented by the following general formula (1).

In formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an organic group having 1 to 50 carbon atoms.

Preferred specific examples of ^R2 in the above general formula (1) include alkyl groups having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a 2-ethylhexyl group; alkoxyalkyl groups, such as a 2-methoxyethyl group, a 2-ethoxyethyl group, and a 2-methoxybutyl group; and dialkylamino groups, such as an N,N-dimethylaminoethyl group, an N,N-diethylaminoethyl group, an N,N-dimethylaminopropyl group, and an N,N-diethylaminopropyl group.
Specific examples of R ² in the above general formula (1) include the functional groups described in JP-A-2017-39916, JP-A-2017-39917, and WO 2017/033732, in addition to the above.

In the present invention, these monofunctional (meth)acrylates can be used alone or in any combination of two or more.
Among these monofunctional (meth)acrylates, alkyl (meth)acrylates having an alkyl group having 1 to 8 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate, alkoxyalkyl (meth)acrylates such as 2-methoxyethyl acrylate, or N,N-dimethylaminoethyl (meth)acrylate are preferred, and in particular, (meth)acrylates having an alkyl group having 1 to 4 carbon atoms, or alkoxyalkyl (meth)acrylates having an alkyl group having 1 to 2 carbon atoms, which show good reactivity with AZ-RO and are easily available, are preferred.
Furthermore, alkoxyalkyl (meth)acrylates having an alkyl group with 1 to 2 carbon atoms, which promote the dissolution of AZ-RO and exhibit extremely good reactivity, are more preferred, with 2-methoxyethyl (meth)acrylate being particularly preferred.
Furthermore, as the monofunctional (meth)acrylate, acrylate is particularly preferred due to its excellent reactivity.

The ratio of AZ-RO to the monofunctional (meth)acrylate used in the manufacturing method of component (A) is not particularly limited, but 0.4 to 10.0 moles of monofunctional (meth)acrylate per mole of hydroxyl groups in AZ-RO is preferred, and 0.6 to 5.0 moles is more preferred. By using 0.4 moles or more of monofunctional (meth)acrylate, side reactions can be suppressed. Furthermore, by using 10.0 moles or less, the amount of component (A) produced can be increased, improving productivity.

1-3-3. Catalyst In the method for producing the component (A), the following catalysts X and Y are used in combination as transesterification catalysts because they enable the production of (meth)acrylate in high yield.
Catalyst X: one or more compounds selected from the group consisting of cyclic tertiary amines having an azabicyclo structure or salts or complexes thereof (hereinafter referred to as "azabicyclo compounds"), amidines or salts or complexes thereof (hereinafter referred to as "amidine compounds"), compounds having a pyridine ring or salts or complexes thereof (hereinafter referred to as "pyridine compounds"), and phosphines or salts or complexes thereof (hereinafter referred to as "phosphine compounds").
Catalyst Y: A compound containing zinc.
The catalysts X and Y will be described below.

1-3-3-1. Catalyst X
The catalyst X in the process for producing the component (A) is one or more compounds selected from the group consisting of azabicyclo compounds, amidine compounds, pyridine compounds, and phosphine compounds.
As the catalyst X, among the above-mentioned compound groups, one or more compounds selected from the group consisting of azabicyclo compounds, amidine compounds, and pyridine compounds are preferred. These compounds have excellent catalytic activity and can preferably produce the component (A). In addition, they form a complex with the catalyst Y described below during and after the reaction, and the complex can be easily removed from the reaction solution after the reaction is completed by a simple method such as adsorption. In particular, the azacyclo compound can be more easily removed by filtration, adsorption, etc., since the complex with the catalyst Y is poorly soluble in the reaction solution.
On the other hand, although the phosphine-based compound has excellent catalytic activity, it is difficult to form a complex with the catalyst Y, or when a complex is formed, it is easily soluble in the reaction liquid, and most of the phosphine-based compound or complex remains dissolved in the reaction liquid after the reaction is completed, making it difficult to remove from the reaction liquid by a simple method such as filtration, adsorption, etc. For this reason, the phosphine-based catalyst remains in the final product, which may cause storage stability problems such as turbidity or precipitation of the catalyst during storage of the product, or thickening or gelation over time.

Specific examples of the azabicyclo-based compound include various compounds that satisfy the requirements of a cyclic tertiary amine having an azabicyclo structure, a salt of the amine, or a complex of the amine. Preferred compounds include quinuclidine, 3-hydroxyquinuclidine, 3-quinuclidinone, 1-azabicyclo[2.2.2]octane-3-carboxylic acid, and triethylenediamine (also known as 1,4-diazabicyclo[2.2.2]octane, hereinafter referred to as "DABCO").
Specific examples of the azabicyclo-based compound include those described in JP-A-2017-39916, JP-A-2017-39917, and WO 2017/033732, in addition to the above.

Specific examples of amidine compounds include imidazole, N-methylimidazole, N-ethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-vinylimidazole, 1-allylimidazole, 1,8-diazabicyclo[5.4.0]undec-7-ene (hereinafter referred to as "DBU"), 1,5-diazabicyclo[4.3.0]non-5-ene (hereinafter referred to as "DBN"), N-methylimidazole hydrochloride, DBU hydrochloride, DBN hydrochloride, N-methylimidazole acetate, DBU acetate, DBN acetate, N-methylimidazole acrylate, DBU acrylate, DBN acrylate, and phthalimide DBU.

Specific examples of pyridine compounds include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, and N,N-dimethyl-4-aminopyridine (hereinafter referred to as "DMAP").
Specific examples of the pyridine-based compound include those described in JP-A-2017-39916, JP-A-2017-39917, and WO 2017/033732, in addition to the above.

Examples of phosphine compounds include compounds having a structure represented by the following general formula (2):

[In formula (2), R ³ , R ⁴ and R ⁵ represent a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 24 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms. R ³ , R ⁴ and R ⁵ may be the same or different.]

Specific examples of the phosphine compounds include triphenylphosphine, tris(4-methoxyphenyl)phosphine, tri(p-tolyl)phosphine, tri(m-tolyl)phosphine, tris(4-methoxy-3,5-dimethylphenyl)phosphine, and tricyclohexylphosphine.
Specific examples of the phosphine-based compound include those described in JP-A-2017-39916, JP-A-2017-39917, and WO 2017/033732, in addition to the above.

In the present invention, these catalysts X can be used alone or in any combination of two or more. Among these catalysts X, quinuclidine, 3-quinuclidine, 3-hydroxyquinuclidine, DABCO, N-methylimidazole, DBU, DBN and DMAP are preferred, and 3-hydroxyquinuclidine, DABCO, N-methylimidazole, DBU and DMAP are particularly preferred because they exhibit good reactivity with most polyhydric alcohols and are easily available.

There are no particular restrictions on the proportion of catalyst X used in the manufacturing method of component (A), but it is preferable to use 0.0001 to 0.5 moles of catalyst X per mole of hydroxyl groups of AZ-RO, and more preferably 0.0005 to 0.2 moles. Using 0.0001 moles or more of catalyst X can increase the yield of the reaction product containing the target (meth)acrylate, while using 0.5 moles or less can suppress the production of by-products and coloring of the reaction solution, and simplify the purification process after completion of the reaction.

1-3-3-2. Catalyst Y
Catalyst Y is a compound containing zinc.
As the catalyst Y, various compounds containing zinc can be used, but organic acid zinc and zinc diketone enolate are preferred because of their excellent reactivity.
Examples of the organic zinc acid include zinc dibasic acids such as zinc oxalate and compounds represented by the following general formula (3).

[In formula (3), ^R6 and ^R7 represent a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 24 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms. ^R6 and ^R7 may be the same or different.]
The compound of formula (3) is preferably a compound in which ^R6 and ^R7 are linear or branched alkyl or alkenyl groups having 1 to 20 carbon atoms. In ^R6 and ^R7 , the linear or branched alkyl or alkenyl group having 1 to 20 carbon atoms is a functional group that does not have a halogen atom such as fluorine or chlorine, and a catalyst Y having such a functional group is preferred because it can produce a reaction product containing the target (meth)acrylate in high yield.

An example of a zinc diketone enolate is a compound represented by the following general formula (4):

[In formula (4), R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 24 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms. R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ may be the same or different.]

Specific examples of the zinc-containing compound represented by the above general formula (3) include zinc acetate, zinc acetate dihydrate, zinc propionate, zinc octoate, zinc neodecanoate, zinc laurate, zinc myristate, zinc stearate, zinc cyclohexanebutyrate, zinc 2-ethylhexanoate, zinc benzoate, zinc t-butylbenzoate, zinc salicylate, zinc naphthenate, zinc acrylate, and zinc methacrylate.
In addition, when these zinc-containing compounds have hydrates, solvates, or complexes with catalyst X, the hydrates, solvates, and complexes with catalyst X can also be used as catalyst Y in the production method for component (A).

Specific examples of the zinc-containing compound represented by the above general formula (4) include zinc acetylacetonate, zinc acetylacetonate hydrate, zinc bis(2,6-dimethyl-3,5-heptanedionato), zinc bis(2,2,6,6-tetramethyl-3,5-heptanedionato), and zinc bis(5,5-dimethyl-2,4-hexanedionato). In addition, when hydrates or solvates or complexes with catalyst X exist for these zinc-containing compounds, the hydrates and solvates and complexes with catalyst X can also be used as catalyst Y in the manufacturing method of component (A).

As the organic acid zinc and zinc diketone enolate in catalyst Y, the above-mentioned compounds can be used directly, but these compounds can also be generated in the reaction system and used.
For example, a zinc compound such as metallic zinc, zinc oxide, zinc hydroxide, zinc chloride, or zinc nitrate (hereinafter referred to as a "raw zinc compound") is used as a raw material, and in the case of an organic acid zinc compound, the raw zinc compound is reacted with an organic acid. In the case of a zinc diketone enolate, the raw zinc compound is reacted with a 1,3-diketone.

In the present invention, these catalysts Y can be used alone or in any combination of two or more. Among these catalysts Y, zinc acetate, zinc propionate, zinc acrylate, zinc methacrylate, and zinc acetylacetonate are preferred, and zinc acetate, zinc acrylate, and zinc acetylacetonate are particularly preferred because they exhibit good reactivity with most polyhydric alcohols and are easily available.

There are no particular restrictions on the proportion of catalyst Y used in the manufacturing method of component (A), but it is preferable to use 0.0001 to 0.5 moles of catalyst Y, and more preferably 0.0005 to 0.2 moles, per mole of total hydroxyl groups in AZ-RO. Using 0.0001 moles or more of catalyst Y can increase the yield of the reaction product containing the target (meth)acrylate, while using 0.5 moles or less can suppress the production of by-products and coloring of the reaction solution, and simplify the purification process after completion of the reaction.

1-3-4. Preferred Production Method of Component (A) Component (A) is produced by subjecting AZ-RO and a monofunctional (meth)acrylate to a transesterification reaction in the presence of the above-mentioned catalysts X and Y.
AZ-RO (meth)acrylate is a compound that is difficult to produce by conventional dehydration esterification or transesterification reactions. In contrast, the production method used in the present invention makes it possible to produce AZ-RO (meth)acrylate without any problems, and the resulting (meth)acrylate is almost free of coloration and has a low proportion of high molecular weight compounds.
While there are no particular limitations on the ratio of catalyst X to catalyst Y used in the production method of component (A), it is preferable to use 0.005 to 10.0 mol, and more preferably 0.05 to 5.0 mol, of catalyst X per 1 mol of catalyst Y. Using 0.005 mol or more can increase the yield of the target reaction product containing the (meth)acrylate, while using 10.0 mol or less can suppress the production of by-products and coloration of the reaction liquid, and can simplify the purification step after completion of the reaction.

As a combination of catalyst X and catalyst Y used in combination in the present invention, a combination in which catalyst X is an azabicyclo-based compound and catalyst Y is a compound represented by the general formula (3) is preferred, and further, a combination in which the azabicyclo-based compound is DABCO and the compound represented by the general formula (3) is zinc acetate and/or zinc acrylate is particularly preferred.
This combination not only gives a reaction product containing (meth)acrylate in good yield, but also has an excellent color tone (less yellowish) after the reaction is completed, so it can be suitably used for coating applications where colorless transparency is important. Furthermore, since the catalyst is relatively inexpensive, this is an economically advantageous production method.

Catalyst X and catalyst Y used in the present invention may be added from the beginning of the reaction or during the reaction. In addition, the desired amounts may be added all at once or in portions.

The reaction temperature in the manufacturing method of component (A) is preferably 40°C to 180°C, and more preferably 60°C to 160°C. By setting the reaction temperature at 40°C or higher, the reaction rate can be increased, and by setting the reaction temperature at 180°C or lower, thermal polymerization of (meth)acryloyl groups in the raw materials and products can be suppressed, coloration of the reaction liquid can be suppressed, and the purification process after completion of the reaction can be simplified.

The reaction pressure in the method for producing component (A) is not particularly limited as long as the specified reaction temperature can be maintained, and the reaction may be carried out under reduced pressure or under increased pressure. The reaction pressure is preferably 0.000001 to 10 MPa (absolute pressure).

In the method for producing the component (A), as the transesterification reaction proceeds, a monohydric alcohol derived from the monofunctional (meth)acrylate is produced as a by-product.
When a portion (for example, about 50 mol %) of the hydroxyl groups of AZ-RO is converted into (meth)acrylate, the monohydric alcohol is allowed to coexist in the reaction system to achieve an equilibrium state, the catalyst is removed by adsorption or deactivated, and then the monohydric alcohol and the raw material monofunctional (meth)acrylate are distilled off, whereby a product with a controlled acrylate ratio can be stably produced.
On the other hand, when the hydroxyl groups of AZ-RO are actively converted to (meth)acrylates, it is preferable to discharge the monohydric alcohol from the reaction system to further promote the progress of the transesterification reaction.

In the method for producing the component (A), the reaction can be carried out without using a solvent, but a solvent may be used if necessary.
Specific examples of the solvent include hydrocarbons such as n-hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, n-nonane, n-decane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, amylbenzene, diamylbenzene, triamylbenzene, dodecylbenzene, didodecylbenzene, amyltoluene, isopropyltoluene, decalin, and tetralin; diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, diethyl acetal, dihexyl acetal, t-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, trioxane, dioxane, anisole, diphenyl ether, ethers such as dimethyl cellosolve, diglyme, triglyme, and tetraglyme; crown ethers such as 18-crown-6; esters such as methyl benzoate and γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, and benzophenone; carbonate compounds such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, and 1,2-butylene carbonate; sulfones such as sulfolane; sulfoxides such as dimethyl sulfoxide; ureas or derivatives thereof; phosphine oxides such as tributylphosphine oxide, ionic liquids such as imidazolium salts, piperidinium salts, and pyridinium salts; silicone oil; and water.
Among these solvents, at least one solvent selected from the group consisting of hydrocarbons, ethers, carbonate compounds, and ionic liquids is preferred.
These solvents may be used alone or in any combination of two or more to be used as a mixed solvent.

In the method for producing component (A), an inert gas such as argon, helium, nitrogen, or carbon dioxide may be introduced into the system in order to maintain the color tone of the reaction solution in good condition, but an oxygen-containing gas may be introduced into the system in order to prevent polymerization of the (meth)acryloyl group. Specific examples of oxygen-containing gases include air, a mixed gas of oxygen and nitrogen, and a mixed gas of oxygen and helium. Methods for introducing oxygen-containing gas include dissolving it in the reaction solution or blowing it into the reaction solution (so-called bubbling).

In the method for producing the component (A), it is preferable to add a polymerization inhibitor to the reaction liquid for the purpose of preventing polymerization of the (meth)acryloyl group.
Specific examples of the polymerization inhibitor include organic polymerization inhibitors such as hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, 4-tert-butylcatechol, benzoquinone, phenothiazine, N-nitroso-N-phenylhydroxylamine ammonium, 2,2,6,6-tetramethylpiperidine-1-oxyl, and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl; inorganic polymerization inhibitors such as copper chloride, copper sulfate, and iron sulfate; and organic salt-based polymerization inhibitors such as copper dibutyldithiocarbamate and N-nitroso-N-phenylhydroxylamine aluminum salt.
The polymerization inhibitor may be added singly or in any combination of two or more kinds, and may be added from the beginning or during the process of the present invention. A desired amount may be added all at once or in portions. Alternatively, the polymerization inhibitor may be added continuously via a rectification column.
The proportion of the polymerization inhibitor added in the reaction solution is preferably 5 to 30,000 wtppm, more preferably 25 to 10,000 wtppm. By setting the proportion at 5 wtppm or more, the polymerization inhibitor effect can be fully exhibited, and by setting the proportion at 30,000 wtppm or less, coloring of the reaction solution can be suppressed, the purification step after the reaction can be simplified, and a decrease in the curing rate of the obtained component (A) can be prevented.

The reaction time in the manufacturing method of component (A) varies depending on the type and amount of catalyst used, reaction temperature, reaction pressure, etc., but is preferably 0.1 to 150 hours, and more preferably 0.5 to 80 hours.

The method for producing component (A) can be carried out by any of the following methods: batch, semi-batch, and continuous. In one example of the batch method, AZ-RO, monofunctional (meth)acrylate, catalyst, and polymerization inhibitor are charged into a reactor, and the reaction liquid is stirred at a predetermined temperature while oxygen-containing gas is bubbled into the reaction liquid. Thereafter, as the transesterification reaction progresses, the monohydric alcohol by-produced is extracted from the reactor at a predetermined pressure to produce the desired component (A).

The reaction product obtained by the production method of the component (A) is preferably subjected to a separation and purification procedure, since this allows the desired reaction product containing the (meth)acrylate to be obtained with high purity.
Examples of the separation and purification operations include adsorption, crystallization, filtration, distillation, and extraction, and it is preferable to combine these. Examples of the adsorption operation include adsorption of the catalyst by an adsorbent, and examples of the adsorbent include aluminum silicate. Examples of the crystallization operation include cooling crystallization and concentration crystallization. Examples of the filtration operation include pressure filtration, suction filtration, and centrifugal filtration. Examples of the distillation operation include single distillation, fractional distillation, molecular distillation, and steam distillation. Examples of the extraction operation include solid-liquid extraction and liquid-liquid extraction.
In the separation and purification operation, a solvent may be used, and further, a neutralizing agent for neutralizing the catalyst and/or polymerization inhibitor used in the present invention, an acid and/or an alkali for decomposing or removing by-products, activated carbon for improving color tone, diatomaceous earth for improving filtration efficiency and filtration rate, etc. may be used.

2. Water-Removable Curable Composition The present invention relates to a water-removable curable composition which contains the above-mentioned component (A) and which provides a cured product having releasability in water at 20 to 100°C.
In the present invention, the cured product has releasability in water at 20 to 100°C means that the composition is applied to a substrate, laminated with another substrate, cured, and immersed in water at 20 to 100°C, and the two substrates peel off within 60 minutes.

As the method for producing the composition, a production method including a step of producing component (A), which is a mixture of reaction products containing (meth)acrylate obtained by subjecting AZ-RO and a monofunctional (meth)acrylate to an ester exchange reaction in the presence of the catalysts X and Y, is preferred.
According to this production method, the component (A) can be obtained in a high yield, and therefore, it is excellent in cost and productivity. In addition, the component (A) obtained by this production method is preferable because it has a low viscosity and is easy to handle due to a small amount of side-reaction high molecular weight products, and further has excellent fast curing properties, adhesion of the cured product to a workpiece, and peelability when immersed in water.
This step may be carried out in accordance with the above-mentioned method for producing the component (A).
Furthermore, when other components described below are added, the component (A) and the other components may be mixed by stirring.

When mixing the components, they may be heated and stirred as necessary. The temperature when heating and stirring/mixing is preferably in the range of 40 to 90°C. However, when adding a thermal polymerization initiator (described below), it is preferable to carry out the process at 30°C or less to prevent polymerization during the production of the composition.

The viscosity of the composition may be appropriately set depending on the application and purpose of use.
The viscosity is preferably 5 to 30,000 mPa·s, and more preferably 10 to 25,000 mPa·s. If the viscosity is too high, it is difficult to obtain a cured product that is a thin film with excellent surface smoothness, so the viscosity may be adjusted to the desired level with an appropriate solvent.
In the present invention, the viscosity refers to a value measured at 25° C. using an E-type viscometer (cone-plate type viscometer).

The composition of the present invention can be used as either an active energy ray-curable composition or a heat-curable composition, but is preferably used as an active energy ray-curable composition.
The composition of the present invention can be used in any form, such as a solventless composition that does not contain an organic solvent, a solvent-based composition that contains an organic solvent, or an aqueous composition in which the component (A) is dissolved or dispersed in water. In the aqueous composition in which the component (A) is dispersed in water, a commonly used emulsifier or a reactive emulsifier described below can be used as the dispersant.

When the composition of the present invention uses the component (A) as a main component, the content of the component (A) in the composition is preferably 20 to 100% by weight, and more preferably 30 to 100% by weight, relative to 100% by weight of the total amount of the curable components, in order to provide excellent fast curing properties, adhesion to a workpiece, and releasability when immersed in water.
Incidentally, the "curable component" refers to a group of compounds having an ethylenically unsaturated group and means component (A). In the case where a compound having an ethylenically unsaturated group other than component (A) described below [component (D)] is blended, the curable component means both component (A) and component (D).

The composition of the present invention contains the above-mentioned component (A) as an essential component, but various other components can be blended depending on the purpose.
Specific preferred examples of the other components include a photopolymerization initiator (hereinafter referred to as "component (B)"), a thermal polymerization initiator (hereinafter referred to as "component (C)"), and a compound having an ethylenically unsaturated group other than the component (A) (hereinafter referred to as "component (D)").
These components will be described below.
As for the other components described later, the exemplified compounds may be used alone or in combination of two or more.

2-1. Component (B) When the composition of the present invention is used as an active energy ray-curable composition and further as an electron beam-curable composition, it is also possible to cure the composition by electron beam without containing component (B) (photopolymerization initiator).
When the composition of the present invention is used as an active energy ray-curable composition, particularly when ultraviolet light and visible light are used as the active energy rays, it is preferable for the composition to further contain a component (B) from the viewpoints of ease of curing and cost.
When the composition is used as an electron beam curable composition, it is not necessarily required to contain component (B), but a small amount of component (B) can be added as necessary to improve curability.

As the component (B) in the present invention, various known photopolymerization initiators can be used, and the component (B) is preferably a photoradical polymerization initiator.
Specific examples of the component (B) include acetophenone compounds such as 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, diethoxyacetophenone, oligo{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone}, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one;
Benzophenone compounds such as benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide;
α-ketoester compounds such as methylbenzoyl formate, 2-(2-oxo-2-phenylacetoxyethoxy)ethyl ester of oxyphenylacetic acid, and 2-(2-hydroxyethoxy)ethyl ester of oxyphenylacetic acid;
Phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide;
Benzoin-based compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; titanocene-based compounds; acetophenone/benzophenone hybrid photoinitiators such as 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfinyl)propan-1-one;
oxime ester photopolymerization initiators such as 2-(O-benzoyloxime)-1-[4-(phenylthio)]-1,2-octanedione; and camphorquinone.

Among these, acetophenone-based compounds, benzophenone-based compounds, and phosphine oxide-based compounds are preferred, and acetophenone-based compounds are particularly preferred because they can easily achieve good curing properties in air even when the cured product is applied in a thin film of a few μm or less.

The content of component (B) is preferably 0.01 to 10 parts by weight, more preferably 0.5 to 7 parts by weight, and particularly preferably 1 to 5 parts by weight, per 100 parts by weight of the total amount of the curable components. When it is in the above range, the composition has excellent curability, and the resulting cured product has excellent scratch resistance.

2-2. Component (C) Component (C) is a thermal polymerization initiator, and when the composition is used as a thermosetting composition, component (C) can be blended.
The composition of the present invention may also be cured by heating by blending a thermal polymerization initiator therein.
As the thermal polymerization initiator, various compounds can be used, and organic peroxides and azo-based initiators are preferred.

Specific examples of organic peroxides include 1,1-bis(t-butylperoxy)2-methylcyclohexane, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(4,4-di-butylperoxycyclohexyl)propane, 1,1 -Bis(t-butylperoxy)cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di(m-toluoylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate t, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butyl peroxyacetate, 2,2-bis(t-butylperoxy)butane, t-butyl peroxybenzoate, n-butyl-4,4-bis(t-butylperoxy)valerate, di-t-butylperoxyisophthalate, α,α'-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, Examples include t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, and t-butyl hydroperoxide.

Specific examples of azo compounds include 1,1'-azobis(cyclohexane-1-carbonitrile), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, azodi-t-octane, and azodi-t-butane.
These may be used alone or in combination of two or more. The organic peroxide may be combined with a reducing agent to cause a redox reaction.

The content of the component (C) is preferably 10 parts by weight or less per 100 parts by weight of the total amount of the curable components.
When the thermal polymerization initiator is used alone, it may be carried out according to a conventional method for normal radical thermal polymerization. In some cases, it may be used in combination with component (B) (photopolymerization initiator), and after photocuring, thermal curing may be carried out for the purpose of further improving the reaction rate.

2-3. Component (D) Component (D) is a compound having an ethylenically unsaturated group other than the component (A).
As the ethylenically unsaturated group of the component (D), a (meth)acryloyl group is preferred, and an acryloyl group is even more preferred, because this provides excellent curability of the composition.

Examples of the component (D) include a compound having one ethylenically unsaturated group (hereinafter referred to as a "monofunctional unsaturated compound") and a compound having two or more ethylenically unsaturated groups (hereinafter referred to as a "polyfunctional unsaturated compound").
The monofunctional unsaturated compound and the polyfunctional unsaturated compound will be described below.

2-3-1. Monofunctional unsaturated compounds Specific examples of monofunctional unsaturated compounds include compounds having a (meth)acryloyl group and compounds having a vinyl group.
Examples of the compound having a (meth)acryloyl group include
Compounds having a carboxyl group and an ethylenically unsaturated group, such as (meth)acrylic acid, a Michael addition type dimer of acrylic acid, and ω-carboxy-polycaprolactone mono(meth)acrylate;
(meth)acrylates having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl acrylate, and monohydroxyethyl phthalate (meth)acrylate;
Alkyl (meth)acrylates, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate;
Carbitol (meth)acrylates such as ethyl carbitol (meth)acrylate, butyl carbitol (meth)acrylate, and 2-ethylhexyl carbitol (meth)acrylate;
monofunctional (meth)acrylates having an aromatic group, such as benzyl (meth)acrylate, phenyl (meth)acrylate, (meth)acrylates of alkylene oxide adducts of phenol, (meth)acrylates of alkylene oxide adducts of alkylphenol, (meth)acrylates of alkylene oxide adducts of p-cumylphenol, orthophenylphenol (meth)acrylate, (meth)acrylates of alkylene oxide adducts of o-phenylphenol, and 2-hydroxy-3-phenoxypropyl (meth)acrylate;
Examples of the monofunctional (meth)acrylate having an alicyclic group include cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; and monofunctional (meth)acrylate having a heterocycle such as tetrahydrofurfuryl (meth)acrylate, N-(2-(meth)acryloxyethyl)hexahydrophthalimide, and N-(2-(meth)acryloxyethyl)tetrahydrophthalimide.

Examples of monofunctional (meth)acrylamides include N-alkyl(meth)acrylamides such as N,N-dimethyl(meth)acrylamide, (meth)acryloylmorpholine, N-methyl(meth)acrylamide, N-n-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-n-butyl(meth)acrylamide, N-sec-butyl(meth)acrylamide, N-t-butyl(meth)acrylamide, and N-n-hexyl(meth)acrylamide;
N-hydroxyalkyl(meth)acrylamides such as N-hydroxyethyl(meth)acrylamide; and N,N-dialkyl(meth)acrylamides such as N,N-dimethylaminoethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-di-n-propyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, N,N-di-n-butyl(meth)acrylamide and N,N-dihexyl(meth)acrylamide.

Examples of compounds containing vinyl groups include N-vinylpyrrolidone and N-vinylcaprolactam.

Among monofunctional unsaturated compounds, compounds having a homopolymer glass transition temperature of 70° C. or higher and which are water-soluble are preferred in terms of achieving both low viscosity, water strippability, and heat resistance.
Specific examples include acrylic acid (Tg = 103°C), methacrylic acid (Tg = 130°C), N-hydroxyethylacrylamide (Tg = 98°C), N,N-dimethylacrylamide (Tg = 119°C), acryloylmorpholine (Tg = 145°C), N-vinylpyrrolidone (Tg = 80°C), and N-vinylcaprolactam (Tg = 90°C).

2-3-2. Polyfunctional unsaturated compound As the polyfunctional unsaturated compound, a polyfunctional (meth)acrylate is preferable.
Specific examples of the bifunctional (meth)acrylate include polyethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, di(meth)acrylate of an alkylene oxide adduct of bisphenol A, di(meth)acrylate of an alkylene oxide adduct of bisphenol F, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, and nonanediol di(meth)acrylate.

Examples of the trifunctional or higher (meth)acrylate include various compounds having three or more (meth)acryloyl groups, such as polyol poly(meth)acrylates such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri- or tetra(meth)acrylate, ditrimethylolpropane tri- or tetra(meth)acrylate, diglycerin tri- or tetra(meth)acrylate, and dipentaerythritol tri-, tetra-, penta- or hexa(meth)acrylate; and tri(meth)acrylates of glycerin alkylene oxide adducts. acrylate, tri- or tetra(meth)acrylate of a pentaerythritol alkylene oxide adduct, tri- or tetra(meth)acrylate of a ditrimethylolpropane alkylene oxide adduct, tri- or tetra(meth)acrylate of a diglycerin alkylene oxide adduct, tri-, tetra-, penta- or hexa(meth)acrylate of a dipentaerythritol alkylene oxide adduct, poly(meth)acrylates of polyol alkylene oxide adducts such as tri(meth)acrylates of an alkylene oxide adduct of isocyanuric acid, and the like.
Examples of the alkylene oxide adduct include an ethylene oxide adduct, a propylene oxide adduct, and an ethylene oxide and propylene oxide adduct.

In addition, urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, etc. can also be used as multifunctional (meth)acrylate.

Urethane (meth)acrylates include those obtained by the reaction of a polyhydric alcohol, a polyisocyanate, and a hydroxyl-containing (meth)acrylate, and those obtained by the reaction of an organic polyisocyanate and a hydroxyl-containing (meth)acrylate compound without using a polyhydric alcohol (hereafter referred to as "urethane adduct").

Examples of polyhydric alcohols include polyether polyols such as polypropylene glycol and polytetramethylene glycol, polyester polyols obtained by reacting the polyhydric alcohols with the polybasic acids, caprolactone polyols obtained by reacting the polyhydric alcohols with the polybasic acids and ε-caprolactone, and polycarbonate polyols (e.g., polycarbonate polyols obtained by reacting 1,6-hexanediol with diphenyl carbonate).

Examples of organic polyisocyanates include diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate, and dicyclopentanyl diisocyanate;
and organic polyisocyanates having three or more isocyanate groups, such as hexamethylene diisocyanate trimer and isophorone diisocyanate trimer.

Examples of hydroxyl group-containing (meth)acrylates include hydroxyl group-containing mono(meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, hydroxyhexyl (meth)acrylate, and hydroxyoctyl (meth)acrylate, trimethylolpropane mono(meth)acrylate, and pentaerythritol mono(meth)acrylate;
and hydroxyl group-containing polyfunctional (meth)acrylates such as trimethylolpropane di(meth)acrylate, pentaerythritol di- or tri(meth)acrylate, ditrimethylolpropane di- or tri(meth)acrylate, and dipentaerythritol di-, tri-, tetra- or penta(meth)acrylate.

In the urethane adduct, examples of the organic polyisocyanate and the hydroxyl group-containing (meth)acrylate compound include the compounds described above.
In the urethane adduct, it is preferable to use a hydroxyl group-containing polyfunctional (meth)acrylate as the hydroxyl group-containing (meth)acrylate.
Among these, compounds having three or more (meth)acryloyl groups and one hydroxyl group are preferred in that the cured product has superior hardness and scratch resistance. Specific examples thereof include pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate.

Another preferred urethane adduct compound is a reaction product of an organic polyisocyanate having three or more isocyanate groups with a hydroxyl group-containing mono(meth)acrylate.
Examples of the hydroxyl group-containing mono(meth)acrylate include the same compounds as those mentioned above.
Examples of organic polyisocyanates having three or more isocyanate groups include the above-mentioned hexamethylene diisocyanate trimer and isophorone diisocyanate trimer.

The urethane (meth)acrylate used may be one produced by a conventional method.
For example, there can be mentioned a method in which an organic polyisocyanate and a polyol are heated and stirred in the presence of an addition catalyst such as dibutyltin dilaurate to cause an addition reaction to produce an isocyanate group-containing compound, and then a hydroxyl group-containing (meth)acrylate is further added to the compound, followed by heating and stirring to cause an addition reaction.
In the case of a urethane adduct, a method in which an organic polyisocyanate and a hydroxyl group-containing (meth)acrylate are heated and stirred in the presence of an addition catalyst to cause an addition reaction can be mentioned.

Other examples of urethane poly(meth)acrylates include compounds such as those described on pages 70-74 of the publication "UV/EB Curing Materials" [published by CMC Co., Ltd. in 1992].

As the polyfunctional (meth)acrylate, polyethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, pentaerythritol tri- or tetra(meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, and polyester (meth)acrylate are preferred from the viewpoint of achieving both water releasability and heat resistance.

Any of the compounds exemplified as component (D) can be used depending on the purpose.

The content of the component (D) may be appropriately set depending on the purpose.
When the (A) component is used as the main component, the (D) component is preferably contained in an amount of 80% by weight or less, more preferably 70% by weight or less, based on 100% by weight of the total curable components. The preferred lower limit is 20% by weight or more, based on 100% by weight of the total curable components.
By containing 20% by weight or more of the (D) component, it is possible to adjust the hardness of the cured product and its adhesion to various substrates, and by containing 80% by weight or less, it is possible to improve the releasability of the cured product.

In the present invention, these compounds having an ethylenically unsaturated group can be used alone or in any combination of two or more.

2-4. Other components other than those described above As other components other than those described above, known additives can be used. Examples include organic solvents, water, acidic substances, antioxidants, surface modifiers, hydrophilic polymers, fillers, silane coupling agents, acid generators, pigments, dyes, tackifiers, and polymerization inhibitors.
Among these other components, water, organic solvents, acidic substances, antioxidants, surface modifiers, hydrophilic polymers, and fillers will be described below.

<Water and organic solvents>
The composition of the present invention can be used without a solvent, but various organic solvents can be used for the purpose of adjusting the coating viscosity and film thickness.
Any organic solvent can be used, and specific examples thereof include aromatic compounds such as benzene, toluene, and xylene; ester compounds such as propylene glycol monomethyl ether acetate, ethyl acetate, and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ether compounds such as dibutyl ether; and N-methylpyrrolidone.
When the curable composition is mainly composed of component (A), water can be used instead of an organic solvent since the component (A) is compatible with water at any ratio. Also, when component (D) is water-soluble, it can be diluted with water.
Furthermore, in the present invention, it is preferable to add water in order to improve the releasability of the cured product.

The content of the organic solvent and/or water is preferably 0.01 to 200 parts by weight, more preferably 10 to 150 parts by weight, and even more preferably 20 to 100 parts by weight, per 100 parts by weight of the total amount of the curable components.

<Acidic Substances>
The composition of the present invention has excellent adhesion to substrates such as plastics, and the addition of an acidic substance can further improve the adhesion.
Examples of the acidic substance include a photoacid generator that generates an acid upon irradiation with active energy rays, an inorganic acid, and an organic acid. Examples of the inorganic acid include sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid. Examples of the organic acid include organic sulfonic acid compounds such as p-toluenesulfonic acid and methanesulfonic acid.
Among these, inorganic acids or organic acids are preferred, organic sulfonic acid compounds which are organic acids are more preferred, aromatic sulfonic acid compounds are further preferred, and p-toluenesulfonic acid is particularly preferred.
The content of the acidic substance is preferably 0.0001 to 5 parts by weight, more preferably 0.0001 to 1 part by weight, and even more preferably 0.0005 to 0.5 parts by weight, relative to 100 parts by weight of the total amount of the curable components. When the content of the acidic substance is within the above range, the cured product has excellent adhesion to the substrate, and problems such as corrosion of the substrate and decomposition of other components can be prevented.

<Antioxidants>
The composition of the present invention may further contain an antioxidant for the purpose of improving the heat resistance and weather resistance of the cured product.
Examples of the antioxidant used in the present invention include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.
Preferred examples of the phenol-based antioxidant include hindered phenols such as di-t-butylhydroxytoluene, etc. Commercially available antioxidants include AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, and AO-80 manufactured by Adeka Corporation.
Preferred examples of the phosphorus-based antioxidant include phosphines such as trialkylphosphine and triarylphosphine, trialkyl phosphites, triaryl phosphites, etc. Commercially available derivatives of these include Adeka STAB PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, and 3010, all of which are manufactured by Adeka Corporation.
Examples of the sulfur-based antioxidant include thioether-based compounds, and examples of commercially available products include AO-23, AO-412S, and AO-503A manufactured by Adeka Corporation.

The content of the antioxidant is preferably 0.01 to 5% by weight, and more preferably 0.1 to 1% by weight, based on 100% by weight of the total amount of the composition of the present invention. If the content of the antioxidant is within the above range, the composition has excellent stability, and also has good curing properties and adhesive strength.

<Surface Modifier>
A surface modifier may be added to the composition of the present invention for the purposes of improving the leveling properties during application and increasing the slipperiness of the cured product to improve scratch resistance.
Examples of the surface modifier include a surface conditioner, a surfactant other than those mentioned above, a leveling agent, an antifoaming agent, an agent for imparting smoothness, and an agent for imparting antifouling property. Any known surface modifier can be used.
Among them, silicone-based surface modifiers and fluorine-based surface modifiers are preferred.Specific examples include silicone-based polymers and oligomers having a silicone chain and a polyalkylene oxide chain, silicone-based polymers and oligomers having a silicone chain and a polyester chain, fluorine-based polymers and oligomers having a perfluoroalkyl group and a polyalkylene oxide chain, and fluorine-based polymers and oligomers having a perfluoroalkyl ether chain and a polyalkylene oxide chain.
For the purpose of improving the durability of the lubrication property, a surface modifier having an ethylenically unsaturated group, preferably a (meth)acryloyl group, in the molecule may be used.

The content of the surface modifier is preferably 0.01 to 1.0% by weight based on the total amount of the composition of the present invention (100% by weight). When the content of the surface modifier is within the above range, the cured product has excellent surface smoothness.

<Hydrophilic Polymer>
When the curable composition of the present invention is applied to a substrate, depending on the type of substrate and the coating method used, repelling or the like may occur in the coating film after the composition is applied to the substrate and dried, and the final cured product may have a poor appearance.
In this case, it is preferable to add a hydrophilic polymer to the curable composition in order to prevent cissing of the coating film.

The hydrophilic polymer includes a polymer having a hydrophilic group.
Examples of the hydrophilic group include an acidic group and a hydroxyl group, and the acidic group is preferred. Examples of the acidic group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group, and the carboxyl group or the sulfonic acid group is preferred, and the carboxyl group is more preferred.
As the hydrophilic polymer having an acidic group (hereinafter referred to as "acidic group-containing polymer"), a neutralized salt in which the acidic groups are partially or completely neutralized is preferable. The method for producing the neutralized salt of the acidic group-containing polymer includes a method for producing the neutralized salt using a neutralized salt as a raw material vinyl monomer, and a method for producing the acidic group-containing polymer by neutralizing the produced polymer.

As the hydrophilic polymer, a polymer having a vinyl monomer having a hydrophilic group as an essential constituent monomer unit is preferable. Examples of the vinyl monomer having a hydrophilic group include a vinyl monomer having an acidic group and a vinyl monomer having a hydroxyl group.

Examples of the vinyl monomer having an acidic group include an ethylenically unsaturated compound having a carboxyl group, an ethylenically unsaturated compound having a sulfonic acid group, and an ethylenically unsaturated compound having a phosphoric acid group.
Examples of ethylenically unsaturated compounds having a carboxyl group include (meth)acrylic acid, maleic acid, itaconic acid, crotonic acid, and salts of these compounds. Examples of ethylenically unsaturated compounds having a sulfonic acid group include acrylamido 2-methylpropanesulfonic acid, styrenesulfonic acid, and (meth)allylsulfonic acid. Examples of ethylenically unsaturated compounds having a phosphoric acid group include phosphoric acid group-containing (meth)acrylates such as esters of phosphoric acid and (meth)acrylic acid.
When the acidic group-containing polymer is a neutralized salt in which the acidic groups are partially or completely neutralized, it is preferable to use the neutralized salt as the vinyl monomer having an acidic group.
Examples of the alkali compound for forming a neutralized salt of a vinyl monomer having an acidic group include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; ammonia; and amine compounds such as triethylamine and triethanolamine.

Examples of vinyl monomers having a hydroxyl group include hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate.

The hydrophilic polymer may be a copolymer of a vinyl monomer other than the vinyl monomer having a hydrophilic group (hereinafter referred to as "other monomer").
Examples of other monomers include alkyl (meth)acrylates, alkylaminoalkyl (meth)acrylates, styrene, alkyl vinyl ethers, vinylidene chloride, (meth)acrylamide, N-vinylformamide, N-vinylacetamide, vinyl acetate, vinylpyrrolidone, (meth)acrylonitrile, and (meth)acryloylmorpholine.
Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, and decyl (meth)acrylate.
Examples of the dialkylaminoalkyl (meth)acrylate include dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate.

The weight average molecular weight (hereinafter referred to as "Mw") of the hydrophilic polymer is preferably from 5,000 to 100,000, and more preferably from 7,000 to 30,000.
In the present invention, the Mw of a polymer means a value determined by gel permeation chromatography (hereinafter referred to as "GPC") using standard polystyrene as a calibration curve. In the case of a hydrophilic polymer, it is a value measured before neutralizing an acidic group such as a carboxylic acid as an acid component. In addition, when an amine monomer is contained as another monomer, GPC measurement is not possible, so it means a value estimated from the GPC measurement result of a polymer polymerized under the same conditions such as polymerization temperature, initiator concentration, monomer concentration, and solvent concentration using a normal alkyl (meth)acrylate instead of these components.

As the hydrophilic polymer, those produced by using the above-mentioned monomers in accordance with a conventional polymerization method can be used.
For example, radical polymerization, living anionic polymerization, living radical polymerization, etc. may be mentioned.
Examples of the polymerization method include solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization.
When the above-mentioned low molecular weight polymer is produced by a normal polymerization method, it is usually necessary to use a large amount of a chain transfer agent and a polymerization initiator. When a polymer using a large amount of a chain transfer agent is used, the cured product is easily colored by irradiation with active energy rays, and when a polymer using a large amount of a polymerization initiator is used, the storage stability of the composition is easily reduced.
For this reason, a polymer produced by high temperature polymerization that does not require a large amount of a chain transfer agent or a polymerization initiator is preferred.
The temperature of the high-temperature polymerization is preferably from 160 to 350°C, and more preferably from 180 to 300°C.

The form of the hydrophilic polymer may be selected depending on the purpose, and examples thereof include a solution of the hydrophilic polymer, a dispersion of the hydrophilic polymer, and a powder.
Specific examples include an organic solvent solution of a hydrophilic polymer, an aqueous solution or aqueous dispersion of a hydrophilic polymer, a mixed solution or water dispersion of a hydrophilic polymer in an organic solvent and water, and a powder, etc. Among these, an aqueous solution or aqueous dispersion of a hydrophilic polymer, an organic solvent solution, and a mixed solution or water dispersion of a hydrophilic polymer in an organic solvent and water are preferred because of their excellent solubility in the composition.
The solid content of the hydrophilic polymer solution or dispersion is preferably 3 to 70% by weight.
The viscosity of the solution or dispersion of the hydrophilic polymer is preferably 5 to 20,000 mPa·s.

The content of the hydrophilic polymer is preferably 0.5 to 50 parts by weight, more preferably 2 to 30 parts by weight, based on the solid content in either the aqueous solution or the aqueous dispersion, relative to 100 parts by weight of the total amount of the composition.
By setting the content of the hydrophilic polymer to 0.5 parts by weight or more, it is possible to prevent cissing of the cured product and improve adhesion to various substrates, and to prevent deformation and warping of the substrate when the composition of the present invention is applied to a thin substrate such as a film and cured. By setting the content to 50 parts by weight or less, it is possible to prevent poor appearance such as cloudiness, streaks, and orange peel of the cured product.

<Filler>
When the composition of the present invention contains an organic solvent, if either the component (A) or the optionally blended component (D) has a low viscosity, the composition may be repelled from the substrate when the organic solvent evaporates in the drying step after spray coating or spin coating of the composition, which may result in a poor appearance of the coating film.
When the above-mentioned coating method is carried out using a composition containing an organic solvent, it is preferable to add a filler to the composition to increase its viscosity, which can prevent repellency after drying.
As the filler, either an inorganic filler or an organic filler can be used, with the organic filler being preferred.
Examples of inorganic fillers include inorganic compounds such as silica and alumina.
Examples of organic fillers include hydrophobic polymers such as polyurethanes, poly(meth)acrylates, polyamides, polyureas, nylons, polystyrenes, polyethylenes, and polypropylenes, with poly(meth)acrylates being preferred.
As the hydrophobic polymer, one with a high average molecular weight is preferred because it can reduce the number of parts added required for thickening and can prevent a decrease in the antistatic properties of the composition. However, it is preferred that the molecular weight is as high as possible within a range that does not impair compatibility with the composition, and the Mw is preferably 10,000 to 5,000,000, and more preferably 100,000 to 2,000,000.
The filler is preferably in the form of particles, and the average particle size is preferably from 1 to 15 μm, and more preferably from 4 to 12 μm.
The average particle size in the present invention means a value measured by a laser diffraction method at a wavelength of 680 nm.
Considering the effect on peelability, it is preferable that the viscosity can be increased with a smaller amount of filler added, and the content of the filler is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight, per 100 parts by weight of the total amount of the composition excluding the organic solvent.

3. Method of Use The composition of the present invention may be used in a conventional manner.
For example, the composition may be applied or injected onto a substrate to which the composition is to be applied by a conventional method, and then, if necessary, another substrate to which the composition is to be applied may be laminated thereto. The composition may then be cured by irradiating the substrate with active energy rays or by heating, and the substrate may then be processed and immersed in water to peel off the substrate.
Alternatively, two or more sheets of substrates may be used, the pre-laminated substrates may be immersed in the composition to allow the composition to penetrate into the gaps between the substrates, and the composition may be cured by irradiating with active energy rays or by heating. The substrates may then be processed and immersed in water to peel off the substrates.
The method of irradiating with active energy rays may be a general method known as a conventional curing method.
In addition, a method can also be employed in which the composition contains a component (B) (photopolymerization initiator) and a component (C) (thermal polymerization initiator), which are irradiated with active energy rays and then cured by heating to improve adhesion to the substrate.

A preferred method for using the composition of the present invention is a method for producing a processed material by sequentially carrying out the following steps 1 to 4.
Step 1: Coating or injecting the water-peelable curable composition onto a substrate;
Another substrate is laminated to the coated or injected surface of the substrate, or
Step 2: A step of immersing the composition between a plurality of substrates. Step 3: A step of processing at least one of the substrates containing the cured product of the composition. Step 4: A step of immersing the substrate containing the cured product of the composition obtained in step 3 in water at a temperature of 20 to 100°C and peeling off the substrate.

More preferably, in the above-mentioned production method, a substrate having a transmittance of 10% or more at 400 nm is used, a water-peelable curable composition containing the components (A) and (B) is used, and the composition is cured by irradiating with active energy rays.
That is, the present invention relates to a method for producing a processed material, in which at least one of the following base materials has a transmittance of 10% or more at 400 nm, and the following steps 1 to 4 are carried out in order.
Step 1: A water-peelable curable composition containing the components (A) and (B) and having releasability in water at 20 to 100° C. when cured is applied or injected onto a substrate;
Another substrate is laminated to the coated or injected surface of the substrate, or
Step 2: Immersing the composition between a plurality of substrates Step 3: Processing at least one of the substrates containing the cured product of the composition Step 4: Immersing the substrate containing the cured product of the composition obtained in step 3 in water at a temperature of 20 to 100°C and peeling off the substrate

3-1. Substrates Various materials can be used as substrates to which the composition of the present invention can be applied, including wood, inorganic materials, plastics, and paper.
Inorganic materials include glass, quartz, ceramics, metals, mortar, concrete, stone, etc. Metals include steel plates, metals such as aluminum and chromium, metal oxides such as zinc oxide (ZnO) and indium tin oxide (ITO), etc.
Specific examples of plastics include polyolefins such as polyethylene and polypropylene, ABS resins, polyvinyl alcohol, cellulose acetate resins such as triacetyl cellulose and diacetyl cellulose, acrylic resins, polyethylene terephthalate, polycarbonate, polyarylate, polyethersulfone, cyclic polyolefin resins having cyclic olefins as monomers such as norbornene, polyvinyl chloride, epoxy resins, and polyurethane resins.

When an active energy ray-curable composition is used as the composition of the present invention and two substrates are used, at least one of the substrates is preferably a substrate having transparency.
As the transmissive substrate, a substrate having a transmittance of 10% or more at 400 nm is preferable.
Examples of transparent substrates include glass, quartz, and plastic.

3-2. Step 1
Step 1 comprises applying or injecting the water-peelable curable composition onto a substrate;
Another substrate is laminated to the coated or injected surface of the substrate, or
This is a process in which the composition is immersed between a plurality of substrates.

The coating method for coating the composition of the present invention onto the substrate in step 1 may be appropriately selected depending on the purpose, and examples include coating methods using a bar coater, applicator, doctor blade, dip coater, roll coater, spin coater, flow coater, knife coater, comma coater, reverse roll coater, die coater, lip coater, spray coater, gravure coater, microgravure coater, dispenser, etc.

The thickness of the cured composition on the substrate may be set appropriately depending on the purpose. The thickness of the cured product may be selected depending on the substrate to be used and the application of the substrate having the cured product produced, but is preferably 1 to 100 μm, and more preferably 2 to 40 μm.

When the composition contains an organic solvent, it is preferable to apply or pour the composition onto a substrate, and then heat and dry the composition to evaporate the organic solvent.
The drying temperature is not particularly limited as long as it is a temperature below which the substrate to be applied does not cause problems such as deformation. A preferred heating temperature is 40 to 100° C. The drying time may be appropriately set depending on the substrate to be applied and the heating temperature, and is preferably 0.5 to 20 minutes.

In a method for using the composition of the present invention, two substrates are used, the composition is applied or injected into the substrate, and another substrate is laminated to the surface of the substrate to which the composition has been applied or injected.
The substrates 2 may be made of the same material or different materials.
When an active energy ray-curable composition is used as the composition of the present invention, as described above, at least one of the substrates is preferably a substrate having transparency.
As the transmissive substrate, a substrate having a transmittance of 10% or more at 400 nm is preferable.
Examples of the transparent substrate include the same materials as those mentioned above.

It is also possible to use two or more substrates and immerse the composition between the substrates.

3-3. Step 2
Step 2 is a step of curing the composition after application or injection.
When an active energy ray-curable composition is used as the composition of the present invention, the composition is cured by irradiating it with active energy rays.
Examples of the active energy ray include an electron beam, ultraviolet light, and visible light, with ultraviolet light or visible light being preferred, and ultraviolet light being particularly preferred. Examples of the ultraviolet ray irradiation device include a high-pressure mercury lamp, a metal halide lamp, an ultraviolet (UV) electrodeless lamp, a light-emitting diode (LED), and the like.
The irradiation energy should be appropriately set depending on the type of active energy rays and the formulation. For example, when a high-pressure mercury lamp is used, the irradiation energy in the UV-A region is preferably 50 to 8,000 mJ/ ^cm2 , and more preferably 100 to 3,000 mJ/ ^cm2 .

When a thermosetting composition is used as the composition of the present invention, the composition is cured by heating.
As a heating method, the material including the substrate and the coating film can be placed in a heatable dryer or the like to harden the material.
The heating temperature may be appropriately set depending on the substrate used and the purpose, and is preferably 40 to 180° C. If the substrate is plastic, the substrate may be deformed if the temperature is too high, so the heating temperature is preferably 120° C. or lower.
The heating time may be appropriately set depending on the substrate and heating temperature to be applied, and is preferably 0.5 to 60 minutes.

3-4. Step 3
This is a step of processing at least one of the substrates containing a cured product obtained by irradiating with active energy rays or by heating. The processing of the substrate is performed according to the purpose, and the specific processing method is as described later in detail.

3-5. Step 4
Step 4 is a step of immersing the substrate containing the cured product of the composition obtained in step 3 in water at a temperature of 20 to 100° C., and peeling off the substrate.
In order to improve the peelability, a hydrophilic organic solvent may be added to the water.
Examples of the hydrophilic organic solvent include alcohol compounds such as methanol, ethanol, isopropanol, and butanol; and alkylene glycol monoether compounds such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether.
When peeling is performed in water, the water can be heated at room temperature, but it is preferable to heat the water. The heating temperature may be appropriately set depending on the type of component (A) used, the type of substrate, and the purpose, and is preferably 20 to 100°C, more preferably 20 to 90°C.

4. Applications The water-peelable curable composition of the present invention can be used for a variety of applications.
In particular, the composition of the present invention can be used in a variety of applications utilizing the property that the cured product can be easily decomposed by water.
Specific examples of the composition include a temporary fixing adhesive composition, a coating composition, and a molding composition.
These uses will be explained below.

4-1. Temporary fixing adhesive composition Applications to which the temporary fixing adhesive composition (hereinafter referred to as "temporary fixing adhesive" or simply "adhesive") can be applied include temporary fixing in the manufacture of various electronic materials such as semiconductor wafers, optical materials, quartz crystal oscillators, building materials, and wood.

The substrate to be bonded by the adhesive of the present invention is not particularly limited, and may be an inorganic compound, an organic compound, or an inorganic-organic composite, and may be made of the same material or different materials. Specific examples are as described above.
Furthermore, the adhesive of the present invention is capable of adhering solid substrates of any shape.

As a method for producing various products using the temporary fixing adhesive of the present invention, there can be mentioned a method for producing a processed material by carrying out the following steps 1-1 to 1-4 in order.

Step 1-1 (adhesive layer forming step): An adhesive is applied or injected onto a substrate, and another substrate is bonded to the adhesive-applied or injected surface of the substrate, or
An adhesive is immersed between the substrates,
Step of forming an adhesive layer Step 1-2 (temporary adhesion step): A step of temporarily adhering the multiple substrates to each other by curing the adhesive layer formed between the multiple substrates after coating or injection Step 1-3 (processing step): A step of processing at least one of the substrates containing the cured product of the adhesive Step 1-4 (separation step): A step of immersing the substrate containing the cured product of the adhesive obtained in step 1-3 in water at a temperature of 20 to 100°C to peel and separate the multiple substrates from each other

Step 1-1 (adhesive layer forming step) is a step of forming an adhesive layer made of the adhesive of the present invention on at least one of a plurality of substrates or between a plurality of substrates.
The substrate is not particularly limited as long as it is not altered by the adhesive, preferably by water at room temperature to lukewarm water, and examples of the substrate include metals, ceramics, and plastics.

In step 1-1, for example, an adhesive is applied to the bonding surface of one or more substrates to be fixed, and another substrate is placed on the applied portion, and this process is repeated.
As a means for application, a dispenser, a coater, a roll, a brush, a spatula, a spray, a coating jig, or the like may be used depending on the shape of the substrate.
Alternatively, two or more substrates may be used, the substrates being pre-laminated, and the substrates are immersed in the adhesive to allow the adhesive to permeate into gaps between the substrates.

Step 1-2 (temporary bonding step) is a step of curing the adhesive applied between the plurality of base materials to form a cured product, and temporarily bonding the plurality of base materials together with the cured product.
The adhesive of the present invention is cured by heating or by irradiation with active energy rays.
The curing method may be the same as that described above.

Step 1-3 (processing step) is a step of processing the temporarily bonded substrate into a desired shape between step 1-2 (temporary bonding step) and step 1-4 (separation step).
Examples of processing include methods in which the substrate is cut, ground, polished, and/or etched to form a desired shape.

Step 1-4 (separation step) is a step in which the cured product is brought into contact with water to disintegrate it, and the multiple base materials are separated from each other.
In the separation step, the method of contacting the cured product with water includes immersing the substrate in water, exposing it to running water, spraying water on the substrate, etc. The treatment time varies depending on the water contact method and heating temperature, but is preferably in the range of, for example, 10 seconds to 3 minutes.
When the substrate is brought into contact with water at room temperature to lukewarm water, it is also preferable to promote separation by applying a mechanical external force to the substrate or irradiating it with ultrasonic waves.

4-2. Composition for Coating Agent When the composition of the present invention is used as a composition for coating agent (hereinafter referred to as "coating agent"), the cured product formed can be easily removed with water.
Therefore, even if a cured product is formed in an unwanted area, it can be easily peeled off or removed by contacting it with water.

Examples of the method for producing various products using the coating agent of the present invention include a method for producing processed materials by sequentially carrying out the following steps 2-1 to 2-4.

Step 2-1: A step of applying or injecting a coating agent onto a substrate. Step 2-2: A step of curing the coating agent after application or injection. Step 2-3: A step of processing the substrate containing the cured product of the coating agent. Step 2-4: A step of immersing the substrate containing the cured product of the coating agent obtained in step 2-3 in water at a temperature of 20 to 100°C and peeling off the substrate.

The substrate on which the cured product is formed using the coating agent of the present invention is not particularly limited. Examples of the substrate include glass, ceramics, concrete, metal, resin, wood, paper, fabric, leather, etc., and also include living organisms such as nails and skin.
The substrate may have a smooth surface or may have irregularities, voids, etc. The cured product formed using the coating agent of the present invention can be removed with water, so it can be suitably used for substrates having irregularities, voids, etc. on the surface. In addition, since it can be removed without using an organic solvent, it can be suitably used for substrates that are easily denatured by contact with an organic solvent.

Step 2-1 is a step of applying or injecting a coating agent onto a substrate.
Methods for applying or injecting the coating agent onto a substrate include, for example, immersion, dropping, transfer, brushing, screen printing, spin coating, spraying, doctor blade method, roll coater method, and inkjet printing.

In step 2-1, the thickness of the cured product formed using the coating agent is not particularly limited, and can be set taking into consideration the time it takes for the cured product to be formed and the time required to remove the cured product. For example, it may be within the range of 1 μm to 1 mm.

In step 2-2, the method for hardening the coating agent after application or injection can be the same as that described above.

Examples of the method for processing the substrate containing the cured product of the coating agent in step 2-3 include the following.
The coating agent of the present invention can be used for various purposes such as protecting, sealing, and coloring the surface of a substrate.
The coating agent of the present invention can also be suitably used for masking the surface of a substrate (protecting areas where a cured product is not desired to be formed). For example, the coating agent of the present invention can be suitably used in a method in which a first cured product (a masking cured product) is formed on a predetermined area of the surface of a substrate, and then a second cured product is formed on an area including an area where the first cured product is not formed using another coating agent (e.g., a water-insoluble coating agent), and the first cured product is removed with water.

In step 2-4, the substrate containing the cured product of the coating agent obtained in step 2-3 is immersed in water at a temperature of 20 to 100° C., and the substrate is peeled off.
The method for removing the cured product formed by using the coating agent of the present invention is not particularly limited. For example, the method includes wiping the cured product with a cloth soaked in water, immersing the cured product in water, washing the cured product with running water, spraying water on the cured product, etc.
The water used to remove the cured product may contain a solvent, a surfactant, etc., if necessary.

<Masking method>
The coating agent of the present invention may be used for the purpose of masking the surface of a substrate.
For example, a method for producing a processed material by masking includes the steps of applying or injecting the coating agent of the present invention onto the surface of a substrate and curing the composition to form a first cured film (cured film for masking);
forming a second cured film on an area including a portion where the first cured film is not formed, using a coating agent different from the coating agent of the present invention;
and removing the first cured film with water, in that order.

According to the method for producing a processed material using the masking method, for example, a coating agent for forming a second cured film is applied to the entire surface of a substrate on which a first cured film has been formed, and then the first cured film is removed with water.
At this time, the second cured film formed on the first cured film is also removed, but the second cured film formed in the area where the first cured film is not formed remains without being removed, so that the second cured film can be formed only in the area where the first cured film is not formed.

4-3. Modeling composition The modeling composition of the present invention can be preferably used for producing a three-dimensional object.
A method for producing a three-dimensional object using the modeling composition of the present invention includes hardening a model material to form a modeled object, hardening a supporting material to form a support part that supports at least a part of the modeled object, and removing the support part after the modeled object is formed.
In this case, it is preferable that at least one of the model material and the supporting material is the above-mentioned modeling composition of the present invention and is used as the supporting material.

In the method for producing a three-dimensional object of the present invention, specifically, a model is formed by the following method. However, the method is not limited to the following method, and any well-known three-dimensional modeling method such as an inkjet method that ejects droplets of the model material and the supporting material can be applied, except that the modeling composition of the present invention is applied to at least one of the model material and the supporting material.

First, a model material is applied onto a modeling table to form a layer of the model material, and then the layer of the model material is hardened to form a layer that will become a part of the modeled object.
On the other hand, if necessary, a supporting material is applied onto the modeling table to form a layer of the supporting material adjacent to the layer of the model material, and the layer of the supporting material is hardened to form a layer that will become a part of the support portion.
Here, when the upper object has a portion where the width is greater than the width of the lower object (an overhanging portion), the support portion is formed so as to support this overhanging portion from below.
This forms a first layer that is made up of a layer that will become a part of the shaped object and, if necessary, a layer that will become a part of the support portion.

Next, a second layer is formed on the first layer in the same manner as the first layer, the second layer being made up of a layer that will become part of the object and, if necessary, a layer that will become part of the support portion.

Next, the operation of forming the first layer and the second layer is repeated n times until the nth layer is formed. This forms a molded object and a support portion that supports at least a portion of the molded object.

When the modeling composition of the present invention is used as a support material, the support portion is then removed from the model, thereby obtaining a model.
In the support portion removing step, the method for bringing the shaped object into contact with water may be the same as that in step 1-4 (separation step) in 4-1 above.
The water used to remove the support portion may contain an organic solvent, a surfactant, etc., if necessary.

In addition, when the modeling composition of the present invention is used as a model material, when the modeled object is no longer needed, it can be removed in the same manner as the support portion is removed.

Examples of the three-dimensional object produced by the method for producing a three-dimensional object of the present invention include:
Examples of such objects include: 1) sheets with a rough pattern on the surface; 2) miniatures of large buildings; 3) statues of Buddha, people, animals, and imaginary creations; and 4) geometric structures used in teaching materials, educational toys, etc.

The composition for molding of the present invention can also be used in methods for producing objects other than those mentioned above.
For example, there is a method for forming a molded object in which a model material is poured into a mold, hardened, and then the hardened material is removed from the mold to form a molded object.
In this case, the above-mentioned molding composition of the present invention is used as a mold.
Examples of the object produced by the method for producing a structure of the present invention include the same objects as the examples of the three-dimensional objects described above.

The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.
In the following description, unless otherwise specified, "parts" means parts by weight and "%" means % by weight.
The abbreviations in the examples have the following meanings.
MCA: 2-methoxyethyl acrylate MEL: 2-methoxyethanol DABCO: triethylenediamine MEHQ: hydroquinone monomethyl ether TEMPOL: 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl DEHA: N,N-diethylhydroxylamine

1. Production of component (A)
1) Production Example 1 [Production of 38 mol % acrylate of sorbitol 6 mol ethylene oxide adduct (hydroxyl value 734)]
A 3-liter flask equipped with a stirrer, a thermometer, a gas inlet tube, a rectification column, and a cooling tube was charged with 200 g (2.6 moles as hydroxyl groups) of an ethylene oxide adduct of sorbitol (manufactured by Aoki Oil Industries Co., Ltd., hydroxyl value 734 mg KOH/g (13.1 meq/g), average ethylene oxide addition number 6.28, peroxide concentration 0.7 wtppm), 613 g (4.7 moles) of MCA, 0.88 g (0.0078 moles) of DABCO as catalyst X, and 3.26 g (0.0157 moles) of zinc acrylate as catalyst Y, 0.25 g of MEHQ, and 0.05 g of TEMPOL, and the flask was heated and stirred at an internal temperature of 125° C. to 130° C. for 10 hours while bubbling an oxygen-containing gas (oxygen 5% by volume, nitrogen 95% by volume) into the liquid to carry out an ester exchange reaction. During this period, MCA containing MEHQ and TEMPOL was added at any time to the reaction liquid via the rectification column.

The rate of acrylate of hydroxyl groups by the transesterification reaction was determined from the amount of MEL produced by liquid chromatography (hereinafter referred to as "LC") and was found to be 37 mol %.
The quantification of MEL was carried out by the internal standard method using a high performance liquid chromatograph equipped with a differential refractive index detector (column: Atlantis (Part No. 186003748, column inner diameter 4.6 mm, column length 250 mm), solvent: pure water or 10% by volume aqueous isopropanol solution).
Acrylation rate (mol %)=number of moles of MEL produced as a by-product with the progress of ester exchange reaction/(number of moles of alcohol used as raw material×number of alcoholic hydroxyl groups in the alcohol molecule used as raw material)×100

The reaction solution was cooled to room temperature, and then pressure filtered to separate the solid matter. 31 g of aluminum silicate (Kyowa Chemical Industry Co., Ltd., Kyoward 700SEN-S (trade name), hereinafter referred to as "K700") was added to the filtrate and stirred at an internal temperature of 95°C to 100°C for 1 hour to adsorb the catalyst dissolved in the filtrate. Thereafter, the reaction solution was cooled to an internal temperature of 40°C or less, 3.2 g of calcium hydroxide was added, and the mixture was further stirred at room temperature for 3 hours, after which the solid matter was separated by pressure filtration.
The obtained filtrate was placed in a flask equipped with a stirrer, a thermometer, a gas inlet tube, a distillation cooling tube, and a pressure reducing tube, and stirred for 13 hours at an internal temperature of 90 to 100° C. and a pressure of 0.01 to 200 mmHg while bubbling dry air into the flask, thereby distilling off unreacted MCA and the by-product MEL.
The liquid in the flask was cooled to room temperature, 0.076 parts (0.0008 moles) of DEHA was added, and the mixture was stirred for 1 hour at normal pressure and at an internal temperature of 75°C to 85°C. Then, pressure filtration was performed to obtain 239 g of a filtrate. The acrylate mixture obtained in Production Example 1 is hereinafter referred to as Sb-EOA-1.

As a result of ESI-MS analysis of Sb-EOA-1, it was confirmed that the main component was an acrylate of an ethylene oxide adduct of sorbitol.
The amount of MCA remaining in Sb-EOA-1 was measured by gas chromatography (hereinafter referred to as "GC") to be 200 ppm or less, and no odor was detected at all.
The viscosity, solubility in water, hydroxyl value, APHA, Mw, and saponification value of Sb-EOA-1 were measured according to the methods described below. The results are shown below.
Viscosity (25°C): 10.93 Pa·s, solubility in water: 75% or more, hydroxyl value: 276 mg KOH/g, APHA: 92, Mw: 1,206, saponification value: 222 mg KOH/g, number of added acryloyl groups q: 2.3, acrylate ratio: 38 mol%
The number q of added acryloyl groups was calculated according to the method described in JP-A-4-136041.

*Conditions for measuring peroxide concentration : Isopropyl alcohol, glacial acetic acid, and an aqueous solution of potassium iodide were added to an alkylene oxide adduct of sorbitol, and the mixture was heated in a water bath at 85°C for 3 minutes to generate iodine. The treated solution was then removed from the water bath, and the iodine was titrated with sodium thiosulfate before the temperature of the treated solution dropped below 40°C. The active oxygen concentration was calculated from the titration amount, and this was taken as the peroxide concentration.

◆Gas chromatographic measurement conditions and equipment: Shimadzu Corporation GC-17A
Detector: FID detector Carrier gas: Helium Column: Inert Cap (film thickness 0.5 μm, 0.32 mm ID x 60 m)
Injection temperature: 200°C
・FID temperature: 250℃
Column temperature: After maintaining at 120° C. for 5 minutes, the temperature was increased to 240° C. at a rate of 10° C./min, and then maintained for 25 minutes.
Injection volume: 0.2 μL
The content of MEL was determined in weight percent by the internal standard method.

◆ESI-MS measurement conditions・Measurement method: Flow injection method ・Sample pretreatment: Prepare 500 μg/mL solution with acetonitrile ・Apparatus: Quattro Premier (Waters) + AcQuity UPLC (Waters)
Injection volume: 2 μL
・Eluent flow rate: 0.3mL/min
Eluent composition: 10 mM acetic acid NH4 / acetonitrile = 50 / 50 (solution ratio, 0 min → 1 min)
Capillary voltage: 3.0 kV
Cone voltage: 10V
Source temperature: 120°C
Desolvation temperature: 400°C
Desolvation gas volume: 800 L / h
Cone gas volume: 50L/h
Mass analysis range: m/z = 180 to 1200 (SCAN mode)
Ionization mode: ESI+

Viscosity measurement conditions: The viscosity was measured at 25° C. using an E-type viscometer.

Measurement of solubility : At a temperature of 22°C, the obtained component (A) and distilled water were placed in a screw tube in mixing ratios of 5%, 10%, 15%, 20%, 25%, 50% and 75%, and mixed for 2 hours using a mix rotor. After being allowed to stand for 24 hours, the mixture was carefully observed with the naked eye to check for turbidity or layer separation, and for uniformity.
The mixing ratio (%) is defined by the following formula, and the mixing ratio (%) at which no turbidity or layer separation was observed after standing for 24 hours and a homogeneous liquid was maintained was regarded as the solubility (%).

Mixing ratio (%)=(parts by weight of distilled water)/(parts by weight of distilled water+parts by weight of component (A))×100

* Conditions for measuring hydroxyl value: Add a mixture of acetic anhydride and pyridine to the sample and heat it in a hot bath at 92°C for 1 hour. Then add a small amount of water and heat it in a hot bath at 92°C for 10 minutes. After cooling, the acid was titrated with an ethanol solution of potassium hydroxide using a phenolphthalein solution as an indicator to determine the hydroxyl value.

◆APHA
The APHA was measured using a color difference meter (Petroleum Product Color Tester OME-2000, manufactured by Nippon Denshoku Industries Co., Ltd.).

GPC measurement conditions and equipment: Waters Corporation GPC system name 1515 2414 717P RI
Detector: RI detector Column: Guard column: Showa Denko Co., Ltd., Shodex KFG (8 μm, 4.6 × 10 mm), main column: Waters Co., Ltd., styragel HR 4E THF (7.8 × 300 mm) + styragel HR 1THF (7.8 × 300 mm)
Column temperature: 40°C
Eluent composition: THF (containing 0.03% sulfur as an internal standard), flow rate 0.75 mL/min. Calibration curve: A calibration curve was created using standard polystyrene.
The detected peaks having molecular weights of 400 or more were not divided but were regarded as one peak to calculate Mw.

2. Examples 1 to 3 and Comparative Examples 1 to 5 (Active Energy Ray-Curable Compositions)
1) Preparation of the composition
The component (A) obtained in Production Example 1 and the components indicated by the abbreviations below were used and mixed with stirring at 40° C. in the proportions shown in Table 1 to obtain compositions.
Component (A)
Sb-EOA: acrylate obtained in Production Example 1
Component (D)
M-8060: Polyester acrylate (manufactured by Toagosei Co., Ltd., product name: Aronix M-8060)
PEG-DA: polyethylene glycol (average number of moles added: 9) diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name: Light Acrylate 9EG-A)
DMAA: N,N'-dimethylacrylamide (KJ Chemicals Co., Ltd.)
DEAA: N,N'-diethylacrylamide (KJ Chemicals Co., Ltd.)
HEMA: 2-hydroxymethyl acrylate (manufactured by Mitsubishi Gas Chemical Co., Ltd.)
IBXA: Isobornyl acrylate (manufactured by Osaka Organic Chemical Co., Ltd.)
Component (B)
Om184: 1-hydroxycyclohexyl-phenyl ketone (Omnirad 184D, manufactured by IGM Resins)
Other Ingredients
SE-030T: organic fine particles (manufactured by Negami Chemical Industries, Ltd., product name: Artbar SE-030T)

2) Evaluation of the composition (manufacturing method of processed materials)
The evaluation method will be explained based on Figure 1. Figure 1 shows a side view of the evaluation method.
(a1) and (a2) in FIG. 1 represent a white glass slide having a size of 76 mm length × 26 mm width (manufactured by Matsunami Glass Industry Co., Ltd., product name: S-1112), (b1) and (b2) in FIG. 1 represent an untreated cycloolefin polymer having a film thickness of 100 μm cut to a size of 5 mm length × 26 mm width (Zeonor ZF-14, manufactured by Zeon Corporation; hereinafter referred to as "Zeonor"), and (c) in FIG. 1 represents the composition obtained above.
A Zeonor (Fig. 1 (b1)) was placed on the edge of a white glass slide (Fig. 1 (a1)), and another Zeonor (Fig. 1 (b2)) was placed perpendicular to the longitudinal direction, with a gap of 25 mm between them (Fig. 1 (1)).

(1) Step 1
One drop of the obtained compositions of Examples 1 to 3 and Comparative Examples 1 to 5 [Fig. 1: (c)] was placed between two sheets of ZEONOR. Another sheet of white glass slide [Fig. 1: (a2)] was attached so that the lap length (length of adhesive surface) was approximately 25 mm. The part with the ZEONOR film was fixed with a clip and any excess composition was wiped off. This is called the test specimen [Fig. 1: (2)].
Also, an experiment was carried out using an acrylic plate (manufactured by Mitsubishi Chemical Corporation, trade name: Acrylite L#001) instead of the white slide glass.
The transmittance at 400 nm of the white slide glass and the acrylic plate was 91% and 92%, respectively.

(2) Step 2
The test specimen was used and irradiated with ultraviolet light from the (a2) side using a high pressure mercury lamp equipped with a conveyor (H06-L41 manufactured by Eye Graphics Co., Ltd.) under conditions of a UV-A lamp output illuminance of 60 W/cm, an irradiation intensity per pass of 200 mW/ ^cm2 , and an irradiation energy of 500 mJ/ ^cm2 , with the test specimen passed four times to cure the composition.

3) Evaluation method
(1) Adhesive strength : The cured product obtained above was used to measure the tensile shear strength in accordance with JIS K6850:1999 using a tensile tester (room temperature, tensile speed = 10 mm/min).

(2) Hot water peeling [Step 4]
The cured product obtained above was used to test the peelability in water at 25° C. and hot water at 90° C. The cured test specimen was immersed in water at 25° C. or water at 90° C., and the state in which the slide glass or acrylic plate peeled off under its own weight was observed, and the time until peeling was measured.

(3) Evaluation Results The composition of Example 1 had high adhesive strength and good workability during temporary fixing. It also had good water peelability.
The composition of Example 2 is a composition in which water is added to component (A), and the water peeling time is very short and the hot water peeling property is greatly improved. The composition of Example 3 is a composition in which organic fine particles are added to component (A) and water, and the adhesive strength is improved and the workability during temporary fixing is further improved.
On the other hand, the compositions of Comparative Examples 1 and 2, which did not contain component (A) and contained DMAA and DEAA as main components of component (D), respectively, had high adhesive strength, but did not peel off when immersed in water even for 3600 seconds, and had very poor water peelability. Similarly, the composition of Comparative Example 3, which contained HEMA and IBXA, also had very poor water peelability.
Furthermore, the compositions of Comparative Examples 4 and 5, which did not contain the (A) component and contained only the (D) component, had a very short water peeling time and good water peeling properties, but had very low adhesive strength and peeled off during temporary fixation, resulting in very poor workability.

The curable composition of the present invention can be preferably used in various applications requiring temporary fixation because the cured product has releasability in water, and more preferably can be used as a water-removable active energy ray-curable composition. More specifically, the curable composition of the present invention can be preferably used as a temporary fixing adhesive composition, a coating composition, and a modeling composition.

Claims (16)

Component (A): a (meth)acrylate of an alkylene oxide adduct of sorbitol, and
Component (B): Contains a photopolymerization initiator,
the number of moles of alkylene oxide added in the component (A) is 1 to 20,
the (meth)acrylate ratio of hydroxyl groups in the alkylene oxide adduct of sorbitol in the component (A) is less than 50 mol %;
A water-peelable curing composition in which two pieces of glass are bonded together with a water-peelable curing composition having a thickness of 100 μm, the water-peelable curing composition is cured by exposure to ultraviolet light , and the cured composition is immersed in water at 25° C. or water at 90° C. that does not contain a water-soluble organic solvent or a surfactant , and the two pieces of glass peel off under their own weight within 60 minutes. The water-peelable curable composition according to claim 1, wherein the solubility of component (A) in distilled water at a temperature of 22°C is 10% or more. The water-peelable curable composition according to claim 1 or 2, wherein the component (A) has a hydroxyl value of 100 to 400 mg KOH/g. The water-peelable curable composition according to any one of claims 1 to 3, further comprising component (C): a thermal polymerization initiator in addition to component (A). The water-peelable curable composition according to any one of claims 1 to 4, further comprising component (D): a compound having an ethylenically unsaturated group other than component (A). The water-peelable curable composition according to any one of claims 1 to 5, further comprising water and/or an organic solvent in the component (A). A water-peelable active energy ray-curable composition comprising the composition according to any one of claims 1 to 6. The water-strippable active energy ray-curable composition according to claim 7, wherein at least one of the substrates has a transmittance of 10% or more at 400 nm. a step of producing component (A) which is a mixture of compounds having a (meth)acryloyl group by subjecting an alkylene oxide adduct of sorbitol and a compound having one (meth)acryloyl group to a transesterification reaction in the presence of the following catalysts X and Y; and
The method includes a step of stirring and mixing the component (A) and the component (B): a photopolymerization initiator,
A method for producing the water-peelable curable composition according to any one of claims 1 to 6.
Catalyst X: one or more compounds selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure, or a salt or complex thereof, an amidine, or a salt or complex thereof, a compound having a pyridine ring, or a salt or complex thereof, and a phosphine, or a salt or complex thereof.
Catalyst Y: A compound containing zinc. The method for producing a water-peelable curable composition according to claim 9, wherein the solubility of component (A) in distilled water at a temperature of 22°C is 10% or more. The method for producing a water-peelable curable composition according to claim 9 or 10, wherein the component (A) has a hydroxyl value of 100 to 400 mg KOH/g. The method for producing a water-peelable curable composition according to any one of claims 9 to 11, wherein the compound having one (meth)acryloyl group is an alkoxyalkyl (meth)acrylate. The method for producing a water-peelable curable composition according to any one of claims 9 to 12, wherein the catalyst X is one or more compounds selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof, an amidine or a salt or complex thereof, and a compound having a pyridine ring or a salt or complex thereof. The method for producing a water-peelable curable composition according to any one of claims 9 to 13, wherein the catalyst Y is an organic acid zinc or/and a zinc diketone enolate. A method for producing a processed material by sequentially carrying out the following steps 1 to 4.
Step 1: A water-peelable curable composition according to any one of claims 1 to 6, which contains component (A): a (meth)acrylate of an alkylene oxide adduct of sorbitol, is applied to or injected into a substrate;
Another substrate is laminated to the coated or injected surface of the substrate, or
Step 2: A step of immersing the composition between a plurality of substrates. Step 3: A step of processing at least one of the substrates containing the cured product of the composition. Step 4: A step of immersing the substrate containing the cured product of the composition obtained in step 3 in water at a temperature of 20 to 100°C and peeling off the substrate. The method for producing a processing material according to claim 15, wherein at least one of the following substrates has a transmittance of 10% or more at 400 nm, and the following steps 1 to 4 are carried out in order.
Step 1: A water-peelable curable composition according to any one of claims 1 to 8, which contains (A) component: a (meth)acrylate of an alkylene oxide adduct of sorbitol and (B) component: a photopolymerization initiator and is a cured product, is applied or injected onto a substrate;
Another substrate is laminated to the coated or injected surface of the substrate, or
Step 2: Immersing the composition between a plurality of substrates Step 3: Processing at least one of the substrates containing the cured product of the composition Step 4: Immersing the substrate containing the cured product of the composition obtained in step 3 in water at a temperature of 20 to 100°C and peeling off the substrate

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