KR20200120645A - Curable resin composition for forming cured resin film with heat resistance and easy peelability, and method for producing same - Google Patents

Abstract

There is disclosed a curable resin composition that can be applied to the surface of a glass substrate to deposit a cured resin thin film, withstands sintering at 230°C to 300°C, and can be easily peeled off the board without difficulty. The composition is a curable resin composition comprising a chain-shaped polymer having a side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group and a crosslinking agent, wherein (a) the chain polymer is formula A1 [wherein R ^1a , L ¹ , L ² , R ^2a , R ^3a and R ^4a are as described herein], and (b) the crosslinking agent is a triazine-based compound and/or a condensate thereof , A glycoluril-based compound and/or a condensate thereof, and an imidazolidinone-based compound and/or a condensate thereof.

Description

Curable resin composition for forming cured resin film with heat resistance and easy peelability, and method for producing same

The present invention relates to a curable resin composition, and more particularly, to a curable resin composition for forming an easily peelable cured resin film. In particular, it relates to a curable resin composition that can be deposited as a thin film by coating and curing on a substrate such as glass, and then providing a thin film that can be easily peeled off from the substrate. The present invention also relates to a curable resin composition capable of forming a cured resin film having heat resistance and easy peelability having various optical properties.

The base film, which is an example of a substrate used in a display device such as a display device, is required to be thinner every year, but the heat resistance of the base film decreases as the thickness decreases. Therefore, there is a need for a base film material that can withstand firing at a high temperature to maintain the performance of the circuit.

In addition, according to the thickness reduction, it is preferable to use a very thin film of about 300 nm. To do this, the base film is formed by applying a resin composition, which is a base film material, to another substrate (glass substrate, etc.) and curing it by heat curing. It is necessary to make it. Circuit components such as metal wiring are sequentially stacked on this very thin base film formed on a substrate such as glass, and anisotropic conductive film is installed, printed circuit board (PCB) wiring is stacked, and circuit connection is also performed according to the purpose. After lamination of the insulating protective film is performed, the base film is removed from a substrate such as glass as an integral laminate together with each layer formed thereon, whereby a laminate as a circuit component can be obtained.

Here, it should be easy without unreasonableness to pull out the laminated body of the substrate such as glass. Otherwise, a large warpage occurs in the stacked body due to the load when pulling-off, resulting in disconnection of metal wiring and peeling of circuit connections, resulting in a remarkable deterioration in yield of the product.

In particular, although the substrate material itself can withstand heat treatment at a higher temperature than before in the form of a thin film, if the sintering in the process of manufacturing the wiring thereon is performed at that high temperature, adhesion between the substrate material and the surface of the substrate on which it is placed It gets easier. Therefore, it is not enough to withstand firing at a higher temperature than before in the form of a thin film as a substrate material, and it must have the characteristic that it can be easily peeled off the substrate even after such high temperature firing.

Patent Document 1: International Patent Publication No. 2015/016532 Patent Document 2: Japanese Patent Laid-Open Publication No. Hei 9-105896 Patent Document 3: Japanese Patent No. 5200538

The present inventors have found that the use of a curable resin composition containing a specific polymer and a crosslinking agent can form a cured resin film having various optical properties with heat resistance and easy peelability. The present inventors have completed the present invention by finding that the cured resin film of the present invention withstands firing at a high temperature, can be easily peeled off from a substrate after firing at a high temperature, and has good properties (permeability and high speed curing, etc.).

For example, the present invention provides the following items.

(Item 1)

In the curable resin composition comprising a crosslinking agent and a chain polymer having side chains having alcoholic secondary and tertiary OH-containing groups or phenolic OH-containing groups,

(a) the chain polymer is formula A1:

[Formula 1]

[In the above formula,

R ^1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group,

L ¹ is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group, and a substituted or unsubstituted alkenylene group,

L ² is O or NH,

R ^2a , R ^3a and R ^4a are each independently selected from the group consisting of hydrogen and a substituted or unsubstituted hydrocarbon radical, provided that at least one of R ^2a , R ^3a and R ^4a is a substituted or unsubstituted alcoholic secondary or secondary A substituted or unsubstituted cycloalkyl group containing a tertiary OH-containing group or a phenolic OH-containing group, or at least two of R ^2a , R ^3a and R ^4a combined to contain alcoholic secondary or tertiary OH or phenolic OH , To form a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted heteroaromatic group, or a polycyclic body containing them.]

It includes a monomer unit represented by,

(b) The crosslinking agent is a triazine-based compound and/or a condensate thereof, a glycoluril-based compound and/or a condensate thereof, and an imidazolidinone-based compound and/or a condensate thereof

Which is selected from the group consisting of

Curable resin composition.

(Item 2)

The chain polymer is formula A2:

[Formula 2]

[In the above formula

R ^1a , L ¹ and L ² are as described in the above items,

R ^5a to R ^14a are independently of each other hydrogen, a hydroxy group, and

[Formula 3]

It is selected from the group consisting of or is combined to form a ring, provided that at least one of R ^5a to R ^14a or a substituent of the ring is a hydroxy group,

R ^15a is selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted heteroaromatic group. .]

The curable resin composition of the above item comprising a monomer unit represented by.

(Item 3)

The chain polymer is formula A2:

[Formula 4]

[In the above formula

R ^1a and L ¹ are as described in item 1,

R ^5a to R ^14a are independently of each other hydrogen, a hydroxy group, and

[Formula 5]

It is selected from the group consisting of or is combined to form a ring, provided that at least one of R ^5a to R ^14a or a substituent of the ring is a hydroxy group,

R ^15a is selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted heteroaromatic group. .]

Curable resin composition in any one of the above items comprising a monomer unit represented by.

(Item 4)

L ¹ is the curable resin composition of any one of the above items selected from the group consisting of a substituted or unsubstituted alkylene group and a substituted or unsubstituted alkenylene group.

(Item 5)

L ¹ is a substituted or unsubstituted alkylene group, the curable resin composition of any one of the above items.

(Item 6)

L ¹ is a methylene group, the curable resin composition according to any one of the above items.

(Item 7)

The chain polymer is formula A5:

[Formula 6]

[In the above formula

R ^1a and L ¹ are as described in item 1,

R ^19a is selected from the group consisting of a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted heteroaromatic group.]

Curable resin composition in any one of the above items comprising a monomer unit represented by.

(Item 8)

L ¹ is a substituted or unsubstituted alkylene group, the curable resin composition of any one of the above items.

(Item 9)

L ¹ is a methylene group, the curable resin composition according to any one of the above items.

(Item 10)

R ^19a is a phenyl group, the curable resin composition according to any one of the above items.

(Item 11)

The curable resin composition according to any one of the above items, wherein the crosslinking agent is a triazine-based compound and/or a condensation thereof.

(Item 12)

The crosslinking agent,

[Formula 7]

The curable resin composition according to any one of the above items.

(Item 13)

L ¹ is a single bond, the curable resin composition of any one of the above items.

(Item 14)

The curable resin composition according to any one of the above items, wherein at least two of R ^5a to R ^14a are hydroxy groups, and the other is hydrogen.

(Item 15)

One of R ^5a to R ^14a is a hydroxy group, and the other is hydrogen. The curable resin composition according to any one of the above items.

(Item 16)

R ^5a to R ^13a are hydrogen, and R ^14a is a hydroxy group. The curable resin composition according to any one of the above items.

(Item 17)

The curable resin composition according to any one of the above items, wherein the crosslinking agent is a glycoluril-based compound and/or a condensation thereof.

(Item 18)

The crosslinking agent,

[Formula 8]

The curable resin composition according to any one of the above items.

(Item 19)

The crosslinking agent,

[Formula 9]

The curable resin composition according to any one of the above items.

(Item 20)

The composition is the curable resin composition of any one of the above items provided as a solution.

(Item 21)

The curable resin composition of the above item, wherein the solvent of the solution contains alcohol.

(Item 22)

The alcohol is the curable resin composition of the above item containing a primary alcohol.

(Item 23)

The alcohol is the curable resin composition of the item containing ethanol.

(Item 24)

The curable resin composition of any one of the above items, wherein the alcohol is present in an amount of 10% by weight or more of the total amount of the solvent.

(Item 25)

The crosslinking agent is wholly or partially alkoxymethylated melamine and/or condensate thereof, wholly or partially alkoxymethylated guanamine and/or condensate thereof, wholly or partially alkoxymethylated acetoguanamine and/or condensate thereof, wholly or partially alkoxymethylated Among the above items selected from the group consisting of benzoguanamine and/or condensates thereof, wholly or partially alkoxymethylated glycoluril and/or condensates thereof, and wholly or partially alkoxymethylated imidazolidinone and/or condensates thereof Any one curable resin composition.

(Item 26)

The crosslinking agent formula B1:

[Formula 10]

[In the above formula

R ^1b has 1 to 25 carbon atoms, and is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted heteroaromatic group, and

[Formula 11]

It is selected from the group consisting of disubstituted amines represented by,

R ^2b to R ^7b each independently have 1 to 10 carbon atoms, and are selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group.]

A compound represented by and/or a condensate thereof,

Equation B2:

[Formula 12]

[In the above formula, R ^8b to R ^11b each independently have 1 to 10 carbon atoms, and are selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group.]

A compound represented by and/or a condensate thereof, and

Equation B3:

[Formula 13]

[In the above formula

R ^12b and R ^13b independently of each other have 1 to 10 carbon atoms, and are selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group,

R ^14b and R ^15b are each independently hydrogen or have 1 to 10 carbon atoms, and are selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group.]

Compound represented by and/or condensate thereof

The curable resin composition of any one of the above items is selected from the group consisting of.

(Item 27)

The curable resin composition according to any one of the above items, wherein the condensate contains a polymer of the compound represented by formula B1, formula B2, or formula B3.

(Item 28)

The curable resin composition according to any one of the above items, wherein the condensate contains at least one of a dimer, a trimer and a higher order polymer of the compound represented by Formula B1, Formula B2, or Formula B3.

(Item 29)

The curable resin composition according to any one of the preceding items, wherein the crosslinking agent has a weight average polymerization degree of 1.3 to 1.8 with respect to the compound represented by Formula B1, Formula B2, or Formula B3, respectively.

(Item 30)

R ^1b is a substituted or unsubstituted aromatic group and

[Formula 14]

The curable resin composition of any one of the above items is selected from the group consisting of disubstituted amines represented by, R ^2b to R ^13b are each independently a substituted or unsubstituted alkyl group, and R ^14b and R ^15b are each independently hydrogen .

(Item 31)

In the composition, the ratio of the mass of the linear polymer and the mass of the crosslinking agent is 1:2 to 1:0.05, the curable resin composition in any one of the above items.

(Item 32)

The curable resin composition of any one of the above items further comprising an acid catalyst.

(Item 33)

The curable resin composition according to any one of the above items, wherein the acid catalyst is a compound selected from Bronsted acid and/or Lewis acid, or a salt or solvate thereof.

(Item 34)

The acid catalyst is a compound selected from the group consisting of p-toluenesulfonic acid (PTS), dodecyl benzenesulfonic acid, pyridinium-p-toluenesulfonate, and thermal acid generator Sunade SI-100L (Samshin Chemical Industry Co., Ltd.) , Or a salt thereof or a solvate thereof, the curable resin composition according to any one of the above items.

(Item 35)

The curable resin composition of any one of the above items further comprising at least one of a surfactant, a filler, an additive, and a foaming agent.

(Item 36)

The curable resin composition of any one of the above items further comprising a surfactant.

(Item 37)

The curable resin composition of any one of the above items further comprising a foaming agent.

(Item 38)

The curable resin composition according to any one of the above items having curability that is cured by heating at 150° C. for 1 minute.

(Item 39)

A cured resin film obtained by curing the curable resin composition of any one of the above items.

(Item 40)

The cured resin film of the above item has a transmittance (% T) of 99% or more at 400 nm and b* of 0.1 or less.

(Item 41)

The cured resin film of any one of the above items having heat resistance of 230 ℃ to 300 ℃.

(Item 42)

The cured resin film of any one of the above items having heat resistance for 1 to 2 hours at 230°C to 260°C.

(Item 43)

The cured resin film of any one of the above items having heat resistance at 230° C. for 8 hours or more.

(Item 44)

The cured resin film of any one of the above items having heat resistance at 230° C. for 1 to 2 hours.

(Item 45)

An easily peelable cured resin film obtained by curing the curable resin composition of any one of the above items in a film form on the surface of a substrate.

(Item 46)

The cured resin film of any one of the above items having a peeling force in a soda glass substrate of 0.5 N/mm ² or less or an alkali-free glass substrate.

(Item 47)

The cured resin film of any one of the above items having a peeling force in a soda glass substrate of 0.1 N/mm ² or less or an alkali-free glass substrate.

(Item 48)

In the method for producing a cured resin film from the curable resin composition according to any one of the above items,

(I) preparing the chain polymer and the crosslinking agent having a side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group;

(Ii) applying the curable resin composition containing the chain polymer and the crosslinking agent on a substrate and forming a curable resin composition coating film;

(Iii) forming a cured resin film by performing a polymerization reaction in the curable resin composition coating film to cure it;

Manufacturing method comprising a.

(Item 49)

(Iv) The method for manufacturing any one of the above items, further comprising the step of peeling the cured resin film formed on the substrate from the substrate.

(Item 50)

The production method according to any one of the above items, wherein the ratio of the monomer unit having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group of the monomer unit constituting the chain polymer is 30 to 100 mol%.

(Item 51)

The crosslinking agent is selected from the group consisting of wholly or partially alkoxymethylated melamine, wholly or partially alkoxymethylated guanamine, wholly or partially alkoxymethylated acetoguanamine, or wholly or partially alkoxymethylated benzoguanamine and wholly or partially alkoxymethylated glycoluril The manufacturing method of any one of the above items.

(Item 52)

The method for producing any one of the above items wherein the ratio of the mass of the linear polymer and the mass of the crosslinking agent in the composition is 1:2 to 1:0.05.

(Item 53) A composition for producing a circuit by a photolithography method comprising the curable resin composition or cured resin film of any one of the above items.

(Item 54) A composition for manufacturing a flexible electric/electronic circuit component or a flexible display device in the form of a sheet comprising the curable resin composition or cured resin film of any one of the above items.

(Item 55) Used for synthetic resins, pellets, films, plates, fibers, tubes, rubbers, elastomers, etc. including the curable resin composition or cured resin film of any one of the above items, and used for motorcycles (bicycles, motorcycles, etc.) automobiles, airplanes, trains , Ships, rockets, spacecraft, transport, leisure, furniture (eg, tables, chairs, desks, shelves, etc.), bedding (eg, beds, hammocks, etc.), clothing, protective clothing, sports equipment, bathtubs, kitchens , Tableware, cooking utensils, containers and packaging (food containers, cosmetics containers, cargo containers, trash, etc.), construction (buildings, roads, construction parts, etc.), agricultural films, industrial films, water and sewage, paints, cosmetics, electrical industry and electronics Industrial fields (electronic products, computer parts, printed circuit boards, insulators, conductors, wiring coating materials, power generation elements, speakers, microphones, noise cancellers, transducers, etc.), optical communication cables, medical materials and devices (catheter, guide wire, artificial Compositions for the manufacture of blood vessels, artificial muscles, artificial organs, dialysis membranes, endoscopes, etc.), small pumps, actuators, robotic materials (sensors used in industrial robots, etc.), energy generating devices and plants (solar power generation, wind power generation, etc.).

(Item 56) A composition for manufacturing an electronic material, medical material, medical material, life science material, or robot material comprising the curable resin composition or cured resin film of any one of the above items.

(Item 57) A composition for manufacturing a material such as a catheter, a guide wire, a pharmaceutical container, or a tube comprising the curable resin composition or cured resin film of any one of the above items.

(Item 58) Automobile parts (car body panels, bumper belts, rocker panels, side malls, engine parts, drive parts, conduction parts, steering device parts, stabilizer parts, and parts) containing the curable resin composition or curable resin film of any one of the above items, Composition for manufacturing suspension/braking device parts, brake parts, shaft parts, pipes, tanks, wheels, seats, seat belts, etc.).

(Item 59) A composition for producing a vibration isolator for automobiles, paints for automobiles, and synthetic resins for automobiles comprising the curable resin composition or cured resin film of any one of the above items.

(Item 60) Use of the curable resin composition or cured resin film according to any one of the above items for manufacturing a circuit by photolithography.

(Item 61) Use of the curable resin composition or cured resin film according to any of the above items for manufacturing a sheet-shaped flexible electric/electronic circuit component or a flexible display device.

(Item 62) Synthetic resin, pellet, film, plate, fiber, tube, rubber, elastomer, etc., used for two-wheeled vehicles (bicycles, motorcycles, etc.), automobiles, airplanes, trains, ships, rockets, spacecraft, transport, leisure, furniture (e.g. For example, tables, chairs, desks, shelves, etc.), bedding (e.g., beds, hammocks, etc.), clothing, protective clothing, sports goods, bathtubs, kitchenware, tableware, cooking utensils, containers and packaging (food containers, cosmetics Containers, cargo containers, trash cans, etc.), construction (buildings, roads, construction parts, etc.), agricultural films, industrial films, water and sewage, paints, cosmetics, electrical and electronic industries (electronic products, computer parts, printed circuit boards, insulators, etc.) Conductors, wiring coating materials, power generation elements, speakers, microphones, noise cancellers, transducers, etc.), optical communication cables, medical materials and devices (catheter, guide wire, artificial blood vessels, artificial muscles, artificial organs, dialysis membranes, endoscopes, etc.), Use of the curable resin composition or curable resin film according to any of the above items for the manufacture of small pumps, actuators, robotic materials (sensors used in industrial robots, etc.), energy generating devices and plants (solar power generation, wind power generation, etc.).

(Item 63) Use of the curable resin composition or cured resin film of any of the above items for the manufacture of electronic materials, medical materials, medical materials, life science materials, or robotic materials.

(Item 64) Use of the curable resin composition or cured resin film according to any of the above items for the manufacture of materials such as catheters, guide wires, pharmaceutical containers or tubes.

(Item 65) Auto parts (body panels, bumper belts, rocker panels, side malls, engine parts, drive parts, conduction parts, steering parts, ballast parts, suspension/braking parts, brake parts, shaft parts, pipes, Tanks, wheels, seats, seat belts, etc.) using any one of the above-described curable resin composition or curable resin film.

(Item 66) Use of the curable resin composition or cured resin film according to any one of the above items for the production of an automobile dust-proof material, automobile paint, and automobile synthetic resin.

(Item 67) A method of manufacturing a circuit by a photolithography method, comprising the step of forming a curable resin composition or a cured resin film according to any one of the above items through a polymerization reaction.

(Item 68) A method for manufacturing a sheet-shaped flexible electric/electronic circuit component or a flexible display device, comprising the step of forming a curable resin composition or a cured resin film according to any one of the above items through a polymerization reaction.

(Item 69) Used for synthetic resins, pellets, films, plates, fibers, tubes, rubber, elastomers, etc., motorcycles (bicycles, motorcycles, etc.), automobiles, airplanes, trains, ships, rockets, spacecraft, transport, leisure, furniture (e.g. For example, tables, chairs, desks, shelves, etc.), bedding (e.g., beds, hammocks, etc.), clothing, protective clothing, sports goods, bathtubs, kitchenware, tableware, cooking utensils, containers and packaging (food containers, cosmetics Containers, cargo containers, trash cans, etc.), construction (buildings, roads, construction parts, etc.), agricultural films, industrial films, water and sewage, paints, cosmetics, electrical and electronic industries (electronic products, computer parts, printed circuit boards, insulators, etc.) Conductors, wiring coating materials, power generation elements, speakers, microphones, noise cancellers, transducers, etc.), optical communication cables, medical materials and devices (catheter, guide wire, artificial blood vessels, artificial muscles, artificial organs, dialysis membranes, endoscopes, etc.), In a method of manufacturing a small pump, an actuator, a robot material (sensor used in industrial robots, etc.), an energy generating device and a plant (solar power generation, wind power generation, etc.), the curable resin composition of any one of the above items through a polymerization reaction Or a method comprising the step of forming a cured resin film.

(Item 70) A method of manufacturing an electronic material, a medical material, a medical material, a life science material, or a robot material, comprising the step of forming a curable resin composition or a cured resin film of any one of the above items through a polymerization reaction. Way.

(Item 71) A method for manufacturing a material such as a catheter, a guide wire, a pharmaceutical container, or a tube, comprising a step of forming a curable resin composition or a cured resin film according to any one of the above items through a polymerization reaction.

(Item 72) Auto parts (body panels, bumper belts, rocker panels, side malls, engine parts, drive parts, conduction parts, steering system parts, ballast parts, suspension/braking parts, brake parts, shaft parts, pipes, tanks In the method of manufacturing a kind, wheel, seat, seat belt, etc.), a method comprising the step of forming a curable resin composition or a cured resin film of any one of the above items through a polymerization reaction.

(Item 73) A method for manufacturing an automobile anti-vibration material, automobile paint, or automobile synthetic resin, comprising a step of forming a curable resin composition or a cured resin film according to any one of the above items through a polymerization reaction.

According to the present invention, a curable resin composition comprising a specific polymer and a crosslinking agent for preparing a cured resin film having good properties has been developed. By heat-treating this curable resin composition, formation of a cured resin film having heat resistance, easy peelability, and other good properties (permeability and high-speed curing properties, etc.) is achieved.

Hereinafter, the present invention will be described while showing the best mode. Throughout this specification, expressions in the singular are to be understood as including the concept of the plural unless otherwise specified. Therefore, a singular article (eg, "a", "an", "the", etc. in English) should be understood to include the concept of its plural form, unless otherwise noted. In addition, terms used in the present specification should be understood as being used in the meanings commonly used in the corresponding field unless otherwise specified. Accordingly, unless otherwise defined, all terms and scientific and technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. In case of conflict, the present specification (including definitions) shall control. Compound names described herein can be assigned according to software such as ChemDraw Professional. In certain embodiments, common names may be used, and these common names have the same meaning as commonly understood by one of ordinary skill in the art. Compound names appearing herein do not necessarily apply to the IUPAC nomenclature.

Definition of Terms

In the present specification, "heat resistance" refers to a film obtained by curing the curable resin composition to withstand heating up to 150° C., preferably withstands heating at 230° C., more preferably, withstands heating at 300° C., and substantially It does not decompose into or cause other deterioration. Further, the temperature of 230°C is a high enough temperature to be used as a firing temperature in the manufacture of electronic circuits by photolithography. It is also high enough for the firing temperature required to form a thinner film in the manufacture of electronic circuits under conditions harsher than the temperature of 300°C.

In the present specification, "easy release film" refers to a film formed by coating and curing on a substrate, in particular, a glass substrate, which can be easily peeled off without damaging the film from the substrate (that is, without difficulty), and properties of a film such as "easy peelability" Say. Examples of the glass substrate include a glass substrate such as a soda glass substrate and an alkali-free glass substrate. A soda glass substrate is a particularly preferred example.

In the present specification, "easy peeling heat resistance" refers to a property that combines the "heat resistance" and "easy peelability". In particular, the peeling force after pre-baking (for example, 2 minutes at 100°C) and the peeling force after additional heating (for example, 1 hour at 230°C) in the cured resin film formed by coating and heating treatment on the glass substrate is compared. As one, it means that the increase of the peeling force before and after additional heating is about 500% or less (that is, about 5 times or less of the peeling force before heating).

In this specification, "high-speed curing" refers to the property of a composition that cures with a short heating time when a curable resin composition is applied on a substrate and cured by heating. In this specification, a film formed by heat curing at 150° C. or less within 1 minute When there is easy peelability, it is regarded as high speed curing.

In the present specification, "sputtering process resistance" may be used in the main use of the sputtering process (eg, transparent electrode, hard coat, light control, wiring, anti-reflection film, transparent barrier film, photocatalyst, decoration, etc.), or It is a property that has resistance to A curable resin composition is applied on a substrate and cured by heating (e.g., 150°C/15 minutes) to form a cured resin film, and then a photocurable resist is applied as an overcoat material (OC material) on the film, followed by prebaking (e.g. For example, it is determined that the cured resin film after exposure (e.g., 20mW, 100mJ), post-baking (e.g., 230°C/30min) and performing the ITO sputtering process has good peelability. Say.

The ITO sputtering process is a method of forming an ITO (In ₂ O ₃ -SnO ₂ (indium tin oxide) film by a sputtering method known in the relevant field, and the ITO sputtering process known in the relevant field is the cured resin film of the present invention. As an example of the ITO sputtering process, the cured resin film is allowed to stand in a reduced pressure environment for a certain period of time (eg, 0.5 Pa, 3 hours) and Ar is introduced into the cured resin film (eg, 50 sccm). , O ₂ is introduced (for example, 50 sccm) and sputtering (for example, pressure: 0.67 Pa, DC power: 110W) under heating (for example, 90°C) is carried out. It can be changed according to the thickness of the.

In the present specification, "preservation stability" refers to the preservability of the curable resin composition formed as a solution, unless specifically limited, after a general test (storage at 20°C for 9 months or 12 months) and an accelerated test (storage at 50°C for 2 weeks) It means that there is no visual turbidity or solidification in the solution compared to before storage, and there is no significant change in the properties of the solution (viscosity, NV, etc.) and properties (peelability or transmittance, etc.) during film formation. "Storage stability" is described as "Port Life".

In the present specification, the thickness of the "cured resin film" (also referred to as "film thickness") is not limited. When used as a base film for circuit manufacturing, the preferred thickness is 200 to 400 nm, for example, about 300 nm, which is in response to the current request for thinning in the case of electronic components, and the performance of the cured resin film itself is thick. Since it is not limited to the range, the thickness of the cured resin film is optional. In the present specification, "cured resin thin film" is used in the same meaning as "cured resin film".

In the present specification, the word "side chain" in the chain polymer refers to a structural part branched from the main chain, and the "main chain" refers to a chain consisting of atoms connected in a one-dimensional direction of repeating monomer units in the polymer structure. Therefore, for example, when the polymer is a (meth)acrylate polymer, "-COO-" is included in a part of the "side chain" as a part related to the formation of an ester bond in each monomer. In addition, the notation of "(meth)acrylate" indicates acrylate and methacrylate without distinction. Likewise, the notation of "(meth)acrylic" refers to acrylic and methacrylic without distinction, and "(meth)acrylate" refers to acrylic acid and methacrylic acid without distinction.

In the present specification, "alkyl" refers to a monovalent group generated by the loss of one hydrogen atom from an aliphatic hydrocarbon (alkane) such as methane, ethane, and propane, and is generally represented by C _n H _2n+1- (where n is a positive Is an integer). Alkyl can be straight or branched. As an alkyl (C _1-4 alkyl) group having 1 to 4 carbon atoms, for example, methyl, ethyl, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec- Butyl group and the like may be mentioned, but the present invention is not limited to these examples. As an alkyl (C _1-6 alkyl) group having _{1 to 6} carbon atoms, for example, an alkyl group having 1 to 4 carbon atoms, tert-butyl, sec-butyl, n-pentyl group, isoamyl group, n- A hexyl group, an isohexyl group, a cyclohexyl group, and the like, but the present invention is not limited to these examples. As an alkyl (C _1-10 alkyl) group having _{1 to 10} carbon atoms, for example, an alkyl group having 1 to 6 carbon atoms, n-octyl group, n-nonyl group, n-decanyl group, etc. may be mentioned. Is not limited to these examples.

In the present specification, "alkenyl group" refers to a monovalent group generated by the loss of one hydrogen atom in an aliphatic hydrocarbon (alkene) containing at least one double bond such as ethene, propene, and butene, and is generally expressed as C _m H _2m-1 (Where m is an integer greater than or equal to 2). The alkenyl group may be straight or branched. Examples of the alkenyl group having 2 to 6 carbon atoms include ethenyl group, 1-propenyl group, 2-propenyl group, butenyl group, pentenyl group, and hexenyl group, but the present invention is not limited to these examples. . Examples of the alkenyl group having 2 to 10 carbon atoms include an alkenyl group having 2 to 6 carbon atoms, a heptenyl group, an octenyl group, a nonenyl group, and a decenyl group, but the present invention is not limited to these examples. .

In the present specification, "alkylene group" refers to a divalent group generated by the loss of two hydrogen atoms from aliphatic hydrocarbons (alkanes) such as methane, ethane, and propane, and is generally represented by -(C _m H _2m )- (where m Is a positive integer). The alkyl group may be straight or branched. Examples of the alkylene group having 1 to 10 carbon atoms include methylene group, ethylene group, n-propylene group, isopropylene group, n-butyl group, isobutylene group, tert-butyl group, n-pentene group, and n-hexyl group. A silene group, an isohexylene group, and the like may be mentioned, but the present invention is not limited to these examples. An alkylene group having 1 to 6 carbon atoms is preferable, more preferably an alkylene group having 1 to 4 carbon atoms, a methylene group and an ethylene group are more preferable, and an ethylene group is most preferable.

In the present specification, "alkenylene group" refers to a divalent group generated by the loss of two hydrogen atoms in an aliphatic hydrocarbon (alkene) containing at least one double bond such as ethenylene, purophenylene, butenylene, and generally -(C _m H2 _m-2 )- (where m is an integer greater than or equal to 2). The alkenylene group may be straight or branched. As an alkenylene group having 2 to 10 carbon atoms, for example, ethenylene group, n-propenylene group, isophenylene group, n-butenylene group, isobutenylene group, n-pentenylene group, n-hexenylene group, Isohexenylene group, etc., but the present invention is not limited to these examples. An alkenylene group having 2 to 6 carbon atoms is preferable, an alkenylene group having 2 to 4 carbon atoms is more preferable, an ethenylene group and n-propenylene group are more preferable, and an ethenylene group is most preferable.

In the present specification, "alkoxy" refers to a monovalent group generated by the loss of a hydrogen atom in the hydroxy group of an alcohol, and is generally represented by C _n H _2n+10- (where n is an integer greater than or equal to 1). As an alkoxy group having 1 to 6 carbon atoms, for example, methoxy, ethoxy, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, tert-butyloxy group, sec- Butyloxy group, n-pentyloxy group, isoamyloxy group, n-hexyloxy group, isohexyloxy group, and the like, but the present invention is not limited to these examples.

In the present specification, "halo group" refers to an alkyl group in which one or more hydrogen atoms of the alkyl group are substituted with halogen atoms. Further, "perhalogenated alkyl" refers to an alkyl group in which all hydrogen atoms of the alkyl group are substituted with halogen atoms. As a C1-C6 halo group, for example, trifluoromethyl group, trifluoroethyl group, perfluoroethyl group, trifluoro n-propyl group, perfluoro n-propyl group, trifluoroisopropyl group, purple Luoroisopropyl group, trifluoro n-butyl group, perfluoro n-butyl group, trifluoroisobutyl group, perfluoroisobutyl group, trifluoro tert-butyl group, perfluoro tert-butyl Group, trifluoro n-pentyl group, perfluoro n-pentyl group, trifluoro n-hexyl group, perfluoro n-hexyl group, and the like, but the present invention is not limited to these examples.

In the present specification, "cycloalkyl group" refers to a monocyclic or polycyclic saturated hydrocarbon group, and also includes a crosslinked structure. For example, "C _3-12 cycloalkyl" means a cyclic alkyl group having 3 to 12 carbon atoms. As a specific example, in the case of a "C _6-12 cycloalkyl group", a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, an isobornyl group, and the like are mentioned. In the case of a "C _3-12 cycloalkyl group", a cyclopropyl group, a cyclobutyl group, a pentyl group, a C _6-12 cycloalkyl group, and the like can be mentioned. Preferably, a "C _6-12 cycloalkyl group" is used.

In the present specification, "cycloalkenyl group" refers to a monocyclic or polycyclic unsaturated hydrocarbon group including a double bond, and a crosslinked structure is also included. One or more of the inter-carbon bonds of the "cycloalkyl group" may be a double bond. For example, "C _3-12 cycloalkenyl group" means a cyclic alkenyl group having 3 to 12 carbon atoms. As a specific example, in the case of "C _6-12 cycloalkenyl group", 1-cyclohexenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclononenyl group, etc. I can. In the case of a "C _3-12 cycloalkyl group", a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a C _6-12 cycloalkenyl group, and the like can be mentioned. Preferably, "C _6-12 cycloalkenyl group" is mentioned.

In the present specification, the "hydrocarbon group" refers to a monovalent group generated by the loss of one hydrogen atom in a compound consisting of only carbon and hydrogen. The hydrocarbon group includes the above "alkyl", "alkenyl group", "alkylene group", "alkenylene group", "cycloalkyl group" and "cycloalkenyl group" and the following "aromatic group" and "alicyclic group" and the like. Hydrocarbon groups can be saturated or unsaturated. The hydrocarbon group is classified into a chain hydrocarbon group and a cyclic hydrocarbon group according to the carbon bonding method, and the cyclic hydrocarbon group is further classified into an alicyclic hydrocarbon group and an aromatic hydrocarbon group. Examples of saturated or unsaturated hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, cyclohexyl, dicyclopentadienyl, decarinyl, adamantyl, butenyl, hexenyl, cyclohex Senyl, decyl, and others, and various linear, branched, monocyclic, and condensed cyclic groups within the limit of the number of carbon atoms in the side chain, but are not limited thereto. Each group may be a divalent or higher group depending on a bonding relationship with another group when not positioned at the terminal.

In the present specification, "aromatic group" refers to a group generated when one hydrogen atom bonded to an aromatic hydrocarbon ring is removed. For example, phenyl group in benzene (C ₆ H ₅ -), toluene group (CH ₃ C ₆ H ₄ -), xylene to xylyl group ((CH ₃ ) ₂ C ₆ H ₃ -), naphthalene to naphthyl group (C ₁₀ H ₈ -) is induced. In addition, in the present specification, "heteroaromatic group" refers to a monocyclic or polycyclic hetero atom-containing aromatic group, and the group contains one or more homogeneous or heterogeneous heteroatoms selected from a nitrogen atom, a sulfur atom, and an oxygen atom (for example, 1~4 pieces) included.

The "aromatic group" also includes "heteroaromatic group". Examples of the aromatic group include carbocyclic aromatic groups (monocyclic and condensed cyclic groups) such as phenyl, biphenyl, and naphthyl, and heteroaromatic groups such as pyridyl, pyrimidinyl, quinolinyl, and triazinyl (monocyclic and condensed cyclic groups). ), and when each aromatic group is not located at the terminal, it may be a divalent or higher group depending on a bonding relationship with another group. In addition, in the present specification, a group having a saturated or unsaturated hydrocarbon chain moiety forming a ring together with an aromatic ring moiety (for example, tetrahydronaphthyl or dihydronaphthyl) is considered to be a bond with an aromatic group saturated or unsaturated hydrocarbon group.

In the present specification, "alicyclic (group)" refers to a portion (or group) generated by the separation of one hydrogen atom bonded to a ring having no aromatic properties composed of only carbon and hydrogen. The alicyclic group includes the above'cycloalkyl group' and'cycloalkenyl group'. Alicyclic groups can be saturated or unsaturated. Examples of saturated or unsaturated alicyclic groups include cyclohexyl, dicyclopentadienyl, decarinyl, adamantyl, cyclohexenyl, and various monocyclic or condensed cyclic groups within the limit of the number of carbon atoms in the side chain. Not limited. When each group is not located at the terminal, it may be a divalent or higher group depending on the bonding relationship with other groups.

In general the term "substituted (becomes/become)" denotes that a particular substituent radical has been replaced with one or more hydrogen radicals in a given structure. In the present specification, the number of substituents in a group defined using "substituted (to/one)" is not particularly limited, but is 1 or more, as long as it can be substituted. In addition, except in the case of special mention, the description of each group applies even when the group is part of another group or a substituent. In addition, in the present specification, the term “substituted (to/one)” refers to a “unsubstituted” substituent for a substituent not specifically specified. In addition, it is recognized that the phrase "substituted or unsubstituted(s)" is used interchangeably with the phrase "may be substituted" in this specification.

"Substituted alkyl group", "substituted alkenyl group", "substituted cycloalkyl group", "substituted cycloalkenyl group", "substituted hydrocarbon group", "substituted aromatic group", "substituted heteroaromatic group", "substituted alkylene group", " Examples of the substituents on the criteria described herein, including a substituted alkenylene group" and a "substituted or unsubstituted alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group" include halogen, hydroxy, C _1-10 Alkyl group, C _1-10 alkoxy group, C _2-10 alkenyl group, C _6-12 cycloalkyl group, C _6-12 cycloalkenyl group, C _1-10 halo group, C _2-10 haloalkenyl group, C _6-18 hydrocarbon group, C _{6 ~ 18} aromatic group, C _{6 ~ 18} heteroaromatic group, C _6-12 aromatic group-substituted C _{1 ~ 10} alkyl group, C a _6-12 hydrocarbon group-substituted C _{1 ~ 10} alkyl group, C _6-12 a C _{2 ~ 10} substituted by an aromatic alkenyl group, C _{6 ~ 12} hydrocarbon group substituted C _2-10 alkenyl group, -CN, an oxo group (= O), -O (CH 2) 2 O-, -OC (CH ₃ ) ₂ O-, -OCH ₂ O-, -O-, ester group (-COO- or -O-CO-), ester group substituted with C _6-12 hydrocarbon group, ester substituted with C _6-12 aromatic group group, an ester group-substituted C _{6 ~ 18} hydrocarbon group, an alkyl group of C _{1 ~ 10} substituted by an ester, C _{1 ~ 6} alkyl group, C _{2 ~ 6-alkenyl} can be a group including, but the present invention is not limited to this example no.

Preferred examples of the substituent include a hydroxy group, C _{6 ~ 18} hydrocarbon groups, C _{1 ~ 10} alkyl group, C _{6 ~ 12} aromatic group-substituted C _{1 ~ 10} alkyl group, C _{6 ~ 12} hydrocarbons of C _{1 ~ 10} alkyl, the ester substituted with a C _6-18 hydrocarbon group substituted with a group, C _1-10 alkyl group substituted with an ester group, ester group (-COO- or -O-CO-), ester group substituted with a C _6-12 hydrocarbon group, C _6-12 aromatic group substituted with an ester group, C _{2 ~ 10} alkenyl group, C _{6 ~ 12} aromatic group-substituted C _2-10 alkenyl group, C _{6 ~} C _{2 ~ 10} the substituted hydrocarbon ₁₂ alkenyl group, C _{1 ~ 10} alkoxy group, C _6-12 cycloalkyl, C _6-12 cycloalkenyl group can be mentioned, and more specific examples include benzoyl oxy group, a phenyl group, a cyclohexyl group in, cyclohexenyl group, adamantyl substituted by an O group, a hydroxy group-adamantyl group I can.

In the present specification, "an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group" refers to one or two alcoholic secondary or tertiary hydroxy (OH) groups or phenolic hydroxy (OH) groups. It represents a group containing two or more. Thus, "an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group" also includes an alcoholic secondary or tertiary hydroxy group or a phenolic hydroxy group itself. In "substituted or unsubstituted alcoholic secondary or tertiary OH-containing group or phenolic OH-containing group", "substituted or unsubstituted" means alcoholic secondary or tertiary hydroxy (OH) group or phenolic hydroxy In the group containing one or two or more (OH) groups, it indicates that a group portion other than the hydroxy group is substituted or not substituted, but does not indicate that the hydroxy group is substituted or unsubstituted.

In the present specification, the "solvate" refers to a compound or a salt thereof that further includes a certain ratio or an indefinite amount of a solvent bonded by non-covalent intermolecular force unless specifically limited. If the solvent is water, the solvate is a hydrate.

In this specification, "solvent" is used synonymously with "solvent".

In the present specification, "monomer" refers to a compound in which two or more polymers are formed to form a polymer. The "monomer unit" refers to a monomer that becomes a unit forming a polymer.

In the present specification, "polymer" refers to a compound formed by polymerization of several monomers. In the present specification, "homopolymer (single polymer)" is a compound formed by polymerization of only one type of monomer, and "copolymer (copolymer)" is a compound formed by polymerization of two or more types of monomers. The polymers described herein include both homopolymers and copolymers. When described in the polymer structural formula, the homopolymer is

-[Monomer unit A] n- (in the formula, n ≥ 2)

Is written as

The copolymer is

-[Monomer unit A] n- [monomer unit B] m- (in the formula, n ≥ 1, m ≥ 1 stage, n + m ≥ 2)

And the monomer unit (A) and the monomer unit B each represent an arbitrary monomer unit, provided that the monomer unit (A) and the monomer unit B are different from each other. When the polymer used in the present specification is a chain, it is referred to as a "chain polymer". In the present specification, "polymer" is used synonymously with "polymer".

As used herein, "crosslinking agent" refers to a material that changes physical and chemical properties by forming covalent bonds between the same or different polymers.

In this specification, "N.V." (unit: %) represents the heating residue (Non Volatile Organic Compound) of the solution and is synonymous with the solid concentration of the solution. N.V is measured by a heating residual method known in the field according to standards such as JIS K 5601-1-2.

In this specification,'or' is used when employing'at least one or more' of the items listed in the sentence. The same goes for'or'. In the present specification, when specified as'a range of two values', the range includes the two values themselves. Therefore,'X to Y'indicating a range means'X or more and Y or less'. In addition, unless otherwise noted,'weight' and'mass','weight %', or'wt %'and'mass%' are treated as synonyms respectively. The expression'about' has a tolerance of 10%, unless specifically rejected, and in the case of a measurement value, it refers to the whole range of values obtained by rounding off a significant digit or one digit to the displayed digit.

[2] Description of preferred embodiments

Next, a preferred embodiment of the present invention will be described. It is understood that the embodiments provided below are provided for a better understanding of the present invention, and the scope of the present invention should not be limited to the following description. Therefore, it is clear that those skilled in the art can make appropriate corrections within the scope of the present invention, taking into account the description of the present specification. In addition, it is understood that the following embodiments of the present invention may be used alone or in combination.

(2-1) curable resin composition

In a first aspect, the present invention provides a curable resin composition comprising a chain polymer having a side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group and a crosslinking agent,

(a) the chain polymer is formula A1:

[Formula 15]

[In the above formula,

R ^1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group,

L ¹ is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group, and a substituted or unsubstituted alkenylene group,

L ² is O or NH,

R ^2a , R ^3a and R ^4a are each independently selected from the group consisting of hydrogen and a substituted or unsubstituted hydrocarbon group, provided that at least one of R ^2a , R ^3a and R ^4a is a substituted or unsubstituted alcoholic secondary or tertiary A substituted or unsubstituted cycloalkyl group containing an alcoholic secondary or tertiary OH or a phenolic OH by combining a class OH-containing group or a phenolic OH-containing group, or at least two of R ^2a , R ^3a and R ^4a , It is a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted heteroaromatic group, or a polycyclic body containing them.]

It includes a monomer unit represented by,

(b) The crosslinking agent is a triazine-based compound and/or a condensate thereof, a glycoluril-based compound and/or a condensate thereof, and an imidazolidinone-based compound and/or a condensate thereof

It provides a curable resin composition selected from the group consisting of.

In the first aspect, preferably, in the formula A1, L ² is O.

In a second aspect, the present invention is a curable resin composition comprising a chain polymer having a side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group and a crosslinking agent, wherein the chain polymer is formula A2:

[Formula 16]

[In the above formula,

R ^1a , L ¹ and L ² are as described above,

R ^5a to R ^14a are independently of each other hydrogen, a hydroxy group, and

[Formula 17]

It is selected from the group consisting of or is combined to form a ring, provided that at least one of R ^5a to R ^14a or a substituent of the ring is a hydroxy group,

R ^15a is selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted heteroaromatic group. .]

It includes a monomer unit represented by,

(b) the crosslinking agent is a triazine-based compound and/or a condensate thereof, a glycoluril-based compound and/or a condensate thereof, and an imidazolidinone-based compound and/or a condensate thereof

It provides a curable resin composition selected from the group consisting of.

In the second aspect, preferably L ² is O in formula A2.

In a third aspect, more preferably, the present invention is a curable resin composition comprising a chain polymer having a side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group and a crosslinking agent, the chain Phase polymer is formula A2:

[Formula 18]

[In the above formula,

R ^1a is selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group,

L ¹ is selected from the group consisting of a substituted or unsubstituted alkylene group and a substituted or unsubstituted alkenylene group,

R ^5a to R ^14a are independently of each other hydrogen, a hydroxy group, and

[Formula 19]

It is selected from the group consisting of, provided that R ^5a to R ^14a or at least one of the substituents of the ring is a hydroxy group,

R ^15a is selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted heteroaromatic group. .]

It includes a monomer unit represented by,

(b) the crosslinking agent is selected from the group consisting of a triazine-based compound and/or a condensate thereof, a glycoluril-based compound and/or a condensate thereof, and an imidazolidinone-based compound and/or a condensate thereof. Provides.

More preferably in the third aspect, L ¹ is a substituted or unsubstituted alkylene group, and most preferably, L ¹ is a methylene group.

In a fourth aspect, more preferably, the present invention is a curable resin composition comprising a chain polymer having a side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group and a crosslinking agent, Chain polymer is formula A5:

[Formula 20]

[In the above formula,

R ^1a is selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group,

L ¹ is selected from the group consisting of a substituted or unsubstituted alkylene group and a substituted or unsubstituted alkenylene group,

R ^19a is selected from the group consisting of a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted heteroaromatic group.]

It includes a monomer unit represented by,

(b) the crosslinking agent is selected from the group consisting of a triazine-based compound and/or a condensate thereof, a glycoluril-based compound and/or a condensate thereof, and an imidazolidinone-based compound and/or a condensate thereof. Provides.

In the fourth aspect, preferably, in the formula A5, L ¹ is a substituted or unsubstituted alkylene group, and most preferably, L ¹ is a methylene group.

In the fourth aspect, preferably R ^19a in formula A5 is a phenyl group.

In the fourth aspect, preferably, the crosslinking agent is a triazine-based compound and/or a condensate thereof. More preferably, the crosslinking agent,

[Formula 21]

to be.

In a fifth aspect, more preferably, the present invention is a curable resin composition comprising a chain polymer having a side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group and a crosslinking agent, Polymer Formula A2:

[Formula 22]

[In the above formula,

R ^1a is selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group,

L ¹ is selected from the group consisting of a single bond and a substituted or unsubstituted alkylene group,

R ^5a to R ^14a are independently of each other hydrogen and hydroxy groups

It is selected from the group consisting of, provided that R ^5a to R ^14a or at least one of the substituents of the ring is a hydroxy group.]

It includes a monomer unit represented by,

(b) the crosslinking agent is selected from the group consisting of a triazine-based compound and/or a condensate thereof, a glycoluril-based compound and/or a condensate thereof, and an imidazolidinone-based compound and/or a condensate thereof. Provides.

In the fifth aspect, preferably in formula A2, L ¹ is a single bond.

In the fifth aspect, in one embodiment, preferably in formula A2, at least two of R ^5a to R ^14a are hydroxy groups, and the other is hydrogen. In another embodiment, preferably one of R ^5a to R ^14a is a hydroxy group and the other is hydrogen. In a further embodiment preferably R ^5a to R ^13a are hydrogen and R ^14a is a hydroxy group.

In the fifth aspect, in one embodiment, preferably the crosslinking agent is a glycoluril-based compound and/or a condensate thereof. More preferably, the crosslinking agent,

[Formula 23]

to be.

In the fifth aspect, in another embodiment, preferably, the crosslinking agent is a triazine-based compound and/or a condensate thereof. More preferably, the crosslinking agent,

[Formula 24]

to be.

The curable resin composition of the present invention can be said to be a thermosetting resin composition cured by heat treatment.

The chain polymer, which is one of the constituent elements of the curable resin composition of the present invention, includes a side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group.

In the present invention, the number of carbon atoms contained in the side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group of the chain polymer is preferably 3 to 30. The number of corresponding hydroxy groups in the side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group may be one or two or more.

In the present invention, the side chain alcoholic secondary or tertiary OH-containing group or phenolic OH-containing group is easily peeled from the substrate even after the cured resin thin film formed by coating and curing the curable resin composition of the present invention on a glass substrate It's actually a decisive factor because you can maintain your sex. In addition, it is more preferable that the side chain alcoholic secondary or tertiary OH-containing group or the phenolic OH-containing group be bonded to the alicyclic portion in the side chain, and the alicyclic portion of the side chain can also maintain the easy peelability of the cured resin thin film. This is, in fact, a decisive factor. The chain polymer having such a side chain is a suitable crosslinking agent, in particular, a triazine-based compound and/or a condensate thereof, a glycoluril-based compound and/or a condensate thereof, or an imidazolidinone-based compound and/or a condensate thereof. When cured in the form of a thin film with a resin composition, it is possible to provide a heat-resistant easy release film.

Preferred examples of monomers that provide a side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group to the chain polymer include the following, but are not limited thereto.

2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-(cyclohexylcarbonyloxy)propyl (meth)acrylate, 3-benzoyloxy-2-hydroxypropyl (meth)acrylate, 4- Benzoyloxy-3-hydroxycyclohexylmethyl (meth)acrylate, 1,3-adamantyldiol mono (meth)acrylate and 2-hydroxyhexyl (meth)acrylate, 4-undecanoyloxy-3 -(Meth)acrylates such as hydroxycyclohexylmethyl(meth)acrylate and 4-butanoyloxy-3-hydroxycyclohexylmethyl(meth)acrylate.

The chain polymer of the present invention does not have a hydroxy group other than the monomer having the alcoholic secondary or tertiary OH-containing group or the phenolic OH-containing group, and the side chain has 1 to 15 carbon atoms (meth)acrylic monomers, vinyl esters It may be one containing at least one of a monomer, a vinyl ether-based monomer, and a vinyl-based monomer other than these as an additional monomer unit.

Preferred examples of the monomer unit not having a hydroxy group include the following, but are not limited thereto.

(1) Methyl (meth) acrylate, propyl (meth) acrylate, glycidyl (meth) acrylate, butyl (meth) acrylate, ethoxyethyl (meth) acrylate, pentyl (meth) acrylate, tetra Hydrofurfuryl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, dicyclopentadienyl (meth)acrylate, octyl (meth)acrylate, benzyl (meth)acrylate, N ,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, glycidyl (meth)acrylate, etc. Meth)acrylate.

(2) Vinyl acetate, vinyl butanoic acid, vinyl pentanoic acid, vinyl hexanoic acid, vinyl cyclohexanecarboxylic acid, vinyl benzoate, vinyl cyclopentadienylcarboxylic acid, vinyl nonanoic acid, etc. Vinyl ester.

(3) propyl vinyl ether, butyl vinyl ether, ethoxyethyl vinyl ether, glycidyl vinyl ether, pentyl vinyl ether, tetrahydrofurfuryl yl ether, cyclohexyl vinyl ether, phenyl vinyl ether, cyclopentadienyl vinyl ether, Vinyl ethers, such as octyl vinyl ether, benzyl vinyl ether, 2-(vinyloxy)ethyldimethylamine, and 3-(vinyloxy)propyldimethylamine.

(4) Vinyl derivatives, such as 1-butene, 4-ethoxy-1-butene, 1-pentene, 1-hexene, vinylcyclohexane, styrene, vinyltoluene, 1-nonene, and 3-phenylpropene.

(5) Maleic anhydride derivatives such as maleic anhydride, methylmaleic anhydride, butylmaleic anhydride, hexylmaleic anhydride, cyclohexylmaleic anhydride, phenylmaleic anhydride, and octylmaleic anhydride.

(6) Maleimide derivatives such as maleimide, methyl maleimide, ethyl maleimide, butyl maleimide, hexyl maleimide, cyclohexyl maleimide, phenyl maleimide, benzyl maleimide, and octyl maleimide.

The chain polymer of the present invention may be a homopolymer of monomer units, or may be a copolymer including two or three or more types of monomer units, provided that at least one of the monomer units of the copolymer is an alcoholic agent. It is a monomeric unit with a side chain having a secondary or tertiary OH-containing group or a phenolic OH-containing group. Preferably, the copolymer comprises a monomer unit having a side chain having at least one alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group and an additional monomeric unit not having at least one hydroxy group.

The proportion of the monomer unit having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group in the chain polymer of the present invention is not particularly limited, but is preferably 30 to 100 mol%, more preferably 50 to It is 100 mol%, more preferably 60 to 100 mol%, more preferably 80 to 100 mol%, and particularly preferably 90 to 100 mol%.

In the present invention, the chain polymer is carried out by carrying out a polymerization reaction using a conventional radical polymerization catalyst such as 2,2'-azobisisobutyronitrile (AIBN) in a conventional manner using the raw material monomer. Can be manufactured. The weight average molecular weight (Mw) of the chain polymer is usually preferably in the range of 10000 to 100000 (measured by gel permeation chromatography), but is not particularly limited to this range. Examples of gel permeation chromatography include methods known in the art using processes and apparatus known in the art.

An example of gel permeation chromatography is to prepare a sample by diluting a mixture containing a polymer in a suitable solvent (e.g. tetrahydrofuran) (e.g., diluting the obtained mixture to a solid content of 0.1% by weight), and then diluting the diluted solution with an appropriate solvent. It is injected into a commercially available gel permeation chromatography column maintained at a temperature (eg, 40° C.). Then, the eluent (e.g., tetrahydrofuran) is injected into the gel permeation chromatography column into which the diluted solution is injected at an appropriate flow rate (e.g., 1 ml/min) to extract the eluent containing the reamer, and a detector (e.g., differential refractive index Detector) to measure the molecular weight of the polymer. Depending on the type of polymer, the above conditions can be appropriately selected.

The crosslinking agent of the curable resin composition of the present invention is preferably a triazine crosslinking agent, a glycoluril crosslinking agent, or an imidazolidinone crosslinking agent. More specifically, it is preferable that the crosslinking agent is selected from the group consisting of a triazine-based compound and/or a condensate thereof, a glycoluril-based compound and/or a condensate thereof, and an imidazolidinone-based compound and/or a condensate thereof.

Preferred examples of such crosslinking agents include wholly or partially alkoxy (e.g., methoxy, ethoxy) methylated melamine and/or condensates thereof, and wholly or partially alkoxy (e.g. methoxy, ethoxy) methylated guanamine and/or their Condensates, wholly or partially alkoxy (e.g. methoxy, ethoxy) methylated acetguanamine and/or condensates thereof, wholly or partially alkoxymethylated benzoguanamine and/or condensates thereof, wholly or partially alkoxy (e.g. Oxy, ethoxy) methylated glycoluril and/or a condensation product thereof, and a wholly or partially alkoxy methylated imidazolidinone and/or a condensation product thereof.

In the above formula, "alkoxy" preferably has 1 to 4 carbon atoms. As a preferable compound as such a crosslinking agent, more specifically, for example, hexamethoxymethylmelamine, hexaethoxymethylmelamine, tetramethoxymethylmethylolmelamine, tetramethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylgua Namin, tetramethoxymethylacetguanamine, tetramethoxymethylbenzoguanamine, trimethoxymethylbenzoguanamine, tetraethoxymethylbenzoguanamine, tetramethylolbenzoguanamine, 1,3,4,6-tetra Kis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 4,5-dihydroxy-1,3-dimethoxymethyl-2-imidazolidinone, 4,5-dimethoxy-1,3-dimethoxymethyl-2-imidazolidinone, and the like, but are not limited thereto.

In one embodiment preferably the crosslinking agent is formula B1:

[Formula 25]

[In the above formula,

R ^1b has 1 to 25 carbon atoms and is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted heteroaromatic group, and

[Formula 26]

It is selected from the group consisting of disubstituted amines represented by,

R ^2b to R ^7b each independently have 1 to 10 carbon atoms, and are selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group.]

Compound represented by and/or condensate thereof

It is selected from the group consisting of.

More preferably, the crosslinking agent of the present invention in formula B1,

R ^1b is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group, and

[Formula 27]

It is selected from the group consisting of disubstituted amines represented by,

R ^2b to R ^7b are each independently selected from a substituted or unsubstituted alkyl group,

It is a compound and/or a condensate thereof.

In another embodiment, preferably the crosslinking agent is formula B2:

[Formula 28]

[In the above formula, R ^8b to R ^11b each independently have 1 to 10 carbon atoms, and are selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group.]

Compound represented by and/or condensate thereof

It is selected from the group consisting of.

More preferably, the crosslinking agent of the present invention in Formula B2,

R ^8b to R ^11b are each independently selected from a substituted or unsubstituted alkyl group,

It is a compound and/or a condensate thereof.

In another embodiment, preferably the crosslinking agent is formula B3:

[Chemical Formula 29]

[In the above formula,

R ^12b and R ^13b each independently have 1 to 10 carbon atoms and are selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group,

R ^14b and R ^15b are each independently hydrogen or have 1 to 10 carbon atoms, and are selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group.]

Compound represented by and/or condensate thereof

It is selected from the group consisting of.

More preferably, the crosslinking agent of the present invention in formula B3,

R ^12b and R ^13b are each independently selected from a substituted or unsubstituted alkyl group,

R ^14b and R ^15b are each independently selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group,

It is a compound and/or a condensate thereof.

More preferably, in formula B3, R ^14b and R ^15b are each independently hydrogen.

Further preferred specific examples of the crosslinking agent of the curable resin composition of the present invention include those represented by the following structural formulas or compounds having the following compound names and/or condensates thereof:

[Formula 30]

Hexamethoxymethylmelamine;

Hexabutoxymethylmelamine;

1,3,4,6-tetrakis(methoxymethyl)glycoluril;

1,3,4,6-tetrakis(butoxymethyl)glycoluril;

Tetramethoxymethylbenzoguanamine;

4,5-dihydroxy-1,3-bis(alkoxymethyl)imidazolidin-2-one.

As the condensate, preferably a polymer of the compound represented above is mentioned, and more preferably, a dimer, a trimer or a higher order polymer of the compound represented above is used. The crosslinking agent of the curable resin composition of the present invention may be a compound represented above and a condensate thereof, that is, may be a mixture of a compound and a polymer of the compound (ie, a dimer, a trimer, or a higher order polymer). . In other embodiments, the condensate may comprise at least one of a dimer, a trimer and a higher order polymer of the compound.

In another aspect, the crosslinking agent may be one having a weight average polymerization degree greater than 1 and 3 or greater in the compound described above, preferably greater than 1 and up to 1.8, more preferably 1.3 to 1.8, more preferably It may have a weight average polymerization degree of 1.5, but is not limited thereto. In addition, when the weight average polymerization degree of the condensate of the compound is 1, it means that the condensate is the compound itself. The weight average degree of polymerization is a number in the above range, preferably 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 3, 4 or higher, more preferably 1.3, 1.4 , 1.5, 1.6, 1.7, 1.8, and preferably 1.5.

In the curable resin composition of the present invention, the ratio of the mass of the chain polymer and the crosslinking agent is preferably 1:0.03 to 1:2, more preferably 1:0.05 to 1:2, 1:0.05 to 1:1, 1 :0.03 to 1:1, more preferably 1:0.09 to 1:1, 1:0.1 to 1:0.5, even more preferably 1:0.09 to 1:0.3, 1:0.1 to 1:0.3.

In the present invention, the curable resin composition also contains an acid catalyst. The acid catalyst is included as necessary as a polymerization catalyst in the reaction between the monomer unit and the crosslinking agent. The acid catalyst can be appropriately selected and used as a polymerization catalyst. The acid catalyst may be a compound selected from Bronsted acid and/or Lewis acid, or a salt thereof or a solvate thereof.

Examples of the acid catalyst include dinonylnaphthalenedisulfonic acid, dinonylnaphthalene (mono)sulfonic acid, dodecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfonic acid (PTS), phosphoric acid, sulfuric acid and acetic acid. A compound selected from the group consisting of thermal acid generators such as protonic acid and sun-aid SI-100L, SI-150L, SI-110L, SI-60L and SI-80L (Samshin Chemical Industries, Ltd.), or a salt thereof, or a salt thereof Solvates may be mentioned, but are not limited thereto. Preferably, the acid catalyst is a compound selected from the group consisting of p-toluenesulfonic acid (PTS), dodecylbenzenesulfonic acid, and thermal acid generator Sunade SI-100L (Samshin Chemical Industry Co., Ltd.), or a salt thereof, Or its solvate. More preferably, the acid catalyst is pyridinium-p-toluenesulfonic acid, p-toluenesulfonic acid or a hydrate thereof.

If the curable resin composition of the present invention further includes an acid catalyst, the amount of the acid catalyst may be appropriately determined according to the ratio of the mass of the chain polymer of the curable resin composition to the crosslinking agent, but preferably the chain polymer of the curable resin composition The ratio of the mass of the crosslinking agent and the acid catalyst is preferably 1:0.03:0.05 to 1:2:0.1, more preferably 1:0.05:0.05 to 1:2:0.1, more preferably 1:0.09:0.05 ~ 1:1:0.08. Alternatively, if the curable resin composition of the present invention further includes an acid catalyst, the amount of the acid catalyst may be appropriately determined according to the ratio of the mass of the chain polymer and the crosslinking agent of the curable resin composition, but is preferably based on the total weight including the solvent. 0.5 wt%, 0.45 wt%, 0.4 wt%, 0.35 wt%, 0.3 wt%, 0.25 wt%, 0.2 wt%, 0.15 wt% or 0.10 wt%, more preferably 0.3 wt% or 0.25 wt%.

In the present invention, the curable resin composition may be diluted to an appropriate concentration according to a solvent. That is, in the present invention, the curable resin composition further contains a solvent. As long as there is no inconvenience in forming a uniform coating film by drying after applying the curable resin composition to a substrate such as glass due to an excessively low or high boiling point, a conventional aprotic solvent can be appropriately selected and used. have. For example, propylene glycol monomethyl ether is a suitable solvent, but is not limited thereto. Since dilution with a solvent is for convenience in handling such as during the polymerization reaction of the monomer and when applying a crosslinking agent and a curable resin composition to which a catalyst is added, there is no specific upper or lower limit on the degree of dilution.

In one embodiment of the invention the composition is provided as a solution. Preferably, the solvent of the solution contains alcohol. More preferably, the alcohol includes a primary alcohol, preferably ethanol, propanol, 1-butanol, 1-propanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, and dode It includes a primary alcohol selected from the group consisting of canol, more preferably a primary alcohol selected from the group consisting of ethanol, propanol, 1-butanol, 1-propanol and 1-dodecanol, and most preferably Contains ethanol. Preferably, the alcohol is present in at least 10% by weight of the total amount of the solvent. Although we do not wish to be bound by theory, it is because the storage stability is improved by alcohol.

The curable resin composition of the present invention may also contain at least one of a surfactant, a filler, an additive, and a foaming agent for the purpose of imparting a desired function and improving properties.

When a surfactant is included, for example, the wettability of the curable resin composition to the substrate is improved, and the thickness of the cured resin film formed by curing the curable resin composition is made thin or uniform. Surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and modified silicones, and these may be used alone or in combination of two or more.

As the anionic surfactant, preferably, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalene sulfonate, sodium alkyldiphenyldisulfonate, monoethanol lauryl sulfate Polyoxyethylene ole, such as amine, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate ester Il ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate, etc. are mentioned.

Examples of cationic surfactants include alkyl quaternary ammonium salts and ethylene oxide adducts thereof.

Nonionic surfactants include ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, and polyoxyethylene alkyl ether. Nonionic surfactant, polyoxyethylene oleic acid ester, polyoxyethylene distearic acid ester, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, Esters such as polyoxyethylene stearate, acetylene alcohol-based nonionic surfactants such as 3,5-dimethyl-1-hexin-3-ol, 2,4,7,9-tetramethyl-5-decine-4, 7-diol, 3,6-dimethyl-4-octine-3,6-diol, etc. are mentioned.

Examples of amphoteric surfactants include alkyl betaines such as alkyldimethylamino acetate betaine, and alkyl imidazoline.

The modified silicones include polyether-modified polysiloxane, carboxy-modified polysiloxane, epoxy-modified polysiloxane, and amino-modified polysiloxane.

When the filler is included, for example, the hardness and wettability of the cured resin film may be improved, or electrical insulation or electrical conductivity may be provided or improved. Fillers that can impart or improve electrical insulation include metal oxides such as alumina, silicon oxide, beryllium oxide, copper oxide, and nitrous oxide, metal nitrides such as boron nitride, aluminum nitride, and silicon nitride, metal carbides such as silicon carbide, and carbonic acid. Examples include metal carbonates such as magnesium, insulating carbon materials such as diamond, and metal hydroxides such as aluminum hydroxide and magnesium hydroxide. Examples of fillers that can impart or improve electrical conductivity include carbon materials such as graphite and carbon fiber, and metal materials such as metallic silicon, aluminum, and magnesium. A filler that can impart or improve electrical insulation or electrical conductivity may be included in the cured resin film for the purpose of improving thermal conductivity.

When a filler is added for the purpose of improving thermal conductivity, a filler capable of imparting or improving electrical insulation and a filler capable of imparting or improving electrical conductivity may be combined. The shape of the filler is, for example, a variety of shapes such as particulate, fine particle nanoparticle agglomerated particulate wire shape, rod shape, needle shape, plate shape irregular shape, rugby ball shape, hexahedral shape large particles and fine particles and composite fine particles combined with the same. It is possible. In addition, such a filler may be a natural product or a synthetic one. In the case of a natural product, there is no particular limitation on the place of origin, and it can be appropriately selected. In addition, the purpose of including the filler is not particularly limited, and a filler capable of achieving this purpose may be selected for the purpose of improving properties or imparting functions. The type of included filler may be one, or two or more.

When the additive is included, for example, the weather resistance of the cured resin film can be improved. Examples of the additives include antioxidants and ultraviolet absorbers. The purpose of including the additive is not particularly limited, and known additives capable of achieving this purpose may be selected for the purpose of improving properties or imparting functions. The type of additives contained may be one or two or more.

In one embodiment, preferably the curable resin composition of the present invention also comprises a surfactant. In another embodiment, preferably the curable resin composition of the present invention also includes a blowing agent. When the foaming agent is included, the cured resin film formed by curing the curable resin composition can be easily removed. As a preferable foaming agent, a compound that decomposes and foams above a melting temperature, or a combination of a compound that foams by reacting with an acid and an acid can be used. Foaming agents that can be used in the present invention include, for example, azodicarboxylamide, barium azodicarboxylate, 2,2'-azobisisobutyronitrile, dimethyl 2,2'-azo of azo compounds. Azo compounds such as bis(2-methylpropionate), 2,2'-azobis(N-butyl-2-methylpropionamide, etc.), nitroso compounds such as dinitrosopentamethylenetetramine and trinitrotrimethyltriamine, Hydrazide compounds such as p,p'-oxybisbenzenesulfonylhydrazide, sulfonyl semicarbazide compounds such as p,p'-oxybisbenzenesulfonyl semicarbazide, toluenesulfonyl semicarbazide, etc. Can be lifted.

As a compound that foams by reacting with an acid and a compound that foams by reacting with an acid in the combination of an acid, for example, an alkali metal carbonate or bicarbonate, for example, a carbonate such as sodium, potassium, lithium or rubidium, carbonate or hydrogen carbonate. Compounds, and the acids include organic acids, acids containing acidic sodium or potassium phosphate, and mixtures thereof. Examples of the organic acid include citric acid, tartaric acid, succinic acid, fumaric acid, or a mixture thereof.

The curable resin composition of the present invention has the above "high-speed curing property", and is preferably at a heating temperature of 90°C, 100°C, 110°C, 120°C, 130°C, 140°C or 150°C for several minutes. Within, preferably 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50 seconds, 1 minute or 2 minutes of heating time, more preferably 150 ℃ 1 minute by heating the cured film easily peelable Has.

The curable resin composition of the present invention has the above "storage stability", and the curable resin composition formed as a solution is, for example, at an appropriate temperature (eg, 20° C. or 50° C.) for a long period of time (eg, 1 week 2 3 weeks, 4 weeks, 1 month, 2 months, 3 months, 4 months, 6 months, 9 months, 12 months or 14 months, etc.)After storage, there is no visual cloudiness or solidification in the solution compared to before storage. There is no significant change in the properties of (viscosity, NV, etc.) and properties (peel force or transmittance, etc.) during film formation. Preferably, there is no change in the solution compared to before storage after a general test (storage at 20° C. for 9 months or 12 months) and an accelerated test (storage at 50° C. for 2 weeks), not particularly limited.

(2-2) Cured resin film

In one aspect, the present invention provides a cured resin film formed by curing the curable resin composition of (2-1).

In another aspect, the present invention provides an easily peelable cured resin film formed by curing the curable resin composition of (2-1) on a substrate surface in a film form.

The cured resin film formed from the curable resin composition of the present invention is heat-resistant in the sense of "heat resistance" and has easy peelability even after heat treatment in a temperature range that is heat-resistant.

Preferably, the cured resin film formed from the curable resin composition of the present invention has the'easy peelability'. Specifically, after pre-baking (for example, 2 minutes at 100° C.) in a cured resin film formed by coating and heating treatment on a glass substrate of a curable resin composition, the peel force is 10 N/mm ² or less, 1 N/mm ² or less, 0.5 N/mm ² or less, or 0.1 N/mm ² or less.

Preferably, the cured resin film formed from the curable resin composition of the present invention has the above "easy peeling heat resistance". Specifically, after pre-baking (for example, 2 minutes at 100°C) in a cured resin film formed by coating and heating a curable resin composition on a glass substrate, peeling force and additional heating (eg, 1 hour at 230°C) After comparing the peel force, the increase in peel force before and after additional heating is about 500% or less, 450% or less, 400% or less, 350% or less, 300% or less, about 250% or less, 200% or less, 150% or less, 100 % Or less or 50% or less. Additional heating conditions (heating temperature and heating time) can be appropriately changed depending on the curable resin composition and the formed cured resin film. More specifically, in a cured resin film formed by coating and heating treatment on a glass substrate of a curable resin composition, after pre-baking (for example, 2 minutes at 100° C.), peeling force and additional heating (eg, at 230° C.) When comparing the peeling force after 1 hour), the increase in peeling force before and after additional heating is 1 N/mm ² or less, 0.5 N/mm ² or less, or 0.1 N/mm ² or less.

Preferably, the cured resin film formed from the curable resin composition of the present invention has the above "sputtering process resistance". Specifically, a curable resin composition is applied on a substrate and cured by heating (for example, 150°C / 15 minutes) to form a cured resin film, and then a photocurable resist is applied as an overcoat material (OC material) on the film, and free After baking (e.g., 90℃ / 100sec), exposure (e.g., 20mW, 100mJ), post-baking (e.g., 230℃ / 30min) and ITO sputtering process, the cured resin film is easily peelable. It says Gini. The ITO sputtering process is a method of forming an ITO (In ₂ O ₃ -SnO ₂ (indium tin oxide) film by a sputtering method known in the relevant field, and the ITO sputtering process known in the relevant field is the cured resin film of the present invention. As an example of the ITO sputtering process, a cured resin film is installed in the sputtering device, the inside of the device is depressurized (eg 0.5 Pa), air is introduced into the device (eg 50 sccm), and the device is O ₂ Introduced (eg 50 sccm) and heated in a device (eg 90° C.) to perform sputtering (eg pressure: 0.67 Pa, DC power: 110 W) Each process includes the composition of ITO and the thickness of ITO. In addition, the above conditions of pre-baking, exposure, and post-baking are examples, and a known method in the field in which the corresponding cured resin film is used is applied.

The curable resin composition of the present invention typically comprises a chain polymer, a crosslinking agent, and, if necessary, an acid catalyst, a surfactant, a filler, an additive, and a foaming agent, and a solution obtained by dissolving them in a solvent is used as a glass substrate (preferably soda lime glass). By coating on top and curing by heat treatment (100 ℃ ~ 230 ℃, 1 minute or more), it is possible to deposit an easily peelable cured resin film having a thickness of several hundred nm (preferably about 200 nm to about 300 nm) as a transparent thin film. Although not wishing to be bound by theory, as a mechanism, the hydroxy group of the side chain of the chain polymer and the crosslinking agent are a film which can be peeled off due to curing shrinkage during crosslinking by heating.

[Formula 31]

As a method of applying to the glass substrate, a known coating method may be used. Examples include spin coating, spinless coating, die coating, spray coating, roll coating, screen coating, slit coating, dip coating and gravure coating. Preferably, spin coating is used.

The thin film deposited on the substrate can withstand heating up to 150° C., preferably 230° C., and more preferably 300° C. heating (baking). In addition, since the thin film formed by the curable resin composition of the present invention has easy peelability even after heating at such a temperature, although it is a thin film, it can be attached to a circuit manufacturing process including a firing step at a higher temperature than the conventional circuit. It is advantageous in maintaining the characteristics of the circuit, and can be easily peeled off from the substrate even after circuit fabrication. Accordingly, as a base film having excellent characteristics, it can be widely used for manufacturing various kinds of flexible electric/electronic circuit parts in a sheet shape, and for example, it can be used for manufacturing a flexible display device.

The cured resin film of the present invention preferably has heat resistance capable of withstanding heating for a certain period of time (several seconds to several hours or more, etc.) at 230 to 300°C (baking). In one embodiment, it preferably has heat resistance at 230 to 300° C. for 8 hours or more. In another embodiment, it preferably has heat resistance at 230 to 260°C for 1 to 2 hours. In a further embodiment, it more preferably has heat resistance at 230° C. for 8 hours or more. In another embodiment, more preferably, it has heat resistance at 230° C. for 1 to 2 hours. In yet another embodiment, more preferably, it has heat resistance at 300° C. for 1 hour. In yet another embodiment, more preferably, it has heat resistance at 300° C. for 30 minutes.

The cured resin film of the present invention can be produced according to the method described in [3] Method for producing a cured resin film.

The peel force of the cured resin film of the present invention can be measured, for example, by the following measuring method. The curable resin composition of the present invention is typically prepared as a solution in which a chain polymer crosslinking agent and an acid catalyst are dissolved in a solvent, if necessary, and applied to a glass substrate (preferably soda lime glass), and heat treated (100-230° C., for 1 minute or more). ) And cured to prepare a cured resin film on the glass substrate. As a measuring device, for example, the UR-100N-D type is used as a load cell of TENSILON RTG-1310 (A&D Co., Ltd.). The cured resin film Nichiban tape (24 mm wide) is attached to the glass substrate and pulled to the glass substrate at a constant speed of 30 0 mm/min at a peel angle of 90°, and the magnitude of the force (peel force) required for peeling is measured in the above apparatus.

The cured resin film of the present invention preferably has a peeling force on a soda glass substrate or an alkali-free glass substrate of 0.5 N/mm ² or less. The cured resin film of the present invention more preferably has a peeling force of 0.1 N/mm ² or less on a soda glass substrate or an alkali-free glass substrate. The cured resin film of the present invention more preferably has a peeling force of 0.09 N/mm ² or less on a soda glass substrate or an alkali-free glass substrate. Peeling force on the soda glass substrate is preferably 0.5 N/mm ² or less, 0.4 N/mm ² or less, 0.3 N/mm ² or less, 0.2 N/mm ² or less, 0.1 N/mm ² or less, 0.09 N/ mm ² or less, 0.08 N/mm ² or less, 0.07 N/mm ² or less, 0.06 N/mm ² or less, 0.05 N/mm ² or less, 0.04 N/mm ² or less, 0.03 N/mm ² or less, 0.02 N/mm ² or less and 0.01 N/mm ² or less. The peel strength of the alkali-free glass substrate is preferably 0.5 N/mm ² or less, 0.4 N/mm ² or less, 0.3 N/mm ² or less, 0.2 N/mm ² or less, 0.1 N/mm ² or less, 0.09 N/mm ² or less, 0.08 N/mm ² or less, 0.07 N/mm ² or less, 0.06 N/mm ² or less, 0.05 N/mm ² or less, 0.04 N/mm ² or less, 0.03 N/mm ² or less, 0.02 N/mm ² Hereinafter, it is 0.01 N/mm ² or less. When the peeling force on the soda glass substrate or the alkali-free glass substrate is 0.5 N/mm ² or less, the cured resin film may be considered to be easily peelable.

The thickness of the cured resin film of the present invention is the height from the surface of the glass substrate to the surface of the remaining cured resin film by exposing the glass substrate by scratching a part of the cured resin film of the present invention applied on the glass substrate with a knife or a razor blade, etc. It can be measured by measuring with a measuring device. As a measuring device, a stylus type step thickness meter (for example, TP-10, manufactured by KLA-Tencor Corporation) can be used. The thickness of the cured resin film of the present invention is preferably 200 to 400 nm, more preferably 200 nm, 250 nm or 300 nm, but is not limited thereto.

The transmittance of the cured resin film of the present invention can be measured, for example, by the following measuring method. The transmittance (% T) is obtained by measuring the light transmittance of a wavelength of 400 to 700 nm on a glass substrate coated with the cured resin film of the present invention using V-660 (Japan Spectroscopy) as a measuring equipment. The transmittance of the cured resin film of the present invention indicates the degree of whiteness/cloudiness of the film, preferably 95% or more, and more preferably 99% or more. In addition, L*, a*, and b* values can be measured in the CIELAB space as the optical properties of the cured resin film of the present invention. B* of the cured resin film of the present invention represents the yellow color of the film, preferably 0.2 or less, more preferably 0.1 or less.

The liquid viscosity of the curable resin composition prepared from the solution of the present invention can be measured by the following method. That is, the viscosity of the solution can be measured using a viscometer such as ELD (Tokyo Instruments Co., Ltd.) as a measuring device. The viscosity of the curable resin composition of the present invention is preferably 3 mPa·s (cps) or less, more preferably 2.5 mPa·s or less, 2.4 mPa·s or less, 2.3 mPa·s or less, and 2.2 mPa·s Or less, or 2.1 mPa·s or less.

[3] Method for producing cured resin film

In one aspect, the present invention is a method for producing a cured resin film of the curable resin composition of (2-1),

(I) preparing a chain polymer having a side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group and a crosslinking agent;

(Ii) applying the curable resin composition containing the chain polymer and the crosslinking agent on a substrate and forming a curable resin composition coating film;

(Iii) comprising the step of obtaining a cured resin film by curing by proceeding a polymerization reaction in the curable resin composition coating film

Provides a manufacturing method.

The manufacturing method further includes (iv) peeling the cured resin film formed on the substrate from the substrate.

The manufacturing method is carried out by the method described in the following examples and/or the same method known to those skilled in the art.

In one embodiment, the production method further comprises the step of (i') polymerizing at least one raw material monomer to prepare the chain polymer before step (i).

As a method of polymerizing the monomer, for example, a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, and the like may be mentioned, but the present invention is not limited to these examples. Among these polymerization methods, the bulk polymerization method and the solution polymerization method are preferable.

In addition, the polymerization of the monomer can be performed by a method such as a radical polymerization method, a living radical polymerization method, an anionic polymerization method, a cationic polymerization method, an addition polymerization method, and a polycondensation method.

When the monomer is polymerized by a solution polymerization method, for example, the monomer can be polymerized by adding a polymerization initiator to the corresponding solution while stirring the solution obtained by dissolving the monomer in a solvent, and obtained by dissolving the polymerization initiator in the solvent. The monomer can be polymerized by adding the monomer to the corresponding solution while stirring the resulting solution. The solvent is preferably an organic solvent compatible with the monomer.

When polymerizing the monomer, a chain transfer agent that adjusts the molecular weight can be used. The chain transfer agent can generally be used in combination with a monomer. Examples of the chain transfer agent include 2-(dodecylthiocarbonylthio)-2-methylpropionic acid, 2-(dodecylthiocarbonylthioylthio)propionic acid, and methyl 2-(dodecylthiocarbonylthio). Oilthio)-2-methylpropionate, 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid 3-azido-1-propanol ester, 2-(dodecylthiocarbonylthioylthio) -2-methylpropionic acid pentafluorophenyl ester, lauryl mercaptan, dodecyl mercaptan, and mercaptan group-containing compounds such as thioglycerol, inorganic salts such as sodium hypophosphite and sodium hydrogen sulfite, etc., but the present invention It is not limited to these examples. These chain transfer agents may be used individually, respectively, and 2 or more types may be used together. The amount of the chain transfer agent is not particularly limited, but is generally about 0.01 parts by weight to 10 parts by weight per 100 parts by weight of the total monomer.

When polymerizing the monomer, it is preferable to use a polymerization initiator. Polymerization initiators include, for example, thermal polymerization initiators, photopolymerization initiators, redox polymerization initiators, ATRP (atomic transfer radical polymerization) initiators, ICAR ATRP initiators, ARGET ATRP initiators, RAFT (reversible addition-split chain transfer polymerization) agents, NMP (Polymerization through nitroxide) agents, polymer polymerization initiators, and the like. These polymerization initiators may be used alone or in combination of two or more.

Examples of thermal polymerization initiators include azo-based polymerization initiators such as azoisobutyronitrile, methyl azoisobutyrate, and azobisdimethylvaleronitrile, and peroxide-based polymerization initiators such as benzoyl peroxide, potassium persulfate, and ammonium persulfate. However, the present invention is not limited to these examples. These polymerization initiators may be used alone or in combination of two or more.

When a thermal polymerization initiator is used as the polymerization initiator, the amount of the thermal polymerization initiator is generally about 0.01 parts by weight to 20 parts by weight per 100 parts by weight of the total monomer.

As a photoinitiator, for example, 2-oxoglutaric acid, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl[4-(methylthio) Phenyl]-2-morpholinopropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, benzophenone, 1-[4-(2-hydroxyethoxy)phenyl ]-2-hydroxy-2-methyl-1-propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, bis(2,6-dime Oxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and the like, but the present invention is not limited to these examples. These polymerization initiators may be used alone or in combination of two or more.

When a photopolymerization initiator is used as the polymerization initiator, the amount of the photopolymerization initiator is generally about 0.01 parts by weight to 20 parts by weight per 100 parts by weight of the total monomer.

Other polymerization initiators usable in the present invention include redox polymerization initiators such as hydrogen peroxide and iron (II) salts, persulfates and sodium hydrogen sulfite, and ATRP (atomic transfer radical polymerization) initiators using alkyl halides under a metal catalyst. , ICAR ATRP initiator and ARGET ATRP initiator using metal and nitrogen-containing ligands, RAFT (reversible addition-cleavage chain transfer polymerization) agent, NMP (polymerization through nitroxide) agent, polydimethylsiloxane unit-containing polymer azo polymerization initiator, Polymer polymerization initiators, such as a polyethylene glycol unit-containing polymer azo polymerization initiator, etc., but the present invention is not limited to these examples. These polymerization initiators may be used alone or in combination of two or more.

When using the available polymerization initiator as the polymerization initiator, the amount of the polymerization initiator is generally about 0.01 parts by weight to 20 parts by weight per 100 parts by weight of the total monomer.

In one embodiment, electron beam polymerization proceeds by irradiating the monomer with electron beams.

It does not specifically limit about the polymerization reaction temperature and atmosphere when polymerizing a monomer. In general, the polymerization reaction temperature is about 50 °C to about 120 °C. The atmosphere during the polymerization reaction is preferably an inert gas atmosphere such as nitrogen gas. In addition, the polymerization reaction time of the monomer cannot be determined uniformly because it varies depending on the polymerization reaction temperature, etc., but is generally about 3 to 20 hours.

In one embodiment, in step (ii) of the manufacturing method, the substrate is preferably a glass substrate, more preferably soda glass (also referred to as soda lime glass) or alkali-free glass (eg EAGLE-XG Corning). It is preferably a soda glass.

In one embodiment, a known coating method may be used as a method of applying the curable resin composition to the substrate in step (ii) of the manufacturing method. For example, spin coating, die coating, spray coating, roll coating, screen coating, slit coating, dip coating, gravure coating, and the like may be mentioned, but are not limited thereto. Preferably, it can be applied using spin coating.

In another embodiment in step (ii) of the preparation method preferably the composition also comprises an acid catalyst. Without wishing to be bound by theory, it is because the coating film of the curable resin composition contains an acid catalyst, so that the acid catalyst acts as a polymerization catalyst in the polymerization reaction in step (iii) and can accelerate the reaction. Accordingly, in another embodiment, step (i) of the production method further comprises providing an acid catalyst.

In another embodiment, step (iii) in the manufacturing method further includes a step of heat treating the curable resin composition coating film. The heat treatment temperature is preferably 100°C to 300°C, more preferably 150°C to 300°C. The heat treatment time is preferably 1 minute or more, more preferably 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, etc. But is not limited thereto. A particularly preferred heat treatment time is 10 minutes to 2 hours.

The cured resin film prepared by the above manufacturing method has the characteristics of the cured resin film of (2-2) and can be obtained as an easily peelable film, more preferably an easily peelable heat-resistant film.

[4] Use

The curable resin composition or curable resin film of the present invention is used for synthetic resins, pellets, films, plates, fibers, tubes, rubber, elastomers, and the like, and is used for two-wheeled vehicles (bicycles, motorcycles, etc.), automobiles, airplanes, trains, ship rockets, spacecraft, transportation, Leisure, furniture (e.g. tables, chairs, desks, shelves, etc.), bedding (e.g. beds, hammocks, etc.), clothing, protective clothing, sporting goods, bathtubs, kitchenware, tableware, cookware containers and packaging (food containers) , Cosmetic containers, cargo containers, trash bins, etc.), construction (buildings, roads, construction parts, etc.), agricultural films, industrial films, water and sewage, paints, cosmetics, electrical and electronic industries (electronic products, computer parts, printed circuit boards, etc.) Insulators, conductors, wiring coating materials, power generation elements, speakers, microphones, noise cancellers, transducers, etc.), optical communication cables, medical materials and devices (catheter, guide wire, artificial blood vessels, artificial muscles, artificial organs, dialysis membranes, endoscopes, etc.) ), small pumps, actuators, robotic materials (sensors used in industrial robots, etc.), energy generating devices, and plants (solar power, wind power generation, etc.).

The curable resin composition or cured resin film of the present invention can be used for electronic materials, medical materials, medical materials, life science materials, robot materials, and the like. The curable resin composition or cured resin film of the present invention can be used as a material, such as a catheter, a guide wire, a pharmaceutical container, and a tube.

The curable resin composition or cured resin film of the present invention is used for automobile parts (car body panels, bumper belts, rocker panels, side malls, engine parts, driving parts conduction parts, steering device parts, ballast parts, suspension/braking parts, brake parts, and shaft parts). Parts, pipes, tanks, wheels, seats, seat belts, etc.). The polymer of the present invention can be used for automobile vibration isolators, automobile paints, automobile synthetic resins, and the like.

The curable resin composition or cured resin film of the present invention is particularly used in display devices such as display devices (eg, liquid crystal display devices).

Display devices such as liquid crystal display devices can be widely used in vending machines, portable terminals such as ATM smartphones, and other various electric and electronic devices such as computers. The screen of the display device is generally a rigid flat panel. On the other hand, the development of a flexible display device having a screen that can be deformed to some extent is being developed by reflecting the expansion of potential uses of the display device. As a substrate constituting a bendable circuit, there is a resin base film, but when used in a screen of a display device, it is required to be able to produce a fine circuit or to be transparent and as thin and light as possible.

For the production of various fine electric and electronic circuits on a resin base film, for example, photolithography is used, and a metal film is formed on the base film, a photoresist film is coated, prebaked, and the circuit pattern is exposed, and the resist is dissolved. Processes such as developing, rinsing, firing, etching, photoresist removal, etc. are combined and repeated according to the purpose and method to produce a circuit. In addition, an anisotropic conductive film (ACF) is arranged as necessary between the layers produced in this way, and a printed wiring board is arranged on the required part, and heated and pressurized to pass the printed circuit board and metal wiring through the anisotropic conductive film. The circuit connection between is made.

In this case, the entire circuit is made of laminate, which usually involves several firing steps. For the performance of the circuit, firing is preferably carried out at a sufficient temperature (around 230°C), but the upper limit of the firing temperature is limited depending on the heat resistance level of the base film. That is, firing in each step cannot be performed unless the base film is in a region on the low-temperature side that is less than the tolerable limit. Although it is possible to use other materials (silver nanoparticles, etc.) for the metal wiring that can be fired at such low temperatures, the wiring produced by low temperature firing using this is technically not desirable because its characteristics are lower than that of conventional wiring using ITO. not.

In addition, the base film is required to be thinner every year, but the heat resistance of the base film decreases with the thinning. As a result, the upper limit of the heat treatment temperature is currently lowering to about 100 ℃, and assuming that the upper limit of the temperature that can withstand the heat treatment of the base film is further reduced in response to further thinning requests in the future, the temperature at which the performance of the circuit can be maintained. There is a problem that the base film material that can cope with firing is not conspicuous.

Therefore, there is a need for a base film material that withstands higher temperatures.

In addition, according to the thickness reduction, it is preferable to use a very thin film of about 300 nm. To do this, the base film is formed by applying a resin composition, which is a base film material, to another substrate (glass substrate, etc.) and curing it by heat curing. It is necessary to manufacture. Circuit components such as metal wiring are sequentially formed in layers on this very thin base film formed on a substrate such as glass, and anisotropic conductive film is installed, printed circuit board wiring is laminated, and circuit connection is also performed according to the purpose, and insulating protective film is laminated. After performing the process, the base film is removed from a substrate such as glass as an integral laminate together with each layer formed thereon, whereby a laminate as a circuit component can be obtained.

Here, it should be easy without difficulty to remove the laminated body from the substrate such as glass. Otherwise, a large distortion occurs in the stacked body due to the load when pulling and removing it, resulting in disconnection of the metal wiring and separation of the circuit connection, leading to a significant deterioration in yield of the product.

In particular, although the substrate material itself can withstand heat treatment at a higher temperature than before in the form of a thin film, the substrate material and the surface of the substrate on which it is mounted become easier to adhere if the firing in the process of manufacturing the wiring on it is performed at that high temperature . For this reason, it is not enough to withstand firing at high temperatures in the form of a thin film as a substrate material, and it must have a characteristic that can be easily peeled off the substrate even after such high temperature firing.

Moreover, since the base film is very thin as described above, the resin material for forming it is very thin and uniformly expandable without being bounced on the substrate when it is applied to a substrate (such as a glass substrate) (for example, wettability. Have). This affinity for the substrate, on the other hand, is also one of the factors that can cause the easy peelability to be lost because it can lead to sticking with the substrate in the firing process.

In the present invention, a curable resin composition can be applied very thinly to the surface of a substrate (glass, etc.) and cured by heating to deposit a curable resin thin film. In the firing process of producing a circuit by patterning, etc., 230 ℃ ~ 300 By providing a curable resin composition and a cured resin film that can withstand a high temperature of °C and can be easily peeled off a substrate even after being exposed to such a high temperature, it can be applied to various fields such as the above-mentioned uses.

References such as scientific literature, patents, patent applications, etc. cited in this specification are incorporated herein by reference to the same extent as those in which the whole is specifically described.

In the above, preferred embodiments of the present invention have been shown and described for ease of understanding. Hereinafter, the present invention will be described according to examples, but the above description and the following examples are provided for illustrative purposes only and are not intended to limit the present invention. Accordingly, the scope of the present invention is not limited by the embodiments and examples specifically described in the present specification, but only by the claims.

(Example)

Hereinafter, the present invention will be described in more detail with reference to Examples, but it is not intended that the present invention be limited by such Examples. Further, examples obtained by appropriately combining the technical means disclosed in each of the examples are also included in the scope of the present invention.

<Method and material>

The methods and materials used in this Example, Test Example, and Comparative Example were the following unless otherwise noted.

<Gel permeation chromatography>

Gel permeation chromatography columns (TSK GEL 5000HXL, TSK GEL 3000HXL (manufactured by Tosoh Corporation) were prepared by diluting the mixture containing the polymer so that the solid content of the tetrahydrofuran mixture was 0.1% by weight, and maintaining the diluted solution at 40°C. ; Brand name) was injected in series (5000HXL is upstream) in this order. Then, tetrahydrofuran was injected as an eluent at 1 ml/min into the gel permeation chromatography column into which the diluent was injected to extract the eluent containing the polymer, and the polymer molecular weight was measured by a differential refractive index detector (manufactured by Tosoh Corporation).

<crosslinking agent>

MW-30: Hexamethoxymethylmelamine, brand name Nikarak MW-30, Samwha Chemical Co., Ltd.

MX-270: 1,3,4,6-tetrakis (methoxymethyl) glycoluril, brand name Nikarak MW-270, Samwha Chemical Co., Ltd.

BX-4500: Tetramethoxymethylbenzoguanamine, brand name Nikarak BX-4500, Samwha Chemical Co., Ltd.

<Acid catalyst> pyridinium p-toluenesulfonic acid, Tokyo Chemical Industries, Ltd.

<Solvent> Propylene glycol monomethyl ether (PGME)/ethanol = 90/10

<polymer>

The copolymer forming the constituent elements of the curable resin composition was prepared as described in the following Preparation Examples.

(Production Example 1) Preparation of Polymer A-1

The following formula (1-1)

[Formula 32]

Using 2-hydroxypropyl methacrylate as a monomer, 100 parts by mass thereof was dissolved so as to be 30% by weight of propylene glycol monomethyl ether (PGME). The resulting solution was heated to 80° C. while blowing nitrogen gas, 2,2′-azobisisobutyronitrile (AIBN) was added 5 mol% based on the total amount of the monomer, and the reaction was carried out at 80° C. for 8 hours. A-1

[Formula 33]

Was obtained. It was 25,000 as a result of measuring the weight average molecular weight (MW) of this polymer by gel permeation chromatography.

(Production Example 2) Preparation of Polymer A-2

The following formula (1-2)

[Formula 34]

Polymer A-2 in the same manner as in Preparation Example 1 except that 3-benzoyloxy-2-hydroxypropyl methacrylate was used as a monomer.

[Formula 35]

Was obtained. It was 22,000 when the weight average molecular weight (MW) of this polymer was measured by gel permeation chromatography.

(Production Example 3) Preparation of Polymer A-3

The following formula (1-3)

[Formula 36]

Polymer A-3 in the same manner as in Preparation Example 1, except that 4-benzoyloxy-3-hydroxycyclohexylmethylmethacrylate was used as a monomer.

[Formula 37]

Was obtained. It was 32,000 when the weight average molecular weight (MW) of this polymer was measured by gel permeation chromatography.

(Production Example 4) Preparation of Polymer A-4

The following formula (1-4)

[Formula 38]

Polymer A-4 in the same manner as in Example 1 except that 1,3-adamantyldiol monomethacrylate of

[Formula 39]

Was obtained. It was 18,000 when the weight average molecular weight (MW) of this polymer was measured by gel permeation chromatography.

(Production Example 5) Preparation of Polymer A-5

The following formula (1-5)

[Formula 40]

Polymer A-5 in the same manner as in Preparation Example 1 except that 2-hydroxycyclohexyl methacrylate was used as a monomer.

[Formula 41]

Was obtained. It was 36,000 when the weight average molecular weight (MW) of this polymer was measured by gel permeation chromatography.

(Production Example 6) Preparation of Polymer A-6

The following formula (1-6)

[Formula 42]

Polymer A-6 was carried out in the same manner as in Preparation Example 1 except that 4-hydroxycyclohexyl methacrylate was used as a monomer.

[Formula 43]

Was obtained. It was 33,000 when the weight average molecular weight (MW) of this polymer was measured by gel permeation chromatography.

(Production Example 7) Preparation of Polymer A-7

Equation (1-7)

[Formula 44]

Polymer A-7 in the same manner as in Preparation Example 1 except that 4-hydroxyphenyl methacrylate was used as a monomer.

[Formula 45]

Was obtained. It was 30,000 when the weight average molecular weight (MW) of this polymer was measured by gel permeation chromatography.

(Production Example 8) Preparation of Polymer A-8

Equation (1-8)

[Chemical Formula 46]

Polymer A-8 in the same manner as in Preparation Example 1 except that 4-(4-methoxyphenylpropenoyl)oxy-3-hydroxycyclohexylmethylmethacrylate was used as a monomer.

[Chemical Formula 47]

Was obtained. It was 27,700 when the weight average molecular weight (MW) of this polymer was measured by gel permeation chromatography.

(Production Example 9) Preparation of Polymer A-9

Equation (1-9)

[Formula 48]

Polymer A-9 was carried out in the same manner as in Preparation Example 1 except that 4-adamantanecarboxyoxy-3-hydroxycyclohexylmethylmethacrylate was used as a monomer.

[Chemical Formula 49]

Was obtained. It was 31,700 as a result of measuring the weight average molecular weight (MW) of this polymer by gel permeation chromatography.

(Production Example 10) Preparation of Polymer A-10

The following formula (1-10)

[Formula 50]

Polymer A-10 was carried out in the same manner as in Preparation Example 1 except that 2-hydroxyethyl methacrylate was used as a monomer.

[Formula 51]

Was obtained. It was 42,000 when the weight average molecular weight (MW) of this polymer was measured by gel permeation chromatography.

(Production Example 11) Preparation of Polymer A-11

Equation (1-11)

[Formula 52]

Polymer A-11 was carried out in the same manner as in Preparation Example 1 except that 4-(hydroxymethyl)cyclohexylmethylacrylate was used as a monomer.

[Formula 53]

Was obtained. It was 18,000 as a result of measuring the weight average molecular weight (MW) of this polymer by gel permeation chromatography.

The curable resin composition of the present invention was prepared as follows.

(Example 1)

45 parts by mass of polymer A-1, the following formula (B-1) as a crosslinking agent

[Chemical Formula 54]

50 parts by mass of hexamethoxymethylmelamine (Nicarac MW-30, Samwha Chemical Co., Ltd.) and 5 parts by mass of pyridinium p-toluenesulfonic acid as a polymerization catalyst propylene glycol monomethyl ether (PGME)/ethanol = 90/10 Dissolving in solution gave the composition as a solution (NV = 5%).

(Example 2)

45 parts by mass of polymer A-1, the following formula (B-2) as a crosslinking agent

[Chemical Formula 55]

Of 1,3,4,6-tetrakis (methoxymethyl) glycoluril (Nikarak MX-270, Samwha Chemical Co., Ltd.)50 parts by mass and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst propylene glycol The composition was obtained as a solution by dissolving in a solution of monomethyl ether (PGME)/ethanol = 90/10 (NV = 5%).

(Example 3)

45 parts by mass of polymer A-1, the following formula (B-3) as a crosslinking agent

[Formula 56]

50 parts by mass of tetramethoxymethylbenzoguanamine (Nikarac BX-4500, Samwha Chemical Co., Ltd.) and 5 parts by mass of pyridinium p-toluenesulfonic acid as a polymerization catalyst propylene glycol monomethyl ether (PGME)/ethanol = 90 The composition was obtained as a solution by dissolving in /10 solution (NV = 5%).

(Example 4)

45 parts by mass of polymer A-2, 50 parts by mass of crosslinking agent hexamethoxymethylmelamine (formula (B-1)), and 5 parts by mass of pyridinium p-toluenesulfonic acid as a polymerization catalyst propylene glycol monomethyl ether (PGME)/ethanol = Dissolving in a solution of 90/10 gave the composition as a solution (NV = 5%).

(Example 5)

45 parts by mass of polymer A-2, 50 parts by mass of crosslinking agent 1,3,4,6-tetrakis(methoxymethyl)glycoluril (formula (B-2)) and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst Part was dissolved in a solution of propylene glycol monomethyl ether (PGME)/ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

(Example 6)

45 parts by mass of polymer A-2, 50 parts by mass of crosslinking agent tetramethoxymethylbenzoguanamine (formula (B-3)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst propylene glycol monomethyl ether (PGME)/ Dissolving in a solution of ethanol = 90/10 gave the composition as a solution (NV = 5%).

(Example 7)

45 parts by mass of polymer A-3, 50 parts by mass of crosslinking agent hexamethoxymethylmelamine (formula (B-1)) and 5 parts by mass of pyridinium p-toluenesulfonic acid as a polymerization catalyst propylene glycol monomethyl ether (PGME)/ethanol = Dissolving in a solution of 90/10 gave the composition as a solution (NV = 5%).

(Example 8)

45 parts by mass of polymer A-3, 50 parts by mass of crosslinking agent 1,3,4,6-tetrakis(methoxymethyl)glycoluril (formula (B-2)) and 5 parts by mass of pyridinium p-toluenesulfonic acid as a polymerization catalyst Part was dissolved in a solution of propylene glycol monomethyl ether (PGME)/ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

(Example 9)

45 parts by mass of polymer A-3, 50 parts by mass of crosslinking agent tetramethoxymethylbenzoguanamine (formula (B-3)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst propylene glycol monomethyl ether (PGME)/ Dissolving in a solution of ethanol = 90/10 gave the composition as a solution (NV = 5%).

(Example 10)

45 parts by mass of polymer A-4, 50 parts by mass of crosslinking agent hexamethoxymethylmelamine (formula (B-1)), and 5 parts by mass of pyridinium p-toluenesulfonic acid as a polymerization catalyst propylene glycol monomethyl ether (PGME)/ethanol = Dissolving in a solution of 90/10 gave the composition as a solution (NV = 5%).

(Example 11)

45 parts by mass of polymer A-4, 50 parts by mass of crosslinking agent 1,3,4,6-tetrakis(methoxymethyl)glycoluril (formula (B-2)) and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst Part was dissolved in a solution of propylene glycol monomethyl ether (PGME)/ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

(Example 12)

45 parts by mass of polymer A-4, 50 parts by mass of crosslinking agent tetramethoxymethylbenzoguanamine (formula (B-3)) and 5 parts by mass of pyridinium p-toluenesulfonic acid as a polymerization catalyst propylene glycol monomethyl ether (PGME)/ Dissolving in a solution of ethanol = 90/10 gave the composition as a solution (NV = 5%).

(Example 13)

45 parts by mass of polymer A-5, 50 parts by mass of crosslinking agent hexamethoxymethylmelamine (formula (B-1)), and 5 parts by mass of pyridinium p-toluenesulfonic acid as a polymerization catalyst propylene glycol monomethyl ether (PGME)/ethanol = Dissolving in a solution of 90/10 gave the composition as a solution (NV = 5%).

(Example 14)

45 parts by mass of polymer A-5, 50 parts by mass of crosslinking agent 1,3,4,6-tetrakis(methoxymethyl)glycoluril (formula (B-2)) and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst Part was dissolved in a solution of propylene glycol monomethyl ether (PGME)/ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

(Example 15)

45 parts by mass of polymer A-5, 50 parts by mass of crosslinking agent tetramethoxymethylbenzoguanamine (Formula (B-3)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst propylene glycol monomethyl ether (PGME)/ Dissolving in a solution of ethanol = 90/10 gave the composition as a solution (NV = 5%).

(Example 16)

45 parts by mass of polymer A-6, 50 parts by mass of crosslinking agent hexamethoxymethylmelamine (Formula (B-1)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst propylene glycol monomethyl ether (PGME)/ethanol = Dissolving in a solution of 90/10 gave the composition as a solution (NV = 5%).

(Example 17)

45 parts by mass of polymer A-6, 50 parts by mass of crosslinking agent 1,3,4,6-tetrakis(methoxymethyl)glycoluril (formula (B-2)) and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst Part was dissolved in a solution of propylene glycol monomethyl ether (PGME)/ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

(Example 18)

45 parts by mass of polymer A-6, 50 parts by mass of crosslinking agent tetramethoxymethylbenzoguanamine (Formula (B-3)) and 5 parts by mass of pyridinium p-toluenesulfonic acid as a polymerization catalyst propylene glycol monomethyl ether (PGME)/ Dissolving in a solution of ethanol = 90/10 gave the composition as a solution (NV = 5%).

(Example 19)

45 parts by mass of polymer A-7, 50 parts by mass of crosslinking agent hexamethoxymethylmelamine (formula (B-1)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst propylene glycol monomethyl ether (PGME)/ethanol = Dissolving in a solution of 90/10 gave the composition as a solution (NV = 5%).

(Example 20)

45 parts by mass of polymer A-7, 50 parts by mass of crosslinking agent 1,3,4,6-tetrakis(methoxymethyl)glycoluril (formula (B-2)) and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst Part was dissolved in a solution of propylene glycol monomethyl ether (PGME)/ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

(Example 21)

45 parts by mass of polymer A-7, 50 parts by mass of crosslinking agent tetramethoxymethylbenzoguanamine (Formula (B-3)), and 5 parts by mass of pyridinium p-toluenesulfonate as polymerization catalyst propylene glycol monomethyl ether (PGME)/ Dissolving in a solution of ethanol = 90/10 gave the composition as a solution (NV = 5%).

(Example 22)

45 parts by mass of polymer A-8, 50 parts by mass of crosslinking agent hexamethoxymethylmelamine (formula (B-1)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst propylene glycol monomethyl ether (PGME)/ethanol = Dissolving in a solution of 90/10 gave the composition as a solution (NV = 5%).

(Example 23)

45 parts by mass of polymer A-8, 50 parts by mass of crosslinking agent 1,3,4,6-tetrakis(methoxymethyl)glycoluril (formula (B-2)) and 5 parts by mass of pyridinium p-toluenesulfonic acid as a polymerization catalyst Part was dissolved in a solution of propylene glycol monomethyl ether (PGME)/ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

(Example 24)

45 parts by mass of polymer A-8, 50 parts by mass of crosslinking agent tetramethoxymethylbenzoguanamine (Formula (B-3)), and 5 parts by mass of pyridinium p-toluenesulfonic acid as a polymerization catalyst propylene glycol monomethyl ether (PGME)/ Dissolving in a solution of ethanol = 90/10 gave the composition as a solution (NV = 5%).

(Example 25)

45 parts by mass of polymer A-9, 50 parts by mass of crosslinking agent hexamethoxymethylmelamine (formula (B-1)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst propylene glycol monomethyl ether (PGME)/ethanol = Dissolving in a solution of 90/10 gave the composition as a solution (NV = 5%).

(Example 26)

45 parts by mass of polymer A-9, 50 parts by mass of crosslinking agent 1,3,4,6-tetrakis(methoxymethyl)glycoluril (formula (B-2)) and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst Part was dissolved in a solution of propylene glycol monomethyl ether (PGME)/ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

(Example 27)

45 parts by mass of polymer A-9, 50 parts by mass of crosslinking agent tetramethoxymethylbenzoguanamine (formula (B-3)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst propylene glycol monomethyl ether (PGME)/ Dissolving in a solution of ethanol = 90/10 gave the composition as a solution (NV = 5%).

(Example 28)

Polymer A-1 30 parts by mass, crosslinking agent hexamethoxymethylmelamine (formula (B-1)) 65 parts by mass, and 5 parts by mass of pyridinium p-toluenesulfonic acid as a polymerization catalyst propylene glycol monomethyl ether (PGME)/ethanol = Dissolving in a solution of 90/10 gave the composition as a solution (NV = 5%).

(Example 29)

70 parts by mass of polymer A-1, 25 parts by mass of crosslinking agent hexamethoxymethylmelamine (formula (B-1)), and 5 parts by mass of pyridinium p-toluenesulfonic acid as a polymerization catalyst propylene glycol monomethyl ether (PGME)/ethanol = Dissolving in a solution of 90/10 gave the composition as a solution (NV = 5%).

(Example 30)

Polymer A-1 30 parts by mass, crosslinking agent 1,3,4,6-tetrakis(methoxymethyl)glycoluril (formula (B-2)) 65 parts by mass and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst Part was dissolved in a solution of propylene glycol monomethyl ether (PGME)/ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

(Example 31)

70 parts by mass of polymer A-1, 25 parts by mass of crosslinking agent 1,3,4,6-tetrakis(methoxymethyl)glycoluril (formula (B-2)) and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst Part was dissolved in a solution of propylene glycol monomethyl ether (PGME)/ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

(Example 32)

Polymer A-2 30 parts by mass, crosslinking agent hexamethoxymethylmelamine (Formula (B-1)) 65 parts by mass, and 5 parts by mass of pyridinium p-toluenesulfonic acid as a polymerization catalyst propylene glycol monomethyl ether (PGME)/ethanol = Dissolving in a solution of 90/10 gave the composition as a solution (NV = 5%).

(Example 33)

70 parts by mass of polymer A-2, 25 parts by mass of crosslinking agent hexamethoxymethylmelamine (formula (B-1)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst propylene glycol monomethyl ether (PGME)/ethanol = Dissolving in a solution of 90/10 gave the composition as a solution (NV = 5%).

(Example 34)

Polymer A-2 30 parts by mass, crosslinking agent 1,3,4,6-tetrakis(methoxymethyl)glycoluril (formula (B-2)) 65 parts by mass and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst Part was dissolved in a solution of propylene glycol monomethyl ether (PGME)/ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

(Example 35)

70 parts by mass of polymer A-2, 25 parts by mass of crosslinking agent 1,3,4,6-tetrakis(methoxymethyl)glycoluril (formula (B-2)) and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst Part was dissolved in a solution of propylene glycol monomethyl ether (PGME)/ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

(Comparative Example 1)

45 parts by mass of polymer A-10, 50 parts by mass of crosslinking agent hexamethoxymethylmelamine (formula (B-1)), and 5 parts by mass of pyridinium p-toluenesulfonic acid as a polymerization catalyst propylene glycol monomethyl ether (PGME)/ethanol = Dissolving in a solution of 90/10 gave the composition as a solution (NV = 5%).

(Comparative Example 2)

45 parts by mass of polymer A-10, 50 parts by mass of crosslinking agent 1,3,4,6-tetrakis(methoxymethyl)glycoluril (formula (B-2)) and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst Part was dissolved in a solution of propylene glycol monomethyl ether (PGME)/ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

(Comparative Example 3)

45 parts by mass of polymer A-10, 50 parts by mass of crosslinking agent tetramethoxymethylbenzoguanamine (formula (B-3)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst propylene glycol monomethyl ether (PGME)/ Dissolving in a solution of ethanol = 90/10 gave the composition as a solution (NV = 5%).

(Comparative Example 4)

45 parts by mass of polymer A-11, 50 parts by mass of crosslinking agent hexamethoxymethylmelamine (formula (B-1)) and 5 parts by mass of pyridinium p-toluenesulfonic acid as a polymerization catalyst propylene glycol monomethyl ether (PGME)/ethanol = Dissolving in a solution of 90/10 gave the composition as a solution (NV = 5%).

(Comparative Example 5)

45 parts by mass of polymer A-11, 50 parts by mass of crosslinking agent 1,3,4,6-tetrakis(methoxymethyl)glycoluril (formula (B-2)) and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst Part was dissolved in a solution of propylene glycol monomethyl ether (PGME)/ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

(Comparative Example 6)

45 parts by mass of polymer A-11, 50 parts by mass of crosslinking agent tetramethoxymethylbenzoguanamine (formula (B-3)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst propylene glycol monomethyl ether (PGME)/ Dissolving in a solution of ethanol = 90/10 gave the composition as a solution (NV = 5%).

(Comparative Example 7)

45 parts by mass of polymer A-1, 50 parts by mass of crosslinking agent toluene diisocyanate (TDI, Mitsui Chemical Co., Ltd.) and 5 parts by mass of pyridinium p-toluene sulfonic acid as a polymerization catalyst propylene glycol monomethyl ether (PGME)/ethanol = 90 Dissolution in a solution of /10 gave the composition as a solution (NV = 5%).

(Comparative Example 8)

45 parts by mass of polymer A-1, 50 parts by mass of crosslinking agent isophorone diisocyanate (IPDI, Mitsui Chemical Co., Ltd.), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst propylene glycol monomethyl ether (PGME)/ethanol = Dissolving in a solution of 90/10 gave the composition as a solution (NV = 5%).

(Comparative Example 9)

45 parts by mass of polymer A-1, 50 parts by mass of crosslinking agent hexamethylenediisocyanate (HDI, Mitsui Chemical Co., Ltd.) and 5 parts by mass of pyridinium p-toluenesulfonic acid as a polymerization catalyst propylene glycol monomethyl ether (PGME)/ethanol = Dissolving in a solution of 90/10 gave the composition as a solution (NV = 5%).

(Comparative Example 10)

45 parts by mass of polymer A-1, 50 parts by mass of crosslinking agent 1,3-bis(isocyanate methyl)benzene (Takeneto 500, Mitsui Chemical Co., Ltd.) and 5 parts by mass of pyridinium p-toluenesulfonic acid as a polymerization catalyst propylene glycol mono The composition was obtained as a solution by dissolving in a solution of methyl ether (PGME)/ethanol = 90/10 (NV = 5%).

(Measurement Example 1) Evaluation of peel strength and transmittance

The compositions of each of the Examples and Comparative Examples were applied to 0.7 mm of soda glass by spin coating, heated at 100° C. for 2 minutes, heated at 150° C. for 5 minutes, and heated at 230° C. for 2 hours, and at 230° C. for 8 hours. , A film having a thickness of about 300 nm was formed by heating at 260° C. for 2 hours or 300° C. for 30 minutes. Alternatively, the compositions of each of the Examples and Comparative Examples were applied to 0.7 mm of soda glass by spin coating, and heated at 100° C. for 30 seconds to form a film having a thickness of about 300 nm. And the transmittance (λ = 400 nm) of the cured resin thin film prepared on each glass substrate and the peel force and transmittance measurement method evaluated for the magnitude of the force required to peel them off the glass substrate (peel force) are shown below. The measurement results of the peel force and transmittance are shown in Tables 1 to 5.

Peeling force (N/mm ² ): Measurement using TENSILON RTG-1310 (A&D Co., Ltd.) as a load cell, UR-100N-D type as a load cell, a nichiban tape (24mm width) on the cured resin thin film on the glass substrate The glass substrate was pulled at a constant speed of 300 mm/min at a peeling angle of 90° to measure the magnitude of the force (peel force) required for peeling with the above apparatus. In addition, the transmittance was not measured for what was not peeled off from the glass substrate in each Example and each Comparative Example.

Transmittance (%): As a measuring device, the light transmittance at a wavelength of 400 to 700 nm was measured on the same glass substrate using V-660 (Japan Spectroscopy).

From Tables 1 to 5, the following can be seen.

The curable resin film comprising a chain polymer having a side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group as shown in Examples 1 to 35 is an alcoholic secondary or tertiary It can be seen that the easy peeling heat resistance and high speed curing property are higher than that of the curable resin film not containing a chain polymer having a side chain having a grade OH-containing group or a phenolic OH-containing group.

In addition, Examples 1 to 35, wherein the crosslinking agent is selected from the group consisting of a triazine-based compound and/or a condensate thereof and a glycoluril-based compound and/or a condensate thereof, are easily peeled compared to Comparative Examples 7 to 10 using isocyanate as a crosslinking agent It can be seen that the heat resistance is high. In particular, when comparing Examples 1 to 3 and Comparative Examples 7 to 10 containing the same chain polymer and different crosslinking agents, the crosslinking agent is a group consisting of a triazine-based compound and/or a condensate thereof and a glycoluril-based compound and/or a condensate thereof. It can be seen that those selected from are high in easy peeling heat resistance and high speed curing properties.

As described above, although the present invention has been illustrated by using the preferred embodiments of the present invention, it is understood that the scope of the present invention should be interpreted only by the claims. Patents, patent applications, and other documents cited in this specification are understood to be incorporated herein by reference in their contents as if they were specifically described herein.

(Industrial availability)

The present invention is applied very thinly to a substrate such as glass, and then dried and cured after application to deposit an extremely thin curable resin thin film. In the firing process in the process of manufacturing a circuit by patterning, etc., at a high temperature of 230 ℃ to 300 ℃ It relates to a curable resin composition that is durable and can be peeled off the board without difficulty even after being exposed to such high temperatures, and is useful for manufacturing film-type electric/electronic circuit parts.

Claims (50)

In the curable resin composition comprising a crosslinking agent and a chain polymer having side chains having alcoholic secondary and tertiary OH-containing groups or phenolic OH-containing groups,
(a) the chain polymer is formula A1:
[Formula 1]

[In the above formula,
R ^1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group,
L ¹ is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group, and a substituted or unsubstituted alkenylene group,
L ² is O or NH,
R ^2a , R ^3a and R ^4a are each independently selected from the group consisting of hydrogen and a substituted or unsubstituted hydrocarbon radical, provided that at least one of R ^2a , R ^3a and R ^4a is a substituted or unsubstituted alcoholic secondary or secondary A substituted or unsubstituted cycloalkyl group containing a tertiary OH-containing group or a phenolic OH-containing group, or at least two of R ^2a , R ^3a and R ^4a combined to contain alcoholic secondary or tertiary OH or phenolic OH , To form a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted heteroaromatic group, or a polycyclic body containing them.]
It includes a monomer unit represented by,
(b) The crosslinking agent is a triazine-based compound and/or a condensate thereof, a glycoluril-based compound and/or a condensate thereof, and an imidazolidinone-based compound and/or a condensate thereof
Which is selected from the group consisting of
Curable resin composition.
The method of claim 1, wherein the chain polymer is formula A2:
[Formula 2]

[In the above formula
R ^1a , L ¹ and L ² are as described in claim 1,
R ^5a to R ^14a are independently of each other hydrogen, a hydroxy group, and
[Formula 3]

It is selected from the group consisting of or is combined to form a ring, provided that at least one of R ^5a to R ^14a or a substituent of the ring is a hydroxy group,
R ^15a is selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted heteroaromatic group. .]
Curable resin composition containing a monomer unit represented by.
The curable resin composition according to claim 1 or 2, wherein L ¹ is selected from the group consisting of a substituted or unsubstituted alkylene group and a substituted or unsubstituted alkenylene group.
The curable resin composition according to any one of claims 1 to 3, wherein L ¹ is a substituted or unsubstituted alkylene group.
The curable resin composition according to any one of claims 1 to 4, wherein L ¹ is a methylene group.
The method according to any one of claims 1 to 5, wherein the chain polymer is formula A5:
[Formula 4]

[In the above formula
R ^1a and L ¹ are as described in claim 1,
R ^19a is selected from the group consisting of a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted heteroaromatic group.]
Curable resin composition containing a monomer unit represented by.
The curable resin composition according to claim 6, wherein L ¹ is a substituted or unsubstituted alkylene group.
The curable resin composition according to claim 6 or 7, wherein L ¹ is a methylene group.
The curable resin composition according to any one of claims 6 to 8, wherein R ^19a is a phenyl group.
The curable resin composition according to any one of claims 1 to 9, wherein the crosslinking agent is a triazine-based compound and/or a condensation thereof.
The method of any one of claims 1 to 10, wherein the crosslinking agent
[Formula 5]

Phosphorus curable resin composition.
The curable resin composition according to claim 1 or 2, wherein L ¹ is a single bond.
The curable resin composition according to any one of claims 2 to 5 or 12, wherein at least two of R ^5a to R ^14a are hydroxy groups, and the other is hydrogen.
The curable resin composition according to any one of claims 2 to 5 or 12, wherein one of R ^5a to R ^14a is a hydroxy group, and the other is hydrogen.
The curable resin composition according to any one of claims 2 to 5 or 12, wherein R ^5a to R ^13a are hydrogen and R ^14a is a hydroxy group.
The curable resin composition according to any one of claims 1 to 9 or 12 to 15, wherein the crosslinking agent is a glycoluril-based compound and/or a condensation thereof.
The method of any one of claims 1 to 9 or 12 to 15, wherein the crosslinking agent
[Formula 6]

Phosphorus curable resin composition.
The method of any one of claims 1 to 10 or 12 to 15, wherein the crosslinking agent
[Formula 7]

Phosphorus curable resin composition.
The curable resin composition according to any one of claims 1 to 18, wherein the composition is provided as a solution.
The curable resin composition according to claim 19, wherein the solvent of the solution contains alcohol.
The curable resin composition according to claim 20, wherein the alcohol contains primary alcohol.
The curable resin composition of claim 20, wherein the alcohol contains ethanol.
The curable resin composition according to any one of claims 20 to 22, wherein the alcohol is present in an amount of 10% by weight or more of the total amount of the solvent.
The method according to any one of claims 1 to 23, wherein the crosslinking agent is wholly or partially alkoxymethylated melamine and/or condensates thereof, wholly or partially alkoxymethylated guanamine and/or condensates thereof, wholly or partially alkoxymethylated acetogua Namine and/or condensates thereof, wholly or partially alkoxymethylated benzoguanamine and/or condensates thereof, wholly or partially alkoxymethylated glycoluril and/or condensates thereof, and wholly or partially alkoxymethylated imidazolidinone and/or Curable resin composition that is selected from the group consisting of condensates thereof.
The method of any one of claims 1 to 24, wherein the crosslinking agent is formula B1:
[Formula 8]

[In the above formula
R ^1b has 1 to 25 carbon atoms, and is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted heteroaromatic group, and
[Formula 9]

It is selected from the group consisting of disubstituted amines represented by,
R ^2b to R ^7b each independently have 1 to 10 carbon atoms, and are selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group.]
A compound represented by and/or a condensate thereof,
Equation B2:
[Formula 10]

[In the above formula, R ^8b to R ^11b each independently have 1 to 10 carbon atoms, and are selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group.]
A compound represented by and/or a condensate thereof, and
Equation B3:
[Formula 11]

[In the above formula
R ^12b and R ^13b independently of each other have 1 to 10 carbon atoms, and are selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group,
R ^14b and R ^15b are each independently hydrogen or have 1 to 10 carbon atoms, and are selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group.]
Compound represented by and/or condensate thereof
Curable resin composition that is selected from the group consisting of.
The curable resin composition according to any one of claims 1 to 25, wherein the condensation product contains a polymer of a compound represented by formula B1, formula B2, or formula B3.
The curable resin according to any one of claims 1 to 25, wherein the condensate comprises at least one of a dimer, a trimer, and a higher order polymer of a compound represented by Formula B1, Formula B2, or Formula B3. Composition.
The curable resin composition according to any one of claims 1 to 27, wherein the crosslinking agent has a weight average polymerization degree of 1.3 to 1.8 with respect to the compound represented by Formula B1, Formula B2, or Formula B3, respectively.
The method according to any one of claims 25 to 28, wherein R ^1b is a substituted or unsubstituted aromatic group and
[Formula 12]

Is selected from the group consisting of a disubstituted amine represented by, R ^2b to R ^13b are each independently a substituted or unsubstituted alkyl group, and R ^14b and R ^15b are each independently hydrogen.
The curable resin composition according to any one of claims 1 to 29, wherein a ratio of the mass of the linear polymer and the mass of the crosslinking agent in the composition is 1:2 to 1:0.05.
The curable resin composition according to any one of claims 1 to 30, further comprising an acid catalyst.
The curable resin composition according to claim 31, wherein the acid catalyst is a compound selected from Bronsted acid and/or Lewis acid, or a salt thereof or a solvate thereof.
The curable resin composition according to any one of claims 1 to 32, further comprising at least one of a surfactant, a filler, an additive, and a foaming agent.
The curable resin composition according to any one of claims 1 to 32, further comprising a surfactant.
The curable resin composition according to any one of claims 1 to 32, further comprising a foaming agent.
36. The curable resin composition according to any one of claims 1 to 35, which has curability that is cured by heating at 150° C. for 1 minute.
A cured resin film obtained by curing the curable resin composition according to any one of claims 1 to 36.
The cured resin film of claim 37, wherein the cured resin film has a transmittance (% T) of 99% or more and b* of 0.1 or less at 400 nm.
The cured resin film according to claim 37, having heat resistance of 230°C to 300°C.
The cured resin film according to claim 39, having heat resistance at 230° C. to 260° C. for 1 to 2 hours.
The cured resin film according to claim 39, having heat resistance at 230° C. for 8 hours or more.
The cured resin film according to claim 39, having heat resistance at 230° C. for 1 to 2 hours.
An easily peelable cured resin film obtained by curing the curable resin composition according to any one of claims 1 to 36 in the form of a film on the surface of a substrate.
The cured resin film according to any one of claims 37 to 43, which has a peeling force in a soda glass substrate of 0.5 N/mm ² or less or an alkali-free glass substrate.
The cured resin film according to any one of claims 37 to 44, which has a peeling force in a soda glass substrate of 0.1 N/mm ² or less or an alkali-free glass substrate.
In the method for producing a cured resin film from the curable resin composition according to any one of claims 1 to 36,
(I) preparing a chain polymer having a side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group and a crosslinking agent;
(Ii) applying a curable resin composition containing a chain polymer and a crosslinking agent on a substrate and forming a curable resin composition coating film;
(Iii) forming a cured resin film by performing a polymerization reaction in the curable resin composition coating film to cure it;
Manufacturing method comprising a.
The manufacturing method according to claim 46, further comprising: (iv) peeling the cured resin film formed on the substrate from the substrate.
The proportion of the monomer units constituting the chain polymer according to claim 46 or 47, wherein the monomer unit having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group occupies 30 to 100 mol%. Manufacturing method.
The method of any one of claims 46 to 48, wherein the crosslinking agent is wholly or partially alkoxymethylated melamine, wholly or partially alkoxymethylated guanamine, wholly or partially alkoxymethylated acetoguanamine, or wholly or partially alkoxymethylated benzoguanamine and The manufacturing method that is selected from the group consisting of whole or partially alkoxymethylated glycoluril.
The production method according to any one of claims 46 to 49, wherein a ratio of the mass of the linear polymer and the mass of the crosslinking agent in the composition is 1:2 to 1:0.05.