JP7218485B2 - Method for producing photocurable resin composition, photocurable resin composition, adhesive composition, composite structure, and method for producing and dismantling composite structure - Google Patents

Description

The present invention provides a method for producing a photocurable resin composition, a photocurable resin composition obtained by the production method, an adhesive composition containing the photocurable resin composition, and an adhesive composition in which the adhesive composition is used. The present invention relates to a composite structure having a structure and methods of manufacturing and dismantling said composite structure.

It is requested that the components of optical devices such as liquid crystal displays and optical lenses, and the components of electronic devices such as electronic paper and batteries be fixed with an adhesive, and in some cases, be able to release the fixation. may occur.

Conventionally, in response to this demand, methods have been taken such as contacting the hardened adhesive of the fixed part with a solvent to swell it, or immersing it in water to peel off the hardened adhesive from the member ( For example, Patent Document 1).

JP 2010-100831 A

However, conventional cured adhesives such as those disclosed in Patent Document 1 remain in a solid state even when they are brought into contact with a solvent or water. was not easy to remove.

The present invention
A photocurable composition in which a photocurable material is dissolved in a solvent,
An adhesive composition in which a photocurable material is dissolved in a solvent, which contains the photocurable composition;
A composite structure including members bonded with the adhesive composition, a method for manufacturing the same, and
An object of the present invention is to provide a method for dismantling the composite structure, wherein the photocured adhesive composition is removed by contact with a solvent.

The present invention
[1] at least one radically polymerizable unsaturated bond-containing compound selected from the group consisting of oligomer compounds having (meth)acrylate groups, (meth)acrylate monomer compounds, amide compounds and N-vinyl heterocyclic compounds, photopolymerization A method for producing a photocurable resin composition comprising an initiator and a reaction inhibitor,
at least one compound A selected from oligomer compounds having a (meth)acrylate group;
at least one compound B selected from at least one radically polymerizable unsaturated bond-containing compound selected from the group consisting of the (meth)acrylate monomer compound, amide compound and N-vinyl heterocyclic compound;
At least one compound C selected from the photopolymerization initiators, and
Step 1 of selecting at least one compound D selected from the reaction inhibitors;
Step 2 of adjusting the blending amount of the compounds A to D,
Step 3 of blending the compounds A to D with adjusted blending amounts to obtain a blended composition containing the compounds A to D;
step 4 of obtaining a photocured body by irradiating the compounded composition with ultraviolet rays;
as well as,
The following solvent dissolution test for the photocurable material:
Add 0.78 g of a solvent to 0.02 g of the photocuring body, leave it at 25 ° C. under a light-shielding environment for 24 hours, and then visually confirm the state of the photocuring body,
Level 1 when it is confirmed that there is a residue of the photocuring material,
Level 2 when it is confirmed that there is no residue of the photocuring material,
Solvent dissolution test to determine
comprising step 5 of performing
Repeat steps 1 to 5 until the result of the solvent dissolution test reaches level 2,
The compounded composition when the result of the solvent dissolution test is Level 2 is defined as the photocurable resin composition that is the object of the manufacturing method,
In the photocurable resin composition,
With respect to 100 parts by mass of the compound A,
The compounding amount of the compound B is 1 to 1000 parts by mass,
With respect to a total of 100 parts by mass of the compound A and the compound B,
The compounding amount of the compound C is 0.1 to 100 parts by mass,
The amount of the compound D is 0 to 1000 parts by mass,
A method for producing a photocurable resin composition,
[2] A photocurable resin composition obtained by the method for producing a photocurable resin composition described in [1] above,
[3] An adhesive composition obtained by blending the photocurable resin composition described in [2] above.
[4] A composite structure including member 1 and member 2,
Member 1 and Member 2 A composite structure bonded via a photocured body of the adhesive composition described in the preceding item [3],
[5] A method for manufacturing a composite structure including member 1 and member 2,
The solvent described in the preceding item [1] is brought into contact with the photocured body of the adhesive composition in the composite structure described in the preceding item [4], and the photocured body of the adhesive composition of the member 1 and the member 2 is interposed. A method of manufacturing a composite structure, comprising:
[6] The cured body of the adhesive composition is brought into contact with the solvent described in [1] above to release the bonding between the member 1 and the member 2 via the photocured body of the adhesive composition, The method for dismantling a composite structure according to [4] above, wherein the member 1 and the member 2 are separated from each other.

According to the invention,
A photocurable composition in which a photocurable material is dissolved in a solvent,
An adhesive composition in which a photocurable material is dissolved in a solvent, which contains the photocurable composition;
A composite structure including members bonded with the adhesive composition, a method for manufacturing the same, and
A method for dismantling the composite structure can be provided in which the photocured adhesive composition is removed by contact with a solvent.

[Method for producing photocurable resin composition]
The photocurable resin composition of the present invention (hereinafter referred to as photocurable resin composition) is
The following method for producing the photocurable resin composition of the present invention (hereinafter also referred to as composition production method):
At least one radically polymerizable unsaturated bond-containing compound selected from the group consisting of (meth)acrylate group-containing oligomer compounds, (meth)acrylate monomer compounds, amide compounds and N-vinyl heterocyclic compounds, a photopolymerization initiator, and A method for producing a photocurable resin composition comprising a reaction inhibitor,
at least one compound A selected from oligomer compounds having a (meth)acrylate group;
at least one compound B selected from at least one radically polymerizable unsaturated bond-containing compound selected from the group consisting of the (meth)acrylate monomer compound, amide compound and N-vinyl heterocyclic compound;
At least one compound C selected from the photopolymerization initiators, and
Step 1 of selecting at least one compound D selected from the reaction inhibitors;
Step 2 of adjusting the blending amount of the compounds A to D,
Step 3 of blending the compounds A to D with adjusted blending amounts to obtain a blended composition containing the compounds A to D;
step 4 of obtaining a photocured body by irradiating the compounded composition with ultraviolet rays;
as well as,
The following solvent dissolution test for the photocurable material:
Add 0.78 g of a solvent to 0.02 g of the photocuring body, leave it at 25 ° C. under a light-shielding environment for 24 hours, and then visually confirm the state of the photocuring body,
Level 1 when it is confirmed that there is a residue of the photocuring material,
Level 2 when it is confirmed that there is no residue of the photocuring material,
Solvent dissolution test to determine
comprising step 5 of performing
Repeat steps 1 to 5 until the result of the solvent dissolution test reaches level 2,
The compounded composition when the result of the solvent dissolution test is Level 2 is defined as the photocurable resin composition that is the object of the manufacturing method,
In the photocurable resin composition,
With respect to 100 parts by mass of the compound A,
The compounding amount of the compound B is 1 to 1000 parts by mass,
With respect to a total of 100 parts by mass of the compound A and the compound B,
The compounding amount of the compound C is 0.1 to 100 parts by mass,
The amount of the compound D is 0 to 1000 parts by mass,
It can be obtained by a composition manufacturing method.

(1) Process 1
Compounds A to D are compounded compositions obtained by adjusting the amounts of these in steps 2 and 3, and when the photocured body is made into a photocured body in step 4, the photocured body shows a level in the solvent dissolution test in step 5. It is selected in step 1 towards being determined to be 2.

In the following, the level 2 of the photocuring material shown in the solvent dissolution test in step 5 is also referred to as the solvent solubility of the photocurable resin composition.

(1-1) Compound A
From the viewpoint of solvent solubility of the photocurable resin composition, compound A is
It is at least one compound selected from oligomer compounds having a (meth)acrylate group.

The oligomer compound having a (meth)acrylate group preferably has a weight-average molecular weight of 1,000 to 100,000, more preferably 2,000 to 70,000, from the viewpoint of achieving both rapid curing and low curing shrinkage of the photocurable resin composition. , more preferably 5,000 to 50,000.

The weight average molecular weight is measured based on GPC, preferably under the following conditions:
Measuring device: GPC system manufactured by Shimadzu Corporation;
Column type: organic solvent-based SEC column (manufactured by Tosoh Corporation);
Type of solvent: Tetrahydrofuran (THF).

From the viewpoint of solvent solubility of the photocurable resin composition, compound A is preferably selected so that the photocured body of the photocurable resin composition has a low crosslinking density.
Preferably, at least one compound selected from oligomer compounds having a tetrafunctional or less (meth)acrylate group,
More preferably, at least one compound selected from oligomer compounds having a trifunctional or less (meth)acrylate group,
More preferably, at least one compound selected from oligomer compounds having a (meth)acrylate group having a functionality of two or less,
More preferably, it contains an oligomer compound having at least a bifunctional (meth)acrylate group.

Compound A is preferably a (meth)acrylate containing at least one selected from the group consisting of polyisoprene, polybutadiene, poly(meth)acrylate and polyurethane in its skeleton, from the viewpoint of achieving both rapid curing and low cure shrinkage. at least one oligomeric compound having a group.

An oligomer compound having a (meth)acrylate group containing polyisoprene in its skeleton is also called (meth)acrylic-modified polyisoprene. The weight average molecular weight of the (meth)acrylate group-containing oligomer compound having a polyisoprene skeleton is preferably 1,000 to 100,000, more preferably 10,000 to 60,000.
Examples of commercially available oligomer compounds having a polyisoprene skeleton and (meth)acrylate groups include “UC-203” (weight average molecular weight: 25,000) manufactured by Kuraray Co., Ltd.

An oligomer compound having a (meth)acrylate group containing polybutadiene in its skeleton is also called (meth)acrylic-modified polybutadiene. The weight average molecular weight of the oligomer compound having a (meth)acrylate group containing polybutadiene in its skeleton is preferably 500 to 100,000, more preferably 1,000 to 60,000.
Commercially available oligomer compounds having (meth)acrylate groups containing polybutadiene in the skeleton include, for example, “TE2000” (weight average molecular weight: 2000) manufactured by Nippon Soda Co., Ltd.

An oligomer compound having a (meth)acrylate group containing poly(meth)acrylate in its skeleton is also called (meth)acrylic-modified poly(meth)acrylate. The weight average molecular weight of the (meth)acrylate group-containing oligomer compound having a poly(meth)acrylate skeleton is preferably 1,000 to 100,000, more preferably 2,000 to 60,000.
Commercially available oligomer compounds having a (meth)acrylate group with a poly(meth)acrylate skeleton include, for example, "AB-6" (weight average molecular weight: 6000) manufactured by Toagosei Co., Ltd.

An oligomer compound having a (meth)acrylate group containing polyurethane in its skeleton is also called a (meth)acrylic-modified polyurethane. The weight average molecular weight of the (meth)acrylate group-containing oligomer compound containing polyurethane in its skeleton is preferably 1,000 to 100,000, more preferably 10,000 to 60,000.
Commercially available oligomer compounds having (meth)acrylate groups containing polyurethane in the skeleton include, for example, “UN-7700” manufactured by Negami Kogyo Co., Ltd.

Among these, the oligomer compound having a (meth)acrylate group is particularly preferably an oligomer compound having a (meth)acrylate group containing at least one selected from the group consisting of polyurethane and poly(meth)acrylate in its skeleton.

A polyfunctional urethane (meth)acrylate is obtained by reacting a polyhydric alcohol, an organic polyisocyanate and a hydroxy (meth)acrylate compound.

Examples of polyhydric alcohols include neopentyl glycol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, Tricyclodecanedimethylol, bis(hydroxymethyl)cyclohexane, etc., these polyhydric alcohols and polybasic acids (e.g., succinic acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, azelaic acid, tetrahydrophthalic anhydride, etc.) ), caprolactone alcohol obtained by reacting the polyhydric alcohol with ε-caprolactone, polycarbonate polyol (for example, polycarbonate diol obtained by reacting 1,6-hexanediol and diphenyl carbonate, etc. ) or polyether polyols (eg, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide-modified bisphenol A, etc.).

Examples of organic polyisocyanates include isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4'-diisocyanate and dicyclopentanyl isocyanate.

Examples of hydroxy (meth) acrylate compounds include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, dimethylolcyclohexyl mono (meth) acrylate, hydroxycaprolactone (meth) acrylate, 2- Hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol tri(meth)acrylate and the like.

Urethane (meth)acrylate is obtained, for example, by the following reaction.
That is, an organic polyisocyanate is mixed with a polyhydric alcohol so that the isocyanate group is preferably 1.1 to 2.0 equivalents per hydroxyl group equivalent, and the reaction is carried out at a reaction temperature of preferably 70 to 90° C. to obtain a urethane oligomer. to synthesize. Then, a hydroxy (meth)acrylate compound is mixed so that the hydroxyl group is preferably 1 to 1.5 equivalents per isocyanate group equivalent of the urethane oligomer obtained, and the mixture is preferably reacted at 70 to 90° C. to obtain the desired product. A urethane (meth)acrylate is obtained.

(1-2) Compound B
From the viewpoint of solvent solubility of the photocurable resin composition, compound B is
It is at least one compound selected from at least one radically polymerizable unsaturated bond-containing compound selected from the group consisting of (meth)acrylate monomer compounds, amide compounds and N-vinyl heterocyclic compounds.

From the viewpoint of solvent solubility of the photocurable resin composition, compound B is preferably selected so that the photocured body of the photocurable resin composition has a low crosslinking density.

From the viewpoint of low cross-linking density, as a (meth)acrylate monomer compound,
Preferably, at least one compound selected from tetrafunctional or less (meth)acrylate monomer compounds,
More preferably, at least one compound selected from trifunctional or less (meth)acrylate monomer compounds,
More preferably, at least one compound selected from difunctional or less (meth)acrylate monomer compounds,
More preferably, it is at least one compound selected from monofunctional (meth)acrylate monomer compounds.

From the same point of view, compound B preferably contains at least one compound selected from monofunctional (meth)acrylate monomer compounds.

As the compound B, specifically, for example,
Methyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, lauryl (meth)acrylate, etc. Alkyl (meth)acrylate of;
alkoxy-substituted alkyl (meth)acrylates such as methoxyethyl (meth)acrylate;
benzyl (meth)acrylate, phenyl (meth)acrylate and the like;
Hydroxy C _2-10 alkyl (meth)acrylates or C _2-10 alkanediol mono(meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate;
Alicyclic structure-containing (meth)acrylates such as dicyclopentenyloxyethyl (meth)acrylate, norbornene (meth)acrylate, dicyclopentanyl (meth)acrylate, and isobornyl (meth)acrylate;
Alkane polyol mono (meth) acrylates such as glycerin mono (meth) acrylate; amino groups such as 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-t-butylaminoethyl (meth) acrylate (meth)acrylates having
glycidyl (meth)acrylate;
2-(1,2-cyclohexanedicarboximido)ethyl acrylate, piperidinyl (meth)acrylate, alkylpiperidinyl (meth)acrylate (such as pentamethylpiperidinyl (meth)acrylate), morpholino (meth)acrylate, tetrahydrofluoro heterocyclic (meth)acrylates such as furyl (meth)acrylate;
Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, neopentyl Di(meth)acrylates such as glycol di(meth)acrylate and 1,6-hexanediol di(meth)acrylate;
(meth)acrylates having a carboxyl group such as 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate;
acryloylmorpholine, acrylamide compounds such as diethylacrylamide, amide compounds such as N-vinylacetamide, N-vinylformamide;
N-vinyl heterocyclic compounds such as N-vinylpyrrolidone, N-vinylpyridine and N-vinylcaprolactam;
Hydroxy C2-10 alkyl (meth)acrylates, alkanediol mono(meth)acrylates having 2 to 10 carbon atoms, polyalkylene glycol mono(meth)acrylates, alkane polyol mono(meth)acrylates, and acrylamide compounds are more preferable.
More preferred are hydroxy C2-10 alkyl (meth)acrylates and/or alkanediol mono(meth)acrylates having 2 to 10 carbon atoms.

(1-3) Compound C
Compound C is at least one compound selected from photopolymerization initiators.
As compound C, radical photopolymerization initiators and/or cationic photopolymerization initiators are preferred.
The radical photopolymerization initiator is used for curing the acrylate sites in compound A and compound B, and the cationic photopolymerization initiator promotes the dehydration condensation reaction of terminal SiOH and is also used for cationic polymerization of the epoxy moiety.

The radical photopolymerization initiator has a function of initiating radical polymerization by photoexcitation. be done.

Examples of radical photopolymerization initiators include ultraviolet polymerization initiators and visible light polymerization initiators.
Examples of ultraviolet polymerization initiators include benzoin-based, benzophenone-based, and acetophenone-based initiators.
Visible light polymerization initiators include acylphosphine oxide-based, thioxanthone-based, metallocene-based, and quinone-based initiators.

Specifically, as the ultraviolet polymerization initiator,
Benzophenone polymerization initiators such as benzophenone, 4-phenylbenzophenone, benzoylbenzoic acid, and bisdiethylaminobenzophenone;
Acetophenone polymerization initiators such as 2,2-diethoxyacetophenone;
benzoin-based polymerization initiators such as benzyl, benzoin, and benzoin isopropyl ether;
Alkylphenone-based polymerization initiators such as benzyl dimethyl ketal; Thioxanthone-based polymerization initiators such as thioxanthone;
1-hydroxycyclohexylphenyl ketone, 1-(4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, 1-(4-(2-hydroxyethoxy)-phenyl)-2-hydroxy-2-methyl Hydroxyalkylphenone-based polymerization initiators such as -1-propan-1-one and 2-hydroxy-2-methyl-1-phenylpropan-1-one.

Visible light initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4 acylphosphine oxide photoinitiators such as ,4-trimethyl-pentylphosphine oxide;
camphorquinone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1- A ketone-based polymerization initiator such as butanone-1 can be used.

Among the above examples, the compound C is more preferably a hydroxyalkylphenone-based polymerization initiator and/or an acylphosphine oxide-based photopolymerization initiator from the viewpoint of curability in addition to normal strength and durability strength.
1-hydroxycyclohexylphenyl ketone (IRGACURE 184, manufactured by BASF) and/or 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (IRGACURE TPO, manufactured by BASF) are more preferable,
1-Hydroxycyclohexylphenyl ketone (IRGACURE 184, manufactured by BASF) is more preferred.

The cationic photopolymerization initiator preferably acts as a photoacid generator for the cationic polymerizable sites of compound A and compound B, and from the viewpoint of curability in addition to normal strength and durability strength, irradiation of energy rays A compound that generates a Lewis acid or a Bronsted acid is more preferable, and a sulfonium salt and/or an iodonium salt are more preferable.

As a sulfonium salt, from the viewpoint of curability in addition to normal strength and durability strength,
triphenylsulfonium hexafluorophosphate,
triphenylsulfonium hexafluoroantimonate,
triphenylsulfonium tetrakis(pentafluorophenyl)borate,
4,4′-bis[diphenylsulfonio]diphenylsulfide bishexafluorophosphate,
4,4′-bis[di(β-hydroxyethoxy)phenylsulfonio]diphenylsulfide bishexafluoroantimonate,
4,4′-bis[di(β-hydroxyethoxy)phenylsulfonio]diphenylsulfide bishexafluorophosphate,
7-[di(p-toluyl)sulfonio]-2-isopropylthioxanthone hexafluoroantimonate,
7-[di(p-toluyl)sulfonio]-2-isopropylthioxanthone tetrakis(pentafluorophenyl)borate,
4-phenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide hexafluorophosphate,
4-(p-tert-butylphenylcarbonyl)-4′-diphenylsulfonio-diphenylsulfide hexafluoroantimonate,
4-(p-tert-butylphenylcarbonyl)-4′-di(p-toluyl)sulfonio-diphenylsulfide tetrakis(pentafluorophenyl)borate and the like are preferred.

As commercially available sulfonium salt-based cationic photopolymerization initiators, SP-170, SP-172, SP-150, SP-152 manufactured by Adeka Co., Ltd., CPI-210S manufactured by San-Apro Co., Ltd. are preferable, and SP-170 manufactured by Adeka Co., Ltd. , SP-172 or CPI-210S manufactured by San-Apro Co., Ltd. are more preferable.

As an iodonium salt, from the viewpoint of curability in addition to normal strength and durability strength,
diphenyliodonium tetrakis(pentafluorophenyl)borate,
diphenyliodonium hexafluorophosphate,
diphenyliodonium hexafluoroantimonate,
Di(4-nonylphenyl)iodonium hexafluorophosphate and the like are preferred.
As a commercially available iodonium salt-based cationic photopolymerization initiator, PI2074 manufactured by Rhodia is preferred.

(1-4) Compound D
Compound D is at least one compound selected from reaction inhibitors.

The reaction inhibitor means that the photocurable resin composition has solvent solubility, but the compound composition in which only the compound A, the compound B, and the compound C in the photocurable resin composition are left in step 5. It is a compound other than compound A, compound B and compound C in the photocurable resin composition, which becomes level 1 in the solvent dissolution test.

The reaction inhibitor is considered to adjust the polymerization reaction of the compound A and the compound B so that the crosslink density of the photocured body of the photocurable resin composition is low, preferably a plasticizer and / or a chain transfer agent are mentioned.

The plasticizer preferably includes a resin-based plasticizer and an oil-based plasticizer.

The resin-based plasticizer preferably includes one or more selected from the group consisting of rosin-based, terpene-based, petroleum resin-based and coumarone-indene resins, and more preferably,
Rosin-based plasticizers such as gum rosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, maleated rosin, rosin/glycerol ester, and hydrogenated rosin/glycerol ester;
Rosin ester resins such as disproportionated rosin ester resins, polymerized rosin ester resins, and hydrogenated rosin ester resins;
Rosin-based resin such as rosin phenol;
Terpene-based resins include resins, terpene-based resins such as terpene phenolic resins, aromatic modified terpene resins, and hydrogenated terpene resins;
Petroleum resins include petroleum resins such as aliphatic petroleum resins, alicyclic petroleum resins, and aromatic petroleum resins;
(Hydrogenated) polyisoprene, hydroxyl group-containing (hydrogenated) polyisoprene, (hydrogenated) polybutadiene, hydroxyl group-containing (hydrogenated) polybutadiene, rubber polymers such as polybutene;
thermoplastic elastomers;
xylene resin; and one or more selected from the group consisting of acrylic resins such as acrylic polymers and acrylic copolymers.

Oil-based plasticizers preferably include phthalates such as dibutyl phthalate, diisononyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate, and butylbenzyl phthalate;
Polyvalent carboxylic acid esters such as dioctyl adipate, diisononyl adipate, dioctyl sebacate, diisononyl sebacate, and diisononyl 1,2-cyclohexanedicarboxylate;
Phosphate esters such as tricresyl phosphate and tributyl phosphate;
One or more selected from the group consisting of trimellitates, low molecular weight polyesters, tributyl acetylcitrate, epoxidized vegetable oils, sebacates, azelates, maleates and benzoates.

As a chain transfer agent, preferably
Alcohols such as methanol, ethanol, propanol, butanol;
Aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, furfural, and benzaldehyde;
Halogens such as carbon tetrachloride and chloroform;
α-methylstyrene dimer;
and,
One or more selected from the group consisting of mercaptans such as dodecyl mercaptan, lauryl mercaptan, normal mercaptan, thioglycolic acid, octyl thioglycolate and thioglycerol.

(2) Process 2
In step 2, the compounding amounts of the compounds A to D are adjusted so that the photocurable composition is judged to be level 2 in the solvent dissolution test in step 5.

From the viewpoint of solvent solubility of the photocurable composition, when compound A contains an oligomer compound selected from the group consisting of oligomer compounds having a trifunctional or higher (meth)acrylate group,
In the compound A, the amount of the oligomer compound having a trifunctional or higher (meth)acrylate group is preferably 0 to 20% by mass, more preferably 0 to 15% by mass, still more preferably 0 to 10% by mass, still more preferably is 0 to 5% by mass.

From the viewpoint of solvent solubility of the photocurable composition, when compound A contains an oligomer compound having a monofunctional and / or difunctional (meth) acrylate group,
In compound A, the oligomer compound having a monofunctional and/or difunctional (meth)acrylate group is preferably 80 to 100% by mass, more preferably 85 to 100% by mass, still more preferably 90 to 100% by mass, and further It is preferably 95 to 100% by mass, more preferably 100% by mass.

From the viewpoint of solvent solubility and viscosity adjustment of the photocurable composition, the amount of compound B is preferably 1 to 1000 parts by mass with respect to 100 parts by mass of compound A in the photocurable resin composition. parts, more preferably 20 to 700 parts by mass, more preferably 100 to 500 parts by mass

From the viewpoint of solvent solubility and curability of the photocurable composition, the amount of compound C is preferably 0.1 to 50 parts by mass, more preferably 100 parts by mass in total of compound A and compound B. 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, more preferably 1 to 10 parts by mass.

From the viewpoint of the solvent solubility and curability of the photocurable composition, the amount of compound D is 0 to 500 parts by mass, preferably 5 to 100 parts by mass with respect to the total of 100 parts by mass of compound A and compound B. 300 parts by mass, more preferably 10 to 200 parts by mass, and even more preferably 20 to 100 parts by mass.

(3) Process 3
In step 3, compounds A to D, the blending amounts of which were adjusted in step 2, are blended to obtain blended compositions containing compounds A to D.

In step 3, compounds A to D are filled in a SUS container, and the mixture composition is placed in a uniform state without powder remaining undissolved. Stirring with a rotary stirrer is preferred.

(4) Step 4
In step 4, the material obtained in step 3 is irradiated with ultraviolet rays to obtain a photocured body.

In step 4, the compounded composition was placed on a transparent slide glass (S1127 manufactured by Matsunami Glass Co., Ltd.) and a transparent PET film (manufactured by Panac Co., Ltd., product name: Lumirror 100T60, thickness: 20 mm, length: 20 mm, thickness: 0.5 mm). 100 μm), and cured by irradiating with ultraviolet rays using a metal halide lamp (ECS-301 manufactured by Eyegraphics).

When the compounded composition is used to construct the laminates of Examples described later, the ultraviolet rays have an adhesive strength of preferably 1 N or more, more preferably 1 to 1000 N, still more preferably 1 to 500 N, and even more preferably 1 to 500 N. Preferably, the irradiation dose is adjusted to correspond to the irradiation dose in the range of 1 to 300N.

(5) Step 5
In step 5, the photocured body obtained in step 4 is subjected to the following solvent dissolution test:
Add 0.78 g of a solvent to 0.02 g of the photocuring material and allow to stand at 25° C. in a light-shielding environment for 24 hours.
Level 1 when it is confirmed that there is a photocuring agent residue,
Level 2 when it is confirmed that there is no residue of the photocuring material,
Solvent dissolution test to determine
I do.

The residue of the photocured body includes, for example, those in the same state as the photocured body, those in a gelled state, and those in a swollen state, other than those dissolved in a solvent to form a solution.

The solvent is preferably a solvent used for the purpose of dissolving the photocurable composition of the adhesive composition when the photocurable composition described later is used as the adhesive composition of the present invention.
Alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol and benzyl alcohol;
Hydrocarbons such as benzene, toluene, xylene, mineral spirits, cyclohexane, n-hexane, methylcyclohexane, styrene;
ethers such as diethyl ether;
Esters such as ethyl acetate, propyl acetate, butyl acetate, diethylene glycol monoethyl ether acetate, diethyl carbonate, dimethyl carbonate, propylene carbonate;
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, diacetone alcohol;
Nitrogens such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone;
Glycol ethers such as butyl glycol, methyl diglycol, butyl diglycol, 3-methyl-3-methoxybutanol, tetrahydrofuran;
Chlorines such as methylene chloride, chloroform, carbon tetrachloride, and chlorobenzene;
dimethyl sulfoxide; acetonitrile; carboxylic acids such as formic acid and acetic acid; and at least one compound selected from the group consisting of water,
More preferably, at least one compound selected from the group consisting of alcohols, hydrocarbons, esters and ketones,
More preferably, at least one compound selected from the group consisting of acetone, hexane, isopropyl alcohol and diethyl carbonate.

It is preferable that 0.02 g of the photocuring agent and 0.78 g of the solvent are filled in a glass container having a capacity of 10 ml, the container is sealed, and the entire container is covered with aluminum foil to shield from light.

Repeat steps 1 to 5 until the result of the solvent dissolution test reaches level 2,
The compounded composition when the result of the solvent dissolution test is Level 2 is defined as the photocurable resin composition, which is the object of the composition manufacturing method.

In the composition manufacturing method, in step 1, in addition to compounds A to D, if necessary, for example, a surfactant, an ionic liquid, a solvent, an antifoaming agent, an antioxidant, an ultraviolet absorber, a light Additive compounds such as stabilizers, inorganic and organic fillers, and polymers (hereinafter referred to as compound E) are selected, the compounding amount of compound E is adjusted in step 2, and compounded compositions containing compounds A to E are prepared in step 3. is obtained, Steps 4 and 5 are performed to obtain a photocurable composition containing compounds A to E having solvent solubility.

However, compound E is preferably selected in a range that does not impair the solvent solubility of the photocurable composition when only compounds A to D are used, and the blending amount thereof is preferably adjusted.

[Photocurable resin composition]
The photocurable resin composition of the present invention obtained by the composition manufacturing method is selected from the group consisting of an oligomer compound having a (meth)acrylate group, a (meth)acrylate monomer compound, an amide compound and an N-vinyl heterocyclic compound. A composition comprising at least one radically polymerizable unsaturated bond-containing compound, a photopolymerization initiator, and a reaction inhibitor, as described above, as long as it does not inhibit the solvent solubility of the photocurable resin composition. , may contain compound E as an optional component.

The photocurable resin composition of the present invention is in a liquid form with fluidity, and the photocurable resin composition has the effect of being soluble in a solvent.
The photocurable resin composition of the present invention can be suitably used as an adhesive composition for bonding members because it has excellent adhesion to members when it is applied to a member in liquid form and photocured.

[Adhesive composition]

The adhesive composition of the present invention (hereinafter also referred to as an adhesive composition) is obtained by blending the photocurable composition of the present invention, preferably a liquid composition having fluidity, and the photocurable composition is It has solvent solubility.

The adhesive composition can be applied to the member using a dispenser, jet dispenser, inkjet, slit coater, die coater, screen printing, or the like.

The adhesive composition can be, for example, a surfactant, an ionic liquid, a solvent, or , antifoaming agents, antioxidants, ultraviolet absorbers, light stabilizers, various inorganic and organic fillers, polymers, and other additives other than compound E can be included.

The additives other than the compound E in the adhesive composition are additives other than the compound E blended in the photocurable composition, and additives other than the compound E blended together with the photocurable composition. It means a combination of

From the viewpoint of coatability on members, the adhesive composition has a viscosity at a temperature of 25°C of
preferably 0.1 to 100 Pa s or less,
more preferably 0.3 to 50 Pa s or less,
More preferably, it is 0.5 to 10 Pa·s or less.

The viscosity is measured using a rheometer (manufactured by Anton Paar), a cone rotor (φ=25 mm, rotor angle 2°), a shear rate of 10 [1/sec], and 25°C.

From the viewpoint of adhesion, the total amount of compounds A to D in the adhesive composition is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and still more preferably 90 to 100% by mass, more preferably 100% by mass.

[Composite structure]
A composite structure (hereinafter also referred to as a composite structure) of the present invention is a structure that includes a member 1 and a member 2 and that the member 1 and the member 2 are adhered via an adhesive composition.

That the member 1 and the member 2 are adhered via the adhesive composition means that the surfaces of the member 1 and the member 2 are in contact with the adhesive composition with the adhesive composition interposed therebetween ( The relative positions of member 1 and member 2 in the vicinity of the adhesive composition are fixed).

In the composite structure, the adhesive composition bonding the members 1 and 2 is further expected to be dissolved away by contact of a solvent with the adhesive composition to release the adhesion of the members 1 and 2. In this case, the adhesion of the member 1 and the member 2 via the adhesive composition is called temporary fixing, and the adhesive composition when used with the intention of releasing the adhesion of the members 1 and 2 Also called a temporary fixative.

When the member 1 and the member 2 are plates, for example,
Preferably, the surfaces in the thickness direction of the member 1 and the member 2 are adhered or temporarily fixed through the adhesive composition, or more preferably the plate surfaces of the member 1 and the member 2 are adhered or temporarily fixed through the adhesive composition. be fixed,
The member 1 and the member 2 may adhere via the adhesive composition, and the member 1 and the member 2 may constitute a laminate.

A plate is a structure having a thickness smaller than the area of the front and back surfaces, and may be plate-like or thin-film-like, and may be flat or curved.

Examples of the composite structure of the present invention include the following.
(1) A liquid crystal display comprising an optical member such as various films, wherein the optical member is adhered or temporarily fixed to form a laminate or the like.

(2) A liquid crystal display having a liquid crystal cell, wherein the inside of the liquid crystal cell is adhered or temporarily fixed.

(3) A plurality of articles requiring surface smoothness, such as wafers, are temporarily fixed on a base material, subjected to surface treatment simultaneously, and used after removing the base material.

(4) Anti-glare mirrors, electronic paper, batteries, capacitors, and other devices using an electrolytic solution, in which members such as electrodes, separators, current collectors, etc. are adhered or temporarily fixed. When used as a temporary fixing agent, it is preferable to select constituent compounds of the adhesive composition so that even if the dissolved adhesive composition is mixed with the electrolytic solution, the performance of the electrolytic solution is not impaired.

(5) A polishing apparatus for polishing an optical lens, in which the optical lens and a fixed support base for the optical lens are temporarily fixed.
(6) After temporarily fixing a plurality of raw materials such as optical lenses and mechanically processing them into a predetermined shape, the adhesive is removed and each of them is used as a component.

From the viewpoint of the adhesiveness of the adhesive composition, the materials of the members 1 and 2 are glass, PET, TAC, COP, polyimide, PMMA, polycarbonate, vinyl chloride, PVA, polyethylene, polypropylene, silicon, graphite, aluminum, copper, SUS or the like is preferable, and the surface of the member may be treated with an organic hard coat layer or an inorganic hard coat layer, and in order to provide conductivity, a transparent conductive material such as ITO, IZO, or carbon nanotubes is treated. Alternatively, a metal such as silver or copper may be patterned on the surface as an electrode or wiring material.

[Manufacturing method of composite structure]
In the composite structure in which the member 1 and the member 2 are bonded via the photocurable adhesive composition, the adhesive composition of the member 1 and the member 2 is obtained by contacting the photocurable adhesive composition with a solvent. A composite structure in which the member 1 and the member 2 are not fixed to each other and are in close proximity or in contact can be obtained by a method for manufacturing a composite structure including a step of releasing adhesion of objects through a photocured body. .

[Method for dismantling composite structure]
The composite structure obtained in step 2 is exposed to the adhesive composition of member 1 and member 2 via the adhesive composition by contacting the adhesive composition with a solvent and/or by setting the temperature environment to a temperature higher than the temperature Tc. Since the members 1 and 2 can be separated from each other by releasing the adhesion between them, the composite structure can be easily dismantled.

[Compound raw material]
(1) Compound A
(1-1) Compound a1: UA10000B (KSM Co., Ltd., bifunctional polyether polyurethane acrylate), weight average molecular weight: 25000
(1-2) Compound a2: UA-BK1 (KSM Co., tetrafunctional polyether polyurethane acrylate), weight average molecular weight: 25000
(1-3) Compound a3: AB-6 (Toagosei Co., Ltd., monofunctional polybutyl acrylate oligomer), weight average molecular weight: 6000

(2) Compound B
(2-1) Compound b1: SR395 (Sartomer, isodecyl acrylate)
(2-2) Compound b2: FA513AS (Hitachi Chemical Co., Ltd., dicyclopentanyl acrylate)
(2-3) Compound b3: M-140 (Toagosei Co., Ltd., N-acryloyloxyethylhexahydrophthalimide)
(2-4) Compound b4: 4-HBA (Nippon Kasei Co., Ltd., 4-hydroxybutyl acrylate)
(2-5) Compound b5: ACMO (KJ Chemicals, acryloylmorpholine)
(2-6) Compound b6: AE-200 (NOF Co., Ltd., polyethylene glycol monoacrylate)
(2-7) Compound b7: HEAA (KJ Chemicals, hydroxyethylacrylamide)
(2-8) Compound b8: DMAA (KJ Chemicals, dimethylacrylamide)

(3) Compound C
(3-1) Compound c1: I-500 (BASF Corporation, 1-hydroxy-cyclohexyl-phenyl-ketone:benzophenone = 1:1 mixture)
(3-2) Compound c2: I-184 (BASF Corporation, 1-hydroxycyclohexylphenyl ketone)
(3-3) Compound c3: I-TPO (BASF Corporation, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide)

(4) Compound D
(4-1) Compound d1: KE-311 (Arakawa Chemical Industries, Ltd., hydrogenated rosin ester)
(4-2) Compound d2: ME-H (Arakawa Chemical Industries, Ltd., hydrogenated rosin ester)
(4-3) Compound d3: NK-H (Fudo Co., xylene resin)
(4-4) Compound d4: DINCH (BASF Corporation, 1,2-cyclohexanedicarboxylic acid diisononyl ester)
(4-5) Compound d5: RX31-38 (Asia Industry Co., Ltd., polyether polyurethane)
(4-6) Compound d6: MSD-100 (Mitsui Chemicals, α-methylstyrene dimer)

[Examples and Reference Examples]
Examples 1 to 18 are photocurable compositions of the present invention judged to have solvent solubility level 2 in step 5,
Reference Examples 1 to 5 are formulation compositions judged to have level 1 solvent solubility in step 5.

The numerical value described in the column corresponding to each compound of Examples and Reference Examples in Table 1 is the blending amount (g) adjusted in step 2.

(1) Example 1
As compounds A to D, each compound whose numerical value is described in Example 1 of Table 1 is selected (step 1), and each selected compound is weighed according to the blending amount described in Table 1 (step 2 ), filled in a container (made of material SUS316, capacity 700 ml), stirred at 80 ° C. under atmospheric pressure at 200 rpm for 360 minutes using a three-one motor (manufactured by Shinto Kagaku Co., Ltd.), was obtained (Step 3).

The compounded composition was irradiated with ultraviolet rays of 3000 mJ/cm ² from a metal halide lamp (manufactured by Eyegraphics, product number UV-031-A/BM-E1) to obtain a photocured product (Step 4).

At an environmental temperature of 25° C., 0.02 g of the photocuring material was filled in a glass container with a capacity of 10 ml, and 0.78 g of solvent acetone (manufactured by Kanto Kagaku Co., Ltd., special grade) was added, and the container was sealed. , The entire container is covered with aluminum foil to shield from light, left to stand in a room environment of 25 ° C. for 24 hours, then the container is opened and the state of the photocured product is visually observed,
Level 1 when it is confirmed that there is a photocuring agent residue,
Level 2 was determined when it was confirmed that there was no residue of the photocuring material (Step 5).

(2) Examples 2-18 and Reference Examples 1-5
As compounds A to D, each compound whose numerical value is described in each example and each reference example in Table 1 was selected, and the ultraviolet irradiation conditions were changed from Example 1 as described in Table 1. Steps 1-5 were performed in the same manner as in 1.

The irradiation conditions of the ultraviolet rays were such that the irradiation amount was such that the adhesion strength of the following laminate was 1N or more.

[Adhesion Strength of Laminate]
With an ultraviolet irradiation Minebea Co., Ltd. tensile tester (Technograph TG-2kN), the slide glass and PET film are pulled in the shear direction of the PET film of the laminate at a speed of 100 mm / min, respectively, and the stress detected. was taken as the adhesive strength of the read laminate.

[Manufacturing and Dismantling of Composite Structures and Comparative Structures]
Twenty-three pairs of slide glass 1 (plate-shaped member 1) having a spacer with a thickness of 200 μm installed on the plate surface were prepared, and Examples 2 to 18 and Reference Examples 1 to 5 were placed on the surface of the slide glass 1. 0.015 g of the photocurable composition was collected using a spatula, placed, sandwiched between another slide glass 2, and irradiated with ultraviolet rays at the dose shown in Table 1. Slide glass 1 and slide glass 2 Laminates laminated via each composition (composite structures using the photocurable compositions of Examples 2 to 18 and Reference Examples 1 to 5 and the photocurable compositions of Reference Examples 1 to 5 A comparative structure) was obtained.

A laminated body in which the slide glass 1 and the slide glass 2 obtained in the production of the composite structure are laminated with the respective photocurable compositions interposed therebetween was immersed in acetone and allowed to stand for 360 minutes.
The photocurable composition in the composite structure was dissolved in a solvent and removed,
The photocurable composition in the comparative structure had solids left undissolved in the solvent.

After taking out the laminate that had been immersed in acetone and peeling off the laminate,
The laminate, which was a composite structure, could be dismantled by separating the slide glasses 1 and 2 by lightly pulling them apart by hand.
The laminate, which was the comparative structure, could not be separated from the slide glass 1 and the slide glass 2 by lightly pulling them apart by hand, and could not be dismantled.

Table 1 shows the results.

Claims (7)

At least one radically polymerizable unsaturated bond-containing compound selected from the group consisting of (meth)acrylate group-containing oligomer compounds, (meth)acrylate monomer compounds, amide compounds and N-vinyl heterocyclic compounds, a photopolymerization initiator, and A method for producing a photocurable resin composition comprising a reaction inhibitor,
at least one compound A selected from oligomer compounds having a (meth)acrylate group;
at least one compound B selected from at least one radically polymerizable unsaturated bond-containing compound selected from the group consisting of the (meth)acrylate monomer compound, amide compound and N-vinyl heterocyclic compound;
At least one compound C selected from the photopolymerization initiators, and
Step 1 of selecting at least one compound D selected from the reaction inhibitors;
Step 2 of adjusting the blending amount of the compounds A to D,
Step 3 of blending the compounds A to D with adjusted blending amounts to obtain a blended composition containing the compounds A to D;
step 4 of obtaining a photocured body by irradiating the compounded composition with ultraviolet rays;
as well as,
The following solvent dissolution test for the photocurable material:
Add 0.78 g of a solvent to 0.02 g of the photocuring body, leave it at 25 ° C. under a light-shielding environment for 24 hours, and then visually confirm the state of the photocuring body,
Level 1 when it is confirmed that there is a residue of the photocuring material,
Level 2 when it is confirmed that there is no residue of the photocuring material,
Solvent dissolution test to determine
comprising step 5 of performing
Repeat steps 1 to 5 until the result of the solvent dissolution test reaches level 2,
The compounded composition when the result of the solvent dissolution test is Level 2 is defined as the photocurable resin composition that is the object of the manufacturing method,
In the photocurable resin composition,
With respect to 100 parts by mass of the compound A,
The compounding amount of the compound B is 1 to 1000 parts by mass,
With respect to a total of 100 parts by mass of the compound A and the compound B,
The compounding amount of the compound C is 0.1 to 100 parts by mass,
The amount of the compound D is 0 to 1000 parts by mass,
A method for producing a photocurable resin composition. A photocurable resin composition containing compounds A, B, C and D,
The compound A is at least one compound selected from oligomer compounds having a tetrafunctional or less (meth)acrylate group,
The compound B is at least one compound selected from at least one radically polymerizable unsaturated bond-containing compound selected from the group consisting of (meth)acrylate monomer compounds, amide compounds and N-vinyl heterocyclic compounds,
The compound C is at least one compound selected from photopolymerization initiators,
The compound D is at least one compound selected from reaction inhibitors,
The compound D is a resin plasticizer and/or an oil plasticizer (provided that the compound D is a fatty alcohol, alkoxylated fatty alcohol, fatty acid amide, fatty acid ester, metallic soap, paraffin, polyethylene wax and unsaturated oil). not including the vinyl ester of
With respect to 100 parts by mass of the compound A,
The compounding amount of the compound B is 1 to 1000 parts by mass,
With respect to a total of 100 parts by mass of the compound A and the compound B,
The compounding amount of the compound C is 0.1 to 100 parts by mass,
The compounding amount of the compound D is 0 to 1000 parts by mass,
With respect to a total of 100 parts by mass of the compound A and the compound B, the amount of the compound D is 5 to 1000 parts by mass,
The photocurable resin composition was determined to be level 2 in the following solvent dissolution test,
Dismantling of a composite structure including members to which an adhesive composition containing the photocurable resin composition is cured and adhered, wherein the photocured adhesive composition is removed by contact with a solvent. A photocurable resin composition used in a method (provided that in the method for dismantling a composite structure, the member is composed of two circuit boards each having an electrode, and the two circuit boards are composed of the adhesive composition is cured and adhered to provide electrical continuity between the electrodes of the two circuit boards, except for the method of dismantling a composite structure including said member) :
Record
After adding 0.78 g of acetone to 0.02 g of the photocured body of the photocurable resin composition obtained by irradiating the photocurable resin composition with ultraviolet rays, and leaving it at 25 ° C. for 24 hours in a light-shielding environment. , Visually confirm the state of the photocuring material,
Level 1 when it is confirmed that there is a residue of the photocuring material,
Level 2 when it is confirmed that there is no residue of the photocuring material,
Solvent dissolution test (however, the amount of ultraviolet light is the amount of light of the photocurable resin composition, so that the width is 20 mm, the length is 20 mm, and the thickness is 0.5 mm. Transparent slide glass (S1127 manufactured by Matsunami Glass Co., Ltd.) and a transparent PET film (manufactured by Panac Co., product name Lumirror 100T60, thickness 100 μm), a laminate composed of the slide glass, the photocurable resin composition, and the PET film after ultraviolet irradiation After photocuring, the laminated body is irradiated with ultraviolet rays using a tensile tester manufactured by Minebea Co., Ltd. (Technograph TG-2kN). and a light intensity of 100 mJ/cm ² or more that causes the detected stress to be 1 N or more ). An adhesive composition containing the photocurable resin composition according to claim 2 . A composite structure comprising member 1 and member 2,
A composite structure in which the member 1 and the member 2 are bonded via the photocured adhesive composition according to claim 3 . The member 1 and the member 2 are plates,
5. The composite structure according to claim 4, wherein said composite structure is a laminate of said member 1 and said member 2, wherein said member 1 and said member 2 are adhered via a photocured body of said adhesive composition. thing. A method of manufacturing a composite structure comprising member 1 and member 2, comprising:
The solvent according to claim 1 is brought into contact with the photo-cured adhesive composition in the composite structure according to claim 4 or 5, and the photo-cured adhesive composition of the member 1 and the member 2 passes through the photo-cured adhesive composition. A method of manufacturing a composite structure, comprising: The cured body of the adhesive composition is brought into contact with the solvent according to claim 1 to release the adhesion of the member 1 and the member 2 through the photocured body of the adhesive composition, and the member 1 and 6. The method for dismantling a composite structure according to claim 4 or 5, wherein the member (2) is separated.