JP2018178013A - Compatible composition, adhesive composition, composite structure, and manufacturing method and decomposition method of composite structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compatible composition of which a state reversibly changes between a liquid form and a gel form between a high temperature and a low temperature.SOLUTION: There is provided a compatible composition manufactured by dissolving a block copolymer compound and a medium, the block copolymer compound is a (meth)acrylic block copolymer having a (meth)acrylic polymer block having an active energy ray curable group (a), and a (meth)acrylic polymer block having no active energy ray curable group (b), the block copolymer compound has no liquid form-gel form transition temperature (Tc) between 0 and 150°C, the compatible composition has the liquid form-gel form transition temperature (Tc) between 0 and 150°C. There is provided a compatible composition, in which the compatible composition with the gel form is an elastomer and is dissolved in a solvent. There is provided an adhesive composition manufactured by blending the compatible composition. There is provided a composite structure manufactured by adhering members each other via the adhesive composition, and capable of cancel adhesion in environment of higher than Tc temperature after adhesion with the solvent.SELECTED DRAWING: None

Description

  The present invention relates to a compatible composition in which a specific block copolymer compound and a medium are compatible, an adhesive composition containing the compatible composition, and a composite structure in which the adhesive composition is used. The present invention relates to an object and a method of manufacturing and disassembling the composite structure.

  It is required that components of optical system devices such as liquid crystal display main body and optical lens, and components of electronic system devices such as electronic paper and batteries be fixed with an adhesive so that the fixing can be released in some cases. May be

  In response to the demand, conventionally, the cured adhesive of the fixed portion is heated and fluidized, swollen by contacting with a solvent, or peeled from the member by curing the cured adhesive by immersion in water. Have been taken (eg, Patent Document 1).

Unexamined-Japanese-Patent No. 2010-100831

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

The present invention
A compatible composition in which the state reversibly changes between liquid and gel between high temperature and low temperature
An adhesive composition which can be liquid at high temperature, can be easily applied to members, can be gel-like at low temperatures, can bond members to each other, and can be liquid when it becomes high again and can easily cancel adhesion between members.
Composite structure including a member bonded with a gelled adhesive composition and method for producing the same
And
It is an object of the present invention to provide a method of disassembling the composite structure, in which the gelled adhesive composition is liquefied and removed under high temperature.

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

(In formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.) (Meth) acrylic polymer block (a) having an active energy ray-curable group including a partial structure And (meth) acrylic block copolymers having a (meth) acrylic polymer block (b) having no active energy ray-curable group,
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 preceding [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 bonded via the adhesive composition described in the above item [2],
[4] A method of manufacturing a composite structure including a member 1 and a member 2;
In a temperature environment higher than the temperature Tc described in the preceding paragraph [1],
Bonding the member 1 and the member 2 via the adhesive composition;
After the step 1, the temperature environment is made lower than the temperature Tc, and the step 2 of obtaining the composite structure described in the above item [3];
[5] The temperature environment is made higher than the temperature Tc to release the adhesion of the member 1 and the member 2 via the adhesive composition, thereby separating the member 1 and the member 2 A method of disassembling the composite structure according to [3],
[6] A method of 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 preceding paragraph [1],
The member 1 and the member 2 are formed by blending the compatible composition having a thermosetting property and / or a photocurable property, wherein the gel-like compatible composition is an elastic body having viscoelasticity [2 Step 1 ′ of laminating via the adhesive composition described above,
After the step 1 ′, the adhesive composition is thermally cured and / or photocured to obtain the composite structure described in the above [3], and 2 ′.
[7] A method of manufacturing a composite structure including a member 1 and a member 2;
The manufacturing method is
It is a compatible composition as described in said [1], Comprising: The said gel-like compatible composition is an elastic body which has adhesiveness, At least 1 sort (s) chosen from the group which consists of thermosetting and / or photocurable. A thermally curing and / or photocuring the adhesive composition as described in the above item [2], which comprises a compatible composition having the curability of
The method is a method for producing a composite structure, comprising: step 2 ′ ′ in which the member 1 and the member 2 are bonded via the adhesive cured body to obtain the composite structure described in [3].

  The temperature environment of temperature T refers to an environment in which a compatible compound is present such that the temperature of the compatible composition is the temperature T. For example, even if the compatible composition is placed at room temperature, the compatible environment is compatible. If the temperature of the compatibilized composition exceeds 50 ° C. when heated by a heater in contact with the composition, the temperature environment in that case is more than 50 ° C. Hereinafter, the “high temperature environment” and the “high temperature environment” are also referred to as the “high temperature”, and the “low temperature environment” and the “low temperature environment” are also referred to as the “low temperature”.

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

It is a measurement result of storage rigidity G 'and loss rigidity G' in the range of 0-80 degreeC of the compatible composition of Example 1. FIG. 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 generic name of "methacrylic" and "acrylic", and "(meth) acryloyl" described later means a generic name of "methacryloyl" and "acryloyl", which will be described later. "(Meth) acrylate" means a generic name of "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) A (meth) acrylic block copolymer having a (meth) acrylic polymer block (a) and a (meth) acrylic polymer block (b) not having an 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 compatiblizing composition contains the compound A, the elasticity and tackiness of the gel-like compatiblizing composition and the compatibilizing 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, for example, by irradiation of active energy rays. In the present specification, active energy rays mean light rays, electromagnetic waves, particle rays, and combinations thereof. Light rays include far ultraviolet rays, ultraviolet rays (UV), near ultraviolet rays, visible rays and infrared rays, and electromagnetic waves include X rays and γ rays, and particle rays include electron rays (EB) and proton rays (α Wire, neutron beam, 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 an irradiation device, cost and the like.

In the formula (1), the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, 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 group such as hexyl group, 2-methyl pentyl group, 3-methyl pentyl group and n-decyl; cycloalkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group; aryl such as phenyl group and naphthyl group Groups include aralkyl groups such as benzyl group and phenylethyl group. Among them, from the viewpoint of curability of active energy rays, methyl group and ethyl group are preferable, and methyl group is most preferable.

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

(In formula (2), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, An active energy ray represented by 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 preferable that it is a curable group (hereinafter referred to as "active energy ray curable group (2)").

In the formula (2), specific examples and preferred examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ include the same hydrocarbon groups as R ¹ in the 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, using a monomer containing di (meth) acrylate (3) described later From the viewpoint of easy direct introduction, hydrocarbon groups having 1 to 6 carbon atoms are preferable. As such a hydrocarbon group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, 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 alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like; and aryl groups such as phenyl and the like. Among these, from the viewpoint of curing speed, methyl group and ethyl group are preferable, and 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 from the viewpoint of ease of polymerization control Is preferred. When X is N (R ⁶ ), examples of the hydrocarbon group having 1 to 6 carbon atoms represented by R ⁶ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl group, 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 And alkyl groups such as neopentyl group, n-hexyl group, 2-methylpentyl group and 3-methylpentyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group, and phenyl groups.

  In the formula (2), the integer of 1 to 20 represented by n is preferably 2 to 5 from the viewpoint of flowability and curing speed of the compound A.

  The content of the partial structure (1) with respect to all monomer units forming the (meth) acrylic polymer block (a) is preferably 0.2 to 100 mol%, more preferably 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. As such (meth) acrylic acid esters, 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 monofunctional (meth) acrylic acid esters capable of forming the (meth) acrylic polymer block (a) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, 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, (meth) acrylic acid 2 -Aminoethyl, N, N-dimethylaminoethyl (meth) acrylate, (meth) acrylate N, N-diethylaminoethyl lactate, phenyl (meth) acrylate, naphthyl (meth) acrylate, 2- (trimethylsilyloxy) ethyl (meth) acrylate, 3- (trimethylsilyloxy) propyl (meth) acrylate, (( (Meth) acrylic acid glycidyl, γ-((meth) acryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoro (meth) acrylic acid Methyl ethyl, 2-perfluoroethyl ethyl (meth) acrylate, 2-perfluoroethyl 2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, permeth (acrylic acid) Fluoromethyl, (meth) acrylic acid diperfluoro Methyl methyl, 2-perfluoromethyl-2-perfluoroethyl methyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, (meth) acrylate 2-perfluorohexadecylethyl etc. are mentioned. Among these, methacrylic acid alkyl esters having an alkyl group having a carbon number of 5 or less such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate and the like are preferable. And methyl methacrylate are most preferred.

  Moreover, as polyfunctional (meth) acrylic acid ester which can form a (meth) acrylic-type polymer block (a), following formula (3):

(Wherein, R ^{2 ′} and R ^{3 ′} each independently represent a hydrocarbon group having 1 to 6 carbon atoms, R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group, and n is 1 to 1) When a bifunctional (meth) acrylic acid ester (hereinafter referred to as “di (meth) acrylate (3)”) represented by an integer of 20 is used, living anionic polymerization under the conditions described later The (meth) acryloyloxy group (the (meth) acryloyloxy group represented by “CH ₂ CC (R ⁵ ) C (O) O” in the formula (3)) is selectively polymerized to form R ¹ of R ⁴ A methacrylic polymer block (a) having an active energy ray-curable group (2) wherein 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 polymerization selectivity, R ⁴ is preferably a methyl group. Further, from the viewpoint of productivity of the di (meth) acrylate (3), it is preferred that R ⁴ and R ⁵ are the same. From the above viewpoints, it is most preferable that both R ⁴ and R ^{5 be} a methyl group.

  Specific examples of the di (meth) acrylate (3) include, for example, 1,1-dimethylpropane-1,3-diol di (meth) acrylate, 1,1-dimethylbutane-1,4-diol di (meth) acrylate, 1 1,1-Dimethylpentane-1,5-diol di (meth) acrylate, 1,1-dimethyl hexane-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 Etc., 1,1-dimethylpropane-1,3-diol dimethacrylate, 1,1-dimethyl Tan-1,4-diol dimethacrylate, 1,1-dimethylpentane-1,5-diol dimethacrylate, 1,1-dimethylhexane-1,6-diol dimethacrylate, 1,1-diethylpropane-1,3 -Diol dimethacrylate, 1,1-diethylbutane-1,4-diol dimethacrylate, 1,1-diethylpentane-1,5-diol dimethacrylate, and 1,1-diethylhexane-1,6-diol dimethacrylate Preferred are 1,1-dimethylpropane-1,3-diol dimethacrylate, 1,1-dimethylbutane-1,4-diol dimethacrylate, 1,1-dimethylpentane-1,5-diol dimethacrylate, and 1,1-Dimethylhexane-1,6-diol dimethacrylate is more preferable Arbitrariness.

  These (meth) acrylic acid esters may be used alone or in combination of two or more.

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

  The (meth) acrylic polymer block (a) may have a monomer unit formed from another monomer other than the above (meth) acrylic acid ester. Examples of such other monomers 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-alkoxy acrylic esters such as esters; N-isopropyl acrylamide, N-t-butyl acrylamide, N, N-dimethyl acrylamide, acrylamides such as N, N-diethyl acrylamide; N-isopropyl methacrylamide, N-t-butyl Methacrylamides such as methacrylamide, N, N-dimethyl methacrylamide, N, N-diethyl methacrylamide; methyl 2-phenylacrylate, ethyl 2-phenylacrylate, n-butyl 2-bromoacrylate, 2-bromomethylamide Methyl acrylic acid, 2-bromomethyl acrylate, methyl vinyl ketone, ethyl vinyl ketone, methyl isopropenyl ketone, ethyl isopropenyl ketone. These other monomers may be used alone or in combination of two or more.

  The content of monomer units formed from the above-mentioned other monomers in the (meth) acrylic polymer block (a) is the total of monomers forming the (meth) acrylic polymer block (a) The amount 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, etc., 500 to 1,000. The range of 1,000 is preferable, and the range of 1,000 to 300,000 is more preferable. In the present specification, Mn and a molecular weight distribution described later mean standard polystyrene equivalent value measured by gel permeation chromatography (GPC).

  The compound A has the (meth) acrylic polymer block (a) and the (meth) acrylic polymer block (b) not having an active energy ray-curable group, and as a preferred embodiment, the compound A is It consists only of a (meth) acrylic polymer block (a) and a (meth) acrylic polymer block (b). That is, the 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 (meth) acrylic acid ester, and has no active energy ray-curable group It is a polymer block. In the present specification, an active energy ray-curable group means a functional group that exhibits polymerizability by irradiation of the above-mentioned active energy ray. The active energy ray-curable group is, for example, an ethylenic double bond such as (meth) acryloyl group, (meth) acryloyloxy group, vinyl group, allyl group, vinyloxy group, 1,3-dienyl group, styryl group (in particular A functional group having an ethylenic double bond represented by the formula CH ₂ CRCR— (wherein R is 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 (meth) acrylic acid esters capable of forming a (meth) acrylic polymer block (b) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, 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) Phenyl acrylate, naphthyl (meth) acrylate, 2- (trimeth) acrylic acid Rushiriruokishi) ethyl include mono (meth) acrylic acid esters such as (meth) acrylic acid 3- (trimethylsilyloxy) propyl. 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, etc. The methacrylic acid alkyl ester which has a C6 or more alkyl group is preferable. These (meth) acrylic acid esters may be used alone or in combination of two or more.

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

  The (meth) acrylic polymer block (b) may have a monomer unit formed of a monomer other than the (meth) acrylic acid ester. Examples of such other monomers 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, N-t-butyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide Methyl) acrylamide; methyl vinyl ketone, ethyl vinyl ketone, methyl isopropenyl ketone, ethyl isopropenyl ketone etc. are mentioned. These other monomers may be used alone or in combination of two or more.

  The content of the monomer unit formed by the other monomer in the (meth) acrylic polymer block (b) is the total of monomers forming the (meth) acrylic polymer block (b) The amount 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 from the viewpoint of the handleability, fluidity, mechanical properties, etc. of the compound A to be obtained, The range is preferable, and the range of 5,000 to 1,000,000 is more preferable.

  Examples of the compound A include block copolymers in which at least one (meth) acrylic polymer block (a) and at least one (meth) acrylic polymer block (b) are mutually bonded, The number and bonding order of the united blocks are not particularly limited, but it is preferable that the (meth) acrylic polymer block (a) form at least one end of the compound A from the viewpoint of curability of active energy ray, compound A It is more preferable that the polymer is a linear polymer from the viewpoint of easiness of production of the polymer, and one (meth) acrylic polymer block (a) and one (meth) acrylic polymer block (b) And one (meth) acrylic polymer block (a) bonded to each end of the diblock copolymer having one or more bonded groups and one (meth) acrylic polymer block (b) A block copolymer is more preferable, and from the viewpoint of the viscoelastic property after curing of the adhesive composition described later, (meth) acrylic polymer blocks at both ends of one (meth) acrylic polymer block (b) (A) A triblock copolymer in which each one is bonded to each other is more preferable.

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

  The glass transition temperature (Tg) of the (meth) acrylic polymer block (a) is preferably more than 50 ° C. and not more than 180 ° C. because the compatible composition of the present invention is easily obtained, etc. It is preferable that Tg of (meth) acrylic-type polymer block (b) is -100 degreeC or more and 50 degrees C or less. In order to obtain each polymer block having such a Tg, the kind and amount of monomers used in forming them may be appropriately adjusted. The Tg of the compound A is a temperature range in which the preferred Tg of the (meth) acrylic polymer block (a) and the (meth) acrylic polymer block (b) is included, that is, a temperature range of more than 50 ° C. and 180 ° C. or less It is preferable to have Tg in a temperature range of −100 ° C. or more and 50 ° C. or less.

(Measurement conditions of glass transition temperature (Tg))
The compound A is sheet-formed 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. Thereafter, a 45 mm × 10 mm × 0.5 mm strip required for dynamic viscoelasticity measurement is cut out.

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

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

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

  The molecular weight distribution of the 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, 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%, and more preferably in the range of 2 to 15 mol%, based on all monomer units forming the compound A. Is more preferable, and the range of 3 to 10 mol% is more preferable.

  The 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 anionic polymerization method or a living radical polymerization method is more preferable from the viewpoint of polymerization control, and a living anionic polymerization method is more preferable. The monomer used for producing the compound A is preferably dried in advance in an inert gas atmosphere from the viewpoint of promoting the polymerization smoothly. In the drying treatment, a dehydrating agent or desiccant such as calcium hydride, molecular sieves, activated alumina or the like is preferably used.

  As the living radical polymerization method, a polymerization method using a chain transfer agent such as polysulfide, a polymerization method using a cobalt porphyrin complex, a polymerization method using nitroxide (refer to International Publication No. 2004/014926), high cycle heterogeneity such as organic tellurium compound A polymerization method using an elemental compound (see Japanese Patent No. 3839829), a reversible addition / desorption chain transfer polymerization method (RAFT) (see Japanese Patent No. 3639859), an atom transfer radical polymerization method (ATRP) (Japanese Patent No. 3040172) And WO 2004/013192) and the like. Among these living radical polymerization methods, atom transfer radical polymerization method is preferable, and a metal complex having an organic halide or a halogenated sulfonyl compound as an initiator and at least one selected from Fe, Ru, Ni, and Cu as a central metal More preferred is atom transfer radical polymerization as a catalyst.

  As the living anion polymerization method, a method of living polymerization using an organic rare earth metal complex as a polymerization initiator (refer to JP-A 06-93060), salts of an alkali metal or alkaline earth metal with an organic alkali metal compound as a polymerization initiator Living anionic polymerization in the presence of a mineral acid salt (see JP-H05-507737), and living anionic polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organic aluminum compound 11-335432, international publication 2013/141105), etc. are mentioned. Among these living anionic polymerization methods, from the viewpoint that the (meth) acrylic polymer block (a) can be formed directly and efficiently, living anionic polymerization is performed using an organic alkali metal compound as a polymerization initiator in the presence of an organic aluminum compound. Is preferable, and a method of 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 compounds include t-butyllithium, 1,1-dimethylpropyllithium, 1,1-diphenylhexyllithium, 1,1-diphenyl-3-methylpentyllithium, ethyl α-lithioisobutyrate, and butyl. α-lithioisobutyrate, methyl α-lithioisobutyrate, isopropyllithium, sec-butyllithium, 1-methylbutyllithium, 2-ethylpropyllithium, 1-methylpentyllithium, cyclohexyllithium, diphenylmethyllithium, α- Examples include methylbenzyllithium, methyllithium, n-propyllithium, n-butyllithium, n-pentyllithium and the like. Among them, secondary compounds such as isopropyllithium, sec-butyllithium, 1-methylbutyllithium, 1-methylpentyllithium, cyclohexyllithium, diphenylmethyllithium, α-methylbenzyllithium and the like from the viewpoint of easy availability and anionic polymerization initiation ability The C3-C40 organolithium compound which has a chemical structure which makes a carbon atom an anion center is preferable, and sec-butyllithium is especially preferable. These organic lithium compounds may be used alone or in combination of two or more.

  The amount of the organic lithium compound used can be determined by the ratio to the amount of the monomer used, depending on the Mn of the target compound A.

As said organic aluminum compound, a following formula (A-1):
AlR ⁷ (R ⁸ ) (R ⁹ ) (A-1)

(Wherein, R ⁷ represents a monovalent saturated hydrocarbon group, a monovalent aromatic hydrocarbon group, an alkoxy group, an aryloxy group or an N, N-disubstituted amino group, and R ⁸ and R ⁹ are each independently Or an aryloxy group, or R ⁸ and R ⁹ are combined with each other to form an arylenedioxy group), or an organoaluminum compound represented by the following formula (A-2):
AlR ¹⁰ (R ¹¹ ) (R ¹² ) (A-2

(Wherein, R ¹⁰ represents an aryloxy group, and R ¹¹ and R ¹² each independently represent a monovalent saturated hydrocarbon group, a monovalent aromatic hydrocarbon group, an alkoxy group or N, N-disubstituted amino And organoaluminum compounds represented by

As an aryloxy group which R < ⁷ >, R <^8> , R < ⁹ > and R < ¹⁰ > respectively independently represent in Formula (A-1) and (A-2), a phenoxy group, 2-methyl phenoxy group, 4-methyl, for example 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-tert-butyl-4-ethylphenoxy group, 2,6-diphenylphenoxy group, 1-naphthoxy group, 2-naphthoxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 7- A methoxy-2-naphthoxy group etc. are mentioned.

In the formula (A-1), as an arylenedioxy group formed by bonding R ⁸ and R ⁹ to each other, for example, 2,2′-biphenol, 2,2′-methylene bisphenol, 2,2′-methylene bis (4-Methyl-6-t-butylphenol), (R)-(+)-1,1'-bi-2-naphthol, (S)-(-)-1,1'-bi-2-naphthol, etc. The functional group except the hydrogen atom of these 2 phenolic hydroxyl groups in the compound which has 2 phenolic hydroxyl groups of these is mentioned.

  In addition, one or more hydrogen atoms contained in the above aryloxy group and arylenedioxy group may be substituted by a substituent, and examples of the substituent include a methoxy group, an ethoxy group, an isopropoxy group, Examples thereof include alkoxy groups such as t-butoxy group; and halogen atoms such as chlorine atom and bromine atom.

Examples of the monovalent saturated hydrocarbon group represented by R ⁷ , R ¹¹ and R ¹² independently in formulas (A-1) and (A-2) include, for example, methyl group, ethyl group, 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; Examples of the monovalent aromatic hydrocarbon group include an aryl group such as a phenyl group; and an aralkyl group such as a benzyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group and an iso group. Examples thereof include propoxy group and t-butoxy group, and examples of the N, N-disubstituted amino group include dimethylamino group, diethylamino group, and diisopropylamino group. And dialkylamino groups such as groups; bis (trimethylsilyl) amino groups and the like. One or more hydrogen atoms contained in the above-mentioned monovalent saturated hydrocarbon group, monovalent aromatic hydrocarbon group, alkoxy group and N, N-disubstituted amino group may be substituted by a substituent Examples of the substituent include alkoxy groups such as methoxy, ethoxy, isopropoxy and t-butoxy; and halogen atoms such as chlorine and bromine.

  As the organoaluminum compound (A-1), for example, ethyl bis (2,6-di-t-butyl-4-methylphenoxy) aluminum, ethyl bis (2,6-di-t-butylphenoxy) aluminum, 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 -Octyl bis (2, 6-di-t-butyl phenoxy) aluminum, n-octyl [2, 2'-methyl] Len bis (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-tert-butyl-4-methylphenoxy) aluminum, ethoxybis (2,6-di- t-Butylphenoxy) aluminum, ethoxy [2,2'-methylenebis (4-methyl-6-t-butylphenoxy)] aluminum, isopropoxybis (2,6-di-t-butyl-4-methylphenoxy) aluminum , Isopropoxy bis (2,6-di-t-butylphenoxy) aluminum, iso Lopoxy [2,2′-methylenebis (4-methyl-6-t-butylphenoxy)] aluminum, t-butoxybis (2,6-di-t-butyl-4-methylphenoxy) aluminum, t-butoxybis (2,2, 6-di-t-butylphenoxy) aluminum, t-butoxy [2,2'-methylenebis (4-methyl-6-t-butylphenoxy)] aluminum, tris (2,6-di-t-butyl-4- 4 Methyl phenoxy) aluminum, tris (2, 6- diphenyl phenoxy) aluminum, etc. are mentioned. Among them, isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum, isobutylbis (2,6), from the viewpoints of polymerization initiation efficiency, living property of polymerization terminal anion, and availability and handling ease. -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, diisobutyl (2, 6-di-tert-butyl-4-methylphenoxy) aluminum, diisobutyl (2,6-di-tert-butylphenoxy) aluminum, di-n-octyl (2,6-di-tert-butyl-4-methylphenoxy) Aluminum, di n-octyl (2, 6-di-t-butyl phenoxy) aluminum etc. are mentioned. These organoaluminum compounds may be used alone or in combination of two or more.

  As said Lewis base, the compound which has an ether bond and / or tertiary amine structure in a molecule | numerator is mentioned.

  As a compound which has an ether bond in the molecule | numerator used as said Lewis base, an ether is mentioned. As the above ether, cyclic ether having 2 or more ether bonds in the molecule or non-cyclic ether having 1 or more ether bonds in the molecule from the viewpoint of high polymerization initiation efficiency and living property of the polymerization terminal anion Is preferred. Examples of cyclic ethers having two or more ether bonds in the molecule include crown ethers such as 12-crown-4, 15-crown-5, 18-crown-6 and the like. Examples of non-cyclic ethers having one or more ether bonds in the molecule include non-cyclic monoethers such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether and anisole; 1,2-dimethoxyethane, 1,2-diethoxy Ethane, 1,2-diisopropoxyethane, 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, Noncyclic diethers such as 2,4-diisopropoxybutane, 1,4-dibutoxybutane and 1,4-diphenoxybutane; 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 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, acyclic polyethers such as tetramethylammonium butylene glycol diethyl ether. Among them, non-cyclic ethers having one or two ether bonds in the molecule are preferable, and diethyl ether or 1,2-dimethoxyethane is more preferable, from the viewpoint of suppression of side reactions, availability, and the like.

  As a compound which has a tertiary amine structure in a molecule | numerator used as said Lewis base, tertiary polyamines are mentioned. The tertiary polyamine means a compound having two or more tertiary amine structures in the molecule. Examples of the tertiary polyamines include N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetraethylethylenediamine, N, N, N ', N ", N" -pentamethyl Linear polyamines such as diethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetramine, 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 Nonaromatic heterocyclic compounds such as hexaazacyclooctadecane; aromatic heterocyclic compounds such as 2,2'-bipyridyl, 2,2 ': 6', 2 "-terpyridine, etc. .

  Also, compounds 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 per mol of the organic lithium compound, from the viewpoint of the polymerization initiation efficiency, the stability of the polymerization terminal anion, etc. More preferably, it is in the range of 3.0 mol, and more preferably in the range of 1.0 to 2.0 mol. If the amount of the Lewis base used is more than 5.0 mol with respect to 1 mol of the organic lithium compound, the economy tends to be disadvantageous in economy, and if less than 0.3 mol, the polymerization initiation efficiency tends to decrease.

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

  The above living anionic polymerization is preferably performed in the presence of an organic solvent from the viewpoint of temperature control and homogenization of the inside of the system to promote polymerization smoothly. As the organic solvent, hydrocarbons such as toluene, xylene, cyclohexane, methylcyclohexane and the like from the viewpoints of safety, separation from water in water washing of the reaction mixture after polymerization, ease of recovery and reuse, etc .; chloroform, Halogenated 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. The organic solvent is preferably dried in advance in the presence of an inert gas while being subjected to a drying treatment from the viewpoint of promoting the polymerization smoothly.

  Moreover, in the above-mentioned living anionic polymerization, other additives 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 methoxyethoxy ethoxide and potassium t-butoxide; tetraethyl ammonium chloride and tetraethyl phosphonium bromide.

  The living anionic polymerization is preferably performed at -30 to 25 ° C. When the temperature is lower than -30 ° C, the polymerization rate tends to be low, and the productivity tends to be low. On the other hand, when 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 property.

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

  In the above living anionic polymerization, as a method of adding an organolithium compound, an organoaluminum compound, a Lewis base and a monomer to a reaction system of anionic polymerization, the Lewis base contacts with the organoaluminum compound before contact with the organolithium compound. Preferably, it is added as follows. The organoaluminum compound may be added to the reaction system of anionic polymerization prior to the monomer, or may be added simultaneously. When the organoaluminum compound is added to the reaction system for anionic polymerization simultaneously with the monomer, the organoaluminum compound may be added after being separately mixed with the monomer.

  The living anionic polymerization can be terminated by adding a polymerization terminator such as methanol; a methanol solution of acetic acid or hydrochloric acid; a protic compound such as an aqueous solution of acetic acid or hydrochloric acid to the reaction solution. The amount of the polymerization terminator to be used is usually preferably in the range of 1 to 100 moles per mole of the organic lithium compound to be used.

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

  When the metal component derived from the organic lithium compound and the organic aluminum compound remains in the compound A obtained by separation and separation, the physical properties of the compound A may be deteriorated, the transparency may be deteriorated, and the like. Therefore, it is preferable to remove the metal component derived from the organolithium compound and the organoaluminum compound after termination of the anionic polymerization. As a method of removing the metal component, a washing treatment using an acidic aqueous solution, an adsorption treatment using an adsorbent such as ion exchange resin, celite, activated carbon and the like are effective. Here, as the acidic aqueous solution, for example, hydrochloric acid, aqueous sulfuric acid, aqueous nitric acid, aqueous acetic acid, aqueous propionic acid, aqueous citric acid and the like can be used.

  As a method of introducing an active energy ray-curable group containing a partial structure (1) in the production of the compound A, a monomer containing the above di (meth) acrylate (3) is polymerized to obtain (meth) acrylic In addition to the method of forming the polymer block (a), after forming the polymer block including the partial structure (hereinafter referred to as "precursor structure") to be the precursor of the partial structure (1), the precursor structure There is also a method of converting into a partial structure (1). The polymer block containing a precursor structure is obtained by polymerizing a monomer containing a compound containing a polymerizable functional group and 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. As a precursor structure, a hydroxyl group protected by a hydroxyl group and a protecting group (silyloxy group, acyloxy group, alkoxy group etc.), an amino group protected by an amino group and a protecting group, and a thiol protected by a thiol group and a protecting group And isocyanate groups.

  A polymer block containing a hydroxyl group as a precursor structure is reacted with a compound having a partial structure (1) and a partial structure (carboxyl group, ester, carbonyl halide, etc.) capable of reacting with a hydroxyl group (meth) acrylic polymer A block (a) can be formed. Moreover, after removing the said protective group and setting it as a hydroxyl group, the polymer block containing the hydroxyl group protected by the protective group as precursor structure can form a (meth) acrylic-type polymer block (a) similarly.

  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 anhydride, ester, carbonyl halide, aldehyde group, isocyanate group, etc.) The (meth) acrylic polymer block (a) can be formed by reacting with a compound. In addition, a polymer block containing an amino group protected by a protective group as a precursor structure can similarly form a (meth) acrylic polymer block (a) after removing the protective group to form an amino group.

  The polymer block containing a thiol group as a precursor structure is 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 And the like) to form a (meth) acrylic polymer block (a). In addition, a 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 reacted with a compound having a partial structure (1) and a partial structure (such as a hydroxyl group or an amino group) capable of reacting with the isocyanate group to give a (meth) acrylic polymer block (A) can be formed.

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

〔medium〕
(Compound B)
The medium (hereinafter referred to as compound B) in the present invention is compatible with compound A, and the compatible composition according to the present invention (hereinafter referred to as a compound) having a liquid-gel transition temperature (Tc) between temperatures 0 to 150 ° C. It is a compound which comprises the compatible composition).

  As the compound B, a compound compatible with the compound A may be selected as a standard a compound capable of having fluidity, and radically polymerizable unsaturated bonds such as (meth) acrylate monomers, (meth) acrylamide monomers, etc. It may be a containing monomer, a plasticizer, a solvent and the like.

As a monomer compound which the compatibilizing composition with the 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 acrylate; alkoxy substituted alkyl (meth) acrylates such as methoxyethyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate ) Hydroxy substituted alkyl (meth) acrylates such as acrylates; benzyl (meth) acrylates, phenyl (meth) acrylates etc; ethylene glycol di (meth) acrylates, diethylene glycol di (meth) acrylate Triethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di Di (meth) acrylates such as (meth) acrylate; 4-t-butylcyclohexyl acrylate, dicyclopentenyl oxyethyl (meth) acrylate, norbornene (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate And at least one compound selected from the group consisting of alicyclic structure-containing (meth) acrylates, (meth) acryloyl morpholines, (meth) acrylamides such as diethyl (meth) acrylamide, etc.,
More preferably, it is at least one compound selected from the group consisting of isodecyl acrylate, 4-hydroxybutyl acrylate and 4-tert-butylcyclohexyl acrylate.

  From the viewpoint of improving the strength, elasticity and adhesiveness of a gel-like compatible composition and a compatible composition at the time of curing as the compound B, from the viewpoint of radical reactivity, cation reactivity, anion reactivity and moisture reactivity It is preferable to use at least one reactive compound selected from the group consisting of In this specification, the reactivity that causes a polymerization reaction due to moisture (moisture) in the air is called moisture reactivity, and the curing of the curable composition due to the polymerization reaction of the moisture reactive group in the curable composition is wetted. It is called hardening.

From the viewpoint of improving the strength, elasticity and tackiness of the gel-like compatibilizing composition and the compatibilizing composition at the time of curing, as a radical reactive compound,
Preferably, at least one member 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) acrylates, (meth) acrylamides, urethane (meth) acrylates and vinyl ethers
More preferably, at least one radical reactive group selected from the group consisting of (meth) acrylates and urethane (meth) acrylates (preferably a bifunctional or higher polyfunctional group from the viewpoint of the rate and stability of radical reaction) Is a reactive compound having

From the viewpoint of improving the strength, elasticity and tackiness of the gel-like compatibilizing composition and the compatibilizing composition at the time of curing, as a cation reactive compound,
Preferred are reactive compounds 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 tackiness of the gel-like compatibilizing composition and the compatibilizing composition upon curing, the anion reactive compound is preferably at least one selected from the group consisting of epoxy, oxetane and vinyl ether It is a reactive compound having one kind of anion reactivity.

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

  From the viewpoint of improving the strength, elasticity and tackiness of the gel-like compatibilizing composition and the compatibilizing composition at the time of curing, the compatiblizing composition is preferably a combination of the compound A and the compound B which is a radical reactive compound. Configure.

  From the viewpoint of improving the strength, elasticity and tackiness of the gel-like compatibilizing composition and the compatibilizing composition at the time of curing and the easiness of using the compatiblizing composition, the compatibilizing 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, as a polymerization initiator,
Preferably, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, benzophenone, 2,2-dimethoxy -1,2-diphenylethan-1-one, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, 2,4,6-trimethyl benzoyl phenyl ethoxy phosphine oxide, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) butanone-1, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl-1- [4-methylthio] phenyl] -2-morpholinopropane-1-one, benzoin Methyl ether, benzoin ethyl ether, benzoin isobutyl ether , Benzoin isopropyl ether, bis (2,4,6-trimethylbenzoyl) -phenyl phosphine 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-propanone, isopropylthioxanthone, methyl o-benzoylbenzoate, [4- (methylphenylthio) phenyl Phenylmethane, 2,4-diethylthioxanthone, 2-chlorothioxanthone, benzophenone, ethyl anthraquinone, benzophenone ammonium salt, thioxanthone ammonium salt, bis (2,6-dimethoxybenzoyl) -2,4,4-trime Pentyl phosphine oxide, bis (2, 6-dimethoxy benzoyl)-2, 4, 4- trimethyl-pentyl phosphine oxide, 2, 4, 6-trimethyl benzophenone, 4- methyl benzophenone, 4, 4 '-bis diethyl amino benzophenone 1,4 dibenzoylbenzene, 10-butyl-2-chloroacridone, 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-benzoylbiphenyl, 4 -Benzoyldiphenyl ether, acrylated benzophenone, bis ((5-2,4-cyclopentadiene-1-i) ) -Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, o-methyl benzoyl benzoate, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ethyl ester And at least one selected from the group consisting of activated tertiary amines, carbazole / phenone photo initiator compounds, acridine photo initiator compounds, triazine photo initiator compounds and benzoyl photo initiator compounds. A compound,
More preferably, it is 1-hydroxy-cyclohexyl-phenyl-ketone and / or 2,4,6-trimethyl benzoylphenyl ethoxy phosphine oxide.

When the reactive compound is a cation reactive compound, as a polymerization initiator,
Preferably, at least one ionic photoacid generator compound selected from the group consisting of aryldiazonium salts, diarylhalonium salts, triarylsulfonium salts, triphosphonium salts, iron arene complexes, titanocene complexes and arylsilanolaluminum complexes, and 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-hydroxyimidosulfonate.

When the reactive compound is an anion reactive compound, as a polymerization initiator,
Preferably, it is selected from the group consisting of 1,10-diaminodecane, 4,4′-trimethylene dipiperazine, carbamate compounds and derivatives thereof, cobalt-amine complexes, aminooxyiminos compounds and ammonium borate compounds It is at least one compound.

When the reactive compound is a moisture reactive compound, as a polymerization initiator,
Preferably, at least one titanium compound selected from the group consisting of tetrabutyl titanate, tetrapropyl titanate, titanium tetraacetylacetonate and bisacetylacetonatodiisopropoxytitanium as a silanol condensation catalyst,
Dibutyltin diuralate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctoate, dibutyltin diethyl hexanolate, dibutyltin dimethyl maleate, dibutyltin diethyl maleate, dibutyltin dibutyl maleate, dibutyltin dioctyl maleate, dibutyltin ditridecyl Maleate, dibutyltin dibenzyl maleate, dibutyltin diacetate, dioctyltin diethyl maleate, dioctyltin dioctyl maleate, dibutyltin dimethoxide, dibutyltin dinonylphenoxide, dibutenyltin oxide, dibutyltin diacetylacetonate, dibutyltin Diethyl acetoacetonate, reaction product of dibutyltin oxide and silicate compound, and reaction product of dibutyltin oxide and phthalic ester Organotin compound of at least one tetravalent element selected from the group,
At least one organoaluminum compound selected from the group consisting of aluminum trisacetylacetonate, aluminum trisethylacetoacetate and diisopropoxyaluminum ethylacetoacetate,
Zirconium compounds such as zirconium tetraacetylacetonate,
Amine compounds, acidic phosphoric acid esters, reaction products of acidic phosphoric acid esters with amine compounds, reactions of saturated or unsaturated polyvalent carboxylic acids or their acid anhydrides, salts of carboxylic acid compounds with amine 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,
Trialkyl phosphine compounds such as triethyl phosphine,
At least one organotin compound selected from the group consisting of dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, tin octoate and dibutyltin diethyl hexanolate,
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 which the compatibilizing composition with the compound A can have fluidity,
Preferably, phthalic acid esters such as dibutyl phthalate, diisononyl phthalate, dibutyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate;
Polyvalent carboxylic acid esters such as dioctyl adipate, diisononyl adipate, dioctyl sebacate, diisononyl sebacate, diisononyl 1,2-cyclohexanedicarboxylate;
Alkyl benzoate;
Phosphoric acid esters such as tricresyl phosphate, tributyl phosphate;
Trimellitic acid ester

(Hydrogenated) rubber polymers such as polyisoprene, hydroxyl group-containing (hydrogenated) polyisoprene, (hydrogenated) polybutadiene, hydroxyl group-containing (hydrogenated) polybutadiene, polybutene and the like;
Thermoplastic elastomers;
Petroleum resin;
Alicyclic saturated hydrocarbon resin;
Terpene resins such as terpene resin, terpene phenol resin, modified terpene resin, hydrogenated terpene resin, etc.
Rosin-based resin such as rosin phenol;
Rosin ester resins such as disproportionated rosin ester resins, polymerized rosin ester resins, hydrogenated rosin ester resins;
And at least one compound selected from the group consisting of xylene resins; and acrylic resins such as acrylic polymers and acrylic copolymers,
More preferably, it is at least one compound selected from the group consisting of polyhydric carboxylic acid esters and rosin ester resins.

As compound B acting as a solvent for compound A,
Preferably, alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol and benzyl alcohol;
Hydrocarbons such as benzene, toluene, xylene, mineral spirits, cyclohexane, n-hexane, methylcyclohexane and styrene;
Ethers such as diethyl ether;
Esters such as ethyl acetate, propyl acetate, butyl acetate, diethylene glycol monoethyl ether acetate, diethyl carbonate, dimethyl carbonate and 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 and the like;
Glycol ethers such as butyl glycol, methyl diglycol, butyl diglycol, 3-methyl-3-methoxybutanol, tetrahydrofuran;
Chlorines such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene;
Dimethyl sulfoxide; acetonitrile; carboxylic acids such as formic acid, acetic acid and the like; and water, at least one compound selected from the group consisting of
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 compatiblity composition with Compound A has fluidity, but up to a certain compounding amount with respect to Compound A, it has Tc between 0 and 150 ° C., which is compatible with Compound A. A compatibilizing composition can be constituted, Tc becomes less than 0 ° C. if the compounding amount is exceeded, it can not be a compatibilizing composition if room temperature exceeds 0 ° C., and a solution in which compound A is dissolved in compound B There is a possibility that In such a case, the compound B is a medium of the compatible composition when the compounding amount is such that Tc is 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 radically polymerizable unsaturated bond-containing monomer or plasticizer, Tc of the mixed composition is less than 0 ° C. when the amount of the radically polymerizable unsaturated bond-containing monomer or plasticizer exceeds a certain amount. If so, they can be considered to be solvents in the present invention.

The viscosity of the compound B may be in the range capable of producing a compatible composition of the present invention having a liquid-gel transition temperature (Tc) at a temperature of 0 to 150 ° C., while being compatible with the compound A.
From the viewpoint of easily producing a compatible composition with compound A, the viscosity of compound B is
Preferably it is 0.001-10 Pa.s, More preferably, it is 0.001-1 Pa.s, More preferably, it is 0.001-0.5 Pa.s.

  Even when Compound B is an oligomer or the like and has a high viscosity or solid in a low temperature environment higher than temperature Tc, it has a low viscosity in a high temperature environment higher than temperature Tc or is dissolved in another compound B of low viscosity Since they are dissolved in a solvent, they can be combined and mixed with compound A to produce a compatible composition.

When the compatible composition is used as an adhesive composition to be described later, the viscosity of the liquid compatible composition is, from the viewpoint of the coating property to a member,
Preferably it is 0.1-100 Pa.s, More preferably, it is 0.3-50 Pa.s, More preferably, it is 0.5-10 Pa.s.

  In addition, the viscosity of the compound B and compatible composition is measured on the measurement conditions described in the Example.

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

  In the range of 0 to 150 ° C., the temperature Tc is a temperature at which the storage rigidity G ′ and the loss rigidity G ′ ′ measured under the following conditions become equal.

The storage rigidity G ′ and the loss rigidity G ′ ′ of the compatible composition and the compound A are
Use a rheometer (manufactured by Anton Paar),
Cone rotor (φ = 25 mm, rotor angle 2 °), frequency 1 Hz, strain 1%,
From 150 ° C. to 0 ° C., it was measured by cooling at 2 ° C./min.

  The results of measurement of the storage rigidity G ′ and loss rigidity G ′ ′ of the compatible composition of Example 1 in the temperature range of 0 ° C. to 80 ° C. are shown in FIG. There was no temperature at which the loss modulus G "became equal).

  In the case of Example 1, the temperature at which the storage rigidity G ′ and the loss rigidity G ′ ′ become equal (the temperature at which the storage rigidity G ′ curve and the loss rigidity G ′ ′ curve intersect) 44 ° C. corresponds to the compatible composition. The temperature Tc of the

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

  The compatible composition is a gel-like body at a temperature around Tc (preferably in the temperature range of Tc ± 10 ° C., more preferably in the temperature range of Tc ± 15 ° C., still more preferably in the 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., still more preferably, from the viewpoint that the compatible composition can be used in the form of gel and the temperature range is wide and it is not necessary to make it liquid at too high temperature. It is 30-80 ° C.

The temperature Tc is
When the Tg of the (meth) acrylic polymer block (a) is increased or the compounding ratio of the compound B is decreased, the temperature can be set to the high temperature side. The Tg of the (meth) acrylic polymer block (a) is decreased. When the compounding ratio of compound B is increased, the temperature 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 is applied onto the members at a temperature higher than the temperature Tc, and the members are bonded to each other via the compatible composition and brought to a temperature lower than the temperature Tc, the members have a gel-like compatible composition Although it adhere | attaches stably through things, when it makes temperature higher than temperature Tc again, since a compatible composition will change from gel-like to a liquid state, members can be easily separated.

[Compatible Composition Viscoelastic Body]
The compatibilizing composition has radical reactivity, cation reactivity, anion reactivity and as a compound A and a compound B from the viewpoint of improving the elasticity and adhesiveness of the gel-like compatibilizing composition and the compatibilizing composition at the time of curing. It is preferable to contain a reactive compound (preferably, further in combination with a plasticizer) having at least one kind of reactivity selected from the group consisting of moisture reactivity, and a polymerization initiator (hereinafter, as Compound A and Compound B) It contains a reactive compound (preferably, further in combination with a plasticizer) having at least one kind of reactivity selected from the group consisting of radical reactivity, cation reactivity, anion reactivity and moisture reactivity, and a polymerization initiator. Gel-like compatible composition is also referred to as compatible composition viscoelastic body).

  The compatible composition viscoelastic body has elasticity and strength (hereinafter, collectively referred to as "viscoelastic properties") that can constitute a sheet to be bonded to a member constituting a composite structure described later. It is preferable that the compatible composition visco-elastic body having such visco-elastic properties is accompanied by a suitable viscosity which can be used as a pressure-sensitive adhesive sheet.

The elastic modulus at which the sheet can be formed is preferably 0.3 to 1000 kPa, more preferably 0.5 to 500 kPa, and 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 Tc-20 ° C.

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

As an extension that can constitute a sheet,
Preferably it is 10 to 1000%, more preferably 30 to 800%, still more preferably 50 to 500%.
As the breaking strength that can form a sheet,
Preferably it is 1 * 10 < ² > -1 * 10 < ⁷ > Pa, More preferably, it is 1 * 10 < ² > -1 * 10 < ⁶ > Pa, More preferably, it is 1 * 10 < ³ > -1 * 10 < ⁵ > Pa.

  The elongation and breaking strength of the compatible composition viscoelastic body can be measured by a dumbbell tension test. Specifically, when the elastic modulus of the compatible composition viscoelastic body is 0.3 Pa or more at room temperature (25 ° C.), the temperature 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) Make compatible liquid composition viscoelastic body into liquid at temperature Tc + 20 ° C, then pour into dumbbell type and cool to a temperature less than temperature Tc (actually room temperature) to make a 1 mm thick dumbbell specimen

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

  In the case where the compatible composition viscoelastic body has the above-described viscoelastic property, for example, when the sheet is formed of the compatible composition viscoelastic body, the adhesiveness is such that it can be evaluated as O under the measurement conditions described in the examples. The pressure-sensitive adhesive sheet can be configured.

  The compatible composition visco-elastic body can stably bond the pressure-sensitive adhesive sheet to the surface of the member when the pressure-sensitive adhesive sheet is formed, for example, by the adhesiveness.

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

  For example, the following may be mentioned as a laminate in which a pair of plate-like members constituting a composite structure that is an optical member, an optical product or the like is bonded via an adhesive such as a pressure-sensitive adhesive sheet or a curable liquid adhesive. .

(1) Flat panel (2D) display peripheral members:
(1-1) A laminated body in which an anti-scattering film for protecting the broken glass from scattering and a protective glass are laminated by an adhesive sheet;
(1-2) A laminate in which a liquid crystal panel and a protective panel for preventing damage to the liquid crystal panel and light reflection are laminated with an adhesive sheet or a curable liquid adhesive;
(1-3) A touch sensor panel (film) in which functional members are laminated with an adhesive sheet or a curable liquid adhesive and laminated;
(1-4) A backlight in which a plurality of optical films are laminated by an adhesive sheet and laminated.

(2) Three-dimensional panel (2.5D, 3D) protection panel display.
(3) Security glass or security glass for construction laminated with a pressure-sensitive adhesive sheet or a curable liquid adhesive to prevent breakage of broken glass and improve impact strength.
(4) A solar cell module bonded with a pressure-sensitive adhesive sheet or a curable liquid adhesive for sealing a light-receiving surface material and a back surface material.
(5) A packaging film laminated with a pressure-sensitive adhesive sheet or a curable liquid adhesive to improve strength.

The conventional pressure-sensitive adhesive sheet used in the production of the laminate as described above has advantages such as uniform thickness, simple manufacturing process, and less contamination to other members, as compared to a curable liquid adhesive. Have the following issues:
(A) Air bubbles are likely to remain when there is a step on the substrate;
(B) repair is difficult;
(C) handling of thin sheets is difficult;
(D) It is difficult to use a solvent-based pressure-sensitive adhesive for use in in-vehicle applications that require impact resistance because it is difficult to form a thick sheet.

The conventional two-step curable adhesive sheet used in the production of the laminate as described above is a low-elasticity adhesive sheet with a small number of crosslinking points at the stage when it is adhered to a member, and follows the substrate level difference and bubbles. Is less likely to remain, and it is easier to repair than conventional products due to its low adhesive strength, and after bonding, curing by light and heat causes crosslinking to progress, and has the advantage of developing the original strength. There are issues like:
(E) The step on the member side is relatively large with respect to the thickness of the pressure-sensitive adhesive sheet, for example, when the bonding thickness is thin or the step is large, the difficulty of laminating the laminates is not eliminated;
(F) If the elasticity is reduced to absorb the difference in level, handling of the pressure-sensitive adhesive sheet becomes difficult.

The conventional curable liquid adhesive used in the production of the laminate as described above has the advantage that it is liquid, so that there is no concern about air bubbles derived from the substrate step, and the thickness tolerance of the member can be canceled. Have a task like:
(G) It is difficult to control contamination to other members and misalignment during transport because it flows out from the bonding range when bonding.

From the point of view of the bonding method, attempts are made to solve the problems of conventional adhesives:
(A) forming a dam around the coating area of the curable liquid adhesive to prevent the resin from flowing out;
(B) cure the flowing curable liquid adhesive with light and stop it;
(C) injecting a liquid curable liquid adhesive between the substrates whose outer periphery is sealed, for example, by vacuum suction;
(D) using a thixotropic curable liquid adhesive (stencil system);
(E) forming a layer of a curable liquid adhesive uniformly on a member and thereafter irradiating the UV to control the flowability and then bond them;
(F) After the steps of the substrate are canceled with a curable liquid adhesive, they are attached with an adhesive sheet;
(G) The curable liquid adhesive is dropped onto the pressure-sensitive adhesive sheet and then bonded.

However, these methods also have the following challenges:
(H) In the construction method (a), the shape of the dam is semicircular, so that resin defects (voids) can occur on the outer side of the dam. A boundary line is generated depending on the used dam and the curable liquid adhesive. And easy to peel off at the interface of the curable liquid adhesive;
(I) In the method (b), the method of curing and stopping the flowing resin with light has limitations on the shape and material of the base material because it can not stop the flow of the portion where the light can not be irradiated;
(J) The method (c) is complicated in process and difficult to control the tact time of the injection process;
(K) In the method (d), the process becomes complicated, and in many cases, a filler is used as a thixotropic agent, and the yield is lowered due to the appearance defect (filler aggregation, air bubbles);
(L) In the method (e), it is difficult to control the flowability in consideration of the outflow, bubbles and strength.

For example, the following difficulties may occur:
-Since the liquid layer formed on the base material is affected by surface tension and swelling occurs at the end, if the flowability of the layer is lowered (hardened) before bonding, the unevenness of the swelling when bonded Air bubbles are generated in the place;
・ When laminating, it is necessary to push in the thickness direction and to bond until the swelling of the end is cancelled, but if the fluidity of the layer is lowered too much, the strength decreases due to press back, conversely the fluidity If it is left too much flow will occur;
-As in the case of the dam system, since the resin end is semicircular, resin defects (voids) may occur on the outer side depending on the base material structure.

(M) The method (f) requires a liquid resin composition and a pressure-sensitive adhesive sheet, and the process is complicated and peeling at the interface between the liquid resin composition and the pressure-sensitive adhesive sheet tends to occur.
(N) The method (g) requires a liquid resin composition and a pressure sensitive adhesive sheet, and the process is complicated, and it is likely to stick out in order to bond in a liquid state, and peeling at the interface between the liquid resin composition and the pressure sensitive adhesive sheet Is easy to occur.

From the above, in the conventional adhesive sheet and curable liquid adhesive, the demand for design is increasing in recent years, and a laminate using a narrow protective panel or display of a light-shielding printed portion, a 2.5D or 3D-shaped protective panel The following problems are encountered in producing a laminate using a liquid crystal display or a display .
(O) It follows the design shape, there are no air bubbles, and it is difficult to bond without flowing out of the resin.

  If the compatible composition viscoelastic body is coated on one member in a high temperature environment at a temperature Tc or more, the step is canceled even if there is a level difference because it is liquid, and then the temperature is rapidly reduced below the temperature Tc By cooling to a low temperature environment and forming the compatible composition viscoelastic body into a gel, it is possible to form a layer of the compatible composition viscoelastic body with small rise and shoulder drop on one member.

  If one member and another member coated with the layer of the compatible composition viscoelastic body are pasted together in a low temperature environment lower than the temperature Tc, the layer of the compatible composition viscoelastic body is gel-like It is possible to obtain a laminate with a low flow out.

  Furthermore, at least one treatment selected from the group consisting of heating, light irradiation and humidification is applied to the layer of the compatible composition viscoelastic body constituting the above-mentioned laminate to obtain a layer of the compatible composition viscoelastic body. At least one kind of curing selected from the group consisting of heat curing, photo curing and moisture curing is carried out to form a cured product having no liquid-gel transition temperature (Tc), thereby achieving a cured compatible composition viscosity. The layer of the elastic body remains as a non-flowable viscoelastic body even in a high temperature environment at a temperature Tc or higher, and the above-mentioned laminate can maintain a stable laminated form even at high temperatures.

  Further, in a low temperature environment lower than the temperature Tc, the gel-like compatible composition viscoelastic body is a shaped viscoelastic body along the surface of one member and the surface of the other member, and the shaped viscoelastic body is heated; At least one treatment selected from the group consisting of light irradiation and humidification is carried out to cause at least one kind of hardening selected from the group consisting of heat curing, light curing and wet curing to have a liquid-gel transition temperature (Tc) The adhesive cured product does not have

  In addition, a molding visco-elastic body has the same visco-elastic characteristic and liquid-gel-like transition temperature (Tc) as a gel-like compatible composition visco-elastic body.

  For example, when the pair of members is plate-shaped, the compatible composition viscoelastic body is formed into a sheet-like formed viscoelastic body, and at least one treatment selected from the group consisting of heating, light irradiation and humidification, At least one curing selected from the group consisting of heat curing, light curing and moisture curing is carried out to form a sheet-like adhesive cured body having no liquid-gel transition temperature (Tc), which is used as an adhesive sheet can do.

  Furthermore, the sheet-like adhesive cured product having no liquid-gel transition temperature (Tc) controls the degree of elasticity by adjusting the type and the combination of the reactive compound and the plasticizer in the compatible composition viscoelastic body. Since it can be made, it is possible to adjust it to be elastic enough to be rolled, to make it hard to be rolled, or to form a thin sheet, as mentioned above, it is a sheet with small shoulders and small corners Can be formed, so that bonding without a press back or a defect is possible.

  According to the compatible composition visco-elastic body, a sheet-like shaped visco-elastic body having a large thickness can be obtained, and as a result, a large-thickness laminated body made of a tacky-cured body can be obtained.

  As described above, a pair of plate-like members constituting a composite structure, which is an optical component or an optical product or the like, is compatible with each other by using the compatible composition adhesive viscoelastic body or adhesive cured body considered to be a physical gel. The composition visco-elastic body is pasted through a pressure-sensitive adhesive sheet comprising a shaped visco-elastic body obtained by forming the visco-elastic body into a sheet shape in a low temperature environment at a temperature lower than Tc (from heat curing, photo curing and moisture curing as necessary) At least one selected from the group consisting of: at least one selected from the group consisting of the above-mentioned problems (A) to (O), by forming a laminate) by forming a laminated sheet comprising It is possible to solve the problem.

  In the compatible composition, the mass part of the compound B is preferably 200 parts by mass with respect to 100 parts by mass of the compound A, from the viewpoint of the coating property to the member in the liquid state, the adhesiveness of the members in the gel state, and the phase transition property. 1000 parts by mass, more preferably 250 to 800 parts by mass.

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

  When the compatible composition is a compatible composition viscoelastic body, the polymerization initiator to be 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, it is 2.5-7.5 mass%.

[Thixotropic compatible composition]
When fixing a component of an optical system device such as a liquid crystal display and an optical lens, or a component of an electronic system device such as an electronic paper and a battery with an adhesive, no contamination due to the outflow or stringiness of the adhesive occurs. And may be required to be uniformly applied within a particular frame.

  In response to this demand, it has been attempted to use an adhesive having thixotropic properties that is difficult to string, but a light transmitting member is required to have optical transparency to the component of the optical device or the electronic device. When it is contained as an adhesive, adding a filler such as metal oxide fine particles to impart thixotropy to the adhesive makes it difficult to maintain optical transparency, even if an oil gelling agent is added. It is difficult to impart thixotropic properties that can correspond to precise flow control of optical system devices and electronic system devices.

  When the compound A and the compound B are selected, the compatiblizing composition of the present invention constitutes a compatiblizing composition having thixotropy in a gel-like body (hereinafter also referred to as a thixotropic compatiblizing composition), and further, it is optically transparent. It is possible to construct a thixotropic compatible composition compatible with the properties.

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

  The thixotropic compatibilizing composition is thixotropic, the viscosity decreases when the thixotropic compatiblizing composition is subjected to shear stress (when the shear rate is increased), and when the shear stress is released (the shear rate is decreased (shear rate is decreased). Then, it is said to have visco-elastic properties in which the viscosity recovers and the flowability is controlled.

The thixotropic property of the gel of the compatible composition is
Viscosity η _0.1 (Pa · s) of the thixotropic compatible composition at a shear rate of 0.1 (sec ⁻¹ ) as a reference, and the viscosity of the thixotropic compatible composition at a shear rate of 1 (sec ⁻¹ ) The ratio x ₁ = η _0.1 / η ₁ to η ₁ (Pa · s),
The viscosity η ₁ (Pa · s) of the thixotropic compatible composition at a shear rate of 1 (sec ⁻¹ ), which is a reference, and the viscosity Pa ₁₀ (Pa) of the thixotropic compatible composition at a shear rate of 10 (sec ⁻¹ ) The ratio x ₂ = η ₁ / η ₁₀ to s) can be used as a measure.

When a thixotropic compatible composition in which x ₁ and x ₂ are larger than 1 (preferably 1.2 or more) is used as, for example, the adhesive composition described later, a predetermined range is surface-coated using a slit coater. Sometimes, the thixotropic compatible composition flows appropriately when it is extruded from the slit coater, and the flow stops after extrusion, so that it is difficult for contamination due to outflow from a predetermined range or stringing to occur. It becomes possible to apply uniformly in a predetermined range.

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

[Transparency of thixotropic compatible composition]
The thixotropic compatibilizing composition is not only compatibilized with the compound A and the compound B so as to have thixotropic properties, but also has a haze value of 1.0 or less at a thickness of 0.3 mm.

  The HAZE value represents the ratio of the diffuse transmittance in the total light transmittance of the thixotropic compatible composition.

  For example, when an adhesive composition having thixotropic properties is used for an optical material, a conventional adhesive composition adds a filler to a resin composition having curability to impart thixotropic properties, Since the added filler causes light scattering, the HAZE value increases and the transparency based on the total light transmittance of the resin constituting the resin composition decreases.

  On the other hand, in the thixotropic compatible composition, the thixotropic property can be secured only by the resin composition in which the compound A and the compound B are compatibilized without the addition of a filler, and therefore there is no factor to increase the haze value. The transparency based on the total light transmittance of the resin constituting the thixotropic compatible composition can be utilized without much loss.

  Therefore, the thixotropic compatible composition is transparent as having 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. I can secure the sex.

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

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

As a solvent for dissolving the compatible composition,
Preferably, alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol and benzyl alcohol;
Hydrocarbons such as benzene, toluene, xylene, mineral spirits, cyclohexane, n-hexane, methylcyclohexane and styrene;
Ethers such as diethyl ether;
Esters such as ethyl acetate, propyl acetate, butyl acetate, diethylene glycol monoethyl ether acetate, diethyl carbonate, dimethyl carbonate and 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 and the like;
Glycol ethers such as butyl glycol, methyl diglycol, butyl diglycol, 3-methyl-3-methoxybutanol, tetrahydrofuran;
Chlorines such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene;
Dimethyl sulfoxide; acetonitrile; carboxylic acids such as formic acid, acetic acid and the like; and water, at least one compound selected from the group consisting of
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 compatibilizing composition is the compatibility between the compound A and the compound B (at a temperature between 0 and 150 ° C., the compound A has no liquid-gel transition temperature (Tc), and the compatiblizing composition is liquid-gel Additives other than the compound B as described later can be optionally blended within the range not inhibiting the property of having a transition temperature (Tc), and the blending amounts of additives other than compound B in that case are Preferably it is 0-50 mass%, More preferably, it is 0-30 mass% in the total mass of a thing.

[Adhesive composition]
Since the compatible composition of the present invention is applied in liquid form to a member and formed into a gel, it has excellent adhesion to the member, and can be suitably used as an adhesive composition for bonding the members together.

  The adhesive composition of the present invention (hereinafter, also referred to as an adhesive composition) contains the compatible composition because it is blended with the compatible composition of the present invention, and the coating properties to the members, and From the viewpoint of stable adhesion, temperatures around Tc (preferably in the temperature range of Tc ± 10 ° C., more preferably in the temperature range of Tc ± 15 ° C., still more preferably in the temperature range of Tc ± 20 ° C.) It reversibly changes to a gel or liquid (it is also called phase transition that the adhesive composition has the above change).

  The adhesive composition is, for example, an antioxidant, in a range not inhibiting the coatability to the member in the liquid state, the adhesiveness of the members in the gel state (hereinafter collectively referred to as adhesion) and the phase transition. Additives such as wetting agents, surfactants, ionic liquids, antifoaming agents, UV absorbers, light stabilizers, various inorganic and organic fillers, polymers and the like can be included.

  The adhesive composition further has suitable visco-elastic properties of the compatible composition viscoelastic body, when the contained compatible composition is a compatible composition viscoelastic body.

  In the case where the compatible composition is a compatible composition viscoelastic body, the adhesive composition is, for example, an antioxidant, a wetting agent, or a surfactant within a range not inhibiting the adhesive property, phase transition property and viscoelastic property. Additives such as ionic liquids, antifoaming agents, UV absorbers, light stabilizers, inorganic and organic various fillers, polymers and the like can be included.

  The additive in the adhesive composition refers to a combination of an additive to be blended in the compatible composition and an additive to be blended with the compatible composition.

In the adhesive composition, the viscosity of the liquid compatible composition is preferably in the temperature range of Tc + 10 ° C. or more (more preferably in the temperature range of Tc + 15 ° C. or more, still more preferably Tc + 20 ° C.) from the viewpoint of coatability to members. In the above temperature range)
Preferably it is 100 Pa.s or less, More preferably, it is 50 Pa.s or less, More preferably, it is 10 Pa.s or less.

In the adhesive composition, the total amount of the compounds A and B blended in the compatible composition is the total amount of the adhesive composition with respect to the adhesive composition and phase transition property.
Preferably it is 50-100 mass%, More preferably, it is 70-100 mass%.

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

  When the members 1 and 2 are adhered via the adhesive composition, the surfaces of the members 1 and 2 are in contact with the adhesive composition with the adhesive composition therebetween and adhered ( The relative position in the vicinity of the adhesive composition of the member 1 and the member 2 is fixed.

  In the composite structure, the adhesive composition adhering the members 1 and 2 is further, for example, heated to a temperature higher than the temperature Tc to remove the adhesive composition and removed, or remain lower than the temperature Tc The adhesive composition of the members 1 and 2 is intended to release the adhesion of the members 1 and 2 by contacting the solvent with the adhesive composition to dissolve and remove the adhesive composition. The adhesion through the adhesive is referred to as temporary fixing, and the adhesive composition used when scheduled to release the adhesion of the members 1 and 2 is also referred to as a temporary fixing agent.

When the member 1 and the member 2 are plates, for example,
Preferably, the surface in the thickness direction of members 1 and 2 is adhered or temporarily fixed via the adhesive composition, and more preferably, the plate surface of members 1 and 2 is adhered or provisionally bonded via the adhesive composition Fixed or
The members 1 and 2 may be bonded via the adhesive composition, and the members 1 and 2 may constitute a laminate.

  The plate is a thin structure compared to the area of front and back, but may be plate-like, thin-film, flat or curved.

The following can be illustrated as a composite structure of this invention .

(1) A liquid crystal display comprising an optical member such as various films, wherein the optical member is bonded or temporarily fixed to constitute a laminate or the like.

(2) A liquid crystal display comprising 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 simultaneously performed, and the base material is removed and used.

(4) A device using an electrolytic solution such as an antiglare mirror, electronic paper, a battery, or a capacitor, in which a member such as an electrode, a separator, or a current collector is 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 in the electrolytic solution.

(5) A polishing apparatus for polishing an optical lens, wherein the optical lens and a fixed support of the optical lens are temporarily fixed.

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

(7) Flat panel (2D) display peripheral members:
(7-1) A laminated body in which an anti-scattering film for protecting the broken glass from scattering and a protective glass are adhered by an adhesive sheet;
(7-2) A laminate in which a liquid crystal panel and a protective panel for preventing damage to the liquid crystal panel and light reflection are laminated with an adhesive sheet or a curable liquid adhesive;
(7-3) A touch sensor panel (film) in which a functional member is laminated with an adhesive sheet or a curable liquid adhesive and laminated;
(7-4) A backlight in which a plurality of optical films are laminated by an adhesive sheet and laminated.

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

(9) Security glass or security glass for construction laminated with a pressure-sensitive adhesive sheet or a curable liquid adhesive to prevent breakage of broken glass and improve impact strength.

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

(11) A packaging film laminated with a pressure-sensitive 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 gel below the temperature Tc.

  From the viewpoint of adhesion at a temperature Tc or lower, the material of the members 1 and 2 is glass, PET, TAC, COP, polyimide, PMMA, polycarbonate, polyvinyl chloride, PVA, polyethylene, polypropylene, silicone, graphite, aluminum, copper, 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 to give conductivity. Also, a metal such as silver or copper may be patterned on the surface as an electrode or wiring material.

  In the case where the composite structure is, for example, a laminate via a compatible composition visco-elastic body in which preferably the member 1 and / or the member 2 are plate-like, more preferably in recent years, among flat panels (2D) In addition to flat panels (2D) and laminates that use narrow protective panels and displays with light-shielded printing units that require more design, and 2.5D and 3D shaped protective panels and displays that require more design. In the case of the laminated body used, the compatible composition viscoelastic body follows the design shape, and is bonded in a state where there is no air bubble between the member 1 and the member 2 and no resin flows out.

  Therefore, in the case where the composite structure is a laminate via a compatible composition visco-elastic body in which preferably the member 1 and / or the member 2 are plate-like, more preferably one of the members 1 or 2 is a liquid crystal display In the case of a laminate via a compatible composition viscoelastic body when the panel, the organic EL display panel, the protective panel, the touch panel, the glass or the plastic plate and the other is a light transmitting member, the compatible composition viscosity The elastic body follows the design shape, and is bonded in a state in which there are no air bubbles between the members 1 and 2 and no flow of resin.

[Method of Manufacturing Composite Structure]
(Manufacturing method 1)
The composite structure is
In a temperature environment higher than temperature Tc,
Process 1 of bonding the member 1 and the member 2 via an adhesive composition,
It can obtain by the manufacturing method (it is also called "the manufacturing method 1" hereafter) including the process 2 which makes temperature environment temperature low temperature Tc after the process 1, and obtains a composite structure.

In the production method 1, since the adhesive composition is liquid in the first step,
The adhesive composition which has become liquid can be easily applied to the bonding site of the member 1 and the member 2,
In step 2, the coated adhesive composition is gelled, and the members 1 and 2 can be bonded or temporarily fixed.

  In the first step, the adhesive composition is preferably coated using a dispenser, a jet dispenser, an inkjet, a slit coater, a die coater, a screen printing, etc., at a temperature of viscosity suitable for each method.

  If the composite structure is intended to release adhesion of member 1 and member 2 in the final specification, the method of manufacturing the composite structure further comprises, after step 2, an adhesive composition It is preferable to include a step 3 of contacting the substance with a solvent and / or setting the temperature environment higher than the temperature Tc to release the adhesion of the member 1 and the member 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 temperature Tc,
A process 1 'of laminating the member 1 and the member 2 via an adhesive composition formed by blending a compatible composition and a viscoelastic body,
After step 1 ′, the adhesive composition is cured by at least one selected from the group consisting of heat curing, light curing and moisture curing, and members 1 and 2 bonded together via the adhesive elastic body are obtained. It can obtain by the manufacturing method including the process 2 'which obtains the composite structure containing (it is also mentioned the following "manufacturing method 2").

  The adhesive composition in step 1 ′ of production method 2 has a predetermined shape (preferably, sheet-like) in the step of liquefying the adhesive composition in a high temperature environment, for example, higher than Tc and then cooling to gel. ), Or the process may be performed on the surface of the member 1 or 2.

  The production method 2 solves at least one of the problems selected from the group consisting of the problems (A) to (O) as described above by the visco-elastic property that the adhesive composition is derived from the compatible composition viscoelastic body. For example, preferably, when the composite structure is a laminate via a compatible composition viscoelastic body in which the member 1 and / or the member 2 are plate-like, more preferably at least at least the members 1 and 2 In the case of a laminate through the compatible composition visco-elastic body, one of which is in the form of a plate, it is more preferable in recent years to have a narrow protective panel or display with a light-shielding printed portion which is required more in design among flat panels (2D) In manufacturing laminates using a 2.5D or 3D-shaped protective panel or display where designability is more required in addition to a laminate using a flat panel (2D), the compatible composition is viscoelastic. There follows the design shape, no air bubbles between the member and the member 1 and the member 2, it is possible to bond in the absence also flows of resin.

(Manufacturing method 3)
When the compatible composition is a compatible composition viscoelastic body, the composite structure is
The manufacturing method is
Step 1 ′ ′ of obtaining an adhesive cured product by curing the adhesive composition containing the compatible composition viscoelastic body of the present invention at least one selected from the group consisting of heat curing, light curing and wet curing.
It is also possible to obtain a method of producing a composite structure having a step 1 ′ ′ of obtaining a composite structure including the member 1 and the member 2 bonded together through the adhesive cured body with the member 1 and the member 2 (hereinafter “production method 3)).

  In Step 1 ′ ′ of Production Method 3, for example, in a step of liquefying the adhesive composition in a high-temperature environment higher than Tc and then cooling to gel, it is formed in advance into a predetermined shape (preferably, sheet-like) The obtained compatible composition viscoelastic body may be used, or the process may be performed on the surface of the member 1 or 2.

  In the production method 3, step 2 ′ ′ is at least one selected from the group consisting of photocuring and moisture curing in advance of the molded viscoelastic body obtained by molding the sheet into a predetermined shape (preferably, sheet-like) in step 1 ′ ′. It is also possible to cure the seed to form an adhesive cured body of a predetermined shape (preferably, sheet-like), or a predetermined shape (preferably, sheet-like) obtained on the surface of member 1 or 2 in step 1 ′ ′ The molded visco-elastic body may be directly cured on the surface of the member 1 or 2 at least one selected from the group consisting of light curing and moisture curing.

  According to manufacturing method 3, since the adhesive cured product can be manufactured in advance and used as, for example, an adhesive sheet, the entire adhesive sheet is cured even if the member has a light shielding portion, like a conventional curable liquid adhesive In addition, there is no wetting and spreading after coating, and control of coating accuracy is easy.

  In addition, when the compatible composition does not decrease in viscosity as expected at a temperature higher than the temperature Tc, or when the viscosity does not decrease unless the temperature is higher than the temperature Tc, temperature Tc can be obtained by applying the production method 3. It is possible to use the viscoelastic effect of the adhesive cured body while maintaining a low temperature environment.

  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 according to the visco-elastic properties derived from the compatible composition visco-elastic body and the adhesive cured body. For example, preferably, in the case of a laminate via a compatible composition visco-elastic body in which the composite structure is a plate-like member 1 and / or a member 2, for example, the member 1 is more preferable. And, in the case of a laminate via a compatible composition visco-elastic body in which at least one of the members 2 is plate-like, it is more preferable in recent years that a light shielding printed part is required to have more designability among flat panels (2D). When manufacturing laminates using 2.5D or 3D-shaped protective panels or displays where designability is required in addition to laminates using narrow protective panels or displays or flat panels (2D) , Compatible composition viscoelastic body follows the design shape, no air bubbles between the member and the member 1 and the member 2, it is possible to bond in the absence also flows of resin.

[Repair adjustment in manufacturing process of composite structure]
Conventionally, since a conventional pressure-sensitive adhesive sheet is used instead of the compatible composition visco-elastic body between step 1 ′ and step 2 ′ in production method 2, air bubbles derived from the step of the member tend to remain, There was a case where it was necessary to repair between step 1 ′ and step 2 ′ in order to remove air bubbles, but according to production method 2, for example, it becomes compatible at Tc temperature or higher on the substrate where the step exists. By applying the composition viscoelastic body, it is possible to cancel the level difference, and when the composition having the compatible composition viscoelastic body sheet is bonded to the substrate on which the level difference exists, the compatible composition viscosity is Due to the tackiness, strength and elasticity of the elastic sheet, the compatible composition visco-elastic sheet follows the shape having a step of the member, so that air bubbles derived from the step of the member hardly remain, and the frequency of repair is greatly reduced. It becomes possible.

  The effect of canceling the level difference of the compatible composition viscoelastic body sheet is the case where the compatible composition viscoelastic body sheet is formed and bonded on the base material to be bonded, and the compatible composition viscoelastic body sheet in advance. It is preferably expressed either in the case of forming and bonding on a substrate.

  In addition, even in the case where repair is performed between step 1 ′ and step 2 ′ in production method 2, if the repair is performed in a high temperature environment higher than the temperature Tc, the compatible composition viscoelastic body becomes liquid because the repair easily occurs. It is possible to

[Disassembly 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 made higher than the above-mentioned temperature Tc, via the adhesive composition of member 1 and member 2 It is possible to facilitate disassembly of the composite structure by releasing the past adhesion and separating the member 1 and the member 2 from each other.

[Compound materials]
(1) Compound A
(Meth) acrylic polymer block (a) having an active energy ray-curable group obtained in the following synthesis example 1 and (meth) acrylic polymer block (b) having no active energy ray curable group And (meth) acrylic block copolymers (a1) to (a3) were used as compound A.

Synthesis Example 1
After adding 1,800 g of toluene to a 5 L flask, 2.5 g of N, N, N ', N', N'-N'-pentamethyldiethylene triamine and isobutyl bis (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 is added 6.5 g of a cyclohexane solution containing 12% by mass of sec-butyllithium, and then a mixture 133 of 3.6 g of 1,1-dimethylpropane-1,3-diol dimethacrylate and 130 g of methyl methacrylate as a monomer The polymerization was started by adding .6 g at a time. Subsequently, the reaction solution was stirred at -30 ° C for 12 hours, then, 280 g of n-butyl acrylate was added as a monomer and reacted for 2 hours. Subsequently, after 133.6 g of a mixture of 3.6 g of 1,1-dimethylpropane-1,3-diol dimethacrylate and 130 g of methyl methacrylate as monomers is added while the reaction solution is stirred at -30 ° C. The temperature rose to 120 minutes after the addition of the above mixture, the polymerization is terminated by adding 18 g of methanol, and a triblock copolymer in which polymer block (a) -polymer block (b) -polymer block (a) is bonded in order A solution containing the (meth) acrylic block copolymer (a1) was obtained. The solution obtained is then poured into a large amount of a mixed solution of methanol and water (the proportion of methanol is 90% by mass), and the precipitated white precipitate is collected by filtration and dried under reduced pressure to obtain a (meth) acrylic block copolymer. 480 g of polymer (a1) was obtained. The melt flow rate of the obtained (meth) acrylic block copolymer (a1) was measured 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 ′ ′, N ′ ′-pentamethyldiethylene triamine and isobutyl bis (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 is added 7.6 g of a cyclohexane solution containing 10% by mass of sec-butyllithium, and thereafter 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 at once to initiate polymerization. Subsequently, the reaction solution was stirred at -30.degree. C. for 13 hours and then reacted by sequentially adding 315 g of n-butyl acrylate as a monomer over 2 hours. Thereafter, the polymerization is stopped by adding 30 g of methanol, and then the temperature is raised to 25 ° C., and a (block) acrylic which is a diblock copolymer bound in the order of polymer block (a) -polymer block (b) A solution containing the block copolymer (a2) was obtained. The solution obtained is then poured into a large amount of a mixed solution of methanol and water (the proportion of methanol is 90% by mass), and the precipitated white precipitate is collected by filtration and dried under reduced pressure to obtain a (meth) acrylic block copolymer. 460 g of polymer (a2) was obtained. When the melt flow rate of the obtained (meth) acrylic block copolymer (a2) was measured, it was 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 ′ ′, N ′ ′-pentamethyldiethylene triamine and isobutyl bis (2,6-di-t-butyl-4-methylphenoxy 2.) 70 g of a toluene solution containing 26% by mass of aluminum was sequentially added and cooled to -30.degree. To this, 3.9 g of a cyclohexane solution containing 10% by mass of sec-butyllithium is added, and thereafter a mixture 187 of a mixture of 4.4 g of 1,1-dimethylpropane-1,3-diol dimethacrylate and 183 g of methyl methacrylate as monomers .7 g were added at once to initiate polymerization. Subsequently, the reaction solution was stirred at -30 ° C for 12 hours, then, 280 g of n-butyl acrylate was added as a monomer and reacted for 2 hours. Subsequently, the reaction solution was stirred at -30.degree. C. for 13 hours and then reacted by sequentially adding 174 g of n-butyl acrylate as a monomer over 2 hours. Thereafter, the polymerization is stopped by adding 20 g of methanol, and then the temperature is raised to 25 ° C., and a (block) acrylic which is a diblock copolymer bound in the order of polymer block (a) -polymer block (b) A solution containing the block copolymer (a3) was obtained. The solution obtained is then poured into a large amount of a mixed solution of methanol and water (the proportion of methanol is 90% by mass), and the precipitated white precipitate is collected by filtration and dried under reduced pressure to obtain a (meth) acrylic block copolymer. 320 g of polymer (a3) was obtained. The melt flow rate of the obtained (meth) acrylic block copolymer (a3) was measured 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 (Sartmar, SR 395)
Compound b2: 4-t-butylcyclohexyl acrylate (manufactured by Rahn, genomer 1119)
Compound b3: 4-hydroxybutyl acrylate (manufactured by Nippon Kasei Co., Ltd., 4-HBA)
Compound b4: diisononyl cyclohexyl dicarboxylate (manufactured by BASF, DINCH)
Compound b5: hydrogenated rosin ester (manufactured by Arakawa Chemical Industries, KE-311)
Compound b6: Epoxy-based ester (bis (2-ethylhexyl) 4,5-epoxy-1,2-cyclohexanedicarboxylate) (manufactured by DIC, W150)
Compound b7: Disproportionated rosin ester (manufactured by Arakawa Chemical Industries, Ltd., ME-D)
Compound b8: lauryl acrylate (manufactured by Kyoeisha, LA)
Compound b9: Isobornyl acrylate (manufactured by Nippon Kayaku Co., Ltd., RM-1002)
Compound b10: PPG urethane acrylate (manufactured by Daicel Ornex Co., EB 270)
Compound b11: polybutadiene urethane acrylate (manufactured by Nippon Soda Co., Ltd., TE 2000)

(3) Other compounds Compound r1: 1-hydroxycyclohexyl phenyl ketone (polymerization initiator) (manufactured by BASF, I-184)
Compound r2: polyurethane acrylate (manufactured by Japan Synthetic Chemical Co., Ltd., UV3630ID80)

[Compatibility conditions]
(1) Example 1
100 g of compound a1, 150 g of compound b1, 150 g of compound b2, 150 g of compound b4, 200 g of compound b4 and 30 g of compound r1 are respectively weighed and filled in a container (made of material SUS316, volume 2000 ml) at 80 ° C. under atmospheric pressure Stirring was performed for 360 minutes at 200 rotations / minute using Three One Motor (manufactured by Shinto Scientific Co., Ltd.) to obtain a compatible composition (compatible composition viscoelastic body).

(2) Examples 2 to 5 and Comparative Example 1
The compounds used are replaced with the compounds described in Table 1, and the compatible compositions (Compatible composition visco-elastic bodies) of Examples 2 to 5 and Comparative Examples in the same manner as in Example 1 with the composition described in Table 1 A comparative composition of 1 was produced.

(3) Examples 6 to 9
The compounds used were replaced with the compounds described in Table 2, and the compatible compositions (compatible composition visco-elastic bodies) of Examples 6 to 9 were produced in the same manner as in Example 1 in the proportions described in Table 2. .

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

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

  Tables 1 to 3 show the measurement results.

[Measurement conditions of viscosity]
Measurement using a rheometer (Anton Paar) with a cone rotor (φ = 25 mm, rotor angle 2 °), frequency 1 Hz, strain 1%, cooling at 2 ° C./min from 150 ° C. to 0 ° C. did. The numerical value measured in the temperature range above Tc was taken as the complex viscosity.

Using a rheometer (manufactured by Anton Paar), change the shear rate from 0.01 (sec ^-1 ) to 100 (sec ^-1 ) at a cone rotor (φ = 25 mm, rotor angle 2 °) at 25 ° C. The measured values were taken as the viscosity η _0.1 , η ₁ and η ₁₀ , respectively.

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

[Measurement conditions of tackiness]
(1) A liquid compatible composition is obtained at a temperature 20 ° C. higher than Tc, and a release-treated PET film (J0L, 50 μm, manufactured by Nippon Paper Industries) is used, with a dispenser 1 described later, 3 cm wide and 4 cm long Prepare a sheet as a molded visco-elastic body by cooling to room temperature (25 ° C) or a temperature Tc-20 ° C if the elastic modulus is 0.3 MPa or less at 25 ° C in a liquid layer with a thickness of 0.15 mm

(2) When the humidity is 40 to 60% and the elastic modulus is 0.3 MPa or less at room temperature (25 ° C.) or 25 ° C., after adhering it to the glass substrate 2 described later at temperature Tc-20 ° C. Peel 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 temperature is Tc-20 ° C. Settle horizontally in the air to become.
If the adhesive sheet does not fall after 5 minutes of standing still horizontally, ○,
If the adhesive sheet falls after 5 minutes of standing still horizontally, ×,
And

(4) It should be noted that the surface of the glass substrate 2 is dipped in acetone to be cleaned before being tested and then dried before use.

[Measurement conditions of flowability after curing]
On the slide glass, the compatible compositions of Examples 1 to 5 and Comparative Example 1 are formed in a gel state into 5 mmφ × 0.5 mmt and placed with a metal halide lamp (conveyor type manufactured by Eye Graphics Co., Ltd.) The compatible composition was cured at 250 mW / cm ² and 3000 mJ / cm ² . The 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 seen, x,
And

[Measurement conditions of solvent solubility]
In each of the compatible compositions of Examples 1 to 9 and Comparative Example 1,
Using acetone (Kanto Chemical Co., special grade) as a solvent,
0.78 g of the solvent was added to 0.02 g of the gel-like compatible composition, and the mixture was left to stand for 24 hours at 25 ° C. in a light-shielded environment, and judged as follows: Check the presence of objects visually,
When it is confirmed that there is no residue of the gel composition, the solvent solubility is ○;
Solvent solubility is x when it is confirmed that there is a residue of gel-like composition.

[Measurement conditions of HAZE value]
For each of the compatible compositions of Examples 1 to 9 and Comparative Example 1,
A 0.3 mm t spacer is attached to both ends of a glass of 2.5 cm × 3.8 cm × 1 mmt, 250 mw / cm ² and 3000 mJ with a metal halide lamp (igraphics company, conveyor type) sandwiching a compatible composition. The compatible composition was cured at / cm ² . The ratio was measured using a haze meter (NDH 5000 manufactured by Nippon Denshoku Kogyo Co., Ltd.) to determine the ratio of total light transmittance to diffuse transmittance.

[Manufacture of composite structure and comparative structure]
(1) Production of Composite Structure This will be described with reference to FIG.
Prepare five sets of 200 μm thick spacers (3) installed on the plate surface of slide glass 1 (plate-like member 1) (1) (Fig. 2 (2-1 (plan view))) (2 -2 (front view)),
Each of the gel-like compatible compositions (4) of Examples 1 to 5 was collected on five glass slides 1 using a spatula, and 0.015 g was collected and placed (FIG. 2 (2-3));
After heating for 30 seconds on a hot plate set at a temperature 20 ° C. higher than Tc, it was visually confirmed that the compatible composition became the liquid compatible composition (5) on the slide glass 1 (FIG. 2) (2-4)),
After pasting the plate surface of another slide glass 2 (plate-like member 2) (2) (step 1) and leaving it for another 30 seconds (FIG. 2 (2-5)),
Reduce the temperature to the temperature environment (25 ° C) by removing it from the hot plate,
A laminated body (composite structure) in which the slide glass 1 and the slide glass 2 are laminated via the respective compositions was obtained (step 2) (FIG. 2 (2-6)).

(2) Production of Comparative Structure In step 1 of production of the composite structure, the slide glass 1 and the slide glass 2 bonded together via the comparative composition are irradiated with ultraviolet light at 3000 mJ / cm ² to cure the comparative composition. A laminated body (comparative structure) in which the slide glass 1 and the slide glass 2 are laminated via the cured body of the comparative composition was obtained.

[Disassembly of composite structure under high temperature]
The laminate in which the slide glass 1 and the slide glass 2 obtained in the production of the composite structure are laminated via the 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 laminate can be separated by a light peeling operation with fingers, and the laminate can be disassembled (when the peeling was performed, all the compatible compositions were liquid).

  The comparative structure obtained in the manufacture 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 while the slide glass 1 and slide glass 2 of the laminate were solid. And the light peeling operation could not separate.

[Disassembly of composite structure by contact with solvent]
The laminated body in which the slide glass 1 and the slide glass 2 obtained in the production of the composite structure are 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 was able to be peeled off easily and disassembled (when it was peeled off, the compatible compositions were all dissolved and liquid).

  The comparative structure obtained in the manufacture of the comparative structure is immersed in acetone and left to stand for 60 minutes, and the cured product of the comparative composition remains cured or swells, and the slide glass 1 and slide of the laminate are obtained. It was not possible to separate the glass 2 by the light peeling operation.

[Laminate production test]
(1) Tools (1-1) Glass substrate 1 (plate-like member 1)
(1-2) Glass substrate 2 (plate-like member) using a glass substrate of 60 × 80 × 0.8 mm in thickness subjected to light shielding printing (GLS-HF manufactured by Teikoku Ink Mfg. Co., Ltd.) with an outer periphery of 2 mm and a thickness of 50 μm 2)
(1-3) Dispenser 1 using a transparent glass substrate of 60 × 80 × 0.8 mm in thickness
(1-4) Dispenser 2 using flat nozzle (Musashi Engineering Co., Ltd., SHOT MASTER 300)
(1-5) Ultraviolet Irradiation Apparatus Using Nordson PICOJET PV Bulb A conveyor type ultraviolet irradiation apparatus (a metal halide lamp manufactured by Eye Graphics, Inc.) was used.

(2) Manufacturing conditions

(2-1) Production Examples 61 to 5 (see FIG. 3)
The compatible composition viscoelastic body (adhesive composition) of Examples 1 to 5 listed in Table 1
The liquid compatible composition (10) is obtained at a temperature 20 ° C. higher than Tc, and a dispenser 1 (9) is formed on a glass substrate 1 (6) to form a 0.15 mm thick liquid layer at room temperature (25 ° C.) ) And molded into a layer of molded viscoelastic body (11).

  The glass substrate 1 (6) on which each molded viscoelastic body (11) is formed is placed on the glass substrate 2 (7) at room temperature (25 ° C.) lower than Tc, and the glass substrate 1 (6) And the laminated body before hardening which bonded glass substrate 2 (7) through the shaping | molding viscoelastic body (11) was manufactured (process 1 ').

The laminate before curing is photocured with an ultraviolet irradiation device (15) at a peak illuminance of 400 mW / cm ² , an integrated light quantity of 6000 mJ / cm ² (Oak Works' wavelength 350 nm), 100% reaction rate, and a glass substrate 1 and a glass substrate 2 were pasted together via a layer (adhesive cured body) of an adhesive cured body (12) to obtain a laminate (composite structure) (13) of Production Examples 1 to 5 (Step 2 ') .

(2-2) Production Comparative Example 1
The compatible composition visco-elastic body (adhesive composition) of Examples 1 to 5 described in Table 1 is replaced with the comparative composition of Comparative Example 1 described in Table 1 and coated at room temperature (25 ° C.) The laminated body of manufacture comparative example 1 was obtained on the conditions similar to manufacture Examples 1-5.

(2-3) Production Example 6 (See FIG. 4)
The compatible composition visco-elastic body (adhesive composition) of Example 5 described in Table 1 is used as a liquid compatible composition (10) at a temperature 20 ° C. higher than Tc, and a dispenser 1 on a glass substrate 1 (6) A liquid layer having a thickness of 0.15 mm was cooled to room temperature (25 ° C.) using (9) and molded into a layer of molded viscoelastic body (11).

Peak illuminance 400 mW / cm ² , integrated light intensity 6000 mJ / cm ² (oak using a UV irradiation device (15)) the glass substrate 1 (6) on which the molded viscoelastic body (11) is formed at room temperature (25 ° C.) The reaction rate is 95% to photocure the molded viscoelastic body to make a tacky cured body (12) (step 1 ′ ′).

  Production Example 6 in which the glass substrate 1 (6) on which the adhesive cured body (12) is formed is bonded to the glass substrate 2 (7) via the adhesive cured body (12) under reduced pressure at room temperature (25 ° C.) The laminate (composite structure) (14) was obtained (step 2 ′ ′).

(2-4) Production Comparative Example 2
After forming the comparative composition of Comparative Example 1 described in Table 1 to a thickness of 0.15 mm at room temperature (25 ° C.) using a dispenser 1 on a glass substrate 1, using a 365 LED lamp (manufactured by HOYA) The photocuring was carried out at an illuminance of 100 mW / cm ² , an irradiation time of 2 seconds, and a reaction rate of 30%, to obtain a primary cured product having reduced fluidity.

  Under reduced pressure, a laminated body in which the glass substrate 1 on which the primary cured body was formed was bonded to the glass substrate 2 through the primary cured body was obtained.

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

(2-5) Production Comparative Example 3
The laminate of Production Comparative Example 3 was obtained in the same procedure as Production Comparative Example ² except that the photocuring conditions at the time of production of the primary cured product in Comparative Example 3 were changed to illuminance of 100 mW / cm ² , irradiation time 5 sec, reaction rate 60%. The Test pieces for evaluation were produced.

(2-6) Production Comparative Example 4
The photocuring conditions at the time of producing the primary cured body in Comparative Example 3 were changed to illuminance of 100 mW / cm ² , irradiation time of 10 sec, reaction rate of 95%, and a laminate of Production Comparative Example 4 was obtained in the same procedure as Production Comparative Example 2. The Test pieces for evaluation were produced.

(2-7) Production Comparative Example 5
The comparative composition of Comparative Example 1 described in Table 1 is drawn 1 mm wide × 0.2 mm high using Jet Dispenser 2 on the outer periphery of the glass substrate, and the illuminance is 100 mW / cm using a 365 LED lamp (manufactured by Panasonic). ^{2) It} was cured in 5 seconds of irradiation time to form a dam.

  After applying the comparative composition of Comparative Example 1 described in Table 1 using the dispenser 1 on the glass substrate 1, the glass substrate 2 and the comparative composition of Comparative Example 1 on the glass substrate 1 are applied under reduced pressure. It bonded together and adjusted the thickness of a composition by applying pressure so that it might be set to 0.15 mm, and obtained the comparison laminated body before hardening.

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

(2-8) Production Comparative Example 6
The comparative composition of Comparative Example 1 described in Table 1 is coated on a PET release film, another PET release film is laminated, and a 0.15 mm spacer is used to make the thickness of the adhesive composition 0. The laminate was adjusted to be 15 mm to obtain a laminate before curing.

The laminate before curing was cured using a UV irradiation device with a peak illuminance of 400 mW / cm ² and an integrated light quantity of 6000 mJ / cm ² (Oak Works' wavelength 350 nm), and then cut into 60 × 80 mm to obtain an adhesive sheet .

  After sticking an adhesive sheet on the glass substrate 1, under reduced pressure, a test piece in which the glass substrate 2 is bonded via the adhesive sheet on the glass substrate 1 is further added to an autoclave (PBD-20 manufactured by Tototec Corp.) The stack was treated at a pressure of 0.5 MPa and a temperature of 50 ° C. for 30 minutes to obtain a laminate of Production Comparative Example 6.

(3) Evaluation of Lamination State The laminates of Production Examples 1 to 6 and the laminates of Production Comparative Examples 1 to 6 were evaluated by the following criteria using visual observation and a microscope.

(3-1) Flowing out of composition after lamination The shortest position of the tacky-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 set as (circle), and when spreading outside, it was set as x.

(3-2) In-plane air bubbles Air bubbles in the area of the adhesive cured body or the comparative composition cured body in the laminate,
○ when it does not exist, × when it exists.

(3-3) Loss of outer portion A portion in which the adhesive cured body or the comparative composition cured body in the laminate does not satisfy the outer peripheral portion along the light shielding print area is
○ when it does not exist, × when it exists.

(3-4) Step Air Bubbles After placing each laminate in an oven at 80 ° C. for 250 hours, observe the presence or absence of air bubbles in the printing step, and if no air bubbles are present on the printing step, ○, if they exist It was marked 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 dark printing part 9 dispenser 1
DESCRIPTION OF SYMBOLS 10 Liquid compatible composition 11 Molded viscoelastic body 12 Adhesive-hardening body 13 Laminated body 14 before hardening Laminated body 14 of Example 11 Ultraviolet irradiation device

Claims (14)

A compatible composition in which a block copolymer compound and a medium are compatible,
The block copolymer compound has the following formula (1):
(In formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.) (Meth) acrylic polymer block (a) having an active energy ray-curable group including a partial structure And (meth) acrylic block copolymers having a (meth) acrylic polymer block (b) having no active energy ray-curable group,
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 has the following formula (2):
(In formula (2), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, Claim: X is represented by 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 compatible composition as described in 1).   The compatible composition according to claim 1, wherein the gel-like compatible composition is dissolved in a solvent.   Further, the compatible composition according to any one of claims 1 to 3, wherein the gel-like compatible composition is an elastic body.   The compatible composition according to any one of claims 1 to 4, further having a thermosetting property and / or a photocurable property.   The adhesive composition formed by mix | blending the compatible composition of any one of Claims 1-5. A composite structure comprising member 1 and member 2, wherein
The composite structure which the said member 1 and the said member 2 adhere | attach through the adhesive composition of Claim 6. The member 1 and the member 2 are plates,
The composite structure according to claim 7, wherein the member 1 and the member 2 are bonded via the adhesive composition according to claim 6, and the member 1 and the member 2 constitute a laminate.   One of the members 1 and 2 is a liquid crystal display panel, an organic EL display panel, a protection panel, a touch panel, a glass or a plastic plate, and the other one is a light transmitting member. 8. The composite structure according to 8. A method of manufacturing a composite structure including a member 1 and a member 2 comprising:
In a temperature environment higher than the temperature Tc according to claim 1,
Bonding the member 1 and the member 2 via the adhesive composition;
The process according to any one of claims 7 to 9, wherein, after the step 1, the temperature environment is a temperature environment lower than the temperature Tc to obtain the composite structure according to any one of claims 7 to 9.   The method according to claim 10, further comprising the step of bringing the adhesive composition into contact with the solvent according to claim 3 to release the adhesion of the member 1 and the member 2 through the adhesive composition. Method of manufacturing a composite structure.   The adhesive composition according to claim 3 is brought into contact with the adhesive composition and / or the temperature environment is a temperature environment higher than the temperature Tc. The method for disassembling a composite structure according to any one of claims 7 to 9, wherein the adhesion between the member 1 and the member 2 is separated by releasing the adhesion through the gap. A method of manufacturing a composite structure including a member 1 and a member 2 comprising:
The manufacturing method is
In a temperature environment lower than the temperature Tc according to claim 1,
Process 1 'of bonding together the said member 1 and the said member 2 via the adhesive composition of Claim 7 which mix | blends the compatible composition of any one of Claims 4-5.
After the step 1 ′, the adhesive composition is cured at least one selected from the group consisting of heat curing and light curing to obtain the composite structure according to any one of claims 7 to 9. A method of producing a composite structure having 2 '. A method of manufacturing a composite structure including a member 1 and a member 2 comprising:
The manufacturing method is
A step 1 "of thermally curing and / or photocuring the adhesive composition according to claim 6, comprising the compatible composition according to claim 4 or 5, to obtain a tacky cured product,
The manufacturing method of the composite structure which has the process 2 "of bonding the said member 1 and the said member 2 through the said adhesion hardening body, and obtaining the composite structure of any one of Claims 7-9.