JP7178654B2 - Composite manufacturing/dismantling method and gel-like resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for manufacturing/dismantling a composite in which a member is incorporated, and a gel-like resin composition used in the method for manufacturing/dismantling the composite.

Display panels, touch panels, sensors, lenses, battery parts, semiconductor parts, and members such as housings that wrap these parts are used for video/image display devices, imaging devices, communication devices, In the process of manufacturing composites such as consumer electronics, batteries, integrated circuits, etc., there are areas where contamination and/or processing of their surfaces should be avoided.

For example, optical members such as display panels and touch panels are diversifying in terms of design, such as having a curved surface structure, shifting to glass for housing members, and complicating the layout and wiring structure of parts. In the process of manufacturing an optical product that incorporates the above components, the areas of the surface of each component that should be protected from contamination are covered with a protective film or coated with liquid resin to prevent surface contamination such as scratches and stains. (For example, Patent Documents 1 and 2).

For example, when plating wiring to battery parts such as solar cells and electronic parts such as semiconductor parts, it is necessary to protect the areas where plating should be avoided other than the areas to be plated on the surface of each part with a resist material. , screen-printable resist materials are widely used (eg, US Pat.

For example, in the semiconductor manufacturing process, chemical etching such as polishing of the silicon wafer surface, etching of the silicon surface, and etching of the _SiO2 film on the Si substrate may be performed in the silicon wafer manufacturing process. It is necessary to protect regions other than the regions to be chemically etched, which should be avoided from chemical etching, with a resist material (for example, Patent Document 4).

For example, for display panels, touch panels, sensors, lenses, battery parts, semiconductor parts, etc., it is necessary to prevent contamination such as scratches and stains on the surface during the manufacturing process, assembly process, use, and disassembly process of parts. Furthermore, it is necessary to prevent scratches on the surface in order to ensure safety during repair or disassembly and replacement, and to prevent contamination and scratches in order to reuse the member (for example, Patent Document 5).

JP 2013-237171 A JP 2009-289717 A JP-A-2005-138299 Japanese Patent Application Laid-Open No. 2003-045783 JP 2013-141761 A

However, in the process of manufacturing a composite, conventional protection techniques for areas where contamination and/or processing of the surface of a member to be incorporated should be avoided have the following problems, for example.

With the protection technology using film, it is difficult to handle complicated shapes such as curved surfaces of members, and there are issues in terms of workability and yield.

In the protection technology using liquid resin, the liquid resin can become a source of contamination because it flows out to areas other than areas where contamination should be avoided and flows into gaps between members, which increases the process control load. I have a problem.

Screen-printable liquid resist materials are expected to increase workload and cost by incorporating removal or cleaning steps. In addition, conventional liquid resist materials have printability issues, such as being unable to achieve the desired opening width and fine line accuracy during screen printing.

The resist material used in the etching process is hardened on the surface of the member before etching, physically stripped or stripped using a chemical solution, and ashing (ashing) by chemical reaction with gas. The process load is large in the process of removing or washing with, etc.

The present invention provides a region where contamination and/or processing of the surface of a member should be avoided,
Covering without outflow or inflow outside the area,
Avoiding contamination of the surface during the process of incorporating and removing the member from the composite,
An object of the present invention is to provide a method for manufacturing and dismantling a composite using a gel resin composition that enables avoidance of the necessary processing while the surface of the member is being processed, and to provide the gel resin composition. and

The present invention
[1] A step of assembling and/or removing a member having a surface S (hereinafter also referred to as a “assembling/disassembling step”), and/or a member surface processing step of processing the surface S. A method for manufacturing and dismantling a composite,
In the assembling and/or removing step and/or the member surface processing step,
A member surface coating step of coating a region of the surface S where contamination and/or processing should be avoided with a gel resin composition,
The gel resin composition is
having a liquid-to-gel transition temperature (Tc) between 0 and 150° C., and/or
A method for producing and dismantling a composite having thixotropic properties (hereinafter also referred to as "the present invention 1"), and [2] The gel form described in the preceding item [1], which is used in the method for manufacturing the composite described in the preceding item [1]. It relates to a resin composition (hereinafter also referred to as “Invention 2”).
In addition, below, this invention 1 and 2 are collectively called "this invention."

According to the present invention, the area where contamination and/or processing of the surface of the member should be avoided is
Covering without outflow or inflow outside the area,
Avoiding contamination of the surface during the process of incorporating and removing the member from the composite,
It is possible to provide a method for manufacturing and dismantling a composite using a gel resin composition that enables avoidance of the necessary processing while the surface of the member is being processed, and the gel resin composition. can.

Embodiment 1 of member surface coating process Mode example of peeling the gel resin composition sheet of Production Example 3 from the base Embodiment 2 of member surface coating process Embodiment 3 of member surface coating process

[Member provided with surface S and composite in which said member is incorporated]
In the present invention, the member provided with the surface S and the composite in which the member is incorporated can be exemplified below.

(1) Display panels, touch panels, sensors, lenses, battery parts, semiconductor parts, and video/image display devices, imaging devices, communication devices, homes, etc. that incorporate members such as housings that exterior these parts Composites such as electronic products, batteries, integrated circuits, etc.

(2) An optical product such as a display panel, a touch panel, or the like, preferably a composite in which an optical member whose surface S has a curved structure and/or is made of glass is incorporated.
More specifically, liquid crystal display panel; organic EL display panel; protective panel; touch panel; sensor such as ambient light sensor, proximity sensor, fingerprint sensor, authentication sensor; camera; glass or plastic plate; Information display devices such as liquid crystal displays, organic EL displays, touch panel displays, etc., which are composites comprising a member laminated with the electronic Portable electronic terminals such as notebooks, mobile phones, smart phones, portable audio players, personal digital assistants (PDAs), tablet terminals, etc., and information processing equipment such as personal computers, TVs, and car navigation systems.

(3) Electronic components such as solar cells, semiconductors, etc., which are composites in which members to which plated wiring is applied are incorporated, and semiconductors, which are composites in which silicon wafer members are incorporated.

The surface S provided on the members exemplified above is made of, for example, resin, silicon, metal, glass, ceramics, etc. More specifically, glass, PET, TAC, COP, polyimide, PMMA, polycarbonate, vinyl chloride , PVA, polyethylene, polypropylene, silicon, graphite, aluminum, copper, silver, SUS, etc., are preferable, and the surface of the member may be treated with an organic hard coat layer or an inorganic hard coat layer to provide conductivity. A transparent conductive material such as ITO, IZO, or carbon nanotubes may be processed, and a metal such as silver or copper may be patterned on the surface as an electrode or wiring material.

(4) The member having the surface S to be the object of the present invention includes at least one component selected from the group consisting of a display panel, a touch panel, a sensor, a lens, a battery component, and a semiconductor component, and/or the above A housing that covers the parts is preferable, and the composite that is the object of the present invention is preferably configured by a housing in which a member having the surface S is incorporated.

(5) A member having a surface S and a composite into which the member is incorporated have a step of installing and/or removing a member having the surface S and/or a member surface processing step of processing the surface S. When used in a method for manufacturing and dismantling an assembled composite, the member surface processing to be the object of the present invention is at least one selected from the group consisting of wiring forming processing, plating forming processing, and etching processing as described later. A kind of member surface treatment is preferred.

[Gel resin composition]
<Protective film formability>
The gel-like resin composition (hereinafter also referred to as "gel-like resin composition") in the present invention is obtained by applying the gel-like resin composition to a predetermined region of the surface S in the member surface coating step of the first invention. , the coating film formability such that it does not flow out from the predetermined region uniformly on the predetermined region, and when the surface S is subsequently subjected to a predetermined processing or when a contaminant comes into contact, the coating film region is free from the processing. (The coating film-forming property and coating film resistance of the gel resin composition are hereinafter referred to as "protective film-forming properties").

From the viewpoint of protective film formation, the gel resin composition
having a liquid-to-gel transition temperature (Tc) between 0 and 150° C., and/or
It has thixotropic properties.

<Liquid-gel transition temperature (Tc)>
That the gel resin composition has a liquid-gel transition temperature (Tc) at 0 to 150° C. and/or thixotropic properties means that the gel resin composition is a physically crosslinked gel.
The Tc and thixotropic properties are measured under the conditions described in Examples.

Physically crosslinked gels are gels that are crosslinked by non-covalent bonds such as hydrogen bonds, hydrophobic aggregation, and ionic bonds, and the former has Tc (also known as thermoreversible gel) because the crosslinks are generated and disappear due to temperature changes and external forces. ), the latter will have thixotropic properties.

In general, a gel resin composition is a substance in which the fluidity of the composition as a whole is greatly reduced because the compounds that make up the composition are crosslinked to suppress the thermal movement of individual compounds. They are classified into chemical cross-linked gels and physical cross-linked gels according to their lifespan.

A chemically crosslinked gel is a gel that is crosslinked by covalent bonds, and the bonds cannot be broken by thermal motion of constituent compounds, and the crosslink life is practically infinite. The connecting structure (topological three-dimensional structure) of the chemically crosslinked gel remains unchanged as it was when the gel was produced.

Physically crosslinked gels are gels that are crosslinked by non-covalent bonds such as hydrogen bonds, hydrophobic aggregation, and ionic bonds, and the former has Tc (also known as thermoreversible gel) because the crosslinks are generated and disappear due to temperature changes and external forces. ), the latter will have thixotropic properties.

A suitable gel-like resin composition that can be applied to the present invention is preferably a physically crosslinked gel as a whole, even if it is partially chemically crosslinked, from the viewpoint of protective film-forming properties, and is not a chemically crosslinked physical crosslinked gel. is more preferable.

The fact that the gel resin composition has Tc means that the gel resin composition becomes liquid at Tc or higher and is in a gel state (i.e., gel resin composition) that does not naturally flow at temperatures lower than Tc.

The gel resin composition preferably has a Tc of 10 to 100°C, more preferably 20 to 90°C, still more preferably 30 to 80°C, from the viewpoint of protective film-forming properties.

<Thixotropic property>
A gel resin composition having thixotropic properties means that the viscosity η _v of the gel resin composition at a shear rate v is
at 25°C if 30°C<Tc, and at Tc-20°C if 0°C≤Tc≤30°C,
η _0.1 is 10 to 10000 Pa s, preferably 30 to 5000 Pa s, more preferably 50 to 3000 Pa s,
_η10 is 3 to 500 Pa·s, preferably 5 to 300 Pa·s, more preferably 5 to 150 Pa·s.
In addition, the gel-like resin composition having no Tc complies with the case of 30° C.<Tc.
The viscosity _ηv is measured under the conditions described in Examples.

Considering the protective film formability in the member surface coating process,
η _0.1 is 10 to 10000 Pa s, preferably 30 to 5000 Pa s, more preferably 50 to 3000 Pa s,
η ₁ is preferably 10 to 1000 Pa·s, more preferably 20 to 700 Pa·s, still more preferably 30 to 500 Pa·s,
η ₁₀ is preferably 3 to 500 Pa s, more preferably 5 to 300 Pa s, still more preferably 5 to 150 Pa s,
x ₁ =η _0.1 /η ₁ is preferably 1.1-20, more preferably 1.2-15, still more preferably 1.25-10.
x ₂ =η ₁ /η ₁₀ is preferably from 1.1 to 20, more preferably from 1.2 to 15, even more preferably from 1.25 to 10.

When x ₁ and x ₂ are greater than 1 (preferably greater than 1.2), when the gel resin composition is molded into a sheet, for example, when applied to a predetermined range using an applicator, It flows moderately when it is extruded from the applicator, and the flow stops after it is extruded, so it is difficult to cause contamination due to outflow from the specified area or stringiness, and it can be applied evenly to the specified area. becomes possible.

<Storage modulus>
The gel resin composition applicable to the present invention has a storage modulus in the gel state of 25° C. when 30° C.<Tc, and Tc when 0° C. ≤ Tc ≤ 30° C. It is preferably 0.01 to 10000 kPa at -20°C.
The storage modulus is measured under the conditions described in Examples.

In the member surface coating step, when the gel resin composition is applied to a predetermined region of the surface S at a temperature lower than Tc, the gel resin composition is applied to the predetermined region of the surface S to a uniform thickness. Although it is liquid, it is not so fluid that it flows out of the predetermined region and contaminates the portion outside the predetermined region with the gel resin composition itself, which is preferable from the viewpoint of protective film formation.

<Peelability>
Even if the above-mentioned storage synthesis rate of the gel-like resin composition after curing is set to the above-mentioned suitable range, the release property is constant (evaluation of release property in Production Example 3 is about △). However, in the member surface coating step of the present invention 1, a gel resin composition is applied to a predetermined region of the surface S, cured before or after surface processing, and the coating film is applied after surface processing ( It is preferable that it can be easily peeled off and removed (evaluation of peelability in Production Example 3).

When the resin composition has good peelability, as shown in FIG. 2, the gel-like resin composition after curing can be peeled off without breaking the resin while physically maintaining the film form.

For example, when the member surface processing is etching processing such as chemical etching, after etching processing, the gel-like resin composition is cured to become a film that does not break when peeled, so that it can be physically peeled off, and a resist material is used. Since chemicals and ashing residues that occur in other cases do not occur, the process load before and after surface processing is reduced.

In order to impart peelability to the gel resin composition, the peelability of the coating film of the gel resin composition is improved within a range that does not affect the liquid-gel transition temperature (Tc) and the thisotropic properties. A compound that causes the

Compounds that improve the peelability of the gel resin composition include:
Silicone compounds such as polyether-modified silicone, polyester-modified silicone, polydimethylsiloxane, and polymethylalkylsiloxane;
fluorine compounds such as fluoroalkylcarboxylic acids and perfluoroalkylcarboxylic acids;
Silicone-fluorine compounds such as perfluoro-modified silicone;
Examples include acrylic compounds such as poly(meth)acrylate, polyether-modified acrylic polymer, polyester-modified acrylic polymer, perfluoroalkyl-modified acrylic polymer, etc. Commercially available products include polyether-modified siloxane (TEGO GLIDE440, Evonik). be done. These can be used individually by 1 type or in combination of 2 or more types.

The amount of the compound that improves the peelability is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 100 parts by weight, based on a total of 100 parts by weight of compound A and compound B constituting the gel resin composition. 5 parts by weight, more preferably 0.5 to 3 parts by weight.

<Solvent solubility>
When the gel-like resin composition in the present invention is composed of an organic compound having good solvent solubility, for example, like compounds X, Y, or Z described later, for example, the surface processing of the member is etching such as chemical etching. In the case of processing, the coating film of the gel-like resin composition can be easily washed away with a solvent after etching processing, and the chemicals and ashing residues that are generated when using resist materials do not remain, so the processing load before and after surface processing is reduced. mitigated.

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

<Transparency>
By using, for example, a compound Y described later as the gel-like resin composition, both thixotropy and transparency can be achieved.

Transparency can be evaluated by the HAZE value, which is the ratio of diffuse transmittance to total light transmittance of the gel-like resin composition.

For example, when a gel-like resin composition having thixotopic properties is used for optical materials, a filler is added to the resin composition to impart thixotopic properties in conventional curable resin compositions. Since the added filler causes light scattering, the HAZE value increases and the transparency based on the total light transmittance of the resin constituting the resin composition is lowered.

In the gel resin composition, even if no filler is added, for example, compound X1 described later secures thixotropic properties only with the gel resin composition in which compound A1 and/or A2 and compound B are compatible. Therefore, there is no factor that increases the HAZE value, and the transparency based on the total light transmittance of the resin constituting the resin composition can be utilized without much loss.

Therefore, the gel resin composition has a HAZE value of preferably 1.0 or less, more preferably 0 when transparency is required (for example, during display inspection), such as when coating a display that requires display inspection. 0.7 or less, more preferably 0.5 or less, more preferably 0.3 or less, still more preferably 0.2 or less, is preferably configured so as to ensure transparency.

<Example of gel resin composition>
Suitable gel-like resin compositions applicable to the present invention include, for example,
Gel resin composition having Tc (hereinafter referred to as "composition X");
A composition having Tc and having thixotropic properties (hereinafter referred to as "composition Y"); and
A gel-like resin composition having no Tc but having thixotropic properties (hereinafter referred to as "composition Z") can be mentioned.

(Composition X)
Suitable composition X can be exemplified by:
(1) A compatible composition in which a specific (meth)acrylate-based block copolymer compound and a medium are compatible (hereinafter also referred to as “composition X1”);
(2) a compatible composition in which a specific graft copolymer compound and a medium are compatible (hereinafter also referred to as "composition X2"); and (3) a specific styrenic block copolymer compound and a medium Compatible composition (hereinafter also referred to as "composition X3")

(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,
The block copolymer compound is
a polymer block a mainly composed of (meth)acrylate units;
A block copolymer with a polymer block b mainly composed of (meth)acrylate units,
The glass transition temperature of the polymer composed only of (meth)acrylate units constituting the polymer block a is more than 50° C. and 180° C. or less,
The glass transition temperature of the polymer composed only of (meth)acrylate units constituting the polymer block b is −100° C. or more and 50° C. or less,
The block copolymer compound does not have a liquid-gel state transition temperature (Tc) above 25° C. and 150° C. or less,
Examples of the compatible composition include a compatible composition having a liquid-gel state transition temperature (Tc) above 25° C. and 150° C. or less.

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

As the (meth)acrylate compound that can constitute the polymer block a or the polymer block b,
Preferably, methyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, n-octyl Alkyl (meth)acrylates such as (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, and 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 and the like;
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)acrylate acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate containing alicyclic structure (meth)acrylate, acryloylmorpholine, diethylacrylamide, etc. selected from the group consisting of acrylamide at least two compounds;
More preferably
A combination of methyl methacrylate (methyl methacrylate) and n-butyl acrylate (butyl acrylate),
The constituent units of polymer block a or polymer block b are determined based on the Tg of each compound when it constitutes a polymer by itself.

The polymer block a is preferably composed only of (meth)acrylate units, but the block copolymer compound does not have a liquid-gel state transition temperature (Tc) at 0 to 150° C., which will be described later. As long as the compatible compound has a liquid-gel state 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 (meth)acrylate units in polymer block a is preferably 90 to 100 mol %, more preferably 95 to 100 mol %, still more preferably 99 to 100 mol %.

The polymer block b is preferably composed only of (meth)acrylate units, but the block copolymer compound does not have a liquid-gel state transition temperature (Tc) at 0 to 150° C., which will be described later. As long as the compatible compound has a liquid-gel state 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 (meth)acrylate units in polymer block b is preferably 90 to 100 mol %, more preferably 95 to 100 mol %, still more preferably 99 to 100 mol %.

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, so the glass transition point of the block copolymer compound is , that is, the temperature range of more than 50°C to 180°C and the temperature range of -100°C to 50°C. The glass transition point is measured under the conditions described in Examples.

The block copolymer compound, from the viewpoint of the liquid-gel state transition of the compatible composition described later,
It is preferable to have at least one triblock structure in which the polymer block a is bound to both ends of the polymer block b,
Although it is more preferable that it is composed only of a triblock structure,
At 0 to 150° C., the block copolymer compound does not have a liquid-to-gel transition temperature (Tc),
In the range where the compatible composition described later has a liquid-gel state transition temperature (Tc),
A structure other than a triblock structure (for example, a diblock structure in which polymer block a and 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, commercially available "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 polymer block a and polymer block b from the viewpoint of improving the elasticity and adhesiveness of the gel-like compatible composition and compatible composition viscoelastic body described later. Reactivity is further imparted by having at least one reactive functional group selected from the group consisting of a radical-reactive group, a cation-reactive group, an anion-reactive group and a moisture-reactive group at the terminal or side chain of preferably. Suitable aspects of these reactive groups are described in JP-A-2017-66368.

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

As a medium, it is preferable to select a compound that allows a compatible composition with the block copolymer compound to have fluidity. It may be a saturated bond-containing monomer, a plasticizer, a solvent, and the like.

Monomer compounds that allow the compatible composition with the block copolymer compound to have fluidity include:
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)acrylate; hydroxy-substituted alkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and 2-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, 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)acrylate, norbornene (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acryloyl At least one compound selected from the group consisting of (meth)acrylamides 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 that allows the compatible composition with the block copolymer compound to have fluidity,
Preferably, phthalates such as dibutyl phthalate, diisononyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate, butylbenzyl phthalate;
Polyvalent carboxylic acid esters such as dioctyl adipate, diisononyl adipate, dioctyl sebacate, diisononyl sebacate, and diisononyl 1,2-cyclohexanedicarboxylate;
alkyl benzoate;
Phosphate esters such as tricresyl phosphate and tributyl phosphate;
Trimellitate ester;
(Hydrogenated) polyisoprene, hydroxyl group-containing (hydrogenated) polyisoprene, (hydrogenated) polybutadiene, hydroxyl group-containing (hydrogenated) polybutadiene, rubber polymers such as polybutene;
thermoplastic elastomers;
petroleum resin;
Alicyclic saturated hydrocarbon resin;
Terpene resins such as terpene resins, terpene phenolic resins, modified terpene resins, and hydrogenated terpene resins;
Rosin-based resin such as rosin phenol;
Rosin ester resins such as disproportionated rosin ester resins, polymerized rosin ester resins, and hydrogenated rosin ester resins;
xylene resin; and at least one compound selected from the group consisting of acrylic resins such as acrylic polymers and acrylic copolymers;
More preferably, it is at least one compound selected from the group consisting of polyvalent carboxylic acid esters and rosin ester resins.

As a medium acting as a solvent for the block copolymer compound,
Preferably, alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, benzyl alcohol;
Hydrocarbons such as benzene, toluene, xylene, mineral spirits, cyclohexane, n-hexane, methylcyclohexane, styrene;
ethers such as diethyl ether;
Esters such as ethyl acetate, propyl acetate, butyl acetate, diethylene glycol monoethyl ether acetate, diethyl carbonate, dimethyl carbonate, propylene carbonate;
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, diacetone alcohol;
Nitrogens such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone;
Glycol ethers such as butyl glycol, methyl diglycol, butyl diglycol, 3-methyl-3-methoxybutanol, tetrahydrofuran;
Chlorines such as methylene chloride, chloroform, carbon tetrachloride, and chlorobenzene;
dimethyl sulfoxide; acetonitrile; carboxylic acids such as formic acid and acetic acid; and at least one compound selected from the group consisting of water,
More preferably, at least one compound selected from the group consisting of alcohols, hydrocarbons, esters and ketones,
More preferably, 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 a range that is compatible with the block copolymer compound and capable of producing the compatible composition of the present invention having a liquid-gel state transition temperature (Tc) at 0 to 150°C.
From the viewpoint of easily producing a compatible composition with a block copolymer compound, the viscosity of the medium is
It is preferably 0.001 to 10 Pa·s, more preferably 0.001 to 1 Pa·s, still more preferably 0.001 to 0.5 Pa·s.

In addition, even if the medium is an oligomer or the like and has a high viscosity or solid in an environment at a temperature lower than the temperature Tc, the viscosity becomes low in an environment at a temperature higher than the temperature Tc. These can be combined and kneaded with the block copolymer compound to produce a compatible composition.

<Physical properties of compatible composition suitable as composition X1>
A compatible composition in which a block copolymer compound and a medium are compatible with each other has a temperature of 0 to 150° C., and the block copolymer compound does not have a liquid-gel state transition temperature (Tc). is a composition with a liquid-to-gel transition temperature (Tc).

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

The compatible composition is a gel-like body at a temperature around Tc (preferably Tc ± 10 ° C temperature range, more preferably Tc ± 15 ° C temperature range, still more preferably Tc ± 20 ° C temperature range) and reversibly change to a liquid state.

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

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

In the compatible composition, the amount of compound B is preferably 200 to 1,000 parts by mass, more preferably 250 to 800 parts by mass with respect to 100 parts by mass of compound A, from the viewpoint of protective film-forming properties.

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

When the compatible composition is a compatible composition viscoelastic body, the polymerization initiator to be added is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, with respect to the total of at least 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 preferred physical properties of the compatible composition viscoelastic body of composition X1 described below are also the preferred physical properties of the compatible composition viscoelastic body of compositions X1, X2 and X3 and composition Y.

From the viewpoints of protective film-forming properties and peelability, the compatible composition includes compound A (preferably compound A to which reactivity is further imparted) and compound B having radical reactivity, cation reactivity, anion reactivity and moisture reactivity. It is preferable to contain at least one reactive compound having reactivity selected from the group consisting of reactivity (preferably in combination with a plasticizer) and a polymerization initiator (hereinafter referred to as compound A (preferably, reaction 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).

The preferred physical properties of the compatible composition viscoelastic body of composition X1 described below are also the preferred physical properties of the compatible composition viscoelastic body of compositions X1, X2 and X3 and 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 temperature Tc-20°C.

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

As a degree of elongation that can form a sheet,
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 from 1×10 ² to 1×10 ⁷ Pa, more preferably from 1×10 ² to 1×10 ⁶ Pa, still more preferably from 1×10 ³ to 1×10 ⁵ Pa.

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

《Dumbbell test》
(1) After liquefying the compatible composition viscoelastic body at temperature Tc + 20°C, it is poured into a dumbbell mold and cooled to a temperature below temperature Tc (actually room temperature) to prepare a dumbbell test piece with a thickness of 1 mm.
(2) A dumbbell test piece is pulled at a tensile speed of 10 mm/min with a tensile tester (Technograph manufactured by Minebea, TG-2kN), and the elongation rate and breaking strength are read from the measurement results.

The compatible composition viscoelastic body can be stably coated on a predetermined region on the surface S in the member surface coating process due to this adhesiveness.

Further, the compatible composition viscoelastic layer is subjected to at least one treatment selected from the group consisting of heating, light irradiation and humidification, and the compatible composition viscoelastic layer is heat-cured, photo-cured and wet-cured. By curing at least one selected from the group consisting of to obtain a cured body that does not have a liquid-gel state transition temperature (Tc), the layer of the cured compatible composition viscoelastic body has a temperature Tc or higher It remains a non-fluid viscoelastic body even in a high temperature environment, and can form a durable protective film.

(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,
The graft copolymer compound is
a polymer block a mainly composed of (meth)acrylate units;
A graft copolymer compound with a polymer block b mainly composed of (meth)acrylate units,
A polymer composed only of (meth)acrylate units constituting the polymer block a has a glass transition temperature of more than 30° C. and 180° C. or less,
The glass transition temperature of the polymer composed only of (meth)acrylate units constituting the polymer block b is −100° C. or more and 30° C. or less,
The graft copolymer compound does not have a liquid-gel state transition temperature (Tc) at 0 to 150°C,
Examples of the compatible composition include compatible compositions having a liquid-to-gel transition temperature (Tc) at 0 to 150°C.

The (meth)acrylate unit constituting the polymer block a is polymerized with a (meth)acrylate compound having a glass transition temperature of more than 30° C. and 180° C. or less in a polymer (hereinafter referred to as polymer a) composed of the polymer block a. formed when 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 , still more preferably 1×10 ⁵ to 1×10 9 . 1×10 ⁷ .

The (meth)acrylate unit constituting the polymer block b is a (meth)acrylate compound having a glass transition temperature of −100° C. or more and 30° C. or less of a polymer (hereinafter referred to as polymer b) composed of the polymer block b. Formed during polymerization. From the viewpoint of the stability of the glass transition temperature, the weight average molecular weight of the polymer b is preferably 1×10 ⁵ or more, more preferably 1×10 ⁵ to 1×10 ⁹ , and still more preferably 1×10 ⁵ to 1×10 9 . 1×10 ⁷ .

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

As the (meth)acrylate compound that can constitute the polymer block a or the polymer block b,
Preferably, methyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, n-octyl Alkyl (meth)acrylates such as (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, and 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 and the like;
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)acrylate acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate containing alicyclic structure (meth)acrylate, acryloylmorpholine, diethylacrylamide, etc. selected from the group consisting of acrylamide at least two compounds;
More preferably, at least one of them is a methacrylate compound.

The constituent units of polymer block a or polymer block b are determined based on the Tg of each compound when it constitutes a polymer by itself.

The polymer block a is preferably composed only of (meth)acrylate units, but at 0 to 150 ° C., the compound A does not have a liquid-gel state transition temperature (Tc), and a compatible compound described later 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 state transition temperature (Tc).

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

The polymer block b is preferably composed only of (meth)acrylate units, but at 0 to 150 ° C., the compound A does not have a liquid-gel state transition temperature (Tc), and a compatible compound described later 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 state transition temperature (Tc).

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

Since polymer blocks a and b in compound A are considered to have polymer structures substantially equivalent to those of polymers a and b, respectively, the glass transition point of compound A includes the glass transition points of polymers a and b. For example, it preferably has a glass transition temperature in a temperature range of more than 30°C to 180°C and a temperature range of -100°C to 30°C.

The graft copolymer compound is a graft copolymer of polymer block a and 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 as if it were branched from the polymer block a.

When polymer block b is bonded to each of a plurality of constitutional units of polymer block a, polymer block a is called a trunk, and each polymer block b is called a branch.

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

The graft copolymer compound is obtained, for example, by preliminarily producing a polymer block a, copolymerizing the _acrylate units _ae and the (meth)acrylate units be constituting the terminals of the polymer block a to obtain (meth)acrylate The trunk may be composed of a copolymer of units b _e and (meth)acrylate units a _e .
In this case, the polymer of the (meth)acrylate units b _e in which the (meth)acrylate units ae in the trunk are replaced with the (meth)acrylate units _{b e is} regarded as the polymer block b, and from the polymer block a to the (meth) The portion of the polymer block a excluding the acrylate unit a _e is considered a branch.

When the branch is composed of the polymer a, the number average molecular weight according to the GPC method is preferably 3000 to 100000, preferably 5000 to 50000, from the viewpoint of the liquid-gel state transition of the compatible composition described later, and the glass transition The temperature is higher than 30°C and lower than or equal to 180°C, preferably higher than 40°C and lower than or equal to 180°C, more preferably higher than 50°C and lower than or equal to 180°C, still more preferably one end of the branch is preferably higher than 60°C and lower than or equal to 180°C, and (meta) A methacrylate unit having 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 esters, and acrylonitrile may be contained). consists of

When the trunk is composed of the polymer b, the number average molecular weight according to the GPC method is preferably 5000 to 200000, preferably 10000 to 150000, from the viewpoint of the liquid-to-gel state transition property of the liquid compatible composition described later, and the 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, still more preferably -100°C or higher and 0°C or lower, 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 is calculated from the total amount W of the graft copolymer compound and the number average molecular weight (weight average molecular weight) M as N=W/M,
Based on the total amount wa of the pre-synthesized polymer blocks _a constituting the branches and the number average molecular weight (weight average molecular weight) ma, the total number of moles na of the polymer blocks _a can be calculated as _{na = wa} / _ma . Calculate,
The number average molecular weight (weight average molecular weight) m _b of the polymer block b constituting one trunk and the number n _x of branches per trunk are expressed as m _b + n _x · _ma = M, n _x = n _a / N 2 may be defined, m _b may be calculated, and used as the number average molecular weight (weight average molecular weight) of the polymer block b.

From the viewpoint of the liquid-gel state transition 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/ 95-5, more preferably 10-90/90-10, still more preferably 15-85/85-15.

The weight average molecular weight of the graft copolymer compound is preferably 8,000 to 300,000, more preferably 15,000 to 280,000, and still more preferably 30,000 to 250,000, from the viewpoint of the liquid-to-gel transition of the liquid-compatible composition described below.

The graft copolymer compound can be obtained, for example, by the production methods described in JP-A-5-170838 and JP-A-6-234822. Available.

<Compatible composition viscoelastic body suitable as composition X2>
Similar to the compatible composition suitable as the composition X1, the compatible composition suitable as the composition X2 from the viewpoint of protective film formation and peelability is also compound A (preferably, reactivity is further imparted Reactive compounds having at least one reactivity selected from the group consisting of radical reactivity, cation reactivity, anion reactivity and moisture reactivity as compound A) and compound B (preferably in combination with a plasticizer) and preferably contains a polymerization initiator (hereinafter referred to as compound A (preferably compound A to which reactivity is further imparted), compound B consisting of radical reactivity, cation reactivity, anion reactivity and moisture reactivity A gel-like compatible composition containing at least one reactive compound selected from the group (preferably in combination with a plasticizer) and a polymerization initiator is also referred to as a compatible composition viscoelastic body. ).

The medium in composition X2 is the compatible composition of the present invention which is compatible with the graft copolymer compound and has a liquid-to-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 with each other has a temperature of 0 to 150° C., and the compound A does not have a liquid-gel state transition temperature (Tc),
The compatible composition is a composition having a liquid-gel transition temperature (Tc),
It preferably has the same properties as the compatible composition in composition X1.

Note that 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 blending ratio of the compound B is reduced, the temperature can be set to the high temperature side.
The temperature can be set to the low temperature side by configuring the block polymer a with (meth)acrylate units having a low Tg of the polymer a or by increasing the compounding ratio of the compound B.

From the standpoint of the compatibility with the composition when it is in a liquid state, from the viewpoint of the spreadability to the member and the phase transition property, the weight part of the medium is preferably 200 to 1000 parts by weight with respect to 100 parts by weight of the graft copolymer compound. It is preferably 250 to 800 parts by mass.

When the compatible composition is a compatible composition viscoelastic body, the content 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. 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 polymerization initiator to be added is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, with respect to the total of at least the graft copolymer compound and the medium. %, more preferably 2.5 to 7.5 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,
The block copolymer compound is
a polymer block a mainly composed of styrene-based compound units;
Polymer block b ₁ mainly composed of units of at least one hydrocarbon-based compound selected from the group consisting of alkene-based compounds, diene-based compounds and alkyne-based compounds, or polymer block mainly composed of (meth)acrylate units _A compound having a block copolymer structure with b2,
A polymer composed _only of (meth)acrylate units constituting the polymer block b2 has a glass transition temperature of −100° C. or more and 50° C. or less,
Examples of the compatible composition include compatible compositions having a liquid-to-gel transition temperature (Tc) at 0 to 150°C.

Hereinafter, a compound having a block copolymer structure of polymer block _a and polymer block b1 will be referred to as compound A1, and polymer block _a and polymer block b2 mainly composed of ₍ meth)acrylate units. A compound having a block copolymer structure is referred to as compound _A2 .

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

From the viewpoint of the compatibility of the curable resin composition described later and the liquid-to-gel state transition property, the styrenic compound that can constitute the polymer block a includes:
preferably styrene; α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, 4-tert-butylstyrene, alkyl group-substituted styrene such as 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 styrenic compound selected from the group consisting of halogen-substituted styrenes such as
Styrene is more preferred.

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

The molar ratio of the styrenic compound units in the polymer block a is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, from the viewpoint of the liquid-to-gel state transition 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, preferably under the following conditions (the same shall apply hereinafter):
Measuring device: GPC system manufactured by Shimadzu Corporation;
Column type: organic solvent-based SEC column (manufactured by Tosoh Corporation);
Type of solvent: Tetrahydrofuran (THF).

(3.1) Compound A ₁
The specific hydrocarbon _- based compound unit constituting the polymer block b1 is formed when the specific hydrocarbon-based compound described later is polymerized.

The specific hydrocarbon _- based compound that can constitute the polymer block b1 includes, from the viewpoint of compatibility with the curable resin composition described below and liquid-to-gel state transition,
The alkene-based compound is at least one compound selected from alkenes 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 described as a "(co)polymer".

As the specific hydrocarbon _- based compound that can constitute the polymer block b1, from the viewpoint of the compatibility of the curable resin composition described later and the liquid-to-gel state transition property, among the above-mentioned compounds, hydrogenated compounds are preferred. is preferably

From the same point of view, in the preferred specific hydrocarbon-based compound described above,
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 this specification, for example, an alkene that is a constituent of "alkene", "alkene polymer", and "water additive of alkene polymer" is referred to as "base alkene".

In the preferred specific hydrocarbon-based compound described above, from the same point of view, as a base hydrocarbon,
preferably diene and/or alkyne, more preferably diene,
More preferably, it is at least one hydrocarbon compound selected from the group consisting of butadiene, isoprene and acetylene, more preferably butadiene and/or isoprene.

It is preferable that the polymer block b1 is composed _only of specific hydrocarbon-based compound units. It is a polymer structure mainly composed of specific hydrocarbon-based compound units, which is allowed to contain compound units of

From the viewpoint of compatibility and liquid-gel state transition of the curable resin composition described later,
The weight average molecular weight of the polymer b ₂ is preferably 1×10 ⁵ or more, more preferably 1×10 ⁵ to 1×10 ⁹ , still more preferably 1×10 ⁵ to 1×10 ⁷ ,
The molar ratio of the specific hydrocarbon compound units in the polymer block b1 is preferably 90 to ₁₀₀ mol%, more preferably 95 to 100 mol%, still more preferably 99 to 100 mol%.

The weight _average molecular weight of Compound A1 is preferably from 10,000 to 500,000, more preferably from 30,000 to 400,000, and even more preferably from 50,000 to 300,000, from the viewpoint of compatibility and liquid-to-gel state transition of the curable resin composition.

From the viewpoint of compatibility and liquid _- gel state transition property of the curable resin composition, the compound A1 is
It is preferably a triblock structure in which the polymer block _a is bonded to both ends of the polymer block b1 or _a diblock structure in which the polymer block a and the polymer block b1 are bonded, and is preferably a triblock structure. is more preferable.

From the viewpoint of compatibility and liquid-gel state transition of the curable resin composition described later,
It is preferable that the mass % of polymer block a in the total mass of polymer block _a and polymer block b1 is high.

From the viewpoint of the compatibility and liquid-to-gel state transition of the curable resin composition described later, the total mol% of polymer block _a and polymer block b1 in compound A is preferably 90 to 100 mol%, More preferably 95 to 100 mol %, still more preferably 99 to 100 mol %.

_Each structure and bonding form of polymer block _a and polymer block b1 of compound A1 may be selected so that the curable resin composition described later has compatibility and liquid-to-gel state transition. It can be selected from the commercially available products listed in 1.

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

(3.2) Compound _A2
The (meth)acrylate unit that constitutes the polymer block _b2 is a (meth)acrylate whose glass transition temperature is −100° C. or _more and 50° C. or less of a polymer (hereinafter referred to as polymer b2) composed of the polymer block b2. It is formed when a compound polymerizes. From the viewpoint of the stability of the glass transition temperature, the weight _average molecular weight of the polymer b2 is preferably 1×10 ⁵ or more, more preferably 1×10 ⁵ to 1×10 ⁹ , and still more preferably 1×10 ⁵ . ˜1×10 ⁷ .

As the (meth)acrylate compound that can constitute the polymer block _b2 ,
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, and 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 and the like;
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)acrylate acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate containing alicyclic structure (meth)acrylate, acryloylmorpholine, diethylacrylamide, etc. selected from the group consisting of acrylamide is a compound,
More preferred is n-butyl acrylate (butyl acrylate).

From the viewpoint of compatibility and liquid-to-gel state transition of the curable resin composition described later, the polymer block b2 is preferably composed _only of (meth)acrylate units. As long as the compound A does not have a liquid-gel transition temperature (Tc) and the compatible compound described later has a liquid-gel transition temperature (Tc), other copolymerizable compound units are included. is a polymer structure mainly composed of (meth)acrylate units.

From the viewpoint of the compatibility and liquid-to-gel state transition of the curable resin composition described later, the molar ratio of ₍ meth)acrylate units in the polymer block b2 is preferably 90 to 100 mol%, more preferably 95 It is up to 100 mol %, more preferably 99 to 100 mol %.

Since the polymer block _b2 in the compound _A2 is considered to have a polymerization structure almost equivalent to that of the polymer _b2 , the glass transition point of the compound _A2 is the temperature at which the glass transition point of the polymer _b2 is included. It is preferred to have a glass transition temperature in the range, ie -100°C to 50°C.
stomach.

Compound _A2 , from the viewpoint of the liquid-to-gel state transition properties of the liquid-compatible composition described later,
It is preferable to have at least one triblock structure in which the polymer block a is bound to _both ends of the polymer block b2,
Although it is more preferable that it is composed only of a triblock structure,
from 0 to 150° C., compound A has no liquid-to-gel transition temperature (Tc),
In the range where the compatible composition described later has a liquid-gel state transition temperature (Tc),
A structure other than a triblock structure (for example, a diblock structure in which polymer block a and polymer block b2 _are bonded) may be included.

From the above viewpoint, the molar ratio of the triblock structure in compound _A2 is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, still more preferably 99 to 100 mol%.

Compound _A2 is a triblock structure ₍ polymer block a - polymer block b ₂ -polymer blocks a) can be used.

The weight average molecular weight of compound _A2 is preferably 10,000 to 500,000, more preferably 30,000 to 400,000, still more preferably 50,000 to 300,000, from the viewpoint of compatibility of the curable resin composition and liquid-to-gel state transition.

₍ 3.3) Medium The medium in composition X3 is a compatible composition in composition X3 that is compatible with compound A1 or _A2 and has _a liquid-gel state transition temperature (Tc) at 0 to 150 ° C. (hereinafter also referred to as a compatible composition), and suitable examples thereof include the medium in composition X3.

(3.4) Compatible composition _A compatible composition in which compound A1 or _A2 and a medium are compatible,
from 0 to 150°C,
Compound A ₁ or A ₂ does not have a liquid-gel transition temperature (Tc),
The compatible composition is a composition having a liquid-gel transition temperature (Tc),
It preferably has the same properties as the compatible composition in composition X1.

From the standpoints of the compatibility composition when it is in a liquid state, from the viewpoint of the spreadability to members and the phase transition property, the weight part of the medium is preferably 200 to 1000 parts by weight with respect to 100 parts by weight of the compound A ₁ or A ₂ . More preferably 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 the compound A ₁ or A ₂ (preferably the compound A ₁ or A ₂ further provided with reactivity), and the group consisting of radical reactivity, cation reactivity, anion reactivity and moisture reactivity as the compound B It is preferable to contain at least one reactive compound having reactivity selected from (preferably further combined with a plasticizer) and a polymerization initiator (hereinafter, compound A ₁ or A ₂ (preferably, reactive is further provided with a compound A ₁ or A ₂ ), and a reactive compound (preferably is further combined with a plasticizer) and a gel-like compatible composition containing a polymerization initiator is also referred to as a compatible composition viscoelastic body).

When the compatible composition is a compatible composition viscoelastic body, the content 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 compatible composition viscoelastic body, the polymerization initiator to be added is preferably 1 to 10% by mass, more preferably 2 to 8%, relative to the total of at least compound A ₁ or A ₂ and the medium. % by mass, more preferably 2.5 to 7.5% by mass.

The compatible composition in the composition X1, X2 or X3 can optionally contain additives other than the medium as described later within a range that does not impair the property of having a liquid-gel state transition temperature (Tc). , In that case, the amount of additives other than the medium is preferably 0 to 50% by mass, more preferably 0 to 30% by mass, of the total mass of the compound.

The compatible composition includes, for example, an antioxidant, a wetting agent, a surfactant, an ionic liquid, an antifoaming agent, an ultraviolet absorber, a light stabilizer, a Additives such as inorganic and organic fillers and polymers can be included.

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

Compositions X1, X2 and X3 can be transparent without the addition of light-scattering compounds such as fillers, preferably with a HAZE value of 1.0 or less at a thickness of 0.3 mm. Therefore, efficient light irradiation can be performed when photocurability is utilized.

The HAZE value represents the ratio of diffuse transmittance to the total light transmittance of the compatible composition, and from the viewpoint of efficient light irradiation, the HAZE value is preferably 0.7 or less, more preferably 0.5 or less. , more preferably 0.3 or less, more preferably 0.2 or less.

(Composition Y)
For example, in composition X1, when a block copolymer compound and a medium for obtaining a compatible composition are selected, a compatible composition having thixotropic properties in a gel form (hereinafter also referred to as a thixotropic compatible composition ) and can also constitute thixotropic compatible compositions that are compatible with optical clarity.

From the viewpoint that the compatible composition has compatibility and thixotropic properties, the medium is preferably 100 to 1000 parts by mass, more preferably 120 to 600 parts by mass, with respect to 100 parts by mass of the block copolymer compound in the compatible composition. Combine parts by mass.

(Composition Z)
Composition Z, which is a thixotropic gel-like resin composition having no Tc, is, for example, a composition imparted with thixotropic properties by adding a rheology modifier to a liquid medium having no thixotropic properties. mentioned.

Media that can be used in preparing composition Z include:
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;
Composition Z can be obtained by adding a rheology modifier having low reactivity to these to impart thixotropic properties.

Examples of rheology modifiers include:
Silica, fumed silica, precipitated silica, asbestos powder, copper oxide, copper hydroxide, iron oxide, alumina, zinc oxide, lead oxide, magnesia, tin oxide and other metal oxide particles, calcium carbonate, carbon, silica, mica , smectite, inorganic fine particles such as carbon black;
Organic fine particles such as polystyrene beads, polyethylene particles, acrylic particles, polysiloxane resin particles, isoprene rubber particles, polyamide particles;
Polymer compounds such as polyethylene, polysiloxane, polyacryl, polyamide, polyvinyl alcohol, alkyl-modified cellulose, peptide, polypeptide; and amide wax, hydrogenated castor oil derivative, 1,3,5-tris(trialkoxysilylalkyl) isocyanate Organic compounds such as nurate, modified polyester polyol, ethyl cellulose, methyl cellulose, cellulose derivatives, and organic bentonite can be used.

Rheology modifiers may more specifically include:
Organic compounds such as amide wax, 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 (Bic Chemie Co., Ltd.), Disparlon thixotropic agent series (Kusumoto Kasei);
Polysiloxane, polyacryl, polyamide, polyvinyl alcohol, alkyl-modified cellulose, peptide, polypeptide, and copolymers having two or more structures thereof;
Organic fine particles such as polystyrene beads, polyethylene particles, acrylic particles, polysiloxane resin particles, isoprene rubber particles, 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, which are exemplified in JP-A-2014-082328 and inorganic thixotropic agents such as fumed silica, precipitated silica and asbestos powder, also called thixotropic agents exemplified in JP-A-2014-019802; organic bentonites, modified polyester polyols, fatty acid amides, etc. organic thixotropic agents; hydrogenated castor oil derivatives, fatty acid amide waxes, aluminum stearate, barium stearate and the like.

As the non-thixopic liquid medium in composition Z, the suitable mediums listed for compositions X and Y can be used.

As rheology modifiers in composition Z,
Silica, fumed silica, precipitated silica, amide wax, hydrogenated castor oil derivatives, and cellulose derivatives are preferred.
Amide wax, hydrogenated castor oil derivatives, and cellulose derivatives are more preferred.
Amide waxes are more preferred.

In addition, in a composition in which a rheology modifier is added to a liquid medium that does not have thixotropic properties to impart thixotropic properties, the regularity of the arrangement of the rheology modifier in the liquid medium may change rapidly even with temperature. may lead to having a Tc and such compositions would belong to composition Y.

(5) A more suitable gel resin composition The gel resin composition to be applied to the present inventions 1 and 2 is, for example, molded into a sheet, coated with the sheet gel resin composition, Appropriate curing by moisture, heat or light improves protective film formation and releasability.

For example, regarding the compounds A and B in the compositions X1, X2 and X3 and the composition Y, the following aspects are preferable.

From the viewpoint of protective film-forming property and releasability, compound A has a radical-reactive group, a cation-reactive group, and an anion-reactive group at the end or side chain of the block copolymer of polymer block a and polymer block b. Reactivity is preferably further imparted by having at least one reactive functional group selected from the group consisting of groups and moisture-reactive groups.

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

From the viewpoint of protective film formation and releasability, in order to improve the elasticity and adhesiveness of the gel-like compatible composition and the compatible composition at the time of curing, the above-mentioned radical-reactive groups include:
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)acrylates, (meth)acrylamides, urethane (meth)acrylates and vinyl ethers,
More preferably, it is at least one radical reactive group selected from the group consisting of (meth)acrylates and urethane (meth)acrylates.

From the viewpoint of protective film formation and releasability, in order to improve the elasticity and adhesiveness of the gel-like compatible composition and the compatible composition at the time of curing, the above-mentioned cation-reactive groups include:
Preferably, it is at least one cationic reactive group selected from the group consisting of epoxy, oxetane and vinyl ether.

From the viewpoint of protective film formation and releasability, in order to improve the elasticity and adhesiveness of the gel-type compatible composition and the compatible composition at the time of curing, the above-described anion-reactive groups are preferably epoxy and oxetane. and at least one anion-reactive group selected from the group consisting of vinyl ethers.

From the viewpoint of protective film formability and releasability, in order to improve the elasticity and adhesiveness of the gel compatible composition and the compatible composition at the time of curing, the above-mentioned moisture-reactive groups are preferably isocyanate groups and /or an alkoxysilyl group.

From the viewpoint of protective film formation and releasability, the compound B is radical-reactive, cationic-reactive, and anionic-reactive, in order to improve the elasticity and adhesiveness of the gel-like compatible composition and the compatible composition when cured. It is preferred to use a reactive compound having at least one reactivity selected from the group consisting of moisture reactivity and moisture reactivity.

From the viewpoint of protective film formability and releasability, in order to improve the 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
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)acrylates, (meth)acrylamides, urethane (meth)acrylates and vinyl ethers,
More preferably, at least one radical-reactive group selected from the group consisting of (meth)acrylates and urethane (meth)acrylates (preferably bifunctional or higher polyfunctional from the viewpoint of radical reaction speed and stability) It is a reactive compound with

From the viewpoint of protective film formability and releasability, in order to improve the elasticity and adhesiveness of the gel-like compatible composition and the compatible composition at the time of curing, the cation-reactive compound in compound B is:
Preferably, it is at least one cationic reactive compound selected from the group consisting of epoxy, oxetane and vinyl ether.

From the viewpoint of protective film formability and releasability, the anion-reactive compound is preferably epoxy or oxetane in order to improve the strength, elasticity, and adhesiveness of the gel-type compatible composition and the compatible composition when cured. and at least one anion-reactive compound selected from the group consisting of vinyl ethers.

From the viewpoint of protective film formability and releasability, the moisture-reactive compound in compound B is preferably They are isocyanate groups and/or alkoxysilane groups.

From the viewpoint of protective film formability and releasability, in order to improve the strength, elasticity and adhesiveness of the gel compatible composition and the compatible composition at the time of curing, preferably:
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 cation-reactive group and compound B, which is a cation-reactive compound;
A combination of a compound A having an anion-reactive group and a compound B that is an anion-reactive compound, and
A compatible composition is composed of at least one combination selected from the group consisting of compound A having a moisture-reactive group and compound B that is a moisture-reactive compound.

From the viewpoint of protective film formation and releasability, in order to improve the strength, elasticity and adhesiveness of the gel-like compatible composition and the compatible composition at the time of curing, the compatible composition is selected according to the type of reactive compound. It is preferable to contain an appropriate polymerization initiator accordingly.

When the reactive compound is a radical reactive compound, the polymerization initiator is
preferably 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, benzophenone, 2,2-dimethoxy -1,2-diphenylethan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, 2-benzyl-2-dimethylamino-1-(4 -morpholinophenyl)butanone-1,2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl-1-[4-methylthio]phenyl]-2-morpholinopropan-1-one, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, 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-propanone, isopropylthioxanthone, methyl o-benzoylbenzoate , [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-chloroacridone, 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, acrylated benzophenone, bis(η5-2,4-cyclopentadien-1-yl)-bis( 2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl) titanium, o-methylbenzoyl benzoate, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamylethyl ester, active tertiary at least one compound selected from the group consisting of amines, carbazole-phenone photoinitiator compounds, acridine photoinitiator compounds, and triazine photoinitiator compounds;
More preferred are 1-hydroxy-cyclohexyl-phenyl-ketone and/or 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide.

When the reactive compound is a cationic reactive compound, the polymerization initiator is
at least one ionic photoacid generator compound preferably selected from the group consisting of aryldiazonium salts, diarylhalonium salts, triarylsulfonium salts, triphosphonium salts, iron allene complexes, titanocene complexes and arylsilanol aluminum complexes, and or at least one nonionic photoacid generator compound selected from the group consisting of nitrobenzyl esters, sulfonic acid derivatives, phosphoric esters, phenolsulfonic acid esters, diazonaphthoquinones and N-hydroxyimidosulfonates.

When the reactive compound is an anion-reactive compound, the polymerization initiator is
Preferably, it is selected from the group consisting of 1,10-diaminodecane, 4,4′-trimethylenedipiperazine, carbamate compounds and derivatives thereof, cobalt-amine complex compounds, aminooxyimino compounds and ammonium borate compounds. at least one compound;

When the reactive compound is a moisture-reactive compound, the polymerization initiator is
Preferably, at least one titanium compound selected from the group consisting of tetrabutyl titanate, tetrapropyl titanate, titanium tetraacetylacetonate and bisacetylacetonato diisopropoxytitanium as a silanol condensation catalyst;
Dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctate, dibutyltin diethylhexanolate, dibutyltin dimethyl maleate, dibutyltin diethyl maleate, dibutyltin dibutyl maleate, dibutyltin dioctyl maleate, dibutyltin ditridecyl Maleate, dibutyltin dibenzyl maleate, dibutyltin diacetate, dioctyltin diethyl maleate, dioctyltin dioctyl maleate, dibutyltin dimethoxide, dibutyltin dinonylphenoxide, dibutenyltin oxide, dibutyltin diacetylacetonate, dibutyltin at least one tetravalent organotin 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;
at least one organoaluminum compound selected from the group consisting of aluminum trisacetylacetonate, aluminum trisethylacetoacetate and diisopropoxyaluminumethylacetoacetate;
zirconium compounds such as zirconium tetraacetylacetonate,
Reactants such as amine compounds, acidic phosphoric esters, reaction products of acidic phosphoric esters and amine compounds, saturated or unsaturated polycarboxylic acids or their acid anhydrides, salts of carboxylic acid compounds and amine compounds, etc. , lead octylate, and
It is at least one compound selected from the group consisting of isocyanate reaction catalysts.

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

When the compatible composition is curable, the content 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 polymerization initiator to be added is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, and still more preferably 2.5 to 7.5% by mass.

Moisture-curable compounds include, for example, isocyanate groups, alkoxysilyl groups, or reactive silicon groups having hydroxyl groups or hydrolyzable groups bonded to silicon atoms and capable of cross-linking by forming siloxane bonds. A cured product can be obtained by cross-linking through a hydrolysis reaction or the like of a moisture-reactive group.

Examples of thermosetting component compounds include epoxy-based, oxetane-based, vinyl ether-based, phenol-based, thermosetting polyurethane-based, unsaturated polyester-based, ( Monomers and/or oligomers such as meth)acrylate compounds, (meth)acrylamides, (meth)acrylonitrile, vinyl compounds, allyl ethers, maleimide and maleic anhydride, epoxy arylates, urethane acrylates, and polyester acrylates. be done.

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

From the viewpoint of forming a protective film, the cured product of the gel resin composition preferably has an elastic modulus range of 0.1 to 10,000,000 kPa, more preferably 1 to 1,000,000 kPa, and still more preferably 10 to 100,000 kPa at 25°C. be.

As described above, the gel resin composition is preferably in the form of a sheet when used as a bonding material for the member 1 and the member 2. Therefore, the composition X1, X2 or X3 can be easily formed into a sheet. Preferably.

The composition X1, X2, X3 or Y preferably has a curability to be cured by moisture, heat or light, more preferably by heat or light, still more preferably by light, from the viewpoint of protective film-forming property and peelability. It is preferable that the composition after curing is a compatible composition viscoelastic body described in paragraph 0062 of JP-A-2017-066368.

<Embodiment Example of Gel Resin Composition>
(1) Embodiment Examples of Composition X1 Description will be made with reference to Tables 3 and 4.
100 g of compound a1 and 400 g of compound b1 are weighed, filled in a container (made of SUS316, capacity 2000 ml), and rotated 200 times at 80° C. under atmospheric pressure using a three-one motor (manufactured by Shinto Kagaku Co., Ltd.). /min for 360 minutes to obtain the compatible composition of Embodiment 1-1.

Compound a1 and compound b1 were replaced with the compounds shown in Tables 3 and 4, and the formulations shown in Tables 3 and 4 were used to prepare compatible compositions of Examples 1-2 to 1-23 in the same manner as in Embodiment Example 1-1. can get.

<Compound raw material of composition X1>
(1-1) Compound A
polymer block a is composed of methyl methacrylate,
polymer block b is composed of butyl acrylate,
A triblock copolymer compound of polymer block a—polymer block b—polymer block a and a diblock copolymer compound of 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 Co., Ltd.)
Compound a2: KURARITY LA2250 (registered trademark, Kuraray Co., Ltd.)
Compound a3: KURARITY LA2330 (registered trademark, Kuraray Co., Ltd.)
Compound a4: KURARITY LA4285 (registered trademark, Kuraray Co., Ltd.)

In the total mass of polymer block a and polymer block b, polymer block a
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,
LA2140, LA2250, LA2330 and LA4285 are triblocks;
LA1892 and LA1114 described later are diblock bodies,
The molecular weights are LA2330>LA2140=LA2250=LA4285=LA1114=LA1892.

(1-2) Compound B
Compound b1: isodecyl acrylate (SR395, manufactured by Sartomer)
Compound b2: 4-tert-butylcyclohexyl acrylate (manufactured by Rahn, genomer1119)
Compound b3: 4-hydroxybutyl acrylate (manufactured by Nippon Kasei Co., Ltd., 4-HBA)
Compound b4: diisononylcyclohexyl dicarboxylate (manufactured by BASF, DINCH)
Compound b5: alkyl benzoate (alkyl has 12 to 16 carbon atoms) (Liponate NEB, manufactured by Lipo Chemicals)
Compound b6: hydrogenated rosin ester (KE-311, manufactured by Arakawa Chemical Industries, Ltd.)
Compound b7: Epoxy ester (4,5-epoxy-1,2-cyclohexanedicarboxylic acid bis(2-ethylhexyl)) (manufactured by DIC, W150)
Compound b8: Disproportionated rosin ester (manufactured by Arakawa Chemical Co., Ltd., ME-D)
Compound b9: triethylene glycol bis(2-ethylhexanoate) (manufactured by Proviron, Proviplast 1783)

(1-3) Compound B1 (radical-reactive bifunctional compound and polyfunctional compound)
Compound b1-1: PPG urethane acrylate (UA10000B manufactured by KSM)
Compound b1-2: Aliphatic urethane acrylate (EB270, manufactured by Daicel Allnex)
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 Nippon Kasei Co., Ltd., 4-HBA)
Compound b2-2: Lauryl acrylate (manufactured by Kyoeisha Chemical Co., LA)
Compound b2-3: isodecyl acrylate (Sartomer, SR395)
Compound b2-4: isobornyl acrylate (manufactured by Nippon Kayaku, RM-1002)
Compound b2-5: 4-tert-butylcyclohexyl acrylate (genomer 1119 manufactured by Rahn)
Compound b2-6: Pentamethylpiperidyl methacrylate (manufactured by Hitachi Chemical 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) Embodiment Examples of Composition X2 Description will be made with reference to Tables 5 and 6.
100 g of compound a1 and 200 g of compound b1 are weighed, filled in a container (made of SUS316, capacity 2000 ml), and rotated 200 times at 80 ° C. under atmospheric pressure using a three-one motor (manufactured by Shinto Kagaku Co., Ltd.). /min for 360 minutes to obtain the compatible composition of Embodiment 2-1.

Compound a1 and compound b1 in Embodiment Example 2-1 are replaced with the compounds described in Tables 5 and 6, and the formulations described in Tables 5 and 6 are used in the same manner as in Example Embodiment 2-1. Embodiment Example 2- 2-14 can be obtained.

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

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 Co., Ltd.)
Compound a-2: NB5065 (Mitsubishi Rayon Co., Ltd.)
Compound a-3: NB5066 (Mitsubishi Rayon Co., Ltd.)
Compound a-4: NB5073 (Mitsubishi Rayon Co., Ltd.)
Compound a-5: NB5088 (Mitsubishi Rayon Co., Ltd.)

(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: Proviplast 1783 (triethylene glycol bis(2-ethylhexanoate, Proviron)
Compound b-4: DINCH (diisononylcyclohexyl dicarboxylate, BASF)
Compound b1-1: Hydrogenated rosin ester (KE-311, manufactured by Arakawa Chemical Industries, Ltd.)
Compound b1-2: DINCH (diisononylcyclohexyl dicarboxylate, BASF)
Compound b2-1: TE-2000 (polybutadiene urethane acrylate, Nippon Soda Co., Ltd.)
Compound b2-2: Aliphatic urethane acrylate (EB270, manufactured by Daicel Allnex)
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: pentamethylpiperidyl methacrylate (manufactured by Hitachi Chemical 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) Embodiment Examples of Composition X3 Description will be made with reference to Tables 7 to 11.
₁₀₀ g of compound a1-1 as compound A1 and 200 g of compound b-4 as compound B are weighed, filled in a container (made of SUS316, capacity: 2000 ml), 80 ° C., under atmospheric pressure, three-one motor (new manufactured by Tokagaku) and stirred at 200 rpm for 360 minutes to obtain the compatible composition of Embodiment 3-1-1.

Replace compound A ₁ in Example 3-1-1 with compound A ₁ or A ₂ listed in Tables 8 to 10, replace compound B with another compound B listed in Tables 8 to 10, and add other compounds , the compatible compositions of Examples 3-1-2 to 3-1-16 and 3-2-1 to 3-2-1 can be obtained in the same manner as in Example 3-1-1 with the formulations shown in Tables 8 to 10.

<Compound raw material of composition X3>
(3-1) Compound A
Compounds listed in Table 7 can be used. _The glass transition temperature of polymer b2 is -25°C.

(3-2) Compound B
Compound b-1: Salacos 99 (isononyl isononanoate, Nisshin OilliO Co., Ltd.)
Compound b-2: DINCH (diisononylcyclohexyl dicarboxylate, BASF)
Compound b-3: Salacos P-8 (2-ethylhexyl palmitate, Nisshin OilliO Co., Ltd.)
Compound b-4: genomer1119 (4-tertbutylcyclohexyl acrylate, Rahn)
Compound b-5: SR395 (isodecyl acrylate, Sartomer)
Compound b-6: KE-311 (hydrogenated rosin ester, Arakawa Chemical Co., Ltd.)
Compound b-7: Alcon P-100 (hydrocarbon resin, Arakawa Chemical Co., Ltd.)
Compound b-8: Clearon M-105 (hydrogenated aromatic modified terpene resin, Yasuhara Chemical Co.)
Compound b-9: TE-2000 (polybutadiene urethane acrylate, Nippon Soda Co., Ltd.)
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)

[Embodiment example of member surface coating process]
A. Embodiment 1: In the case of a composite with a built-in display device In the process of assembling and dismantling a composite composed of a housing in which a display device such as a mobile phone, a personal computer, or a display is built,
In the final composite assembly step, a member surface coating step of coating the entire surface S with a gel resin composition in order to prevent the surface S of the curved display device from being soiled;
and a member surface coating film removing step of removing the coating film in the step of using or repairing the composite.

By using a gel resin composition, it can be handled as a liquid resin at the time of coating, and after the coating film is formed, the temperature drops or the ejection stress disappears, suppressing fluidity and preventing outflow to areas other than the coating film. can. Furthermore, by adjusting the properties after photocuring to film physical properties that can be handled as a film and surface adhesion to the extent that it can be peeled off, it can be used as a substitute sheet for protective films (hereinafter also referred to as "gel-like resin composition sheet") that has been conventionally used. can handle.

If necessary, there may be a coating film curing step for curing the coating film with light or the like between the member surface coating film step and the member surface coating film removing step, and the cured coating film can be physically easily peeled off. (Fig. 2).

A coating film that uses a gel-like resin composition that has transparency and photo-curing properties has the effect of not affecting the inspection process of the display or foreign matter inspection even after curing. The entire coating film is photocured to maintain good protective properties and peelability.

Description will be made below with reference to FIGS.

<Member surface coating process>
(1) Aspect example 1
As a coating device, for example, coating devices such as slit coat, knife coat, curtain coat, and spray coat, coating devices such as dispensers and jet dispensers, and printing devices such as screen printing and gravure printing,
The gel resin composition is preferably heated to Tc+5° C. or higher, more preferably Tc+10° C. or higher, and still more preferably Tc+15° C. or higher, and coated on the surface S of the display device in a desired region and shape,
It is preferably Tc-5°C or lower, more preferably Tc-10°C or lower, still more preferably Tc-15°C or lower, and naturally cooled to form a gel resin composition sheet.

(2) Aspect example 2
Alternatively, a gel resin composition sheet may be prepared on a releasable base in advance, cut into a desired shape, and transferred to the surface S to form a coating film.
The gel resin composition sheet can be obtained by heating the gel resin composition and coating it with a coating device, or by diluting the gel resin composition with a solvent and applying it at room temperature to volatilize the solvent to form a gel composition. You can use it as a seat.
If the gel resin composition has thixotropy, it can be coated even at a temperature of Tc or lower.

If the gel-like resin composition is photocurable, a coating film curing step of photocuring the coating film by, for example, irradiating ultraviolet rays from a light irradiation device can be provided after the coating film.

The coating thickness is preferably 1 to 3000 μm, more preferably 5 to 1000 μm, still more preferably 10 to 500 μm, from the viewpoints of protective film formation and releasability.

<Part surface coating removal process>
(1) Aspect example 1
After being used as a protective sheet, the coating film of the gel-like resin composition can be liquefied by heating to Tc or higher or dissolved in a solvent to be removed.

(2) Aspect example 2
The photocured gel-like resin composition exhibits a film property that can withstand peeling and an appropriate interfacial strength, thereby physically peeling off the coating film of the gel-like resin composition formed on the surface S of the display device. can do.

B. Embodiment 2: Composite in which Wiring Forming Member is Built When wiring is plated on an electronic member such as a semiconductor component,
It has a member surface coating step of coating with a gel-like resin composition to protect a region other than the region to be plated in the member surface processing step, where plating should be avoided.
A coating film that uses a gel-like resin composition that has transparency and photo-curing properties has the effect of not affecting the damage on the surface of the member or affecting the foreign matter inspection even after curing. Even when the coating is applied, the entire coating film is photocured and good protective properties and peelability are maintained.

Description will be made below with reference to FIG.

<Member surface coating process>
(1) Aspect example 1
As a coating device, for example, coating devices such as slit coat, knife coat, curtain coat, and spray coat, coating devices such as dispensers and jet dispensers, and printing devices such as screen printing and gravure printing,
The gel resin composition is preferably heated to Tc+5° C. or higher, more preferably Tc+10° C. or higher, and still more preferably Tc+15° C. or higher, and coated on the surface S of the display device in a desired region and shape,
Natural cooling is preferably performed in an environment of Tc-5°C or lower, more preferably Tc-10°C or lower, and still more preferably Tc-15°C or lower.
(2) Aspect example 2
Alternatively, a gel resin composition sheet may be prepared on a releasable base in advance, cut into a desired shape, and transferred to the surface S to form a coating film.
The gel resin composition sheet can be obtained by heating the gel resin composition and coating it with a coating device, or by diluting the gel resin composition with a solvent and applying it at room temperature to volatilize the solvent to form a gel composition. You can use it as a seat.
If the gel resin composition has thixotropy, it can be coated even at a temperature of Tc or lower.

If the gel-like resin composition is photocurable, a coating film curing step of photocuring the coating film by, for example, irradiating ultraviolet rays from a light irradiation device can be provided after the coating film.

The coating thickness is preferably 1 to 3000 μm, more preferably 5 to 1000 μm, still more preferably 10 to 500 μm, from the viewpoints of protective film formation and releasability.

When a gel-like resin composition that exhibits thixotropy and transparency even after photocuring is used, screen printing is possible, and transparency is maintained even after photocuring. In some cases, it can be used as a plating protective film that does not require a removal step.

<Part surface coating removal process>
(1) Aspect example 1
After being used as a protective sheet, the coating film of the gel resin composition can be liquefied by heating to Tc or higher or dissolved in a solvent to be removed.

(2) Aspect example 2
The photocured gel-like resin composition exhibits a film property that can withstand peeling and an appropriate interfacial strength, thereby physically peeling off the coating film of the gel-like resin composition formed on the surface S of the display device. can do.

C. Embodiment 3: In the case of a composite incorporating a member to be chemically etched For example, as a member surface processing step for silicon-based members used for semiconductor parts and optical parts,
Polishing of the wafer surface for wafer members as silicon substrates,
Silicon etching to form a fine three-dimensional pattern on the surface of a silicon member,
A chemical etching process such as an etching process of a _SiO2 film on a silicon substrate can be mentioned.

A member surface coating step of coating with a gel-like resin composition a portion of the surface S other than the portion to be etched in the chemical etching step;
If necessary, a member surface coating film removing step for removing the coating film.

By using a temperature-responsive gel as a protective film, the gel resin composition can be coated only on the part to be coated, and the gel resin composition can be, for example, a compatible composition having solvent solubility. By using viscoelastic material, it is possible to create a protective film that does not require a curing process, and it can be removed by dissolution and cleaning without going through a physical removal process, reducing the process load compared to conventional resist coatings. can be reduced.

Description will be made below with reference to FIG.

<Member surface coating process>
(1) Aspect example 1
As a coating device, for example, coating devices such as slit coat, knife coat, curtain coat, and spray coat, coating devices such as dispensers and jet dispensers, and printing devices such as screen printing and gravure printing,
The gel resin composition is preferably heated to Tc+5° C. or higher, more preferably Tc+10° C. or higher, and still more preferably Tc+15° C. or higher, and coated on the surface S of the display device in a desired region and shape,
Natural cooling is preferably performed in an environment of Tc-5°C or lower, more preferably Tc-10°C or lower, and still more preferably Tc-15°C or lower.
(2) Aspect example 2
Alternatively, a gel resin composition sheet may be prepared on a releasable base in advance, cut into a desired shape, and transferred to the surface S to form a coating film.
The gel resin composition sheet can be obtained by heating the gel resin composition and coating it with a coating device, or by diluting the gel resin composition with a solvent and applying it at room temperature to volatilize the solvent to form a gel composition. You can use it as a seat.
If the gel resin composition has thixotropy, it can be coated even at a temperature of Tc or lower.

If the gel-like resin composition is photocurable, a coating film curing step of photocuring the coating film by irradiating ultraviolet rays, for example, can be provided after the coating film.

The coating thickness is preferably 1 to 3000 μm, more preferably 5 to 1000 μm, still more preferably 10 to 500 μm, from the viewpoints of protective film formation and releasability.

If necessary, a photocurable gel-like resin composition can be used, and the coating film is photocured by, for example, ultraviolet irradiation after the coating film.

<Part surface coating removal process>
(1) Aspect example 1
After being used as a protective sheet, the coating film of the gel resin composition can be liquefied by heating to Tc or higher or dissolved in a solvent to be removed.

(2) Aspect example 2
The photocured gel-like resin composition exhibits a film property that can withstand peeling and an appropriate interfacial strength, thereby physically peeling off the coating film of the gel-like resin composition formed on the surface S of the display device. can do.

〔Example〕
Compositions X1 and Y were prepared and used in Examples of Invention 1.

(1) compound raw material (1-1) compound A
Compound a1: KURARITY LA2270 (registered trademark, manufactured by Kuraray Co., Ltd.)
Compound a2: KURARITY LA1892 (registered trademark, manufactured by Kuraray Co., Ltd.)
Compound a3: KURARITY LA2250 (registered trademark, manufactured by Kuraray Co., Ltd.)

In LA2270, polymer block a is about 40% by mass in the total mass of polymer block a and polymer block b.

(1-2) Compound B
Compound b1: PPG urethane acrylate (UA10000B, manufactured by KSM)
Compound b2: urethane acrylate oligomer (UN9200A, Negami Industry)
Compound b3: isobornyl acrylate (RM1002, manufactured by Nippon Shokubai Co., Ltd.)
Compound b4: Pentamethylpiperidyl methacrylate (FA-711MM, manufactured by Hitachi Chemical Co., Ltd.)
Compound b5: acryloylmorpholine (ACMO, manufactured by KJ Chemicals)
Compound b6: a mixture of tripentaerythritol octaacrylate and tripentaerythritol heptaacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., Viscoat #802)
Compound b7: polybutadiene urethane acrylate (TE-2000, manufactured by Nippon Soda Co., Ltd.)
Compound b8: Lauryl acrylate (LA, manufactured by Kyoeisha Chemical Co., Ltd.)
Compound b9: 4-hydroxybutyl acrylate (4-HBA, manufactured by Nippon Kasei Co., Ltd.)
Compound b10: hydrogenated rosin ester (KE-311, manufactured by Arakawa Chemical Industries, Ltd.)
Compound b11: bis (2-butoxyethyl) adipate (D931, manufactured by J-Plus)
Compound b12: diisononylcyclohexyl dicarboxylate (DINCH, BASF)
Compound b13: Compound b16: Acrylic polymer (manufactured by Toagosei Co., Ltd., UP1110)

(1-3) Compounds that improve peelability Compound c1: polyether-modified siloxane (manufactured by Evonik, TEGO GLIDE440)

(1-4) Other compounds Compound r1: 1-hydroxycyclohexylphenyl ketone (I-184, manufactured by BASF)

(2) Gel resin composition Description will be made with reference to Table 1.

(2-1) 300 g of compound a2 as compound A, compounds b1, b3 to 10 and b12 and r1 as compound B were weighed so as to be the parts by weight shown in Table 11, and a container (made of material SUS316, capacity 2000 ml ) and stirred at 200 rpm for 360 minutes at 80° C. under atmospheric pressure using a Three-One Motor (manufactured by Shinto Kagaku Co., Ltd.) to obtain a compatible composition of Example 1.

Compounds A, B and r1 of Example 1 listed in Table 1,
In Examples 2 and 3, the compound shown in Table 1 was substituted, and a gel resin composition was produced in the same manner with the formulation shown in Table 1,
Liquid compositions were produced in the same manner as described in Table 1 except that the compounds A, B and r1 of Example 1 were replaced with the compounds listed in Table 1 for Comparative Examples 1 to 3.

(2-2) The following physical properties were measured for each example and comparative example.

(2-2-1) Glass transition points of butyl acrylate polymer (polymer a) and methyl methacrylate polymer (polymer b).
(2-2-2) liquid-gel transition temperature (Tc)
(2-2-3) Complex viscosity (Pa s)
(2-2-4) Storage modulus (kPa) at 25°C
(2-2-5) Viscosity η ₁ (Pa·s) at 25°C and a shear rate of 1 (sec ^-1 )
(2-2-6) Viscosity η ₁₀ (Pa·s) at 25°C and a shear rate of 10 (sec ^-1 )
(2-2-7) thixotropic ratio (X ₁ = η ₁ / η ₁₀ )
(3) Measurement conditions

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

<Liquid-gel transition temperature Tc and storage rigidity>
The storage modulus G′ and the loss modulus G″ of the gel resin composition are
Using a rheometer (manufactured by Anton Paar),
Cone rotor (φ = 25 mm, rotor angle 2 °), frequency 1 Hz, strain 1%,
measured by cooling from 150°C to 0°C at 2°C/min,
Tc is the temperature at which the storage modulus G′ and the loss modulus G″ are equal in the range of more than 25° C. and 150° C. or less.

<Complex Viscosity>
Using a rheometer (manufactured by Anton Paar), 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. A numerical value measured in a temperature range of Tc or higher was defined as a complex viscosity.

<Storage modulus>
Using a rheometer (manufactured by Anton Paar),
Cone rotor (φ = 25 mm, rotor angle 2 °), frequency 1 Hz, strain 1%,
It was measured by cooling from 150°C to 0°C at a rate of 2°C/min.
Storage modulus values measured at 25° C. were read. However, when the transition temperature was 0°C ≤ Tc ≤ 30°C, the storage modulus at Tc-20°C was used.

<Viscosity _ηv >
Using a rheometer (manufactured by Anton Paar),
Cone rotor (φ = 25mm, rotor angle 2°),
At 25° C., the viscosity η _v at shear rate v is read while varying the shear rate from 0.01 (sec ⁻¹ ) to 100 (sec ⁻¹ ).
When no resistance based on the structural viscosity of the gel composition was generated in the cone rotor and the measured value could not be measured, it was judged as "impossible".

<Thixotropic ratio>
In measuring the viscosity η _v , the viscosity ratio X ₁ =η ₁ /η ₁₀ at a shear rate of 1 (sec ^-1 ) and a shear rate of 10 (sec ^-1 ) was calculated and used as a thixotropic ratio.

(Conditions for measuring HAZE value)
A 2.5 cm × 3.8 cm × 1 mmt glass was affixed with 0.3 mmt spacers on both ends, and a metal halide lamp (manufactured by igraphics, conveyor type) was used to apply 250 mW/cm and 3000 mJ with a curable resin composition sandwiched therebetween. /cm ² to cure the curable resin composition. Measure with a haze meter (NDH5000, manufactured by Nippon Denshoku Kogyo Co., Ltd.) to determine the ratio of total light transmittance and diffuse transmittance.

[Production Example 1 and Production Comparative Example 1]
(Protective film formability)
The compositions described in Example 1 and Comparative Example 1 were printed on a glass substrate 2 at 25° C. using a screen printer (manufactured by Newlong Co., Ltd.), with a screen thickness of 0.024 mm, a non-printed portion width of 1.5 mm, and a coating speed of 100 mm. /sec. After being left for 300 seconds after application, a conveyer-type ultraviolet irradiation device (metal halide lamp manufactured by Aigfic) was used with a peak illuminance of 400 mW/cm2, an integrated light intensity of 6000 mJ/ ^cm2 (wavelength of 350 nm manufactured by ORC), and a reaction rate of 100%. It was cured to produce a cured protective film on the glass substrate 2 .
The coating shape was measured using a laser microscope (LEXT OLS4000, manufactured by Olympus), and the width of the non-printed portion was measured.
If the width of the non-printed portion was maintained at 1.2 mm or more, it was evaluated as ◯, and if it was 1.2 mm or less, it was evaluated as ×.

[Production Example 2 and Comparative Production Examples 2-1 and 2-2]
(1) Formability of protective film

(1-1) Composition described in Example 2: Liquid compatible composition at 80°C.

(1-2) Composition described in Comparative Example 2: A composition that is liquid at 25°C.

(1-3) The composition described in Example 2 was at 80 ° C., and the composition described in Comparative Example 2 was at 25 ° C. on the glass substrate 3 using an air dispenser (manufactured by Musashi Engineering Co., Ltd., SHOT MASTER 300). The coating layer was applied using a needle of 0.61 ^mm and left for 300 seconds after application. ² (made by Oak Co., wavelength 350 nm), photocured at a reaction rate of 100%, and the composition of Example 2 was cooled to room temperature to prepare a protective layer on the glass substrate 3 .
Using a laser microscope (LEXT OLS4000, manufactured by Olympus), the coating shape is measured and the coating width is measured.
○ when the distance of the coating width is 1.0 mm or less,
× when the distance of the coating width exceeds 1.0 mm
and

(2) Solvent Solubility The composition described in Comparative Example 2 was applied in the same manner as in (1), and the peak illuminance was 400 mW/cm ² using a conveyer-type ultraviolet irradiation device (Aigfic, metal halide lamp). A light amount of 6000 mJ/cm ² (a wavelength of 350 nm manufactured by Oak Co., Ltd.) and a reaction rate of 100% cured and a non-cured sample were prepared as Comparative Examples 2-1 and 2-2, respectively.
Each protective layer is immersed in acetone (manufactured by Kanto Kagaku, special grade) and left for 10 minutes.
○ when the protective layer has dissolved and disappeared,
The case where the protective layer remained was evaluated as x.

[Production Example 3 and Production Comparative Example 3]
(1) Formation of protective film The composition described in Example 3 was formed into a liquid compatible composition at 80°C, and the composition described in Comparative Example 1 was applied at 25°C to a glass substrate 1 with a flat nozzle (30 mm, manufactured by Musashi Engineering Co., Ltd.). Width, SHOT MASTER 300) was used to coat to a thickness of 0.15 mm. After being left for 300 seconds after application, light curing is performed with a conveyor type ultraviolet irradiation device (Aigfic, metal halide lamp) with a peak illuminance of 400 mW/cm2, an integrated light intensity of 6000 mJ/cm2 (oak company, wavelength 350 nm), and a reaction rate of 100%. Then, a cured product protective film was formed on the glass substrate 1 .
The coating shape is measured using a laser microscope (LEXT OLS4000, manufactured by Olympus Co., Ltd.), and the part where the uniform film thickness can sufficiently demonstrate the protective performance, and the liquid dripping width as the part where the liquid dripping part is contaminated or the protective performance is not sufficient. was measured.
If the distance of the liquid dripping width was 0.5 mm or less, it was evaluated as ◯, and if it was 0.5 mm or more, it was evaluated as x.

(2) Peelability The corners of the cured product film on the glass substrate 1 used in the test of (1) were pinched off with tweezers,
If the resin peels off without breakage,
△ when the resin was broken although it could be peeled off from the interface,
X if the peeling was not possible
and

Table 11 summarizes the results of the above examples and comparative examples.

1 surface S
2 Member having surface S 3 Gel-like resin composition 31 Photo-cured gel-like resin composition 4 Light irradiation device 5 Plating 6 Resist

Claims (5)

A method for manufacturing and dismantling a composite in which the member is incorporated, which includes a step of assembling and/or removing a member having a surface S and/or a member surface processing step of processing the surface S,
In the assembling and/or removing step and/or the member surface processing step,
A member surface coating step of coating a region of the surface S where contamination and/or processing should be avoided with a gel resin composition,
The gel resin composition is
having a liquid-to-gel transition temperature (Tc) between 0 and 150° C., and/or
having thixotropic properties,
The degree of thixotropic property is 1.1 to 20 when the thixotropic ratio (η ₁ /η ₁₀ ) is 1.1 to 20 when the viscosity η _v (Pa·s) at the shear rate v (sec ⁻¹ ) of the gel-like resin composition is taken. is the degree of
The surface S is smooth,
A method for manufacturing and dismantling a composite, wherein the member surface processing is at least one member surface processing selected from the group consisting of wiring formation processing, plating formation processing, and etching processing on the surface S (however, the composite is Except when the manufacturing/dismantling method is in the following manner:
When the area of the surface S where contamination and/or processing should be avoided is coated with the gel composition, the polymer film is coated with the gel resin composition supported thereon). 2. The method for manufacturing and dismantling a composite according to claim 1, wherein said gel resin composition has heat and/or photocurability. 3. The member is at least one component selected from the group consisting of a display panel, a touch panel, a sensor, a lens, a battery component and a semiconductor component, and/ or a housing that covers the component. A method for manufacturing and dismantling a composite according to any one of Claims 1 to 3. The method for manufacturing and dismantling a composite according to any one of claims 1 to 3 , wherein the composite is composed of a housing in which the member is incorporated. A gel resin composition used in the method for manufacturing and dismantling a composite according to any one of claims 1 to 4 ,
The gel resin composition is
having a liquid-to-gel transition temperature (Tc) between 0 and 150° C., and/or
having thixotropic properties,
The degree of thixotropic property is 1.1 to 20 when the thixotropic ratio (η ₁ /η ₁₀ ) is 1.1 to 20 when the viscosity η _v (Pa·s) at the shear rate v (sec ⁻¹ ) of the gel-like resin composition is taken. The gel-like resin composition that is the degree of

Images