JP2021004276A - Photocurable resin composition for temporary adhesion fixing - Google Patents

Abstract

To provide a photocurable resin composition for temporary adhesion fixing, which gives a cured material having a high solubility in water.SOLUTION: Provided is a photocurable resin composition for temporary adhesion fixing, comprising a radically polymerizable monomer (A), a chain transfer agent (B), and a photoinitiator (C), where the component (A) comprises a radically polymerizable monomer (A1) having one or more OH groups in a molecule.SELECTED DRAWING: None

Description

The present invention relates to a photocurable resin composition for temporary fixing by bonding.

Water-soluble polymers are used in a variety of applications. Temporary fixing, in which one member is temporarily bonded to some other member, is one such application. In the use of temporary fixing, it is necessary to remove the adhesive used for temporary fixing after the desired processing or the like, so a polymer that can be removed by washing with water is preferable. However, when a water-soluble polymer is used for temporary fixing, it is necessary to first dissolve it in a solvent such as water to prepare a solution, apply a required amount, and then heat the polymer for a certain period of time to disperse the solvent.

On the other hand, ultraviolet (UV) curable plastics are widely used as optical-related materials due to their features such as ease of molding and light weight. Patent Document 1 discloses an ultraviolet curable resin composition containing a hydrophobic component as a temporary fixing material when processing a member. Patent Document 1 discloses that a base material having a cured film of a temporary fixing material is immersed in water at a high temperature of about 80 ° C. for several tens of minutes to swell the cured film of the temporary fixing material and then peel it off. ing.

Japanese Unexamined Patent Publication No. 2010-100831

The ultraviolet curable resin composition containing a hydrophobic component as described in Patent Document 1 has almost no solubility in water because the molecules are crosslinked once it is cured. The method for removing the temporary fixing material disclosed in Patent Document 1 is time-consuming and cannot be used for heat-sensitive members. On the other hand, the method of dissolving the temporary fixing material in an organic solvent may have an impact on the environment. Therefore, the development of a temporary fixing agent that easily dissolves in water, a detergent aqueous solution, a weakly acidic aqueous solution such as citric acid, or an aqueous solvent having a small environmental load is awaited.

An object of the present invention is to provide a photocurable resin composition for temporary fixing by bonding, which provides a cured product having high solubility in water.

The present invention relates to the following.
[1] A photocurable resin composition for bonding temporary fixing containing a radical polymerization-reactive monomer (A), a chain transfer agent (B), and a photopolymerization initiator (C), wherein the component (A) is , A photocurable resin composition for temporary fixing for bonding, which contains a radical polymerization-reactive monomer (A1) having one or more OH groups in the molecule.
[2] The photocurable resin composition of [1], which further contains a water-soluble plasticizer (d1).
[3] The photocurable resin composition of [2], wherein the weight average molecular weight of the component (d1) is 50 to 500.
[4] The photocurable resin composition according to any one of [1] to [3], which further contains a water-soluble filler (d2).
[5] The photocurable resin composition of [1], which further contains a water-soluble filler (d2) but does not contain a water-soluble plasticizer (d1).
[6] The photocurable resin composition according to any one of [1] to [5], wherein the component (B) is a compound having a thiol group or an α-methylstyrene dimer.
[7] The photocurable resin composition according to any one of [1] to [6], wherein the content of the component (B) in the photocurable resin composition is 0.7 to 15% by weight.
[8] The component (d2) is a combination of the first water-soluble filler (d2-1) and the second water-soluble filler (d2-2), and here, the component (d2-1) and the component (d2). The combination of -2) is a photocurable resin composition according to any one of [4] to [7], which has foamability.
[9] The photocurable resin composition according to any one of [4] to [8], wherein the aqueous solvent in which the third water-soluble filler (d2-3) is dissolved is a temporary use of the photocurable resin composition. It is used as an aqueous solvent for releasing the fixation, and the combination of at least a part of the component (d2) contained in the photocurable resin composition and the component (d2-3) has foamability, [4] to The photocurable resin composition according to any one of [8].

According to the present invention, it is possible to provide a photocurable resin composition for temporary fixing by bonding, which gives a cured product having high solubility in water.

[Definition of terms]
"(Meta) acrylate" has the meaning of at least one of acrylate and methacrylate.
"(Meta) acryloyl group" has the meaning of at least one of an acryloyl group and a methacryloyl group.
The "radical polymerization reactive monomer (A)" is also referred to as "component (A)". The same applies to "chain transfer agent (B)" and the like.

[Photocurable resin composition for bonding temporary fixing]
The photocurable resin composition for bonding temporary fixing (hereinafter, also simply referred to as “photocurable resin composition”) is a radical polymerization reactive monomer (A), a chain transfer agent (B), and a photopolymerization initiator (C). ), And the component (A) contains a radical polymerization-reactive monomer (A1) having one or more OH groups in the molecule.

The photocurable resin composition can be applied to a member by a dispenser, various printing methods, or the like, then bonded to another member, and instantly cured and fixed by UV irradiation.
Since the cured product of the photocurable resin composition has high solubility in water, the photocurable resin composition is excellent in peelability between the members fixed by the photocurable resin composition when an aqueous solvent is used. In particular, the above-mentioned is carried out by washing with water at a low temperature (for example, 25 to 70 ° C.) (washing with water, washing with a weakly alkaline, weakly acidic, or neutral detergent aqueous solution, or washing with a weakly acidic aqueous solution such as citric acid). The fixed members can be easily peeled off from each other.

<Radical polymerization reactive monomer (A)>
The radical polymerization-reactive monomer (A) is not particularly limited as long as it has a radical polymerization-reactive functional group. The radical polymerization-reactive functional group is not particularly limited as long as it is an unsaturated double bond-containing group, but an alkenyl group (for example, a vinyl group, an allyl group, etc.) or a (meth) acryloyl group is preferable, and a (meth) acryloyl group is preferable. Is particularly preferable.

<< Radical polymerization reactive monomer (A1) having one or more OH groups in the molecule >>
The radical polymerization-reactive monomer (A) contains a radical polymerization-reactive monomer (A1) having one or more OH groups in the molecule. The number of OH groups in the component (A1) is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1. Therefore, the component (A1) preferably contains a radical polymerization-reactive monomer having 1 to 5 OH groups in the molecule, and may contain a radical polymerization-reactive monomer having 1 to 3 OH groups in the molecule. More preferably, it contains a radical polymerization-reactive monomer having one OH group in the molecule.

The component (A1) includes a hydroxyalkyl (meth) acrylate monomer, a hydroxyalkyl (meth) acrylate monomer in which an alkyl group is interrupted by one or more oxygen atoms, and a poly (meth) acrylate monomer of a polyol (however, a hydroxyl group is contained). , N-Hydroxyalkyl (meth) acrylamide monomer, (meth) acrylamide monomer having an aryl group substituted with a hydroxy group, and the like.

Here, the total number of carbon atoms of the alkyl group, the hydroxyalkyl group in which the alkyl group is interrupted by one or more oxygen atoms, and the alkyl portion of the hydroxyalkyl group is preferably 1 to 18, and is preferably 1 to 6. Is more preferable, and 2 to 4 is particularly preferable. The aryl group preferably has 6 to 20 carbon atoms. Further, the aryl group is preferably a phenyl group.

Examples of the hydroxyalkyl (meth) acrylate monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.

Examples of the hydroxyalkyl (meth) acrylate monomer in which the alkyl group is interrupted by one or more oxygen atoms include diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, and triethylene glycol mono (meth) acrylate. Be done.

Examples of the poly (meth) acrylate monomer of the polyol (provided that it contains a hydroxyl group) include trimethylolpropane di (meth) acrylate and poly (meth) acrylate of polypentaerythritol.

Examples of the N-hydroxyalkyl (meth) acrylamide monomer include N- (2-hydroxyethyl) (meth) acrylamide, N- (3-hydroxypropyl) (meth) acrylamide, and N- (4-hydroxybutyl) (meth) acrylamide. And so on.

Examples of the (meth) acrylamide monomer having an aryl group substituted with a hydroxy group include N- (2-hydroxyphenyl) (meth) acrylamide, N- (3-hydroxyphenyl) (meth) acrylamide, and N- (4-hydroxy). Examples thereof include phenyl) (meth) acrylamide.

Examples of the radical polymerization-reactive monomer having two or more OH groups in the molecule include glycerin mono (meth) acrylate and the like.

As the component (A1), hydroxyalkyl (meth) acrylate monomer, glycerin mono (meth) acrylate and N-hydroxy from the viewpoint of further increasing the solubility (water solubility) of the cured product of the photocurable resin composition in water. One or more selected from the group consisting of alkyl (meth) acrylamide monomers is preferable.
The component (A1) may be one kind or a combination of two or more kinds.

<< Radical polymerization reactive monomer (A2) other than component (A1) >>
The radical polymerization-reactive monomer (A2) other than the component (A1) is not particularly limited as long as it has a radical polymerization-reactive functional group other than the component (A1). Examples of the component (A2) include a (meth) acrylate monomer having a (meth) acryloyl group, a (meth) acrylamide monomer having a (meth) acrylamide group, and the like. The (meth) acrylate monomer having a (meth) acryloyl group does not contain the (meth) acrylate monomer having a (meth) acrylamide group.

<<< (Meta) Acrylate Monomer >>>
Examples of the (meth) acrylate monomer include an alicyclic (meth) acrylate monomer, an aromatic (meth) acrylate monomer, an alkyl (meth) acrylate monomer, a (poly) alkylene glycol monoalkyl ether (meth) acrylate monomer, and a heterocyclic structure. (Meta) acrylate monomer having the above, and the like can be mentioned.

Examples of the alicyclic (meth) acrylate monomer include isobornyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, norbornene (meth) acrylate, dicyclopentanyl (meth) acrylate, and cyclohexyl (meth) acrylate. ..

Examples of the alkyl (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, tert-butyl (meth) acrylate, isooctyl (meth) acrylate, isomyristyl (meth) acrylate, and lauryl (meth) acrylate. Be done.

Examples of the (meth) acrylate monomer of (poly) alkylene glycol monoalkyl ether include diethylene glycol monoethyl ether (meth) acrylate.

Examples of the (meth) acrylate monomer having a heterocyclic structure include tetrahydrofurfuryl (meth) acrylate.

Aromatic (meth) acrylate monomers include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, ethoxylated o-phenylphenol acrylate, phenoxybenzyl (meth) acrylate, naphthalene (meth) acrylate, and ethoxylated bisphenol A di (meth). ) Acrylate, modified bisphenol A di (meth) acrylate and the like.

The (meth) acrylate monomer preferably contains a (meth) acrylate monomer of a (poly) alkylene glycol monoalkyl ether or a (meth) acrylate monomer having a heterocyclic structure.

<<< (meth) acrylamide monomer >>>
Examples of the (meth) acrylamide monomer include compounds represented by the following formula (1).

[In the formula,
R ¹ is a hydrogen atom or a methyl group and
R ² and R ³ are independent of each other, an aryl group substituted with a hydrogen atom, an alkyl group, or an unsubstituted or alkyl group, or an aryl group.
R ² and R ³ together with the N atoms to which they bind form an alicyclic group (preferably a morpholino group) that can contain an oxygen atom].

The number of carbon atoms and the aryl group of the alkyl group are as described above, including those which are preferable. The morpholino group is a monovalent group from which the hydrogen atom of the secondary amine portion of morpholine has been removed.

Specific examples of the (meth) acrylamide monomer include (meth) acrylamide; carbons such as N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, and N-butyl (meth) acrylamide. N-alkyl (meth) acrylamide having an alkyl group of 1 to 4; N, having an alkyl group of 1 to 4 carbons such as N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, etc. N-Dialkyl (meth) acrylamide; (meth) acrylamide having an aryl group substituted with an unsubstituted or alkyl group such as N-phenyl (meth) acrylamide, N- (2-methylphenyl) (meth) acrylamide; 4- Examples thereof include (meth) acrylamide having a cyclic structure such as (meth) acryloylmorpholin.

The component (A2) may be one kind or a combination of two or more kinds.

<Chain transfer agent (B)>
The chain transfer agent (B) is a component that causes a chain transfer reaction. Here, the chain transfer reaction refers to a reaction in which a growing radical reacts with another chemical species in the polymerization system in radical polymerization, accompanied by growth arrest, radical migration, and growth restart. The component (B) includes α-methylstyrene, α-methylstyrene dimer; alcohols such as methanol, ethanol, propanol and butanol; aldehydes such as acetaldehyde, propionaldehyde, n-butylaldehyde, furfural and benzaldehyde; carbon tetrachloride. , Halogens such as chloroform; and pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, dodecyl mercaptan, lauryl mercaptan, normal mercaptan, thioglycolic acid, thioglycol One or more selected from the group consisting of compounds having a thiol group such as octyl acid and thioglycerol are mentioned, and a compound having a thiol group or an α-methylstyrene dimer is preferable.
The component (B) may be one kind or a combination of two or more kinds.

<Photopolymerization initiator (C)>
The photopolymerization initiator (C) is not particularly limited as long as it is a compound that generates radicals by irradiation with energy rays. The component (C) is 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, benzophenone, 2, 2-Dimethoxy-1,2-diphenylethane-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, 2-benzyl-2-dimethylamino-1 -(4-Molholinophenyl) Butanone-1,2-Hydroxy-2-methyl-1-phenyl-Propane-1-one, 2-Methyl-1- [4-Methylthio] phenyl] -2-morpholinopropane-1- On, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone], oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] ] Propanone], benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, oligo 2-hydroxy-2-methyl-1- [4-] (1-Methylvinyl) phenyl] propanol, oligo 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanol, 2-hydroxy-2-methyl-1-phenyl-1-propanol, Isopropylthioxanthone, methyl o-benzoyl benzoate, [4- (methylphenylthio) phenyl] phenylmethane, 2,4-diethylthioxanthone, 2-chlorothioxanthone, benzophenone, ethylanthraquinone, benzophenone ammonium salt, thioxanthone ammonium salt, bis ( 2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzophenone , 4-Methylbenzophenone, 4,4'-bisdiethylaminobenzophenone, 1,4 dibenzoylbenzene, 10-butyl-2-chloroacrydone, 2,2'bis (o-chlorophenyl) 4,5,4', 5 '-Tetrax (3,4,5-trimethoxyphenyl) 1,2'-biimidazole, 2,2' bis (o-chlorophenyl) 4,5,4', 5'-tetra Phenyl-1,2'-biimidazole, 4-benzoyldiphenyl ether, acrylicized benzophenone, bis (η5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-) 1-yl) -Phenyl) Titanium, o-methylbenzoylbenzoate, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamylethyl ester, active tertiary amine, carbazole-phenone-based photopolymerization initiator, aclysin-based Examples thereof include a photopolymerization initiator, a triazine-based photopolymerization initiator, and a benzoyl-based photopolymerization initiator.

Commercially available products of the component (C) include KIP-150 manufactured by DKSH Japan, Irgacure (registered trademark) series such as Irgacure184, Irgacure819, Irgacure127, and Irgacure1173 manufactured by BASF, and Darocur (registered trademark) series such as Darocur1173. Lucirin (registered trademark) series, ESACURE 1001M manufactured by ESACUR Nippon Siber Hegner, and the like. Irgacure 1173 (Irgacure 1173) and Irgacure 184 (Irgacure 184) are used from the viewpoint of making the component (A) less susceptible to oxygen inhibition, which causes uncuredness in the radical reaction, and further from the viewpoint of solubility in the component (A) and water. preferable.
The component (C) may be one kind or a combination of two or more kinds.

<Additional component (D)>
The photocurable resin composition may contain a further component (D), if necessary, as long as the effects of the present invention are not impaired. As the component (D), a water-soluble plasticizer (d1), a water-soluble filler (d2), a thixo-imparting agent containing an inorganic substance (d3), a water-soluble polymer (d4), a water-insoluble filler, a silane coupling agent, and a surfactant. Examples thereof include activators, slip agents, polymerization inhibitors, photosensitizers, antioxidants, stabilizers, colorants, solvents, radical polymerization reactive components other than the component (A), and water-soluble plasticizers (d1). , Water-soluble filler (d2) is preferable. When the photocurable resin composition contains a water-soluble plasticizer (d1), a water-soluble filler (d2) and / or a thixotropy-imparting agent (d3) containing an inorganic substance, the peelability is further enhanced.
The component (D) may be one kind or a combination of two or more kinds, respectively.

<< Water-soluble plasticizer (d1) >>
The water-soluble plasticizer (d1) is a component added when controlling properties such as hardness of the photocurable resin composition and the cured product thereof. The water-soluble plasticizer (d1) is not a polymer, but a material that is soluble in both water and a photocurable resin composition and has no radical reactivity. The component (d1) includes glycerin, polyethylene glycol, polypropylene glycol, polyoxyalkylene such as a copolymer of polyethylene glycol and polypropylene glycol, polyvinyl alcohol; cellulose derivatives such as hydroxymethyl cellulose, hydroxypropyl cellulose and carboxymethyl cellulose; starch decomposition products. , Hydroxypropyl etherified starch, polysaccharides such as sodium alginate, gelatin, xanthan gum; and the like.

The weight average molecular weight of the component (d1) is less than 1,000, preferably 50 to 500, and particularly preferably 50 to 300. When the weight average molecular weight of the component (d1) is in the above range, the viscosity of the photocurable resin composition can be efficiently increased, and the water solubility of the photocurable resin composition after UV curing is also high. As a method for measuring the weight average molecular weight, for components having a relatively high molecular weight such as oligomers and polymers, a method of converting the measurement result of gel permeation chromatography (GPC) using a standard polystyrene calibration curve is generally known. Has been done. Moreover, since the monomer does not have a molecular weight distribution, it can be obtained from the structural formula.
The component (d1) may be one kind or a combination of two or more kinds.

<< Water-soluble filler (d2) >>
The water-soluble filler (d2) refers to a filler that is insoluble in the photocurable resin composition but is soluble in water. The water-soluble filler (d2) is a component added when controlling properties such as hardness of the photocurable resin composition and the cured product thereof. Examples of the water-soluble filler (d2) include carbonate compound-based fillers such as sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, and ammonium nitrite; percarbonate compound-based fillers such as sodium percarbonate; halogens such as sodium chloride and ammonium chloride. Compound-based fillers; Phosphate compound-based fillers such as polyphosphate amide, ammonium polyphosphate, melamine phosphate; Light metal-based fillers such as magnesium powder and aluminum powder; Hydrochloride-based fillers such as sodium hydride and sodium hydride; Examples thereof include organic acid-based fillers such as citric acid, tartrate, vitamin C (that is, L-ascorbic acid); and the like.

The component (d2) is preferably a carbonate compound-based filler, a halide-based filler, or an organic acid-based filler from the viewpoint of further increasing the solubility in an aqueous solvent.
The component (d2) may be one kind or a combination of two or more kinds.

The component (d2) is a combination of two or more kinds of water-soluble fillers, and the combination of the water-soluble fillers is preferably foamable. Here, the effervescent property means a property of effervescence when it comes into contact with water. The component (d2) serving as a foaming agent having such foaming properties is composed of a first water-soluble filler (d2-1) and a second water-soluble filler (d2-2). Here, the combination of the component (d2-1) and the component (d2-2) has effervescence, but only one of the component (d2-1) and the component (d2-2) does not have effervescence.

When the photocurable resin composition contains a foaming agent, when the cured product is peeled off with an aqueous solvent, the component (d2-1) and the component (d2-2) foam due to contact with water. As a result, the cured product of the photocurable resin composition is likely to disintegrate, and the peeling efficiency is further increased. Examples of the combination of such a component (d2-1) and the component (d2-2) include a combination of a carbonate compound-based filler and an organic acid-based filler, a combination of sodium percarbonate and an organic acid-based filler, and the like. The component (d2-1) and the component (d2-2) may contain an additional water-soluble filler as long as the combination of the component (d2-1) and the component (d2-2) has effervescence.

Further, a part of the water-soluble filler constituting the foaming agent may be present in the water-based solvent, and at least the rest of the water-soluble filler constituting the foaming agent may be present in the photocurable resin composition. That is, a water-soluble filler corresponding to the component (d2-1) (or the component (d2-2)) is present in the photocurable resin composition, and the component (d2-2) (or the component (d2-1)) is present. ) May be present in the aqueous solvent. Even in such a case, when the cured product of the photocurable resin composition is peeled off with an aqueous solvent, the component (d2-1) and the component (d2-2) come into contact with each other, so that the same reason as described above can be applied. Peeling efficiency is higher. Therefore, in the photocurable resin composition containing an arbitrary water-soluble filler (d2), the aqueous solvent in which the third water-soluble filler (d2-3) is dissolved releases the temporary fixing of the photocurable resin composition. It is also preferable that the combination of at least a part of the component (d2) and the component (d2-3) is a photocurable resin composition having foamability.

Here, the combination of at least a part of the arbitrary water-soluble filler (d2) contained in the photocurable resin composition and the third water-soluble filler (d2-3) contained in the aqueous solvent has foamability. The "arbitrary water-soluble filler (d2)" may be a component (d2-1) or a combination of the component (d2-1) and the component (d2-2). It should be noted that the above-mentioned "at least a part of the arbitrary water-soluble filler (d2)" or the component (d2-3) alone does not have foaming property. Further, the component (d2-3) is not particularly limited as long as the combination with at least a part of the arbitrary component (d2) has effervescence, and is a component (d2-1) or a component (d2-2). You may. As a specific example of the combination of such an arbitrary component (d2) and the component (d2-3), the arbitrary component (d2) is a carbonate compound-based filler, or a carbonate compound-based filler and an organic acid-based filler. Examples of the component (d2-3) include a carbonate compound and an organic acid-based filler.

<< Thixotropy containing inorganic substances (d3) >>
The thixotropic agent (d3) containing an inorganic substance is not particularly limited as long as it has a high thickening or thixotropic effect with a small amount of addition. Inorganic substances contained in the component (d3) include fumed silica, calcium carbonate, carbon black, kaolin, clay, activated clay, silica sand, diatomaceous earth, diatomaceous earth, anhydrous aluminum silicate, hydrous magnesium silicate, talc, etc. Examples include pearlite, white carbon, fine mica powder, bentonite and the like. Further, the component (d3) may be composed of only an inorganic substance, or may be an inorganic substance surface-treated with a fatty acid and / or a resin acid.
The component (d3) may be one kind or a combination of two or more kinds.

<< Water-soluble polymer (d4) >>
The water-soluble polymer (d4) is not particularly limited as long as it does not have a radical polymerization-reactive functional group and has a property of being soluble in both water and a photocurable resin composition. Examples of the component (d4) include the components exemplified in the water-soluble plasticizer (d1).

The weight average molecular weight of the water-soluble polymer (d4) is 1,000 or more, preferably 1,000 to 100,000, more preferably 1,000 to 50,000 or less, and 1, It is particularly preferably 000 to 20,000 or less. When the weight average molecular weight of the component (d4) is in the above range, the viscosity of the photocurable resin composition can be efficiently increased.
The component (d4) may be one kind or a combination of two or more kinds.

<< Radical polymerization reactive components other than component (A) >>
The radical polymerization-reactive component other than the component (A) is not particularly limited as long as it has a radical polymerization-reactive functional group. Examples of the radical polymerization reactive component other than the component (A) include (meth) acrylate oligomer, and urethane (meth) acrylate oligomer and epoxy (meth) acrylate oligomer are preferable.

Examples of the urethane (meth) acrylate oligomer include aliphatic, polyether, polycarbonate, polyester and polyurethane (meth) acrylate oligomers in combination thereof.

Epoxy (meth) acrylate oligomers are oligomers in which all epoxy groups in the epoxy resin have reacted with (meth) acrylic acid. The epoxy (meth) acrylate oligomer contains an oligomer in which some epoxy groups in the epoxy resin react with (meth) acrylic acid, that is, an oligomer having an epoxy group and a (meth) acryloyl group in the resin. May be good. Here, examples of the epoxy resin include aromatic epoxy resins, aliphatic epoxy resins, alicyclic epoxy resins, and other epoxy resins.

The weight average molecular weight of the radical polymerization reactive component other than the component (A) is not particularly limited, but is preferably more than 1,000, more preferably 3,000 to 100,000, and 5,000 to. It is particularly preferably 50,000. That is, the weight average molecular weight of the component (A) is not particularly limited, but is preferably 1,000 or less.

Further components other than the above-mentioned components are not particularly limited as long as they are components usually used in the photocurable resin composition, and can be appropriately selected depending on the intended purpose.

<< Preferred embodiment of component (D) >>
The photocurable resin composition preferably contains a water-soluble plasticizer (d1) and / or a water-soluble filler (d2). Further, when the photocurable resin composition contains the water-soluble filler (d2), the photocurable resin composition may not contain the water-soluble plasticizer (d1).

(Composition and characteristics, etc.)
<Viscosity>
The viscosity of the photocurable resin composition is not particularly limited, but is preferably 100 to 100,000 mPa · s at 25 ° C. When the viscosity of the photocurable resin composition is within the above range, it may be more easily applied by a dispenser, various printing methods, or the like. The viscosity can be measured using an E-type viscometer at 25 ° C. under atmospheric pressure by selecting an appropriate cone plate and rotation speed.

<Composition>
In the photocurable resin composition, the content of the component (A1) in the component (A) is 30 to 100% by weight. From the viewpoint of more excellent UV curability, the content of the component (A1) in the component (A) is preferably 35 to 100% by weight, more preferably 40 to 100% by weight, and 80% by weight. ~ 100% by weight is more preferable, and 100% by weight is particularly preferable.

The component (A), as the main component of the photocurable resin composition, is preferably 52% by weight or more, more preferably 55% by weight or more, and 70% by weight or more in the photocurable resin composition. It is more preferably 80% by weight or more.

The component (B) is preferably 0.7 to 15% by weight, preferably 0.9 to 10% by weight, in the photocurable resin composition from the viewpoint of energy ray curability and water solubility after UV curing. Is more preferable, and 1.0 to 7.0% by weight is particularly preferable.

The component (C) is preferably 0.1 to 10% by weight in the photocurable resin composition from the viewpoint of energy ray curability and water solubility after UV curing, and is 0.5 to 8.0. It is more preferably by weight%, and particularly preferably 1.0 to 7.0% by weight.

When the photocurable resin composition contains the component (d1), the content of the component (d1) may be less than 50 parts by weight with respect to a total of 100 parts by weight of the component (A) and the component (d1). It is preferably 1 to 40 parts by weight, and particularly preferably 1 to 35 parts by weight.

When the photocurable resin composition contains the component (d2), the content of the component (d2) is preferably less than 70 parts by weight, preferably 1 to 60 parts by weight, based on 100 parts by weight of the component (A). It is more preferably parts, and particularly preferably 5 to 50 parts by weight.

When the photocurable resin composition contains a component (D) other than the component (d1) and (d2), the content of the component (D) other than the component (d1) and (d2) is the component (A) and the component (D2). The total amount of the component (D) other than (d1) and (d2) is 100 parts by weight, preferably less than 50 parts by weight, more preferably 1 to 40 parts by weight, and 1 to 20 parts by weight. It is particularly preferable to have.

(Manufacturing method of photocurable resin composition)
The photocurable resin composition is obtained by a production method including a step of mixing the component (A), the component (B), the component (C), and a further component (component (D), etc.) which is an optional component.

[Use]
The photocurable resin composition can be used as a temporary fixing material. The photocurable resin composition can be applied to temporary fixing in the processing of crystal oscillators, glass lenses, plastic lenses and optical disks.

(Temporary fixing material)
Temporary fixing means temporarily adhering one member to the other member via a cured product of the photocurable resin composition. The cured product of the photocurable resin composition is later removed, whereby the adhesiveness of the cured product of the photocurable resin composition between one member and the other member is lost, and the temporary fixing is released. To. As a result, the purpose of temporary fixing is achieved. The cured product of the photocurable resin composition is preferably removed by an aqueous solvent.

<Temporary fixing method>
The method of temporarily fixing the member using the photocurable resin composition includes a step of bonding the base materials using the photocurable resin composition and a step of curing the photocurable resin composition to bond the base materials. It includes a step of temporarily fixing, a step of processing the temporarily fixed base material, and a step of bringing the processed base material into contact with an aqueous solvent to remove the cured photocurable resin composition.

Further, as a method for producing a processed product using the photocurable resin composition, a method including the following steps (A) to (D) can be mentioned.
(A) (a1) A step of applying a photocurable resin composition to one of the base materials to form a photocurable resin composition layer, and (a2) another step on the photocurable resin composition layer. The process of laminating one base material to obtain a laminate,
(B) A step of irradiating the laminate obtained in the step (A) with energy rays to obtain an adhesive, and
(C) The process of processing the adhesive body to obtain a rough processed body,
(D) The method includes a method of removing a cured product of a photocurable resin composition from a rough processed product to obtain a processed product.

The step (A) is a step (a1) and a step (b1). The step (a1) is a step of applying the photocurable resin composition to one of the base materials to form the photocurable resin composition layer. The material of the base material is not particularly limited, but a base material made of a material capable of transmitting ultraviolet rays is preferable. Examples of materials capable of transmitting such ultraviolet rays include quartz, glass, and plastic.

The method of applying the photocurable resin composition to the substrate is not particularly limited, and is limited to a brush coating method, a screen printing method, a gravure printing method, a spray method, a dip method, a bar coater, a roll coater, a spin coater, a die coater, and a dispenser. , Other known coating means. The thickness of the photocurable resin composition layer formed by applying the photocurable resin composition is not particularly limited, but is preferably 10 to 1,000 μm, and particularly preferably 50 to 500 μm.

The step (a2) is a step of laminating the other base material on the photocurable resin composition layer to obtain a laminate. A laminate is obtained by placing the other base material on the base material on which the photocurable resin composition layer is formed so as to be in contact with the photocurable resin composition layer and laminating the base materials together. Be done. The step (a2) may include a step of pressurizing the laminated body.

The step (B) is a step of irradiating the laminate obtained in the step (A) with energy rays to obtain an adhesive. By irradiating the laminate with energy rays, the photocurable resin composition between one base material and the other base material is cured, and the base materials are adhered to each other.

The energy beam is not particularly limited, and active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams can be used. The energy ray is preferably ultraviolet light. As the light source of ultraviolet rays, a light source that emits ultraviolet rays (UV) can be used. Examples of the light source of ultraviolet rays include metal halide lamps, high-pressure mercury lamps, xenon lamps, mercury xenon lamps, halogen lamps, pulse xenon lamps, and LEDs. The integrated light intensity of the energy rays is, for example, preferably 500 to 10,000 mJ / cm ² at 365 nm, and particularly preferably 1,000 to 8,000 mJ / cm ² .

The step (C) is a step of processing the adhesive body to obtain a rough processed body. Examples of the processing include cutting, grinding, polishing, drilling, and painting a temporarily fixed adhesive body in a desired shape, which is appropriately set according to the obtained processed body.

The step (D) is a method of removing a cured product of the photocurable resin composition from the rough processed product to obtain a processed product. Examples of the method for removing the cured product of the photocurable resin composition include a method of bringing the rough-processed product into contact with an aqueous solvent, for example, a method of spray-applying the aqueous solvent to the cured product of the photocurable resin composition. Examples thereof include a method of immersing the rough-processed material in an aqueous solvent. By the method of bringing the rough-processed body into contact with an aqueous solvent, the cured product of the photocurable resin composition is removed from the rough-processed body by peeling from the substrate or dissolving.

Examples of the aqueous solvent include water, a mixed solvent of water and an organic acid, a mixed solvent of water and a surfactant, and a mixed solvent of water and a hydrophilic organic solvent. Moreover, the water-based solvent may be an water-based solvent in which the component (2d-3) is dissolved.
The organic acid is an acid of an organic compound having a group such as a carboxyl group and a sulfo group, and examples thereof include citric acid, tartaric acid, lactic acid, and vitamin C. The organic acid may be one kind or a combination of two or more kinds.
Surfactants include those consisting of nonionic, anionic and cationic surfactants. The surfactant may be one kind or a combination of two or more kinds.
Examples of the hydrophilic organic solvent include alcohols such as methanol, ethanol, 2-propanol and 1,2-propanediol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethyl cellosolve, propylene glycol monopropyl ether and propylene glycol monoisopropyl ether, Glycol ethers such as butyl cellosolve, ethylene glycol monoisobutyl ether, propylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and dipropylene glycol monomethyl ether; cyclohexanone and the like can be mentioned. The hydrophilic organic solvent may be one kind or a combination of two or more kinds.
The aqueous solvent is preferably water or a mixed solvent of water and an organic acid. In particular, when the photocurable resin composition contains a carbonate compound-based filler (for example, sodium bicarbonate) and the aqueous solvent contains an organic acid (for example, citric acid), the contact between the crude product and the aqueous solvent Foaming occurs due to contact between the carbonate compound and the organic acid, and the cured product of the photocurable resin composition can be efficiently removed.

The temperature of the aqueous solvent in the step (D) is not particularly limited, and is preferably 25 to 70 ° C. Further, the contact time between the rough-processed body and the aqueous solvent in the step (D) is not particularly limited as long as the cured product of the photocurable resin composition can be removed from the rough-processed body, and is appropriately set by those skilled in the art. it can. From the viewpoint of accelerating the dissolution of the cured product of the photocurable resin composition in water, it is preferable to vibrate the aqueous solvent by ultrasonic waves or the like. In step (D), the temporary fixing is released, and the purpose of the temporary fixing is achieved.

Examples of the processed product obtained by the method for producing the processed product using the photocurable resin composition include a crystal oscillator, a glass lens, a plastic lens and an optical disk.

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Values in the table are parts by weight unless otherwise noted.

(Ingredients used)
<Component (A): Radical polymerization reactive monomer>
<< Component (A1): Radical polymerization reactive monomer having one or more OH groups in the molecule >>
HEAA: N- (2-hydroxyethyl) acrylamide (manufactured by KJ Chemical)
HO-250: 2-Hydroxyethyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)
<< Component (A2): Other Radical Polymerization Reactive Monomers >>
IB: Isobornyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd.)
<Component (B): Chain transfer agent>
MSD-100: α-methylstyrene dimer (manufactured by Mitsui Chemicals)
Karenz MT PE1: Pentaerythritol Tetrakis (3-mercaptobutyrate) (Showa Denko)
Karenz MT BD 1: 1,4-Bis (3-mercaptobutylyloxy) butane (Showa Denko)
<Component (C): Photopolymerization Initiator>
Irgacure 1173: 2-Hydroxy-2-methyl-1-phenyl-propane-1-one (manufactured by BASF)

<Component (D): Further component>
<< Ingredient (d1): Water-soluble plasticizer >>
Purified glycerin: glycerin (manufactured by Sakamoto Yakuhin Kogyo) (weight average molecular weight (Mw): 92)
PEG # 300: Polyethylene glycol (manufactured by Lion) (Weight average molecular weight (Mw): 300)
<< Ingredient (d2): Water-soluble filler >>
Baking soda: Sodium bicarbonate (manufactured by Tokuyama)
Citric acid: Citric acid (made by Miyoshi Soap)
<< Ingredient (d3): Thixotropy >>
Aerosil 200: Fumed Silica (made by Aerosil)
NKC130: Fumed Silica (made by Aerosil)
<< Component (d4): Water-soluble polymer >>
PEG # 1000: Polyethylene glycol (made by Lion) (Weight average molecular weight (Mw): 1,000)
Penon JE66: Hydroxypropyl etherified starch (manufactured by Nissho Chemical Co., Ltd.) (Weight average molecular weight (Mw): 16,000)

[Evaluation conditions]
(1) Fixability Two slide glass substrates were prepared. After applying 30 mg of the photocurable resin composition on one slide glass substrate, another slide glass was attached and the composition was crushed so as to have a thickness of 100 μm. After irradiating UV of 3,000 mJ / cm ^{2 with} a metal halide lamp (M06-L31 manufactured by Eye Graphics), the two pieces of glass were moved by hand to check if they could be peeled off.
○: Does not come off ×: Does come off

(2) Peelability A test piece confirmed to have "(1) fixability" above was placed in a 2 L beaker, and about 500 g of water at 50 ° C. (in Examples 13 and 14 was a 2 wt% aqueous solution of citric acid) was poured. The beaker was placed in an ultrasonic cleaner (manufactured by SND, US-20PS) and ultrasonic waves at the weakest level (first stage of five stages) were applied while keeping the liquid temperature at 50 ° C. Then, it was confirmed how long it took for the composition to melt and the two glasses to peel off.
⊚: The photocurable resin composition was melted within 20 minutes and the glass was peeled off. ○: The photocurable resin composition was melted within 40 minutes and the glass was peeled off. Δ: The photocurable resin composition was 1 Melted within 1 hour and peeled glass ×: The photocurable resin composition did not peel off from each other within 1 hour.

[Manufacturing method of photocurable resin composition]
According to the compounding ratios shown in Tables 1 and 2, each component was stirred and mixed in a flask equipped with a stirrer for 30 minutes until uniform. Of these, those containing PEG # 1000 or Penon JE66 were further stirred for 30 minutes to 1 hour while heating at 60 ° C. to dissolve the solid components, whereby the liquid photocurable resins of Examples and Comparative Examples were used. The composition was obtained.

The results are shown in Tables 1 and 2. The values of the blending amount of each component are all parts by weight.

From Tables 1 and 2, the photocurable resin compositions of Examples were excellent in fixability. From the comparison between Examples 1 to 6 and Examples 7 to 8, when the component (D) is the component (d1), the component (D) is not included or the component (D) is the component (d4). In contrast, it was excellent in peelability.
From the comparison between Examples 8 to 9 and Example 10, when the component (D) contains the component (d3) in addition to the component (d1), the component (D) contains only the component (d1). Similarly, it was excellent in peelability.
From the comparison between Example 11 and Example 8, when the component (d2) was a foaming agent, the peelability was particularly excellent.
From the comparison between Example 12 and Example 8, the peelability was excellent even when the component (d2) was only a part of the water-soluble filler contained in the foaming agent.
From the comparison between Example 13 and Example 11, when the combination of the third water-soluble filler contained in the water-based cleaning liquid and the water-soluble filler contained in the photocurable resin composition has foamability, these components are added. As in the case where both were contained in the photocurable resin composition, the peelability was particularly excellent.
A comparison between Example 14 and Example 1 shows that the photocurable resin composition contains the component (d2) but does not contain the component (d1), and the water-soluble filler contained in the water-based cleaning liquid and light When the combination with the water-soluble filler contained in the curable resin composition had foamability, it was superior in peelability.
On the other hand, the composition of Comparative Example 1 was inferior in peelability because it did not contain the component (B). Moreover, since the composition of Comparative Example 2 did not contain the component (A1), the peelability was inferior.

Claims (9)

A photocurable resin composition for bonding temporary fixing containing a radical polymerization-reactive monomer (A), a chain transfer agent (B), and a photopolymerization initiator (C), wherein the component (A) is intramolecular. A photocurable resin composition for temporary fixing for bonding, which comprises a radical polymerization-reactive monomer (A1) having one or more OH groups. The photocurable resin composition according to claim 1, further containing a water-soluble plasticizer (d1). The photocurable resin composition according to claim 2, wherein the weight average molecular weight of the component (d1) is 50 to 500. The photocurable resin composition according to any one of claims 1 to 3, further comprising a water-soluble filler (d2). The photocurable resin composition according to claim 1, further comprising a water-soluble filler (d2) but not a water-soluble plasticizer (d1). The photocurable resin composition according to any one of claims 1 to 5, wherein the component (B) is a compound having a thiol group or an α-methylstyrene dimer. The photocurable resin composition according to any one of claims 1 to 6, wherein the content of the component (B) in the photocurable resin composition is 0.7 to 15% by weight. The component (d2) is a combination of the first water-soluble filler (d2-1) and the second water-soluble filler (d2-2), where the component (d2-1) and the component (d2-2) are used. The photocurable resin composition according to any one of claims 4 to 7, wherein the combination of is foamable. The photocurable resin composition according to any one of claims 4 to 8, wherein the aqueous solvent in which the third water-soluble filler (d2-3) is dissolved temporarily fixes the photocurable resin composition. The combination of at least a part of the component (d2) contained in the photocurable resin composition and the component (d2-3), which is used as an aqueous solvent for releasing, has foamability, according to claims 4 to 8. The photocurable resin composition according to any one of the above.