JP6856935B2 - Method for producing complex and gel composition - Google Patents

Description

The present invention relates to a method for producing a complex in which a member 1 and a member 2 are bonded together via a bonding material, and a gel-like composition used in the method for producing the composite.

A composite such as an optical display device includes, for example, a bonded body in which a display panel member and a transparent surface member are bonded via an adhesive layer, and an adhesive tape used for the adhesive layer for bonding these. , Curable liquid resin compositions and the like have been proposed (for example, Patent Documents 1 and 2).

JP-A-2017-110127A WO2015 / 087807

However, when manufacturing a bonded body in which a plurality of liquid crystal display panel members are laminated, a decorative portion, printing, an FPC (flexible printed circuit board) connection portion, a bezel, a housing, etc. are placed on the surface of the member or on one or both of the members. Since they are arranged in the periphery, members having different height portions that form different heights with respect to the surface of the members may be bonded together.

Using an adhesive sheet as an adhesive layer for a member having such different heights has advantages such as uniform thickness, simple manufacturing process, and less contamination of other members, but the surface of the adhesive sheet has different heights. Unevenness derived from the part occurs and the smoothness is impaired and the bonding between members is not stable, air bubbles are likely to remain in the vicinity of the different height part, stress and distortion are likely to occur, it is difficult to repair the adhesive sheet, and the thin adhesive sheet There are problems such as difficulty in handling.

When a curable liquid resin composition is used as an adhesive layer of a member having such a different height portion, unevenness that leads to non-uniformity of the surface shape derived from the different height portion is unlikely to occur, so that the members can be bonded to each other. It has advantages such as stability and reduction of residual air bubbles near the stepped portion, but since the liquid composition flows out from the bonding range at the time of bonding, it contaminates other members around the bonded body and is a curable liquid resin during transportation. There is a problem such as misalignment in which the composition is not sufficiently cured and the positions of the members of the bonded body are displaced.

The present invention is a method for producing a composite including a bonded body in which a member 1 and a member 2 having different height portions on at least one of the surfaces are bonded with a bonding material having an interface with the surface. Therefore, while suppressing the occurrence of contamination of other members and misalignment during transportation, the surface S1 of the member 1 and the surface S2 of the member 2 and the surface of the bonded material are different from each other at the interface near the different height portion or the surface of the bonded body. A gel-like composition is used as the bonding material, which is less likely to cause irregularities that lead to non-uniformity of the surface shape derived from the high portion, so that the bonding between the members is stable, and more preferably, the residue of air bubbles can be suppressed. An object of the present invention is to provide a method for producing a composite and a gel-like composition used in the production method.

The present invention
[1] A composite including the member 1, the laminating material, and a laminated body in which the laminating material 2 is laminated, which is obtained by laminating the surface S1 of the member 1 and the surface S2 of the member 2 via a laminating material. It is a manufacturing method of
The laminating material is a gel-like composition having a liquid-gel transition temperature (Tc) at 0 to 150 ° C.
At least one of the surface S1 and the surface S2 has a different height portion, and the surface S1 and the surface S2 are provided with different height portions.
A step of arranging a laminating material between the surface S1 and the surface S2 so as to cover the different height portion with the laminating material to obtain a laminate of the member 1, the laminating material, and the member 2. 1 and
Including the step 2 of pressurizing and heating the laminate in a temperature range of Tc or higher and / or pressurizing and heating in a temperature range of Tc-30 to Tc + 30 ° C. in an autoclave.
In the steps 1 and 2, a method for producing a complex in which the temperature of the bonding material is less than Tc except during the pressure heating (hereinafter, also referred to as “the present invention 1”), and [2] the preceding paragraph [2]. 1] The gel-like composition according to the previous item [1] (hereinafter, also referred to as "the present invention 2") used in the method for producing the complex according to the above.

According to the present invention, a method for producing a composite including a bonded body in which a member 1 and a member 2 having different height portions on at least one of the surfaces are bonded with a bonding material having an interface with the surface. Therefore, while suppressing the occurrence of contamination of other members and misalignment during transportation, the surface S1 of the member 1 and the surface S2 of the member 2 and the surface of the bonded material near the different height portion of the bonded material are on the interface or the surface of the bonded body. As a bonding material, a gel-like composition is used as a bonding material, which is less likely to cause irregularities that lead to non-uniformity of the surface shape derived from different heights, so that bonding between members is stable, and more preferably, residual air bubbles can be suppressed. It is possible to provide a method for producing a composite to be used and a gel-like composition to be used in the production method.

Comparison of Leveling Example 5 ((a)) and Comparative Example ((b)). Comparison of Example 5 ((a) (b)) with low bubble persistence and Comparative Example ((p) (q)).

[Complex and bonding]
The present invention 1 describes, for example, a liquid crystal display panel; an organic EL display panel; a protective panel; a touch panel; a sensor such as an ambient light sensor, a proximity sensor, a fingerprint sensor, and an authentication sensor; a camera; a glass or plastic plate; Examples include information display devices such as liquid crystal displays, organic EL displays, touch panel displays, etc., which are composites having bonded members, and further, composites including these information display devices and other electronic elements. Examples thereof include mobile electronic terminals such as electronic notebooks, mobile phones, smartphones, portable audio players, mobile information terminals (PDAs) and tablet terminals, and information processing devices such as personal computers, TVs and car navigation systems.

The above-mentioned bonded body corresponds to further miniaturization, thinning, and high information delicacy of the composite, and members of various materials are used.
For example, when a transparent protective panel is attached to protect an information display module such as an LCD module or an organic EL module, a glass panel has been conventionally used as the protective panel. In recent years, base materials such as resin films and resin plates have been used to reduce the weight of electronic devices.
In addition, for example, in the display field in recent years, due to technological advances such as weight reduction, thickness reduction, and resinification of displays, development of displays that are hard to break even if dropped, displays that can be folded and wound, displays that can be stretched, and the like. Is underway.
Examples of the foldable display include a liquid crystal display, an organic EL display, an electronic paper, and the like, and these are manufactured as a bonded body in which members such as a touch panel, a protective film, and a polarizing plate are bonded to a display substrate.

Considering the above-mentioned bonded bodies and complexes, the size of the bonded bodies is
It is preferably a size contained in a rectangular parallelepiped region having a length of 5 to 3000 mm, a width of 5 to 3000 mm, and a thickness of 0.5 to 100 mm.
More preferably, it is a size contained in a rectangular parallelepiped region having a length of 10 to 2000 mm, a width of 10 to 2000 mm, and a thickness of 1 to 70 mm.
More preferably, it is a size contained in a rectangular parallelepiped region having a length of 20 to 1000 mm, a width of 20 to 1000 mm, and a thickness of 2 to 50 mm.

[Different height part]
The member 1 and the member 2 in the present invention 1 are provided with different height portions on the surface of at least one member. In the case of a display board, the extra-height portion may include a decorative portion attached to the surface of at least one member, a printed circuit board, an FPC connection portion, a bezel, a convex portion of a housing, and the like. it can.

In the present invention 1, the maximum of the surface of the member having the different height portion, the plane surrounded by the boundary line of the different height portion, and the intersection surface (including the intersection point) of the different height portion cut out by the plane parallel to the plane. The distance (hereinafter referred to as "height of the different height portion") is preferably 0.001 to 5 mm, more preferably 0.005 to 3 mm, still more preferably 0.01 to 2 mm, still more preferably 0.01 to 1 mm. is there.

The material of the predetermined surface of the member 2 to be bonded to the surface S having the different height portion of the member 1 and the surface S of the member 2 is glass, PET, or the like in consideration of the adhesiveness of the gel-like composition described later. TAC, COP, polyimide, PMMA, polycarbonate, vinyl chloride, PVA, polyethylene, polypropylene, silicon, graphite, aluminum, copper, SUS, etc. are preferable, and the surface of the member is treated with an organic hard coat layer or an inorganic hard coat layer. Also, a transparent conductive material such as ITO, IZO, or carbon nanotube may be treated in order to have conductivity, and a metal such as silver or copper may be patterned on the surface as an electrode or wiring material. ..

The material of the different height portion of the member 1 is glass, PET, TAC, COP, polyimide, PMMA, polycarbonate, vinyl chloride, PVA, polyethylene, polypropylene, silicon, graphite, in consideration of the adhesiveness of the gel-like composition described later. Aluminum, copper, SUS, epoxy resin, acrylic resin, other ink materials, etc. are preferable, and an organic hard coat layer or an inorganic hard coat layer may be treated on the surface of the member, and ITO or IZO is used to provide conductivity. , A transparent conductive material such as carbon nanotube may be treated, a metal such as silver or copper may be patterned on the surface as an electrode or a wiring material, or a pigment or a dye may be contained as a coloring. ..

[Gel-like composition]
The gel-like compositions according to the present inventions 1 and 2 are obtained from the viewpoint of leveling property and low residual air bubbles.
It has a liquid-gel transition temperature (Tc) from 0 to 150 ° C.
The storage rigidity of the gel-like composition is
When 30 ° C. <Tc, it is 25 ° C., and when 0 ° C. ≦ Tc ≦ 30 ° C., it is Tc-20 ° C., which is 0.01 to 10000 kPa.
The measurement of Tc and the storage rigidity is performed under the conditions described in the examples.

When the gel-like composition has a liquid-gel-like transition temperature (Tc) from 0 to 150 ° C., it means that the gel-like composition is a physically crosslinked gel.

In general, a gel-like composition is a substance in which the fluidity of the entire composition is greatly reduced because the compounds constituting the composition are crosslinked and the thermal motion of each compound is suppressed, and the structure and life of the crosslinks are significantly reduced. It is classified into a chemically crosslinked gel and a physically crosslinked gel.
A chemically crosslinked gel is a gel that is covalently crosslinked, and the bond is not broken by the thermal motion of the constituent compounds, and the crosslinking life is substantially infinite. The linked structure (topological three-dimensional structure) of the chemically crosslinked gel remains unchanged at the time the gel was formed. on the other hand,
A physically crosslinked gel is a gel that is crosslinked by non-covalent bonds such as hydrogen bonds, hydrophobic agglomerations, and ionic bonds, and has Tc (also called a thermoreversible gel) because the crosslinks are formed and disappeared due to temperature changes. ..

From the viewpoint of leveling property and low residual air bubbles, the suitable gel-like composition applicable to the present inventions 1 and 2 is preferably a physically crosslinked gel even if it is partially chemically crosslinked, and is chemically crosslinked. It is more preferable that the gel is not physically crosslinked.

The gel-like composition applicable to the present inventions 1 and 2 has a storage rigidity of such a physically crosslinked gel composition in a gel state of 25 ° C. when <Tc is 30 ° C., and 0 ° C. ≤ Tc ≤ 30 ° C. In the case of Tc-20 ° C., it is 0.01 to 10000 kPa, so that leveling property and low residual air bubbles are suitably ensured.

When the gel-like composition has Tc, it means that the gel-like composition is in a gel state (that is, a gel-like composition) in which the gel-like composition becomes liquid above Tc and does not naturally flow below the temperature Tc.

From the viewpoint of leveling property and low residual air bubbles, the gel-like composition preferably has Tc in the range of 10 to 100 ° C., more preferably 20 to 90 ° C., and further preferably 30 to 80 ° C. Have.

When the storage rigidity of the gel-like composition is in the above range, the following effects are obtained:
In step 1, when the surface S is coated with the gel-like composition at a temperature of less than Tc to obtain a laminate of the member 1 and the gel-like composition, the gel-like composition is formed into a sheet on the surface S. However, it is not fluid enough to flow out to other members and contaminate it, and the gel-like composition itself is flexible, so that voids that cause residual bubbles are less likely to occur around the different heights. effect;
In step 2, the gel-like composition in the laminate is heated to a temperature of Tc or higher, so that the gel-like composition becomes liquid, and in step 1, the unevenness of the gel-like composition derived from the different height portion under the coating Is generated, the unevenness of the gel-like composition is leveled to obtain a smooth outer surface of the gel-like composition, and residual bubbles are unlikely to be generated in step 1 or are easily removed even if they are generated. The effect of being able to.

Examples of suitable gel-like compositions applicable to the present inventions 1 and 2 include the following.
(1) A compatible composition in which a specific (meth) acrylate-based block copolymer compound and a medium are compatible with each other (hereinafter, also referred to as “composition X1”);
(2) A compatible composition in which a specific graft copolymer compound and a medium are compatible with each other (hereinafter, also referred to as "composition X2"); and (3) a specific styrene-based block copolymer compound and a medium. (Hereinafter, also referred to as “composition X3”); and (4) a composition obtained by adding a rheology modifier to a liquid medium having no Tc (hereinafter, “composition X3”). Composition X4 ").

(1) Composition X1
<Compatible composition suitable as composition X1>
As the composition X1,
A compatible composition in which a block copolymer compound and a medium are compatible with each other.
The block copolymer compound is
Polymer block a mainly composed of (meth) acrylate units and
It is a block copolymer with a polymer block b mainly composed of (meth) acrylate units.
The glass transition temperature of the polymer composed of only the (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 of only the (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) above 25 ° C. and 150 ° C. or lower.
Examples of the compatible composition include a compatible composition having a liquid-gel transition temperature (Tc) at a temperature of more than 25 ° C. and 150 ° C. or lower.

A preferred embodiment of the composition X1 is described in detail in JP-A-2017-66368, but a more preferred embodiment will be described in the present invention 1. The same terms as those described in JP-A-2017-66368 mean the same contents as those described in JP-A-2017-66368. In JP-A-2017-66368, the block copolymer compound is compound A and the medium is compound. It is described as B, and is also described in the present specification.

As the (meth) acrylate compound that can form 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, n-octyl. Alkyl (meth) acrylates such as (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate;
Alkoxy-substituted alkyl (meth) acrylates such as methoxyethyl (meth) acrylate and phenoxyethyl (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, 1,6-hexanediol di (meth) acrylate; and dicyclopentenyloxyethyl (meth) acrylate, norbornene (meth) acrylate, dicyclopentanyl (meth). Selected from the group consisting of alicyclic structure-containing (meth) acrylates such as acrylates, isobornyl (meth) acrylates, cyclohexyl (meth) acrylates and 4-tert-butylcyclohexyl (meth) acrylates, and acrylamides such as acryloylmorpholine and diethylacrylamide. At least two compounds
More preferably
A combination of methyl methacrylate (methyl methacrylate) and n-butyl acrylate (butyl acrylate).
Based on the Tg shown when each compound independently constitutes a polymer, it is used as a constituent unit of the polymer block a or the polymer block b.

The polymer block a is preferably composed of only (meth) acrylate units, but the block copolymer compound does not have a liquid-gel transition temperature (Tc) at 0 to 150 ° C., which will be described later. As long as the compatible 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 of only (meth) acrylate units, but the block copolymer compound does not have a liquid-gel transition temperature (Tc) at 0 to 150 ° C. and will be described later. As long as the compatible 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 block copolymer compound are considered to have substantially the same polymerization structure as the polymers a and b, respectively, the glass transition point of the block copolymer compound is the polymer a and b. It is preferable to have the glass transition temperature in the temperature range including the glass transition point of the above, that is, the temperature range of more than 50 ° C. and 180 ° C. or lower and the temperature range of -100 ° C. or higher and 50 ° C. or lower. The glass transition point is measured under the conditions described in the examples.

The block copolymer compound is used from the viewpoint of the liquid-gel transition property of the compatible composition described later.
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.
It is more preferable that it is composed only of a triblock structure,
At 0-150 ° C, the block copolymer compound does not have a liquid-gel transition temperature (Tc).
As long as 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 block copolymer compound is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, still more preferably 99 to 100 mol%.

As the block copolymer compound, a commercially available product "KURARITY" (registered trademark, Kuraray Co., Ltd.) (for example, LA2140, LA2250, LA4285, LA2330, LA2270, LA1114, LA1892) can be used.

The block copolymer compound is a block copolymer of the polymer block a and the polymer block b from the viewpoint of improving the elasticity and adhesiveness of the gel-like compatible composition and the viscoelastic body of the compatible composition, which will be described later. Reactivity is further imparted by having at least one reactive functional group selected from the group consisting of radical reactive groups, cationic reactive groups, anionic reactive groups and moisture reactive groups at the terminal or side chain of. Is preferable. Suitable embodiments of these reactive groups are described in JP-A-2017-66368.

The medium in the composition X1 is compatible with the block copolymer compound and has a liquid-gel transition temperature (Tc) at 0 to 150 ° C., which is also referred to as a compatible composition of the present invention (hereinafter, also referred to as a compatible composition). ) Is a compound.

As the medium, it is preferable to select a compound in which the compatible composition with the block copolymer compound can have fluidity as a guide, and the (meth) acrylate-based monomer, the (meth) acrylamide-based monomer, and the like are not radically polymerizable. It may be a saturated bond-containing monomer, a plasticizer, a solvent, or the like.

As a monomer compound in which the compatible composition with the block copolymer compound 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, n-octyl. Alkyl (meth) acrylates such as (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate; methoxyethyl (meth) acrylate, phenoxy. Alkoxy-substituted alkyl (meth) acrylates such as ethyl (meth) acrylates; hydroxy-substituted alkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylates, 2-hydroxypropyl (meth) acrylates and 2-hydroxybutyl (meth) acrylates. 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, Di (meth) acrylates such as 1,4-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate; 4-tert-butylcyclohexyl acrylate, dicyclo Alicyclic structure-containing (meth) acrylates such as pentenyloxyethyl (meth) acrylates, norbornene (meth) acrylates, dicyclopentanyl (meth) acrylates, isobornyl (meth) acrylates, cyclohexyl (meth) acrylates, etc. At least one compound selected from the group consisting of (meth) acrylamide such as morpholine and diethyl (meth) acrylamide,
More preferably, it is at least one compound selected from the group consisting of isodecyl acrylate, 4-hydroxybutyl acrylate and 4-tert-butylcyclohexyl acrylate.

As a plasticizer in which the compatible composition with the block copolymer compound can have fluidity,
Preferably, phthalates 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-cyclohexanedicarboxylic acid;
Alkyl benzoate;
Phosphate esters such as tricresyl phosphate and tributyl phosphate;
Trimellitic acid ester;
Rubber-based polymers such as (hydrogenated) polyisoprene, hydroxylated (hydrogenated) polyisoprene, (hydrogenated) polybutadiene, hydroxylated (hydrogenated) polybutadiene, polybutene;
Thermoplastic elastomer;
Petroleum resin;
Alicyclic saturated hydrocarbon resin;
Terpene resins such as terpene resin, terpene phenol resin, modified terpene resin, hydrogenated terpene resin;
Rosin resin such as rosin phenol;
Rosin ester-based resins such as disproportionate rosin ester-based resins, polymerized rosin ester-based resins, and hydrogenated rosin ester-based resins;
Xylene resin; and at least one compound selected from the group consisting of acrylic resins such as acrylic polymers and acrylic copolymers.
More preferably, it is at least one compound selected from the group consisting of polyvalent carboxylic acid esters and rosin ester-based resins.

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

The viscosity of the medium may be within the range in which the compatible composition of the present invention having a liquid-gel transition temperature (Tc) at 0 to 150 ° C. can be produced by being compatible with the block copolymer compound.
From the viewpoint of easily producing a compatible composition with a block copolymer compound, the viscosity of the medium is determined.
It is preferably 0.001 to 10 Pa · s, more preferably 0.001 to 1 Pa · s, and even more preferably 0.001 to 0.5 Pa · s.

Even if the medium is an oligomer or the like and has a high viscosity or a solid in an environment lower than the temperature Tc, the viscosity becomes lower in an environment higher than the temperature Tc, or is dissolved in another medium having a low viscosity, or a solvent. Since they are dissolved in, they can be combined and kneaded with a block copolymer compound to produce a compatible composition.

The compatible composition in which the block copolymer compound and the medium are compatible is 0 to 150 ° C., and the block copolymer compound does not have a liquid-gel transition temperature (Tc), and is a compatible composition. Is a composition having a liquid-gel transition temperature (Tc).

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

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

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

Temperature Tc is
If the block polymer a is composed of (meth) acrylate units having a high Tg of the polymer a, or if the mixing ratio of the medium is reduced, the high temperature side can be set.
The low temperature side can be set by forming the block polymer a in units of (meth) acrylates having a low Tg of the polymer a or by increasing the blending ratio of the medium.

The compatible composition preferably has 100 parts by mass of compound A and preferably 100 parts by mass of compound B from the viewpoint of coatability to members in liquid state, adhesion between members in gel form, and phase transition. It is 200 to 1000 parts by mass, more preferably 250 to 800 parts by mass.

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

When the compatible composition is a viscoelastic body of the compatible composition, the 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 to 7.5% by mass.

<Compatible composition viscoelastic body suitable as composition X1>
The compatible composition is a compound A (preferably, a compound A further imparted with reactivity) or a compound from the viewpoint of improving the elasticity and adhesiveness of the gel-like compatible composition and the compatible composition at the time of curing. As B, a reactive compound having at least one reactivity selected from the group consisting of radical-reactive, cationic-reactive, anionic-reactive and moisture-reactive (preferably further in combination with a plasticizer) and a polymerization initiator. It is preferably contained (hereinafter, compound A (preferably, compound A further imparted with reactivity), and compound B is at least selected from the group consisting of radical reactivity, cation reactivity, anion reactivity and moisture reactivity. A gel-like compatible composition containing a reactive compound having one kind of reactivity (preferably further in combination with a plasticizer) and a polymerization initiator is also referred to as a compatible composition viscoelastic body).

The viscoelastic body of the compatible composition preferably has elasticity and strength suitable for forming a sheet with the compatible composition (hereinafter, these are also collectively referred to as viscoelastic properties), and such viscoelastic properties. The viscoelastic body of the compatible composition having the above can be used as a suitable pressure-sensitive adhesive sheet for bonding the surface S1 and the surface S2 having different height portions.

The suitable physical properties of the compatible composition viscoelastic body of the composition X1 described below are also the suitable physical properties of the compatible composition viscoelastic body of the compositions X1, X2 and X3 and the composition Y.

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

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

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

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

《Dumbbell test》
(1) Soluble Composition A viscoelastic body is liquefied at a temperature of Tc + 20 ° C. and then poured into a dumbbell mold and cooled to a temperature lower than the temperature of Tc (actually at room temperature) to prepare a dumbbell test piece having a thickness of 1 mm.
(2) The dumbbell test piece is pulled with a tensile tester (Minebea technograph, TG-2 kN) at a tensile speed of 10 mm / min, and the elongation rate and breaking strength are read from the measurement results.

Due to this adhesiveness of the compatible composition viscoelastic body, for example, when the adhesive sheet is formed, the adhesive sheet can be stably attached to the surface of the member, so that the surfaces S1 and S2 are stable in step 1. Can be pasted together.

Further, 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, and the layer of the compatible composition viscoelastic body is heat-cured, photo-cured and wet-cured. By curing at least one selected from the group consisting of the above to obtain a cured product having no liquid-gel transition temperature (Tc), the layer of the cured compatible composition viscoelastic body has a temperature of Tc or higher. It remains a non-fluid viscoelastic body even in a high temperature environment, and a durable bonded body can be produced.

(2) Composition X2
<Compatible composition suitable as composition X2>
As the composition X2,
A compatible composition in which a graft copolymer compound and a medium are compatible with each other.
The graft copolymer compound is
Polymer block a mainly composed of (meth) acrylate units and
It is a graft copolymer compound with a polymer block b mainly composed of a (meth) acrylate unit.
The glass transition temperature of the polymer composed of only the (meth) acrylate units constituting the polymer block a is more than 30 ° C. and 180 ° C. or lower.
The glass transition temperature of the polymer composed of only the (meth) acrylate units constituting the polymer block b is −100 ° C. or higher and 30 ° C. or lower.
The graft copolymer compound has no liquid-gel transition temperature (Tc) at 0-150 ° C.
Examples of the compatible composition include a compatible composition having a liquid-gel transition temperature (Tc) at 0 to 150 ° C.

The (meth) acrylate unit constituting the polymer block a is a polymer (meth) acrylate compound having a glass transition temperature of more than 30 ° C. and 180 ° C. or lower of a polymer (hereinafter referred to as polymer a) composed of the polymer block a alone. It is formed when it is polymerized. 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 further preferably 1 × 10 ⁵ to 1. it is a 1 × 10 ^7.

The (meth) acrylate unit constituting the polymer block b is a (meth) acrylate compound in which the glass transition temperature of the polymer (hereinafter referred to as polymer b) composed of the polymer block b is -100 ° C. or higher and 30 ° C. or lower. 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 further preferably 1 × 10 ⁵ to 1. it is a 1 × 10 ^7.

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

As the (meth) acrylate compound that can form 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, n-octyl. Alkyl (meth) acrylates such as (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate;
Alkoxy-substituted alkyl (meth) acrylates such as methoxyethyl (meth) acrylate and phenoxyethyl (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, 1,6-hexanediol di (meth) acrylate; and dicyclopentenyloxyethyl (meth) acrylate, norbornene (meth) acrylate, dicyclopentanyl (meth). Selected from the group consisting of alicyclic structure-containing (meth) acrylates such as acrylates, isobornyl (meth) acrylates, cyclohexyl (meth) acrylates and 4-tert-butylcyclohexyl (meth) acrylates, and acrylamides such as acryloylmorpholine and diethylacrylamide. At least two compounds
More preferably, at least one of them is a methacrylate compound.

Based on the Tg shown when each compound independently constitutes a polymer, it is used as a constituent unit of the polymer block a or the polymer block b.

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

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 of only (meth) acrylate units, but the compound A does not have a liquid-gel transition temperature (Tc) at 0 to 150 ° C., and is a compatible compound described later. It is a polymer structure mainly composed of (meth) acrylate units, which is allowed to contain other copolymerizable compound units as long as it has a liquid-gel transition temperature (Tc).

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 substantially the same polymerization structure as the polymers a and b, respectively, the glass transition point of the compound A includes the glass transition point of the polymers a and b. It is preferable to have a glass transition temperature in a temperature range of more than 30 ° C. and 180 ° C. or lower and a temperature range of -100 ° C. or higher and 30 ° C. or lower.

The graft copolymer compound is a graft copolymer of the polymer block a and the polymer block b.
For example, the polymer block a has a structure in which (meth) acrylate units are linearly bonded, and at least one of the constituent units of the polymer block a is further bonded to the (meth) acrylate unit constituting the polymer block b. It has a structure in which the polymer block b is bonded so as to be branched from the polymer block a.

When the polymer block b is bonded to each of the plurality of structural units of the polymer block a, the polymer block a is referred to as a trunk, and each polymer block b is referred to as a branch.

The graft copolymer compound may be a graft copolymer having a polymer block a as a trunk and a polymer block b as a branch, or a graft copolymer having a polymer block b as a trunk and a polymer block a as a branch. Good.

The graft copolymer compound, for example, previously preparing polymer blocks a, polymer and acrylate units a _e which constitute the ends of the blocks a and (meth) acrylate units b _e copolymerized, (meth) acrylate stem is sometimes composed of a copolymer of units b _e a (meth) acrylate units a _e.
In this case, in the stem of the (meth) acrylate unit a _e (meth) were replaced with acrylate units b _e a (meth) polymer of acrylate units b _e deemed polymer block b, a polymer block a (meth) regarded as branch portions of the polymer block a excluding the acrylate units a _e.

When the branch is composed of the polymer a, the compatible composition described later has a number average molecular weight of 3,000 to 100,000, preferably 5,000 to 50,000 by the GPC method from the viewpoint of liquid-gel transition, and the glass transition. The temperature is more than 30 ° C. and 180 ° C. or less, preferably more than 40 ° C. and 180 ° C. or less, more preferably more than 50 ° C. and 180 ° C. or less, and more preferably one end of the branch is preferably more than 60 ° C. and 180 ° C. or less, (meth). It has an acryloyl group, preferably a methacrylate unit, more preferably a methacrylate unit such as a methyl methacrylate unit (MMA) (however, a small amount of vinyl monomer units such as methacrylic acid, acrylic acid ester, and acrylonitrile may be contained). Consists of.

When the stem is composed of the polymer b, the liquid phase-soluble composition described later has a number average molecular weight of 5,000 to 20000, preferably 1000 to 150,000 according to the GPC method from the viewpoint of liquid-gel transition, and is glass. The transition temperature is -100 ° C or higher and 30 ° C or lower, preferably -100 ° C or higher and 20 ° C or lower, more preferably -100 ° C or higher and 10 ° C or lower, further preferably -100 ° C or higher and 0 ° C or lower, and preferably ethyl acrylate. At least one (meth) acrylate unit selected from the group consisting of units (EA), n-butyl acrylate units (nBA) and lauryl methacrylate units (LMA), more preferably ethyl acrylate units (EA) and / or n- It is composed of butyl acrylate units (n-BA).

The total number of moles N of the graft copolymer compound was calculated from N = W / M from the total amount W of the graft copolymer compound and the number average molecular weight (weight average molecular weight) M.
The total amount w _a and the number average molecular weight of pre-synthesized polymer blocks a constituting the branches and a (weight average molecular weight) m _a, the total number of moles n _a polymer block a in n _{a =} w a _/ m _a Calculate,
The number _{n x} of the branch number-average molecular weight (weight average molecular weight) _{m b} and stem 1 per this polymer block b constituting a single _{stem, m b + n x · m} a = M, n x = n a / It may be defined as N, _mb may be calculated, and this may be used as the number average molecular weight (weight average molecular weight) of the polymer block b.

From the viewpoint of the liquid-gel transition property of the compatible composition described later, the mass ratio (a / b) of the polymer block a and the polymer block b constituting the graft copolymer compound is preferably 5 to 95 /. It is 95 to 5, more preferably 10 to 90/90 to 10, and even more preferably 15 to 85/85 to 15.

From the viewpoint of the liquid-gel-like transition property of the liquid phase-soluble composition described later, the weight average molecular weight of the graft copolymer compound is preferably 8000 to 30000, more preferably 1500 to 280000, and further preferably 30,000 to 250,000.

The graft copolymer compound can be obtained, for example, by the production method described in JP-A-5-170838 and JP-A-6-234822. For example, a commercially available product of Mitsubishi Rayon Co., Ltd. described in Table 1 can be obtained. Can be used.

<Compatible composition viscoelastic body suitable as composition X2>
From the same viewpoint as the compatible composition suitable as the composition X1, the compatible composition suitable as the composition X2 also improves the elasticity and adhesiveness of the gel-like compatible composition and the compatible composition at the time of curing. From this point of view, at least one reaction selected from the group consisting of compound A (preferably compound A further imparted with reactivity) and compound B as radical-reactive, cationic-reactive, anionic-reactive and moisture-reactive. It is preferable to contain a reactive compound having reactivity (preferably in combination with a plastic agent) and a polymerization initiator (hereinafter, compound A (preferably compound A further imparted reactivity), as compound B. It contains at least one reactive reactive compound (preferably further in combination with a plasticizer) selected from the group consisting of radical-reactive, cationic-reactive, anionic-reactive and moisture-reactive, and a polymerization initiator. A gel-like compatible composition is also referred to as a compatible composition viscoelastic body).

The medium in the composition X2 is a compatible composition of the present invention (hereinafter, also referred to as a compatible composition) which is compatible with the graft copolymer compound and has a liquid-gel transition temperature (Tc) at 0 to 150 ° C. ), And for example, the medium in the composition X1 can be preferably mentioned.

The compatible composition in which the graft copolymer compound and the medium are compatible is 0 to 150 ° C., and compound A does not have a liquid-gel transition temperature (Tc).
The compatible composition is a composition having a liquid-gel transition temperature (Tc).
It is preferable that the composition X1 has the same properties as the compatible composition.

The temperature Tc is
If the block polymer a is composed of (meth) acrylate units having a high Tg of the polymer a, or if the compounding ratio of the compound B is reduced, the high temperature side can be set.
The low temperature side can be set by forming the block polymer a in units of (meth) acrylates having a low Tg of the polymer a or by increasing the compounding ratio of the compound B.

The compatible composition is preferably 200 to 1000 parts by mass, more preferably 200 to 1000 parts by mass, based on 100 parts by mass of the graft copolymer compound, from the viewpoint of coatability and phase transition property when in liquid form. It is preferably 250 to 800 parts by mass.

When the compatible composition is a viscoelastic body of the compatible composition, the content ratio of the reactive compound in the medium is preferably 20 to 100% by mass from the viewpoint of viscoelastic properties suitable for durability and stress relaxation. It is more preferably 25 to 95% by mass, still more preferably 30 to 90% by mass.

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

(3) Composition X3
<Compatible composition suitable as composition X3>
As the composition X3,
A compatible composition in which a block copolymer compound and a medium are compatible with each other.
The block copolymer compound is
Polymer block a mainly composed of styrene compound units and
Alkene compounds, polymer block b ₁ mainly of units of at least one hydrocarbon compound selected from the group consisting of diene-based compound and an alkyne _compound, or (meth) polymer block composed mainly of acrylate units A compound having a block copolymer structure with b ₂
The glass transition temperature of the polymer composed of only the (meth) acrylate units constituting the polymer block b _{2 is −100 ° C. or higher and 50 ° C. or lower.}
Examples of the compatible composition include a compatible composition having a liquid-gel transition temperature (Tc) at 0 to 150 ° C.

Hereinafter, a compound having a block copolymer structure of a polymer block a and a polymer block b _{1 is referred to as a compound A 1, and a polymer block a and a polymer block b 2} mainly composed of a (meth) acrylate unit are used. A compound having a block copolymer structure is referred to as compound A ₂ .

The styrene-based compound unit constituting the polymer block a is formed when a styrene-based compound styrene and / or a vinyl group and a styrene derivative maintaining an aromatic ring structure are polymerized. Hereinafter, styrene or a derivative of styrene used for polymerization is referred to as a base compound.

As the styrene-based compound that can form the polymer block a, from the viewpoint of compatibility and liquid-gel transferability of the curable resin composition described later,
Preferably, styrene; alkyl group substituted styrenes such as α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, 4-tert-butylstyrene, 4-hexylstyrene; Hydroxyl group-substituted styrenes such as p-hydroxystyrene; alkoxy group-substituted styrenes such as p-methoxystyrene and 4-tert-butoxystyrene; amino group-substituted styrenes such as 4-aminostyrene; and 4-chlorostyrene and 4-bromostyrene. At least one styrene-based compound selected from the group consisting of halogen-substituted styrenes such as
More preferably, it is styrene.

The polymer block a is preferably composed of only styrene-based compound units, but other copolymerizable compound units as long as the curable resin composition described later has compatibility and liquid-gel transition. It is a polymer structure mainly composed of a styrene-based compound unit, which is allowed to contain.

The molar ratio of the styrene compound unit in the polymer block a is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, from the viewpoint of the liquid-gel transition property of the curable resin composition described later. More preferably, it is 99 to 100 mol%.

The weight average molecular weight is measured based on GPC, and is preferably measured under the following conditions (hereinafter, the same applies):
Measuring device: GPC system manufactured by Shimadzu Corporation;
Column type: Organic solvent-based SEC column (manufactured by Tosoh Corporation);
Solvent type: tetrahydrofuran (THF).

(3.1) Compound A ₁
The specific hydrocarbon compound unit constituting the polymer block b ₁ is formed when the specific hydrocarbon compound described later is polymerized.

The specific hydrocarbon compound that can form the polymer block b ₁ is a curable resin composition described later from the viewpoint of compatibility and liquid-gel transition.
The alkene compound is at least one compound selected from alkene such as ethylene and propylene and / or (co) polymers thereof and hydrogenated compounds thereof.
The diene compound is at least one compound selected from dienes such as butadiene and isoprene and / or (co) polymers thereof and hydrogenated compounds thereof.
The alkyne compound is at least one compound selected from the group consisting of alkynes such as acetylene and / or (co) polymers thereof and hydrogenated compounds thereof.
In addition, in this specification, a polymer or a copolymer is referred to as a "(co) polymer".

The specific hydrocarbon compound that can form the polymer block b ₁ is an aspect of the hydrogenated compound among the above-mentioned compounds from the viewpoint of compatibility and liquid-gel transition property of the curable resin composition described later. Is preferable.

In the above-mentioned suitable specific hydrocarbon compounds, from the same viewpoint,
The base alkene is preferably ethylene and / or propylene.
The base diene is preferably butadiene and / or isoprene.
The base alkyne is preferably acetylene.
In the present specification, for example, the alkene which is a component of "alkene", "alkene polymer" and "hydraulic additive of alkene polymer" is referred to as "base alkene".

In the above-mentioned suitable specific hydrocarbon compound, from the same viewpoint, the base hydrocarbon may be used.
It is preferably a diene and / or an alkyne, and more preferably a diene.
More preferably, it is at least one hydrocarbon compound selected from the group consisting of butadiene, isoprene and acetylene, and even more preferably butadiene and / or isoprene.

The polymer block b ₁ is preferably composed of only the specific hydrocarbon compound unit, but can be copolymerized as long as the curable resin composition described later has compatibility and liquid-gel transition. It is a polymer structure mainly composed of a specific hydrocarbon-based compound unit, which is allowed to contain the compound unit of.

From the viewpoint of compatibility and liquid-gel transferability of the curable resin composition described later,
The weight average molecular weight of polymer _{b 2} is preferably 1 × 10 ⁵ or more, more preferably 1 × ¹⁰ 5 to 1 × 10 ^9, and more preferably at 1 × ¹⁰ 5 to 1 × 10 ^7,
The molar ratio of the specific hydrocarbon compound unit in polymer block _{b 1} is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, more preferably 99 to 100 mol%.

From the viewpoint of compatibility and liquid-gel transition property of the curable resin composition, the _{weight average molecular weight of Compound A 1} is preferably 1000 to 500000, more preferably 30,000 to 400000, and further preferably 50,000 to 300,000.

From the viewpoint of compatibility and liquid-gel transition property of the curable resin composition, compound A ₁ is a compound.
Preferably polymer a triblock structure or a polymer block (a) and the polymer block b ₁ polymer block a is bonded to both ends of the block b ₁ is a di-block structure that binds, is a triblock structure Is more preferable.

From the viewpoint of compatibility and liquid-gel transferability of the curable resin composition described later,
Weight% of the polymer block a in the total mass of the polymer block (a) and the polymer block b ₁ is preferably higher.

Compatibility with the curable liquid resin composition to be described later - in terms of the gel metastatic, polymer block (a) and the total mole% of the polymer block b ₁ in the compound A is preferably 90 to 100 mol%, It is more preferably 95 to 100 mol%, still more preferably 99 to 100 mol%.

Bonding mode with the structure of the polymer block a of Compound A ₁ and polymer block b ₁ is described below curable resin composition is compatible with the liquid - may be selected to have a gel-like metastatic, eg, Table It can be selected from the commercially available products listed in 1.

In Table 2, Hybler, Septon, Clayton and Tough Tech are registered trademarks.
S is a styrene-based unit, B is a butadiene-based unit, I is an isoprene-based unit, and n-BA is an n-butyl acrylate-based unit.
“A” is the polymer block a, “b ₁ ” is the polymer block b ₁ , “b ₂ ” is the polymer block b ₂ , and “ab ₁ ” is the polymer block a and the polymer block b ₁ . The block copolymers "ab _1- a" and "ab _2- a" represent the polymer block a and the triblock copolymer of the polymer block b ₁ or b ₂ , respectively.

(3.2) Compound A ₂
The (meth) acrylate unit constituting the polymer block b ₂ is a (meth) acrylate in which the glass transition temperature of the polymer (hereinafter referred to as polymer b ₂ ) composed of the polymer block b 2 is -100 ° C. or higher and 50 ° C. or lower. It is formed when the compound is polymerized. In view of the stability of the glass transition temperature, the weight average molecular weight of polymer _{b 2} is preferably 1 × 10 ⁵ or more, more preferably 1 × ¹⁰ 5 to 1 × 10 ^9, more preferably 1 × 10 ⁵ is ~1 × 10 ^7.

As a (meth) acrylate compound capable of forming the polymer block b _2,
Preferably, methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, n-octyl. Alkyl (meth) acrylates such as (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate;
Alkoxy-substituted alkyl (meth) acrylates such as methoxyethyl (meth) acrylate and phenoxyethyl (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, 1,6-hexanediol di (meth) acrylate; and dicyclopentenyloxyethyl (meth) acrylate, norbornene (meth) acrylate, dicyclopentanyl (meth). Selected from the group consisting of alicyclic structure-containing (meth) acrylates such as acrylates, isobornyl (meth) acrylates, cyclohexyl (meth) acrylates and 4-tert-butylcyclohexyl (meth) acrylates, and acrylamides such as acryloylmorpholine and diethylacrylamide. Is a compound
More preferably, it is n-butyl acrylate (butyl acrylate).

From the viewpoint of compatibility and liquid-gel-like transition of the curable resin composition described later, the polymer block b ₂ is preferably composed of only (meth) acrylate units, but at 0 to 150 ° C. As long as compound A does not have a liquid-gel transition temperature (Tc) and the compatible compound described below has a liquid-gel transition temperature (Tc), it contains other copolymerizable compound units. Is an acceptable polymer structure mainly composed of (meth) acrylate units.

Later cured resin composition is compatible with the liquid - the molar ratio in terms of the gel metastatic polymer block b ₂ in the (meth) acrylate units, preferably 90 to 100 mol%, more preferably 95 It is ~ 100 mol%, more preferably 99-100 mol%.

Polymer blocks b ₂ in the compound A ₂ are polymer b ₂ and than believed to have substantially the same polymeric structure, the glass transition point of the compound A ₂ include the glass transition point of the polymer b ₂ Temperature It is preferable to have the glass transition temperature in a range, that is, a temperature range of −100 ° C. or higher and 50 ° C. or lower.
I.

Compound A ₂ has a liquid-to-gel transitional composition, which will be 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 _2.
It is more preferable that it is composed only of a triblock structure,
At 0-150 ° C, compound A has no liquid-gel transition temperature (Tc).
As long as the compatible composition described later has a liquid-gel transition temperature (Tc),
Structures other than tri-block structure (for example, di-block structure the polymer block (a) and the polymer block b ₂ are attached) may be included.

From the above viewpoint, _{the molar ratio of the triblock structure in Compound A 2} is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, still more preferably 99 to 100 mol%.

The compound A ₂ is a triblock structure (polymer block a-polymer block) commercially available from Alchema, which is a polymer block a having styrene as a unit and a polymer block b _{2 having n-butyl acrylate as a unit.} b ₂ -polymer block a) can be used.

From the viewpoint of compatibility and liquid-gel transition property of the curable resin composition, the _{weight average molecular weight of Compound A 2} is preferably 10,000 to 500,000, more preferably 30,000 to 400,000, and even more preferably 50,000 to 300,000.

(3.3) medium in the medium composition X3 is Compound _{A 1} or _{A 2} and compatibilized liquid at 0 to 150 ° C. - compatible composition in the composition _{X 3} having the gel transition temperature (Tc) It is a compound constituting (hereinafter, also referred to as a compatible composition), and for example, the medium in the composition X3 can be preferably mentioned.

(3.4) Compatible composition A compatible composition obtained by incompatible with compound A ₁ or A ₂ and a medium is a compatible composition.
At 0-150 ° C
Compound A ₁ or A ₂ has no liquid-gel transition temperature (Tc) and has no liquid-gel transition temperature (Tc).
The compatible composition is a composition having a liquid-gel transition temperature (Tc).
It is preferable that the composition X1 has the same properties as the compatible composition.

The compatible composition has a mass of 200 to 1000 parts by mass of the medium, preferably 200 to 1000 parts by mass, based on 100 parts by mass of _{the compound A 1} or A ₂ from the viewpoint of coatability and phase transition property when in liquid form. More preferably, it is 250 to 800 parts by mass.

<Compatible composition viscoelastic body suitable as composition X3>
From the same viewpoint as the compatible composition suitable as the composition X1, the compatible composition suitable as the composition X3 also improves the elasticity and adhesiveness of the gel-like compatible composition and the compatible composition at the time of curing. from the viewpoint of compound A ₁ or A _{2 (preferably,} reactivity was further granted compound A ₁ or A _2), a radical reactive as the compound B, a cationic reactive, the group consisting of anionic reactivity and moisture-reactive It is preferable to contain at least one reactive reactive compound selected from the above (preferably in combination with a plastic agent) and a polymerization initiator (hereinafter, compound A ₁ or A ₂ (preferably reactive). _{Compound A 1} or A ₂ ) to which is further added, and as compound B, a reactive compound having at least one reactivity selected from the group consisting of radical reactivity, cation reactivity, anion reactivity and moisture reactivity (preferably). Further, a gel-like compatible composition containing a combination with a plasticizer) and a polymerization initiator is also referred to as a compatible composition viscoelastic body).

When the compatible composition is a viscoelastic body of the compatible composition, the content ratio of the reactive compound in the medium is preferably 20 to 100% by mass, more preferably 25 to 95% by mass, from the viewpoint of viscoelastic properties. , More preferably 30 to 90% by mass.

When the compatible composition is a viscoelastic body of the compatible composition, the amount of the polymerization initiator added is preferably 1 to 10% by mass, more preferably 2 to 8% based on the total amount of the _{compound A 1} or A _{2 and the medium.} It is by mass, more preferably 2.5 to 7.5% by mass.

The compatible composition in the compositions X1, X2 or X3 can optionally contain an additive other than the medium as described later, as long as it does not impair the property of having a liquid-gel transition temperature (Tc). In that case, the blending amount of the additive other than the medium is preferably 0 to 50% by mass, more preferably 0 to 30% by mass, based on the total mass of the blend.

The compatible composition is, for example, an antioxidant, a wetting agent, a surfactant, an ionic liquid, a defoaming agent, an ultraviolet absorber, a light stabilizer, as long as the phase transition property and / or the viscoelastic property is not impaired. Additives such as various inorganic and organic fillers and polymers can be included.

The additive in the compatible composition refers to a combination of the additive blended in the compatible composition and the additive blended together with the compatible composition.

The compositions X1, X2 and X3 can be made transparent without the addition of a light-scattering compound such as a filler, preferably having a HAZE value of 1.0 or less at a thickness of 0.3 mm. Therefore, efficient light irradiation can be performed when the photocurability is utilized.

The HAZE value represents the ratio of the diffusion transmittance to the total light transmittance of the compatible composition, and the HAZE value is preferably 0.7 or less, more preferably 0.5 or less from the viewpoint of efficient light irradiation. , More preferably 0.3 or less, still more preferably 0.2 or less.
(4) Composition X4

As a medium that can be used when preparing the composition X4,
Aqueous media such as water, alcohol, acetic acid, formic acid, acetone, acetonitrile, ethylene glycol, glycerin;
Non-aqueous media such as benzene, toluene, xylene, diethyl ether, hexane, ethyl acetate and diethyl carbonate; and oil-based media such as fats and oils, mineral oils and petroleum-based solvents can be mentioned.
A rheology modifier having low reactivity can be added to these to give Tc, and the composition X4 can be obtained.

As a rheology adjuster, for example
Metal oxide particles such as silica, fumed silica, precipitated silica, asbestos powder, copper oxide, copper hydroxide, iron oxide, alumina, zinc oxide, lead oxide, magnesia, tin oxide, calcium carbonate, carbon, silica, mica , Smectite, carbon black and other inorganic fine particles;
Organic fine particles such as polystyrene beads, polyethylene particles, acrylic particles, polysiloxane resin particles, isoprene rubber particles, and polyamide particles;
Polymer compounds such as polyethylene, polysiloxane, polyacrylic, polyamide, polyvinyl alcohol, alkyl-modified cellulose, peptides, polypeptides; and amido wax, hydrogenated castor oil derivatives, 1,3,5-tris (trialkoxysilylalkyl) isocia. Examples thereof include organic compounds such as nurate, modified polyester polyol, ethyl cellulose, methyl cellulose, cellulose derivative, and organic bentonite.

More specifically, rheology modifiers include:
Organic compounds such as amidowax, hydrogenated castor oil, and 1,3,5-tris (trialkoxysilylalkyl) isocyanurate exemplified in JP-A-2017-066278; inorganic compounds such as fumed silica and carbon black;
Commercial products such as ethyl cellulose, BYK-405, 410, 411, 415, 420, 425, 420, 430, 431, etc. (Big Chemie Co., Ltd.), Disparlon thixotropic agent series (Kusumoto Kasei);
Polysiloxane, polyacrylic, polyamide, polyvinyl alcohol, alkyl-modified cellulose, peptides, polypeptides, and copolymers having two or more of these structures;
Organic fine particles such as polystyrene beads, polyethylene particles, acrylic particles, polysiloxane resin particles, isoprene rubber particles, and polyamide particles;
Metal oxide particles such as copper oxide, copper hydroxide, iron oxide, alumina, zinc oxide, lead oxide, magnesia, tin oxide, calcium carbonate, carbon, silica, mica, smectite exemplified in JP-A-2014-082328. Inorganic fine particles such as; and inorganic shaking agents such as fumed silica, precipitated silica, and asbestos powder, which are also referred to as shaking agents exemplified in JP-A-2014-019802; organic bentonite, modified polyester polyol, fatty acid amide, etc. Organic shaker; hydrogenated castor oil derivative, fatty acid amide wax, aluminum stearylate, barium stearylate, etc.

As the liquid medium having no Tc in the composition X4, the suitable mediums mentioned in the compositions X1 to 3 can be used.

As a rheology adjuster in composition X4,
Silica, fumed silica, precipitated silica, amide wax, hydrogenated castor oil derivative, and cellulose derivative are preferable.
Amido wax, hydrogenated castor oil derivative, cellulose derivative are more preferable,
Amido wax is more preferred.

(5) More Suitable Gel-like Composition The gel-like composition applied to the present inventions 1 and 2 is formed into, for example, a sheet, and the sheet-like gel-like composition is bonded to the sheet-like gel composition in step 2, and then the gel-like composition is prepared. Appropriate curing by moisture, heat or light makes the bonded state more stable and less likely to cause misalignment.

For example, with respect to Compound A and Compound B in the compositions X1, X2 and X3, the following aspects are suitable.

From the viewpoint of improving the elasticity and adhesiveness of the compatible composition at the time of curing, the compound A has a radical reactive group and a cation at the end or side chain of the block copolymer of the polymer block a and the polymer block b. It is preferable that the reactivity is further imparted by having at least one reactive functional group selected from the group consisting of a reactive group, an anionic reactive group and a moisture reactive group.

In the present specification, a reactive group that undergoes a polymerization reaction due to moisture (moisture) in the air is referred to as a moisture-reactive group, and the curable composition is cured by the polymerization reaction of the moisture-reactive group in the curable composition. Is called wet curing.

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

From the viewpoint of improving the elasticity and adhesiveness of the gel-like compatible composition and the compatible composition at the time of curing, the above-mentioned anionic reactive group is preferably at least one selected from the group consisting of epoxy, oxetane and vinyl ether. It is an anionic reactive group of the species.

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

Compound B is at least one reaction selected from the group consisting of radical reactivity, cation reactivity, anion reactivity and moisture reactivity from the viewpoint of improving the strength, elasticity and adhesiveness of the compatible composition at the time of curing. It is preferable to use a reactive compound having a property.

From the viewpoint of improving the strength, elasticity and adhesiveness of the gel-like compatible composition and the compatible composition at the time of curing, the radical-reactive compound in Compound B is selected 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) acrylate and urethane (meth) acrylate (preferably bifunctional or higher polyfunctional from the viewpoint of radical reaction rate and stability). It is a reactive compound having.

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

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

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

From the viewpoint of improving the strength, elasticity and adhesiveness of the gel-like compatible composition and the compatible composition at the time of curing, it is preferable.
A combination of compound A having a radical-reactive group and compound B which is a radical-reactive compound,
A combination of compound A having a cationically reactive group and compound B which is a cationically reactive compound,
Combination of compound A having an anionic reactive group and compound B which is an anionic reactive compound, and
A compatible composition is composed of at least one combination selected from the group consisting of a combination of a compound A having a moisture-reactive group and a compound B which is a moisture-reactive compound.

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

When the reactive compound is a radical reactive compound, the polymerization initiator may be used as a polymerization initiator.
Preferably, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, benzophenone, 2,2-dimethoxy -1,2-diphenylethane-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, 2-benzyl-2-dimethylamino-1- (4) -Morphorinophenyl) Butanone-1, 2-Hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl-1- [4-methylthio] phenyl] -2-morpholinopropan-1-one, benzoyl Methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] Propanol oligomer, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, 2-hydroxy-2-methyl-1-phenyl-1-propanol, isopropylthioxanthone, methyl o-benzoyl benzoate , [4- (Methylphenylthio) phenyl] phenylmethane, 2,4-diethylthioxanthone, 2-chlorothioxanthone, ethylanthraquinone, benzophenone ammonium salt, thioxanthone ammonium salt, bis (2,6-dimethoxybenzoyl) -2,4 , 4-trimethyl-pentylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 4,4'- Bisdiethylaminobenzophenone, 1,4 dibenzoylbenzene, 10-butyl-2-chloroacrydone, 2,2'bis (o-chlorophenyl) 4,5,4', 5'-tetrakis (3,4,5-tri) Methoxyphenyl) 1,2'-biimidazole, 2,2'bis (o-chlorophenyl) 4,5,4', 5'-tetraphenyl-1,2'-biimidazole, 2-benzoylnaphthalene, 4-benzoyl Biphenyl, 4-benzoyldiphenyl ether, acrylicized benzophenone, bis (η5-2,4-cyclopentadiene-1-yl) -bis ( 2,6-Difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium, o-methylbenzoylbenzoate, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamylethyl ester, active tershalia It is at least one compound selected from the group consisting of min, a carbazole-phenyl photoreaction initiator compound, an aclysin-based photoreaction initiator compound, and a triazine-based photoreaction initiator compound.
More preferably, it is 1-hydroxy-cyclohexyl-phenyl-ketone and / or 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide.

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

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

When the reactive compound is a moisture-reactive compound, the polymerization initiator may be
Preferably, the silanol condensation catalyst is at least one titanium compound selected from the group consisting of tetrabutyl titanate, tetrapropyl titanate, titanium tetraacetylacetonate and bisacetylacetonatodiisopropoxytitanium.
Dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctate, dibutyltin diethylhexanolate, dibutyltin dimethylmalate, dibutyltin diethylmalate, dibutyltin dibutylmalate, dibutyltin dioctylmalate, dibutyltin ditridecyl Maleate, Dibutyltin Dibenzylmaleate, Dibutyltin Diacetate, Dioctyltin diethylmaleate, Dioctyltin Dioctylmaleate, Dibutyltin dimethoxide, Dibutyltin dimethoxyside, Dibutenyl tin oxide, Dibutyltin diacetylacetonate, Dibutyltin At least one tetravalent organic tin compound selected from the group consisting of diethylacetoacetonate, a reaction product of dibutyltin oxide and a silicate compound, and a reaction product of dibutyltin oxide and a phthalate ester.
At least one organoaluminum compound selected from the group consisting of aluminum tris acetylacetonate, aluminum tris ethyl acetoacetate and diisopropoxyaluminum ethyl acetoacetate,
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 thereof, salts of carboxylic acid compounds and amine compounds , Lead octylate, and
It is at least one compound selected from the group consisting of isocyanate reaction catalysts.

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

When the compatible composition is curable, the content ratio of the reactive compound in Compound B is preferably 20 to 100% by mass, more preferably 25 to 95% by mass, from the viewpoint of durability and stress relaxation. , More preferably 30 to 90% by mass.

When the compatible composition is curable, the amount of the polymerization initiator added is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, still more preferably 2 to 8% by mass, based on at least the total amount of the block copolymer compound and the medium. It is 2.5 to 7.5% by mass.

The moisture-curable compound is, for example, a moisture-reactive compound having an isocyanate group, an alkoxysilyl group, or a hydroxyl group or a hydrolyzable group bonded to a silicon atom and which can be crosslinked by forming a siloxane bond. Examples thereof include organic compounds having a group, and a cured product can be obtained by cross-linking by a hydrolysis reaction of a moisture-reactive group or the like.

Examples of the thermosetting component compound include epoxy-based, oxetane-based, vinyl ether-based, phenol-based, thermosetting polyurethane-based, and unsaturated polyester-based compounds that react by heating in the presence of a curing agent and / or a thermosetting initiator. Examples include monomers and / or oligomers such as (meth) acrylic acid ester compounds, (meth) acrylamide-based, (meth) acrylonitrile-based, vinyl-based compounds, allyl ether-based, maleimide and maleic anhydride, epoxy allylates, urethane acrylates, and polyester acrylates. Be done.

Examples of the photocurable component compound include epoxy-based, oxetane-based, vinyl ether-based, (meth) acrylic acid ester compounds, and (meth) acrylamide that react with ultraviolet irradiation in the presence of a photopolymerization initiator and / or a photosensitizer. Examples thereof include monomers and / or oligomers such as (meth) acrylonitrile-based, vinyl-based, vinyl ether-based, allyl ether-based, maleimide and maleic anhydride, epoxy allylate, urethane acrylate, and polyester acrylate.

From the viewpoint of the stability of the bonded body, the cured product of the gel-like composition preferably has an elastic modulus in the range of 25 ° C., preferably 0.1 to 10,000,000 kPa, more preferably 1-1000000 kPa, and further preferably 10 to 100,000 kPa. Is.

As described above, the gel-like composition is preferably in the form of a sheet when used as a laminating material for the member 1 and the member 2, and is therefore the composition X1, X2 or X3 from the viewpoint of being easily formed into a sheet. Is preferable.

Since the compositions X1, X2 or X3 are liquid at a temperature of Tc or higher, they can be easily filled in a mold for forming a sheet, for example, and have gel-like fluidity only by cooling to a temperature of less than Tc. It becomes a smooth sheet and is suitable as a laminating material.

The composition X1, X2 or X3 is stable even after the laminate of the member 1, the laminating material and the member 2 obtained through the step 2 is incorporated into the subsequent step of manufacturing the composite and the composite. From the viewpoint of maintaining the laminate, the composition is curable, preferably cured by moisture, heat or light, more preferably by heat or light, and more preferably by light, and the cured composition is described in JP-A-2017. -066368 The compatible composition described in paragraph 0062 is preferably a viscoelastic body.

[Composite manufacturing process]
The bonded body is preferably manufactured at Tc-5, except that it is heated to Tc or higher in order to form the gel-like composition, such as heating in the gel sheet manufacturing process described later and pressure heating in step 2. The temperature is controlled at ° C. or lower, more preferably Tc-10 ° C. or lower, and even more preferably Tc-15 ° C. or lower.

(Gel sheet manufacturing process)
The gel-like composition used in step 1 of the present invention 1 can cover at least the different height portion of the surface S1 and / or the surface S2 and its periphery, and preferably can cover the desired portions of the surface S1 and the surface S2. From the viewpoint of thinning the entire bonded body, it is preferable that the sheet has a shape and an area and has a desired thickness (hereinafter, also referred to as “gel sheet”).

The gel sheet is preferably Tc-5 ° C. or lower because the filled surface of the mold becomes smooth when the gel-like composition is filled in a mold having a predetermined depth and heated to Tc or more to be fluidized. When cooled to Tc-10 ° C. or lower, more preferably Tc-15 ° C. or lower, a sheet having the depth as the thickness and having a bottom-shaped surface of the mold can be obtained.

After filling the mold with the gel-like composition, the packed surface may be covered with a smooth plate or film, and the gel-like composition may be heated and cooled while having an interface between the plate or film surface and the gel-like composition.

The gel-like composition may be applied to the member 1 or the member 2 in a heated state using a coating device such as a slit coater, and then cooled to form a sheet directly on the member.
The gel-like composition may be applied onto a film using a coating device such as a slit coater, coated with the other film, and cooled to obtain a sheet sandwiched between films.

(Step 1)
In step 1, the laminating material is arranged between the surface S1 and the surface S2 so as to cover the different height portion with the laminating material, and a laminated body of the member 1, the laminating material, and the member 2 is obtained.

(Step 2)
In step 2, the laminate obtained in step 1 is pressurized and heated in a temperature range of Tc or higher, and / or autoclaved in a temperature range of Tc-30 to Tc + 30 ° C.

The pressurization may be performed by the weight of the member placed on the upper part of the laminating material of the member 1 or the member 2, or may be further pressed on the member.

The pressurization is preferably performed at a weak pressure (preferably 1000 to 500,000 Pa, more preferably 3,000 to 1,000,000 Pa) such that the unevenness of the bonding material derived from the different height portion is smoothly leveled by heating.

The heating may be performed as long as the gel sheet becomes less viscous under the above pressure and the unevenness of the laminating material derived from the different height portion is smoothly leveled, and is preferably in the temperature range of Tc to Tc + 50 ° C. Is a temperature range of Tc to Tc + 40 ° C., more preferably a temperature range of Tc to Tc + 30 ° C., still more preferably a temperature range of Tc to Tc + 25 ° C., still more preferably a temperature range of Tc to Tc + 20 ° C., still more preferably Tc ~. The temperature range is Tc + 15 ° C, more preferably Tc to Tc + 10 ° C.

From the viewpoint of low residual air bubbles, it is preferable that the pressure heating is performed in the autoclave or in the autoclave in addition to the press.

For pressurization in the autoclave, the pressure is preferably set to 200,000 to 700,000 Pa, more preferably 300,000 to 600,000 Pa, and even more preferably 400,000 to 600,000 Pa.

For heating in the autoclave, preferably Tc-30 to Tc + 30 ° C. for 5 to 60 minutes, more preferably Tc-20 to Tc + 20 ° C. for 10 to 40 minutes, and even more preferably Tc-15 to Tc + 15 ° C. for 15 to 30 minutes. Warm in minutes.
(Incorporation process of bonding)
When the bonded body is, for example, a display, the portable information terminal which is a composite body is manufactured by combining the bonded body together with a backlight unit, a battery, a circuit board, and the like in a housing.

(Example of Embodiment of gel-like composition)
(1) Example of Embodiment X1 The description will be made with reference to Table 11.
Weigh 100 g of compound a1 and 400 g of compound b1, fill a container (material SUS316, capacity 2000 ml), and rotate 200 times at 80 ° C. and atmospheric pressure using a three-one motor (manufactured by Shinto Kagaku Co., Ltd.). The compatible composition of Example 1-1 can be obtained by stirring at / min for 360 minutes.

Compounds a1 and b1 are replaced with the compounds shown in Tables 3 and 4, and the compatible compositions of Examples 1-2 to 23 are prepared in the same manner as in Example 1-1 with the formulations shown in Tables 3 and 4. You can get it.

<Compound raw material of composition X1>
(1-1) Compound A
Polymer block a is composed of methyl methacrylate,
The polymer block b was composed of butyl acrylate.
The triblock copolymer compound of the polymer block a-polymer block b-polymer block a and the diblock copolymer compound of the polymer block a-polymer block b were used.

The glass transition temperature of the butyl acrylate polymer (polymer a) is -25 ° C.
The glass transition temperature of the methyl methacrylate polymer (polymer b) is 140 ° C.

Compound a1: KURARITY LA2140 (registered trademark, Kuraray)
Compound a2: KURARITY LA2250 (registered trademark, Kuraray)
Compound a3: KURARITY LA2330 (registered trademark, Kuraray)
Compound a4: KURARITY LA4285 (registered trademark, Kuraray)

In the total mass of the polymer block a and the polymer block b, the polymer block a is
About 20% by mass for LA2140, about 30% by mass for LA2250,
About 20% by mass for LA2330, about 50% by mass for LA4285,
LA1892 is about 50% by mass, LA1114 is about 10% by mass, and so on.
LA2140, LA2250, LA2330, LA4285 are triblock bodies,
LA1892 and LA1114, which will be described later, are diblock bodies.
The molecular weight is LA2330> LA2140 = LA2250 = LA4285 = LA1114 = LA1892.

(1-2) Compound B
Compound b1: Isodecyl acrylate (manufactured by Sartmer, SR395)
Compound b2: 4-tert-Butylcyclohexylacrylate (Genomer1119, manufactured by Rahn)
Compound b3: 4-Hydroxybutyl acrylate (manufactured by Nihon Kasei Co., Ltd., 4-HBA)
Compound b4: Diisononylcyclohexyldicarboxylate (manufactured by BASF, DINCH)
Compound b5: Alkyl benzoate (alkyl carbon atoms 12 to 16) (Liponate NEB, manufactured by Lipo Chemicals)
Compound b6: Hydrogenated rosin ester (manufactured by Arakawa Chemical Industry Co., Ltd., KE-311)
Compound b7: Epoxy ester (4,5-epoxy-1,2-cyclohexanedicarboxylic acid bis (2-ethylhexyl)) (manufactured by DIC Corporation, W150)
Compound b8: Disproportionated rosin ester (manufactured by Arakawa Chemical Co., Ltd., ME-D)
Compound b9: Triethylene glycol bis (2-ethylhexanoate) (Proviron, Proviblast 1783)

(1-3) Compound B1 (radical-reactive bifunctional compound and polyfunctional compound)
Compound b1-1: PPG urethane acrylate (manufactured by KSM, UA10000B)
Compound b1-2: Aliphatic urethane acrylate (manufactured by Daicel Ornex, EB270)
Compound b1-3: 1.9-nonanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., 1,9-NDA)
Compound b1-4: Polybutadiene urethane acrylate (Nippon Soda, TE-2000)

(1-4) Compound B2 (radical reactive monomer compound)
Compound b2-1: 4-Hydroxybutyl acrylate (manufactured by Nihon Kasei Co., Ltd., 4-HBA)
Compound b2-2: Lauryl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., LA)
Compound b2-3: Isodecyl acrylate (manufactured by Sartmer, SR395)
Compound b2-4: Isobornyl acrylate (manufactured by Nippon Kayaku Co., Ltd., RM-1002)
Compound b2-5: 4-tert-Butylcyclohexylacrylate (genomer1119 manufactured by Rahn)
Compound b2-6: Pentamethylpiperidylmethacrylate (manufactured by Hitachi Kasei Co., Ltd., FA-711MM)

(1-5) Other Compounds Compound r1: 1-Hydroxycyclohexylphenyl ketone (manufactured by BASF, I-184)
Compound r2: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by BASF, I-TPO)

(2) Examples of Embodiment X2 will be described with reference to Tables 5 and 6.
Weigh 100 g of compound a1 and 200 g of compound b1, fill a container (material SUS316, capacity 2000 ml), and rotate 200 times at 80 ° C. and atmospheric pressure using a three-one motor (manufactured by Shinto Kagaku Co., Ltd.). The compatible composition of Example 2-1 can be obtained by stirring at / min for 360 minutes.

In the same manner as in Example 2-1 of Example 2-, the compounds a1 and b1 in Example 2-1 are replaced with the compounds shown in Tables 5 and 6 and the formulations shown in Tables 5 and 6 are used. 2 to 14 can be obtained.

<Compound raw material of composition X2>
(2-1) Compound A
Polymer block a is composed of methyl methacrylate units (MMA) and
The polymer block b is composed of n-butyl acrylate units (nBA) and is composed of n-butyl acrylate units (nBA).
A graft copolymer compound in which the trunk is the polymer block b and the branches are the polymer block a was used.

The glass transition temperature of the methyl methacrylate polymer (polymer a) is 140 ° C.
The glass transition temperature of the n-butyl acrylate polymer (polymer b) is −25 ° C.

Compound a-1: NB5015 (Mitsubishi Rayon)
Compound a-2: NB5065 (Mitsubishi Rayon)
Compound a-3: NB5066 (Mitsubishi Rayon)
Compound a-4: NB5073 (Mitsubishi Rayon)
Compound a-5: NB5088 (Mitsubishi Rayon)

(2-2) Compound B
Compound b-1: Light acrylate LA (lauryl acrylate, Kyoeisha Chemical Co., Ltd.)
Compound b-2: SR395 (isodecyl acrylate, Sartomer)
Compound b-3: Providelast1783 (triethylene glycol bis (2-ethylhexanoate, Proviron))
Compound b-4: DINCH (diisononylcyclohexyldicarboxylate, BASF)
Compound b1-1: Hydrogenated rosin ester (manufactured by Arakawa Chemical Industry Co., Ltd., KE-311)
Compound b1-2: DINCH (diisononylcyclohexyldicarboxylate, BASF)
Compound b2-1: TE-2000 (polybutadiene urethane acrylate, Nippon Soda)
Compound b2-2: Aliphatic urethane acrylate (manufactured by Daicel Ornex, EB270)
Compound b2-3: PPG urethane acrylate (manufactured by KSM, UA10000B)
Compound b3-1: Light acrylate LA (lauryl acrylate, Kyoeisha Chemical Co., Ltd.)
Compound b3-2: Pentamethylpiperidylmethacrylate (manufactured by Hitachi Kasei Co., Ltd., FA-711MM)
Compound b3-3: Isobornyl acrylate (manufactured by Nippon Kayaku Co., Ltd., RM-1002)

(2-3) Other compounds Compound r-1: I-184 (1-hydroxycyclohexylphenyl ketone, BASF)

(3) Example of Embodiment X3 The description will be made with reference to Tables 7 to 11.
Compound _A Compound b-4 a compound a1-1 as 100g and Compound B as ₁ to 200g Review amount, the container (material made SUS316, capacity 2000 ml) was charged to, 80 ° C., at atmospheric pressure, a three-one motor (New The compatible composition of Example 3-1-1 can be obtained by stirring at 200 rpm for 360 minutes using (manufactured by Togaku Co., Ltd.).

_{Compound A 1} in Example 3-1-1 is replaced with compound A ₁ or A _{2 shown} in Tables 8-10, compound B is replaced with another compound B shown in Table 8-10, and other compounds are added. , The compatible compositions of Examples 3-1 to 2-16 and 3-2-1 to 3 can be obtained in the same manner as in Example 3-1-1 with the formulations shown in Tables 8-10.

<Compound raw material of composition X3>
(3-1) Compound A
The compounds listed in Table 7 can be used. The glass transition temperature of the polymer b _{2 is −25 ° C.}

(3-2) Compound B
Compound b-1: Saracos 99 (Isononyl isononanoate, Nisshin Oillio Co., Ltd.)
Compound b-2: DINCH (diisononylcyclohexyldicarboxylate, BASF)
Compound b-3: Saracos P-8 (-2-ethylhexyl palmitate, Nisshin Oillio Co., Ltd.)
Compound b-4: genomer1119 (4-tert-butylcyclohexylacrylate, Rahn)
Compound b-5: SR395 (isodecyl acrylate, Sartomer)
Compound b-6: KE-311 (hydrogenated rosin ester, Arakawa Chemical Co., Ltd.)
Compound b-7: Archon P-100 (hydrocarbon resin, Arakawa Chemical Co., Ltd.)
Compound b-8: Clearon M-105 (hydrogenated aromatic-modified terpene resin, Yasuhara Chemical Co., Ltd.)
Compound b-9: TE-2000 (polybutadiene urethane acrylate, Nippon Soda)
Compound b-10: 1.9ND-A (nonanediol diacrylate, Kyoeisha)
Compound b-11: Estemol N-01 (neopentyl glycol dicaprate, Nisshin Oillio Co., Ltd.)
Compound b-12: HOB (2-hydroxybutyl methacrylate, Kyoeisha)

(3-3) Other compounds Compound r-1: I-184 (1-hydroxycyclohexylphenyl ketone, BASF)

〔Example〕
The composition X1 was produced and used in the examples of the present invention 1.

(1) Compound raw material (1-1) Compound A
Compound a1: KURARITY LA2250 (registered trademark, manufactured by Kuraray)

(1-2) Compound B
Compound b1: Polybutadiene urethane acrylate (TE-2000, manufactured by Nippon Soda)
Compound b2: Isodecyl acrylate (SR395, manufactured by Sartmer)
Compound b3: Isobornyl acrylate (RM1002, manufactured by Nippon Kayaku Co., Ltd.)
Compound b4: Disproportionated rosin ester (manufactured by Arakawa Chemical Co., Ltd., ME-D)
Compound b5: 4-Hydroxybutyl acrylate (4-HBA, manufactured by Nihon Kasei Co., Ltd.)
Compound b6: Hydrogenated rosin ester (KE-311, manufactured by Arakawa Chemical Industry Co., Ltd.)
Compound b7: Lauryl acrylate (light acrylate LA, Kyoeisha Chemical Co., Ltd.)
Compound b8: Pentamethylpiperidylmethacrylate (FA-711MM, manufactured by Hitachi Kasei Co., Ltd.)
Compound b9: Isononyl isononanoate (Saracos 99, Nisshin Oillio Co., Ltd.)
Compound b10: 4-tert-butylcyclohexylacrylate (genomer1119, Rahn)

(1-3) Other compounds Compound r1: PPG urethane acrylate (UA10000B, manufactured by KSM)
Compound r2: 1-Hydroxycyclohexylphenyl ketone (I-184, manufactured by BASF)

(2) Gel-like composition This will be described with reference to Table 11.

(2-1) Weigh 100 g of compound a1 and 300 g of compound b1, fill a container (material SUS316, capacity 2000 ml), and use a three-one motor (manufactured by Shinto Kagaku Co., Ltd.) at 80 ° C. and atmospheric pressure. It was used and stirred at 200 rpm for 360 minutes to obtain a compatible composition of the embodiment composition X1.

Compound a1 and compound b1 were replaced with the compounds shown in Table 11 to obtain Comparative Composition 1 with the formulations shown in Table 11. The comparative composition 1 is a UV curable pressure-sensitive adhesive.

(2-2) The following physical properties were measured with respect to the implementation composition X1 and the comparative composition 1.

(2-2-1) Liquid-gel transition temperature (Tc)
(2-2-2) Storage rigidity at 25 ° C (kPa)
(2-2-3) Complex viscosity (Pa · s)
(2-2-4) The glass transition point of the butyl acrylate polymer (polymer a) and the methyl methacrylate polymer (polymer b).

(3) Measurement conditions

<Liquid-gel transition temperature Tc and storage rigidity>
The storage rigidity G'and the loss rigidity G'of the gel-like composition,
Using a rheometer (manufactured by Antonio Par),
Cone rotor (φ = 25 mm, rotor angle 2 °), frequency 1 Hz, strain 1%,
Measure by cooling at 2 ° C / min from 150 ° C to 0 ° C.
In the range of more than 25 ° C. and 150 ° C. or lower, the temperature at which the storage rigidity G'and the loss rigidity G'are equal is defined as Tc.

<Storage rigidity>
Using a rheometer (manufactured by Antonio Par), measure with 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 numerical value of the storage rigidity measured at 25 ° C. was read. However, when the transition temperature was 0 ° C. ≤ Tc ≤ 30 ° C., the storage rigidity at Tc-20 ° C. was used.

<Complex viscosity η _v >
Using a rheometer (manufactured by Antonio Par), change ^{the shear rate from 0.01 (sec -1} ) to 100 (sec ^-1 ) at a cone rotor (φ = 25 mm, rotor angle 2 °) and 25 ° C. Read the _{viscosity η v} at the shear rate v.
In addition, when the measured value could not be measured because the cone rotor did not generate resistance based on the structural viscosity of the gel composition, it was regarded as "unmeasured".

<Glass transition point>
Each of the polymer a, the polymer b and the block copolymer compound is sheet-molded to a thickness of 0.5 mm at a pressure of 10 MPa using a hydraulic hot press machine manufactured by Shinto Metal Industry Co., Ltd. set at 200 ° C. Then, a strip piece of 45 mm × 10 mm × 0.5 mm necessary for dynamic viscoelasticity measurement is cut out.
Using a dynamic viscoelastic device (DMS6100) manufactured by Seiko Instruments, Inc.
In the chart obtained by measuring in the tension mode under the conditions of a temperature range of -100 ° C to 200 ° C (heating rate 3 ° C / min) and a frequency of 11 Hz.
The peak temperature of tan δ is read and used as the glass transition point of each of the polymer a, the polymer b, and the block copolymer compound constituting the strip.

(4) Material and equipment (4-1) Material (4-1-1) Member 1
Filler tape with different heights (spacer: thicknesses of 15, 30, 45, 60, 70, 90 μm, respectively) in the center of the glass plate (manufactured by NSG Interior Co., Ltd., product number glass 2.9 T, 10 cm × 10 cm, thickness 2.7 mm) (SK hardened steel)) was pasted to form a member 1 having a different height portion.
(4-1-2) Member 2
A transparent PET film (manufactured by Panac Co., Ltd., product number Lumirror 100T60) was cut into a member 2 having a size of 38 mm × 25 mm and a thickness of 0.1 mm.
(4-1-3) Release film 1
Toyobo E7002, 10 cm x 10 cm, thickness 38 μm
(4-1-4) Release film 2
Toyobo E7006, 10 cm x 10 cm, thickness 50 μm
(4-1-5) Spacer 1
Made using 3 cellophane tapes (50 μm)

(4-2) Equipment (4-2-1) Roller: Product name: SA-1003-B Tape crimping roll Manual type (manufactured by Tester Sangyo Co., Ltd., 2 kg)
(4-2-2) Ultraviolet irradiation device: Conveyor type ultraviolet irradiation device (Metal halide lamp manufactured by Aigfic)
(4-2-3) Autoclave: PBD-30 manufactured by Toto Tech Co., Ltd.
(4-2-4) Laser microscope: Olympus, OLS-4000
(4-2-5) Microscope: UHX-500 manufactured by KEYENCE CORPORATION

(5) Forming Step of Laminated Material (5-1) A release film 1 having a spacer 1 arranged on the outer periphery was placed on a glass plate to form a composition filling tank (form).

(5-2) The implementation composition X1 is filled in the center of the composition filling tank, sandwiched between the release films 2, and the implementation composition X1 is sandwiched between another glass plate member, and then heated to 80 ° C. Then, it was naturally cooled to 25 ° C. to prepare a gel sheet of the implementation composition X1 sandwiched between the release films 1 and 2 and used as an implementation laminating material.

(5-3) The comparative composition 1 is filled in the center of the composition filling tank, sandwiched between the release films 2, and each implementation composition is sandwiched between another glass plate member, and then ultraviolet rays are emitted from the glass plate member side. An adhesive sheet was prepared by curing at a peak illuminance of 400 mW / cm2 and an integrated light intensity of 3000 mJ / cm ² (manufactured by Oak Co., Ltd., wavelength 350 nm) using an irradiation device, and used as a comparative bonding material.

(6) Example 1
(6-1) Step 1
(6-1-1) Implementation After cutting the bonding material and the comparative bonding material to 38 mm × 25 mm, the release film 1 on one side is peeled off and attached to a member 2 of the same size, and each bonding material and the member 2 are attached. A laminate A with the above was produced.

(6-1-2) The member 1 is arranged so that the different height portion (height 30 μm) faces each of the bonding materials from which the remaining release film 2 of the laminated body A has been peeled off, and the member 1 is bonded. A laminate B composed of a material and a member 2 was obtained.

(6-1-3) Two rotations were made on the laminated body B by the weight of the roller to familiarize the bonding of the member 1, the bonding material and the member 2.

(6-2) Step 2
The laminate B was placed on a hot plate heated to 60 ° C. with the surface on the member 2 side facing down, left for 5 minutes, naturally cooled at room temperature of 25 ° C., and pressurized and heated. B1 was manufactured.
The laminate B was put into an autoclave, pressurized at 35 ° C. and 0.5 MP for 15 minutes, and then naturally cooled at room temperature of 25 ° C. to produce a laminate B2 that was pressurized and heated.

(7) Examples 2-9 and Comparative Examples 1-2
(7-1) Example 2
Laminated bodies B1 and B2 were pressurized and heated in the same procedure as in Example 1 except that the height of the different height portion was set to 45 μm.

(7-2) Example 3
Laminated bodies B1 and B2 were pressurized and heated in the same procedure as in Example 1 except that the height of the different height portion was set to 60 μm.

(7-3) Example 4
Laminates B1 and B2 were pressure-heated in the same procedure as in Example 1 except that the height of the different height portion was 90 μm.

(7-4) Example 5
The laminate B having a height of 70 μm at a different height in step 2 was placed on a hot plate heated to 60 ° C. with the PET surface facing down, left for 10 minutes, and then naturally cooled at room temperature of 25 ° C. A laminated body B1 heated under pressure was produced.

(7-5) Example 6
The laminate B having a height of 70 μm at a different height in step 2 was placed on a hot plate heated to 50 ° C. with the PET surface facing down, left for 10 minutes, and then naturally cooled at room temperature of 25 ° C. A laminated body B1 heated under pressure was produced.

(7-6) Example 7
The laminated body B having a height of 70 μm at a different height was placed on a hot plate heated to 40 ° C. with the surface on the member 2 side facing down, left for 30 minutes, naturally cooled at room temperature of 25 ° C., and then added. A pressure-heated laminate B1 was produced.

(7-7) Example 8
The embodiment composition X1 was replaced with the embodiment composition X2 shown in Table 11, and a gel sheet, a laminate B1 and a laminate B2 were produced under the same conditions as in Example 5.

(7-7) Example 9
The embodiment composition X1 was replaced with the embodiment composition X3 shown in Table 11, and a gel sheet, a laminate B1 and a laminate B2 were produced under the same conditions as in Example 5.

(8) Evaluation of leveling property The height of the surface of the member to which the gel sheet and the comparative adhesive sheet were attached was measured with a laser microscope before and after pressurization heating, and the height was measured at a different height before pressurization heating. The highest height h _B in the corresponding part and the height after pressurization heating The ratio h _{A of the highest height h A in the part corresponding to the different height part and the height h 0 in} the part where the different height part does not exist Calculate / h ₀ and h _B / h _0,
When h _A / h ₀ and h _B / h ₀ <20%, 〇,
The case of 20% ≤ h _A / h ₀ and h _B / h ₀ was defined as x.

(9) Evaluation of Low Residuality of Bubbles Regarding the laminate B after pressurization and heating obtained in step 2,
By observing with a microscope, visually observing the residual air bubbles near the different heights before and after pressurization heating,
If the air bubbles have disappeared,
The case where air bubbles remained was defined as x.

The results of the above Examples and Comparative Examples are summarized in Table 11.
As shown in Table 11, when the comparative laminating material formed of Comparative Composition 1, which is a chemically crosslinked gel having no Tc, is applied to Steps 1 and 2 of the present invention 1, leveling property and low residual air bubbles remain. Is inadequate,
When the implementation laminating material (the present invention 2) formed of the embodiment compositions X1, X2 and X3 of the present invention 2 which is a physically crosslinked gel having Tc is applied to the steps 1 and 2 of the present invention 1, the leveling property And the low residual air bubbles are good.

In Example 5 and Comparative Example 2, the thickness in the width direction of the laminated body B before and after pressurizing and heating in step 2 was measured by scanning with a laser microscope. The results are shown in FIG.

As shown in FIG.
In Example 5, it can be seen that the convex portion derived from the different height portion was generated before the pressurization heating, but the convex portion disappeared after the pressurization heating and the surface of the laminated body B became smooth. (Fig. 1 (a)),
In Comparative Example 2, it can be seen that the convex portion derived from the different height portion generated before the pressurization heating does not disappear even after the pressurization heating (FIG. 1 (b)).

In Example 1 and Comparative Example 1, the laminated body B before and after pressurizing and heating in step 2 was viewed in a plan view from the member 2 (PET film) side, and the residual state of bubbles near the boundary of the different height portion was observed. The results are shown in FIG.

As shown in FIG. 2, in the vicinity of the boundary of the different height portion,
In Example 5, it can be seen that the bubbles generated before the pressurization heating (FIG. 2A) and the convex portions disappear after the pressurization heating (FIG. 2B).
In Comparative Example 2, it can be seen that the bubbles generated before the pressurization heating (FIG. 2 (p)) but the convex portions did not disappear after the pressurization heating (FIG. 2 (q)).
In addition, a wide mass of bubbles exists horizontally in the area surrounded by the white line pointed by the pointer of FIG. 2 (p), and these bubbles remain as minute bubbles even after the autoclave treatment, and the figure (q). ) Looks white.

Claims (6)

A method for producing a composite including the member 1, the bonding material, and a laminated body in which the member 2 is laminated, which is obtained by bonding the surface S1 of the member 1 and the surface S2 of the member 2 via a bonding material. And
The laminating material is a gel-like composition having a liquid-gel transition temperature (Tc) at 0 to 150 ° C.
At least one of the surface S1 and the surface S2 has a different height portion, and the surface S1 and the surface S2 are provided with different height portions.
A step of arranging a laminating material between the surface S1 and the surface S2 so as to cover the different height portion with the laminating material to obtain a laminate of the member 1, the laminating material, and the member 2. 1 and
The step 2 comprises pressurizing and heating the laminate in a temperature range of Tc or higher, and / or pressurizing and heating in a temperature range of Tc to Tc + 30 ° C. in an autoclave.
A method for producing a complex in which the temperature of the bonding material is less than Tc in steps 1 and 2 except during the pressure heating. A method for producing a composite including the member 1, the bonding material, and a laminated body in which the member 2 is laminated, which is obtained by bonding the surface S1 of the member 1 and the surface S2 of the member 2 via a bonding material. And
The laminating material is a gel-like composition having a liquid-gel transition temperature (Tc) at 0 to 150 ° C.
At least one of the surface S1 and the surface S2 has a different height portion, and the surface S1 and the surface S2 are provided with different height portions.
A step of arranging a laminating material between the surface S1 and the surface S2 so as to cover the different height portion with the laminating material to obtain a laminate of the member 1, the laminating material, and the member 2. 1 and
Said laminate, after a pressurizing and heating to step (a) in the temperature range above Tc, step through the step (b) for pressurizing and heating in the temperature range of Tc-30 ℃ ~Tc + 30 ℃ in autoclave Including 2
In the step 1 and 2, the temperature of the Hagozai is above except at the pressurizing and heating, process for preparing the composite is less than Tc (except, in step (a) in the factory about 2, Tc by autoclaving Except for pressurizing and heating in the above temperature range). The method for producing a complex according to claim 1 or 2, wherein the gel-like composition has heat and / or photocurability. The member 1 and / or the member 2 is a liquid crystal display panel; an organic EL display panel; a protective panel; a touch panel, an ambient light sensor, a proximity sensor, a fingerprint sensor, a sensor such as an authentication sensor; a camera; a glass or plastic plate and a plastic film. The method for producing a composite according to any one of claims 1 to 3, which is at least one member selected from the group consisting of. The method for producing a composite according to any one of claims 1 to 4, wherein the composite is at least one device selected from the group consisting of a liquid crystal display, an organic EL display, and a touch panel display. The gel-like composition according to any one of claims 1 to 5, which is used in the method for producing a complex according to any one of claims 1 to 5.

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