JP6966759B2 - Method for producing / disassembling the complex and gel-like resin composition - Google Patents

Description

The present invention relates to a gel-like resin composition which is used in a method for manufacturing / disassembling a composite in which a member is incorporated and a method for manufacturing / disassembling the composite, and which is suitable for mechanical peeling after coating film.

Members such as display panels, touch panels, sensors, lenses, battery parts, semiconductor parts, and housings that exterior these parts include video / image display devices, image pickup devices, and communication devices that incorporate these members. In the process of manufacturing composites such as household electrical products, batteries, integrated circuits, etc., there are areas where surface contamination and / or processing should be avoided.

For example, optical members such as display panels and touch panels have diversified designs such as having a curved structure, the transition of housing members to glass, and the complicated arrangement and wiring structure of parts. In the process of manufacturing optical products in which the members of the above are incorporated, a protective film is attached to the area where contamination of the surface of each member should be avoided or covered with liquid resin to prevent contamination such as scratches and stains on the surface. (For example, Patent Documents 1 and 2).

For example, when plating and wiring to battery parts such as solar cells and electronic parts such as semiconductor parts, it is necessary to protect the area other than the area to be plated on the surface of each member with a resist material to avoid plating. , Screen-printable resist materials are widely used (for example, Patent Document 3).

For example, in the semiconductor manufacturing process, for example, in the silicon wafer manufacturing process, chemical etching processing such as polishing processing of the silicon wafer surface, etching processing of the silicon surface, and etching processing of the SiO _{2 film on the Si substrate may be performed.} It is necessary to protect the region other than the region to be chemically etched to avoid the chemical etching with a resist material (for example, Patent Document 4).

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

In the process of manufacturing the composite, when the area to be avoided is coated with a film (hereinafter, also referred to as "protective film") in order to avoid contamination and / or processing of the surface of the member to be incorporated as described above, the final In some cases, the coating film may be removed from the composite using an organic solvent (for example, Patent Document 6).

Japanese Unexamined Patent Publication No. 2013-237171 Japanese Unexamined Patent Publication No. 2009-289717 Japanese Unexamined Patent Publication No. 2005-138299 Japanese Patent Application Laid-Open No. 2003-045783 Japanese Unexamined Patent Publication No. 2013-141761 Japanese Unexamined Patent Publication No. 2006-128233

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

With the protection technology using a film, it is difficult to deal with complicated shapes such as curved surface shapes of members, and there are problems in terms of workability and yield.

In the protection technology using liquid resin, the liquid resin can be a pollution source because there is an outflow to areas other than the area where contamination should be avoided and the resin flows into the gaps between members, which increases the process control load. There are challenges.

The liquid resist material that can be screen-printed is expected to increase the workload and cost by incorporating a removal or cleaning process. Further, the conventional liquid resist material has a problem in printability, such as the opening width and fine line accuracy aimed at in screen printing cannot be obtained.

The resist material used during etching is a process of curing on the surface of the member before etching, a method of mechanically peeling or peeling using a chemical solution, and a method of ashing (ashing) by chemically reacting with gas. The process load in the process of removing or cleaning by etching is large.

When removing the protective film from the complex using an organic solvent, for example, there are the following problems:
(1) If the organic solvent cannot enter or if there is a member that is damaged by the organic solvent, the organic solvent cannot be used to remove the protective film;
(2) The volatilization of the organic solvent deteriorates the manufacturing environment of the complex;
(3) Waste liquid treatment of organic solvent after use is required.

The present invention provides areas where contamination and / or processing of the surface of the member should be avoided.
The coating film is applied without flowing out or flowing into the area other than the relevant area.
Avoiding contamination of the surface during the process of incorporating and removing the member into the complex,
It is possible to avoid the processing while performing the necessary processing on the surface of the member.
Further, it is an object of the present invention to provide a method for producing and disassembling a composite using a gel-like resin composition that can mechanically peel off and remove the coating film, and to provide the gel-like resin composition.

The present invention
[1] A method for manufacturing / disassembling a composite in which the member having a member surface processing step of incorporating and / or removing the member having the surface S and / or a member surface processing process for processing the surface S is incorporated.
In the assembling and / or removing step and / or in 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-like resin composition, and
It has a step of mechanically peeling off the gel-like resin composition coated in the coating film step.
The gel-like resin composition is
Has a liquid-gel transition temperature (Tc) from 0 to 150 ° C. and / or
It has thixotropic properties and also has thixotropic properties.
Polyether-modified polysiloxane (Compound C1), acrylic block copolymer having polysiloxane in the side chain (Compound C2), nonionic fluorine-containing surfactant compound (Compound C3), ethylene glycol monoalkyl ethers and / or A method for producing and disassembling a complex containing at least one compound C selected from the group consisting of propylene glycol monoalkyl ethers (Compound C4) and a side chain crystalline α-olefin polymer (Compound C5), and a method for producing and disassembling the complex. ,
[2] The present invention relates to the gel-like resin composition (hereinafter, also referred to as "the present invention 2") according to the preceding item [1], which is used in the method for producing the complex according to the preceding item [1].
Hereinafter, the present inventions 1 and 2 are collectively referred to as the "invention".

According to the present invention, areas where contamination and / or processing of the surface of the member should be avoided.
The coating film is applied without flowing out or flowing into the area other than the relevant area.
Avoiding contamination of the surface during the process of incorporating and removing the member into the complex,
It is possible to avoid the processing while performing the necessary processing on the surface of the member.
Further, a method for producing and disassembling a composite using a gel-like resin composition that can be mechanically peeled off and removed (hereinafter, also referred to as "mechanical peelability"), and the gel-like resin composition. Can be provided.

Example 1 of the member surface coating film process Example of the embodiment in which the gel-like resin composition sheet of Production Example 3 is peeled off from the base. Example 2 of the member surface coating film process Example 3 of the member surface coating film process

[Member having surface S and complex in which the member is incorporated]
In the present invention, the member provided with the surface S and the complex in which the member is incorporated can exemplify the following.

(1) Video / image display devices, image pickup devices, communication devices, homes, etc., in which members such as display panels, touch panels, sensors, lenses, battery parts, semiconductor parts, and housings that exterior these parts are incorporated. Complexes of electrical 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 having a curved surface structure and / or a glass material is incorporated.
More specifically, a liquid crystal display panel; an organic EL display panel; a protective panel; a touch panel; a sensor such as an ambient light sensor, a proximity sensor, a fingerprint sensor, and an authentication sensor; a camera; a glass or plastic plate; a plurality of members such as a rustic film. Examples include information display devices such as liquid crystal displays, organic EL displays, touch panel displays, etc., which are composites including members to which the information is bonded, and further, electrons which are composites including these information display devices and other electronic elements. Examples include mobile electronic terminals such as notebooks, mobile phones, smartphones, portable audio players, personal digital assistants (PDAs), and tablet terminals, and information processing devices such as personal computers, TVs, and car navigation systems.

(3) Examples thereof include a solar cell which is a composite in which a member to be plated and wired is incorporated, an electronic component such as a semiconductor, and a semiconductor which is a composite in which a silicon wafer member is incorporated.

The surface S provided on the above-exemplified member is made of, for example, resin, silicon, metal, glass, ceramics, etc., and 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 in order to have conductivity. A transparent conductive material such as ITO, IZO, or carbon nanotube may be treated, or a metal such as silver or copper may be patterned on the surface as an electrode or wiring material.

(4) As the member provided with the surface S which is the object of the present invention, 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 for exteriorizing parts is preferable, and the composite to which the present invention is intended is preferably composed of a housing in which a member having a surface S is incorporated.

(5) The member having the surface S and the composite in which the member is incorporated has a step of incorporating and / or removing the member having the surface S, and / or a member having a member surface processing step of processing the surface S. When used in a method for manufacturing and disassembling an incorporated composite, the member surface treatment to be the subject of the present invention is at least one selected from the group consisting of wiring formation processing, plating formation processing and etching processing as described later. Surface treatment of seed members is preferred.

[Gel-like resin composition]
<Protective film forming property>
The gel-like resin composition in the present invention (hereinafter, also referred to as “gel-like resin composition”) is used when the gel-like resin composition is applied to a predetermined region of the surface S in the member surface coating film step of the present invention 1. The coating film forming property does not uniformly flow out from the predetermined region to the predetermined region, and the coating film region is not processed when the surface S is subsequently subjected to the predetermined processing or when a contaminant comes into contact with the surface S. It is necessary to have coating film resistance to the extent that it is not damaged or damaged by contaminants (the coating film forming property and coating film resistance of the gel-like resin composition are hereinafter referred to as "protective film forming property").

The gel-like resin composition has a liquid-gel-like transition temperature (Tc) at 0 to 150 ° C. and / or thixotropic property from the viewpoint of protective film forming property.

<Liquid-gel transition temperature (Tc)>
When the gel-like resin composition has a liquid-gel-like transition temperature (Tc) and / or thixotropic property at 0 to 150 ° C., it means that the gel-like resin composition is a physically crosslinked gel.
The measurement of Tc and thixotropic property is performed under the conditions described in the examples.

Physically cross-linked gels are gels that are cross-linked by non-covalent bonds such as hydrogen bonds, hydrophobic agglomerations, and ionic bonds. Since cross-linking is generated and disappears due to temperature changes or external forces, the former has Tc (also known as thermoreversible gel). (Called), the latter will have thixotropic properties.

In general, a gel-like resin composition is a substance in which the compounds constituting the composition are crosslinked and the thermal motion of each compound is suppressed, so that the fluidity of the entire composition is greatly reduced. It is classified into a chemically crosslinked gel and a physically crosslinked gel according to the service life.

A chemically crosslinked gel is a gel crosslinked by a covalent bond, and the bond is not broken by the thermal motion of the constituent compounds, and the crosslinking life is substantially infinite under the thermal motion. The linked structure (topological three-dimensional structure) of the chemically crosslinked gel remains unchanged as it was when the gel was formed.

Physically cross-linked gels are gels that are cross-linked by non-covalent bonds such as hydrogen bonds, hydrophobic agglomerations, and ionic bonds. (Called), the latter will have thixotropic properties.

From the viewpoint of protective film forming property, the suitable gel-like resin composition applicable to the present invention is preferably a physically cross-linked gel, even if it is partially chemically cross-linked, and is a physically cross-linked gel that is not chemically cross-linked. Is more preferable.

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

From the viewpoint of protective film forming property, the gel-like resin composition has Tc preferably in the range of 10 to 100 ° C, more preferably in the range of 20 to 90 ° C, and further preferably in the range of 30 to 80 ° C.

<Thixotropic property>
The gel-like resin composition has thixotropic properties when the viscosity η _{v at} the shear rate v of the gel-like resin composition is determined.
When 30 ° C <Tc, 25 ° C, and when 0 ° C ≤ Tc ≤ 30 ° C, Tc-20 ° C.
η _0.1 is 10 to 10000 Pa · s, preferably 30 to 5000 Pa · s, and more preferably 50 to 3000 Pa · s.
η ₁₀ has a property of 3 to 500 Pa · s, preferably 5 to 300 Pa · s, and more preferably 5 to 150 Pa · s.
The gel-like resin composition having no Tc follows the case of 30 ° C. <Tc.
The viscosity η _v is measured under the conditions described in the examples.

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

When x ₁ and x ₂ are larger than 1 (preferably larger than 1.2), when the gel-like resin composition is formed into a sheet, for example, when it is applied to a predetermined range using a coating device, When extruded from the coating device, it flows moderately, and after it is extruded, the flow stops. Is possible.

<Storage rigidity>
From the viewpoint of protective film forming property, the gel-like resin composition applicable to the present invention has a storage rigidity of 25 ° C. when the storage rigidity in the gel state is 30 ° C. <Tc, and Tc when 0 ° C. ≤ Tc ≤ 30 ° C. It is preferably 0.01 to 10000 kPa at −20 ° C.
The storage rigidity is measured under the conditions described in the examples.

In the member surface coating process, when the gel-like resin composition is applied to a predetermined area of the surface S at a temperature of less than Tc, the gel-like resin composition is coated on the predetermined area of the surface S with a uniform thickness. Although it is liquid, it is not so fluid as to flow out of the predetermined region and contaminate the portion outside the predetermined region with the gel-like resin composition itself, which is preferable from the viewpoint of protective film forming property.

<Mechanical peelability>
Mechanical peelability means that in the member surface coating process of the present invention 1, a gel-like resin composition is coated on a predetermined region of the surface S, cured before or after surface treatment, and then cured after surface treatment. The coating film is dissolved in an organic solvent, washed with a surfactant, decomposed by radiation, etc., without physical and chemical operations such as being grasped by a gripping tool such as a tweezers (as shown in FIG. 2), and sucked by a suction device. It can be peeled off only by physical operation such as adsorption with an adhesive device or jig.

With good mechanical peelability, as shown in FIG. 2, the cured gel-like resin composition can be peeled off without breaking the resin while the coating film physically maintains the film form.

For example, when the surface treatment of a member is an etching process such as chemical etching, the gel-like resin composition is cured after the etching process to form a film that does not break at the time of peeling, so that the film can be mechanically peeled off, and a resist material is used. Since the chemicals and ashing residues that are generated in some cases are not generated, the process load before and after surface processing is reduced.

In order to impart mechanical peelability to the gel-like resin composition, the coating film of the gel-like resin composition is mechanically treated within a range that does not affect the liquid-gel transition temperature (Tc) and the thisotropic property. The compound C that improves the peelability is blended into the gel-like resin composition.

Compound C is a polyether-modified polysiloxane (Compound C1), an acrylic block copolymer having a polysiloxane in the side chain (Compound C2), a nonionic fluorine-containing surfactant compound (Compound C3), and an ethylene glycol monoalkyl ether. And / or at least one compound selected from the group consisting of propylene glycol monoalkyl ethers (Compound C4) and side chain crystalline α-olefin polymer (Compound C5).

（式（Ｃ１−１）中、Ｒ_４及びＲ_５は炭素数１以上６以下のアルキル基を表し、ａは１０以上８０以下の整数を表し、Ｘ_１及びＸ_２は下記式（Ｃ１−２）：

（前記一般式（Ｃ１−２）中、Ｒ_６は水素原子、炭素数１以上６以下のアルキル基又は（メタ）アクリル基を表し、ＥＯはエチレンオキシド基を表し、ＰＯはプロピレンオキシド基を表す。ｂは１以上の整数を表し、ｃが０以上の整数を表し、さらにｂ＋ｃが１以上３０以下の整数を表す。ＥＯ及びＰＯの順序についてはランダムであってもよい。）で表されるポリエーテル（ポリオキシアルキレン）基を表す）で表されるポリエーテル変性ポリシロキサンであることが好ましい。 (Compound C1)
Compound C1 is a polyether-modified polysiloxane, and from the viewpoint of mechanical peelability, for example, the following formula (C1-1):

(In the formula (C1-1), R ₄ and R ₅ represent an alkyl group having 1 or more and 6 or less carbon atoms, a represents an integer of 10 or more and 80 or less, and X ₁ and X ₂ represent the following formula (C1-2). ):

(In the general formula (C1-2), R ₆ represents a hydrogen atom, an alkyl group having 1 or more and 6 or less carbon atoms or a (meth) acrylic group, EO represents an ethylene oxide group, and PO represents a propylene oxide group. b represents an integer of 1 or more, c represents an integer of 0 or more, and b + c represents an integer of 1 or more and 30 or less. The order of EO and PO may be random). It is preferably a polyether-modified polysiloxane represented by (representing an ether (polyoxyalkylene) group).

As the compound C1, a commercially available product can be used, for example,
Evonik Degussa TEGO GLIDE 410, TEGO GLIDE432, TEGO GLIDE 435, TEGO GLIDE 440, TEGO GLIDE 450; Toray Dow Corning Co., Ltd. BY16-201, SF8427; Big Chemie, BYK-333, BYK-UV3500, Etc., and these may be used alone.

（式（（Ｃ２−１）及び（Ｃ２−２）中、Ｒ_１は水素原子又はメチル基を、Ｒ_２はメチル基、エチル基、フェニル基又は下記式（Ｃ２−３）：

（式（Ｃ２−３）中、Ｒ_５は水素原子、フェニル基又はＣｐＨ２ｐ＋１を、Ｒ_６はメチル基、エチル基はフェニル基をそれぞれ示し、ｍは１以上の整数、ｐは１〜１０の整数を示す）で表される基を示し、Ｒ_３は水素原子、フェニル基又はＣ_ｐＨ_２ｐ＋１を、Ｒ_４はメチル基、エチル基又はフェニル基をそれぞれ示し、ｎは１以上の整数、ｐは１〜１０の整数である。Ｒ_１、Ｒ_２，Ｒ_３，Ｒ_４は、上記で規定した置換基の中で同一であっても、異なっても良い）で表される群から選ばれるポリシロキサン基含有化合物の１種以上の混合物と、 メタクリル酸、メタクリル酸エステル、アクリル酸、アクリル酸エステルおよび脂肪酸ビニルエステルからなる群から選ばれる単量体の１種以上の混合物とのグラフト共重合体であるポリシロキサン基含有共重合体部分と、 メタクリル酸、メタクリル酸エステル、アクリル酸、アクリル酸エステルおよび脂肪酸ビニルエステルからなる群から選ばれる単量体の１種以上の重合体であるポリシロキサン基を含有しない重合体部分とからなるブロック共重合体（以下「ポリシロキサン基含有重合体」ともいう」０．１〜１０重量部とが混合してなる化合物である。 (Compound C2)
Compound C2 has the following formulas (C2-1) and (C2-2):

(In the formula ((C2-1) and (C2-2), R ₁ is a hydrogen atom or a methyl group, R ₂ is a methyl group, an ethyl group, a phenyl group or the following formula (C2-3):

(In the formula (C2-3), R ₅ represents a hydrogen atom, a phenyl group or CpH 2p + 1, R ₆ represents a methyl group and an ethyl group represents a phenyl group, where m is an integer of 1 or more and p is an integer of 1 to 10. Indicates a group represented by), where R ₃ indicates a hydrogen atom, a phenyl group or C _p H _{2p + 1} , R ₄ indicates a methyl group, an ethyl group or a phenyl group, n is an integer of 1 or more, and p is. It is an integer of 1 to 10. R ₁ , R ₂ , R ₃ , and R ₄ may be the same or different among the substituents specified above), and are one or more of polysiloxane group-containing compounds selected from the group represented by. And a polysiloxane group-containing co-weight which is a graft copolymer of a mixture of one or more of monomers selected from the group consisting of methacrylic acid, methacrylic acid ester, acrylic acid, acrylic acid ester and fatty acid vinyl ester. From the coalesced moiety and the polymer moiety not containing a polysiloxane group, which is one or more polymers of monomers selected from the group consisting of methacrylic acid, methacrylic acid ester, acrylic acid, acrylic acid ester and fatty acid vinyl ester. It is a compound obtained by mixing 0.1 to 10 parts by weight of a block copolymer (hereinafter, also referred to as “polysiloxane group-containing polymer””.

From the viewpoint of mechanical peelability, the polysiloxane group-containing polymer is preferably preferred.
From 5 to 85% by weight of a structural unit based on a mixture of one or more of the compounds represented by the formulas (C2-1) and (C2-2), methacrylic acid, methacrylic acid ester, acrylic acid, acrylic acid ester, fatty acid vinyl ester. Polysiloxane group-containing copolymer consisting of 15 to 95% by weight of a structural unit based on one or more selected from the group (hereinafter referred to as "polysiloxane group-containing polymer A"),
or,
A block copolymer composed of a polysiloxane group-containing copolymer portion and a polysiloxane group-free polymer portion.
Polysiloxane group-containing copolymer moiety is a structural unit based on a mixture of one or more compounds represented by the formulas (C2-1) and (C2-2), 5 to 85% by weight, and methacrylic acid, methacrylic acid ester, acrylic acid. , Acrylic acid ester, fatty acid vinyl ester, a constituent unit based on one or more monomers selected from the group consisting of 15 to 95% by weight.
A polysiloxane composed of a structural unit based on a mixture of one or more of monomers selected from the group consisting of methacrylic acid, methacrylic acid ester, acrylic acid, acrylic acid ester, and fatty acid vinyl ester as a polymer portion containing no polysiloxane group. It is a group-containing polymer (hereinafter referred to as “polysiloxane group-containing polymer B”).

From the viewpoint of mechanical peelability, the number average molecular weight of the polysiloxanes of the formulas (C2-1) and (C2-2) is preferably 5000 to 40,000, more preferably 1000 to 30000.

Commercially available products can be used as the polysiloxane of the formula (C2-1), and examples thereof include FM 0711, FM0715, FM0721, and FM0725 manufactured by Chisso.

（式（Ｃ２−４）中、Ｒ_１は水素原子又はメチル基を、Ｒ_２及びＲ_３はメチル基、エチル基、又はフェニル基をそれぞれ示す。）２モルを室温から６０℃程度の温度範囲で反応させて得られる化合物を式（Ｃ２−２）のポリシロキサン使用できる。なお、式（Ｃ２−４）の化合物は、（メタ）アクリル酸アリルエステルとケイ素化合物との反応によって得ることができる。 The polysiloxane of formula (C2-2) can be obtained by a generally known reaction, for example, a biterminal silanol polysiloxane (for example, Chisso's PS series) of a commercially available product (for example, Chisso's PS series). In the presence of basic catalysts such as triethylamine and pyridine, the following formula (C2-4):

(In the formula (C2-4), R ₁ represents a hydrogen atom or a methyl group, and R ₂ and R ₃ represent a methyl group, an ethyl group, or a phenyl group, respectively.) 2 mol is in a temperature range of about 60 ° C. from room temperature. The compound obtained by the reaction in (C2-2) can be used as a polysiloxane of the formula (C2-2). The compound of the formula (C2-4) can be obtained by the reaction of the (meth) acrylic acid allyl ester with the silicon compound.

From the viewpoint of mechanical peelability, the polysiloxanes represented by the formulas (C2-1) and (C2-2) are
It is preferably 5 to 85% by weight of the polysiloxane group-containing polymer portion in the polysiloxane group-containing polymer A or the polysiloxane group-containing polymer B, and further.
Although it may contain free polysiloxane mixed with the formulas (3) and (4), 100 parts by weight of the polysiloxane group-containing copolymer portion dissolved in the polysiloxane group-containing polymer A or the polysiloxane group-containing polymer B. It is preferably 50 parts by weight or less.

From the viewpoint of mechanical peelability, the monomer copolymerized in the process of obtaining the polysiloxane group-containing polymer is a monomer selected from methacrylic acid, methacrylic acid ester, acrylic acid, alryl acid ester, and fatty acid vinyl ester. One or more, preferably
Methyl (meth) acrylate [(meth) Methyl acrylate refers to methyl methacrylate or methyl acrylate. The same applies below. ] Lower alkyl (meth) acrylates such as ethyl (meth) acrylate, n-propyl (meth) acrylate, glycidyl (meth) acrylate; n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Higher (meth) acrylates such as lauryl (meth) acrylate, stearyl (meth) acrylate; fatty acid vinyl such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, (meth) acrylic It is to be selected from hydroxyl group-containing (meth) acrylic acid esters such as hydroxyethyl acid, hydroxypropyl (meth) acrylic acid, and (meth) acrylic acid.

From the viewpoint of mechanical exfoliation, the compound C2 preferably has a higher glass transition temperature of the polymer component, and the amount of methyl methacrylate used may be increased.

From the viewpoint of mechanical peelability, the weight ratio of the polysiloxane group-containing copolymer portion and the polysiloxane group-free polymer portion in the polysiloxane group-containing polymer B is preferably 25/75 to 90/10. ..

The polysiloxane group-containing polymer B can be synthesized, for example, by ordinary radical polymerization.

The polysiloxane group-containing polymer B is obtained, for example, by two-step polymerization using a polymeric peroxide as an initiator. That is, for example, the following polypeptide peroxide is used to polymerize one or more of the monomers that can be a polymer portion miscible with the acrylic pressure-sensitive adhesive.
At this time, a polymer containing a peroxy bond can be obtained by terminating the polymerization when the amount of active oxygen of the polypeptide peroxide remains at about 50%. Further, using this as an initiator, one or more of the polysiloxanes represented by the formulas (3) and (4), which can be a polysiloxane group-containing copolymer moiety, and other monomers are copolymerized. Can be used to obtain a polysiloxane group-containing polymer B.

Examples of commercially available products that can be used as compound C2 include NOF Corporation's Modiper FS700, Modiper FS710, Modiper FS720, Modiper FS730, and Modiper FS770.

(Compound C3)
Compound C3 is a nonionic fluorine-containing surfactant compound, and from the viewpoint of mechanical exfoliation, for example, a perfluoroalkenylethylene oxide adduct, a perfluoroalkyl group adduct, a perfluorobutane sulfonic acid group adduct, etc. Examples thereof include those containing a high molecular weight polymer.

From the viewpoint of mechanical peelability,
(1) A substance having a perfluoroalkenyl structure branched with a double bond in the molecule, for example, a hexafluoropropene oligomer [(CF ₃ ) ₂ CF] ₂ C = C (F) CF ₃ ] (as a commercial product). Neos's Footergent 100, Footergent 100C, Footergent 110, Footergent 140A, Footergent 150, Footergent 150CH, Footergent AK, Footergent 501, Footergent 250, Footergent 251, Footergent 222F, Footergent 300, Footergent 310, Footergent 400SW, etc.);
(2) Those having a perfluorobutane sulfonic acid group (commercially available products include FC-4430 and FC-4432 manufactured by Sumitomo 3M) are preferable, and those having a perfluorobutane sulfonic acid group are more preferable.

From the viewpoint of mechanical exfoliation, the compound C3 preferably has a reactive group that reacts with other components by external energy such as light and heat.

Examples of the reactive group include an alkoxysilyl group, a silyl ether group, a silanol group obtained by hydrolyzing an alkoxysilyl group, a carboxyl group, a hydroxyl group, an epoxy group, a vinyl group, an allyl group, an acryloyl group, a methacryloyl group and the like. .. As the reactive group, an alkoxysilyl group, a silyl ether group, a silanol group, an epoxy group, a vinyl group, an allyl group, an acryloyl group or a methacryloyl group is preferable, and a vinyl group and an allyl group are preferable from the viewpoint of reactivity and handleability. , Acryloyl group or methacryloyl group is more preferable, and acryloyl group or methacryloyl group is further preferable.

Compound C3 comprises a moiety containing at least one selected from the group consisting of a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkandyl group, and a fluorooxyalkandyl group in addition to the reactive group. It is preferable to have.
The fluoroalkyl group, fluorooxyalkyl group, fluoroalkenyl group, fluoroalcandiyl group, and fluorooxyalcandiyl group have an alkyl group, an oxyalkyl group, an alkenyl group, an alcandiyl group, and an oxyalcandiyl group, respectively. It is a substituent in which at least a part of the hydrogen atom contained is substituted with a fluorine atom. The fluoroalkyl group, the fluorooxyalkyl group, the fluoroalkenyl group, the fluoroalkandyl group, and the fluorooxyalkandyl group are all substituents mainly composed of a fluorine atom and a carbon atom, and are branched in the structure thereof. The moiety may be present, and a plurality of these substituents may be linked.

The fluorine-containing monomer, which is a constituent of compound C3, includes the following formula (C3-1):
R ^f1- R ^2- D ¹ (C3-1)
(In formula (6), R ^f1 comprises a site containing at least one selected from the group consisting of a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkandyl group, and a fluorooxyalkandyl group. ^{R 2} represents an alkanediyl group, an alkanetriyl group, or an ester structure, a urethane structure, an ether structure, or a triazine structure derived from them. D ¹ represents a reactive group). It is preferably a fluorine-containing monomer.

Examples of the fluorine-containing monomer represented by the above formula (C3-1) include, for example.
2,2,2-trifluoroethyl acrylate,
2,2,3,3-tetrafluoropropyl acrylate 2,2,3,3,3-pentafluoropropyl acrylate,
1H, 1H, 5H-octafluoropentyl acrylate 2-perfluorobutyl ethyl acrylate,
3-Perfluorobutyl-2-hydroxypropyl acrylate,
2-Perfluorohexyl ethyl acrylate,
3-Perfluorohexyl-2-hydroxypropyl acrylate,
2-Perfluorooctyl ethyl acrylate,
3-Perfluorooctyl-2-hydroxypropyl acrylate,
2-Perfluorodecylethyl acrylate,
2-Perfluoro-3-methylbutylethyl acrylate,
3-Perfluoro-3-methoxybutyl-2-hydroxypropyl acrylate,
2-Perfluoro-5-methylhexyl ethyl acrylate,
3-Perfluoro-5-methylhexyl-2-hydroxypropyl acrylate,
2-Perfluoro-7-methyloctyl-2-hydroxypropyl acrylate,
Tetrafluoropropyl acrylate, octafluoropentyl acrylate,
Dodecafluoroheptyl acrylate, hexadecafluorononyl acrylate,
Hexafluorobutyl acrylate,
2,2,2-trifluoroethyl methacrylate,
2,2,3,3-tetrafluoropropyl methacrylate 2,2,3,3,3-pentafluoropropyl methacrylate,
1H, 1H, 5H-Octafluoropentyl methacrylate 2-perfluorobutyl ethyl methacrylate,
3-Perfluorobutyl-2-hydroxypropyl methacrylate,
2-Perfluorooctylethyl methacrylate,
3-Perfluorooctyl-2-hydroxypropylmethacrylate,
2-Perfluorodecylethyl methacrylate,
2-Perfluoro-3-methylbutylethylmethacrylate,
3-Perfluoro-3-methylbutyl-2-hydroxypropylmethacrylate,
2-Perfluoro-5-Methylhexyl Ethyl Methacrylate,
3-Perfluoro-5-Methylhexyl-2-hydroxypropylmethacrylate,
2-Perfluoro-7-Methyloctylethylmethacrylate,
3-Perfluoro-7-Methyloctylethylmethacrylate,
Tetrafluoropropyl methacrylate,
Octafluoropentyl methacrylate,
Dodecafluoroheptyl methacrylate,
Hexadecafluorononyl methacrylate,
1-Trifluoromethyltrifluoroethyl methacrylate,
Hexafluorobutyl methacrylate,
Examples thereof include triacryloyl-heptadecafluorononenyl-pentaerythritol, and the like is preferable.
2,2,2-trifluoroethyl acrylate,
2,2,2-trifluoroethyl methacrylate,
2,2,3,3-tetrafluoropropyl acrylate,
2,2,3,3-tetrafluoropropylmethacrylate,
1H, 1H, 5H-octafluoropentyl acrylate,
2-Perfluorohexyl ethyl acrylate,
2-Perfluorohexyl ethyl methacrylate and
It is one or more fluorine-containing monomers selected from the group consisting of 1H, 1H, 5H-octafluoropentyl methacrylate, and more preferably.
2,2,3,3-tetrafluoropropyl acrylate,
2,2,3,3-tetrafluoropropylmethacrylate,
2-Perfluorohexyl ethyl acrylate and
It is one or more fluorine-containing monomers selected from the group consisting of 2-perfluorohexyl ethyl methacrylate, and more preferably.
2-Perfluorohexyl ethyl acrylate and / or 2-perfluorohexyl ethyl methacrylate.

Suitable materials for the fluorine-containing monomer include, for example, materials having a fluoropolyether moiety. The fluoropolyether moiety is a moiety composed of a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkyldiyl group, or the like, and has the following formula (C3-2) or (C3-3) :.
CF _n1 H _(3-n1) -(CF _n2 H _(2-n2) ) _k O- (CF _n3 H _(2-n3) ) _m O- (C3-2)
-(CF _n4 H _(2-n4) ) _p O- (CF _n5 H _(2-n5) ) _s O- (C3-3)
(In equations (C3-2) and (C2-3), n1 is an integer of 1 to 3, n2 to n5 is 1 or 2, and k, m, p, and s are integers of 0 or more. A preferred combination of n1 to n5 is a combination in which n1 is 2 or 3, and a more preferable combination is n1 being 3, n2 and n4 being 2, n3 and n5. It is a structure represented by 1 or a combination of 2).

The number of carbon atoms contained in the fluoropolyether moiety is preferably 4 or more and 12 or less, more preferably 4 or more and 10 or less, and further preferably 6 or more and 8 or less. If the number of carbon atoms is less than 4, there is a concern that the surface energy will decrease. If the number of carbon atoms is more than 12, there is a concern that the solubility in a solvent may decrease. The fluorine-containing monomer may have a plurality of fluoropolyether moieties per molecule.

As a commercially available product that can be used as compound C3, for example,
Fluorine-based additive manufactured by Daikin Industries, Ltd. (Product name: Optool (registered trademark) DAC-HP),
Afluid manufactured by Asahi Glass Co., Ltd .; Mega Fvck RS-76-NS manufactured by DIC Corporation, Mega Fvck RS-78, Mega Fvck RS-90); Can be mentioned.

(Compound C4)
Compound C4 is an ethylene glycol monoalkyl ether and / or a propylene glycol monoalkyl ether .

More specifically, compound C4 is
Ethylene glycol monooctyl ether,
Diethylene glycol monooctyl ether,
Triethylene glycol monooctyl ether,
Ethylene glycol monodecyl ether,
Diethylene glycol monodecyl ether,
Triethylene glycol monodecyl ether,
Tetra ethylene glycol monodecyl ether,
Ethylene glycol monolauryl ether,
Diethylene glycol monolauryl ether,
Triethylene glycol monolauryl ether,
Tetra ethylene glycol monolauryl ether,
Diethylene glycol monomyristyl ether,
Ethylene glycol monocetyl ethers Ethylene glycol monoalkyl ethers such as diethylene glycol monocetyl ethers:
Propylene glycol monodecyl ether,
Dipropylene glycol monodecyl ether,
Tripropylene glycol monodecyl ether,
Propylene glycol monoisodecyl ether,
Dipropylene glycol monoisodecyl ether,
Tripropylene glycol monododecyl ether,
Propylene glycol monoundecyl ether,
Propylene glycol monoalkyl ethers such as dipropylene glycol monoundecyl ether can be mentioned, but preferred.
Diethylene glycol monolauryl ether,
Diethylene glycol monomyristyl ether,
Ethylene glycol monocetyl ether and
One or more (poly) alkylene glycol monoalkyl ethers selected from the group consisting of diethylene glycol monocetyl ethers, more preferably.
Ethylene glycol monocetyl ether and / or diethylene glycol monocetyl ether, more preferably.
Ethylene glycol monocetyl ether.

(Compound C5)
Compound C5 is a side chain crystalline α-olefin polymer, and is a side chain crystalline group synthesized by polymerizing a high-purity α-olefin monomer as a raw material with a metallocene catalyst from the viewpoint of mechanical peelability. The side chain crystalline α-olefin polymer () having the above is preferable.

Commercially available CPAO products that can be used as compound C5 include, for example, CPAO-1 (oil, melting point: 28 ° C.) in the El Crysta series manufactured by Idemitsu Kosan Co., Ltd. and 4100 (melting point: 42 ° C.) in the HS Cryster series manufactured by Toyokuni Essential Oil Co., Ltd. ), 6100 (melting point: 58 ° C.), 7100 (melting point: 76 ° C.) and the like.

From the viewpoint of mechanical peelability, the blending amount of the compound C is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 10 parts by weight, based on 100 parts by weight of the total of the compound A and the compound B constituting the gel resin composition. It is 0.1 to 5 parts by weight, more preferably 0.5 to 2 parts by weight.

As a compound for improving the mechanical peelability of the gel-like resin composition,
Silicone-based compounds such as polyether-modified silicone, polyester-modified silicone, polydimethylsiloxane, and polymethylalkylsiloxane;
Fluorine compounds such as fluoroalkylcarboxylic acid and perfluoroalkylcarboxylic acid;
Silicone-fluorine compounds such as perfluoro-modified silicone;
Examples thereof include acrylic compounds such as poly (meth) acrylate, polyether-modified acrylic polymer, polyester-modified acrylic polymer, and perfluoroalkyl-modified acrylic polymer, and examples of commercially available products include polyether-modified siloxane (TEGO GLIDE440, Ebonic). Be done. These can be used alone or in combination of two or more.

The blending amount of the compound for improving the mechanical peelability is preferably 0.01 to 10 parts by weight, more preferably 0, with respect to 100 parts by weight of the total of the compound A and the compound B constituting the gel resin composition. It is 1 to 5 parts by weight, more preferably 0.5 to 3 parts by weight.

<Transparency>
When, for example, the compound Y described later is used 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 the diffusion transmittance to the total light transmittance of the gel-like resin composition.

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

In the gel-like resin composition, for example, compound X1 described later ensures thixotopy property only with the gel-like resin composition in which compound A1 and / or A2 and compound B are compatible with each other without adding a filler. Therefore, there is no factor for increasing the HAZE value, and the transparency based on the total light transmittance of the resin constituting the resin composition can be utilized without being significantly impaired.

Therefore, the gel-like resin composition has a HAZE value of preferably 1.0 or less, more preferably 0, when transparency is required (for example, at the time of display inspection), such as when coating a display that requires display inspection. It is preferable to configure the structure so that transparency of 0.7 or less, more preferably 0.5 or less, still more preferably 0.3 or less, still more preferably 0.2 or less can be ensured.

<Example of gel-like resin composition>
Suitable gel-like resin compositions applicable to the present invention include, for example, as components other than compound C, for example.
Gel-like resin composition having Tc (hereinafter referred to as "composition X");
A composition having Tc and having thixotropic properties (hereinafter referred to as "composition Y"); or
A gel-like resin composition having no Tc but having thixotropic properties (hereinafter referred to as "composition Z") is used as a component.

(Composition X)
The following can be exemplified as a suitable composition X;
(1) A compatible composition in which a specific (meth) acrylate-based block copolymer compound and a medium are compatible with each other (hereinafter, also referred to as “composition X1”);
(2) A compatible composition in which a specific graft copolymer compound and a medium are incompatible with each other (hereinafter, also referred to as "composition X2"); and (3) a specific styrene-based block copolymer compound and a medium. Incompatible 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 with each other.
The block copolymer compound is
Polymer block a mainly composed of (meth) acrylate units, and
It is a block copolymer with a polymer block b mainly composed of (meth) acrylate units, and is a block copolymer.
The glass transition temperature of the polymer composed of only the (meth) acrylate units constituting the polymer block a is more than 50 ° C. and 180 ° C. or lower.
The glass transition temperature of the polymer composed of only the (meth) acrylate units constituting the polymer block b is −100 ° C. or higher and 50 ° C. or lower.
The block copolymer compound does not have a liquid-gel transition temperature (Tc) above 25 ° C. and 150 ° C. or lower.
Examples of the compatible composition include a compatible composition having a liquid-gel transition temperature (Tc) at a temperature of more than 25 ° C and 150 ° C or lower.

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

As the (meth) acrylate compound that can form the polymer block a or the polymer block b,
Preferably, methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, n-octyl. Alkyl (meth) acrylates such as (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate;
Alkoxy-substituted alkyl (meth) acrylates such as methoxyethyl (meth) acrylate and phenoxyethyl (meth) acrylate;
Hydroxy-substituted alkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate;
Benzyl (meth) acrylate, phenyl (meth) acrylate, etc .;
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, neopentyl Di (meth) acrylates such as glycol di (meth) acrylates, 1,6-hexanediol di (meth) acrylates; and dicyclopentenyloxyethyl (meth) acrylates, norbornene (meth) acrylates, dicyclopentanyl (meth). Selected from the group consisting of alicyclic structure-containing (meth) acrylates such as acrylates, isobornyl (meth) acrylates, cyclohexyl (meth) acrylates and 4-tert-butylcyclohexyl (meth) acrylates, and acrylamides such as acryloylmorpholine and diethylacrylamide. At least two compounds
More preferably
A combination of methyl methacrylate (methyl methacrylate) and n-butyl acrylate (butyl acrylate).
Based on the Tg shown when each compound independently constitutes a polymer, it is used as a constituent unit of the polymer block a or the polymer block b.

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

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

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

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

Since the polymer blocks a and b in the block copolymer compound are considered to have substantially the same polymerization structure as the polymers a and b, respectively, the glass transition point of the block copolymer compound is the polymer a and b. It is preferable to have the glass transition temperature in the temperature range including the glass transition point, that is, the temperature range of more than 50 ° C. and 180 ° C. or lower, and the temperature range of −100 ° C. or higher and 50 ° C. or lower. The glass transition point is measured under the conditions described in the examples.

The block copolymer compound is used from the viewpoint of the liquid-gel transition property of the compatible composition described later.
It is preferable to have at least one triblock structure in which the polymer block a is bonded to both ends of the polymer block b.
It is more preferable that it is composed only of a triblock structure,
At 0-150 ° C, the block copolymer compound has no liquid-gel transition temperature (Tc).
As long as the compatible composition described later has a liquid-gel transition temperature (Tc),
A structure other than the triblock structure (for example, a diblock structure in which the polymer block a and the polymer block b are bonded) may be included.

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

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

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

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

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

As a monomer compound in which the compatible composition with the block copolymer compound can have fluidity,
Preferably, methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, n-octyl. Alkyl (meth) acrylates such as (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate; methoxyethyl (meth) acrylate, phenoxy. Alkoxy-substituted alkyl (meth) acrylates such as ethyl (meth) acrylates; hydroxy-substituted alkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylates, 2-hydroxypropyl (meth) acrylates and 2-hydroxybutyl (meth) acrylates. Benzyl (meth) acrylate, phenyl (meth) acrylate, etc .; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, Di (meth) acrylates such as 1,4-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate; 4-tert-butylcyclohexyl acrylate, dicyclo Acrylic structure-containing (meth) acrylates such as pentenyloxyethyl (meth) acrylates, norbornene (meth) acrylates, dicyclopentanyl (meth) acrylates, isobornyl (meth) acrylates, cyclohexyl (meth) acrylates, etc. At least one compound selected from the group consisting of (meth) acrylamide such as morpholine and diethyl (meth) acrylamide,
More preferably, it is at least one compound selected from the group consisting of isodecyl acrylate, 4-hydroxybutyl acrylate and 4-tert-butylcyclohexyl acrylate.

As a plasticizer in which the compatible composition with the block copolymer compound can have fluidity, it is preferable.
Phthalate esters such as dibutylphthalate, diisononylphthalate, diheptylphthalate, di (2-ethylhexyl) phthalate, diisodecylphthalate, butylbenzylphthalate;
Polyvalent carboxylic acid esters such as dioctyl adipate, diisononyl adipate, dioctyl sebacate, diisononyl sebacate, diisononyl 1,2-cyclohexanedicarboxylate;
Alkyl benzoate;
Phosphate esters such as tricresyl phosphate and tributyl phosphate;
Trimellitic acid ester;
Rubber-based polymers such as (hydrogenated) polyisoprene, hydroxylated (hydrogenated) polyisoprene, (hydrogenated) polybutadiene, hydroxylated (hydrogenated) polybutadiene, polybutene;
Thermoplastic elastomer;
Petroleum resin;
Alicyclic saturated hydrocarbon resin;
Terpene resins such as terpene resin, terpene phenol resin, modified terpene resin, hydrogenated terpene resin;
Rosin resin such as rosin phenol;
Rosin ester-based resins such as disproportionated rosin ester-based resins, polymerized rosin ester-based resins, and hydrogenated rosin ester-based resins;
It is at least one compound selected from the group consisting of xylene resins; and acrylic resins such as acrylic polymers and acrylic copolymers, and more preferably.
It is at least one compound selected from the group consisting of a polyvalent carboxylic acid ester and a rosin ester resin.

As a medium that acts as a solvent for the block copolymer compound, it is preferable.
Alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, benzyl alcohol;
Hydrocarbons such as benzene, toluene, xylene, mineral spirit, cyclohexane, n-hexane, methylcyclohexane, styrene;
Ethers such as diethyl ether;
Esters such as ethyl acetate, propyl acetate, butyl acetate, diethylene glycol monoethyl ether acetate, diethyl carbonate, dimethyl carbonate, propylene carbonate;
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, diacetone alcohol;
Nitrogens such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone;
Glycol ethers such as butyl glycol, methyl diglycol, butyl diglycol, 3-methyl-3-methoxybutanol, and tetrahydrofuran;
Chlorines such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene;
Dimethyl sulfoxide; acetonitrile; carboxylic acids such as formic acid and acetic acid; and at least one compound selected from the group consisting of water, more preferably.
It is at least one compound selected from the group consisting of alcohols, hydrocarbons, esters and ketones, and 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 as long as it is compatible with the block copolymer compound and can produce the compatible composition of the present invention having a liquid-gel 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 determined.
It is preferably 0.001 to 10 Pa · s, more preferably 0.001 to 1 Pa · s, and even more preferably 0.001 to 0.5 Pa · s.

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

<Physical characteristics of compatible composition suitable for composition X1>
The compatible composition in which the block copolymer compound and the medium are compatible is 0 to 150 ° C., and the block copolymer compound does not have a liquid-gel transition temperature (Tc), and is a compatible composition. Is a composition having a liquid-gel transition temperature (Tc).

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

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

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

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

From the viewpoint of protective film forming property, the compatible composition has a mass portion of compound B of preferably 200 to 1000 parts by mass, and more preferably 250 to 800 parts by mass with respect to 100 parts by mass of compound A.

When the compatible composition is a viscoelastic body of the compatible composition, the content ratio of the reactive compound in the compound B is preferably 20 to 80% by mass from the viewpoint of viscoelastic properties suitable for the protective film forming property. It is 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, based on at least the total of Compound A and Compound B. More preferably, it is 2.5 to 7.5% by mass.

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

From the viewpoint of protective film forming property, the compatible composition is prepared from the viewpoints of compound A (preferably compound A to which reactivity is further imparted), and as compound B, radical reactivity, cationic reactivity, anion reactivity and moisture reactivity. It is preferable to contain at least one reactive reactive compound (preferably in combination with a plasticizer) selected from the above group and a polymerization initiator (hereinafter, compound A (preferably, further reactive). The added compound A), as the compound B, a reactive compound having at least one reactivity selected from the group consisting of radical reactivity, cationic reactivity, anion reactivity and moisture reactivity (preferably further with a plasticizer). The gel-like compatible composition containing the above-mentioned combination) and the polymerization initiator is also referred to as a compatible composition viscoelastic body).

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

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

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

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

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

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

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

Further, the layer of the compatible composition viscoelastic body is subjected to at least one treatment selected from the group consisting of heating, light irradiation and humidification, and the layer of the compatible composition viscoelastic body is heat-cured, photo-cured and wet-cured. By curing at least one selected from the group consisting of two to form a cured body having no liquid-gel transition temperature (Tc), the layer of the cured compatible composition viscoelastic body has a temperature of Tc or higher. Even in a high temperature environment, it remains a non-fluid viscoelastic body and can form a durable protective film.

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

The (meth) acrylate unit constituting the polymer block a is polymerized by a (meth) acrylate compound having a glass transition temperature of more than 30 ° C and 180 ° C or less of a polymer (hereinafter referred to as polymer a) composed of itself. It is formed when it is polymerized. From the viewpoint of the stability of the glass transition temperature, the weight average molecular weight of the polymer a is preferably 1 × 10 ⁵ or more, more preferably 1 × 10 ⁵ to 1 × 10 ⁹ , and further preferably 1 × 10 ⁵ to 1. It is 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 higher and 30 ° C. or lower for a polymer (hereinafter referred to as polymer b) composed of the polymer block b alone. 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 further preferably 1 × 10 ⁵ to 1. It is 1 × 10 ⁷ .

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

As the (meth) acrylate compound that can form the polymer block a or the polymer block b,
Preferably, methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, n-octyl. Alkyl (meth) acrylates such as (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate;
Alkoxy-substituted alkyl (meth) acrylates such as methoxyethyl (meth) acrylate and phenoxyethyl (meth) acrylate;
Hydroxy-substituted alkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate;
Benzyl (meth) acrylate, phenyl (meth) acrylate, etc .;
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, neopentyl Di (meth) acrylates such as glycol di (meth) acrylates, 1,6-hexanediol di (meth) acrylates; and dicyclopentenyloxyethyl (meth) acrylates, norbornene (meth) acrylates, dicyclopentanyl (meth). Selected from the group consisting of alicyclic structure-containing (meth) acrylates such as acrylates, isobornyl (meth) acrylates, cyclohexyl (meth) acrylates and 4-tert-butylcyclohexyl (meth) acrylates, and acrylamides such as acryloylmorpholine and diethylacrylamide. At least two compounds
More preferably, at least one of them is a methacrylate compound.

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

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

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

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

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

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

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

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

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

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

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

When the stem is composed of the polymer b, the liquid phase-soluble composition described later has a number average molecular weight of 5000 to 20000, preferably 1000 to 150,000 according to the GPC method from the viewpoint of liquid-gel transition, and is glass. The transition temperature is -100 ° C. or higher and 30 ° C. or lower, preferably -100 ° C. or higher and 20 ° C. or lower, more preferably -100 ° C. or higher and 10 ° C. or lower, further preferably -100 ° C. or higher and 0 ° C. or lower, and preferably ethyl acrylate. At least one (meth) acrylate unit selected from the group consisting of units (EA), n-butyl acrylate units (nBA) and lauryl methacrylate units (LMA), more preferably ethyl acrylate units (EA) and / or n-. It is composed of a butyl acrylate unit (n-BA).

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

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

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

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

<Compatible composition viscoelastic body suitable for composition X2>
Similar to the compatible composition suitable for the composition X1, the compatible composition suitable for the composition X2 from the viewpoint of protective film forming property is also compound A (preferably, compound A further imparted with reactivity). , A reactive compound having at least one reactivity selected from the group consisting of radical-reactive, cationic-reactive, anionic-reactive and moisture-reactive as compound B (preferably further in combination with a plasticizer) and initiation of polymerization. It is preferable to contain an agent (hereinafter, compound A (preferably compound A to which reactivity is further imparted)), and as compound B, it is selected from the group consisting of radical reactive, cationic reactive, anionic reactive and moisture reactive. A gel-like compatible composition containing at least one reactive reactive compound (preferably further in combination with a plasticizer) and a polymerization initiator is also referred to as a compatible composition viscoelastic body).

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

The compatible composition in which the graft copolymer compound and the medium are compatible is 0 to 150 ° C., and compound A has no liquid-gel transition temperature (Tc).
The compatible composition is a composition having a liquid-gel transition temperature (Tc).
It is preferable that the composition X1 has the same properties as the compatible composition.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Compatibility with the curable liquid resin composition - in terms of the gel metastatic, weight average molecular weight of the compound _{A 1} is preferably 10,000 to 500,000, more preferably 30,000 to 400,000, more preferably from 50000 to 300000.

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

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

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

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

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

(3.2) Compound A ₂
Constituting the polymer block b ₂ (meth) acrylate units, polymers constituted by itself (hereinafter, referred to as polymer b ₂₎ a glass transition temperature of the -100 ° C. or higher 50 ° C. or less (meth) acrylate It is formed when the compound is polymerized. From the viewpoint of the stability of the glass transition temperature, 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 , and further preferably 1 × 10 ^5. ~ 1 × 10 ⁷ .

As the (meth) acrylate compound that can form the polymer block b _2,
Preferably, methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, n-octyl. Alkyl (meth) acrylates such as (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate;
Alkoxy-substituted alkyl (meth) acrylates such as methoxyethyl (meth) acrylate and phenoxyethyl (meth) acrylate;
Hydroxy-substituted alkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate;
Benzyl (meth) acrylate, phenyl (meth) acrylate, etc .;
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, neopentyl Di (meth) acrylates such as glycol di (meth) acrylates, 1,6-hexanediol di (meth) acrylates; and dicyclopentenyloxyethyl (meth) acrylates, norbornene (meth) acrylates, dicyclopentanyl (meth). Selected from the group consisting of alicyclic structure-containing (meth) acrylates such as acrylates, isobornyl (meth) acrylates, cyclohexyl (meth) acrylates and 4-tert-butylcyclohexyl (meth) acrylates, and acrylamides such as acryloylmorpholine and diethylacrylamide. It is a compound
More preferably, it is n-butyl acrylate (butyl acrylate).

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

From the viewpoint of compatibility and liquid-gel transition of the curable resin composition described later, the molar ratio of the (meth) acrylate unit in the _{polymer block b 2 is preferably 90 to 100 mol%, more preferably 95.} It is ~ 100 mol%, more preferably 99-100 mol%.

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

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

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

The compound A _2, triblock structure and polymer block b ₂ in units of the polymer blocks a and n- butyl acrylate in units of styrene, commercially available from Arkema (polymer block a- polymer block b ₂ -Polymer block a) can be used.

From the viewpoint of compatibility and liquid-gel transferability of the curable resin composition, the _{weight average molecular weight of compound A 2} is preferably 1000 to 500000, more preferably 30,000 to 40000, and even more preferably 50,000 to 300,000.

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

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

The compatible composition is preferably 200 to 1000 parts by mass, preferably 200 to 1000 parts by mass, with respect to 100 parts by mass of _{compound A 1} or A ₂ from the viewpoint of applicability to a member in a liquid state and phase transition. More preferably, it is 250 to 800 parts by mass.

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

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

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

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

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

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

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

The HAZE value represents the ratio of the diffuse transmittance to the total light transmittance of the compatible composition, and the HAZE value is preferably 0.7 or less, more preferably 0.5 or less from the viewpoint of efficient light irradiation. It is more preferably 0.3 or less, still 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 thixotropy in a gel form (hereinafter, also referred to as a thixotropic compatible composition). ), And further, a thixotropically compatible composition compatible with optical transparency can be constructed.

From the viewpoint that the compatible composition has compatibility and thixotropy, 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. Mix parts by mass.

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

As a medium that can be used when adjusting the composition Z,
Aqueous media such as water, alcohol, acetic acid, formic acid, acetone, acetonitrile, ethylene glycol, glycerin;
Non-aqueous media such as benzene, toluene, xylene, diethyl ether, hexane, ethyl acetate and diethyl carbonate; and oil-based media such as fats and oils, mineral oils and petroleum-based solvents can be mentioned.
A rheological adjuster having low reactivity can be added to these to impart thixotropic properties to obtain the composition Z.

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

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

As the liquid medium having no thixotropic property in the composition Z, the suitable media mentioned in the compositions X and Y can be used.

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

In a composition in which a rheology adjuster is added to a liquid medium having no thixotropic property to impart thixotropic properties, the regularity of the arrangement of the rheology adjuster in the liquid medium may change rapidly depending on the temperature. May have Tc, and such a composition would belong to composition Y.

(5) More Suitable Gel-like Resin Composition The gel-like resin composition applied to the present inventions 1 and 2 is, for example, formed into a sheet and coated with the sheet-like gel-like resin composition. Appropriate curing by moisture, heat or light improves the protective film forming property.

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

From the viewpoint of protective film forming property, compound A has a radical reactive group, a cationic reactive group, an anionic reactive group and a moisture on the terminal or side chain of the block copolymer of the polymer block a and the polymer block b. It is preferable that the reactivity is further imparted by having at least one reactive functional group selected from the group consisting of reactive groups.

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

From the viewpoint of protective film forming property, 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 group is used as the above-mentioned radical reactive group.
Preferably, at least one selected from the group consisting of (meth) acrylate, (meth) acrylamide, (meth) acrylonitrile, urethane (meth) acrylate, vinyl group, vinyl ether, allyl ether, maleimide and maleic anhydride.
More preferably, at least one selected from the group consisting of (meth) acrylate, (meth) acrylamide, urethane (meth) acrylate and vinyl ether.
More preferably, it is at least one radical reactive group selected from the group consisting of (meth) acrylate and urethane (meth) acrylate.

From the viewpoint of protective film forming property, 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 cationically reactive group is used as the above-mentioned cationically reactive group.
Preferably, it is at least one cationically reactive group selected from the group consisting of epoxy, oxetane and vinyl ether.

From the viewpoint of protective film forming property, 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 anionic reactive group is preferably selected from epoxy, oxetane and vinyl ether. It is at least one anionic reactive group selected from the group consisting of.

From the viewpoint of protective film forming property, 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 moisture-reactive group is preferably an isocyanate group and / or an alkoxy. It is a silyl group.

From the viewpoint of protective film forming property, compound B has radical reactivity, cationic reactivity, anion reactivity and moisture in order to improve the elasticity and adhesiveness of the gel-like compatible composition and the compatible composition at the time of curing. It is preferable to use at least one reactive reactive compound selected from the reactive group.

In order to improve the elasticity and adhesiveness of the gel-like compatible composition and the compatible composition at the time of curing from the viewpoint of protective film forming property, the radically reactive compound in Compound B is selected as a radically reactive compound.
Preferably, at least one selected from the group consisting of (meth) acrylate, (meth) acrylamide, (meth) acrylonitrile, urethane (meth) acrylate, vinyl group, vinyl ether, allyl ether, maleimide and maleic anhydride.
More preferably, at least one selected from the group consisting of (meth) acrylate, (meth) acrylamide, urethane (meth) acrylate and vinyl ether.
More preferably, at least one radical reactive group selected from the group consisting of (meth) acrylate and urethane (meth) acrylate (preferably bifunctional or higher polyfunctional from the viewpoint of radical reaction rate and stability). It is a reactive compound having.

In order to improve the elasticity and adhesiveness of the gel-like compatible composition and the compatible composition at the time of curing from the viewpoint of protective film forming property, the cationically reactive compound in Compound B is selected as a cationically reactive compound.
Preferably, it is a reactive compound having at least one cationic reactivity selected from the group consisting of epoxy, oxetane and vinyl ether.

From the viewpoint of protective film forming property, the anionic reactive compound is preferably selected from epoxy, oxetane and vinyl ether in order to improve the strength, elasticity and adhesiveness of the gel-like compatible composition and the compatible composition at the time of curing. It is at least one anion-reactive compound selected from the group.

From the viewpoint of protective film forming property, 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 moisture-reactive compound in compound B is preferably an isocyanate group and preferably. / Or an alkoxysilane group.

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

From the viewpoint of protective film forming property, the compatible composition is suitable depending on the type of the reactive compound in order to improve the strength, elasticity and adhesiveness of the gel-like compatible composition and the compatible composition at the time of curing. It is preferable that the polymerization initiator is contained.

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

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

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

When the reactive compound is a moisture-reactive compound, the polymerization initiator may be
Preferably, the silanol condensation catalyst is at least one titanium compound selected from the group consisting of tetrabutyl titanate, tetrapropyl titanate, titanium tetraacetylacetonate and bisacetylacetonatodiisopropoxytitanium.
Dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctate, dibutyltin diethylhexanolate, dibutyltin dimethylmaleate, dibutyltin diethylmaleate, dibutyltin dibutylmaleate, dibutyltin dioctylmaleate, dibutyltin ditridecyl Maleate, Dibutyltin Dibenzylmaleate, Dibutyltin Diacetate, Dioctyltin diethylmaleate, Dioctyltin Dioctylmaleate, Dibutyltin dimethoxide, Dibutyltin dimethoxyside, Dibutenyl tin oxide, Dibutyltin diacetylacetonate, Dibutyltin At least one tetravalent organic tin compound selected from the group consisting of diethylacetoacetonate, a reaction product of dibutyltin oxide and a silicate compound, and a reaction product of dibutyltin oxide and a phthalate ester.
At least one organoaluminum compound selected from the group consisting of aluminumtris acetylacetonate, aluminumtrisethylacetate and diisopropoxyaluminum ethylacetate,
Zirconium compounds such as zirconium tetraacetylacetonate,
Reactants such as amine compounds, acidic phosphate esters, reactants of acidic phosphate esters and amine compounds, saturated or unsaturated polyvalent carboxylic acids or acid anhydrides thereof, salts of carboxylic acid compounds and amine compounds , Lead octylate, as well,
It is at least one compound selected from the group consisting of isocyanate reaction catalysts.

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

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

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

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

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

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

From the viewpoint of forming a protective film, the cured product of the gel-like resin composition has an elastic modulus in the range of preferably 0.1 to 1000000 kPa, more preferably 1-10000 kPa, and further preferably 10 to 100,000 kPa at 25 ° C. be.

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

The composition X1, X2, X3 or Y has a curability that is preferably cured by moisture, heat or light, more preferably by heat or light, and further preferably by light from the viewpoint of protective film forming property. It is preferable that the cured composition is a viscoelastic body of a compatible composition described in Japanese Patent Laid-Open No. 2017-066368, paragraph 0062.

<Example of Embodiment of gel-like resin composition>
(1) Examples of Embodiment X1 will be described with reference to Tables 3 and 4.
Weigh 100 g of compound a1 and 400 g of compound b1, fill a container (material SUS316, capacity 2000 ml), and rotate 200 times at 80 ° C. under atmospheric pressure using a three-one motor (manufactured by Shinto Kagaku Co., Ltd.). The compatible composition of Embodiment 1-1 can be obtained by stirring at / min for 360 minutes.

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

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

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

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

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

(1-2) Compound B
Compound b1: Isodecyl acrylate (manufactured by Sartmer, SR395)
Compound b2: 4-tert-butylcyclohexyl acrylate (Genomer 1119, manufactured by Rahn).
Compound b3: 4-Hydroxybutyl acrylate (manufactured by Nihon Kasei Co., Ltd., 4-HBA)
Compound b4: Diisononylcyclohexyl dicarboxylate (manufactured by BASF, DINCH)
Compound b5: Alkyl benzoate (alkyl carbon atoms 12 to 16) (Lipo Chemicals, Liponate NEB)
Compound b6: Hydrogenated rosin ester (manufactured by Arakawa Chemical Industry Co., Ltd., KE-311)
Compound b7: Epoxy ester (4,5-epoxy-1,2-cyclohexanedicarboxylic acid bis (2-ethylhexyl)) (manufactured by DIC Corporation, W150)
Compound b8: Disproportionated rosin ester (manufactured by Arakawa Chemical Co., Ltd., ME-D)
Compound b9: Triethylene glycol bis (2-ethylhexanoate) (Proviron, Proviplast1783)

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

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

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

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

Embodiment 2-in the same manner as in Example 2-1 by substituting the compounds a1 and b1 in Example 2-1 with the compounds shown in Tables 5 and 6 and using the formulations shown in Tables 5 and 6. 2 to 14 can be obtained.

<Compound raw material of composition X2>
(2-1) Compound A
Polymer block a is composed of methyl methacrylate units (MMA) and
The polymer block b is composed of n-butyl acrylate units (nBA) and is composed of n-butyl acrylate units (nBA).
A graft copolymer compound having a stem as a polymer block b and a branch as a polymer block a was used.

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

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

(2-2) Compound B
Compound b-1: Light acrylate LA (lauryl acrylate, Kyoeisha Chemical Co., Ltd.)
Compound b-2: SR395 (isodecylacrylate, Sartmer)
Compound b-3: Proviplast1783 (triethylene glycol bis (2-ethylhexanoate, Proviron))
Compound b-4: DINCH (diisononylcyclohexyldicarboxylate, BASF)
Compound b1-1: Hydrogenated rosin ester (manufactured by Arakawa Chemical Industry Co., Ltd., KE-311)
Compound b1-2: DINCH (diisononylcyclohexyldicarboxylate, BASF)
Compound b2-1: TE-2000 (polybutadiene urethane acrylate, Nippon Soda)
Compound b2-2: Aliphatic urethane acrylate (manufactured by Dycel Ornex, EB270)
Compound b2-3: PPG urethane acrylate (manufactured by KSM, UA10000B)
Compound b3-1: Light acrylate LA (lauryl acrylate, Kyoeisha Chemical Co., Ltd.)
Compound b3-2: Pentamethylpiperidylmethacrylate (manufactured by Hitachi Kasei Co., Ltd., FA-711MM)
Compound b3-3: Isobornyl acrylate (manufactured by Nippon Kayaku Co., Ltd., RM-1002)

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

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

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

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

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

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

[Example of Embodiment of member surface coating film process]
A. Example 1: In the case of a complex in which a display device is incorporated In the process of incorporating / disassembling a complex composed of a housing in which a display device such as a mobile phone, a personal computer, or a display is incorporated,
In the final composite assembly step, in order to prevent the surface S of the curved display device from being contaminated, a member surface coating step of coating the entire surface S with a gel-like resin composition and a member surface coating step.
It has a member surface coating film removing step of removing the coating film at the stage of using or repairing the composite.

In the complex dismantling process, for example,
For protective glass, cameras, touch panels, etc., when the coating film made to protect from dirt and scratches in the assembly process is to be removed before use by the user and these complexes are used. ,
Back covers, housings, battery packs, display modules, touch panels, protective glasses, cameras, sensors, speaker components, IC chips, various boards, etc. should be cleaned, repaired, inspected, etc. from dirt and scratches. In order to protect it, it is conceivable to coat the desired part.

By using the gel-like resin composition, it can be treated as a liquid resin at the time of coating film formation, and after the coating film is formed, the temperature drop or the discharge stress disappears, the fluidity is suppressed, and the outflow to other than the coating film portion can be prevented. can. Furthermore, as a protective film substitute sheet (hereinafter also referred to as "gel-like resin composition sheet") that has been conventionally used by adjusting the characteristics after photocuring to a film physical property that can be handled as a film and a surface adhesion that can be peeled off. Can be handled.

If necessary, there may be a coating film curing step of 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 is physically easily peeled off. Can be done (Fig. 2).

A coating film using a gel-like resin composition having transparency and photocurability has the effect of not affecting the display process and foreign matter inspection even after curing, and is a thick film to enhance protection. Even when it is set to, the entire coating film is photocured to maintain good protection and mechanical peelability.

Hereinafter, description will be made with reference to FIGS. 1 and 2.

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

(2) Example 2
A gel-like resin composition sheet may be produced on a base in advance, cut into a desired shape, and transferred to the surface S to form a coating film.
Even if the gel-like resin composition sheet is applied by heating the gel-like resin composition with a coating device, the gel-like resin composition is diluted with a solvent and applied at room temperature to volatilize the solvent to form a gel-like composition. It may be a sheet.
If the gel-like resin composition has thixotropic properties, it can be coated even at a temperature of Tc or less.

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

The coating film thickness is preferably 1 to 3000 μm, more preferably 5 to 1000 μm, and further preferably 10 to 500 μm from the viewpoint of protective film forming property and mechanical peeling property.

<Member surface coating film removal process>
In the member surface coating film removing step, the photo-cured gel-like resin composition exhibits a film property that can withstand peeling and an appropriate interfacial strength, so that the gel-like resin composition is formed on the surface S of the display device. The coating film is mechanically peeled off.

B. Example 2: In the case of a complex in which a wiring forming member is incorporated When plating wiring to an electronic member such as a semiconductor component,
It has a member surface coating process for protecting a region other than the region to be plated in the member surface processing step by coating with a gel-like resin composition.
A coating film using a gel-like resin composition having transparency and photocurability has the effect of not affecting the damage to the surface of the member or the inspection of foreign matter even after curing, and it is made into a thick film to enhance the protection. Even when this is done, the entire coating film is photocured to maintain good protection and mechanical peelability.

Hereinafter, it will be described with reference to FIG.

<Member surface coating process>
(1) Example 1
As the coating film device, for example, a coating device such as a slit coat, a knife coat, a curtain coat, a spray coat, a coating device such as a dispenser and a jet dispenser, and a printing device such as screen printing and gravure printing are used.
The gel-like resin composition is heated to Tc + 5 ° C. or higher, more preferably Tc + 10 ° C. or higher, still more preferably Tc + 15 ° C. or higher, and coated on the surface S of the display device in a desired region / shape.
Natural cooling is preferably performed in an environment of Tc-5 ° C. or lower, more preferably Tc-10 ° C. or lower, and even more preferably Tc-15 ° C. or lower.

(2) Example 2
A gel-like resin composition sheet may be produced on a base in advance, cut into a desired shape, and transferred to the surface S to form a coating film.
Even if the gel-like resin composition sheet is applied by heating the gel-like resin composition with a coating device, the gel-like resin composition is diluted with a solvent and applied at room temperature to volatilize the solvent to form a gel-like composition. It may be a sheet.
If the gel-like resin composition has thixotropic properties, it can be coated even at a temperature of Tc or less.

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

The coating film thickness is preferably 1 to 3000 μm, more preferably 5 to 1000 μm, and further preferably 10 to 500 μm from the viewpoint of protective film forming property and mechanical peeling property.

When a gel-like resin composition that exhibits transparency even after photo-curing is used, screen printing is possible and transparency is maintained even after photo-curing. Therefore, for example, it was used for a member requiring an inspection process. In some cases, it can be used as a plating protective film that does not require a removal step.

<Member surface coating film removal process>
In the member surface coating film removing step, the photo-cured gel-like resin composition exhibits a film property that can withstand peeling and an appropriate interfacial strength, so that the gel-like resin composition is formed on the surface S of the display device. The coating film is mechanically peeled off.

C. Example 3: In the case of a complex incorporating a member to be chemically etched, for example, as a member surface processing step of a silicon-based member used for a semiconductor part / optical part.
For wafer members as silicon substrates, polishing the wafer surface,
Silicon etching that forms a fine three-dimensional pattern on the surface of a silicon member,
Examples include chemical etching processing such as etching processing _{of a SiO 2} film on a silicon substrate.

In the chemical etching process, a member surface coating process in which a gel-like resin composition is applied to a portion other than the etching target portion of the surface S, and a member surface coating process.
If necessary, it has a member surface coating film removing step of removing the coating film.

By using a temperature-responsive gel as a protective film, the gel-like resin composition can be coated only on the target portion of the coating film, and as the gel-like resin composition, for example, a compatible composition having solvent solubility. If a viscoelastic material is used, it is possible to produce a protective film that does not require a curing step, and it can be removed by dissolution cleaning without going through a physical removal step, which reduces the process load compared to conventional resist coating films. Can be reduced.

Hereinafter, it will be described with reference to FIG.

<Member surface coating process>
(1) Example 1
As the coating film device, for example, a coating device such as a slit coat, a knife coat, a curtain coat, a spray coat, a coating device such as a dispenser and a jet dispenser, and a printing device such as screen printing and gravure printing are used.
The gel-like resin composition is heated to Tc + 5 ° C. or higher, more preferably Tc + 10 ° C. or higher, still more preferably Tc + 15 ° C. or higher, and coated on the surface S of the display device in a desired region / shape.
Natural cooling is preferably performed in an environment of Tc-5 ° C. or lower, more preferably Tc-10 ° C. or lower, and even more preferably Tc-15 ° C. or lower.

(2) Example 2
A gel-like resin composition sheet may be produced on a base in advance, cut into a desired shape, and transferred to the surface S to form a coating film.
Even if the gel-like resin composition sheet is applied by heating the gel-like resin composition with a coating device, the gel-like resin composition is diluted with a solvent and applied at room temperature to volatilize the solvent to form a gel-like composition. It may be a sheet.
If the gel-like resin composition has thixotropic properties, it can be coated even at a temperature of Tc or less.

If the gel-like resin composition is photocurable, a coating film curing step of irradiating the coating film with ultraviolet rays to cure the coating film can be provided after the coating film.

The coating film thickness is preferably 1 to 3000 μm, more preferably 5 to 1000 μm, and further preferably 10 to 500 μm from the viewpoint of protective film forming property and mechanical peeling property.

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

<Member surface coating film removal process>
In the member surface coating film removing step, the photo-cured gel-like resin composition exhibits a film property that can withstand peeling and an appropriate interfacial strength, so that the gel-like resin composition is formed on the surface S of the display device. The coating film is mechanically peeled off.

〔Example〕
(1) Compound raw material (1-1) Compound A
Compound a1: KURARITY LA2270 (Kuraray)

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

(1-2) Compound B
Compound b1: UA10000 (BPPG urethane acrylate, KSM)
Compound b2: RM1002 (isobornyl acrylate, Nippon Shokubai Co., Ltd.)
Compound b3: FA-711MM (Pentamethylpiperidyl Methrate, Hitachi Kasei Co., Ltd.)
Compound b4: ACMO (acryloyl morpholine, KJ Chemicals)
Compound b5: Viscote # 802 (mixture of tripentaerythritol octaacrylate and tripentaerythritol heptaacrylate, Osaka Organic Chemical Industry Co., Ltd.)
Compound b6: LA (lauryl acrylate, Kyoeisha Chemical Co., Ltd.)

(1-3) Compound C

(1-3-1) Compound C1
Compound c11: TEGO GLIDE440 (Evonik)
Compound c12: TEGO GLIDE410 (Evonik)
Compound c13: TEGO GLIDE432 (Evonik)
Compound c14: TEGO GLIDE450 (Evonik)

(1-3-2) Compound C2
Compound c21: Modiver FS700 (NOF)

(1-3-3) Compound C3
Compound c31: FC4430 (3M)
Compound c32: Megafuck RS-78 (3M)

(1-3-4) Compound C4
Compound c41: LIPCOOL C-2 (diethylene glycol monocetyl ether, LIPO Chemicals)

(1-3-5) Compound C5
Compound c51: HS Crysta 6100 (Toyokuni Oil Co., Ltd.)

(1-4) Other compounds Compound r1: LV-7 (polybutene (Mn = 300), JXTG Energy Co., Ltd.)
Compound r2: ARUFON1110 (Acrylic polymer (Mw = 2500), Toagosei Co., Ltd.)
Compound r3: I-184 (1-hydroxycyclohexylphenyl ketone, BASF)

(2) Gel-like resin composition

(2-1) Example 1
As compound A, 300 g of compound a1 was weighed to 30 parts by weight, compounds b1 to b6 as compound B, compound c11 as compound C1 and compound r3 were weighed to be parts by weight shown in Table 11, and the container (material: SUS316) was manufactured. , Capacity 2000 ml), and stirred at 200 rpm for 360 minutes using a three-one motor (manufactured by Shinto Kagaku Co., Ltd.) at 80 ° C. and atmospheric pressure to obtain the compatible composition of Example 1. rice field.

(2-2) Examples 2-9
Compounds A, B, C1 and r1 of Example 1 shown in Table 11 are:
Substituting with the compounds shown in Table 11, the gel-like resin compositions of Examples 2 to 9 were produced in the same manner with the formulations shown in Table 11.

(2-3) Comparative Examples 1 to 4
Compounds A, B and r1 of Example 1 were replaced with the compounds of Comparative Examples 1 to 4 shown in Table 11 to prepare a liquid composition in the same manner with the formulations shown in Table 11.

(2-2) The following physical properties were measured for each Example and Comparative Example.

(2-2-1) The glass transition point of the butyl acrylate polymer (polymer a) and the methyl methacrylate polymer (polymer b).
(2-2-2) Liquid-gel transition temperature (Tc)
(2-2-3) Complex viscosity at Tc + 20 ° C (Pa · s)
(2-2-4) Complex viscosity at 80 ° C. (Pa · s)
(2-2-5) Storage rigidity at 25 ° C (kPa)
(2-2-6) Elastic modulus after curing (MPa) at 25 ° C.
(2-2-7) HAZE value

(3) Measurement conditions for gel-like composition physical properties <Glass transition point>
For each of the polymer a, the polymer b and the block copolymer compound, a hydraulic hot press machine manufactured by Kondo Metal Industry Co., Ltd. set at 200 ° C. was used, and the pressure was 0.5 mm at a pressure of 10 MPa.
Sheet to the thickness. After that, 45 mm x 10 mm x 0.5 m required for dynamic viscoelasticity measurement
Cut out a strip of m.
Using a dynamic viscoelastic device (DMS6100) manufactured by Seiko Instruments, Inc.
In the chart obtained by measuring in the tension mode under the conditions of a temperature range of -100 ° C to 200 ° C (heating rate 3 ° C / min) and a frequency of 11 Hz.
The peak temperature of tan δ is read and used as the glass transition point of each of the polymer a, the polymer b and the block copolymer compound constituting the strip piece.

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

If Tc cannot be confirmed under measurement condition 1, the Tc confirmed under measurement condition 2 below is used.

[Measurement condition 2]
The storage rigidity G'and the loss rigidity G'of the photocurable resin composition,
Using a rheometer (manufactured by Antonio Par),
Cone rotor (φ = 25 mm, rotor angle 2 °), frequency 1 Hz, strain 1%,
Measure by heating at 2 ° C / min from 0 ° C to 150 ° C.
In the range of more than 25 ° C. and 150 ° C. or lower, the temperature at which the storage rigidity G'and the loss rigidity G'are equal is defined as Tc.

<Complex viscosity>
Using a rheometer (manufactured by Antonio Par), measure with a cone rotor (φ = 25 mm, rotor angle 2 °), frequency 1 Hz, strain 1%, cooled from 150 ° C to 0 ° C at 2 ° C / min. bottom. The values measured in the temperature range of Tc + 20 ° C. and 80 ° C. were defined as complex viscosities.

<Thixotropic ratio>
In the measurement of the viscosity ηv, the viscosity ratio X1 = η1 / η10 at the shear rate 1 (sec-1) and the shear rate 10 (sec-1) was calculated and used as the thixotropic ratio.

<Store rigidity>
Using a rheometer (manufactured by Antonio Par),
Cone rotor (φ = 25 mm, rotor angle 2 °), frequency 1 Hz, strain 1%,
The measurement was carried out by cooling at 2 ° C./min from 150 ° C. to 0 ° C.
The numerical value of the storage rigidity measured at 25 ° C. was read. However, when the transition temperature was 0 ° C. ≤ Tc ≤ 30 ° C., the storage rigidity at Tc-20 ° C. was used.

<Elastic modulus after curing>
(1) After liquefying the gel-like resin composition at a temperature of Tc + 20 ° C., it is poured into a dumbbell mold prepared by punching out a silicone sheet and cooled to a temperature lower than the temperature Tc (actually at room temperature) to prepare a dumbbell test piece having a thickness of 1 mm. do.
(2) The dumbbell test piece is pulled with a tensile tester (Minebea technograph, TG-2kN) at a tensile speed of 10 mm / min, and the elastic modulus is read from the measurement results.

<HAZE value>
Attach 0.3 mmt spacers to both ends of 2.5 cm x 3.8 cm x 1 mmt glass, sandwich the curable resin composition, and use a metal halide lamp (conveyor type manufactured by Eye Graphics) at 250 mW / cm2, 3000 mJ. The curable resin composition was cured at / cm2.
Measure with a haze meter (NDH5000, manufactured by Nippon Denshoku Kogyo Co., Ltd.) to determine the ratio of total light transmittance to diffuse transmittance.

(4) Measurement conditions for coating film characteristics of gel-like composition <Protective film formability>

(1) The compositions of Examples 1 to 9 and Comparative Examples 1 to 3 were made into a liquid compatible composition at 80 ° C., and the composition of Comparative Example 4 was made into a glass substrate (width 50 mm, length) at 25 ° C. Using a flat nozzle (width 30 mm, SHOT MASTER 300, manufactured by Musashi Engineering) on 50 mm, thickness 0.7 mm, Eagle XG, manufactured by Corning Inc., the coating was applied to a thickness of 0.15 mm.

After leaving it for 300 seconds after application, using a conveyor type ultraviolet irradiation device (Metal halide lamp manufactured by Aigfic), the peak illuminance is 400 mW / cm ² , the integrated light amount is 6000 mJ / cm ² (wavelength 350 nm manufactured by Oak), and the reaction rate is 100%. It was photocured to form a cured product protective film on a glass substrate.

The coating shape is measured using a laser microscope (LEXT OLS4000 manufactured by Olympus), and the liquid dripping width is defined as the part where the uniform film thickness part is fully exhibiting the protection performance and the part where the liquid dripping part is contaminated or the protection performance is not sufficient. Was measured.
If the distance of the liquid dripping width is 0.5 mm or less, it is evaluated as ◯, and if it is 0.5 mm or more, it is evaluated as ×.

(2) The compositions of Examples 1 to 3 and 6 to 7 and Comparative Examples 1 to 3 were made into a liquid compatible composition at 80 ° C., and the composition of Comparative Example 4 was made into a SUS substrate (width) at 25 ° C. 50 mm, length 50 mm, thickness 2.0 mm, SUS304, manufactured by Engineering Test Serves, using a flat nozzle (width 30 mm, SHOT MASTER 300, manufactured by Sashi Engineering) to a thickness of 0.15 mm. Painted.

After leaving it for 300 seconds after application, using a conveyor type ultraviolet irradiation device (Metal halide lamp manufactured by Aigfic), the peak illuminance is 400 mW / cm ² , the integrated light amount is 6000 mJ / cm ² (wavelength 350 nm manufactured by Oak), and the reaction rate is 100%. It was photocured to form a cured product protective film on the glass substrate 2.

The coating shape is measured using a laser microscope (LEXT OLS4000 manufactured by Olympus), and the liquid dripping width is defined as the part where the uniform film thickness part is fully exhibiting the protection performance and the part where the liquid dripping part is contaminated or the protection performance is not sufficient. Was measured.
If the distance of the liquid dripping width is 0.5 mm or less, it is evaluated as ◯, and if it is 0.5 mm or more, it is evaluated as ×.

<Mechanical peelability>
Peel off the corners of the glass substrate used in the protective film forming property test and the cured film on SUS with tweezers.
When the resin peels off without breaking ○,
△, when the resin was broken although it could be peeled off from the interface
If it could not be peeled off, ×
And said.

The results of the above Examples and Comparative Examples are summarized in Tables 11 and 12.

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

Claims (7)

A method for manufacturing and disassembling a composite in which the member having a member having a member having a surface S and / or a member having a surface processing step for processing the surface S is incorporated.
In the assembling and / or removing step and / or in 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-like resin composition, and
It has a step of mechanically peeling off the gel-like resin composition coated in the coating film step.
The gel-like resin composition is
Has a liquid-gel transition temperature (Tc) from 0 to 150 ° C. and / or
It has thixotropic properties and also has thixotropic properties.
Polyether-modified polysiloxane (Compound C1), acrylic block copolymer having polysiloxane in the side chain (Compound C2), nonionic fluorine-containing surfactant compound (Compound C3) , ( poly) alkylene glycol monoalkyl ether (poly) compound C4) and side chain crystalline α-olefin polymer (being at least one compound C selected from the group consisting of compounds C5) is blended Ri Na,
A method for producing and disassembling a composite in which the compound C4 is ethylene glycol monoalkyl ethers and / or propylene glycol monoalkyl ethers (however, when the gel-like resin composition contains urethane (meth) acrylate, the urethane (Except when the urethane (meth) acrylate obtained from the polyester polyol is 5 to 45% by weight in the (meth) acrylate) . The method for producing and disassembling a complex according to claim 1, wherein the gel-like resin composition has heat and / or photocurability. The surface S is, manufacturing and disassembly method of a composite body according to claim 1 or 2, wherein is formed by silicon-containing ceramics and / or metal. The composite according to any one of claims 1 to 3, wherein the member surface processing is at least one member surface processing selected from the group consisting of wiring forming processing, plating forming processing, and etching processing on the surface S. Manufacturing and dismantling method. Claims 1 to 4 wherein 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 for exteriorizing the component. The method for producing / disassembling the complex according to any one of the above items. The method for manufacturing and disassembling a complex according to any one of claims 1 to 5, wherein the complex is composed of a housing in which the member is incorporated. The gel-like resin composition according to claim 1 or 2, which is used in the method for producing and disassembling the complex according to any one of claims 1 to 6.

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