JP2017066368A - Compatible composition, adhesive composition, composite structure, and method for producing composite structure, and method for decomposing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compatible composition which reversibly changes its state from a liquid to a gel between a high temperature and a low temperature.SOLUTION: Provided is a compatible composition having a block copolymer compound compatibilized with a medium. The block copolymer compound is a block copolymer comprising polymer block a having (meth)acrylate units as a main constituent and polymer block b having (meth)acrylate units as a main constituent. A polymer composed of only the (meth)acrylate monomers which constitute the polymer block a has a glass transition temperature of more than 50°C and 180°C or less, and a polymer composed of only the (meth)acrylate monomers which constitute the polymer block b has a glass transition temperature of -100°C or more and 50°C or less. The block copolymer compound does not have a liquid-gel transition temperature (Tc) between 0 and 150°C, and the compatible composition has a liquid-gel transition temperature (Tc) between 0 to 150°C.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. And a manufacturing method and a disassembling method of the composite structure.

  It is required to fix components of optical devices such as liquid crystal displays and optical lenses, and components of electronic devices such as electronic paper and batteries with an adhesive, and in some cases, release the fixation. There is a case.

  In response to this requirement, conventionally, a method of peeling a cured adhesive from a member by heating and fluidizing the cured adhesive of the fixed portion, swelling it by contacting with a solvent, or immersing it in water. (For example, Patent Document 1).

JP 2010-1000083 A

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

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

The present invention
[1] A compatible composition in which a block copolymer compound and a medium are compatible,
The block copolymer compound is
A polymer block a mainly composed of (meth) acrylate units;
It is a block copolymer with a polymer block b mainly composed of (meth) acrylate units,
The glass transition temperature of the polymer composed only of (meth) acrylate units constituting the polymer block a is more than 50 ° C. and 180 ° C. or less,
The glass transition temperature of the polymer composed only of (meth) acrylate units constituting the polymer block b is -100 ° C or higher and 50 ° C or lower,
The block copolymer compound does not have a liquid-gel transition temperature (Tc) between 0-150 ° C,
The compatible composition has a liquid-gel transition temperature (Tc) between 0-150 ° C.,
[2] An adhesive composition comprising the compatible composition according to [1] above,
[3] A composite structure including member 1 and member 2,
A composite structure in which the member 1 and the member 2 are bonded via the adhesive composition according to [2] above;
[4] A method for producing a composite structure including the member 1 and the member 2,
In a temperature environment higher than the temperature Tc described in [1] above,
Step 1 for laminating 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 to obtain the composite structure according to the preceding item [3], and a method 2 for producing a composite structure,
[5] The temperature environment is set to a temperature higher than the temperature Tc, the adhesion of the member 1 and the member 2 through the adhesive composition is released, and the member 1 and the member 2 are separated from each other. , The dismantling method for the composite structure according to [3] above,
[6] A method for producing a composite structure including member 1 and member 2,
The manufacturing method is
In a temperature environment lower than the temperature Tc described in [1] above,
The member 1 and the member 2 are at least one curable material selected from the group consisting of thermosetting, photocurable, and wet curable, wherein the gel-like compatible composition has an adhesive property. Step 1 ′ for bonding via the adhesive composition according to [2] above, wherein a compatible composition comprising
After the step 1 ′, the adhesive composition is cured at least one selected from the group consisting of heat curing, photocuring and wet curing to obtain the composite structure according to the above item [3]; And a method for producing a composite structure having
[7] A method for producing a composite structure including member 1 and member 2,
The manufacturing method is
The compatible composition according to [1], wherein the gel-like compatible composition is an elastic body having adhesiveness, and is at least selected from the group consisting of thermosetting, photocurable, and wet curable. The adhesive composition described in [2] above, which is formulated with one type of curable compatible composition, is subjected to at least one curing selected from the group consisting of thermal curing, photocuring, and wet curing, and is adhesive. Step 1 "to obtain a cured body,
The member 1 and the member 2 are bonded to each other through the adhesive hardened body to obtain a composite structure according to the above item [3] 2 ″.

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

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

It is a measurement result of the storage rigidity G 'and the loss rigidity G "in the range of 0-80 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.

[Block copolymer compound]
(Compound A)
The block copolymer compound (hereinafter referred to as compound A) in the present invention is:
A polymer block a mainly composed of (meth) acrylate units;
It is a block copolymer with a polymer block b mainly composed of (meth) acrylate units,
The glass transition temperature of the polymer composed only of (meth) acrylate units constituting the polymer block a is more than 50 ° C. and 180 ° C. or less,
The glass transition temperature of the polymer composed only of (meth) acrylate units constituting the polymer block b is -100 ° C or higher and 50 ° C or lower,
The block copolymer compound does not have a liquid-gel transition temperature (Tc) between 0-150 ° C.

The (meth) acrylate unit constituting the polymer block a is polymerized by a (meth) acrylate compound in which the glass transition temperature of a single polymer (hereinafter referred to as polymer a) is more than 50 ° C. and 180 ° C. or less. When formed. From the viewpoint of the stability of the glass transition temperature, the weight average molecular weight of the polymer a is preferably 1 × 10 ⁵ or more, more preferably 1 × 10 ⁵ to 1 × 10 ⁹ , and still more preferably 1 × 10 ⁵ to 1 × 10 ⁷ .

The (meth) acrylate unit constituting the polymer block b is a (meth) acrylate compound having a glass transition temperature of -100 ° C. or more and 50 ° C. or less of a polymer (hereinafter referred to as “polymer b”) constituted by itself. Formed when polymerized. From the viewpoint of the stability of the glass transition temperature, the weight average molecular weight of the polymer b is preferably 1 × 10 ⁵ or more, more preferably 1 × 10 ⁵ to 1 × 10 ⁹ , and still more preferably 1 × 10 ⁵ to 1 × 10 ⁷ .

As the (meth) acrylate compound that can constitute the polymer block a or the polymer block b,
Preferably, methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, lauryl (meth) ) Alkyl (meth) acrylates such as acrylates;
Alkoxy-substituted alkyl (meth) acrylates such as methoxyethyl (meth) acrylate;
Hydroxy-substituted alkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate;
Benzyl (meth) acrylate, phenyl (meth) acrylate, etc .;
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, neopentyl Di (meth) acrylates such as glycol di (meth) acrylate and 1,6-hexanediol di (meth) acrylate; and dicyclopentenyloxyethyl (meth) acrylate, norbornene (meth) acrylate, dicyclopentanyl (meth) An alicyclic structure-containing (meth) acrylate such as acrylate and isobornyl (meth) acrylate, at least two compounds selected from the group consisting of acrylamide such as acryloylmorpholine and diethylacrylamide The
More preferably, a combination of methyl methacrylate (methyl methacrylate) and n-butyl acrylate (butyl acrylate),
Based on the Tg indicated when each compound constitutes a polymer alone, it is used as a constituent unit of the polymer block a or the polymer block b.

  The polymer block a is preferably composed only of (meth) acrylate units, but the compound A does not have a liquid-gel transition temperature (Tc) between 0 to 150 ° C. As long as the soluble compound has a liquid-gel transition temperature (Tc), it is a polymer structure mainly composed of (meth) acrylate units, which is allowed to contain other copolymerizable compound units.

  The molar ratio of the (meth) acrylate unit in the polymer block a is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, still more preferably 99 to 100 mol%.

  The polymer block b is preferably composed only of (meth) acrylate units, but the compound A does not have a liquid-gel transition temperature (Tc) between 0 to 150 ° C. As long as the soluble compound has a liquid-gel transition temperature (Tc), it is a polymer structure mainly composed of (meth) acrylate units, which is allowed to contain other copolymerizable compound units.

  The molar ratio of the (meth) acrylate unit in the polymer block b is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, still more preferably 99 to 100 mol%.

  Since the polymer blocks a and b in the compound A are considered to have a polymer structure substantially equivalent to the polymers a and b, respectively, the glass transition point of the compound A includes the glass transition points of the polymers a and b. It is preferable to have a glass transition temperature in a temperature range that is higher than 50 ° C., that is, a temperature range that is greater than or equal to 50 ° C. and less than or equal to 180 ° C.

(Adjustment conditions for polymer a, polymer b and compound A)
About each of the polymer a, the polymer b, and the compound A, sheet | seat shaping | molding is carried out to the thickness of 0.5 mm by the pressure of 10 MPa using the hydraulic hot press machine made from Shinto Metal Industry Co., Ltd. set to 200 degreeC. Thereafter, a strip of 45 mm × 10 mm × 0.5 mm necessary for dynamic viscoelasticity measurement is cut out.

(Glass transition point measurement conditions)
Using a dynamic viscoelastic device (DMS6100) manufactured by Seiko Instruments Inc.
In the chart obtained by measurement under the temperature range of −100 ° C. to 200 ° C. (temperature increase rate 3 ° C./min) and the frequency of 11 Hz in the pulling mode,
The peak temperature of tan δ is read and used as the glass transition points of polymer a, polymer b and compound A constituting the strip.

Compound A has a liquid-compatible composition described later from the viewpoint of liquid-gel transition,
It is preferable to have at least one triblock structure in which the polymer block a is bonded to both ends of the polymer block b.
More preferably, it is composed only of a triblock structure,
Between 0-150 ° C, compound A does not have a liquid-gel transition temperature (Tc)
In a range in which the compatible composition described later has a liquid-gel transition temperature (Tc),
A structure other than the triblock structure (for example, a diblock structure in which the polymer block a and the polymer block b are bonded) may be included.

  From the above viewpoint, the molar ratio of the triblock structure in the compound A is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, still more preferably 99 to 100 mol%.

  As the compound A, a commercially available “KULARITY” (registered trademark, Kuraray Co., Ltd.) (for example, LA2140, LA2250, LA4285, LA2330, LA3270, LA1114, LA1892) can be used.

(Compound A further imparted with reactivity)
From the viewpoint of improving the elasticity and tackiness of the gel-like compatible composition and the compatible composition at the time of curing, the compound A is an end of the block copolymer of the polymer block a and the polymer block b or Reactivity is further imparted by having at least one reactive functional group selected from the group consisting of a radical reactive group, a cation reactive group, an anion reactive group and a moisture reactive group in the side chain. Is preferred.

  In the present specification, a reactive group that undergoes a polymerization reaction by moisture (humidity) in the air is called a moisture reactive group, and the curing of the curable composition by the polymerization reaction of the moisture reactive group in the curable composition. This is called wet curing.

From the viewpoint of improving the elasticity and tackiness of the gel-like compatible composition and the compatible composition at the time of curing, as the above-mentioned radical reactive group,
Preferably, at least one selected from the group consisting of (meth) acrylate, (meth) acrylamide, (meth) acrylonitrile, urethane (meth) acrylate, vinyl group, vinyl ether, allyl ether, maleimide and maleic anhydride,
More preferably, at least one selected from the group consisting of (meth) acrylate, (meth) acrylamide, urethane (meth) acrylate and vinyl ether,
More preferably, it is at least one radical reactive group selected from the group consisting of (meth) acrylate and urethane (meth) acrylate.

From the viewpoint of improving the elasticity and tackiness of the gel-like compatible composition and the compatible composition at the time of curing, as the above-mentioned cation reactive group,
Preferably, it is at least one cation reactive group selected from the group consisting of epoxy, oxetane and vinyl ether.

  From the viewpoint of improving the elasticity and tackiness of the gel compatible composition and the compatible composition upon curing, the anion reactive group is preferably at least one selected from the group consisting of epoxy, oxetane and vinyl ether. A kind of anion reactive group.

  From the viewpoint of improving the elasticity and tackiness of the gel-like compatible composition and the compatible composition upon curing, the moisture-reactive group is preferably an isocyanate group and / or an alkoxysilyl group.

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

  As the compound B, a compound having a compatible composition with the compound A may be selected as a guide, and a radical polymerizable unsaturated bond such as a (meth) acrylate monomer or a (meth) acrylamide monomer may be selected. It may be a contained monomer, a plasticizer, a solvent and the like.

As a monomer compound in which the compatible composition with compound A can have fluidity,
Preferably, methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, lauryl (meth) ) Alkyl (meth) acrylates such as acrylate; Alkoxy-substituted alkyl (meth) acrylates such as methoxyethyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) ) Hydroxy-substituted alkyl (meth) acrylates such as acrylate; benzyl (meth) acrylate, phenyl (meth) acrylate, etc .; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate , Triethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di Di (meth) acrylates such as (meth) acrylate; 4-tert-butylcyclohexyl acrylate, dicyclopentenyloxyethyl (meth) acrylate, norbornene (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate At least one compound selected from the group consisting of (meth) acrylamides such as alicyclic structure-containing (meth) acrylates, (meth) acryloylmorpholine, diethyl (meth) acrylamide, and the like,
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 tackiness of the gel-like compatible composition and the 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 a reactive compound having at least one reactivity selected from the group consisting of:

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, as a radical reactive compound,
Preferably, at least one selected from the group consisting of (meth) acrylate, (meth) acrylamide, (meth) acrylonitrile, urethane (meth) acrylate, vinyl group, vinyl ether, allyl ether, maleimide and maleic anhydride,
More preferably, at least one selected from the group consisting of (meth) acrylate, (meth) acrylamide, urethane (meth) acrylate and vinyl ether,
More preferably, at least one radical-reactive group selected from the group consisting of (meth) acrylates and urethane (meth) acrylates (preferably bifunctional or more polyfunctional from the viewpoint of the speed and stability of the radical reaction). It has a reactive compound.

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, as the cation-reactive compound,
Preferably, it is a reactive compound having at least one cation 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 compatible composition and the compatible 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 kind of anion reactive compound.

  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, 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 compatible composition and the compatible composition at the time of curing,
A combination of a compound A having a radical reactive group and a compound B which is a radical reactive compound;
A combination of Compound A having a cation reactive group and Compound B which is a cation reactive compound;
A combination of Compound A having an anion reactive group and Compound B which is an anion reactive compound; and
The compatible composition is composed of at least one combination selected from the group consisting of a combination of Compound A having a moisture-reactive group and Compound B which is a moisture-reactive compound.

  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, and from the viewpoint of ease of use of the compatible composition, the compatible composition is a reactive compound. It is preferable to contain a suitable 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-diphenylethane-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine 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-morpholinopropan-1-one, benzoin Methyl ether, benzoin ethyl ether, benzoin isobutyl ether, Nzoin isopropyl ether, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, 2-hydroxy-2- Methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, 2-hydroxy-2-methyl-1-phenyl-1-propanone, isopropylthioxanthone, methyl o-benzoylbenzoate, [4- (methylphenylthio) Phenyl] phenylmethane, 2,4-diethylthioxanthone, 2-chlorothioxanthone, ethyl anthraquinone, benzophenone ammonium salt, thioxanthone ammonium salt, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphi Oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 4,4′-bisdiethylaminobenzophenone, 1,4 Dibenzoylbenzene, 10-butyl-2-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 (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difur Oro-3- (1H-pyrrol-1-yl) -phenyl) titanium, o-methylbenzoylbenzoate, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ethyl ester, active tertiary amine, carbazole It is at least one compound selected from the group consisting of a phenone photoinitiator compound, an acridine photoinitiator compound, and a triazine photoinitiator compound,
More preferred are 1-hydroxy-cyclohexyl-phenyl-ketone and / or 2,4,6-trimethylbenzoylphenylethoxyphosphine 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 allene complexes, titanocene complexes and arylsilanol aluminum 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-hydroxyimide sulfonate.

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′-trimethylenedipiperazine, carbamate compounds and derivatives thereof, cobalt-amine complex compounds, aminooxyimino compounds and ammonium borate compounds. At least one compound.

When the reactive compound is a moisture reactive compound, 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 dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctate, dibutyltin diethylhexanolate, dibutyltin dimethylmaleate, dibutyltin diethylmaleate, dibutyltin dibutylmaleate, dibutyltin dioctylmaleate, dibutyltin ditridecyl Maleate, Dibutyltin dibenzyl maleate, Dibutyltin diacetate, Dioctyltin diethyl maleate, Dioctyltin dioctylmaleate, Dibutyltin dimethoxide, Dibutyltin dinonylphenoxide, Dibutenyltin oxide, Dibutyltin diacetylacetonate, Dibutyltin It consists of a reaction product of diethyl acetoacetonate, dibutyltin oxide and silicate compound, and a reaction product of dibutyltin oxide and phthalate. 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,
Reactants such as amine compounds, acidic phosphate esters, reactants of acidic phosphate esters and amine compounds, saturated or unsaturated polyvalent carboxylic acids or acid anhydrides, salts of carboxylic acid compounds and amine compounds, etc. , Lead octylate, and
It is at least one compound selected from the group consisting of isocyanate reaction catalysts.

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

(Plasticizer)
As a plasticizer in which the compatible composition with compound A can have fluidity,
Preferably, phthalic acid esters such as dibutyl phthalate, diisononyl phthalate, diheptyl 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 benzoates;
Phosphate esters such as tricresyl phosphate and tributyl phosphate;
Trimellitic acid ester;
Rubber-based polymers such as (hydrogenated) polyisoprene, hydroxyl group-containing (hydrogenated) polyisoprene, (hydrogenated) polybutadiene, hydroxyl group-containing (hydrogenated) polybutadiene, polybutene;
Thermoplastic elastomers;
Petroleum resin;
Alicyclic saturated hydrocarbon resins;
Terpene resins such as terpene resin, terpene phenol resin, modified terpene resin, hydrogenated terpene resin;
Rosin-based resins such as rosin phenol;
Rosin ester resins such as disproportionated rosin ester resins, polymerized rosin ester resins, hydrogenated rosin ester resins;
Xylene resin; and at least one compound selected from the group consisting of acrylic resins such as acrylic polymers and acrylic copolymers,
More preferably, it is at least one compound selected from the group consisting of polyvalent carboxylic acid esters and rosin ester resins.

As compound B that acts as a solvent for compound A,
Preferably, alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, benzyl alcohol;
Hydrocarbons such as benzene, toluene, xylene, mineral spirits, cyclohexane, n-hexane, methylcyclohexane, styrene;
Ethers such as diethyl ether;
Esters such as ethyl acetate, propyl acetate, butyl acetate, diethylene glycol monoethyl ether acetate, diethyl carbonate, dimethyl carbonate, propylene carbonate;
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, diacetone alcohol;
Nitrogens such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone;
Glycol ethers such as butyl glycol, methyl diglycol, butyl diglycol, 3-methyl-3-methoxybutanol, tetrahydrofuran;
Chlorines such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene;
Dimethyl sulfoxide; acetonitrile; carboxylic acids such as formic acid and acetic acid; and at least one compound selected from the group consisting of water,
More preferably, at least one compound selected from the group consisting of alcohols, hydrocarbons, esters and ketones,
More preferably, it can be selected from the group consisting of acetone, hexane, isopropyl alcohol and diethyl carbonate.

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

  The solvent in the present invention can be said to be a compound in which the Tc of the mixed composition of the solvent and the solvent-compatible composition is less than 0 ° C. when the amount of the solvent exceeds a certain amount. Therefore, even if it is a radically polymerizable unsaturated bond-containing monomer or plasticizer, the Tc of the mixed composition becomes less than 0 ° C. when the amount of the radically polymerizable unsaturated bond-containing monomer or plasticizer exceeds a certain amount. If not, they can be considered as solvents in the present invention.

The viscosity of the compound B may be within a range in which the compatible composition of the present invention having a liquid-gel transition temperature (Tc) between 0 ° C. and 150 ° C. can be produced by 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 the compound B is an oligomer or the like, even if it is highly viscous or solid in an environment lower than the temperature Tc, it becomes lower in an environment higher than the temperature Tc or is dissolved in another compound B having a lower viscosity. Since these are dissolved in a solvent, they can be combined and kneaded with compound A to produce a compatible composition.

When using the compatible composition as an adhesive composition to be described later, from the viewpoint of applicability to the member, the viscosity of the liquid compatible composition is:
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 the compatible composition is measured under the measurement conditions described in the examples.

[Compatible composition]
The compatible composition formed by compatibilizing Compound A and Compound B is between 0-150 ° C.
Compound A does not have a liquid-gel transition temperature (Tc)
The compatible composition is a composition having a liquid-gel transition temperature (Tc).

The temperature Tc is a temperature at which the storage rigidity G ′ and the loss rigidity G ″ measured under the following conditions are equal in the range of 0 to 150 ° C. of the compatible composition.
The storage rigidity G ′ and the loss rigidity G ”of the compatible composition are
Using a rheometer (Anton Paar)
Cone rotor (φ = 25mm, rotor angle 2 °), frequency 1Hz, strain 1%,
Measurement was performed by cooling at a rate of 2 ° C./min from 150 ° C. to 0 ° C.

FIG. 1 shows the measurement results in the temperature range of 0 to 80 ° C. for the storage rigidity G ′ and the loss rigidity G ″ of the compatible composition of Example 1.
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) 39 ° C. is about the compatible composition. Temperature Tc.

The compatible composition is
Glass that is horizontal at atmospheric pressure at a temperature of Tc or higher (preferably higher than 10 ° C higher than temperature Tc, more preferably higher than 15 ° C higher than temperature Tc, more preferably higher than 20 ° C higher than temperature Tc). Although it is a liquid that naturally flows when 0.01 g or more is dropped on the plate,
A glass that is horizontal under atmospheric pressure at a temperature lower than the temperature Tc (preferably lower than the temperature Tc by 10 ° C. or lower, more preferably lower than the temperature Tc by 15 ° C. or lower, more preferably lower than the temperature Tc by 20 ° C. or lower). It is a gel-like body that does not flow even if it is left on the plate at 0.01 g or more.

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

  The temperature Tc is preferably 10 to 100 ° C., more preferably 20 to 90 ° C., and still more preferably from the viewpoint that the temperature range in which the compatible composition can be used in a gel form is wide and it is not necessary to make it liquid at a very high temperature. 30 to 80 ° C.

The temperature Tc is
If the block polymer a is composed of (meth) acrylate units having a high Tg of the polymer a or the compounding ratio of the compound B is reduced, it can be set on the high temperature side,
When the block polymer a is composed of (meth) acrylate units having a low Tg of the polymer a or the compounding ratio of the compound B is increased, the polymer a can be set on the low temperature side.

For example, when the compatible composition is used as an adhesive composition described later,
When a liquid compatible composition at a temperature higher than the temperature Tc is applied onto the member, the members are bonded together via the compatible composition, and the temperature is lower than the temperature Tc, the members are in a gel-like compatible composition. Although it adhere | attaches stably through a thing, since it will change from gel form to a liquid state when a temperature higher than temperature Tc again, a member can be made into the state isolate | separated easily.

(Compatible composition viscoelastic body)
From the viewpoint of improving the elasticity and tackiness of the gel-like compatible composition and the compatible composition at the time of curing, the compatible composition is compound A (preferably compound A to which reactivity is further imparted), compound B represents at least one reactive compound (preferably in combination with a plasticizer) and a polymerization initiator selected from the group consisting of radical reactivity, cation reactivity, anion reactivity and moisture reactivity. It is preferable to contain (hereinafter referred to as compound A (preferably compound A to which reactivity is further imparted), and compound B is selected from the group consisting of radical reactivity, cation reactivity, anion reactivity and moisture reactivity). A gel-like compatible composition containing one type of reactive compound (preferably further in combination with a plasticizer) and a polymerization initiator is used as a compatible composition viscoelasticity. Also called).

  The compatible composition viscoelastic body may have sufficient elasticity and strength (hereinafter, collectively referred to as viscoelastic characteristics) to form a sheet for bonding onto a member constituting the composite structure described later. Preferably, the compatible composition viscoelastic body having such viscoelastic properties is accompanied by an appropriate viscosity that can be used as an adhesive sheet.

The modulus of elasticity that can form the sheet 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.), the temperature is preferably 0.5 to 500 kPa, more preferably 1 to 200 kPa at the temperature Tc−20 ° C.

  In addition, the elasticity modulus of a compatible composition viscoelastic body is measured on the measurement conditions described in the Example.

As the elongation that can constitute the sheet,
Preferably it is 10 to 1000%, more preferably 30 to 800%, still more preferably 50 to 500%,
As the breaking strength to the extent that the sheet can be configured,
It is preferably 1 × 10 ² to 1 × 10 ⁷ Pa, more preferably 1 × 10 ² to 1 × 10 ⁶ Pa, and still more preferably 1 × 10 ³ to 1 × 10 ⁵ Pa.

  The elongation and breaking strength of the compatible composition viscoelastic body can be measured by a dumbbell tensile test. Specifically, when the elastic modulus of the compatible composition viscoelastic body is 0.3 Pa or more at room temperature (25 ° C.), it is 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) The compatible composition viscoelastic body is liquefied at a temperature Tc + 20 ° C., then poured into a dumbbell mold and cooled to a temperature lower than the temperature Tc (actually room temperature) to prepare a dumbbell test piece having a thickness of 1 mm.
(2) The dumbbell test piece is pulled at a pulling rate of 10 mm / min with a tensile tester (Minebea Technograph, TG-2kN), and the elongation and breaking strength are read from the measurement results.

  When the compatible composition viscoelastic body has the above-mentioned viscoelastic properties, for example, when a sheet is formed with the compatible composition viscoelastic body, the adhesive composition has a degree of tackiness that can be evaluated as ◯ under the measurement conditions described in the examples. The adhesive sheet which has can be comprised.

  The compatible composition viscoelastic body can stably adhere the pressure-sensitive adhesive sheet to the surface of the member when the pressure-sensitive adhesive sheet is constituted, for example.

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

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

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

(2) 3D panel (2.5D, 3D) protection panel display.
(3) Architectural crime prevention glass or safety glass bonded with an adhesive sheet or curable liquid adhesive to prevent scattering of broken glass and improve impact strength.
(4) A solar cell module bonded with an adhesive sheet or a curable liquid adhesive for sealing the light receiving surface material and the back surface material.
(5) A packaging film bonded with an adhesive sheet or a curable liquid adhesive for strength improvement.

The conventional pressure-sensitive adhesive sheet used in the production of the laminate as described above has an advantage that the thickness is uniform, the production process is simple, and contamination to other members is less than that of the curable liquid adhesive. Has the following challenges:
(A) Air bubbles tend to remain when there is a step in the substrate.
(B) Repair is difficult.
(C) It is difficult to handle a thin sheet.
(D) Since it is difficult to produce a thick sheet with a solvent-type pressure-sensitive adhesive, it is difficult to cope with use in an in-vehicle application that requires impact resistance.

The conventional two-stage curable pressure-sensitive adhesive sheet used in the production of the laminate as described above is a low-elasticity pressure-sensitive adhesive sheet with few cross-linking points at the stage where it is adhered to the member. Is less likely to remain and is easier to repair than conventional products due to its low adhesive strength, and after bonding, it cures with light and heat to advance cross-linking and has the advantage of expressing the original strength. There is a problem like this.
(E) Difficulty in laminating the laminate is not eliminated when 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 when the step is large.
(F) Handling of the adhesive sheet becomes difficult when the elasticity is lowered to absorb the level difference.

The conventional curable liquid adhesive used in the production of the laminate as described above is liquid, so there is no concern about bubbles derived from the step of the base material, and there is an advantage that the thickness tolerance of the member can be canceled. It has the following problems.
(G) Since it flows out from the adhesion range when bonded, it is difficult to manage contamination to other members and alignment misalignment during conveyance.

From the viewpoint of the bonding method, attempts have been made to solve the problems of conventional adhesives.
(A) A dam is formed on the outer periphery of the coating area of the curable liquid adhesive to prevent the resin from flowing out.
(B) The flowing curable liquid adhesive is cured by light and stopped.
(C) A liquid curable liquid adhesive is injected between the substrates whose outer periphery is sealed, for example, by vacuuming.
(D) A curable liquid adhesive imparted with thixotropy is used (stencil method).
(E) A layer of a curable liquid adhesive is uniformly formed on the member, and then bonded by controlling the flowability by irradiating UV.
(F) After canceling the level difference of the base material with the curable liquid adhesive, it is pasted with the pressure-sensitive adhesive sheet.
(G) A curable liquid adhesive is dropped on the pressure-sensitive adhesive sheet and then bonded.

However, these methods also have the following problems.
(H) The construction method (a) has a semicircular dam shape, so there is a resin defect (void) on the outside of the dam. Depending on the dam used and the curable liquid adhesive, a boundary line is generated. It is easy to peel off at the interface of the curable liquid adhesive.
(I) In the method (b), the method in which the resin that has flowed is cured and stopped is not limited to the shape and material of the base material because it cannot stop the flow out of the portion that cannot be irradiated with light.
(J) Method (c) is complicated in process and difficult to manage the tact time of the injection process.
(K) The method (d) has a complicated process, and a filler is often used for the thixotropic agent, resulting in a decrease in yield due to poor appearance (filler aggregation, bubbles).
(L) In the method (e), it is difficult to control flowability in consideration of flow-out, bubbles and strength.
For example, the following difficulties can occur:
-Since the liquid layer formed on the base material is affected by the surface tension and swells at the end, if the fluidity of the layer is lowered (cured) too much before bonding, Bubbles are generated at the level difference;
・ When laminating, it is necessary to push in the thickness direction until the swell of the end is canceled, but when the layer fluidity is lowered too much, the strength decreases due to pressback, and conversely the fluidity If too much is left out, it will flow out;
・ Since the end of the resin is semicircular as in the dam system, a resin deficiency (void) may occur on the outside depending on the substrate structure.
(M) The construction method (f) requires a liquid resin composition and a pressure-sensitive adhesive sheet. The process is complicated, and peeling at the interface between the liquid resin composition and the pressure-sensitive adhesive sheet is likely to occur.
(N) Method (g) requires a liquid resin composition and a pressure-sensitive adhesive sheet, has a complicated process, and is liable to stick out in a liquid state, and further peels off at the interface between the liquid resin composition and the pressure-sensitive adhesive sheet. Is likely to occur.

From the above, the conventional pressure-sensitive adhesive sheet and curable liquid adhesive have recently been increasingly demanded, and a protective panel with a narrow light-shielding printing portion and a laminate using a display, or a 2.5D or 3D-shaped protective panel in search of design. And manufacturing a laminate using a display have the following problems.
(O) It is difficult to follow the design shape, have no air bubbles, and stick together without the resin flowing out.

If the compatible composition viscoelastic body is applied on one member in a high temperature environment of temperature Tc or higher, the step can be canceled even if there is a step because it is liquid, and then suddenly below the temperature Tc. If the compatible composition viscoelastic body is made into a gel by cooling to a low temperature environment, a layer of the compatible composition viscoelastic body with a small rise and shoulder drop can be formed on one member.
If one member covered with the layer of the compatible composition viscoelastic body and the other member are bonded together in a low temperature environment lower than the temperature Tc, the layer of the compatible composition viscoelastic body is in a gel form. Therefore, it is possible to obtain a laminated body with less flow-out.

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

  Further, in a low temperature environment lower than the temperature Tc, the gel-like compatible composition viscoelastic body is formed into a molded viscoelastic body along the surface of one member and the surface of the other member, and the molded viscoelastic body is heated. Liquid-gel transition temperature (Tc) by performing at least one treatment selected from the group consisting of light irradiation and humidification and curing at least one selected from the group consisting of thermal curing, photocuring and wet curing Adhesive hardened body having no

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

  For example, if the pair of members is plate-like, the compatible composition viscoelastic body is formed into a sheet-like molded viscoelastic body, and at least one treatment selected from the group consisting of heating, light irradiation, and humidification is performed. Curing at least one selected from the group consisting of curing, photocuring and wet curing is used to form a sheet-like adhesive cured body having no liquid-gel transition temperature (Tc), and this is used as an adhesive sheet. be able to.

  Furthermore, the sheet-like adhesive cured body that does not have a liquid-gel transition temperature (Tc) controls the degree of elasticity by adjusting the types and blends of reactive compounds and plasticizers in the compatible composition viscoelastic body. It is possible to adjust the elasticity so that it can be wound in a roll shape, it can be hard enough not to be wound in a roll shape, or a thin sheet can be formed. Therefore, it is possible to perform bonding without pressing back or chipping.

  According to the compatible composition viscoelastic body, a thick sheet-like molded viscoelastic body can be obtained, and as a result, a thick laminate composed of a cured adhesive body can be obtained.

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

  The compatible composition is preferably such that the mass part of the compound B with respect to 100 parts by mass of the compound A is from the viewpoint of the application property to the member in the liquid state and the adhesiveness between the members in the gel state and the phase transition property. It is 200-1000 mass parts, More preferably, it is 250-800 mass parts.

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

(Thixotopic compatible composition)
When fixing components of optical devices, such as liquid crystal displays and optical lenses, and components of electronic devices, such as electronic paper and batteries, with adhesives, contamination due to outflow of adhesive or stringing does not occur. And it may be required to be applied evenly within a specific frame.

  In response to this requirement, attempts have been made to use an adhesive having thixotropy that is difficult to thread, but a light transmissive member that is required to have a light transmissive property for components of optical and electronic devices. Is added as an adhesive, it is difficult to maintain optical transparency when a filler such as metal oxide fine particles is added to impart thixotropy of the adhesive, and even if an oil gelling agent is added. It is difficult to provide thixotropy that can cope with precise fluidity control for optical device and electronic device applications.

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

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. Blend.
A thixotropic compatible composition has thixotropic properties. When the thixotropic compatible composition is subjected to shear stress (when the shear rate is increased), the viscosity decreases, and when the shear stress is released (the shear rate is decreased). Then, it means having a viscoelastic property in which the viscosity is recovered and the flow is suppressed.

The thixotropic property in the gel-like body 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 ) Ratio x ₁ = η _0.1 / η ₁ with η ₁ (Pa · s),
The viscosity η ₁ (Pa · s) of the thixotropic compatible composition at a reference shear rate of 1 (sec ⁻¹ ) and the viscosity η ₁₀ of the thixotropic compatible composition at a shear rate of 10 (sec ⁻¹ ) (Pa The ratio x ₂ = η ₁ / η ₁₀ with s) can be taken as a scale.

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, an adhesive composition described later, a predetermined range is surface-coated using a slit coater. Sometimes, a thixotropic compatible composition flows moderately when extruded from a slit coater and stops flowing after being extruded, so that contamination due to outflow or stringing from a predetermined range is unlikely to occur. It becomes possible to apply uniformly to a predetermined range.

From the viewpoint of the applicability of such a thixotropic compatible composition and maintaining the coating shape,
η _0.1 is preferably 10 to 10000 Pa · s, more preferably 30 to 5000 Pa · s, still more preferably 50 to 3000 Pa · s,
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 from 1.1 to 20, more preferably from 1.2 to 15, more preferably from 1.25 to 10.
x ₂ is preferably 1.1 to 20, more preferably from 1.2 to 15, more preferably from 1.25 to 10.

(Transparency of thixotropic compatible composition)
The thixotropic compatible composition is not only formed by compound A and 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 diffuse transmittance in the total light transmittance of the thixotropic compatible composition.

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

  On the other hand, a thixotropic compatible composition can ensure thixotropy only with a resin composition in which compound A and compound B are compatible, without adding a filler, so 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 has 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, and still more preferably 0.2 or less. Can be secured.

〔solvent〕
A solvent for dissolving the compatible composition can be selected.
For example, when the compatible composition is used as an adhesive composition to be described later, the compatible composition dissolved in the solvent is bonded via the gel-like compatible composition even if the temperature is not higher than the temperature Tc. The members are separated from each other by bringing the solvent into contact with the gel-like compatible composition to dissolve the compatible composition and removing the gel-like compatible composition without leaving a solid content. It can be in the state.

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

  The compatible composition is compatible with compound A and compound B (between temperatures 0 to 150 ° C., compound A does not have a liquid-gel transition temperature (Tc), and the compatible composition is liquid-gel. As long as it does not inhibit the transition temperature (Tc), additives other than Compound B as described below can be arbitrarily blended, and the blending amount of additives other than Compound B in that case is blended. Preferably it is 0-50 mass% in the total mass of a thing, More preferably, it is 0-30 mass%.

[Adhesive composition]
The compatible composition of the present invention can be suitably used as an adhesive composition for adhering members to each other because it is excellent in adhesion to members when applied to a member in a liquid state and gelled.

  The adhesive composition of the present invention (hereinafter also referred to as the adhesive composition) contains the compatible composition because it is blended with the compatible composition of the present invention. From the viewpoint of stable adhesion, the temperature straddles the temperature before and after the temperature Tc (preferably a temperature range of Tc ± 10 ° C., more preferably a temperature range of Tc ± 15 ° C., further preferably a temperature range of Tc ± 20 ° C.). , Reversibly changes into a gel-like body and a liquid body (the adhesive composition having the above-mentioned changes is also referred to as phase transition).

  The adhesive composition is, for example, antioxidant within a range that does not impair the applicability to a member in a liquid state and the adhesion between members in a gel state (hereinafter collectively referred to as adhesiveness) and phase transition. Additives such as agents, wetting agents, surfactants, ionic liquids, antifoaming agents, ultraviolet absorbers, light stabilizers, inorganic and various organic fillers, and polymers can be included.

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

  When the compatible composition is a compatible composition viscoelastic body, the adhesive composition can be used as long as the adhesive property, phase transition property and viscoelastic property are not impaired, for example, an antioxidant, a wetting agent, a surfactant. Additives such as ionic liquids, antifoaming agents, ultraviolet absorbers, light stabilizers, various inorganic and organic fillers, and polymers can be included.

  In addition, the additive in an adhesive composition means what combined the additive mix | blended in a compatible composition and the additive mix | blended with a compatible composition.

In the adhesive composition, the viscosity of the liquid compatible composition is preferably a temperature range of Tc + 10 ° C. or more (more preferably a temperature range of Tc + 15 ° C. or more, more preferably Tc + 20 ° C. 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.

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

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

  That the member 1 and the member 2 are bonded via the adhesive composition means that the surfaces of the member 1 and the member 2 are in contact with and bonded to the adhesive composition with the adhesive composition in between ( The relative positions of the members 1 and 2 in the vicinity of the adhesive composition are fixed).

  In the composite structure, the adhesive composition adhering the members 1 and 2 is further removed by making the adhesive composition liquid, for example, at a temperature higher than the temperature Tc, If the adhesive of the members 1 and 2 is planned to be released by contacting the adhesive composition with a solvent at a temperature lower than the temperature Tc to dissolve and remove the adhesive composition, Adhesion of the member 2 via the adhesive composition is referred to as temporary fixing, and the adhesive composition when the member 2 is used with the intention of releasing the adhesion of the members 1 and 2 is also referred to as temporary fixing agent.

When the member 1 and the member 2 are plates, for example,
Preferably, the surfaces in the thickness direction of the members 1 and 2 are bonded or temporarily fixed via the adhesive composition, or more preferably, the plate surfaces of the members 1 and 2 are bonded or temporarily fixed via the adhesive composition. Fixed,
The member 1 and the member 2 may adhere | attach via the said adhesive composition, and the member 1 and the member 2 may comprise the laminated body.

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

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 form a laminate or the like.

(2) A liquid crystal display comprising a liquid crystal cell, wherein the liquid crystal cell is bonded or temporarily fixed.

(3) A plurality of articles such as wafers that require surface smoothness are temporarily fixed on a substrate, surface treatment is simultaneously performed, and the substrate is removed for use.

(4) A device using an electrolytic solution such as an antiglare mirror, electronic paper, a battery, or a capacitor, wherein 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 inhibited 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 base for 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, and then the adhesive is removed to use each as a part.

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

(8) 3D panel (2.5D, 3D) protection panel display.
(9) Security glass or safety glass for buildings bonded with an adhesive sheet or curable liquid adhesive to prevent scattering of broken glass and improve impact strength.
(10) A solar cell module bonded with an adhesive sheet or a curable liquid adhesive for sealing the light receiving surface material and the back surface material.
(11) A packaging film bonded with an adhesive sheet or a curable liquid adhesive for strength improvement.

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

  From the viewpoint of adhesiveness at a temperature Tc or lower, the materials of the members 1 and 2 are glass, PET, TAC, COP, polyimide, PMMA, polycarbonate, vinyl chloride, PVA, polyethylene, polypropylene, silicon, graphite, aluminum, copper, SUS or the like is preferable, and 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. Alternatively, 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, preferably a laminated body via a compatible composition viscoelastic body in which the member 1 and / or the member 2 are plate-shaped, more preferably, among the flat panels (2D) in recent years. Laminates using protective panels and displays with narrow light-blocking printing parts that require more design, and 2.5D and 3D-shaped protection panels and displays that require more design in addition to flat panels (2D) The laminated body used is bonded in a state where the compatible composition viscoelastic body follows the design shape, there are no bubbles between the members 1 and 2 and the member, and no resin flows out.

  Therefore, in the case where the composite structure is preferably a laminated body through a compatible composition viscoelastic body in which the member 1 and / or the member 2 are plate-like, more preferably one of the member 1 or the member 2 is a liquid crystal display. A laminated body through a compatible composition viscoelastic body when the panel, organic EL display panel, protective panel, touch panel, glass or plastic plate and the other is a light transmissive member is a compatible composition viscoelasticity The body follows the design shape, and there is no air bubble between the member 1 and the member 2 and the member, and the members are bonded together without any resin flowing out.

[Production method of composite structure]
(Manufacturing method 1)
Composite structures
In a temperature environment higher than the temperature Tc,
The process 1 which bonds the member 1 and the member 2 together through an adhesive composition,
After step 1, it can be obtained by a manufacturing method (hereinafter also referred to as manufacturing method 1) including step 2 of obtaining a composite structure by setting the temperature environment to be lower than temperature Tc.

In the manufacturing method 1, since the adhesive composition is liquid in the first step,
The adhesive composition in liquid form can be easily applied to the bonding site of member 1 and member 2,
In step 2, the coated adhesive composition becomes a gel, and the members 1 and 2 can be bonded or fixed.

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

  In the final specification of the composite structure, when the adhesion between the member 1 and the member 2 is scheduled to be released, the composite structure manufacturing method further includes an adhesive composition after step 2 It is preferable to include a step 3 in which the solvent is brought into contact with the object and / or the temperature environment is set 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 the temperature Tc,
The process 1 'which bonds the member 1 and the member 2 together through the adhesive composition formed by mix | blending a compatible composition viscoelastic body,
After Step 1 ′, the adhesive composition is subjected to at least one curing selected from the group consisting of heat curing, photocuring, and wet curing, and includes a member 1 and a member 2 that are bonded via an adhesive elastic body. It can be obtained by a production method including step 2 ′ for obtaining a composite structure (hereinafter also referred to as production method 2).

  The adhesive composition in the step 1 ′ of the production method 2 is a step in which the adhesive composition is liquefied in a temperature environment higher than Tc, for example, and then cooled to form a gel. ), Or the process may be performed on the surface of the member 1 or the member 2.

  The production method 2 solves at least one problem selected from the group consisting of the problems (A) to (O) as described above, due to the viscoelastic characteristics of the adhesive composition derived from the compatible composition viscoelastic body. For example, in the case where the composite structure is preferably a laminated body through a compatible composition viscoelastic body in which the member 1 and / or the member 2 are plate-like, more preferably at least one of the member 1 and the member 2 In the case of a laminate through a compatible composition viscoelastic body having a plate-like shape, it is more preferable that a protective panel or display having a narrow light-shielding printing portion, which is required to be more designed in recent years, among flat panels (2D). When manufacturing laminates using 2.5D and 3D protective panels and displays that require more design in addition to the laminates used and flat panels (2D), viscoelastic bodies that are compatible compositions To follow the design shape, no air bubbles between the member 1 and the member 2 and the member, 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
A step 1 "of obtaining an adhesive cured body by curing at least one selected from the group consisting of heat curing, photocuring and wet curing the adhesive composition containing the compatible composition viscoelastic body of the present invention;
The member 1 and the member 2 can also be obtained by a manufacturing method of a composite structure having a composite structure including the member 1 and the member 2 bonded through an adhesive hardened body 2 ″ (hereinafter, manufacturing method) 3).

  In step 1 ″ of production method 3, for example, the adhesive composition is formed into a predetermined shape (preferably a sheet shape) in advance by cooling it into a gel after cooling it to a liquid at a temperature higher than Tc. The obtained compatible composition viscoelastic body may be used, or the process may be performed on the surface of the member 1 or the member 2.

  In production method 3, step 2 ″ is at least one selected from the group consisting of photocuring and wet curing in advance of a molded viscoelastic body obtained by molding in a predetermined shape (preferably a sheet) in step 1 ″. It is good also as an adhesive hardening body of predetermined shape (preferably sheet shape) by hardening | curing seed | species, or the predetermined shape (preferably sheet shape) obtained beforehand on the surface of the member 1 or the member 2 at the process 1 ''. The molded viscoelastic body may be subjected to at least one curing selected from the group consisting of photocuring and wet curing on the surface of the member 1 or the member 2 as it is.

  According to the manufacturing method 3, since an adhesive hardened body can be manufactured in advance and used as, for example, an adhesive sheet, even if the member has a light-shielding portion, the entire adhesive sheet is cured, which is like a conventional curable liquid adhesive. In addition, the coating system is easy to control without spreading after coating.

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

  Therefore, the production method 2 is also at least selected from the group consisting of the problems (A) to (O) as described above due to the viscoelastic properties of the adhesive composition derived from the compatible composition viscoelastic body and the adhesive cured body. 1 can be solved. For example, in the case where the composite structure is preferably a laminated body via a compatible composition viscoelastic body in which the member 1 and / or the member 2 are plate-like, more preferably the member 1 In addition, in the case of a laminate through a compatible composition viscoelastic body in which at least one of the members 2 is plate-shaped, more preferably, in recent years, a light-shielding printing portion that is required to be more designed in a flat panel (2D). When manufacturing a laminate using a narrow protective panel or display, or a laminate using a 2.5D or 3D protective panel or display that requires more design than a flat panel (2D) , Compatible composition viscoelastic body follows the design shape member 1 and member 2 and no air bubbles between the member, it is possible to bond in the absence also flows of resin.

[Repair adjustment in the manufacturing process of composite structures]
Conventionally, since the conventional adhesive sheet was used instead of the compatible composition viscoelastic body between the step 1 ′ and the step 2 ′ in the production method 2, bubbles derived from the step of the member are likely to remain. In some cases, it was necessary to repair between step 1 ′ and step 2 ′ in order to remove bubbles. However, according to the manufacturing method 2, for example, the solution is compatible at a temperature equal to or higher than the Tc temperature on the substrate on which a step exists. By applying the composition viscoelastic body, the step can be canceled, and when the compatible composition viscoelastic body sheet is bonded to a substrate having a step, the compatible composition viscosity Due to the adhesiveness, strength, and elasticity of the elastic sheet, the composition viscoelastic sheet follows the shape having the step of the member, so that bubbles from the step of the member hardly remain, and the frequency of repair can be greatly reduced. It becomes possible.

  The effect of canceling the step of the compatible composition viscoelastic sheet is the case where the compatible composition viscoelastic sheet is formed on the base material to be bonded and bonded, and the composition viscoelastic sheet is formed in advance. Thus, even when pasted on a substrate, it is suitably expressed.

  Further, even in the case of repairing between Step 1 ′ and Step 2 ′ in the production method 2, if the repair is performed in a high-temperature environment equal to or higher than the temperature Tc, the compatible composition viscoelastic body becomes liquid, so that it is easily repaired. It becomes possible to do.

[Method of dismantling composite structure]
The composite structure obtained in the step 2 is brought into contact with the adhesive composition with a solvent and / or the temperature environment is set higher than the temperature Tc, and the adhesive composition of the members 1 and 2 is interposed. The composite structure can be easily disassembled by releasing the adhesion and separating the member 1 and the member 2 from each other.

Compound raw materials
(1) Compound A
The polymer block a is composed of methyl methacrylate,
The polymer block b was composed of butyl acrylate,
Polymer block a-polymer block b-triblock copolymer compound of polymer block a and diblock copolymer compound of polymer block a-polymer block b were used.
(1-1) Compound a1: KULARITY LA2140 (registered trademark, Kuraray Co., Ltd.)
(1-2) Compound a2: KULARITY LA2250 (registered trademark, Kuraray Co., Ltd.)
(1-3) Compound a3: KULARITY LA2330 (registered trademark, Kuraray Co., Ltd.)
(1-4) Compound a4: KULARITY LA4285 (registered trademark, Kuraray Co., Ltd.)
(1-5) Compound a5: KULARITY LA1892 (registered trademark, manufactured by Kuraray Co., Ltd.)
(1-6) Compound a6: KULARITY LA1114 (registered trademark, manufactured by Kuraray Co., Ltd.)

In the total mass of the polymer block a and the polymer block b, the polymer block a is
LA2140 is about 20% by mass, LA2250 is about 30% by mass,
LA2330 is about 20% by mass, LA4285 is about 50% by mass,
LA1892 is about 50% by mass, LA1114 is about 10% by mass,
LA2140, LA2250, LA2330, LA4285 are triblock bodies,
LA1892 and LA1114 are diblock bodies.
The molecular weight is LA2330> LA2140 = LA2250 = LA4285 = LA1114 = LA1892.

(2) Glass transition temperature of polymers a and b (2-1) Glass transition temperature of butyl acrylate polymer (polymer a): −25 ° C.
(2-2) Glass transition temperature of polymer of methyl methacrylate (polymer b): 140 ° C.

(3) Compound B
(3-1) Compound b1: Isodecyl acrylate (manufactured by Sartomer, SR395)
(3-2) Compound b2: 4-tert-butylcyclohexyl acrylate (manufactured by Rahn, genomer 1119)
(3-3) Compound b3: 4-hydroxybutyl acrylate (Nihon Kasei Co., Ltd., 4-HBA)
(3-4) Compound b4: diisononyl cyclohexyl dicarboxylate (manufactured by BASF, DINCH)
(3-5) Compound b5: alkyl benzoate (alkyl having 12 to 16 carbon atoms) (Liponate NEB manufactured by Lipo Chemicals)
(3-6) Compound b6: Hydrogenated rosin ester (Arakawa Chemical Industries, KE-311)
(3-7) Compound b7: Epoxy ester (4,5-epoxy-1,2-cyclohexanedicarboxylic acid bis (2-ethylhexyl)) (manufactured by DIC, W150)
(3-8) Compound b8: Disproportionated rosin ester (Arakawa Chemical Industries, ME-D)
(3-9) Compound b9: Triethylene glycol bis (2-ethylhexanoate) (Proviron, Proviplast 1783)

(4) Compound B1 (radical reactive bifunctional compound and polyfunctional compound)
(4-1) Compound b1-1: PPG urethane acrylate (manufactured by KSM, UA10000B)
(4-2) Compound b1-2: Aliphatic urethane acrylate (manufactured by Daicel Ornex Co., Ltd., EB270)
(4-3) Compound b1-3: 1.9-nonanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., 1,9-NDA)
(4-4) Compound b1-4: polybutadiene urethane acrylate (Nihon Soda, TE-2000)
(4-5) Compound b1-5: Pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMMT)
(4-6) Compound b1-6: Urethane acrylate (Nippon Gosei Co., Ltd., UV7605B)

(5) Compound B2 (radical reactive monomer compound)
(5-1) Compound b2-1: 4-hydroxybutyl acrylate (Nihon Kasei Co., Ltd., 4-HBA)
(5-2) Compound b2-2: Lauryl acrylate (Kyoeisha Chemical Co., Ltd., LA)
(5-3) Compound b2-3: Isodecyl acrylate (manufactured by Sartomer, SR395)
(5-4) Compound b2-4: Isobornyl acrylate (manufactured by Nippon Kayaku Co., Ltd., RM-1002)
(5-5) Compound b2-5: 4-tert-butylcyclohexyl acrylate (genomer 1119 manufactured by Rahn)
(5-6) Compound b2-6: Pentamethylpiperidyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., FA-711MM)

(6) Other compounds (6-1) Compound r1 (b1-4): Polybutadiene urethane acrylate (manufactured by Nippon Soda Co., Ltd., TE-2000)
(6-2) Compound r2: Dicyclopentenyloxyethyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., FA512M)
(6-3) Compound r3: 2-hydroxyethyl methacrylate (manufactured by Kyoeisha Chemical Co., HO-250)
(6-4) Compound r4: 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF, I-184)
(6-5) Compound r5: Acrylic polymer (manufactured by Toagosei Co., Ltd., UP1110)
(6-6) Compound r6: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (BASF, I-TPO)
(6-7) Compound r7: Polyurethane acrylate (Nihon Gosei Co., Ltd., UV3630ID80)
(6-8) Compound r8 (b4): diisononyl cyclohexyl dicarboxylate (BASIN, DINCH)
(6-9) Compound r9 (b6): Hydrogenated rosin ester (Arakawa Chemical Industries, KE-311)
(6-10) Compound r10 (b2-1): 4-hydroxybutyl acrylate (Nihon Kasei Co., Ltd., 4-HBA)
(6-11) Compound r11 (b2-3): Isodecyl acrylate (manufactured by Sartomer, SR395)

[Compatibility conditions]
(1) Example 1
100 g of compound a1 and 400 g of compound b1 were weighed and filled into a container (material SUS316, capacity 2000 ml) and 200 rpm using a three-one motor (manufactured by Shinto Kagaku) at 80 ° C. and atmospheric pressure. / Min for 360 minutes to obtain a compatible composition.
(2) Examples 2 to 23 and 34 to 39
Compound a1 and compound b1 are replaced with the compounds described in Tables 1, 2, and 4, and the formulations of Tables 1, 2, and 4 are used, and compatibility of Examples 2-23 and 34-39 is the same as in Example 1. A composition was prepared.

〔Measurement item〕
The following physical properties were measured for the compatible compositions of Examples 1 to 23 and 34 to 39.
(1) Glass transition point of a polymer of butyl acrylate (polymer a) and a polymer of methyl methacrylate (polymer b).
(2) Liquid-gel transition temperature (Tc) of the compatible composition
(3) A temperature at which the viscosity of the compatible composition is 1 Pa · s or less.
(4) Solvent solubility (5) Viscosity η ₁ (Pa · s) at 25 ° C. and shear rate 1 (sec ⁻¹ )
(6) Viscosity η ₁₀ (Pa · s) at 25 ° C. and a shear rate of 10 (sec ⁻¹ )
(7) HAZE value

  Table 1 shows the results.

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

[Measurement conditions of viscosity η ₁ (Pa · s) and viscosity η ₁₀ (Pa · s)]
Using a rheometer (manufactured by Anton Paar), changing the shear rate from 0.01 (sec ⁻¹ ) to 100 (sec ⁻¹ ) at 25 ° C. with a cone rotor (φ = 25 mm, rotor angle 2 °). Measured.

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

[Adhesive measurement conditions]
(1) A liquid compatible composition at a temperature 20 ° C. higher than Tc, and a PET film (manufactured by Nipper, J0L, 50 μm) on a mold release treatment, using a dispenser 1 described later, is 3 cm wide and 4 cm long. When the elastic layer has a modulus of 0.3 MPa or less at room temperature (25 ° C.) or at 25 ° C., it is cooled to a temperature Tc−20 ° C. to produce a sheet as a molded viscoelastic body. .
(2) When the elastic modulus is 0.3 MPa or less at a humidity of 40 to 60%, room temperature (25 ° C.) or 25 ° C., the temperature is Tc−20 ° C. The PET film is peeled off.
(3) When the elastic modulus is 0.3 MPa or less at a humidity of 40 to 60%, room temperature (25 ° C.) or 25 ° C., the glass substrate 2 on which the sheet is pasted at the temperature Tc-20 ° C. Leave it horizontally in the air.
○ If the adhesive sheet does not fall after 5 minutes after standing still horizontally,
If the adhesive sheet falls after 5 minutes after standing still horizontally,
It was.
(4) In addition, the surface of the glass substrate 2 is used after being dipped in acetone before the test to be cleaned and then dried.

[Measurement conditions for solvent solubility]
For each of the compatible compositions of Examples 1-23 and 34-39,
Using acetone (made by Kanto Chemical Co., Ltd., special grade) as a solvent,
0.78 g of a solvent was added to 0.02 g of the gel-like compatible composition, and the mixture was allowed to stand for 24 hours in a light-shielding environment at 25 ° C., and was judged as follows: Check visually for any residue,
When it is confirmed that there is no residue of the gel composition, the solvent solubility is ○;
When it is confirmed that there is a gel-like composition residue, the solvent solubility is x.

[Measurement conditions of HAZE value]
For each of the compatible compositions of Examples 34-39,
A spacer of 0.3 mmt is attached to both ends of a 2.5 cm × 3.8 cm × 1 mmt glass, and a compatible composition is sandwiched between them with a metal halide lamp (made by Eye Graphics Co., Ltd., conveyor type), 250 mW / cm2, 3000 mJ / curing the compatible composition cm ^2. Measurement was performed with a haze meter (NDH5000, manufactured by Nippon Denshoku Kogyo Co., Ltd.), and the ratio of total light transmittance to diffuse transmittance was determined.

[Manufacture of composite structures and comparative structures]
(1) Manufacture of composite structure It demonstrates referring FIG.
14 sets of slide glass 1 (plate-shaped member 1) (1) on which a spacer (3) having a thickness of 200 μm is installed are prepared (FIG. 2 (2-1 (plan view)) (2 -2 (front view)),
On 14 slide glasses 1, 0.015 g of each of the gel compatible compositions (4) of Examples 1 to 14 was collected and installed using a spatula (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 a liquid compatible composition (5) on the slide glass 1 (FIG. 2). (2-4)),
The other slide glass 2 (plate-shaped member 2) (2) is bonded to the plate surface (step 1), and left for another 30 seconds (FIG. 2 (2-5)).
The temperature is lowered to the temperature environment (25 ° C) by removing it from the hot plate,
The laminated body (composite structure) which the slide glass 1 and the slide glass 2 laminate | stack through each composition was obtained (process 2) (FIG. 2 (2-6)).

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

[Disassembly of composite structure at high temperature]
The laminated body in which the slide glass 1 and the slide glass 2 obtained in the production of the composite structure are laminated through the compatible compositions is placed on a hot plate set at a temperature 20 ° C. higher than Tc, and left for 1 minute. The slide glass 1 and the slide glass 2 of the laminated body could be separated by a light peeling operation with fingers, and the laminated body could be disassembled (when the peeled off, the compatible compositions were all liquid).

  The comparative structure obtained in the manufacture of the comparative structure was placed on a hot plate set at 100 ° C. and allowed to stand for 5 minutes, but the cured product of the compatible composition remained solid and the slide glass 1 and slide glass of the laminate 2 could not be separated by light escort operation.

[Dismantling 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 compatible compositions was immersed in acetone and left for 60 minutes.
Thereafter, when the laminate was peeled off, the laminate could be easily peeled off and disassembled (when the peeled off, all of the compatible compositions were dissolved and liquid).

  Even if the comparative structure obtained in the manufacture of the comparative structure is immersed in acetone and left for 60 minutes, the cured product of the compatible composition remains cured or only swelled, and the laminated glass slide 1 The slide glass 2 could not be separated by a light peeling operation.

[Laminate production test]
(1) Tool (1-1) Glass substrate 1 (plate-shaped member 1)
A glass substrate having a length of 60 × width 80 × thickness 0.8 mm subjected to light-shielding printing (GLS-HF manufactured by Teikoku Inc.) having an outer periphery of 2 mm and a thickness of 50 μm was used.
(1-2) Glass substrate 2 (plate-like member 2)
A transparent glass substrate having a length of 60 × width of 80 × thickness of 0.8 mm was used.
(1-3) Dispenser 1
A flat nozzle (Musashi Engineering Co., Ltd., SHOT MASTER 300) was used.
(1-5) Dispenser 2
A PICOJET PV valve manufactured by Nordson was used.
(1-6) Ultraviolet irradiation device A conveyor type ultraviolet irradiation device (manufactured by Aigfick, metal halide lamp) was used.

(2) Manufacturing conditions (2-1) Examples 24-33 (refer FIG. 3)
The compatible compositions viscoelastic bodies (adhesive compositions) of Examples 15 to 23 described in Table 2
A liquid compatible composition (10) is obtained at a temperature 20 ° C. higher than Tc, and a dispenser 1 (9) is used on the glass substrate 1 (6) to form a liquid layer having a thickness of 0.15 mm at room temperature (25 ° C. ) To form a layer of the 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.), which is lower than Tc, and the glass substrate 1 (6). And the laminated body before hardening which bonded the glass substrate 2 (7) through the shaping viscoelastic body (11) was manufactured (process 1 ').
The laminated body before curing is photocured by using an ultraviolet irradiation device (15) at a peak illuminance of 400 mW / cm ² , an integrated light amount of 6000 mJ / cm ² (wavelength 350 nm, manufactured by Oak Co.), and a reaction rate of 100%. And the glass substrate 2 was bonded together through the layer (adhesion hardening body) of the adhesion hardening body (12), and the laminated body (composite structure) (13) of Examples 24-32 was obtained (process 2 ').

(2-2) Example 40 (see FIG. 3)
In Example 24, the compatible composition viscoelastic body (adhesive composition) of Example 15 was replaced with the thixotropic compatible composition of Example 34, and the laminate (composite structure) of Example 40 was similarly prepared. Product).

(2-3) Comparative Example 3
Except that the compatible composition viscoelastic body (adhesive composition) of Examples 15 to 23 described in Table 2 was replaced with the comparative composition of Comparative Example 2 described in Table 2 and applied at room temperature (25 ° C.). The laminated body of the comparative example 3 was obtained on the conditions similar to Examples 15-23.

(2-4) Example 33 (see FIG. 4)
The compatible composition viscoelastic body (adhesive composition) of Example 23 described in Table 2 was made into a liquid compatible composition (10) at a temperature 20 ° C. higher than Tc, and dispenser 1 was placed on glass substrate 1 (6). (9) was used to form a liquid layer having a thickness of 0.15 mm, cooled to room temperature (25 ° C.), and formed into a layer of the molded viscoelastic body (11).
The glass substrate 1 (6) on which the molded viscoelastic body (11) is formed at room temperature (25 ° C.) is measured using a UV irradiation device (15) with a peak illuminance of 400 mW / cm ² and an integrated light quantity of 6000 mJ / cm ² (oak). 350 nm), the reaction rate is 95%, and the molded viscoelastic body is photocured to form an adhesive cured body (12) (step 1 ″).
In Example 33, the glass substrate 1 (6) on which the adhesive cured body (12) was formed was bonded via the glass substrate 2 (7) and the adhesive cured body (12) under reduced pressure at room temperature (25 ° C). A laminate (composite structure) (14) was obtained (step 2 ″).

(2-5) Comparative Example 4
Using the dispenser 1 on the glass substrate 1 and forming the comparative composition of Comparative Example 2 shown in Table 2 to a thickness of 0.15 mm at room temperature (25 ° C.), using a 365 LED lamp (manufactured by HOYA). Photocured at an illuminance of 100 mW / cm ² , an irradiation time of 2 sec, and a reaction rate of 30%, to obtain a primary cured body having reduced fluidity.
The laminated body which bonded together the glass substrate 1 which formed the primary hardening body under reduced pressure with the glass substrate 2 via the primary hardening body was obtained.
The laminate was further cured with an ultraviolet irradiation device at a peak illuminance of 400 mW / cm ² and an integrated light amount of 6000 mJ / cm ² (Oak company wavelength 350 nm) to obtain a laminate of Comparative Example 4.

(2-6) Comparative Example 5
The photocuring conditions at the time of producing the primary cured product in Comparative Example 4 were changed to an illuminance of 100 mW / cm ² , an irradiation time of 5 sec, and a reaction rate of 60%, and a laminate of Comparative Example 5 was obtained in the same procedure as Comparative Example 4. An evaluation test piece was prepared.

(2-7) Comparative Example 6
The photocuring conditions at the time of producing the primary cured product in Comparative Example 4 were changed to an illuminance of 100 mW / cm ² , an irradiation time of 10 sec, and a reaction rate of 95%, and a laminate of Comparative Example 5 was obtained in the same procedure as Comparative Example 4. An evaluation test piece was prepared.

(2-8) Comparative Example 7
Using the jet dispenser 2 on the outer periphery of the glass substrate, the comparative composition of Comparative Example 2 shown in Table 2 is drawn to a width of 1 mm × a height of 0.2 mm, and an illuminance of 100 mW / cm using a 365 LED lamp (manufactured by Panasonic). ^2. Cured with an irradiation time of 5 seconds to form a dam.
After applying the comparative composition of Comparative Example 2 described in Table 2 on the glass substrate 1 using the dispenser 1, the glass substrate 2 and the comparative substrate 2 of Comparative Example 2 on the glass substrate 1 were applied under reduced pressure. The laminate was laminated and adjusted by applying pressure so that the thickness of the composition was 0.15 mm to obtain a comparative laminate before curing.
The comparative laminate before curing was photocured with an ultraviolet irradiation device at a peak illuminance of 400 mW / cm ² and an integrated light amount of 6000 mJ / cm ² (Oak company wavelength 350 nm) to obtain a laminate of Comparative Example 7.

(2-9) Comparative Example 8
The comparative composition of Comparative Example 2 described in Table 2 was coated on a PET release film, another PET release film was bonded, and the thickness of the pressure-sensitive adhesive composition was 0.1 mm using a 0.15 mm spacer. The laminate before curing was obtained by adjusting to 15 mm.
The laminate before curing was cured with an ultraviolet irradiation device at a peak illuminance of 400 mW / cm ² and an integrated light amount of 6000 mJ / cm ² (Oak company wavelength 350 nm), and then cut to 60 × 80 mm to obtain an adhesive sheet.
After affixing the adhesive sheet on the glass substrate 1, the test piece obtained by adhering the glass substrate 2 through the adhesive sheet on the glass substrate 1 under reduced pressure is further applied to an autoclave (PBD-20 manufactured by Toto Tec Corporation). The laminated body of Comparative Example 8 was obtained by processing at atmospheric pressure 0.5 MPa, temperature 50 ° C., and time 30 minutes.

(3) Evaluation of lamination | stacking state About the laminated body of Examples 24-33 and 40 and the laminated body of Comparative Examples 3-8, it evaluated on the following references | standards using visual observation and a microscope.

(3-1) Composition flow-out after lamination About Examples 24-33,
The shortest position of the adhesive cured body or the comparative composition cured body in the laminate is
From the most extreme position of the compatible composition viscoelastic body formed on the glass substrate 1 or the comparative composition liquid tank,
◯ when there is no change, × when it spreads outside.

About Example 40, the adhesion state of the member 1 and the member 2 was visually observed.
In the case of the laminate of Example 40, the resin composition flowed from the part applied in Step 1 ′ and was bonded without flowing outward.

(3-2) Bubbles in the area of the adhesive cured body or the comparative composition cured body in the in-plane foam laminate,
○ when there was no, and × when there was.

(3-3) Step bubbles After each laminate is placed in an oven at 80 ° C. for 250 hours, the presence or absence of bubbles in the printing step is observed, and when there is no bubble on the printing step, ○, X.

1 slide glass 1 (member 1)
2 Slide glass 2 (member 2)
3 spacer 4 gel compatible composition 5 liquid compatible composition 6 glass substrate 1 (member 1)
7 Glass substrate 2 (member 2)
8 Shading printing part 9 Dispenser 1
DESCRIPTION OF SYMBOLS 10 Liquid compatible composition 11 Molding viscoelastic body 12 Adhesive hardening body 13 Laminated body 14 before hardening Laminated body 15 of Example 33 Ultraviolet irradiation apparatus

Claims (14)

A compatible composition in which a block copolymer compound and a medium are compatible,
The block copolymer compound is
A polymer block a mainly composed of (meth) acrylate units;
It is a block copolymer with a polymer block b mainly composed of (meth) acrylate units,
The glass transition temperature of the polymer composed only of (meth) acrylate units constituting the polymer block a is more than 50 ° C. and 180 ° C. or less,
The glass transition temperature of the polymer composed only of (meth) acrylate units constituting the polymer block b is -100 ° C or higher and 50 ° C or lower,
The block copolymer compound does not have a liquid-gel transition temperature (Tc) between 0-150 ° C,
The compatible composition has a liquid-gel transition temperature (Tc) between 0 ° C. and 150 ° C.   The compatible composition according to claim 1, wherein the gel-like compatible composition is dissolved in a solvent.   The compatible composition according to claim 1 or 2, wherein the gel-like compatible composition is an elastic body.   The compatible composition according to any one of claims 1 to 3, wherein the gel-like compatible composition has thixotropic properties.   Furthermore, the compatible composition of any one of Claims 1-4 which has at least 1 sort (s) of curability chosen from the group which consists of thermosetting, photocurability, and wet-curing property.   The adhesive composition formed by mix | blending the compatible composition of any one of Claims 1-5. A composite structure including member 1 and member 2,
The composite structure which the said member 1 and the said member 2 adhere | attached through the adhesive composition of Claim 6. The member 1 and the member 2 are plates,
The composite member 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.   The one member of the member 1 and the member 2 is a liquid crystal display panel, an organic EL display panel, a protective panel, a touch panel, glass or a plastic plate, and the other member is a light transmissive member. 8 composite structures. A method of manufacturing a composite structure including member 1 and member 2,
In a temperature environment higher than the temperature Tc according to claim 1,
Step 1 for laminating the member 1 and the member 2 via the adhesive composition;
The manufacturing method of the composite structure which has the process 2 which obtains the composite structure of any one of Claims 7-9 after making the said temperature environment into the temperature environment lower than the said temperature Tc after the said process 1. FIG.   Furthermore, the process of making the solvent of Claim 2 contact the said adhesive composition, and releasing the adhesion | attachment through the said adhesive composition of the said member 1 and the said member 2 is included of Claim 10. A method for manufacturing a composite structure.   The adhesive composition of the member 1 and the member 2 by contacting the adhesive composition with the solvent according to claim 2 and / or setting the temperature environment to 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 member 1 and the member 2 are separated from each other by releasing the adhesion via the contact. A method of manufacturing a composite structure including member 1 and member 2,
The manufacturing method is
In a temperature environment lower than the temperature Tc according to claim 1,
The process 1 'which bonds the said member 1 and the said member 2 through the adhesive composition of Claim 6 formed by mix | blending the compatible composition of any one of Claims 3-5,
The composite structure according to any one of claims 7 to 9, wherein after the step 1 ', the adhesive composition is cured at least one selected from the group consisting of heat curing, light curing, and wet curing. A process for producing a composite structure comprising the step 2 ′ of obtaining A method of manufacturing a composite structure including member 1 and member 2,
The manufacturing method is
The adhesive composition according to claim 6, which is formed by blending the compatible composition according to claim 3, and at least one curing selected from the group consisting of thermosetting, photocuring and wet curing. 1) to obtain a cured adhesive body by
The manufacturing method of the composite structure which has the process 2 '' which bonds the said member 1 and the said member 2 through the said adhesion hardening body, and obtains the composite structure of any one of Claims 7-9.