JP6807081B2 - Compatibility composition, adhesive composition, composite structure, manufacturing method and disassembling method of composite structure - Google Patents

Description

The present invention uses a compatible composition in which a specific block copolymer compound and a medium are compatible with each other, an adhesive composition containing the compatible composition, and a composite structure in which the adhesive composition is used. The present invention relates to a product and a method for producing and disassembling the composite structure.

It is requested that the components of the optical system device such as the liquid crystal display body and the optical lens and the component members of the electronic system device such as the electronic paper and the battery be fixed with an adhesive so that the fixing can be released in some cases. May occur.

In response to this request, conventionally, a method of heating and fluidizing a cured adhesive of a fixed portion, contacting with a solvent to swell, or immersing in water to peel off the cured adhesive from a member. (For example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2010-100831

However, the cured product of the conventional adhesive as disclosed in Patent Document 1 does not sufficiently reduce its viscosity even when heated, and remains in a solid state even when it is brought into contact with a solvent or water. Even if the bond could be released, it was not easy to remove the adhesive once cured.

The present invention
A compatible composition whose state reversibly changes between liquid and gel between high and low temperatures,
An adhesive composition that becomes liquid at high temperatures and can be easily applied to members, becomes gel-like at low temperatures and can bond members to each other, and becomes liquid at high temperatures again to easily release the adhesion between members.
A composite structure containing a member bonded with a gelled adhesive composition and a method for producing the same,
And
An object of the present invention is to provide a method for disassembling the composite structure, which liquefies and removes the gelled adhesive composition at a high temperature.

The present invention
[1] A compatible composition in which a block copolymer compound and a medium are compatible with each other.
The block copolymer compound has the following formula (1):

(In the formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms). A (meth) acrylic polymer block (a) having an active energy ray-curable group containing a partial structure represented by the above. ) And a (meth) acrylic block copolymer having no active energy ray-curable group (b).
The block copolymer compound has no liquid-gel transition temperature (Tc) between 0 and 150 ° C.
The compatible composition is a compatible composition having a liquid-gel transition temperature (Tc) between 0 and 150 ° C.
[2] An adhesive composition obtained by blending the compatible composition according to the previous item [1].
[3] A composite structure including a member 1 and a member 2.
A composite structure in which the member 1 and the member 2 are adhered to each other via the adhesive composition according to the preceding item [2].
[4] A method for manufacturing a composite structure including a member 1 and a member 2.
In a temperature environment higher than the temperature Tc described in the previous section [1],
Step 1 in which the member 1 and the member 2 are bonded to each other via the adhesive composition, and
A method for producing a composite structure, which comprises the step 2 of obtaining the composite structure according to the previous item [3] by lowering the temperature environment to a temperature lower than the temperature Tc after the step 1.
[5] The temperature environment is set to a temperature higher than the temperature Tc, the adhesion between the member 1 and the member 2 is released via the adhesive composition, and the member 1 and the member 2 are separated from each other. , The method for disassembling the composite structure described in the previous section [3],
[6] A method for manufacturing a composite structure including a member 1 and a member 2.
The manufacturing method is
In a temperature environment lower than the temperature Tc described in the previous section [1],
The previous section [2], wherein the member 1 and the member 2 are blended with a compatible composition in which the gel-like compatible composition is an elastic body having viscoelasticity and has thermosetting property and / or photocuring property. ] And the step 1'of bonding via the described adhesive composition,
After the step 1', the method for producing a composite structure having the step 2'by thermosetting and / or photocuring the adhesive composition to obtain the composite structure according to the preceding item [3], and
[7] A method for manufacturing a composite structure including a member 1 and a member 2.
The manufacturing method is
At least one of the compatible compositions according to the preceding item [1], wherein the gel-like compatible composition is an elastic body having adhesiveness, and is selected from the group consisting of thermosetting and / or photocurable. Step 1 "to obtain a pressure-sensitive adhesive composition by thermosetting and / or photocuring the adhesive composition according to the previous item [2], which is obtained by blending the compatible composition having the curability of.
This is a method for manufacturing a composite structure having the step 2 ”of the member 1 and the member 2 being bonded to each other via the adhesive cured body to obtain the composite structure according to the previous item [3].

The temperature environment of the temperature T means an environment in which a compatible compound exists such that the temperature of the compatible composition becomes the temperature T. For example, even if the compatible composition is placed at room temperature, the compatible composition is compatible. If the temperature of the compatible composition exceeds 50 ° C. by being heated by a heater in contact with the composition, the temperature environment in that case is over 50 ° C. Hereinafter, the "high temperature environment" and the "high temperature environment" are also referred to as "high temperature", and the "low temperature environment" and "low temperature environment" are also referred to as "low temperature".

According to the present invention
A compatible composition whose state reversibly changes between liquid and gel between high and low temperatures,
An adhesive composition that becomes liquid at high temperatures and can be easily applied to members, becomes gel-like at low temperatures and can bond members to each other, and becomes liquid at high temperatures again to easily release the adhesion between members.
A composite structure containing a member bonded with a gelled adhesive composition and a method for producing the same,
And
It is possible to provide a method for disassembling the composite structure in which the gelled adhesive composition is liquefied and removed at a high temperature.

It is a measurement result of the storage rigidity G'and the loss rigidity G'in the range of 0 to 80 ° C. of the compatible composition of Example 1. It is a schematic diagram of the manufacturing method 1 of a composite structure. It is a schematic diagram of the manufacturing method 2 of a composite structure. It is a schematic diagram of the manufacturing method 3 of a composite structure.

In the present specification, "(meth) acrylic" means a general term for "methacryl" and "acrylic", and "(meth) acryloyl" described later means a general term for "methacryloyl" and "acryloyl", which will be described later. "(Meta) acrylate" means a general term for "methacrylate" and "acrylate".

[Block copolymer compound]
(Compound A)
The block copolymer compound (hereinafter referred to as compound A) in the present invention has the following formula (1):

An active energy ray-curable group containing a partial structure (hereinafter referred to as "partial structure (1)") represented by (in the formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms). It is a (meth) acrylic block copolymer having a (meth) acrylic polymer block (a) having an active energy ray-curable group and a (meth) acrylic polymer block (b) having no active energy ray-curable group.
The block copolymer compound does not have a liquid-gel transition temperature (Tc) between 0 and 150 ° C.

When the compatible composition contains compound A, the elasticity and adhesiveness of the gel-like compatible composition and the compatible composition at the time of curing are improved. Further, as a result of the compound A having an active energy ray-curable group containing the partial structure (1), the compatible composition containing the compound A can be cured by, for example, irradiation with an active energy ray. In the present specification, the active energy ray means a light ray, an electromagnetic wave, a particle beam, or a combination thereof. Examples of light rays include far ultraviolet rays, ultraviolet rays (UV), near ultraviolet rays, visible rays, and infrared rays, examples of electromagnetic waves include X-rays and γ rays, and particle beams include electron beams (EB) and proton rays (α). Lines), neutron rays, etc. Among these active energy rays, ultraviolet rays and electron beams are preferable, and ultraviolet rays are more preferable, from the viewpoints of curing speed, availability of irradiation device, price, and the like.

In the formula (1), examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a sec-butyl group. t-Butyl group, 2-methylbutyl group, 3-methylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-pentyl group, neopentyl group, n -Alkyl groups such as hexyl group, 2-methylpentyl group, 3-methylpentyl group, n-decyl; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group; aryl such as phenyl group and naphthyl group Group: An aralkyl group such as a benzyl group or a phenylethyl group can be mentioned. Among them, a methyl group and an ethyl group are preferable, and a methyl group is most preferable, from the viewpoint of active energy ray curability.

From the viewpoint of compatibility with compound B and a plasticizer, which will be described later, the active energy ray-curable group of the (meth) acrylic polymer block (a) has the following formula (2):

(In the formula (2), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ² and R ³ independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. X represents O, S, or N (R ⁶ ) (R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms), and n represents an integer of 1 to 20). It is preferably a curable group (hereinafter referred to as "active energy ray-curable group (2)").

In the formula (2), specific examples and suitable examples of the hydrocarbon groups having 1 to 20 carbon atoms represented by R ¹ include the same hydrocarbon groups as R ^{1 in the} above formula (1).

In formula (2), R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and a monomer containing di (meth) acrylate (3) described later is used. From the viewpoint of easy direct introduction, a hydrocarbon group having 1 to 6 carbon atoms is preferable. Examples of such hydrocarbon groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, 2-methylbutyl group and 3-methylbutyl group. 2-ethylbutyl group, 3-ethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-pentyl group, neopentyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group Alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cycloalkyl group and the like; aryl groups such as phenyl group and the like. Of these, from the viewpoint of curing rate, a methyl group and an ethyl group are preferable, and a methyl group is most preferable.

In the formula (2), X represents O, S or N (R ⁶ ) (R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms), and is O because of ease of polymerization control. Is preferable. When X is N (R ⁶ ), the hydrocarbon group having 1 to 6 carbon atoms represented by R ⁶ includes, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and the like. sec-butyl group, t-butyl group, 2-methylbutyl group, 3-methylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-pentyl group , Neopentyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group and other alkyl groups; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and other cycloalkyl groups, phenyl group and the like.

In the formula (2), the integers 1 to 20 represented by n are preferably 2 to 5 from the viewpoint of the fluidity and curing rate of the compound A.

The content of the partial structure (1) with respect to all the monomer units forming the (meth) acrylic polymer block (a) is preferably in the range of 0.2 to 100 mol%, more preferably in the range of 0.5 to 90 mol%. preferable.

The (meth) acrylic polymer block (a) contains a monomer unit formed by polymerizing a monomer containing a (meth) acrylic acid ester. Such (meth) acrylic acid esters include monofunctional (meth) acrylic acid esters having one (meth) acryloyl group and / or polyfunctional (meth) acrylic acid esters having two or more (meth) acryloyl groups. Can be used.

Examples of the monofunctional (meth) acrylic acid ester capable of forming the (meth) acrylic polymer block (a) include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, and ( Isopropyl acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, (meth) Dodecyl acrylate, 2-methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, 2 (meth) acrylate -Aminoethyl, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, 2-2-. Ethylene oxide adducts of (trimethylsilyloxy) ethyl, 3- (trimethylsilyloxy) propyl (meth) acrylate, glycidyl (meth) acrylate, γ-((meth) acryloyloxypropyl) trimethoxysilane, (meth) acrylic acid , (Meta) Acrylic Acid Trifluoromethyl Methyl, (Meta) Acrylic Acid 2-Trifluoromethyl Ethyl, (Meta) Acrylic Acid 2-Perfluoroethyl Ethyl, (Meta) Acrylic Acid 2-Perfluoroethyl-2-Perfluoro Butylethyl, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethyl (meth) acrylate Examples thereof include methyl, 2-perfluorohexyl ethyl (meth) acrylate, 2-perfluorodecyl ethyl (meth) acrylate, and 2-perfluorohexadecyl ethyl (meth) acrylate. Among these, alkyl methacrylate esters having an alkyl group having 5 or less carbon atoms such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate and t-butyl methacrylate are preferable. , Methyl methacrylate is most preferred.

Further, as a polyfunctional (meth) acrylic acid ester capable of forming the (meth) acrylic polymer block (a), the following formula (3):

(Wherein, R 2 ^'and R ^3' each independently represents a hydrocarbon group having 1 to 6 carbon atoms, R ⁴ and R ⁵ represents a hydrogen atom or a methyl group independently, n represents 1 When a bifunctional (meth) acrylic acid ester (hereinafter referred to as "di (meth) acrylate (3)") represented by (representing an integer of 20) is used, one of them is subjected to living anion polymerization under the conditions described later. The (meth) acryloyloxy group (the (meth) acryloyloxy group represented by "CH ₂ = C (R ⁵ ) C (O) O" in the formula (3)) is selectively polymerized, and R ¹ becomes R ⁴ A methacrylic polymer block (a) having an active energy ray-curable group (2) in which R ² is R ² ', R ³ is R ³ ', and X is O is obtained.

In the formula (3), examples of the hydrocarbon group having 1 to 6 carbon atoms represented by ^{R 2} 'and ^{R 3'} include the same hydrocarbon groups as ^{R 2} and ^{R 3} in the formula (2).

From the viewpoint of enhancing the selectivity of the polymerization, it is preferred that R ⁴ is a methyl group. Further, from the viewpoint of the productivity of the di (meth) acrylate (3), it is preferable that R ⁴ and R ⁵ are the same. From the above viewpoint, it is most preferable that both R ⁴ and R ⁵ are methyl groups.

Specific examples of the di (meth) acrylate (3) include 1,1-dimethylpropane-1,3-diol di (meth) acrylate, 1,1-dimethylbutane-1,4-diol di (meth) acrylate, and 1 , 1-Dimethylpentane-1,5-diol di (meth) acrylate, 1,1-dimethylhexane-1,6-diol di (meth) acrylate, 1,1-diethylpropane-1,3-diol di (meth) acrylate, 1,1-diethylbutane-1,4-diol di (meth) acrylate, 1,1-diethylpentane-1,5-diol di (meth) acrylate, 1,1-diethylhexane-1,6-diol di (meth) acrylate 1,1-Dimethylpropane-1,3-diol dimethacrylate, 1,1-dimethylbutane-1,4-diol dimethacrylate, 1,1-dimethylpentane-1,5-diol dimethacrylate, etc. 1,1-Dimethylhexane-1,6-diol dimethacrylate, 1,1-diethylpropane-1,3-diol dimethacrylate, 1,1-diethylbutane-1,4-diol dimethacrylate, 1,1-diethyl Pentane-1,5-diol dimethacrylate and 1,1-diethylhexane-1,6-diol dimethacrylate are preferred, 1,1-dimethylpropane-1,3-diol dimethacrylate, 1,1-dimethylbutane- More preferred are 1,4-diol dimethacrylate, 1,1-dimethylpentane-1,5-diol dimethacrylate, and 1,1-dimethylhexane-1,6-diol dimethacrylate.

One of these (meth) acrylic acid esters may be used alone, or two or more thereof may be used in combination.

The content of the monomer unit formed from the (meth) acrylic acid ester in the (meth) acrylic polymer block (a) is the total monomer forming the (meth) acrylic polymer block (a). The range is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and may be 100 mol% with respect to the unit. When the (meth) acrylic polymer block (a) contains a monomer unit formed from the di (meth) acrylate (3), it is simply formed from the di (meth) acrylate (3). The content of the meter unit is preferably in the range of 0.2 to 100 mol%, preferably in the range of 10 to 90 mol%, based on all the monomer units forming the (meth) acrylic polymer block (a). More preferably, the range of 25 to 80 mol% is further preferable. Further, in the (meth) acrylic polymer block (a), the content of the monomer unit formed from methyl methacrylate and the content of the monomer unit formed from the di (meth) acrylate (3). The total is preferably in the range of 80-100 mol%, more preferably in the range of 90-100 mol%, preferably in the range of 95-100 mol% with respect to all the monomeric units formed from the (meth) acrylic acid ester. More preferably, it may be 100 mol%.

The (meth) acrylic polymer block (a) may have a monomer unit formed from a monomer other than the above (meth) acrylic acid ester. Examples of the other monomer include α-alkoxyacrylic acid esters such as methyl α-methoxyacrylate and methyl α-ethoxyacrylate; crotonic acid esters such as methyl crotonate and ethyl crotonate; 3-methoxyacrylic acid. 3-alkoxyacrylic acid esters such as esters; acrylamides such as N-isopropylacrylamide, N-t-butylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide; N-isopropylmethacrylate, N-t-butyl Methoxylamides such as methacrylamide, N, N-dimethylmethacrylate, N, N-diethylmethacrylate; methyl 2-phenylacrylate, ethyl 2-phenylacrylate, n-butyl 2-bromoacrylate, 2-bromomethyl Examples thereof include methyl acrylate, ethyl 2-bromomethylacrylate, methylvinyl ketone, ethyl vinyl ketone, methylisopropenyl ketone, ethyl isopropenyl ketone and the like. These other monomers may be used alone or in combination of two or more.

The content of the monomer unit formed from the above other monomers in the (meth) acrylic polymer block (a) is the total monomer forming the (meth) acrylic polymer block (a). It is preferably 10 mol% or less, more preferably 5 mol% or less, based on the unit.

The number average molecular weight (Mn) per (meth) acrylic polymer block (a) is not particularly limited, but from the viewpoints of handleability, fluidity, mechanical properties of the obtained cured product, and the like, 500 to 1,000. The range of 000 is preferable, and the range of 1,000 to 300,000 is more preferable. In addition, in this specification, Mn and the molecular weight distribution described later mean the standard polystyrene conversion value measured by the gel permeation chromatography (GPC) method.

Compound A has the above-mentioned (meth) acrylic polymer block (a) and the (meth) acrylic polymer block (b) having no active energy ray-curable group. In a preferred embodiment, compound A contains It is composed of only the (meth) acrylic polymer block (a) and the (meth) acrylic polymer block (b). That is, compound A contains a (meth) acrylic polymer block (b).

The (meth) acrylic polymer block (b) contains a monomer unit formed by polymerizing a monomer containing a (meth) acrylic acid ester, and does not have an active energy ray-curable group. It is a polymer block. In the present specification, the active energy ray-curable group means a functional group exhibiting polymerizability by irradiation with the above active energy rays. Examples of the active energy ray-curable group include ethylenic double bonds such as (meth) acryloyl group, (meth) acryloyloxy group, vinyl group, allyl group, vinyloxy group, 1,3-dienyl group and styryl group (particularly). Functional groups having the formula CH ₂ = CR- (in the formula, R is an ethylenic double bond represented by an alkyl group or a hydrogen atom); an epoxy group, an oxetanyl group, a thiol group, a maleimide group and the like can be mentioned.

Examples of the (meth) acrylic acid ester capable of forming the (meth) acrylic polymer block (b) include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, and (meth). Isopropyl acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylate Dodecyl, trimethoxysilylpropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth) Examples thereof include mono (meth) acrylic acid esters such as phenyl acrylate, naphthyl (meth) acrylate, 2- (trimethylsilyloxy) ethyl (meth) acrylate, and 3- (trimethylsilyloxy) propyl (meth) acrylate. Among them, acrylic acid alkyl esters having an alkyl group having 4 or more carbon atoms such as n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and dodecyl acrylate; 2-ethylhexyl methacrylate, dodecyl methacrylate and the like. A methacrylic acid alkyl ester having an alkyl group having 6 or more carbon atoms is preferable. One of these (meth) acrylic acid esters may be used alone, or two or more thereof may be used in combination.

The content of the monomer unit formed by the (meth) acrylic acid ester in the (meth) acrylic polymer block (b) is the total monomer forming the (meth) acrylic polymer block (b). It is preferably 90 mol% or more, more preferably 95 mol% or more, and may be 100 mol% with respect to the unit.

The (meth) acrylic polymer block (b) may have a monomer unit formed from a monomer other than the (meth) acrylic acid ester. Examples of the other monomer include α-alkoxyacrylic acid esters such as methyl α-methoxyacrylate and methyl α-ethoxyacrylate; crotonic acid esters such as methyl crotonate and ethyl crotonate; 3-methoxyacrylic acid. 3-alkoxyacrylic acid esters such as esters; N-isopropyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide and the like ( Meta) Alkoxy; examples thereof include methyl vinyl ketone, ethyl vinyl ketone, methyl isopropenyl ketone, ethyl isopropenyl ketone and the like. These other monomers may be used alone or in combination of two or more.

The content of the monomer unit formed by the other monomers in the (meth) acrylic polymer block (b) is the total monomer forming the (meth) acrylic polymer block (b). It is preferably 10 mol% or less, more preferably 5 mol% or less, based on the unit.

The Mn per (meth) acrylic polymer block (b) is not particularly limited, but is 3,000 to 2,000,000 from the viewpoint of handleability, fluidity, mechanical properties, etc. of the obtained compound A. The range is preferred, more preferably the range of 5,000 to 1,000,000.

Examples of the compound A include a block copolymer in which at least one (meth) acrylic polymer block (a) and at least one (meth) acrylic polymer block (b) are bonded to each other, and each weight thereof. Although the number of coalesced blocks and the bonding order are not particularly limited, it is preferable that the (meth) acrylic polymer block (a) forms at least one end of the compound A from the viewpoint of active energy ray curability, and the compound A is preferable. From the viewpoint of ease of production, it is more preferable that the polymer is a linear polymer, and one (meth) acrylic polymer block (a) and one (meth) acrylic polymer block (b). A diblock copolymer to which is bonded and a triblock copolymer in which one (meth) acrylic polymer block (a) is bonded to both ends of one (meth) acrylic polymer block (b). More preferably, from the viewpoint of the viscoelastic property after curing of the adhesive composition described later, one (meth) acrylic polymer block (a) is provided at both ends of one (meth) acrylic polymer block (b). A triblock copolymer in which the individual is bonded is even more preferable.

Ratio of the mass of the (meth) acrylic polymer block (a) constituting the compound A to the mass of the (meth) acrylic polymer block (b) ((meth) acrylic polymer block (a) :( meta) ) Acrylic polymer block (b)) is not particularly limited, but is preferably 85: 15-5: 95, more preferably 80: 20-7: 93, and 75: 25-10 :. It is more preferably 90. Curing when the mass of the (meth) acrylic polymer block (a) with respect to the total mass of the (meth) acrylic polymer block (a) and the (meth) acrylic polymer block (b) is 5% or more. The speed is increased, and when it is 85% or less, the toughness of the cured product is increased, which is preferable.

The glass transition temperature (Tg) of the (meth) acrylic polymer block (a) is preferably more than 50 ° C. and 180 ° C. or lower, because the compatible composition of the present invention can be easily obtained. The Tg of the (meth) acrylic polymer block (b) is preferably −100 ° C. or higher and 50 ° C. or lower. The type and amount of the monomers used in forming these blocks may be appropriately adjusted so that each polymer block having such Tg can be obtained. The Tg of the compound A is a temperature range containing the preferable Tg of the (meth) acrylic polymer block (a) and the (meth) acrylic polymer block (b), that is, a temperature range of more than 50 ° C. and 180 ° C. or lower. , It is preferable to have Tg in a temperature range of −100 ° C. or higher and 50 ° C. or lower.

(Measurement conditions for glass transition temperature (Tg))
Compound A is sheet-molded to a thickness of 0.5 mm at a pressure of 10 MPa using a hydraulic heat press machine manufactured by Shinto Metal Industry Co., Ltd. set at 200 ° C. Then, a strip piece of 45 mm × 10 mm × 0.5 mm necessary for dynamic viscoelasticity measurement is cut out.

Using a dynamic viscoelastic device (DMS6100) manufactured by Seiko Instruments, Inc.
In the chart obtained by measuring in the tension mode under the conditions of a temperature range of -100 ° C to 200 ° C (heating rate 3 ° C / min) and a frequency of 11 Hz.
The peak temperature of tan δ is read and used as Tg of compound A constituting the strip.

In compound A, the content of the monomer unit formed from the methacrylic acid ester is preferably 5 to 85% by mass, more preferably 7 to 80% by mass, and 10 to 75% by mass. Is even more preferable. Further, in compound A, the content of the monomer unit formed from the acrylic acid ester is preferably 15 to 95% by mass, more preferably 20 to 93% by mass, and 25 to 90% by mass. Is more preferable.

The Mn of compound A is not particularly limited, but from the viewpoint of fluidity, the range is preferably in the range of 4,000 to 3,000,000, more preferably in the range of 7,000 to 2,000,000, and 10,000 to 1. A range of ¥ 1,000,000 is even more preferred.

The molecular weight distribution of compound A, that is, the weight average molecular weight / number average molecular weight (Mw / Mn) is preferably in the range of 1.02 to 2.00, more preferably in the range of 1.05 to 1.80, and 1.10 to 1. A range of .50 is more preferred.

The content of the partial structure (1) in the compound A is preferably in the range of 0.1 to 20 mol%, preferably in the range of 2 to 15 mol%, based on all the monomer units forming the compound A. More preferably, the range of 3 to 10 mol% is further preferable.

Compound A is obtained by forming the (meth) acrylic polymer block (a) and the (meth) acrylic polymer block (b) in a desired order.

The method for producing the compound A is not particularly limited, but an anionic polymerization method or a radical polymerization method is preferable, a living anion polymerization method or a living radical polymerization method is more preferable, and a living anion polymerization method is further preferable from the viewpoint of polymerization control. The monomer used in the production of compound A is preferably preliminarily dried in an inert gas atmosphere from the viewpoint of allowing the polymerization to proceed smoothly. In the drying treatment, a dehydrating agent or a desiccant such as calcium hydride, molecular sieves, or activated alumina is preferably used.

Examples of the living radical polymerization method include a polymerization method using a chain transfer agent such as polysulfide, a polymerization method using a cobalt porphyrin complex, a polymerization method using nitroxide (see International Publication No. 2004/014926), and a high-period heteroatom such as an organic tellurium compound. Polymerization method using element compounds (see Patent No. 3389829), reversible addition / desorption chain transfer polymerization method (RAFT) (see Patent No. 3369859), atom transfer radical polymerization method (ATRP) (Patent No. 3040172). , International Publication No. 2004/013192) and the like. Among these living radical polymerization methods, the atom transfer radical polymerization method is preferable, and a metal complex having an organic halide or a sulfonyl halide compound as an initiator and at least one selected from Fe, Ru, Ni, and Cu as a central metal is used. Atom transfer radical polymerization method as a catalyst is more preferable.

Examples of the living anion polymerization method include a method of living polymerization using an organic rare earth metal complex as a polymerization initiator (see JP-A-06-93060), an alkali metal or an alkaline earth metal salt using an organoalkali metal compound as a polymerization initiator, and the like. A method of living anion polymerization in the presence of the above-mentioned mineral acid salt (see Japanese Patent Application Laid-Open No. 05-507737), and a method of living anion polymerization using an organoalkali metal compound as a polymerization initiator in the presence of an organoaluminum compound. No. 11-335432, International Publication No. 2013/141105) and the like. Among these living anionic polymerization methods, living anionic polymerization using an organoalkali metal compound as a polymerization initiator in the presence of an organoaluminum compound from the viewpoint that the (meth) acrylic polymer block (a) can be directly and efficiently formed. A method of performing living anionic polymerization using an organolithium compound as a polymerization initiator in the presence of an organoaluminum compound and a Lewis base is more preferable.

Examples of the organic lithium compound include t-butyl lithium, 1,1-dimethylpropyl lithium, 1,1-diphenylhexyl lithium, 1,1-diphenyl-3-methylpentyl lithium, ethyl α-lithioisobutyrate, and butyl. α-Lithioisobutyrate, Methyl α-Lithioisobutyrate, Isopropyllithium, sec-Butyllithium, 1-Methylbutyllithium, 2-Eethylpropyllithium, 1-Methylpentyllithium, Cyclohexyllithium, Diphenylmethyllithium, α- Examples thereof include methylbenzyllithium, methyllithium, n-propyllithium, n-butyllithium, n-pentyllithium and the like. Among them, secondary grades such as isopropyllithium, sec-butyllithium, 1-methylbutyllithium, 1-methylpentyllithium, cyclohexyllithium, diphenylmethyllithium and α-methylbenzyllithium from the viewpoint of availability and anionic polymerization initiation ability. Organolithium compounds having 3 to 40 carbon atoms having a chemical structure centered on a carbon atom as an anion center are preferable, and sec-butyllithium is particularly preferable. One of these organolithium compounds may be used alone, or two or more thereof may be used in combination.

The amount of the organolithium compound used can be determined by the ratio with the amount of the monomer used, depending on the Mn of the target compound A.

Examples of the organoaluminum compound include the following formula (A-1):
AlR ⁷ (R ⁸ ) (R ⁹ ) (A-1)

(In the formula, R ⁷ represents a monovalent saturated hydrocarbon group, a monovalent aromatic hydrocarbon group, an alkoxy group, an aryloxy group or an N, N-2-substituted amino group, and R ⁸ and R ⁹ are independent of each other. Represents an aryloxy group, or R ⁸ and R ⁹ are bonded to each other to form an allylene oxy group), or an organic aluminum compound represented by the following formula (A-2):
AlR ¹⁰ (R ¹¹ ) (R ¹² ) (A-2)

(In the formula, R ¹⁰ represents an aryloxy group, and R ¹¹ and R ¹² are independently monovalent saturated hydrocarbon groups, monovalent aromatic hydrocarbon groups, alkoxy groups or N, N-disubstituted aminos, respectively. Included are organic aluminum compounds represented by (representing a group).

Examples of the aryloxy group independently represented by R ⁷ , R ⁸ , R ⁹ and R ^{10 in the} formulas (A-1) and (A-2) include a phenoxy group, a 2-methylphenoxy group and a 4-methyl group. Phenoxy group, 2,6-dimethylphenoxy group, 2,4-di-t-butylphenoxy group, 2,6-di-t-butylphenoxy group, 2,6-di-t-butyl-4-methylphenoxy group , 2,6-di-t-butyl-4-ethylphenoxy group, 2,6-diphenylphenoxy group, 1-naphthoxy group, 2-naphthoxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 7- Examples thereof include a methoxy-2-naphthoxy group.

In the formula (A-1), examples of the allylene oxy group formed by bonding R ⁸ and R ⁹ to each other include 2,2'-biphenol, 2,2'-methylenebisphenol, and 2,2'-methylenebis. (4-Methyl-6-t-butylphenol), (R)-(+)-1,1'-bi-2-naphthol, (S)-(-)-1,1'-bi-2-naphthol, etc. In the compound having two phenolic hydroxyl groups, the functional group excluding the hydrogen atom of the two phenolic hydroxyl groups can be mentioned.

In addition, one or more hydrogen atoms contained in the above-mentioned aryloxy group and allylene oxy group may be substituted with a substituent, and the substituent includes, for example, a methoxy group, an ethoxy group, an isopropoxy group, and the like. An alkoxy group such as a t-butoxy group; a halogen atom such as a chlorine atom and a bromine atom, and the like can be mentioned.

In the formulas (A-1) and (A-2), the monovalent saturated hydrocarbon groups represented by R ⁷ , R ¹¹ and R ¹² independently include, for example, a methyl group, an ethyl group and an n-propyl group. Alkyl groups such as isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, 2-methylbutyl group, 3-methylbutyl group, n-octyl group and 2-ethylhexyl group; cyclohexyl group and the like. Examples of the monovalent aromatic hydrocarbon group include an alkyl group and the like; an aryl group such as a phenyl group; an aralkyl group such as a benzyl group, and examples of the alkoxy group include a methoxy group, an ethoxy group and an iso group. Examples thereof include a propoxy group and a t-butoxy group, and examples of the N, N-disubstituted amino group include a dialkylamino group such as a dimethylamino group, a diethylamino group and a diisopropylamino group; and a bis (trimethylsilyl) amino group. .. One or more hydrogen atoms contained in the monovalent saturated hydrocarbon group, the monovalent aromatic hydrocarbon group, the alkoxy group and the N, N-2-substituted amino group described above may be substituted with the substituent. Examples of the substituent include an alkoxy group such as a methoxy group, an ethoxy group, an isopropoxy group and a t-butoxy group; a halogen atom such as a chlorine atom and a bromine atom.

Examples of the organic aluminum compound (A-1) include ethylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum, ethylbis (2,6-di-t-butylphenoxy) aluminum, and ethyl [2. 2'-Methylenebis (4-Methyl-6-t-Butylphenoxy)] Aluminum, Isobutylbis (2,6-di-t-Butyl-4-Methylphenoxy) Aluminum, Isobutylbis (2,6-di-t-) Butylphenoxy) aluminum, isobutyl [2,2'-methylenebis (4-methyl-6-t-butylphenoxy)] aluminum, n-octylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum, n -Octylbis (2,6-di-t-butylphenoxy) aluminum, n-octyl [2,2'-methylenebis (4-methyl-6-t-butylphenoxy)] aluminum, methoxybis (2,6-di-t) -Butyl-4-methylphenoxy) aluminum, methoxybis (2,6-di-t-butylphenoxy) aluminum, methoxy [2,2'-methylenebis (4-methyl-6-t-butylphenoxy)] aluminum, ethoxybis (2,6-di-t-butylphenoxy) 2,6-di-t-butyl-4-methylphenoxy) aluminum, ethoxybis (2,6-di-t-butylphenoxy) aluminum, ethoxy [2,2'-methylenebis (4-methyl-6-t-butyl) Phenoxy)] Aluminum, isopropoxybis (2,6-di-t-butyl-4-methylphenoxy) aluminum, isopropoxybis (2,6-di-t-butylphenoxy) aluminum, isopropoxy [2,2' -Methylenebis (4-methyl-6-t-butylphenoxy)] aluminum, t-butoxybis (2,6-di-t-butyl-4-methylphenoxy) aluminum, t-butoxybis (2,6-di-t-) Butylphenoxy) aluminum, t-butoxy [2,2'-methylenebis (4-methyl-6-t-butylphenoxy)] aluminum, tris (2,6-di-t-butyl-4-methylphenoxy) aluminum, tris (2,6-Diphenylphenoxy) Aluminum and the like can be mentioned. Among them, isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum and isobutylbis (2,6) are considered from the viewpoints of polymerization initiation efficiency, living property of polymerization terminal anion, availability and handling, etc. -Di-t-butylphenoxy) aluminum, isobutyl [2,2'-methylenebis (4-methyl-6-t-butylphenoxy)] aluminum and the like are preferable.

Examples of the organoaluminum compound (A-2) include diethyl (2,6-di-t-butyl-4-methylphenoxy) aluminum, diethyl (2,6-di-t-butylphenoxy) aluminum, and diisobutyl (2,). 6-di-t-butyl-4-methylphenoxy) aluminum, diisobutyl (2,6-di-t-butylphenoxy) aluminum, din-octyl (2,6-di-t-butyl-4-methylphenoxy) Examples thereof include aluminum and din-octyl (2,6-di-t-butylphenoxy) aluminum. One of these organoaluminum compounds may be used alone, or two or more thereof may be used in combination.

Examples of the Lewis base include compounds having an ether bond and / or a tertiary amine structure in the molecule.

Examples of the compound having an ether bond in the molecule used as the Lewis base include ether. The ether is a cyclic ether having two or more ether bonds in the molecule or an acyclic ether having one or more ether bonds in the molecule from the viewpoint of high polymerization initiation efficiency and living property of the polymerization terminal anion. Is preferable. Examples of the cyclic ether having two or more ether bonds in the molecule include crown ethers such as 12-crown-4, 15-crown-5, and 18-crown-6. Examples of the acyclic ether having one or more ether bonds in the molecule include acyclic monoethers such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether and anisole; 1,2-dimethoxyethane and 1,2-diethoxy. Ether, 1,2-diisopropoxyetane, 1,2-dibutoxyethane, 1,2-diphenoxyethane, 1,2-dimethoxypropane, 1,2-diethoxypropane, 1,2-diisopropoxypropane , 1,2-Dibutoxypropane, 1,2-Diphenoxypropane, 1,3-dimethoxypropane, 1,3-diethoxypropane, 1,3-diisopropoxypropane, 1,3-dibutoxypropane, 1 , 3-Diphenoxypropane, 1,4-dimethoxybutane, 1,4-diethoxybutane, 1,4-diisopropoxybutane, 1,4-dibutoxybutane, 1,4-diphenoxybutane and the like. Diether: Diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dibutylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol diethyl ether, dibutylene glycol diethyl ether, triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, tributylene glycol dimethyl ether, triethylene glycol diethyl Acyclic such as ether, tripropylene glycol diethyl ether, tributylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetrapropylene glycol dimethyl ether, tetrabutylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetrapropylene glycol diethyl ether, tetrabutylene glycol diethyl ether and the like. Polyether can be mentioned. Among them, acyclic ether having 1 or 2 ether bonds in the molecule is preferable, and diethyl ether or 1,2-dimethoxyethane is more preferable, from the viewpoint of suppressing side reactions and availability.

Examples of the compound having a tertiary amine structure in the molecule used as the Lewis base include tertiary polyamines. The tertiary polyamine means a compound having two or more tertiary amine structures in the molecule. Examples of the tertiary polyamine include N, N, N', N'-tetramethylethylenediamine, N, N, N', N'-tetraethylethylenediamine, N, N, N', N ", N" -pentamethyl. Chain polyamines such as diethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetraamine, tris [2- (dimethylamino) ethyl] amine; 1,3,5-trimethylhexahydro-1, 3,5-triazine, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,4,7,10,13,16-hexamethyl-1,4,7,10,13,16 -Non-aromatic heterocyclic compounds such as hexaazacyclooctadecane; aromatic heterocyclic compounds such as 2,2'-bipyridyl, 2,2': 6', 2 "-terpyridine and the like can be mentioned.

Further, a compound having one or more ether bonds and one or more tertiary amine structures in the molecule may be used as a Lewis base. Examples of such a compound include tris [2- (2-methoxyethoxy) ethyl] amine and the like.

These Lewis bases may be used alone or in combination of two or more.

The amount of the Lewis base used is preferably in the range of 0.3 to 5.0 mol, preferably 0.5 to 5.0 mol, with respect to 1 mol of the organolithium compound, from the viewpoint of polymerization initiation efficiency, stability of the polymerization terminal anion, and the like. It is more preferably in the range of 3.0 mol, even more preferably in the range of 1.0 to 2.0 mol. If the amount of the Lewis base used exceeds 5.0 mol with respect to 1 mol of the organolithium compound, it tends to be disadvantageous in terms of economy, and if it is less than 0.3 mol, the polymerization initiation efficiency tends to decrease.

The amount of the Lewis base used is preferably in the range of 0.2 to 1.2 mol, more preferably in the range of 0.3 to 1.0 mol, with respect to 1 mol of the organoaluminum compound. ..

The living anionic polymerization is preferably carried out in the presence of an organic solvent from the viewpoint of temperature control and homogenization in the system to allow the polymerization to proceed smoothly. As an organic solvent, hydrocarbons such as toluene, xylene, cyclohexane, and methylcyclohexane; chloroform, from the viewpoints of safety, separability of the reaction mixture after polymerization from water in washing with water, and ease of recovery and reuse, etc. Halogenized hydrocarbons such as methylene chloride and carbon tetrachloride; esters such as dimethyl phthalate are preferable. These organic solvents may be used alone or in combination of two or more. From the viewpoint of smooth progress of the polymerization, the organic solvent is preferably subjected to a drying treatment and degassed in advance in the presence of an inert gas.

Further, in the above-mentioned living anionic polymerization, another additive may be present in the reaction system, if necessary. Examples of the other additives include inorganic salts such as lithium chloride; metal alkoxides such as lithium methoxyethoxyethoxyd and potassium t-butoxide; tetraethylammonium chloride and tetraethylphosphonium bromide.

The living anionic polymerization is preferably carried out at -30 to 25 ° C. If it is lower than -30 ° C, the polymerization rate tends to decrease and the productivity tends to decrease. On the other hand, if the temperature is higher than 25 ° C., it tends to be difficult to polymerize the (meth) acrylic polymer block (a) containing the partial structure (1) with good living properties.

The living anionic polymerization is preferably carried out in an atmosphere of an inert gas such as nitrogen, argon or helium. Moreover, it is preferable to carry out under sufficient stirring conditions so that the reaction system becomes uniform. Moreover, it is preferable to carry out under sufficient stirring conditions so that the reaction system becomes uniform. In addition, the monomer to be used is preferably dried in advance in an inert gas atmosphere from the viewpoint of smoothly proceeding with living anionic polymerization. In the drying treatment, a dehydrating agent or a desiccant such as calcium hydride, molecular sieves, or activated alumina is preferably used.

In the above-mentioned living anionic polymerization, as a method of adding an organolithium compound, an organoaluminum compound, a Lewis base and a monomer to the reaction system of anionic polymerization, the Lewis base comes into contact with the organoaluminum compound before the contact with the organolithium compound. It is preferable to add as such. Further, the organoaluminum compound may be added to the reaction system of anionic polymerization before the monomer, or may be added at the same time. When the organoaluminum compound is added to the reaction system of anionic polymerization at the same time as the monomer, the organoaluminum compound may be added after being separately mixed with the monomer.

The living anionic polymerization can be stopped by adding a polymerization terminator such as methanol; a methanol solution of acetic acid or hydrochloric acid; a protonic compound such as an aqueous solution of acetic acid or hydrochloric acid to the reaction solution. The amount of the polymerization inhibitor used is usually preferably in the range of 1 to 100 mol with respect to 1 mol of the organolithium compound used.

A known method can be adopted as a method for separating and obtaining the compound A from the reaction solution after the termination of anionic polymerization. For example, a method of pouring the reaction solution into a poor solvent of the compound A to precipitate the compound A, a method of distilling off an organic solvent from the reaction solution to obtain the compound A, and the like can be mentioned.

If the metal components derived from the organolithium compound and the organoaluminum compound remain in the separated and obtained compound A, the physical properties of the compound A may be deteriorated, the transparency may be poor, and the like. Therefore, it is preferable to remove the metal component derived from the organolithium compound and the organoaluminum compound after the anionic polymerization is stopped. As a method for removing the metal component, a cleaning treatment using an acidic aqueous solution, an adsorption treatment using an adsorbent such as an ion exchange resin, Celite, or activated carbon, or the like is effective. Here, as the acidic aqueous solution, for example, hydrochloric acid, sulfuric acid aqueous solution, nitric acid aqueous solution, acetic acid aqueous solution, propionic acid aqueous solution, citric acid aqueous solution and the like can be used.

As a method for introducing an active energy ray-curable group containing a partial structure (1) in the production of the compound A, the monomer containing the di (meth) acrylate (3) described above is polymerized to (meth) acrylic. In addition to the method for forming the system polymer block (a), after forming a polymer block containing a partial structure (hereinafter referred to as “precursor structure”) which is a precursor of the partial structure (1), the precursor structure Can also be mentioned as a method of converting the above into a partial structure (1). A polymer block containing a precursor structure can be obtained by polymerizing a monomer containing a polymerizable functional group and a compound containing a precursor structure. Examples of the polymerizable functional group include a styryl group, a 1,3-dienyl group, a vinyloxy group, a (meth) acryloyl group and the like, and a (meth) acryloyl group is preferable. The precursor structure includes a hydroxyl group protected by a hydroxyl group and a protective group (silyloxy group, acyloxy group, alkoxy group, etc.), an amino group protected by an amino group and a protective group, and a thiol protected by a thiol group and a protective group. Examples include a group and an isocyanate group.

A polymer block containing a hydroxyl group as a precursor structure is a (meth) acrylic polymer by reacting with a compound having a partial structure (1) and a partial structure (carboxyl group, ester, carbonyl halide, etc.) capable of reacting with the hydroxyl group. The block (a) can be formed. Further, the polymer block containing a hydroxyl group protected by a protecting group as a precursor structure can form the (meth) acrylic polymer block (a) in the same manner after removing the protecting group to form a hydroxyl group.

The polymer block containing an amino group as a precursor structure has a partial structure (1) and a partial structure capable of reacting with the amino group (carboxyl group, carboxylic acid anhydride, ester, carbonyl halide, aldehyde group, isocyanate group, etc.). A (meth) acrylic polymer block (a) can be formed by reacting with a compound. Further, the polymer block containing an amino group protected by a protecting group as a precursor structure can similarly form a (meth) acrylic polymer block (a) after removing the protecting group to form an amino group.

The polymer block containing a thiol group as a precursor structure has a partial structure (1) and a partial structure capable of reacting with the thiol group (carboxyl group, carboxylic acid anhydride, ester, carbonyl halide, isocyanate group, carbon-carbon double bond. The (meth) acrylic polymer block (a) can be formed by reacting with a compound having (such as). Further, the polymer block containing a thiol group protected by a protecting group as a precursor structure can similarly form a (meth) acrylic polymer block (a) after removing the protecting group to form a thiol group.

A polymer block containing an isocyanate group as a precursor structure is a (meth) acrylic polymer block by reacting with a compound having a partial structure (1) and a partial structure (hydroxyl group, amino group, etc.) capable of reacting with the isocyanate group. (A) can be formed.

In the production of compound A, as a method for forming the (meth) acrylic polymer block (a), di (meth) acrylate (3) is contained from the viewpoint that an active energy ray-curable group can be easily directly introduced. A method of polymerizing a monomer, typically a method of living anionic polymerization, is preferable.

〔medium〕
(Compound B)
The medium (hereinafter referred to as compound B) in the present invention is compatible with compound A and has a liquid-gel transition temperature (Tc) between 0 and 150 ° C. (hereinafter referred to as compound B). It is a compound that constitutes (also referred to as a compatible composition).

As the compound B, it is preferable to select a compound in which the compatible composition with the compound A can have fluidity as a guide, and a radically polymerizable unsaturated bond such as a (meth) acrylate-based monomer or a (meth) acrylamide-based monomer. It may be a contained monomer, a plasticizer, a solvent, or the like.

As a monomer compound in which the compatible composition with compound A can have fluidity,
Preferably, methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, lauryl (meth). ) Alkyl (meth) acrylates such as acrylates; alkoxy-substituted alkyl (meth) acrylates such as methoxyethyl (meth) acrylates; 2-hydroxyethyl (meth) acrylates, 2-hydroxypropyl (meth) acrylates, 2-hydroxybutyl (meth) ) Hydroxy-substituted alkyl (meth) acrylates such as acrylates; benzyl (meth) acrylates, phenyl (meth) acrylates, etc .; ethylene glycol di (meth) acrylates, diethylene glycol di (meth) acrylates, triethylene glycol di (meth) acrylates, 1 , 3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate and other di (meth) acrylates. Alicyclic structure-containing (meth) acrylates such as 4-t-butylcyclohexyl acrylate, dicyclopentenyloxyethyl (meth) acrylate, norbornene (meth) acrylate, dicyclopentanyl (meth) acrylate, and isobornyl (meth) acrylate, At least one compound selected from the group consisting of (meth) acrylamide such as (meth) acryloylmorpholine and diethyl (meth) acrylamide.
More preferably, it is at least one compound selected from the group consisting of isodecyl acrylate, 4-hydroxybutyl acrylate and 4-tert-butylcyclohexyl acrylate.

As compound B, from the viewpoint of improving the strength, elasticity and adhesiveness of the gel-like compatible composition described later and the compatible composition at the time of curing, from the viewpoint of radical reactivity, cation reactivity, anion reactivity and moisture reactivity. It is preferable to use at least one reactive reactive compound selected from the above group. In the present specification, the reactivity of polymerization reaction by moisture (moisture) in air is referred to as moisture reactivity, and the curing of curable composition by the polymerization reaction of moisture-reactive groups in the curable composition is wet. It is called curing.

From the viewpoint of improving the strength, elasticity and adhesiveness of the gel-like compatible composition and the compatible composition at the time of curing, the radical-reactive compound may be used.
Preferably, at least one selected from the group consisting of (meth) acrylate, (meth) acrylamide, (meth) acrylonitrile, urethane (meth) acrylate, vinyl group, vinyl ether, allyl ether, maleimide and maleic anhydride,
More preferably, at least one selected from the group consisting of (meth) acrylate, (meth) acrylamide, urethane (meth) acrylate and vinyl ether.
More preferably, at least one radical reactive group selected from the group consisting of (meth) acrylate and urethane (meth) acrylate (preferably a bifunctional or higher polyfunctional group from the viewpoint of radical reaction rate and stability). It is a reactive compound having.

From the viewpoint of improving the strength, elasticity and adhesiveness of the gel-like compatible composition and the compatible composition at the time of curing, the cationically reactive compound is selected.
Preferably, it is a reactive compound having at least one cationic reactivity selected from the group consisting of epoxy, oxetane and vinyl ether.

From the viewpoint of improving the strength, elasticity and adhesiveness of the gel-like compatible composition and the compatible composition at the time of curing, the anion-reactive compound is preferably at least selected from the group consisting of epoxy, oxetane and vinyl ether. It is a reactive compound having one kind of anion reactivity.

From the viewpoint of improving the strength, elasticity and adhesiveness of the gel-like compatible composition and the compatible composition at the time of curing, the moisture-reactive compound is preferably an isocyanate group and / or an alkoxysilane group.

From the viewpoint of improving the strength, elasticity and adhesiveness of the gel-like compatible composition and the compatible composition at the time of curing, the compatible composition is preferably prepared by combining compound A and compound B which is a radically reactive compound. Constitute.

From the viewpoint of improving the strength, elasticity and adhesiveness of the gel-like compatible composition and the compatible composition at the time of curing and the ease of use of the compatible composition, the compatible composition is a reactive compound. It is preferable to contain an appropriate polymerization initiator depending on the type.

When the reactive compound is a radical reactive compound, the polymerization initiator may be
Preferably, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-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) -Morholinophenyl) Butanone-1, 2-Hydroxy-2-methyl-1-phenyl-propane-1-one, 2-methyl-1- [4-methylthio] phenyl] -2-morpholinopropan-1-one, benzoyl Methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] Propanol oligomer, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, 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'-tetrakis (3,4,5 -Trimethoxyphenyl) 1,2'-biimidazole, 2,2'bis (o-chlorophenyl) 4,5,4', 5'-tetraphenyl-1,2'-biimidazole, 2-benzoylnaphthalene, 4 − Benzoyl biphenyl, 4-benzoyl diphenyl ether, acrylicized benzophenone, bis (η5-2,4-cyclopentadi) En-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium, o-methylbenzoylbenzoate, p-dimethylaminobenzoic acid ethyl ester, p-dimethylamino It is selected from the group consisting of isoamyl ethyl ester benzoate, active tertiary amine, carbazole / phenone-based photoreaction initiator compound, aclysin-based photoreaction initiator compound, triazine-based photoreaction initiator compound and benzoyl-based photoreaction initiator compound. At least one or more compounds
More preferably, it is 1-hydroxy-cyclohexyl-phenyl-ketone and / or 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide.

When the reactive compound is a cationically reactive compound, the polymerization initiator may be
Preferably, at least one ionic photoacid generator compound selected from the group consisting of aryldiazonium salt, diarylhalonium salt, triarylsulfonium salt, triphosphonium salt, iron allene complex, titanosen complex and arylsilanol aluminum complex, and / Or at least one nonionic photoacid generator compound selected from the group consisting of nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenol sulfonic acid ester, diazonaphthoquinone and N-hydroxyimide sulfonate.

When the reactive compound is an anionic reactive compound, the polymerization initiator may be
Preferably, it is selected from the group consisting of 1,10-diaminodecane, 4,4'-trymethylenedipiperazine, carbamate compounds and derivatives thereof, cobalt-amine complex compounds, aminooxyimino compounds and ammonium borate compounds. At least one compound.

When the reactive compound is a moisture-reactive compound, the polymerization initiator may be
Preferably, the silanol condensation catalyst is at least one titanium compound selected from the group consisting of tetrabutyl titanate, tetrapropyl titanate, titanium tetraacetylacetonate and bisacetylacetonatodiisopropoxytitanium.
Dibutyltin diuralate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctate, dibutyltin diethylhexanolate, dibutyltin dimethylmalate, dibutyltin diethylmalate, dibutyltin dibutylmalate, dibutyltin dioctylmalate, dibutyltin ditridecyl Maleate, Dibutyltin Dibenzylmaleate, Dibutyltin Diacetate, Dioctyltin diethylmaleate, Dioctyltin Dioctylmaleate, Dibutyltin dimethoxide, Dibutyltin dimethoxyside, Dibutenyl tin oxide, Dibutyltin diacetylacetonate, Dibutyltin At least one tetravalent organic tin compound selected from the group consisting of diethylacetoacetonate, a reaction product of dibutyltin oxide and a silicate compound, and a reaction product of dibutyltin oxide and a phthalate ester.
At least one organoaluminum compound selected from the group consisting of aluminum trisacetylacetonate, aluminumtrisethylacetate and diisopropoxyaluminum ethylacetate,
Zirconium compounds such as zirconium tetraacetylacetonate,
Reactions of amine compounds, acidic phosphate esters, reactants of acidic phosphate esters with amine compounds, saturated or unsaturated polyvalent carboxylic acids or their acid anhydrides, salts of carboxylic acid compounds with amine compounds, etc. Compounds, lead octylate, and
It is at least one compound selected from the group consisting of isocyanate reaction catalysts.

As an isocyanate reaction catalyst,
Preferably, at least one amine compound selected from the group consisting of triethylamine, benzylmethylamine, N, N', N'-trimethylaminoethylpiperazine, triethylenediamine and dimethylethanolamine,
Trialkylphosphine compounds such as triethylphosphine,
At least one organotin compound selected from the group consisting of dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, tin octoate and dibutyltin diethylhexanolate,
It is at least one compound selected from lead di (2-ethylhexanoic acid), lead naphthenate, copper naphthenate, cobalt naphthenate, and zinc naphthenate.

As a plasticizer in which the compatible composition with compound A can have fluidity,
Preferred are phthalates such as dibutylphthalate, diisononylphthalate, dibutylphthalate, di (2-ethylhexyl) phthalate, diisodecylphthalate, butylbenzylphthalate;
Polyvalent carboxylic acid esters such as dioctyl adipate, diisononyl adipate, dioctyl sebacate, diisononyl sebacate, diisononyl 1,2-cyclohexanedicarboxylic acid;
Alkylate benzoate;
Phosphates such as tricresyl phosphate and tributyl phosphate;
Trimellitic acid ester

Rubber-based polymers such as (hydrogenated) polyisoprene, hydroxylated (hydrogenated) polyisoprene, (hydrogenated) polybutadiene, hydroxylated (hydrogenated) polybutadiene, polybutene;
Thermoplastic elastomer;
Petroleum resin;
Alicyclic saturated hydrocarbon resin;
Terpene resins such as terpene resin, terpene phenol resin, modified terpene resin, hydrogenated terpene resin;
Rosin resin such as rosin phenol;
Rosin ester-based resins such as disproportionated rosin ester-based resins, polymerized rosin ester-based resins, and hydrogenated rosin ester-based resins;
Xylene resin; and at least one compound selected from the group consisting of acrylic resins such as acrylic polymers and acrylic copolymers.
More preferably, it is at least one compound selected from the group consisting of polyvalent carboxylic acid esters and rosin ester-based resins.

As compound B, which acts as a solvent for compound A,
Preferably, alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, benzyl alcohol;
Hydrocarbons such as benzene, toluene, xylene, mineral spirit, 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, 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, it can be selected from the group consisting of acetone, hexane, isopropyl alcohol and diethyl carbonate.

Compound B is a compound in which the compatible composition with compound A has fluidity, but the compound B is compatible with compound A and has Tc between 0 and 150 ° C. up to a certain compounding amount with respect to compound A. A compatible composition can be formed, and if the blending amount is exceeded, Tc becomes less than 0 ° C., and if the room temperature exceeds 0 ° C., the compatible composition cannot be formed, resulting in a solution in which compound A is dissolved in compound B. It may end up. In such a case, compound B is a medium of the compatible composition when Tc is in a blending amount of 0 to 150 ° C., and is a solvent of the compatible composition when Tc is less than 0 ° C.

The solvent in the present invention can be said to be a compound in which the Tc of the mixed composition of the solvent and the solvent-compatible composition becomes less than 0 ° C. when the blending amount of the solvent exceeds a certain amount. Therefore, even if the monomer or plasticizer contains a radically polymerizable unsaturated bond, the Tc of the mixed composition becomes less than 0 ° C. when the amount of the monomer or plasticizer containing the radically polymerizable unsaturated bond exceeds a certain amount. If so, they can be considered to be the solvents in the present invention.

The viscosity of compound B may be within the range in which the compatible composition of the present invention can be produced, which is compatible with compound A and has a liquid-gel transition temperature (Tc) between 0 and 150 ° C.
From the viewpoint of easily producing a compatible composition with compound A, the viscosity of compound B is determined.
It is preferably 0.001 to 10 Pa · s, more preferably 0.001 to 1 Pa · s, and further preferably 0.001 to 0.5 Pa · s.

Even if compound B is an oligomer or the like and has a high viscosity or a solid in an environment lower than the temperature Tc, it may have a lower viscosity in an environment higher than the temperature Tc or may be dissolved in another compound B having a lower viscosity. , Since they are dissolved in a solvent, these can be combined and kneaded with compound A to produce a compatible composition.

When the compatible composition is used as an adhesive composition described later, the viscosity of the liquid compatible composition is determined from the viewpoint of applicability to the member.
It is preferably 0.1 to 100 Pa · s, more preferably 0.3 to 50 Pa · s, and even more preferably 0.5 to 10 Pa · s.

The viscosities of compound B and the compatible composition are measured under the measurement conditions described in Examples.

[Compatible composition]
The compatible composition in which compound A and compound B are compatible is prepared at a temperature between 0 and 150 ° C.
Compound A has no liquid-gel transition temperature (Tc) and
The compatible composition is a composition having a liquid-gel transition temperature (Tc).

The temperature Tc is a temperature in the range of 0 to 150 ° C. at which the storage rigidity G'measured under the following conditions and the loss rigidity G'are equal to each other.

The storage rigidity G'and the loss rigidity G'of the compatible composition and the compound A are
Using a rheometer (manufactured by Antonio Par),
Cone rotor (φ = 25 mm, rotor angle 2 °), frequency 1 Hz, strain 1%,
The measurement was carried out by cooling at 2 ° C./min from 150 ° C. to 0 ° C.

Regarding the storage rigidity G'and the loss rigidity G'of the compatible composition of Example 1, the measurement results in the temperature range of 0 to 80 ° C. are shown in FIG. 1 (Note that in Compound A, the storage rigidity G'and There was no temperature at which the loss rigidity G ”is equal).

In the case of Example 1, the temperature at which the storage rigidity G'and the loss rigidity G'is equal to each other (the temperature at which the storage rigidity G'curve and the loss rigidity G'curve intersect) is 44 ° C. for the compatible composition. Temperature Tc.

The compatible composition is
Horizontal glass under atmospheric pressure at temperatures above Tc (preferably 10 ° C or higher above temperature Tc, more preferably 15 ° C or higher above temperature Tc, more preferably 20 ° C or higher above temperature Tc). It is a liquid that naturally flows when 0.01 g or more is dropped onto the plate, but the temperature is lower than Tc (preferably 10 ° C. or higher lower than the temperature Tc, more preferably 15 ° C. or higher lower than the temperature Tc, and more preferably the temperature Tc. At a temperature of 20 ° C. or higher), it is a gel-like body that does not flow even if 0.01 g or more is allowed to stand on a horizontal glass plate under atmospheric pressure.

The compatible composition is a gel-like product at a temperature before and after the temperature Tc (preferably a temperature range of Tc ± 10 ° C., more preferably a temperature range of Tc ± 15 ° C., and further preferably a temperature range of Tc ± 20 ° C.). And reversibly change to liquid.

The temperature Tc is preferably 10 to 100 ° C., more preferably 20 to 90 ° C., and even more preferably, from the viewpoint that the compatible composition can be used in the form of a gel in a wide temperature range and does not need to be liquefied at a very high temperature. It is 30 to 80 ° C.

Temperature Tc is
If the Tg of the (meth) acrylic polymer block (a) is increased or the compounding ratio of compound B is reduced, the temperature can be set to a higher temperature side, or the Tg of the (meth) acrylic polymer block (a) is decreased. By increasing the compounding ratio of compound B, it can be set to the low temperature side.

For example, when the compatible composition is used as an adhesive composition described later,
When a liquid compatible composition having a temperature higher than the temperature Tc is applied onto the members, the members are bonded to each other via the compatible composition, and the temperature is lower than the temperature Tc, the members have a gel-like compatible composition. It is stably adhered to the material, but when the temperature is higher than the temperature Tc again, the compatible composition changes from a gel state to a liquid state, so that the members can be easily separated from each other.

[Compatible composition viscoelastic body]
From the viewpoint of improving the elasticity and adhesiveness of the gel-like compatible composition and the compatible composition at the time of curing, the compatible composition is radically reactive, cationically reactive, anionic reactive and as compound A and compound B. It is preferable to contain at least one reactive reactive compound (preferably in combination with a plastic agent) selected from the group consisting of moisture reactivity and a polymerization initiator (hereinafter, as Compound A and Compound B). It contains at least one reactive reactive compound (preferably in combination with a plasticizer) selected from the group consisting of radical-reactive, cationic-reactive, anionic-reactive and moisture-reactive, and a polymerization initiator. A gel-like compatible composition is also referred to as a compatible composition viscoelastic body).

The compatible composition viscoelastic body has sufficient elasticity and strength (hereinafter, collectively referred to as "viscoelastic property") to form a sheet for bonding on a member constituting a composite structure described later. It is preferable that the compatible composition viscoelastic body having such viscoelastic properties has an appropriate viscoelasticity that can be used as an adhesive sheet.

The elastic modulus to the extent that the sheet can be formed is preferably 0.3 to 1000 kPa, more preferably 0.5 to 500 kPa, still more preferably 0.5 to 200 kPa at room temperature (25 ° C.).
When the elastic modulus is less than 0.3 kPa at room temperature (25 ° C.), it is preferably 0.5 to 500 kPa, more preferably 1 to 200 kPa at a temperature of Tc-20 ° C.

The elastic modulus of the viscoelastic body of the compatible composition is measured under the measurement conditions described in the examples.

As an extension that can form a sheet
It is preferably 10 to 1000%, more preferably 30 to 800%, still more preferably 50 to 500%.
As a breaking strength that can form a sheet
It is preferably 1 × 10 ² to 1 × 10 ⁷ Pa, more preferably 1 × 10 ² to 1 × 10 ⁶ Pa, and even more preferably 1 × 10 ³ to 1 × 10 ⁵ Pa.

The elongation and breaking strength of the viscoelastic body of the compatible composition can be measured by a dumbbell tensile test. Specifically, when the elastic modulus of the viscoelastic body of the compatible composition is 0.3 Pa or more at room temperature (25 ° C), it is at room temperature (25 ° C), and when it is less than 0.3 Pa, the temperature is Tc-20 ° C. It can be measured under the following conditions.

(1) Soluble composition A viscoelastic body is liquefied at a temperature of Tc + 20 ° C. and then poured into a dumbbell mold and cooled to a temperature lower than the temperature of Tc (actually at room temperature) to prepare a dumbbell test piece having a thickness of 1 mm.

(2) The dumbbell test piece is pulled with a tensile tester (Minebea technograph, TG-2 kN) at a tensile speed of 10 mm / min, and the elongation rate and breaking strength are read from the measurement results.

When the compatible composition viscoelastic body has the above-mentioned viscoelastic properties, for example, when a sheet is formed from the compatible composition viscoelastic body, the adhesiveness can be evaluated as ◯ under the measurement conditions described in the examples. The adhesive sheet to have can be constructed.

Due to this adhesiveness of the compatible composition viscoelastic body, for example, when a pressure-sensitive adhesive sheet is formed, the pressure-sensitive adhesive sheet can be stably bonded to the surface of the member.

The compatible composition viscoelastic body can solve the following problems in producing a composite structure described later.

For example, the following can be mentioned as a laminate in which a pair of plate-shaped members constituting a composite structure such as an optical member or an optical product are bonded via an adhesive such as an adhesive sheet or a curable liquid adhesive. ..

(1) Flat panel (2D) Display peripheral members:
(1-1) A laminate in which a shatterproof film for preventing shattering of broken glass and a protective glass are bonded with an adhesive sheet;
(1-2) A laminate in which a protective panel for preventing damage and light reflection of the liquid crystal panel and the liquid crystal panel are bonded with an adhesive sheet or a curable liquid adhesive;
(1-3) Touch sensor panel (film) in which functional members are laminated with an adhesive sheet or a curable liquid adhesive;
(1-4) A backlight in which a plurality of optical films are laminated with an adhesive sheet.

(2) Three-dimensional panel (2.5D, 3D) protective panel display.
(3) Security glass and safety glass for construction, which are bonded with an adhesive sheet or a curable liquid adhesive to prevent the broken glass from scattering and improve the impact strength.
(4) A solar cell module bonded with an adhesive sheet or a curable liquid adhesive for sealing the light receiving surface material and the back surface material.
(5) A packaging film bonded with an adhesive sheet or a curable liquid adhesive to improve strength.

The conventional pressure-sensitive adhesive sheet used in the production of the above-mentioned laminate has the advantages of a uniform thickness, a simple manufacturing process, and less contamination of other members as compared with a curable liquid adhesive. It has the following issues:
(A) Bubbles tend to remain when there is a step on the base material;
(B) Repair is difficult;
(C) Difficult to handle thin sheets;
(D) Since it is difficult to produce a thick sheet of the solvent-based pressure-sensitive adhesive, it is difficult to use it in an in-vehicle application that requires impact resistance.

The conventional two-step curing type adhesive sheet used in the production of the above-mentioned laminate is a low-elasticity adhesive sheet having few cross-linking points at the stage of being adhered to the member, so that bubbles follow the step of the base material. It is hard to remain, and it is easier to repair than the conventional product due to its low adhesive strength. After bonding, it is cured by light and heat to promote cross-linking and exhibit the original strength. There are challenges like:
(E) When the step on the member side is relatively large with respect to the thickness of the adhesive sheet, for example, when the bonding thickness is thin or the step is large, the difficulty of bonding the laminated body is not solved;
(F) If the elasticity is lowered to absorb the step, it becomes difficult to handle the adhesive sheet.

Since the conventional curable liquid adhesive used in the production of the above-mentioned laminate is liquid, there is no concern about air bubbles derived from the step of the base material, and there is an advantage that the thickness tolerance of the member can be canceled. Has challenges such as:
(G) Since it flows out of the bonding range when bonded, it is difficult to control contamination of other members and misalignment during transportation.

Attempts have been made to solve the problems of conventional adhesives from the viewpoint of adhesive construction method:
(A) A dam is formed on the outer periphery of the coating area of the curable liquid adhesive to prevent the resin from flowing out;
(B) The flowing curable liquid adhesive is cured with light to stop it;
(C) A liquid-curable liquid adhesive is injected between the substrates whose outer circumference is sealed, for example, by vacuuming;
(D) A curable liquid adhesive imparted with thixotropy is used (stencil method);
(E) After forming a uniform layer of curable liquid adhesive on the member, UV is irradiated to control the fluidity, and then the adhesive is bonded;
(F) After canceling the step of the base material with a curable liquid adhesive, it is bonded with an adhesive sheet;
(G) A curable liquid adhesive is dropped onto the adhesive sheet and then bonded.

However, these construction methods also have the following problems:
In the method (H) method (a), since the shape of the dam is semicircular, resin defects (voids) are formed on the outside of the dam. Depending on the dam used and the curable liquid adhesive, a boundary line is generated and the dam is formed. Easy to peel off at the interface between and the curable liquid adhesive;
(I) In the method (b), the method of curing the flowing resin with light to stop it cannot stop the outflow of the part that cannot be irradiated with light, so that the shape and material of the base material are limited;
(J) Method (c) has a complicated process and it is difficult to control the takt time of the injection process;
In the method (K) method (d), the process becomes complicated, a filler is often used as the thixotropic agent, and the yield is lowered due to poor appearance (filler aggregation, air bubbles);
In the method (L) (e), it is difficult to control the fluidity in consideration of the outflow, air bubbles and strength.

For example, the following difficulties can occur:
-Since the liquid layer formed on the base material is affected by surface tension and swells at the edges, if the fluidity of the layer is reduced (cured) too much before bonding, the level of swelling when bonded Bubbles are generated in places;
・ When laminating, it is necessary to push in the thickness direction until the swelling of the end is canceled, but if the fluidity of the layer is reduced too much, the strength will be reduced by press back, and on the contrary, the fluidity will be reduced. If too much is left, outflow will occur;
-Since the resin end is semicircular as in the dam method, resin defects (voids) may occur on the outside depending on the base material structure.

The method (M) (f) requires a liquid resin composition and an adhesive sheet, the process is complicated, and peeling at the interface between the liquid resin composition and the adhesive sheet is likely to occur.
(N) Method (g) requires a liquid resin composition and an adhesive sheet, the process is complicated, and sticking out easily occurs because the liquid resin is bonded together, and further, peeling at the interface between the liquid resin composition and the adhesive sheet. Is likely to occur.

Based on the above, with regard to conventional adhesive sheets and curable liquid adhesives, there have been increasing demands in recent years for designability, such as a protective panel with a narrow light-shielding printing part, a laminate using a display, and a 2.5D or 3D-shaped protective panel. It has the following problems in manufacturing a laminated body using a display or a display .
(O) It follows the design shape, has no air bubbles, and is difficult to bond without the resin flowing out.

If the viscoelastic body of the compatible composition is coated on one of the members in a high temperature environment of temperature Tc or higher, the step can be canceled even if there is a step because it is liquid, and then suddenly lower than the temperature Tc. If the compatible composition viscoelastic body is made into a gel by cooling to a low temperature environment of the above, a layer of the compatible composition viscoelastic body with less swelling and shoulder drop can be formed on one member.

If one member coated with the layer of the compatible composition viscoelastic body and the other member are bonded together in a low temperature environment of less than the temperature Tc, the layer of the compatible composition viscoelastic body is gel-like. A laminated body with less outflow can be obtained.

Further, the layer of the compatible composition viscoelastic body constituting the above-mentioned laminate is subjected to at least one treatment selected from the group consisting of heating, light irradiation and humidification to obtain the compatible composition viscoelastic body layer. A cured compatible composition viscoelasticity is obtained by curing at least one selected from the group consisting of heat curing, photocuring and wet curing to obtain a cured product having no liquid-gel transition temperature (Tc). The layer of the elastic body remains a viscoelastic body having no fluidity even in a high temperature environment having a temperature of Tc or higher, and the above-mentioned laminated body can maintain a stable laminated form even at a high temperature.

Further, in a low temperature environment of less than Tc, the gel-like compatible composition viscoelastic body is made into a molded viscoelastic body along the surface of one member and the surface of the other member, and the molded viscoelastic body is heated. At least one treatment selected from the group consisting of light irradiation and humidification is performed to cure at least one selected from the group consisting of thermosetting, photocuring and wet curing, and the liquid-gel transition temperature (Tc) is obtained. It is an adhesive cured product that does not have.

The molded viscoelastic body has the same viscoelastic properties and liquid-gel-like transition temperature (Tc) as the gel-like compatible composition viscoelastic body.

For example, if the pair of members is plate-shaped, the compatible composition viscoelastic body is made into a sheet-shaped molded viscoelastic body, and at least one treatment selected from the group consisting of heating, light irradiation, and humidification is performed. At least one type of curing selected from the group consisting of thermosetting, photocuring and wet curing is performed to obtain a sheet-like viscoelastic body having no liquid-gel transition temperature (Tc), which is used as an adhesive sheet. can do.

Further, in the sheet-like adhesive cured product having no liquid-gel transition temperature (Tc), the degree of elasticity is controlled by adjusting the type and composition of the reactive compound and plasticizer in the viscoelastic body of the compatible composition. Therefore, it is possible to adjust the elasticity so that it can be rolled into a roll, to make it so hard that it cannot be rolled into a roll, or to mold a thin sheet. As mentioned above, a sheet with small shoulder drop and small corners. Can be molded, so pressback and bonding without defects are possible.

According to the compatible composition viscoelastic body, a sheet-shaped molded viscoelastic body having a large thickness can be obtained, and as a result, a thick laminated body made of an adhesive cured product can be obtained.

As described above, a pair of plate-shaped members constituting a composite structure such as an optical component or an optical product are compatible with each other by using a compatible composition adhesive viscoelastic body or adhesive cured body considered to be a physical gel. Composition The viscoelastic body is bonded via an adhesive sheet made of a molded viscoelastic body obtained by molding it into a sheet in a low temperature environment of less than Tc (from thermosetting, photocuring and wet curing, if necessary). At least one selected from the group consisting of the above tasks (A) to (O) by forming a laminate (to form an adhesive sheet made of an adhesive cured product) by curing at least one selected from the group consisting of The problem can be solved.

The compatible composition is preferably 200 parts by mass with respect to 100 parts by mass of compound A from the viewpoint of coatability to members when in liquid form, adhesiveness between members when in gel form, and phase transition property. It is ~ 1000 parts by mass, more preferably 250 to 800 parts by mass.

When the compatible composition is a viscoelastic body of the compatible composition, the content ratio of the reactive compound in Compound B is preferably 20 to 80% by mass, more preferably 25 to 70% by mass, from the viewpoint of viscoelastic properties. %, More preferably 30 to 60% by mass.

When the compatible composition is a viscoelastic body of the compatible composition, the amount of the polymerization initiator added is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, based on at least the total of Compound A and Compound B. , More preferably 2.5 to 7.5% by mass.

[Thixotropic compatible composition]
When fixing 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 with adhesive, contamination due to adhesive outflow or stringing does not occur. In some cases, it may be required that the coating be applied uniformly within a specific frame.

In response to this request, attempts have been made to use an adhesive having a thixotropic property that is difficult to draw, but a light-transmitting member that requires light transmission from components of an optical system device or an electronic system device. When is contained as an adhesive, if a filler such as metal oxide fine particles is added in order to impart the thixotropic property of the adhesive, it becomes difficult to maintain optical transparency, and even if an oil gelling agent is added. , It is difficult to impart thixotropic properties that can support precise fluidity control for optical devices and electronic devices.

When compound A and compound B are selected, the compatible composition of the present invention further constitutes a compatible composition having thixotropy in a gel form (hereinafter, also referred to as thixotropic compatible composition), and is further optically transparent. A thixotropic compatible composition compatible with the properties can be constructed.

From the viewpoint that the compatible composition has compatibility and thixotropy, compound B is preferably 100 to 1000 parts by mass, more preferably 120 to 600 parts by mass, based on 100 parts by mass of compound A in the compatible composition. Is compounded.

The thixotropic compatible composition has thixotropic properties. When the thixotropic compatible composition is subjected to shear stress (increasing the shear rate), its viscosity decreases, and when the shear stress is released (decreasing the shear rate). Then) it means that it has viscoelastic properties in which the viscosity is restored and the fluidity is controlled.

The thixotropic property of the compatible composition in the gel form is
Viscosity of thixotropic compatible composition at a reference shear rate of 0.1 (sec ^-1 ) η _0.1 (Pa · s) and viscosity of thixotropic compatible composition at a shear rate of 1 (sec ^-1 ) Ratio with η ₁ (Pa · s) x ₁ = η _0.1 / η ₁ and
Viscosity η ₁ (Pa · s) of thixotropic compatible composition at a reference shear rate of 1 (sec ^-1 ) and viscosity η ₁₀ (Pa) of thixotropic compatible composition at a shear rate of 10 (sec ^-1 ). The ratio to s) x ₂ = η ₁ / η ₁₀ can be used as a scale.

When a thixotropic compatible composition having x ₁ and x ₂ greater than 1 (preferably 1.2 or more) is used, for example, as an adhesive composition described later, a predetermined range is surface-coated using a slit coater. Occasionally, the thixotropic compatible composition flows moderately when extruded from a slit coater and stops flowing after being extruded, so that contamination due to outflow from a predetermined range or stringing is unlikely to occur. , It becomes possible to apply evenly to a predetermined range.

From the viewpoint of coatability and retention of coating shape of such thixotropic compatible composition, η _0.1 is preferably 10 to 10000 Pa · s, more preferably 30 to 5000 Pa · s, still more preferably 50 to 3000 Pa · s. s and
η ₁ is preferably 10 to 1000 Pa · s, more preferably 20 to 700 Pa · s, and even more preferably 30 to 500 Pa · s.
η ₁₀ is preferably 3 to 500 Pa · s, more preferably 5 to 300 Pa · s, and even more preferably 5 to 150 Pa · s.
x ₁ is preferably 1.1 to 20, more preferably 1.2 to 15, and even more preferably 1.25 to 10.
x ₂ is preferably 1.1 to 20, more preferably 1.2 to 15, and even more preferably 1.25 to 10.

[Transparency of thixotropic compatible composition]
In the thixotropic compatible composition, not only the compound A and the compound B are compatible with each other so as to have thixotropic properties, but also the HAZE value at a thickness of 0.3 mm is 1.0 or less.

The HAZE value represents the ratio of the diffusion transmittance to the total light transmittance of the thixotropic compatible composition.

For example, when an adhesive composition having a thixotropic property is used for an optical material, a filler is added to the curable resin composition in order to impart the thixotropic property to the conventional adhesive composition. Since light scattering is caused by the added filler, the HAZE value is increased, and the transparency based on the total light transmittance of the resin constituting the resin composition is lowered.

On the other hand, in the thixotropic compatible composition, the thixotropy property can be ensured only by the resin composition in which the compound A and the compound B are compatible with each other without adding a filler, so that there is no factor for increasing the HAZE value. , The transparency based on the total light transmittance of the resin constituting the thixotropic compatible composition can be utilized without significantly impairing the transparency.

Therefore, the thixotropic compatible composition is transparent with a HAZE value of 1.0 or less, preferably 0.7 or less, more preferably 0.5 or less, still more preferably 0.3 or less, still more preferably 0.2 or less. You can secure sex.

〔solvent〕
A solvent that dissolves the compatible composition can be selected.

The compatible composition that dissolves in the solvent is adhered via the gel-like compatible composition, for example, when the compatible composition is used as an adhesive composition described later, even if the temperature is not higher than the temperature Tc. The members are separated from each other by contacting the gel-like compatible composition with a solvent to dissolve the compatible composition and removing the gel-like compatible composition without leaving solid content. Can be in the state of

As a solvent for dissolving the compatible composition,
Preferably, alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, benzyl alcohol;
Hydrocarbons such as benzene, toluene, xylene, mineral spirit, 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, 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, it is at least one compound selected from the group consisting of acetone, hexane, isopropyl alcohol and diethyl carbonate.

The compatible composition is compatible with compound A and compound B (between temperatures 0 to 150 ° C., compound A does not have a liquid-gel transition temperature (Tc), and the compatible composition is liquid-gel. Additives other than compound B as described later can be arbitrarily blended as long as the transition temperature (Tc) is not impaired), and the blending amount of the additive other than compound B in that case is blended. It is preferably 0 to 50% by mass, more preferably 0 to 30% by mass, based on the total mass of the compound.

[Adhesive composition]
When the compatible composition of the present invention is applied to a member in a liquid state to form a gel, the adhesive force to the member is excellent, and therefore, the compatible composition can be suitably used as an adhesive composition for adhering the members to each other.

Since the adhesive composition of the present invention (hereinafter, also referred to as an adhesive composition) is made by blending the compatible composition of the present invention, it contains the compatible composition, and has the applicability to the members and the adhesive properties between the members. From the viewpoint of stable adhesion, the temperature before and after the temperature Tc (preferably a temperature range of Tc ± 10 ° C., more preferably a temperature range of Tc ± 15 ° C., still more preferably a temperature range of Tc ± 20 ° C.) It reversibly changes into a gel-like form and a liquid form (the fact that the adhesive composition has the above-mentioned change is also referred to as phase transition).

The adhesive composition is, for example, an antioxidant, as long as it does not impair the coatability to the members in the liquid state, the adhesiveness between the members in the gel state (hereinafter collectively referred to as adhesiveness), and the phase transition property. Additives such as wetting agents, surfactants, ionic liquids, defoaming agents, UV absorbers, light stabilizers, inorganic and organic fillers, polymers and the like can be included.

When the compatible composition contained is a viscoelastic body of the compatible composition, the adhesive composition further has suitable viscoelastic properties of the viscoelastic body of the compatible composition.

When the compatible composition is a viscoelastic body of the compatible composition, the adhesive composition is, for example, an antioxidant, a wetting agent, a surfactant, as long as it does not impair the adhesiveness, phase transferability and viscoelastic properties. Additives such as ionic liquids, defoaming agents, UV absorbers, light stabilizers, inorganic and organic fillers, polymers and the like can be included.

The additive in the adhesive composition is a combination of the additive blended in the compatible composition and the additive blended together with the compatible composition.

From the viewpoint of coatability to the member, the adhesive composition has a viscosity of the liquid compatible composition preferably in a temperature range of Tc + 10 ° C. or higher (more preferably in a temperature range of Tc + 15 ° C. or higher, still more preferably Tc + 20 ° C.). In the above temperature range),
It is preferably 100 Pa · s or less, more preferably 50 Pa · s or less, and further preferably 10 Pa · s or less.

From the viewpoint of adhesiveness and phase transition, the adhesive composition has a total amount of compounds A and B to be blended in the compatible composition with respect to the total amount of the adhesive composition.
It is preferably 50 to 100% by mass, more preferably 70 to 100% by mass.

[Composite structure]
The composite structure of the present invention (hereinafter, also referred to as a composite structure) is a structure including a member 1 and a member 2 to which the member 1 and the member 2 are adhered to each other via an adhesive composition.

When the member 1 and the member 2 are adhered to each other via the adhesive composition, the surfaces of the member 1 and the member 2 are in contact with and adhere to the adhesive composition with the adhesive composition sandwiched between them ( The relative positions of the member 1 and the member 2 in the vicinity of the adhesive composition are fixed).

In the composite structure, the adhesive composition adhering the members 1 and 2 is further, for example, made hotter than the temperature Tc to liquefy and remove the adhesive composition, or remains colder than the temperature Tc. When it is planned to release the adhesion of the members 1 and 2 by contacting the adhesive composition with a solvent to dissolve and remove the adhesive composition, the adhesive composition of the members 1 and 2 The adhesive composition is also referred to as a temporary fixing agent, and the adhesive composition when the members 1 and 2 are planned to be released from the adhesive is also referred to as a temporary fixing agent.

When the member 1 and the member 2 are plates, for example,
Preferably, the thickness-wise surfaces of the member 1 and the member 2 are adhered or temporarily fixed via the adhesive composition, or more preferably, the plate surfaces of the member 1 and the member 2 are adhered or temporarily fixed via the adhesive composition. Is it fixed?
The member 1 and the member 2 may be adhered to each other via the adhesive composition, and the member 1 and the member 2 may form a laminated body.

The plate is a structure that is thinner than the area of the front and back surfaces, but may be plate-shaped, thin-film-shaped, flat-shaped, or curved-shaped.

The following can be exemplified as the composite structure of the present invention .

(1) A liquid crystal display body including optical members such as various films, wherein the optical members are adhered or temporarily fixed to form a laminated body or the like.

(2) A liquid crystal display body including 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, surface processing is performed at the same time, and the base material is removed before use.

(4) A device that uses an electrolytic solution such as an antiglare mirror, electronic paper, a battery, or a capacitor, to which members such as electrodes, separators, and current collectors are adhered or temporarily fixed. When used as a temporary fixing agent, it is preferable to select a constituent compound of the adhesive composition so that the performance of the electrolytic solution is not impaired even if the dissolved adhesive composition is mixed with the electrolytic solution.

(5) A polishing device for polishing an optical lens, in which the optical lens and the fixed support of the optical lens are temporarily fixed.

(6) A plurality of raw materials such as optical lenses are temporarily fixed, mechanically processed into a predetermined shape, and then the adhesive is removed and each is used as a part.

(7) Flat panel (2D) display peripheral members:
(7-1) Laminated body in which a shatterproof film for preventing shattering of broken glass and a protective glass are bonded with an adhesive sheet;
(7-2) A laminate in which a protective panel for preventing damage and light reflection of the liquid crystal panel and the liquid crystal panel are bonded with an adhesive sheet or a curable liquid adhesive;
(7-3) Touch sensor panel (film) in which functional members are laminated with an adhesive sheet or a curable liquid adhesive;
(7-4) A backlight in which a plurality of optical films are laminated with an adhesive sheet.

(8) Three-dimensional panel (2.5D, 3D) protective panel display.

(9) Security glass or safety glass for construction, which is bonded with an adhesive sheet or a curable liquid adhesive to prevent the broken glass from scattering and improve the impact strength.

(10) A solar cell module bonded with an adhesive sheet or a curable liquid adhesive for sealing the light receiving surface material and the back surface material .

(11) A packaging film bonded with an adhesive sheet or a curable liquid adhesive to improve strength.

The composite structure is usually used in a state where the adhesive composition is in the form of a gel at a temperature of Tc or less.

From the viewpoint of adhesiveness at a temperature of Tc or less, the materials of members 1 and 2 are glass, PET, TAC, COP, polyimide, PMMA, polycarbonate, vinyl chloride, PVA, polyethylene, polypropylene, silicone, graphite, aluminum, copper, etc. SUS or the like is preferable, and an organic hard coat layer or an inorganic hard coat layer may be treated on the surface of the member, and a transparent conductive material such as ITO, IZO, or carbon nanotube is treated in order to have conductivity. Also, a metal such as silver or copper may be patterned on the surface as an electrode or a wiring material.

When the composite structure is, for example, preferably a laminated body via a compatible composition viscoelastic body in which the member 1 and / or the member 2 is plate-shaped, more preferably, in recent years, even among flat panels (2D). Laminates using protective panels and displays with narrow light-shielding printing areas that require more design, and 2.5D and 3D-shaped protective panels and displays that require more design in addition to flat panels (2D) In the case of the laminated body used, the viscoelastic body of the compatible composition follows the design shape, and is bonded in a state where there are no bubbles between the members 1 and the member 2 and the resin does not flow out.

Therefore, when the composite structure is preferably a laminated body via a compatible composition viscoelastic body in which the member 1 and / or the member 2 is in the form of a plate, one of the member 1 and the member 2 is displayed in a liquid crystal display. Compatibility composition when a panel, an organic EL display panel, a protective panel, a touch panel, a glass or a plastic plate, and the other is a light-transmitting member In the case of a laminated body via a viscoelastic body, the compatibility composition stickiness The elastic body follows the design shape, and is bonded in a state where there are no air bubbles between the member 1 and the member 2 and the resin does not flow out.

[Manufacturing method of composite structure]
(Manufacturing method 1)
The composite structure is
In a temperature environment higher than the temperature Tc,
Step 1 of bonding the member 1 and the member 2 via the adhesive composition, and
After the step 1, it can be obtained by a manufacturing method (hereinafter, also referred to as “manufacturing method 1”) including the step 2 of obtaining a composite structure by lowering the temperature environment to a temperature lower than the temperature Tc.

In the production method 1, since the adhesive composition is liquid in the first step,
A liquefied adhesive composition can be easily applied to the adhesive portion of the member 1 and the member 2.
In step 2, the coated adhesive composition becomes a gel, and the member 1 and the member 2 can be adhered or temporarily fixed.

In the first step, the adhesive composition is preferably applied at a temperature suitable for each method using a dispenser, a jet dispenser, an inkjet, a slit coater, a die coater, screen printing and the like.

If the composite structure is expected to be unbonded from the members 1 and 2 in the final specifications, then the method of manufacturing the composite structure further includes, after step 2, an adhesive composition. It is preferable to include a step 3 of bringing the solvent into contact with the object and / or raising the temperature environment to a temperature higher than the temperature Tc to release the adhesion of the members 1 and 2 via the adhesive composition.

(Manufacturing method 2)
When the compatible composition is a compatible composition viscoelastic body, the composite structure is
In a temperature environment lower than the temperature Tc,
Step 1'to attach the member 1 and the member 2 to each other via an adhesive composition containing a compatible composition viscoelastic body.
After step 1', the adhesive composition is cured at least one selected from the group consisting of thermosetting, photocuring and wet curing, and the members 1 and 2 bonded via the adhesive elastic body are formed. It can be obtained by a manufacturing method including step 2'to obtain a composite structure containing the same (hereinafter, also referred to as "manufacturing method 2").

The adhesive composition in step 1'of the production method 2 is a step of liquefying the adhesive composition in an environment higher than Tc and then cooling it to form a gel, for example, in a predetermined shape (preferably in the form of a sheet). ), Or the step may be performed on the surface of the member 1 or the member 2.

The production method 2 solves at least one problem selected from the group consisting of problems (A) to (O) as described above due to the viscoelastic property of the adhesive composition derived from the viscoelastic body of the compatible composition. For example, preferably, when the composite structure is a laminated body via a compatible composition viscoelastic body in which the member 1 and / or the member 2 is in the shape of a plate, at least the members 1 and 2 are more preferable. In the case of a laminated body via a viscoelastic body of a compatible composition having a plate shape on one side, more preferably, a protective panel or a display having a narrow light-shielding printing portion, which requires more design among flat panels (2D) in recent years. Viscoelasticity of compatible composition when manufacturing a laminate using 2.5D or 3D-shaped protective panel or display, which requires more design in addition to a flat panel (2D). The body follows the design shape, and it is possible to bond the members 1 and the member 2 in a state where there are no air bubbles and no resin flows out.

(Manufacturing method 3)
When the compatible composition is a compatible composition viscoelastic body, the composite structure is
The manufacturing method is
A step 1 of obtaining an adhesive cured product by curing an adhesive composition containing a viscoelastic body of the present invention at least one selected from the group consisting of thermosetting, photo-curing and wet-curing.
The member 1 and the member 2 can also be obtained by a method for manufacturing a composite structure having a step 2 ”for obtaining a composite structure including the member 1 and the member 2 bonded together via an adhesive cured body (hereinafter,“ manufacturing method ”. 3 ").

In step 1 ”of the manufacturing method 3, for example, the adhesive composition is liquefied in an environment higher than Tc and then cooled to form a gel, which is previously molded into a predetermined shape (preferably sheet shape). The obtained compatible composition viscoelastic body may be used, or the step may be performed on the surface of the member 1 or the member 2.

In the production method 3, step 2 "is at least one selected from the group consisting of photo-curing and wet-curing in advance of a molded viscoelastic body obtained by pre-molding into a predetermined shape (preferably sheet shape) in step 1". The seeds may be cured to obtain an adhesive cured product having a predetermined shape (preferably sheet-like), or a predetermined shape (preferably sheet-like) obtained on the surface of member 1 or member 2 in step 1 ". The molded viscoelastic body of No. 1 may be cured on the surface of the member 1 or the member 2 as it is at least one selected from the group consisting of photocuring and wet curing.

According to the manufacturing method 3, since the pressure-sensitive adhesive can be manufactured in advance and used as a pressure-sensitive adhesive sheet, for example, the entire pressure-sensitive adhesive sheet is cured even if the member has a light-shielding portion, and is similar to a conventional curable liquid adhesive. In addition, it does not get wet and spread after coating, and it is easy to control the coating accuracy.

Further, if the viscosity of the compatible composition does not decrease as expected at a temperature higher than the temperature Tc, or if the viscosity does not decrease unless the temperature is excessively higher than the temperature Tc, the temperature Tc can be applied by applying the production method 3. It is possible to utilize the viscoelastic effect of the adhesive cured product in a low temperature environment of less than.

Therefore, also in the production method 2, at least the adhesive composition is selected from the group consisting of the problems (A) to (O) as described above due to the viscoelastic properties derived from the compatible composition viscoelastic body and the adhesive cured body. The problem of 1 can be solved, and for example, when the composite structure is a laminated body via a compatible composition viscoelastic body in which the member 1 and / or the member 2 is plate-shaped, the member 1 is more preferable. And in the case of a laminated body via a viscoelastic body of a compatible composition in which at least one of the members 2 is in the shape of a plate, more preferably, in recent years, a light-shielding printing portion that requires more design among flat panels (2D). When manufacturing a laminate using a narrow protective panel or display, or a laminate using a 2.5D or 3D-shaped protective panel or display that requires more design in addition to a flat panel (2D), it is a phase. The viscoelastic body of the melt composition follows the design shape, and it is possible to bond the members 1 and the member 2 in a state where there are no bubbles and no resin flows out.

[Repair adjustment in the manufacturing process of composite structures]
Conventionally, since a conventional pressure-sensitive adhesive sheet was used instead of the viscoelastic body of the compatible composition between steps 1'and 2'in the manufacturing method 2, air bubbles derived from the steps of the members tend to remain. In some cases, it was necessary to repair between steps 1'and 2'in order to remove air bubbles, but according to the manufacturing method 2, for example, it is compatible at Tc temperature or higher on a base material having a step. The step can be canceled by applying the composition viscoelastic body, and when the compatible composition viscoelastic body sheet is attached to the base material having the step, the compatible composition viscoelastic body is applied. Due to the adhesiveness, strength and elasticity of the elastic sheet, the compatible composition viscoelastic sheet follows the shape of the member having a step, so that air bubbles derived from the step of the member are less likely to remain, and the frequency of repair is greatly reduced. It becomes possible.

The effect of canceling the step of the compatible composition viscoelastic body sheet is when the compatible composition viscoelastic body sheet is formed and bonded on the substrate to be bonded, and the compatible composition viscoelastic body sheet is previously applied. It is preferably expressed in either case of forming and sticking on a substrate.

Further, even in the case of repairing between steps 1'and 2'in the manufacturing method 2, if the repair is performed in a high temperature environment having a temperature of Tc or higher, the viscoelastic body of the compatible composition becomes liquid, so that the repair can be easily performed. It becomes possible to do.

[Dismantling method of composite structure]
In the composite structure obtained in step 2, the adhesive composition is brought into contact with a solvent and / or the temperature environment is set to a temperature higher than the temperature Tc, and the adhesive composition of the members 1 and 2 is used. By releasing the adhesive and separating the member 1 and the member 2, the dismantling of the composite structure can be facilitated.

[Compound raw material]
(1) Compound A
The (meth) acrylic polymer block (a) having an active energy ray-curable group and the (meth) acrylic polymer block (b) having no active energy ray-curable group obtained in Synthesis Example 1 below. ) (Meta) acrylic block copolymers (a1) to (a3) were used as compound A.

[Synthesis Example 1]
After adding 1800 g of toluene to a 5 L flask, 2.5 g of N, N, N', N', N''-pentamethyldiethylenetriamine and isobutylbis (2,6-di-t-butyl-4-methylphenoxy) ) 67 g of a toluene solution containing 23% by mass of aluminum was sequentially added and cooled to −30 ° C. To this, 6.5 g of a cyclohexane solution containing 12% by mass of sec-butyllithium was added, and then 3.6 g of 1,1-dimethylpropane-1,3-diol dimethacrylate and 130 g of methyl methacrylate as a monomer were mixed 133 g. .6 g was added in a batch to initiate polymerization. Subsequently, the reaction solution was stirred at −30 ° C. for 12 hours, and then 280 g of n-butyl acrylate was added as a monomer to react for 2 hours. Subsequently, while stirring the reaction solution at −30 ° C., 133.6 g of a mixture of 1,1-dimethylpropane-1,3-diol dimethacrylate and 130 g of methyl methacrylate was added as a monomer, and then 133.6 g was added, and then 25 ° C. The temperature was raised to. 120 minutes after the addition of the above mixture, the polymerization was stopped by adding 18 g of methanol, and the triblock copolymer bonded in the order of polymer block (a) -polymer block (b) -polymer block (a). A solution containing the (meth) acrylic block copolymer (a1) was obtained. Next, the obtained solution was poured into a large amount of mixed solution of methanol and water (methanol ratio was 90% by mass), and the precipitated white precipitate was collected by filtration and dried under reduced pressure to form both the (meth) acrylic block. 480 g of the polymer (a1) was obtained. The melt flow rate of the obtained (meth) acrylic block copolymer (a1) was measured and found to be 6.4 g / 10 min (evaluation conditions: 190 ° C., 2.16 kgf).
The glass transition temperature of the polymer block (a) is 120 ° C., the glass transition temperature of the polymer block (b) is −30 ° C., and the compound (a1) has a temperature Tc in the range of 0 to 150 ° C. Absent.

[Synthesis Example 2]
After adding 1300 g of toluene to a 5 L flask, 2.9 g of N, N, N', N', N''-pentamethyldiethylenetriamine and isobutylbis (2,6-di-t-butyl-4-methylphenoxy) ) 58 g of a toluene solution containing 26% by mass of aluminum was sequentially added and cooled to −30 ° C. To this, 7.6 g of a cyclohexane solution containing 10% by mass of sec-butyllithium was added, and then 245 g of a mixture of 8.6 g of 1,1-dimethylpropane-1,3-diol dimethacrylate and 237 g of methyl methacrylate as a monomer. Was added all at once to start polymerization. Subsequently, the reaction solution was stirred at −30 ° C. for 13 hours, and then 315 g of n-butyl acrylate as a monomer was sequentially added over 2 hours for the reaction. Then, after terminating the polymerization by adding 30 g of methanol, the temperature was raised to 25 ° C., and the (meth) acrylic was a diblock copolymer bonded in the order of the polymer block (a) and the polymer block (b). A solution containing the system block copolymer (a2) was obtained. Next, the obtained solution was poured into a large amount of mixed solution of methanol and water (methanol ratio was 90% by mass), and the precipitated white precipitate was collected by filtration and dried under reduced pressure to form both the (meth) acrylic block. 460 g of the polymer (a2) was obtained. The melt flow rate of the obtained (meth) acrylic block copolymer (a2) was measured and found to be 9.3 g / 10 min (evaluation conditions: 190 ° C., 2.16 kgf).
The glass transition temperature of the polymer block (a) is 120 ° C., the glass transition temperature of the polymer block (b) is −30 ° C., and the compound (a2) has a temperature Tc in the range of 0 to 150 ° C. Absent.

[Synthesis Example 3]
After adding 1730 g of toluene to a 5 L flask, 1.5 g of N, N, N', N', N''-pentamethyldiethylenetriamine and isobutylbis (2,6-di-t-butyl-4-methylphenoxy) ) 70 g of a toluene solution containing 26% by mass of aluminum was sequentially added and cooled to −30 ° C. To this, 3.9 g of a cyclohexane solution containing 10% by mass of sec-butyllithium was added, and then 4.4 g of 1,1-dimethylpropane-1,3-diol dimethacrylate and 183 g1 of methyl methacrylate were mixed 187 as a monomer. .7 g was added in a batch to initiate polymerization. Subsequently, the reaction solution was stirred at −30 ° C. for 12 hours, and then 280 g of n-butyl acrylate was added as a monomer to react for 2 hours. Subsequently, the reaction solution was stirred at −30 ° C. for 13 hours, and then 174 g of n-butyl acrylate as a monomer was sequentially added over 2 hours for the reaction. Then, after terminating the polymerization by adding 20 g of methanol, the temperature was raised to 25 ° C., and the (meth) acrylic was a diblock copolymer bonded in the order of the polymer block (a) and the polymer block (b). A solution containing the system block copolymer (a3) was obtained. Next, the obtained solution was poured into a large amount of mixed solution of methanol and water (methanol ratio was 90% by mass), and the precipitated white precipitate was collected by filtration and dried under reduced pressure to form both the (meth) acrylic block. 320 g of the polymer (a3) was obtained. The melt flow rate of the obtained (meth) acrylic block copolymer (a3) was measured and found to be 3.7 g / 10 min (evaluation conditions: 190 ° C., 2.16 kgf).
The glass transition temperature of the polymer block (a) is 120 ° C., the glass transition temperature of the polymer block (b) is −30 ° C., and the compound (a3) has a temperature Tc in the range of 0 to 150 ° C. Absent.

(2) Compound B
Compound b1: Isodecyl acrylate (manufactured by Sartmer, SR395)
Compound b2: 4-t-Butylcyclohexylacrylate (Genomer1119, manufactured by Rahn)
Compound b3: 4-Hydroxybutyl acrylate (manufactured by Nihon Kasei, 4-HBA)
Compound b4: Diisononylcyclohexyldicarboxylate (manufactured by BASF, DINCH)
Compound b5: Hydrogenated rosin ester (manufactured by Arakawa Chemical Industries, Ltd., KE-311)
Compound b6: Epoxy ester (4,5-epoxy-1,2-cyclohexanedicarboxylic acid bis (2-ethylhexyl)) (manufactured by DIC Corporation, W150)
Compound b7: Disproportionated rosin ester (manufactured by Arakawa Chemical Industries, Ltd., ME-D)
Compound b8: Lauryl acrylate (manufactured by Kyoei, LA)
Compound b9: Isobornyl acrylate (manufactured by Nippon Kayaku Co., Ltd., RM-1002)
Compound b10: PPG urethane acrylate (manufactured by Daicel Ornex, EB270)
Compound b11: Polybutadiene urethane acrylate (manufactured by Nippon Soda, TE2000)

(3) Other Compounds Compound r1: 1-Hydroxycyclohexylphenyl ketone (polymerization initiator) (manufactured by BASF, I-184)
Compound r2: Polyurethane acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., UV3630ID80)

[Compatibility conditions]
(1) Example 1
100 g of compound a1, 150 g of compound b1, 150 g of compound b2, 200 g of compound b4, and 30 g of compound r1 were weighed and filled in a container (material: SUS316, capacity: 2000 ml) at 80 ° C. and under atmospheric pressure. , A three-one motor (manufactured by Shinto Kagaku Co., Ltd.) was used to stir at 200 rpm for 360 minutes to obtain a compatible composition (compatible composition viscoelastic body).

(2) Examples 2 to 5 and Comparative Example 1
The compound used was replaced with the compound shown in Table 1, and the compatible composition (compatible composition viscoelastic body) and Comparative Example of Examples 2 to 5 were prepared in the same manner as in Example 1 in the formulation shown in Table 1. The comparative composition of 1 was produced.

(3) Examples 6 to 9
The compound used was replaced with the compound shown in Table 2, and the compatible composition (compatible composition viscoelastic body) of Examples 6 to 9 was produced in the same manner as in Example 1 at the ratio shown in Table 2. ..

〔Measurement item〕
The following physical properties were measured with respect to the compatible compositions of Examples 1 to 5 and Comparative Example 1. (1) Liquid-gel transition temperature Tc (° C.) of the compatible composition
(2) Temperature (° C.) at which the viscosity of the compatible composition is 1 Pa · s or less
(3) Complex viscosity at Tc + 20 ° C (Pa · s)
(4) Elastic modulus (kPa)
(5) Adhesiveness (6) Fluidity after curing (7) Solvent solubility (8) HAZE value (9) Laminated body peeling test (heating, solvent immersion)

The following physical properties were measured with respect to the compatible compositions of Examples 6 to 9.
(1) Liquid-gel transition temperature Tc (° C.) of the compatible composition
(2) Temperature (° C.) at which the viscosity of the compatible composition is 1 Pa · s or less
(3) Solvent solubility (4) Viscosity η _0.1 (Pa · s) at 25 ° C. and shear rate 0.1 (sec ^-1 )
(5) Viscosity η _{1 (} Pa · s) at 25 ° C. and shear rate 1 (sec ^-1 )
(6) Viscosity η ₁₀ (Pa · s) at 25 ° C. and shear rate 10 (sec ^-1 )
(7) HAZE value

The measurement results are shown in Tables 1 to 3.

[Viscosity measurement conditions]
Measured using a rheometer (manufactured by Antonio Par) with a cone rotor (φ = 25 mm, rotor angle 2 °), frequency 1 Hz, strain 1%, cooled from 150 ° C to 0 ° C at 2 ° C / min. did. The value measured in the temperature range above Tc was defined as the complex viscosity.

Using a rheometer (manufactured by Antonio Par), the shear rate is changed from 0.01 (sec ^-1 ) to 100 (sec ^-1 ) at a cone rotor (φ = 25 mm, rotor angle 2 °) and 25 ° C. The values measured in the above were taken as viscosities η _0.1 , η ₁ and η ₁₀ .

[Measurement conditions for elastic modulus]
Measured using a rheometer (manufactured by Antonio Par) with a cone rotor (φ = 25 mm, rotor angle 2 °), frequency 1 Hz, strain 1%, cooled from 150 ° C to 0 ° C at 2 ° C / min. did. The numerical value of the storage rigidity measured at 25 ° C. was defined as the elastic modulus. However, when the elastic modulus was 0.3 MPa or less at 25 ° C., the storage rigidity at a temperature Tc-20 ° C. was defined as the elastic modulus.

[Measurement conditions for adhesiveness]
(1) A liquid compatible composition was prepared at a temperature 20 ° C. higher than Tc, and on a PET film (manufactured by Nipper, J0L, 50 μm) that had been mold-released, a dispenser 1 described later was used to make a width of 3 cm and a length of 4 cm. When the elastic modulus is 0.3 MPa or less at room temperature (25 ° C.) or 25 ° C., a liquid layer having a thickness of 0.15 mm is cooled to a temperature of Tc-20 ° C. to produce a sheet as a molded viscoelastic body.

(2) When the elastic modulus is 0.3 MPa or less at a humidity of 40 to 60%, room temperature (25 ° C.) or 25 ° C., the temperature is Tc-20 ° C., and the glass substrate 2 described later is adhered to the glass substrate 2 and then bonded. Peel off the PET film

(3) When the elastic modulus is 0.3 MPa or less at a humidity of 40 to 60%, room temperature (25 ° C.) or 25 ° C., the glass substrate 2 to which the sheet is attached is placed on the lower side at a temperature of Tc-20 ° C. Let it stand horizontally in the air so that it becomes.
If the adhesive sheet does not fall after 5 minutes have passed since it was left to stand horizontally, ○,
If the adhesive sheet falls after 5 minutes of standing horizontally, ×,
And

(4) The surface of the glass substrate 2 is immersed in acetone to clean it before the test, and then dried before use.

[Measurement conditions for fluidity after curing]
The compatible compositions of Examples 1 to 5 and Comparative Example 1 were molded into a gel state to 5 mmΦ × 0.5 mmt on a slide glass, and a metal halide lamp (conveyor type manufactured by Eye Graphics Co., Ltd.) was used. , 250 mW / cm ² , 3000 mJ / cm ² , and the compatible composition was cured. A slide glass on which the compatible composition was placed was placed on a hot plate set at each temperature and left for 10 minutes.
If the shape of the cured product changes and no flow is seen, ○,
If the shape of the cured product is deformed and flow is observed, ×,
And said.

[Solvent solubility measurement conditions]
In each of the compatible compositions of Examples 1 to 9 and Comparative Example 1,
Using acetone (manufactured by Kanto Chemical Co., Inc., special grade) as a solvent,
0.78 g of a solvent was added to 0.02 g of the gel-like compatible composition, and the mixture was allowed to stand at 25 ° C. for 24 hours in a light-shielded environment, and the following judgment was made: Residual gel-like compatible composition Visually check for the presence of objects
If it is confirmed that there is no residue of the gel-like composition, the solvent solubility is ○;
If it is confirmed that there is a residue of the gel-like composition, the solvent solubility is ×.

[Measurement conditions for HAZE value]
For each of the compatible compositions of Examples 1-9 and Comparative Example 1,
A 0.3 mmt spacer is attached to both ends of a 2.5 cm x 3.8 cm x 1 mmt glass, and a metal halide lamp (conveyor type manufactured by Eye Graphics Co., Ltd.) is used with a compatible composition sandwiched between them, 250 mW / cm ² , 3000 mJ. The compatible composition was cured at / cm ² . The measurement was performed with a haze meter (NDH5000 manufactured by Nippon Denshoku Kogyo Co., Ltd.), and the ratio of the total light transmittance to the diffusion transmittance was determined.

[Manufacturing of composite structures and comparative structures]
(1) Manufacture of Composite Structure This will be described with reference to FIG.
Five sets of slide glass 1 (plate-shaped member 1) (1) having spacers (3) having a thickness of 200 μm installed on the plate surface were prepared (FIGS. 2 (2-1 (plan view)) (2). -2 (front view)),
0.015 g of each of the gel-like compatible compositions (4) of Examples 1 to 5 was collected and placed on five slide glasses 1 using a spatula (FIG. 2 (2-3)).
After heating for 30 seconds on a hot plate set to a temperature 20 ° C. higher than Tc, it was visually confirmed on the slide glass 1 that the compatible composition became the liquid compatible composition (5) (FIG. 2). (2-4)),
The plate surfaces of the other slide glass 2 (plate-shaped member 2) (2) are bonded together (step 1), and left as it is for another 30 seconds (FIG. 2 (2-5)).
By removing it from the hot plate, the temperature is lowered to the temperature environment (25 ° C),
A laminate (composite structure) in which the slide glass 1 and the slide glass 2 are laminated via their respective compositions was obtained (step 2) (FIG. 2 (2-6)).

(2) Manufacture of Comparative Structure In step 1 of manufacturing a composite structure, the slide glass 1 and the slide glass 2 bonded to each other via the comparative composition were irradiated with ultraviolet rays at 3000 mJ / cm ² to cure the comparative composition. Then, a laminated body (comparative structure) in which the slide glass 1 and the slide glass 2 were laminated via the cured body of the comparative composition was obtained.

[Dismantling of composite structures at high temperatures]
A laminate in which the slide glass 1 and the slide glass 2 obtained in the production of the composite structure are laminated via their respective compatible compositions is placed on a hot plate set at a temperature 20 ° C. higher than Tc and left for 1 minute. The slide glass 1 and the slide glass 2 of the laminated body could be separated from each other by a light peeling operation with fingers, and the laminated body could be disassembled (when peeled, both of the compatible compositions were liquid).

The comparative structure obtained in the production of the comparative structure was placed on a hot plate set at 100 ° C. and left for 5 minutes, but the cured product of the comparative composition remained solid, and the laminated slide glass 1 and slide glass 2 were left as they were. And could not be separated by a light peeling operation.

[Disassembly of composite structure by contact with solvent]
The laminate in which the slide glass 1 and the slide glass 2 obtained in the production of the composite structure were laminated via the respective compatible compositions was immersed in acetone and left for 60 minutes.
After that, when the laminate was peeled off, the laminate could be easily peeled off and disassembled (when peeled off, all the compatible compositions were dissolved and liquid).

Even when the comparative structure obtained in the production of the comparative structure was immersed in acetone and left for 60 minutes, the cured product of the comparative composition remained cured or only swelled, and the slide glass 1 and the slide of the laminated body were slid. It was not possible to separate the glass 2 from the glass 2 by a light peeling operation.

[Laminated product manufacturing test]
(1) Tool (1-1) Glass substrate 1 (plate-shaped member 1)
A glass substrate having a length of 60 × width of 80 × thickness of 0.8 mm and having a light-shielding printing (GLS-HF manufactured by Teikoku Inks Manufacturing Co., Ltd.) having an outer circumference of 2 mm and a thickness of 50 μm was used (1-2) Glass substrate 2 (plate-shaped member). 2)
Dispenser 1 using a transparent glass substrate with a length of 60 × width of 80 × thickness of 0.8 mm (1-3)
(1-4) Dispenser 2 using a flat nozzle (SHOT MASTER 300 manufactured by Musashi Engineering Co., Ltd.)
(1-5) Ultraviolet irradiation device using PICOJET PV bulb manufactured by Nordson Conveyor type ultraviolet irradiation device (Metal halide lamp manufactured by Eye Graphics) was used.

(2) Manufacturing conditions

(2-1) Manufacturing Examples 61-5 (see FIG. 3)
The viscoelastic body (adhesive composition) of the compatible composition of Examples 1 to 5 shown in Table 1 was used.
A liquid compatible composition (10) was prepared at a temperature 20 ° C. higher than Tc, and a liquid layer having a thickness of 0.15 mm was formed on a glass substrate 1 (6) using a dispenser 1 (9) at room temperature (25 ° C.). ), And molded into the layer of the molded viscoelastic body (11).

At room temperature (25 ° C.), which is lower than Tc, the glass substrate 1 (6) on which each molded viscoelastic body (11) is formed is placed on the glass substrate 2 (7), and the glass substrate 1 (6) is placed. And the glass substrate 2 (7) was bonded to each other via the molded viscoelastic body (11) to produce a laminated body before curing (step 1').

The laminated body before curing is photo-cured using an ultraviolet irradiation device (15) at a peak illuminance of 400 mW / cm ² , an integrated light intensity of 6000 mJ / cm ² (wavelength 350 nm manufactured by ORC Manufacturing Co., Ltd.), and a reaction rate of 100% to obtain a glass substrate. 1 and the glass substrate 2 were bonded together via a layer (adhesive cured product) of the pressure-sensitive adhesive body (12) to obtain a laminate (composite structure) (13) of Production Examples 1 to 5 (step 2'). ..

(2-2) Manufacturing Comparative Example 1
Except that the viscoelastic body (adhesive composition) of the compatible compositions of Examples 1 to 5 shown in Table 1 was replaced with the comparative composition of Comparative Example 1 shown in Table 1 and applied at room temperature (25 ° C.). A laminate of Production Comparative Example 1 was obtained under the same conditions as in Production Examples 1 to 5.

(2-3) Manufacturing Example 6 (see FIG. 4)
The viscous elastic body (adhesive composition) of Example 5 shown in Table 1 was made into a liquid compatible composition (10) at a temperature 20 ° C. higher than Tc, and the dispenser 1 was placed on the glass substrate 1 (6). Using (9), a liquid layer having a thickness of 0.15 mm was formed and cooled to room temperature (25 ° C.) to form a layer of a molded viscoelastic body (11).

At room temperature (25 ° C.), the glass substrate 1 (6) on which the molded viscoelastic body (11) was formed was subjected to a peak illuminance of 400 mW / cm ² and an integrated light intensity of 6000 mJ / cm ² (orc) using an ultraviolet irradiation device (15). (350 nm manufactured by Mfg. Co., Ltd.), the reaction rate is 95%, and the molded viscoelastic body is photocured to obtain an adhesive cured body (12) (step 1 ″).

Production Example 6 in which the glass substrate 1 (6) on which the adhesive cured product (12) is formed is bonded to the glass substrate 2 (7) via the adhesive cured product (12) under a reduced pressure of room temperature (25 ° C.). (Step 2 ") was obtained from the above-mentioned laminate (composite structure) (14).

(2-4) Manufacturing Comparative Example 2
The comparative composition of Comparative Example 1 shown in Table 1 was formed to a thickness of 0.15 mm at room temperature (25 ° C.) using a dispenser 1 on a glass substrate 1, and then a 365 LED lamp (manufactured by HOYA Corporation) was used. A primary cured product was obtained by photocuring at an illuminance of 100 mW / cm ² , an irradiation time of 2 sec, and a reaction rate of 30% to reduce fluidity.

A laminated body was obtained in which the glass substrate 1 on which the primary cured product was formed was bonded to the glass substrate 2 via the primary cured product under reduced pressure.

The laminate was further cured with an ultraviolet irradiation device at a peak illuminance of 400 mW / cm ² and an integrated light intensity of 6000 mJ / cm ² (wavelength 350 nm manufactured by ORC Manufacturing Co., Ltd.) to obtain a laminate of Production Comparative Example 2.

(2-5) Manufacturing Comparative Example 3
The photocuring conditions at the time of producing the primary cured product in Comparative Example 3 were changed to an illuminance of 100 mW / cm ² , an irradiation time of 5 sec, and a reaction rate of 60%, and a laminate of Production Comparative Example 3 was obtained in the same procedure as in Production Comparative Example 2. It was. An evaluation test piece was prepared.

(2-6) Manufacturing Comparative Example 4
The photocuring conditions at the time of producing the primary cured product in Comparative Example 3 were changed to an illuminance of 100 mW / cm ² , an irradiation time of 10 sec, and a reaction rate of 95%, and a laminate of Production Comparative Example 4 was obtained in the same procedure as in Production Comparative Example 2. It was. An evaluation test piece was prepared.

(2-7) Production Comparative Example 5
Using the jet dispenser 2 on the outer circumference of the glass substrate, the comparative composition of Comparative Example 1 shown in Table 1 was drawn in a width of 1 mm × a height of 0.2 mm, and an illuminance of 100 mW / cm was drawn using a 365 LED lamp (manufactured by Panasonic). ^{2. It} was cured in an irradiation time of 5 seconds to form a dam.

After applying the comparative composition of Comparative Example 1 shown in Table 1 on the glass substrate 1 using the dispenser 1, the comparative composition of Comparative Example 1 shown in Table 1 is applied to the glass substrate 2 via the comparative composition of Comparative Example 1 on the glass substrate 1 under reduced pressure. After bonding, the thickness of the composition was adjusted by applying pressure so as to be 0.15 mm to obtain a comparative laminate before curing.

The comparative laminate before curing was photocured using an ultraviolet irradiation device at a peak illuminance of 400 mW / cm ² and an integrated light intensity of 6000 mJ / cm ² (wavelength 350 nm manufactured by ORC Manufacturing Co., Ltd.) to obtain the laminate of Production Comparative Example 5. ..

(2-8) Production Comparative Example 6
The comparative composition of Comparative Example 1 shown in Table 1 was applied onto a PET release film, another PET release film was attached, and a 0.15 mm spacer was used to make the pressure-sensitive adhesive composition 0. The thickness was adjusted to 15 mm to obtain a laminate before curing.

The laminate before curing was cured with a peak illuminance of 400 mW / cm ² and an integrated light intensity of 6000 mJ / cm ² (wavelength 350 nm manufactured by ORC Manufacturing Co., Ltd.) using an ultraviolet irradiation device, and then cut into an adhesive sheet of 60 x 80 mm. ..

After the adhesive sheet is attached on the glass substrate 1, the test piece to which the glass substrate 2 is attached via the adhesive sheet on the glass substrate 1 is further placed in an autoclave (PBD-20 manufactured by Toto Tech Co., Ltd.) under reduced pressure. The mixture was treated at an atmospheric pressure of 0.5 MPa, a temperature of 50 ° C., and a time of 30 minutes to obtain a laminate of Production Comparative Example 6.

(3) Evaluation of Laminated State The laminated bodies of Production Examples 1 to 6 and the laminated bodies of Production Comparative Examples 1 to 6 were evaluated according to the following criteria by visual inspection and using a microscope.

(3-1) Outflow of composition after lamination The shortest position of the adhesive cured product or the comparative composition cured product in the laminate is
From the end position of the compatible composition viscoelastic body or the comparative composition liquid layer formed on the glass substrate 1.
When it did not change, it was marked as ◯, and when it spread outward, it was marked as x.

(3-2) In-plane bubbles Bubbles are generated in the region of the adhesive cured product or the comparative composition cured product in the laminated body.
If it does not exist, it is marked as ◯, and if it exists, it is marked as x.

(3-3) Defects on the outer side The portion where the adhesive cured product or the comparative composition cured product in the laminated body does not fill the outer peripheral portion along the light-shielding printing area is
If it does not exist, it is marked as ◯, and if it exists, it is marked as x.

(3-4) Stepped air bubbles After putting each laminate in an oven at 80 ° C. for 250 hours, observe the presence or absence of air bubbles on the printed step, and if there are no air bubbles on the printed step, ○, if they are present It was marked as x.

1 Slide glass 1 (member 1)
2 Slide glass 2 (member 2)
3 Spacer 4 Gel-like compatible composition 5 Liquid compatible composition 6 Glass substrate 1 (member 1)
7 Glass substrate 2 (member 2)
8 Light-shielding printing part 9 Dispenser 1
10 Liquid compatible composition 11 Molded viscoelastic body 12 Adhesive cured body 13 Laminated body before curing 14 Laminated body of Example 11 15 Ultraviolet irradiation device

Claims (16)

A compatible composition in which a block copolymer compound and a medium are compatible with each other.
The block copolymer compound has the following formula (1):
(In the formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms). A (meth) acrylic polymer block (a) having an active energy ray-curable group containing a partial structure represented by the above. ) And a (meth) acrylic block copolymer having no active energy ray-curable group (b).
The block copolymer compound has no liquid-gel transition temperature (Tc) between 0 and 150 ° C.
The compatible composition has a liquid-gel transition temperature (Tc) between 0 and 150 ° C.
The active energy ray-curable group of the formula (1) is the following formula (2):
(In the formula (2), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ² and R ³ independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. X represents O, S, or N (R ⁶ ) (R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms), and n represents an integer of 1 to 20).
The block copolymer compound is a diblock copolymer in which the (meth) acrylic polymer block (a) and the (meth) acrylic polymer block (b) are bonded.
The medium is based on 100 parts by mass of the block copolymer compound.
75-200 parts by mass of rosin ester resin,
40-100 parts by mass of alkyl (meth) acrylate,
25-67 parts by mass of hydroxy-substituted alkyl (meth) acrylate and
It contains 50 to 133 parts by mass of alicyclic structure-containing (meth) acrylate, and further
Containing at least one compound selected from the group consisting of polyvalent carboxylic acid ester, PPG urethane acrylate, and polybutadiene urethane acrylate.
When the polyvalent carboxylic acid ester is contained, the mass portion is more than 0 parts by mass and 67 parts by mass or less.
When the PPG urethane acrylate is contained, the mass part is more than 0 parts by mass and 50 parts by mass or less.
When the polybutadiene urethane acrylate is contained, the mass portion is more than 0 parts by mass to 50 parts by mass or less.
A compatible composition in which the total mass of the rosin ester resin, the alkyl (meth) acrylate, the hydroxy-substituted alkyl (meth) acrylate, and the alicyclic structure-containing (meth) acrylate is 280 to 467 parts by mass. Viscosity η _0.1 (Pa · s) of the compatible composition at a shear rate of 0.1 (sec ^-1 ),
Viscosity η ₁ (Pa · s) at shear rate 1 (sec ^-1 ),
Viscosity η ₁₀ (Pa · s) at shear rate 10 (sec ^-1 ),
The ratio of viscosity η _0.1 (Pa · s) to viscosity η ₁ (Pa · s) x ₁ = η _0.1 / η ₁ and
At the ratio of viscosity η ₁ (Pa · s) to viscosity η ₁₀ (Pa · s) x ₂ = η ₁ / η ₁₀
x ₁ is 1.1 to 7.55,
The compatible composition according to claim 1, wherein x ₂ is 1.1 to 5.68. A compatible composition in which a block copolymer compound and a medium are compatible with each other.
The block copolymer compound has the following formula (1):
(In the formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms). A (meth) acrylic polymer block (a) having an active energy ray-curable group containing a partial structure represented by the above. ) And a (meth) acrylic block copolymer having no active energy ray-curable group (b).
The block copolymer compound has no liquid-gel transition temperature (Tc) between 0 and 150 ° C.
The compatible composition has a liquid-gel transition temperature (Tc) between 0 and 150 ° C.
The active energy ray-curable group of the formula (1) is the following formula (2):
(In the formula (2), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ² and R ³ independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. X represents O, S, or N (R ⁶ ) (R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms), and n represents an integer of 1 to 20).
The block copolymer compound is a triblock copolymer in which one each of the (meth) acrylic polymer block (a) is bonded to both ends of one (meth) acrylic polymer block (b). And
The medium is
Contains alkyl (meth) acrylates and alicyclic-containing (meth) acrylates
Further, it contains at least one compound selected from the group consisting of rosin ester-based resins and polyvalent carboxylic acid esters.
A compatible composition having a Tc of 10 to 44 ° C. The compatible compound according to claim 3, wherein the Tc is 10 to 25 ° C. The compatible composition according to any one of claims 1 to 4, wherein the gel-like compatible composition is dissolved in a solvent. The compatible composition according to any one of claims 1 to 5, wherein the gel-like compatible composition is an elastic body. The compatible composition according to any one of claims 1 to 6, further having thermosetting property and / or photocuring property. An adhesive composition comprising the compatible composition according to any one of claims 1 to 7. A composite structure including a member 1 and a member 2.
A composite structure in which the member 1 and the member 2 are adhered to each other via the adhesive composition according to claim 8. The member 1 and the member 2 are plates.
The composite structure according to claim 9, wherein the member 1 and the member 2 are adhered to each other via the adhesive composition according to claim 8, and the member 1 and the member 2 form a laminated body. 9. or claim 9, wherein one member of the member 1 and the member 2 is a liquid crystal display panel, an organic EL display panel, a protective panel, a touch panel, a glass or a plastic plate, and the other member is a light transmitting member. 10. The composite structure according to 10. A method for manufacturing a composite structure including a member 1 and a member 2.
In a temperature environment higher than the temperature Tc,
Step 1 in which the member 1 and the member 2 are bonded to each other via the adhesive composition, and
A method for producing a composite structure, comprising the step 2 of obtaining the composite structure according to any one of claims 9 to 11 by setting the temperature environment to a temperature environment lower than the temperature Tc after the step 1. 12. The method of claim 12, further comprising a step 3 of bringing the solvent according to claim 5 into contact with the adhesive composition to release the adhesion between the member 1 and the member 2 via the adhesive composition. A method for manufacturing a composite structure. The adhesive composition of the member 1 and the member 2 is brought into contact with the solvent according to claim 5 and / or the temperature environment is set to a temperature environment higher than the temperature Tc. The method for disassembling a composite structure according to any one of claims 9 to 11, wherein the adhesive is released from the member 1 and the member 2 is separated from each other. A method for manufacturing a composite structure including a member 1 and a member 2.
The manufacturing method is
In a temperature environment lower than the temperature Tc,
The step 1'in which the member 1 and the member 2 are bonded to each other via the adhesive composition according to claim 8, which is formed by blending the compatible composition according to claim 7.
After the step 1', the adhesive composition is cured at least one selected from the group consisting of thermosetting and photocuring to obtain the composite structure according to any one of claims 9 to 11. A method for producing a composite structure having 2'and. A method for manufacturing a composite structure including a member 1 and a member 2.
The manufacturing method is
Step 1 "to obtain a pressure-sensitive adhesive composition by thermosetting and / or photocuring the adhesive composition according to claim 8, which is a blend of the compatible composition according to claim 7.
A method for manufacturing a composite structure according to the step 2 "in which the member 1 and the member 2 are bonded to each other via the adhesive cured body to obtain the composite structure according to any one of claims 9 to 11.