WO2019159248A1

WO2019159248A1 - Curable resin composition for forming heat-resistant and easily peelable cured resin film, and method for producing same

Info

Publication number: WO2019159248A1
Application number: PCT/JP2018/005038
Authority: WO
Inventors: 幸樹椿; 茂樹阿波
Original assignee: 大阪有機化学工業株式会社
Priority date: 2018-02-14
Filing date: 2018-02-14
Publication date: 2019-08-22
Also published as: KR20200120645A; KR102501982B1; JPWO2019159248A1; CN111936573A

Abstract

Disclosed herein is a curable resin composition that is capable of being applied to a surface of a glass substrate to form a cured resin thin film, withstands firing at 230°C to 300°C, inclusive, and can easily be peeled off the substrate without effort. Said composition is a curable resin composition containing a cross-linking agent and a chained polymer comprising an alcoholic secondary or tertiary OH-comprising group or a phenolic OH-comprising group, wherein: (a) the chained polymer comprises a monomer unit represented by formula A1 (where R1a, L1, L2, R2a, R3a, and R4a are as disclosed in the description); and (b) the cross-linking agent is selected from the group consisting of triazine compounds and/or condensates thereof, glycoluril compounds and/or condensates thereof, and imidazolidinone compounds and/or condensates thereof.

Description

Curable resin composition for forming heat-resistant and easily peelable cured resin film and method for producing the 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, and in particular, can be applied to a substrate such as glass and cured to form a thin film. Then, the present invention relates to a curable resin composition that gives a thin film that can be easily peeled off from a substrate without difficulty. The present invention further relates to a curable resin composition capable of forming a heat-resistant and easily peelable cured resin film having various optical properties.

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

In addition, as the thickness of the base film decreases, it is desired to use a very thin film of about 300 nm. For this purpose, a resin composition as a base film material is applied to another substrate (such as a glass substrate). It is necessary to produce a base film by a method of forming a film by curing by heat curing or the like. On this extremely thin base film formed on a substrate such as glass, circuit components such as metal wiring are sequentially formed in layers, for the purpose of installation of anisotropic conductive film, lamination of printed circuit board wiring, circuit connection, etc. Then, after the insulating protective film is laminated, the base film is peeled off from the substrate such as glass together with the layers formed thereon as an integral laminated body to obtain a laminated body as a circuit component.

Here, the laminate must be easily peeled off from the substrate such as glass. Otherwise, a large distortion occurs in the laminate due to the load at the time of peeling, thereby causing disconnection of the metal wiring and peeling of the circuit connection, leading to a significant deterioration in the yield of the product.

In particular, even if the substrate material itself withstands heat treatment at a higher temperature than the conventional one in the form of a thin film, if the firing in the process of forming the wiring thereon is performed at a higher temperature, the substrate material and it will be placed. It becomes easy to adhere to the substrate surface. For this reason, as a substrate material, it is not sufficient to endure baking at a higher temperature than the conventional one in a thin film form, and it should not have such characteristics that it can be easily and easily separated from the substrate even after such high temperature baking. Don't be.

International Publication No. 2015/016532 JP-A-9-105896 Japanese Patent No. 5200538

The present inventors can form a heat-resistant and easily peelable cured resin film having various optical properties when a curable resin composition containing a specific polymer and a crosslinking agent is used. I found. The present inventors have found that the cured resin film of the present invention can withstand firing at a high temperature, can be easily peeled off from the substrate after high-temperature firing, and has better properties (permeability, high-speed curability, etc.). The present invention has been completed.

For example, the present invention provides the following items.
(Item 1)
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 represented by the formula A1:

[Wherein 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 independently selected from the group consisting of hydrogen and substituted or unsubstituted hydrocarbon groups, provided that at least one of R ^2a , R ^3a , and R ^4a is A substituted or unsubstituted alcoholic secondary or tertiary OH-containing group or phenolic OH-containing group, or at least two of R ^2a , R ^3a , and R ^{4a taken} together to form an alcohol A substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted heteroaromatic group, which contains a secondary or tertiary OH or phenolic OH, Or the polycycle containing these is formed. ]
Comprising a monomer unit represented by
(B) The crosslinking agent is selected from the group consisting of triazine compounds and / or condensates thereof, glycoluril compounds and / or condensates thereof, and imidazolidinone compounds and / or condensates thereof. ,
Curable resin composition.
(Item 2)
The chain polymer is represented by the formula A2:

[Where 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

Selected from the group consisting of or together 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 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 Selected from the group consisting of ]
A curable resin composition according to the above item, comprising a monomer unit represented by
(Item 3)
The chain polymer is represented by the formula A2:

[Where 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

Selected from the group consisting of or together 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 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 Selected from the group consisting of ]
A curable resin composition according to any one of the above items, comprising a monomer unit represented by:
(Item 4)
L ¹ is a curable resin composition according to 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 curable resin composition according to any one of the above items, wherein L ¹ is a substituted or unsubstituted alkylene group.
(Item 6)
L ¹ is a methylene group, The curable resin composition in any one of the said item.
(Item 7)
The chain polymer is represented by formula A5:

[Where 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. ]
A curable resin composition according to any one of the above items, comprising a monomer unit represented by:
(Item 8)
L ¹ is a curable resin composition according to any one of the above items, wherein L ¹ is a substituted or unsubstituted alkylene group.
(Item 9)
L ¹ is a methylene group, The curable resin composition in any one of the said item.
(Item 10)
The curable resin composition according to any one of the above items, wherein R ^19a is a phenyl group.
(Item 11)
The curable resin composition according to any of the above items, wherein the crosslinking agent is a triazine compound and / or a condensate thereof.
(Item 12)
The cross-linking agent

The curable resin composition according to any one of the above items.
(Item 13)
L ¹ is a curable resin composition according to any one of the above items, which is a single bond.
(Item 14)
The curable resin composition according to any one of the above items, wherein any two or more of R ^5a to R ^14a are a hydroxy group and the other is hydrogen.
(Item 15)
The curable resin composition according to any one of the above items, wherein any one of R ^5a to R ^14a is a hydroxy group and the other is hydrogen.
(Item 16)
The curable resin composition according to any one of the above items, wherein R ^5a to R ^13a are hydrogen and R ^14a is a hydroxy group.
(Item 17)
The curable resin composition according to any one of the above items, wherein the crosslinking agent is a glycoluril compound and / or a condensate thereof.
(Item 18)
The cross-linking agent

The curable resin composition according to any one of the above items.
(Item 19)
The cross-linking agent

The curable resin composition according to any one of the above items.
(Item 20)
The curable resin composition according to any one of the above items, wherein the composition is provided as a solution.
(Item 21)
The curable resin composition according to the above item, wherein the solvent of the solution contains alcohol.
(Item 22)
The curable resin composition according to the above item, wherein the alcohol comprises a primary alcohol.
(Item 23)
The curable resin composition according to the above item, wherein the alcohol comprises ethanol.
(Item 24)
The curable resin composition according to any one of the above items, wherein the alcohol is present in an amount of 10% by weight or more based on the total amount of the solvent.
(Item 25)
The cross-linking agent is a fully or partially alkoxymethylated melamine and / or its condensate, a fully or partially alkoxymethylated guanamine and / or its condensate, a complete or partially alkoxymethylated acetoguanamine and / or its condensate, fully or One selected from the group consisting of partially alkoxymethylated benzoguanamine and / or its condensate, fully or partially alkoxymethylated glycoluril and / or its condensate, and fully or partially alkoxymethylated imidazolidinone and / or its condensate The curable resin composition according to any one of the above items.
(Item 26)
The crosslinking agent is of formula B1:

[Wherein 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

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. ]
And / or a condensate thereof,
Formula B2:

[R ^8b to R ^11b are independently selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group having 1 to 10 carbon atoms. ]
And / or a condensate thereof, and Formula B3:

[Wherein R ^12b and R ^13b are independently selected from the group consisting of 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted alkenyl group;
R ^14b and R ^15b are independently of each other hydrogen or selected from the group consisting of substituted or unsubstituted alkyl groups and substituted or unsubstituted alkenyl groups having 1 to 10 carbon atoms. ]
A curable resin composition according to any one of the above items, wherein the curable resin composition is selected from the group consisting of a compound represented by:
(Item 27)
The curable resin composition according to any one of the above items, wherein the condensate comprises a polymer of the compound represented by formula B1, formula B2, or formula B3.
(Item 28)
The curability of any of the preceding items, wherein the condensate comprises at least one of a dimer, trimer, and higher order polymer of the compound of formula B1, formula B2, or formula B3 Resin composition.
(Item 29)
The curable resin according to any one of the above items, wherein the crosslinking agent has a weight average degree of polymerization of 1.3 to 1.8 for the compound represented by formula B1, formula B2, or formula B3, respectively. Composition.
(Item 30)
R ^1b is a substituted or unsubstituted aromatic group, and

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 of any of the above items.
(Item 31)
The curable resin composition according to any one of the above items, wherein the ratio of the mass of the linear polymer to the mass of the crosslinking agent in the composition is 1: 2 to 1: 0.05.
(Item 32)
The curable resin composition according to 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 thereof, or a solvate thereof.
(Item 34)
The acid catalyst is selected from the group consisting of p-toluenesulfonic acid (PTS), dodecylbenzenesulfonic acid, pyridinium-p-toluenesulfonic acid, and thermal acid generator Sun-Aid SI-100L (Sanshin Chemical Industry Co., Ltd.) The curable resin composition according to any of the above items, which is a compound or a salt thereof, or a solvate thereof.
(Item 35)
The curable resin composition according to 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 according to any one of the above items, further comprising a surfactant.
(Item 37)
The curable resin composition according to 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, which has a 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 of the above items.
(Item 40)
The cured resin film according to the above item, wherein the cured resin film has a transmittance (% T) of 99% or more at 400 nm and b * of 0.1 or less.
(Item 41)
The cured resin film according to any one of the above items, having heat resistance of 230 ° C. to 300 ° C.
(Item 42)
The cured resin film according to any one of the above items, which has heat resistance at 230 ° C. to 260 ° C. for 1 to 2 hours.
(Item 43)
The cured resin film according to any one of the above items, which has heat resistance at 230 ° C. for 8 hours or more.
(Item 44)
The cured resin film according to any one of the above items, which has 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 of the above items on a substrate surface in a film shape.
(Item 46)
The cured resin film according to any one of the above items, which has a peeling force on a soda glass substrate or an alkali-free glass substrate of 0.5 N / mm ² or less.
(Item 47)
The cured resin film according to any one of the above items, having a peeling force on a soda glass substrate or a non-alkali glass substrate of 0.1 N / mm ² or less.
(Item 48)
A method for producing a cured resin film from the curable resin composition of any of the above items,
(I) providing the chain polymer with a side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group and the crosslinking agent;
(Ii) applying the curable resin composition containing the chain polymer and the crosslinking agent on a substrate to form a curable resin composition coating film;
(Iii) performing a polymerization reaction in the curable resin composition coating film and curing it to form a cured resin film,
Production method.
(Item 49)
(Iv) The method according to 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)
Any of the above items, wherein the proportion of monomer units having an alcoholic secondary or tertiary OH-containing group or phenolic OH-containing group in the monomer units constituting the chain polymer is 30 to 100 mol% Production method.
(Item 51)
The cross-linking agent consists of fully or partially alkoxymethylated melamine, fully or partially alkoxymethylated guanamine, fully or partially alkoxymethylated acetoguanamine, or fully or partially alkoxymethylated benzoguanamine, and fully or partially alkoxymethylated glycoluril. The production method of any of the above items, which is selected from the group.
(Item 52)
The method according to any one of the above items, wherein the ratio of the mass of the linear polymer to 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 of the above items.
(Item 54) A composition for producing a sheet-like flexible electrical / electronic circuit component or a flexible display device, comprising the curable resin composition or cured resin film of any of the above items.
(Item 55) Used for synthetic resins, pellets, films, plates, fibers, tubes, rubber, elastomers, etc., including curable resin compositions or cured resin films of any of the above items, and motorcycles (bicycles, motorcycles, etc.) Cars, airplanes, trains, ships, rockets, spacecraft, transportation, leisure, furniture (eg, tables, chairs, desks, shelves, etc.), bedding (eg, beds, hammocks, etc.), clothes, protective clothing, sports equipment, Bathtub, kitchen, tableware, cooking utensils, containers and packaging materials (food containers, cosmetic containers, cargo containers, trash cans, etc.), architecture (buildings, roads, building parts, etc.), agricultural films, industrial films, water and sewage systems , Paints, cosmetics, electrical industry and electronics industry (electric appliances, computer parts, printed circuit boards, insulators, conductors, wiring coating materials, power generation elements, Car, microphone, noise canceller, transducer, etc.), optical communication cable, medical materials and instruments (catheter, guide wire, artificial blood vessel, artificial muscle, artificial organ, dialysis membrane, endoscope, etc.), small pump, actuator, robot material (Sensors used in industrial robots, etc.), energy generators, and compositions for producing plants (solar power, wind power, etc.).
(Item 56) A composition for producing an electronic material, a medical material, a health care material, a life science material, or a robot material, comprising the curable resin composition or cured resin film of any of the above items.
(Item 57) A composition for producing 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 of the above items.
(Item 58) An automobile part (body panel, bumper band, rocker panel, side molding, engine part, driving part, conduction part, steering part, etc.) containing the curable resin composition or cured resin film of any of the above items Stabilizer parts, suspension / brake device parts, brake parts, shaft parts, pipes, tanks, wheels, seats, seat belts, etc.).
(Item 59) A composition for producing an anti-vibration material for automobiles, a paint for automobiles, and a synthetic resin for automobiles, comprising the curable resin composition or cured resin film of any of the above items.
(Item 60) Use of the curable resin composition or cured resin film of any of the above items for the production of a circuit by a photolithography method.
(Item 61) Use of the curable resin composition or cured resin film of any of the above items for the production of a sheet-like flexible electrical / electronic circuit component or a flexible display device.
(Item 62) Used for synthetic resins, pellets, films, plates, fibers, tubes, rubber, elastomers, etc., motorcycles (bicycles, motorcycles, etc.), automobiles, airplanes, trains, ships, rockets, spacecrafts, transportation, leisure, Furniture (eg, table, chair, desk, shelf, etc.), bedding (eg, bed, hammock, etc.), clothing, protective clothing, sports equipment, bathtub, kitchen, tableware, cooking utensils, containers and packaging materials (food containers, Cosmetic containers, freight containers, waste bins, etc.), architecture (buildings, roads, building parts, etc.), agricultural films, industrial films, water and sewage, paints, cosmetics, electrical industry and electronics industry (electric appliances, computers) Components, printed circuit boards, insulators, conductors, wiring coating materials, power generation elements, speakers, microphones, noise cancellers, transducers Etc.), optical communication cables, medical materials and instruments (catheters, guide wires, artificial blood vessels, artificial muscles, artificial organs, dialysis membranes, endoscopes, etc.), small pumps, actuators, robot materials (industrial robots, etc.) Sensor), energy generator and plant (solar power generation, wind power generation, etc.), the use of the curable resin composition or cured resin film of any of the above items.
(Item 63) Use of the curable resin composition or cured resin film of any of the above items for the production of an electronic material, a medical material, a health care material, a life science material, or a robot material.
(Item 64) Use of the curable resin composition or cured resin film of any of the above items for the production of materials such as catheters, guide wires, pharmaceutical containers, or tubes.
(Item 65) Automobile parts (body panels, bumper bands, rocker panels, side moldings, engine parts, drive parts, transmission parts, steering parts, stabilizer parts, suspension / brake parts, brake parts, shaft parts, pipes, Use of the curable resin composition or cured resin film of any of the above items for the production of tanks, wheels, seats, seat belts, etc.).
(Item 66) Use of the curable resin composition or cured resin film of any of the above items for the production of an anti-vibration material for automobiles, paints for automobiles, and synthetic resins for automobiles.
(Item 67) A method for producing a circuit by a photolithography method, comprising a step of forming a curable resin composition or a cured resin film of any of the above items by causing a polymerization reaction.
(Item 68) A method for producing a sheet-like flexible electrical / electronic circuit component or a flexible display device, wherein a curable resin composition or a cured resin film according to any of the above items is obtained by performing a polymerization reaction. A method comprising the step of forming.
(Item 69) Used for synthetic resins, pellets, films, plates, fibers, tubes, rubber, elastomers, etc., motorcycles (bicycles, motorcycles, etc.), automobiles, airplanes, trains, ships, rockets, spacecrafts, transportation, leisure, Furniture (eg, table, chair, desk, shelf, etc.), bedding (eg, bed, hammock, etc.), clothing, protective clothing, sports equipment, bathtub, kitchen, tableware, cooking utensils, containers and packaging materials (food containers, Cosmetic containers, freight containers, waste bins, etc.), architecture (buildings, roads, building parts, etc.), agricultural films, industrial films, water and sewage, paints, cosmetics, electrical industry and electronics industry (electric appliances, computers) Components, printed circuit boards, insulators, conductors, wiring coating materials, power generation elements, speakers, microphones, noise cancellers, transducers Etc.), optical communication cables, medical materials and instruments (catheters, guide wires, artificial blood vessels, artificial muscles, artificial organs, dialysis membranes, endoscopes, etc.), small pumps, actuators, robot materials (industrial robots, etc.) Sensor), energy generation device, and plant (solar power generation, wind power generation, etc.), wherein a curable resin composition or a cured resin film of any of the above items is obtained by performing a polymerization reaction. A method comprising the step of forming.
(Item 70) A method for producing an electronic material, a medical material, a health care material, a life science material, or a robot material, wherein the curable resin composition or cured resin according to any one of the above items is caused by performing a polymerization reaction. Forming a film.
(Item 71) A method for producing a material such as a catheter, a guide wire, a pharmaceutical container, or a tube, and forming a curable resin composition or a cured resin film according to any of the above items by causing a polymerization reaction. A method comprising the steps of:
(Item 72) Automobile parts (body panels, bumper belts, rocker panels, side moldings, engine parts, drive parts, transmission parts, steering parts, stabilizer parts, suspension / brake parts, brake parts, shaft parts, pipes, etc. Tanks, wheels, seats, seat belts, etc.), which comprises a step of forming a curable resin composition or a cured resin film of any of the above items by performing a polymerization reaction.
(Item 73) A method for producing a vibration isolator for automobiles, a paint for automobiles, and a synthetic resin for automobiles, wherein a curable resin composition or a cured resin film of any of the above items is formed by performing a polymerization reaction. A method comprising the steps of:

According to the present invention, a curable resin composition containing a specific polymer and a crosslinking agent has been developed to produce a cured resin film having good properties. By heat-treating this curable resin composition, formation of a cured resin film that is heat-resistant and easily peelable and has other good properties (such as permeability and high-speed curability) was achieved. .

Hereinafter, the present invention will be described while showing the best mode. Throughout this specification, it should be understood that the singular forms also include the plural concept unless specifically stated otherwise. Thus, it should be understood that singular articles (eg, “a”, “an”, “the”, etc. in the case of English) also include the plural concept unless otherwise stated. In addition, it is to be understood that the terms used in the present specification are used in the meaning normally used in the art unless otherwise specified. Thus, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control. The compound names described herein can be named according to software such as ChemDraw Professional. In certain instances, a generic name may be used, which has the same meaning as commonly understood by one of ordinary skill in the art. The compound names given herein do not necessarily follow IUPAC nomenclature.

[1] Definition of terms

In this specification, “heat resistance” means that a film obtained by curing a curable resin composition can withstand heating up to 150 ° C., preferably withstands heating at 230 ° C., more preferably heating at 300 ° C. It means that it can withstand and substantially does not cause degradation or other deterioration. Note that the temperature of 230 ° C. is high enough to be used as a baking temperature in the manufacture of an electronic circuit by a photolithography method. Furthermore, the temperature of 300 ° C. is a sufficiently high firing temperature necessary for producing electronic circuits under more severe conditions and for forming a thinner film.

In this specification, an “easy release film” is a film that is formed by applying and curing a substrate, particularly a glass substrate, and can be easily peeled off without damaging the film (ie, without unreasonableness). Some say, "easy peelability" refers to the properties of such a film. Examples of the glass substrate include appropriate glass substrates such as a soda glass substrate and a non-alkali glass substrate. A soda glass substrate is a particularly preferred example.

In this specification, “easy peeling heat resistance” means a property having both the above “heat resistance” and “easy peeling property”. In particular, in a cured resin film formed by applying and heating to a glass substrate, the peel force after pre-baking (for example, 100 ° C. for 2 minutes) and the peel force after additional heating (for example, 230 ° C. for 1 hour) And the increase in peel force before and after additional heating is about 500% or less (that is, about 5 times or less of the peel force before heating).

In the present specification, “fast curing” refers to the property of a composition that is cured in a short heating time when the curable resin composition is applied on a substrate and cured by heating. Then, if a film formed by heat curing at 150 ° C. or less for 1 minute or less has easy peelability, it is regarded as having high-speed curability.

In this specification, “sputtering process resistance” can be used for the main application of the sputtering process (for example, transparent electrode, hard coat, photothermal control, wiring, antireflection film, transparent barrier film, photocatalyst, decoration, etc.). Or having the resistance to this application. A curable resin composition is applied onto a substrate, heated and cured (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. The cured resin film after being applied, pre-baked (for example, 90 ° C./100 seconds), exposed (for example, 20 mW, 100 mJ), post-baked (for example, 230 ° C./30 minutes), and subjected to an ITO sputtering process Means having good peelability. 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 art. The ITO sputtering process known in the art is applied to 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 time (for example, 0.5 Pa, 3 hours), and Ar is introduced into the cured resin film (for example, 50 sccm). Then, O ₂ is introduced (for example, 50 sccm), and sputtering (for example, pressure: 0.67 Pa, DC power: 110 W) is performed under heating (for example, 90 ° C.) Each process depends on the ITO composition, the ITO film thickness, and the like. Can be changed.

In the present specification, “storage stability” is storage stability of the curable resin composition formed as a solution, and unless otherwise limited, a normal test (storage at 20 ° C. for 9 months or 12 months) and an accelerated test After storage (stored at 50 ° C. for 2 weeks), the solution has no visual turbidity or solidification compared to before storage, and the properties of the solution (viscosity, NV, etc.) and properties at the time of film formation (peeling) Force, transmittance, etc.). “Storage stability” can also be described as “pot life”.

In this specification, the thickness (also referred to as “film thickness”) of the “cured resin film” is not limited. When used as a base film for circuit fabrication, a preferred thickness is 200 to 400 nm, for example, about 300 nm. This is in response to the current demand for thin film in the case of electronic parts, and is a cured resin. Since the performance of the film itself is not limited to this thickness range, the thickness of the cured resin film is arbitrary. In this specification, “cured resin film” is used synonymously with “cured resin film”.

In this specification, the term “side chain” in a chain polymer refers to a structural portion branched from the main chain, and the “main chain” is linked in a one-dimensional direction to repeating monomer units in the polymer structure. A chain of atoms that are attached. Therefore, for example, when the polymer is a polymer of (meth) acrylate, “—COO—”, which is a portion that contributes to the formation of an ester bond in each monomer, is included in a part of the “side chain”. The notation “(meth) acrylate” indicates acrylate and methacrylate without distinction. Similarly, the notation “(meth) acryl” indicates acrylic and methacrylic without distinction, and “(meth) acrylic acid” indicates acrylic acid and methacrylic acid without distinction.

In the present specification, the “alkyl group” refers to a monovalent group formed by losing one hydrogen atom from an aliphatic hydrocarbon (alkane) such as methane, ethane, or propane, and is generally represented by C _n H _{2n + 1} —. Where n is a positive integer. Alkyl can be linear or branched. Examples of the alkyl group having 1 to 4 carbon atoms (C _1-4 alkyl) include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec- Although a butyl group etc. are mentioned, this invention is not limited only to this illustration. Examples of the alkyl group having 1 to 6 carbon atoms (C _1-6 alkyl) include, for example, an alkyl group having 1 to 4 carbon atoms, a tert-butyl group, a sec-butyl group, an n-pentyl group, an isoamyl group, n -Hexyl group, isohexyl group, cyclohexyl group and the like are mentioned, but the present invention is not limited only to such examples. Examples of the alkyl group having 1 to 10 carbon atoms (C _1-10 alkyl) include an alkyl group having 1 to 6 carbon atoms, an n-octyl group, an n-nonyl group, and an n-decanyl group. The present invention is not limited to such examples.

As used herein, the term “alkenyl group” refers to a monovalent group formed by loss of one hydrogen atom from an aliphatic hydrocarbon (alkene) containing at least one double bond such as ethene, propene, or butene. In general, it is represented by C _m H _2m−1 (where m is an integer of 2 or more). An alkenyl group can be straight or branched. Examples of the alkenyl group having 2 to 6 carbon atoms include an ethenyl group, a 1-propenyl group, a 2-propenyl group, a butenyl group, a pentenyl group, and a hexenyl group. However, the present invention is limited only to such examples. Is not to be done. 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, a decenyl group, and the like, but the present invention is limited only to such examples. Is not to be done.

In the present specification, the “alkylene group” refers to a divalent group formed by losing two hydrogen atoms from an aliphatic hydrocarbon (alkane) such as methane, ethane, or propane, and is generally — (C _m H _2m )-(Where m is a positive integer). The alkylene group can be linear or branched. Examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, tert-butylene, n-pentene, and n-hexylene. Group, isohexylene group and the like are mentioned, but the present invention is not limited only to such illustration. An alkylene group having 1 to 6 carbon atoms is preferable, an alkylene group having 1 to 4 carbon atoms is more preferable, a methylene group and an ethylene group are further preferable, and an ethylene group is still more preferable.

In the present specification, the “alkenylene group” is a divalent group formed by losing two hydrogen atoms from an aliphatic hydrocarbon (alkene) containing at least one double bond, such as ethenylene, propenylene, and butenylene. And is generally represented _by- (C _m H _2m-2 )-(where m is an integer of 2 or more). An alkenylene group can be straight or branched. Examples of the alkenylene group having 2 to 10 carbon atoms include ethenylene group, n-propenylene group, isopropenylene group, n-butenylene group, isobutenylene group, n-pentenylene group, n-hexenylene group, isohexenylene group and the like. However, the present invention is not limited to such 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 an n-propenylene group are further preferable, and an ethenylene group is still more preferable.

In the present specification, the “alkoxy group” refers to a monovalent group generated by loss of a hydrogen atom of a hydroxy group of an alcohol, and is generally represented by C _n H _{2n + 1} O— (where n is 1 or more). Is an integer). Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, 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 can be mentioned, but the present invention is not limited to such examples.

In the present specification, the “haloalkyl group” refers to an alkyl group in which one or more hydrogen atoms on the alkyl group are substituted with halogen atoms. “Perhaloalkyl” refers to an alkyl group in which all hydrogen atoms on the alkyl group are substituted with halogen atoms. Examples of the haloalkyl group having 1 to 6 carbon atoms include trifluoromethyl group, trifluoroethyl group, perfluoroethyl group, trifluoro n-propyl group, perfluoro n-propyl group, trifluoroisopropyl group, perfluoroisopropyl group, Fluoro 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 Examples include a -hexyl group and a perfluoro n-hexyl group, but the present invention is not limited to such examples.

In the present specification, the “cycloalkyl group” means a monocyclic or polycyclic saturated hydrocarbon group, and includes a bridged structure. For example, “C _3-12 cycloalkyl group” means a cyclic alkyl group having 3 to 12 carbon atoms. Specific examples of the “C _6-12 cycloalkyl group” include a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, an isobornyl group, and the like. In the case of “C _3-12 cycloalkyl group”, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a C _6-12 cycloalkyl group and the like can be mentioned. Preferably, “C _6-12 cycloalkyl group” is used.

In the present specification, the “cycloalkenyl group” means a monocyclic or polycyclic unsaturated hydrocarbon group containing a double bond, and includes a bridged structure. Examples include one in which one or more carbon-carbon bonds of the “cycloalkyl group” are double bonds. For example, “C _3-12 cycloalkenyl group” means a cyclic alkenyl group having 3 to 12 carbon atoms. Specific examples of the “C _6-12 cycloalkenyl group” include 1-cyclohexenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclononenyl group and the like. It is done. In the case of “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 used.

In the present specification, the “hydrocarbon group” refers to a monovalent group produced by losing one hydrogen atom from a compound composed only of carbon and hydrogen. The hydrocarbon group also includes the above “alkyl group”, “alkenyl group”, “alkylene group”, “alkenylene group”, “cycloalkyl group”, and “cycloalkenyl group”, as well as the following “aromatic group” and “ An alicyclic group "and the like. The hydrocarbon group can be saturated or unsaturated. The hydrocarbon group is classified into a chain hydrocarbon group and a cyclic hydrocarbon group depending on how carbon is bonded, and the cyclic hydrocarbon group is further divided 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, decalinyl, adamantyl, butenyl, hexenyl, cyclohexenyl, decyl and others Examples include 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. When each of these groups is not located at the terminal, it may be a divalent or higher group depending on the bonding relationship with other groups.

In the present specification, the “aromatic group” refers to a group formed by leaving one hydrogen atom bonded to an aromatic hydrocarbon ring. For example, from benzene, phenyl group (C ₆ H ₅ —), from toluene, tolyl group (CH ₃ C ₆ H ₄ —), from xylene, xylyl group ((CH ₃ ) ₂ C ₆ H ₃ —), from naphthalene Is derived from a naphthyl group (C ₁₀ H ₈ —). In the present specification, the “heteroaromatic group” means a monocyclic or polycyclic heteroatom-containing aromatic group, and the group is the same kind selected from a nitrogen atom, a sulfur atom and an oxygen atom. Alternatively, it contains one or more (for example, 1 to 4) heterogeneous heteroatoms. The above “aromatic group” also includes “heteroaromatic group”. Examples of aromatic groups include carbocyclic aromatic groups (monocyclic and condensed ring groups) such as phenyl, biphenylyl, naphthyl, and heteroaromatic groups (monocyclic) such as pyridyl, pyrimidinyl, quinolinyl, triazinyl, etc. Group and a condensed ring group), and when each aromatic group is not located at the terminal, it may be a divalent or higher group depending on the bonding relationship with other groups. In the present specification, a group having a saturated or unsaturated hydrocarbon chain part that forms a ring together with an aromatic ring part (for example, tetrahydronaphthyl or dihydronaphthyl) is an aromatic group and a saturated or unsaturated hydrocarbon group. Think of it as a combination.

As used herein, “alicyclic (group)” refers to a moiety (or group) formed by the removal of one hydrogen atom bonded to a non-aromatic ring composed only of carbon and hydrogen. The alicyclic group also includes the above “cycloalkyl group” and “cycloalkenyl group”. The alicyclic group can be saturated or unsaturated. Examples of saturated or unsaturated alicyclic groups include cyclohexyl, dicyclopentadienyl, decalinyl, adamantyl, cyclohexenyl, and various other monocyclic and condensed cyclic groups within the limits of the number of carbon atoms in the side chain. Groups, but not limited to. When each of these groups is not located at the terminal, it may be a divalent or higher group depending on the bonding relationship with other groups.

Usually, the term “substituted” is referring to the replacement of one or more hydrogen radicals in a given structure by a radical of a particular substituent. In the present specification, the number of substituents in a group defined using “substituted (has / was)” is not particularly limited as long as substitution is possible, and is one or more. In addition, unless otherwise specified, the description of each group also applies when the group is a part of another group or a substituent. In addition, in the present specification, a substituent that does not clearly indicate the term “substituted (has / is)” means a “non-substituted” substituent. Further, it is recognized herein that the phrase “substituted or unsubstituted” is used interchangeably with the phrase “optionally substituted”.

“Substituted alkyl group”, “substituted alkenyl group”, “substituted cycloalkyl group”, “substituted cycloalkenyl group”, “substituted hydrocarbon group”, “substituted aromatic group”, “substituted heteroaromatic group”, “substituted” Substituents on groups described herein including "alkylene groups", "substituted alkenylene groups", and "substituted or unsubstituted alcoholic secondary or tertiary OH-containing groups or phenolic OH-containing groups" Examples of are halogen, hydroxy group, 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} haloalkyl _{group, C 2 ~ 10} haloalkenyl _{group, C 6 ~ 18} hydrocarbon _{group, C 6 ~ 18} aromatic _{group, C 6 ~ 18} heteroaromatic _group, _{C 1} substituted with _{C 6 ~ 12} aromatic group _{to 10} A Kill _{_{group, C 6 ~ 12 C 1 ~}} 10 alkyl group substituted with a hydrocarbon _group, _{C 2 ~ 10} alkenyl group substituted with _{C 6 ~ 12} aromatic _group, substituted with _{C 6 ~ 12} hydrocarbon radicals C _2-10 alkenyl group, —CN, oxo group (═O), —O (CH ₂ ) ₂ O—, —OC (CH ₃ ) ₂ O—, —OCH ₂ O—, —O—, ester group ( -COO- or _{-O-CO -), C 6} ~ 12 -substituted ester group with a hydrocarbon _{group, C 6 ~ 12} aromatic-substituted ester group in group, _{C 6 ~ 18} carbon substituted with an ester group hydrogen group, C _{1 ~ 10} alkyl group substituted with an ester group, C 1 _{~ 6} alkylene group, and C 2 _{~ 6} alkenylene group, the present invention is not limited only to those exemplified. Preferred examples of the substituent group, hydroxy _{group, C 6 ~ 18} hydrocarbon _{group, C 1 ~ 10} alkyl _group, _{C 1 ~ 10} alkyl group substituted with a _{C 6 ~ 12} aromatic _{group, C 6 ~ 12} carbon _{C 1 ~ 10} alkyl group substituted with a hydrogen group, _{~ C 6} substituted with an ester group ₁₈ hydrocarbon group, _{C 1 ~ 10} alkyl group substituted with an ester group, an ester group (-COO- or -O- CO _-), substituted with _{C 6 ~ 12-substituted} ester group with a hydrocarbon _{group, C 6 ~ 12} aromatic-substituted ester group with a _{group, C 2 ~ 10} alkenyl _{group, C 6 ~ 12} aromatic group C _{2 ~ 10} alkenyl _{_{group, C 6 ~ 12 C 2 ~}} 10 alkenyl group substituted with a hydrocarbon _{group, C 1 ~ 10} alkoxy _{group, C 6-12} cycloalkyl group _includes a _{C 6-12} cycloalkenyl group , With more specific examples Te is benzoyloxy group, a phenyl group, a cyclohexyl group, cyclohexenyl group, adamantyl group, an adamantyl group substituted by a hydroxy group.

In the present specification, “alcoholic secondary or tertiary OH-containing group or phenolic OH-containing group” means an alcoholic secondary or tertiary hydroxy (OH) group or a phenolic hydroxy (OH) group. The group which contains 1 or 2 or more is shown. Therefore, the “alcoholic secondary or tertiary OH-containing group or phenolic OH-containing group” also includes an alcoholic secondary or tertiary hydroxy group or a phenolic hydroxy group itself. “Substituted or unsubstituted” in “substituted or unsubstituted alcoholic secondary or tertiary OH-containing group or phenolic OH-containing group” means alcoholic secondary or tertiary hydroxy (OH) group or phenol This means that a group containing one or more functional hydroxy (OH) groups is substituted or unsubstituted in a group other than the hydroxy group, and the hydroxy group is substituted. Does not indicate that it is present or unsubstituted.

In the present specification, unless otherwise specified, “solvate” means a compound or a salt thereof further containing a stoichiometric or non-stoichiometric amount of solvent bonded by non-covalent intermolecular forces. When the solvent is water, the solvate is a hydrate.

In this specification, “solvent” is used synonymously with “solvent”.

In this specification, “monomer” refers to a compound that polymerizes two or more to form a polymer. The “monomer unit” refers to a monomer that is a unit that forms a polymer.

In the present specification, “polymer” refers to a compound formed by polymerizing a plurality of monomers. In the present specification, “homopolymer” (homopolymer) is a compound formed by polymerization of only one type of monomer, and “copolymer” (copolymer) means two or more types. This is a compound formed by polymerization of the monomer. The polymers described herein include both homopolymers and copolymers. When the polymer is described by a structural formula, the homopolymer is
— [Monomer unit A] _n − (where n ≧ 2)
Described as
The copolymer is
-[Monomer unit A] _n- [monomer unit B] _m- (where n ≧ 1, m ≧ 1, n + m ≧ 2)
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. In this specification, when a polymer is a chain, it is referred to as a “chain polymer”. In the present specification, “polymer” is used synonymously with “polymer”.

In this specification, “crosslinking agent” refers to a substance that forms a covalent bond between the same or different polymers and changes physical and chemical properties.

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

In this specification, “or” is used when “at least one or more” of the items listed in the sentence can be adopted. The same applies to “or”. In this specification, when “within the range of two values” is specified, the range includes the two values themselves. Therefore, “X to Y” indicating a range means “X or more and Y or less”. Unless otherwise noted, “weight” and “mass”, “wt%” or “wt%” and “mass%” are treated as synonyms. Unless otherwise specified, the expression “about” has a tolerance of 10%, and in the case of a measured value, it is an arbitrary value obtained by rounding off significant digits or one digit below the displayed number. A value in the range of.

[2] Description of Preferred Embodiments Hereinafter, preferred embodiments of the present invention will be described. The embodiments provided below are provided for a better understanding of the present invention, and it is understood that the scope of the present invention should not be limited to the following description. Therefore, it is obvious that those skilled in the art can make appropriate modifications within the scope of the present invention with reference to the description in the present specification. It will also be appreciated that the following embodiments of the invention may be used alone or in combination.

(2-1) Curable resin composition In the first aspect, the present invention provides a chain polymer having a side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group; A curable resin composition comprising a crosslinking agent,
(A) The chain polymer is represented by the formula A1:

[Wherein 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 independently selected from the group consisting of hydrogen and substituted or unsubstituted hydrocarbon groups, provided that at least one of R ^2a , R ^3a , and R ^4a is A substituted or unsubstituted alcoholic secondary or tertiary OH-containing group or phenolic OH-containing group, or at least two of R ^2a , R ^3a , and R ^{4a taken} together to form an alcohol A substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted heteroaromatic group, which contains a secondary or tertiary OH or phenolic OH, Or it is a polycycle containing these. ]
Comprising a monomer unit represented by
(B) The crosslinking agent is selected from the group consisting of triazine compounds and / or condensates thereof, glycoluril compounds and / or condensates thereof, and imidazolidinone compounds and / or condensates thereof. A curable resin composition is provided.

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

In a second aspect, the present invention provides a curable resin 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 composition, wherein the chain polymer is of formula A2:

Selected from the group consisting of or together 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 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 Selected from the group consisting of ]
Comprising a monomer unit represented by
(B) The crosslinking agent is selected from the group consisting of triazine compounds and / or condensates thereof, glycoluril compounds and / or condensates thereof, and imidazolidinone compounds and / or condensates thereof. A curable resin composition is provided.

In the second aspect described above, preferably, in Formula A2, L ² is O.

In the third aspect, more preferably, the present invention includes 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 curable resin composition having the formula A2:

[Wherein 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

Wherein R ^5a to R ^14a or at least one of the substituents on the ring is a hydroxy group,
R ^15a is 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 Selected from the group consisting of ]
Comprising a monomer unit represented by
(B) The crosslinking agent is selected from the group consisting of triazine compounds and / or condensates thereof, glycoluril compounds and / or condensates thereof, and imidazolidinone compounds and / or condensates thereof. A curable resin composition is provided.
In the third aspect, more preferably, L ¹ is a substituted or unsubstituted alkylene group, and most preferably, L ¹ is a methylene group.

In the fourth aspect, more preferably, the present invention includes 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 curable resin composition comprising the chain polymer of formula A5:

[Wherein 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. ]
Comprising a monomer unit represented by
(B) The crosslinking agent is selected from the group consisting of triazine compounds and / or condensates thereof, glycoluril compounds and / or condensates thereof, and imidazolidinone compounds and / or condensates thereof. A curable resin composition is provided.
In the fourth aspect, preferably, in 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, in Formula A5, R ^19a is a phenyl group.
In the fourth aspect, preferably, the crosslinking agent is a triazine compound and / or a condensate thereof. More preferably, the crosslinking agent is

It is.

In the fifth aspect, more preferably, the present invention includes 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 curable resin composition having the formula A2:

[Wherein 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 selected from the group consisting of hydrogen and a hydroxy group, provided that at least one of R ^5a to R ^14a or a substituent on the ring is a hydroxy group. ]
Comprising a monomer unit represented by
(B) The crosslinking agent is selected from the group consisting of triazine compounds and / or condensates thereof, glycoluril compounds and / or condensates thereof, and imidazolidinone compounds and / or condensates thereof. A curable resin composition is provided.
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, any two or more of R ^5a to R ^14a are a hydroxy group, and the other is hydrogen. In another embodiment, preferably any 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 compound and / or a condensate thereof. More preferably, the crosslinking agent is

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

It is.

Since the curable resin composition of the present invention is cured by heat treatment, it can be said to be a thermosetting resin composition.

The chain polymer that 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 phenolic OH-containing group of the chain polymer is preferably 3 to 30. The number of the hydroxy groups in the side chain having an alcoholic secondary or tertiary OH-containing group or phenolic OH-containing group can be 1 or 2 or more.

In the present invention, the alcoholic secondary or tertiary OH-containing group or phenolic OH-containing group in the side chain is a cured resin formed by coating and curing the curable resin composition of the present invention on a glass substrate. The thin film is a substantially decisive factor for maintaining easy peelability from the substrate even after firing. Further, it is more preferred that the alcoholic secondary or tertiary OH-containing group or phenolic OH-containing group in the side chain is bonded to the alicyclic part of the side chain, and the alicyclic part of the side chain is also a cured resin. This is a decisive factor for maintaining the easy peelability of the thin film. A chain polymer having such a side chain is a suitable crosslinking agent, particularly a triazine compound and / or a condensate thereof, a glycoluril compound and / or a condensate thereof, or an imidazolidinone compound and / or a compound thereof. When it is made into a resin composition with any of the condensates and cured in the form of a thin film, a heat-resistant easily peelable film can be provided.

Preferred examples of the monomer that gives the chain polymer a side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group 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-hydroxycyclohexyl (meth) acrylate, 4-undecanoyloxy-3-hydroxycyclohexylmethyl (meth) acrylate, 4-butanoyloxy- (Meth) acrylates such as 3-hydroxycyclohexylmethyl (meth) acrylate;

The chain polymer in the present invention has, in addition to the monomer having the alcoholic secondary or tertiary OH-containing group or the phenolic OH-containing group, a hydroxyl group and a side chain having 1 to 15 (meth) acrylic monomer, vinyl ester monomer, vinyl ether monomer, and at least one of vinyl monomers other than these can be included as an additional monomer unit.

Preferable examples of the monomer unit having no 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, tetrahydrofurfuryl (meth) acrylate, cyclohexyl ( (Meth) acrylate, phenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, octyl (meth) acrylate, benzyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylamino (Meth) acrylates such as propyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and glycidyl (meth) acrylate.
(2) Vinyl esters such as vinyl acetate, butanoic acid vinyl ester, pentanoic acid vinyl ester, hexanoic acid vinyl ester, cyclohexanecarboxylic acid vinyl ester, benzoic acid vinyl ester, cyclopentadienylcarboxylic acid vinyl ester, and nonanoic acid vinyl ester .
(3) Propyl vinyl ether, butyl vinyl ether, ethoxyethyl vinyl ether, glycidyl vinyl ether, pentyl vinyl ether, tetrahydrofurfuryl vinyl ether, cyclohexyl vinyl ether, phenyl vinyl ether, cyclopentadienyl vinyl ether, octyl vinyl ether, benzyl vinyl ether, 2- (vinyloxy) ethyldimethylamine , Vinyl ethers such as 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, octylmaleic anhydride .
(6) Maleimide derivatives such as maleimide, methylmaleimide, ethylmaleimide, butylmaleimide, hexylmaleimide, cyclohexylmaleimide, phenylmaleimide, benzylmaleimide and octylmaleimide.

The chain polymer in the present invention may be a homopolymer of monomer units, or may be a copolymer containing two or three or more types of monomer units. At least one of the monomer units in the coalescence is a monomer unit having a side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group. Preferably, the copolymer has a monomer unit having a side chain having at least one alcoholic secondary or tertiary OH-containing group or phenolic OH-containing group, and at least one hydroxy group. Not contain additional monomer units.

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

In the present invention, the chain polymer is subjected to a polymerization reaction using its raw material monomers in a conventional manner, for example, using a conventional radical polymerization catalyst such as 2,2′-azobisisobutyronitrile (AIBN). Can be manufactured. The weight average molecular weight (Mw) of the chain polymer is usually preferably in the range of 10,000 to 100,000 (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 procedures and equipment known in the art. An example of gel permeation chromatography is to prepare a sample by diluting a mixture containing a polymer in an appropriate solvent (eg, tetrahydrofuran) (eg, diluting so that the solid content of the obtained mixture is 0.1% by mass). The diluted solution is injected into a commercially available gel permeation chromatography column maintained at an appropriate temperature (eg, 40 ° C.). The eluent containing the polymer is then extracted by pouring the eluent (eg, tetrahydrofuran) into the gel permeation chromatography column into which the diluent has been injected at an appropriate flow rate (eg, 1 ml / min) and the detector (eg, differential refractive index). The molecular weight of the polymer is measured by a detector. The above conditions can be appropriately selected depending on the type of polymer.

As the crosslinking agent in the curable resin composition of the present invention, a triazine-based crosslinking agent, a glycoluril-based crosslinking agent, or an imidazolidinone-based crosslinking agent is preferable. More specifically, the crosslinking agent is selected from the group consisting of triazine compounds and / or condensates thereof, glycoluril compounds and / or condensates thereof, and imidazolidinone compounds and / or condensates thereof. Is preferred. Preferred examples of these crosslinking agents include fully or partially alkoxy (eg methoxy, ethoxy) methylated melamine and / or condensates thereof, fully or partially alkoxy (eg methoxy, ethoxy) methylated guanamine and / or condensates thereof. Fully or partially alkoxy (eg methoxy, ethoxy) methylated acetoguanamine and / or condensates thereof, fully or partially alkoxymethylated benzoguanamine and / or condensates thereof, fully or partially alkoxy (eg methoxy, ethoxy) methylated glycoluril And / or condensates thereof, fully or partially alkoxymethylated imidazolidinone and / or condensates thereof. Here, “alkoxy” preferably has 1 to 4 carbon atoms. More specifically, preferred compounds as such a crosslinking agent include, for example, hexamethoxymethyl melamine, hexaethoxymethyl melamine, tetramethoxymethyl methylol melamine, tetramethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl guanamine, tetra Methoxymethylacetoguanamine, tetramethoxymethylbenzoguanamine, trimethoxymethylbenzoguanamine, tetraethoxymethylbenzoguanamine, tetramethylolbenzoguanamine, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis ( Butoxymethyl) glycoluril, 4,5-dihydroxy-1,3-dimethoxymethyl-2-imidazolidinone, 4,5-dimethoxy-1,3- Methoxymethyl-2-imidazolidinone, but not limited thereto.

In one embodiment, preferably the crosslinker is of formula B1:

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. ]
And / or a condensate thereof.

More preferably, the crosslinking agent in the present invention is represented by the formula B1:
R ^1b is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group, and

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,
A compound and / or a condensate thereof.

In another embodiment, preferably the crosslinker is of formula B2:

[R ^8b to R ^11b are independently selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group having 1 to 10 carbon atoms. ]
And / or a condensate thereof.

More preferably, the crosslinking agent in the present invention is represented by the formula B2:
R ^8b to R ^11b are each independently selected from a substituted or unsubstituted alkyl group,
A compound and / or a condensate thereof.

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

[Wherein R ^12b and R ^13b are independently selected from the group consisting of 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted alkenyl group;
R ^14b and R ^15b are independently of each other hydrogen or selected from the group consisting of substituted or unsubstituted alkyl groups and substituted or unsubstituted alkenyl groups having 1 to 10 carbon atoms. ]
And / or a condensate thereof.

More preferably, the crosslinking agent in the present invention is represented by the formula B3:
R ^12b and R ^13b are independently of each other selected from substituted or unsubstituted alkyl groups;
R ^14b and R ^15b are independently of each other selected from the group consisting of hydrogen and substituted or unsubstituted alkyl groups;
A compound and / or a condensate thereof.
More preferably, in formula B3, R ^14b and R ^15b are independently of each other hydrogen.

Further preferred specific examples of the crosslinking agent in the curable resin composition of the present invention include compounds having the compound names shown in the following structural formulas or listed below and / or condensates thereof:

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.

The condensate is preferably a polymer of the compound shown above, more preferably a dimer, trimer or higher order polymer of the compound shown above. The cross-linking agent in the curable resin composition of the present invention may be a compound shown above and a condensate thereof, that is, a compound and a polymer of the compound (that is, a dimer, a trimer, or a higher compound). It may be a mixture of the following polymers). In another embodiment, the condensate may comprise at least one of a dimer, trimer, and higher order polymer of the compound. From another point of view, the cross-linking agent may have a weight average degree of polymerization of greater than 1 and greater than or equal to 3 for the compounds shown above, preferably greater than 1 and up to 1.8, and more Preferably, it may have a weight average degree of polymerization of 1.3 to 1.8, more preferably 1.5, but is not limited thereto. When the weight average polymerization degree in the condensate of the compound is 1, it means that the condensate is the compound itself. The weight average degree of polymerization is an arbitrary numerical value within the above range, and preferably 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1. 8, 1.9, 2, 3, 4 or larger, more preferably 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, Preferably it is 1.5.

The mass ratio of the chain polymer to the crosslinking agent in the curable resin composition of the present invention 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 further 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. As the acid catalyst, those conventionally used as polymerization catalysts can be appropriately selected and used. 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. Or a compound selected from the group consisting of thermal acid generators such as Sun-Aid SI-100L, SI-150L, SI-110L, SI-60L, and SI-80L (Sanshin Chemical Industry Co., Ltd.) Examples thereof include, but are not limited to, salts thereof and solvates thereof. Preferably, the acid catalyst is a compound selected from the group consisting of p-toluenesulfonic acid (PTS), dodecylbenzenesulfonic acid, and thermal acid generator Sun-Aid SI-100L (Sanshin Chemical Industry Co., Ltd.), or A salt, or a solvate thereof. More preferably, the acid catalyst is pyridinium-p-toluenesulfonic acid, p-toluenesulfonic acid, or a hydrate thereof.

When the curable resin composition of the present invention further contains an acid catalyst, the amount of the acid catalyst can be appropriately determined according to the mass ratio of the chain polymer to the crosslinking agent in the curable resin composition, but is preferably The mass ratio of the chain polymer, the crosslinking agent and the acid catalyst in the curable resin composition 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 to 1: 1: 0.08. Alternatively, when the curable resin composition of the present invention further includes an acid catalyst, the amount of the acid catalyst can be appropriately determined according to the mass ratio of the chain polymer and the crosslinking agent in the curable resin composition. , Preferably 0.5 wt., 0.45 wt.%, 0.4 wt.%, 0.35 wt.%, 0.3 wt.%, 0.25 wt. % By weight, 0.15% by weight, or 0.10% by weight, and more preferably 0.3% by weight or 0.25% by weight.

In the present invention, the curable resin composition can be diluted to an appropriate concentration with a solvent. That is, in the present invention, the curable resin composition further contains a solvent. Unless the boiling point is excessively low or high, a conventional aprotic solvent is used unless there is a problem in forming a uniform coating film by drying after the curable resin composition is applied to a substrate made of glass or the like. It can be selected and used as appropriate. For example, propylene glycol monomethyl ether is a suitable solvent, but is not limited thereto. Dilution with a solvent is for convenience of handling at the time of polymerization reaction of a monomer, application of a curable resin composition to which a crosslinking agent and a catalyst are added, and therefore there is no particular upper limit or lower limit in the degree of dilution.

In the present invention, in one embodiment, the composition is provided as a solution. Preferably, the solvent of the solution includes an alcohol. More preferably, the alcohol comprises a primary alcohol, preferably selected from the group consisting of ethanol, propanol, 1-butanol, 1-propanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol and dodecanol. Primary alcohols, more preferably primary alcohols selected from the group consisting of ethanol, propanol, 1-butanol, 1-propanol, and 1-dodecanol, most preferably ethanol. Preferably, the alcohol is present at 10% by weight or more based on the total amount of the solvent. Although it is not desired to be bound by theory, the storage stability is improved by alcohol.

The curable resin composition of the present invention can further 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 the 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 can be reduced or made uniform. Examples of the surfactant include anionic surfactants, chaotic surfactants, nonionic surfactants, amphoteric surfactants, and modified silicones. These may be used alone or in combination of two or more. Can be used.
The anionic surfactant is preferably polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate. Polyethanol such as monoethanolamine, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Oxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Alkyl ether phosphoric acid esters, polyoxyethylene sorbitan monostearate, and the like of polyethylene glycol monolaurate.
Examples of chaotic surfactants include alkyl quaternary ammonium salts and their ethylene oxide adducts.
Nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, and other ethers. Nonionic surfactant, polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene Ester type such as stearate, acetylene alcohol type nonionic surfactant such as 3,5-dimethyl-1-hexyn-3-ol, 2, 4, , 9-tetramethyl-5-decyne-4,7-diol, such as 3,6-dimethyl-4-octyne-3,6-diol.
Examples of amphoteric surfactants include alkylbetaines such as alkyldimethylaminoacetic acid betaines, alkylimidazolines, and the like.
Examples of the modified silicone include polyether-modified polysiloxane, carboxy-modified polysiloxane, epoxy-modified polysiloxane, and amino-modified polysiloxane.

When the filler is included, for example, the hardness and moisture resistance of the cured resin film can be improved, and electrical insulation or electrical conductivity can be imparted or improved. Examples of fillers that can impart or improve electrical insulation include metal oxides such as alumina, silicon oxide, beryllium oxide, copper oxide, and cuprous oxide, and metal nitrides such as boron nitride, aluminum nitride, and silicon nitride. Examples thereof include metal carbides such as silicon carbide, metal carbonates such as magnesium carbonate, insulating carbon materials such as diamond, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and the like. Examples of the filler that can impart or improve electrical conductivity include carbon materials such as graphite and carbon fiber, and metal materials such as metal silicon, aluminum, and magnesium. A filler capable of imparting or improving electrical insulation or electrical conductivity can be included in the cured resin film for the purpose of improving thermal conductivity. When adding a filler for the purpose of improving thermal conductivity, a filler that can impart or improve electrical insulation and a filler that can impart or improve electrical conductivity are combined. Also good. As for the shape of the filler, for example, particles, fine particles, nanoparticles, aggregated particles, wires, rods, needles, plates, irregular shapes, rugby balls, hexahedrons, large particles and fine particles are combined. Various shapes such as composite particles can be applied. These fillers may be natural products or synthesized. In the case of a natural product, there are no particular limitations on the production area and the like, which can be selected as appropriate. The purpose of including the filler is not particularly limited, and a filler capable of achieving this purpose can be selected for the purpose of improving characteristics and imparting functions. One type of filler may be included, or two or more types may be used.

When an additive is included, for example, the weather resistance of the cured resin film can be improved. Examples of the additive include an antioxidant and an ultraviolet absorber. The purpose of including the additive is not particularly limited, and a known additive capable of achieving this purpose can be selected for the purpose of improving characteristics and imparting functions. One type of additive may be included, or two or more types may be included.

In one embodiment, preferably, the curable resin composition of the present invention further includes a surfactant. In another embodiment, preferably, the curable resin composition of the present invention further includes a foaming agent. When a foaming agent is included, the cured resin film formed by curing the curable resin composition can be easily peeled off. As a preferable foaming agent, a compound that foams by decomposing at a melting temperature or higher, a combination of a compound that reacts with an acid and foams, and an acid can be used. Examples of the foaming agent that can be used in the present invention include azo compounds such as azodicarbonamide, barium azodicarboxylate, 2,2′-azobisisobutyronitrile, dimethyl 2,2′-azobis (2-methyl). Propionate), azo compounds such as 2,2′-azobis (N-butyl-2-methylpropionamide), nitroso compounds such as dinitrosopentamethylenetetramine and trinitrotrimethyltriamine, p, p′-oxybisbenzenesulfonyl Examples include hydrazide compounds such as hydrazide, sulfonyl semicarbazide compounds such as p, p′-oxybisbenzenesulfonyl semicarbazide, and toluenesulfonyl semicarbazide.
In the combination of an acid and a compound that reacts with an acid and an acid, the compound that reacts with an acid and foams may be, for example, an alkali metal carbonate or bicarbonate, for example, sodium, potassium, lithium or rubidium carbonate Or carbonate compounds, such as hydrogencarbonate, are mentioned, As an acid, the acid containing organic acid, acidic sodium phosphate, or potassium, and a mixture thereof are mentioned. Examples of the organic acid include citric acid, tartaric acid, succinic acid, fumaric acid, and a mixture thereof.

The curable resin composition of the present invention has the above “high-speed curability” and is heated at 150 ° C. or less, preferably 90 ° C., 100 ° C., 110 ° C., 120 ° C., 130 ° C., 140 ° C. or 150 ° C. Curing within a few minutes at temperature, preferably 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50 seconds, 1 minute or 2 minutes heating time, more preferably by heating at 150 ° C. for 1 minute The formed film has easy peelability.

The curable resin composition of the present invention has the above “storage stability”, and the curable resin composition formed as a solution can be used at a suitable temperature (for example, 20 ° C. or 50 ° C.) for a long time. (For example, 1 week, 2 weeks, 3 weeks, 4 weeks, 1 month, 2 months, 3 months, 4 months, 6 months, 9 months, 12 months, or 14 months, etc.) There is no visual turbidity or solidification of the solution, and there is no significant change in the properties of the solution (viscosity, NV, etc.) and the properties during film formation (peeling force, transmittance, etc.). Preferably, unless otherwise specified, the solution does not change after the normal test (stored at 20 ° C. for 9 months or 12 months) and the accelerated test (stored at 50 ° C. for 2 weeks) compared to before storage.

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

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

The cured resin film formed from the curable resin composition of the present invention is heat-resistant in the above-mentioned meaning of “heat resistance” and also has easy peelability 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, in a cured resin film formed by applying and heating a curable resin composition to a glass substrate, the peel force after pre-baking (for example, at 100 ° C. for 2 minutes) 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 “easy peeling heat resistance”. Specifically, in a cured resin film formed by applying and heating a curable resin composition to a glass substrate, the peeling force after pre-baking (for example, at 100 ° C. for 2 minutes) and additional heating (for example, 230 When compared with the peel strength after 1 hour at a temperature, the increase in peel strength before and after additional heating is about 500% or less, about 450% or less, about 400% or less, about 350% or less, about 300% or less, 250% or less, about 200% or less, about 150% or less, about 100% or less, or about 50% or less. The conditions for additional heating (heating temperature and heating time) can be appropriately changed according to the curable resin composition and the formed cured resin film. More specifically, in a cured resin film formed by applying and heating a curable resin composition to a glass substrate, the peeling force after pre-baking (for example, at 100 ° C. for 2 minutes) and additional heating (for example, When compared with the peel force after 1 hour at 230 ° C., the increase in peel 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 “sputter process resistance”. Specifically, a curable resin composition is applied on a substrate, heated and cured (for example, 150 ° C./15 minutes) to form a cured resin film, and then an overcoat material (OC material) is formed on the film. A photo-curable resist was applied, pre-baked (for example, 90 ° C./100 seconds), exposed (for example, 20 mW, 100 mJ), further post-baked (for example, 230 ° C./30 minutes), and an ITO sputtering process was performed. It means that the later cured resin film has easy peelability. 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 art. As an example of the ITO sputtering process, a cured resin film is installed in a sputtering apparatus, the inside of the apparatus is decompressed (for example, 0.5 Pa), and air is introduced into the apparatus (for example, 50 sccm). O ₂ is introduced (for example, 50 sccm), the inside of the apparatus is heated (for example, 90 ° C.), and sputtering (for example, pressure: 0.67 Pa, DC power: 110 W) is performed. The above conditions for pre-baking, exposure, and post-baking are examples, and the cured resin film is used. Known processes in certain fields can be applied.

The curable resin composition of the present invention typically contains a chain polymer, a crosslinking agent, and, if necessary, an acid catalyst, a surfactant, a filler, an additive, and a foaming agent, and these are dissolved in a solvent. The obtained solution is applied onto a glass substrate (preferably soda lime glass), and cured by heat treatment (100 ° C. to 230 ° C., 1 minute or longer), whereby a film thickness of several hundred nm (preferably about 200 nm to An easily peelable cured resin film having a thickness of about 300 nm can be formed as a transparent thin film. Although not wishing to be bound by theory, the mechanism is that the side chain hydroxy group of the chain polymer and the crosslinking agent are easily peeled off due to curing shrinkage when crosslinked by heating.

As a method of applying to the glass substrate, a known coating method can be used. Examples thereof 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.

Thus, the thin film formed on the substrate can withstand heating up to 150 ° C., preferably withstand heating (firing) at 230 ° C., and more preferably withstand heating (firing) at 300 ° C. In addition, the thin film formed from the curable resin composition of the present invention has easy peelability even after heating at such a temperature. Since it can be subjected to a circuit manufacturing process including a firing step, it is advantageous for maintaining the characteristics of the circuit and can be easily and easily peeled off from the substrate even after the circuit is manufactured. For this reason, as a base film having excellent characteristics, it can be widely used for the production of various sheet-like flexible electric / electronic circuit components. For example, it can also be used for the production of flexible display devices.

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

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

The peeling 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, a cross-linking agent, and, if necessary, an acid catalyst is further dissolved in a solvent, on a glass substrate (preferably soda lime glass). And cured by heat treatment (100 ° C. to 230 ° C., 1 minute or longer) to produce a cured resin film on the glass substrate. For example, TENSILON RTG-1310 (A & D Co., Ltd.) is used as the measuring device, and UR-100ND type is used as the load cell. Nichiban tape (24 mm width) is affixed to the cured resin film on the glass substrate, and the magnitude of the force (peeling force) required for peeling while pulling at a constant speed of 300 mm / min at a peeling angle of 90 ° with respect to the glass substrate is described above. Measure with the instrument.

The cured resin film of the present invention preferably has a peeling force on a soda glass substrate or a non-alkali glass substrate of 0.5 N / mm ² or less. The cured resin film of the present invention more preferably has a peeling force on a soda glass substrate or an alkali-free glass substrate of 0.1 N / mm ² or less. The cured resin film of the present invention more preferably has a peel strength on a soda glass substrate or a non-alkali glass substrate of 0.09 N / mm ² or less. Preferred values of peel strength in the substrate made of soda glass, 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 hereinafter, 0.03 N / mm ² or less, 0.02 N / mm ² or less, 0.01 N / mm ² or less. Preferred values of peel strength in the substrate made of alkali-free glass, 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 below, 0.03 N / mm ² or less, 0.02 N / mm ² or less, 0.01 N / mm ² or less. When the peel force on the soda glass substrate or non-alkali glass substrate is 0.5 N / mm ² or less when the peel force on the soda glass substrate or non-alkali glass substrate is 0.5 N / mm ² or less, the cured resin film is It can be regarded as easily peelable.

The film thickness of the cured resin film of the present invention is, for example, a part of the cured resin film of the present invention applied on the glass substrate is scraped with a knife or razor to expose the glass substrate, and the cured resin remaining from the surface of the glass substrate. It can be measured by measuring the height to the surface of the resin film with a measuring device. As the 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. By using V-660 (JASCO Corporation) as a measuring device and measuring the light transmittance of light having a wavelength of 400 to 700 nm with respect to the glass substrate coated with the cured resin film of the present invention, transmittance (% T) Get. The transmittance of the cured resin film of the present invention shows the whiteness / smoothness of the film, and is preferably 95% or more, and more preferably 99% or more. Furthermore, L *, a *, and b * values in the CIELAB space can be measured as optical characteristics of the cured resin film of the present invention. In the cured resin film of the present invention, b * represents the yellowness of the film, and is preferably 0.2 or less, more preferably 0.1 or less.

The liquid viscosity of the curable resin composition prepared as 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 Keiki 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, 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 provides a method for producing a cured resin film from the curable resin composition according to (2-1),
(I) providing a chain polymer with a side chain having an alcoholic secondary or tertiary OH-containing group or 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 to form a curable resin composition coating film;
(Iii) performing a polymerization reaction in the curable resin composition coating film and curing it to form a cured resin film,
A manufacturing method is provided.

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

The above production method is carried out by the methods described in the following examples and / or similar methods known to those skilled in the art.

In one embodiment, the production method further includes (i ′) polymerizing at least one raw material monomer to produce the chain polymer before step (i).

Examples of the method for polymerizing the monomer include a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, and the like, but the present invention is not limited to such 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, a polycondensation method, or the like.

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

When the monomer is polymerized, a chain transfer agent may be used to adjust the molecular weight. The chain transfer agent can be used usually by mixing with a monomer. Examples of the chain transfer agent include 2- (dodecylthiocarbonothioylthio) -2-methylpropionic acid, 2- (dodecylthiocarbonothioylthio) propionic acid, methyl 2- (dodecylthiocarbonothioylthio)- 2-methylpropionate, 2- (dodecylthiocarbonothioylthio) -2-methylpropionic acid 3-azido-1-propanol ester, 2- (dodecylthiocarbonothioylthio) -2-methylpropionic acid pentafluoro Examples include mercaptan group-containing compounds such as phenyl ester, lauryl mercaptan, dodecyl mercaptan, and thioglycerol, and inorganic salts such as sodium hypophosphite and sodium bisulfite, but the present invention is not limited to such examples. Absent. These chain transfer agents may be used alone or in combination of two or more. The amount of the chain transfer agent is not particularly limited, but is usually about 0.01 to about 10 parts by weight per 100 parts by weight of the total monomers.

When the monomer is polymerized, it is preferable to use a polymerization initiator. Examples of the polymerization initiator include a thermal polymerization initiator, a photopolymerization initiator, a redox polymerization initiator, an ATRP (atom transfer radical polymerization) initiator, an ICAR ATRP initiator, an ARGET ATRP initiator, and a RAFT (reversible addition-cleavage). Chain transfer polymerization) agent, NMP (polymerization via nitroxide) agent, polymer polymerization initiator and the like. These polymerization initiators may be used alone or in combination of two or more.

Examples of thermal polymerization initiators include azo polymerization initiators such as azoisobutyronitrile, methyl azoisobutyrate, and azobisdimethylvaleronitrile, and peroxide polymerization initiations such as benzoyl peroxide, potassium persulfate, and ammonium persulfate. Although an agent etc. are mentioned, this invention is not limited only to this illustration. 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 preferably about 0.01 parts by weight to about 20 parts by weight per 100 parts by weight of all monomers.

Examples of the photopolymerization initiator include 2-oxoglutaric acid, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl [4- (methylthio) phenyl]- 2-morpholinopropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-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-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide However, the present invention is not limited to such 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 preferably about 0.01 parts by weight to about 20 parts by weight per 100 parts by weight of all monomers.

Other polymerization initiators that can be used in the present invention include, for example, redox polymerization initiators such as hydrogen peroxide and iron (II) salts, persulfates and sodium hydrogen sulfite, and ATRP using an alkyl halide under a metal catalyst. (Atom transfer radical polymerization) initiator, ICAR ATRP initiator or ARGET ATRP initiator using metal and nitrogen-containing ligand, RAFT (reversible addition-cleavage chain transfer polymerization) agent, NMP (polymerization via nitroxide) agent And polymer polymerization initiators such as polydimethylsiloxane unit-containing polymer azo polymerization initiator and polyethylene glycol unit-containing polymer azo polymerization initiator, but the present invention is not limited to such examples. . These polymerization initiators may be used alone or in combination of two or more.

When the usable polymerization initiator is used as the polymerization initiator, the amount of the polymerization initiator is preferably about 0.01 parts by weight to about 20 parts by weight per 100 parts by weight of the total monomers.

In one embodiment, electron beam polymerization is performed by irradiating the monomer with an electron beam.

There are no particular limitations on the polymerization reaction temperature and atmosphere when the monomer is polymerized. Usually, 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, for example. In addition, the polymerization reaction time of the monomer varies depending on the polymerization reaction temperature and the like and cannot be determined unconditionally, but is usually about 3 to 20 hours.

In one embodiment, the substrate in step (ii) in the production method is preferably a glass substrate, more preferably soda glass (also referred to as soda lime glass) or alkali-free glass (for example, EAGLE- XG, Corning), and more preferably soda glass.

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

In another embodiment, preferably, in step (ii) of the above production method, the composition further comprises an acid catalyst. Although not wishing to be bound by theory, the curable resin composition coating film contains an acid catalyst, so that the acid catalyst functions as a polymerization catalyst in the polymerization reaction in step (iii) and promotes the reaction. Because you can. Therefore, in another embodiment, step (i) in the above production method further includes the step of providing an acid catalyst.

In another embodiment, step (iii) in the production method further includes a step of heat-treating the curable resin composition coating film. The temperature of the heat treatment 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. However, it is not limited to these. Particularly preferred heat treatment time is 10 minutes to 2 hours.

The cured resin film produced by the above production 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] Applications The curable resin composition or cured resin film of the present invention is used for synthetic resins, pellets, films, plates, fibers, tubes, rubber, elastomers, etc., and is used for two-wheeled vehicles (bicycles, motorcycles, etc.), automobiles, airplanes. , Train, ship, rocket, spacecraft, transportation, leisure, furniture (eg, table, chair, desk, shelf, etc.), bedding (eg, bed, hammock, etc.), clothing, protective clothing, sports equipment, bathtub, kitchen, Tableware, cooking utensils, containers and packaging materials (food containers, cosmetic containers, freight containers, waste bins, etc.), architecture (buildings, roads, building parts, etc.), agricultural films, industrial films, water and sewage, paints, makeup Materials, electrical industry and electronics industry (electric appliances, computer parts, printed circuit boards, insulators, conductors, wiring coating materials, power generation elements, speakers, micros Phones, noise cancellers, transducers, etc.), optical communication cables, medical materials and instruments (catheters, guide wires, artificial blood vessels, artificial muscles, artificial organs, dialysis membranes, endoscopes, etc.), small pumps, actuators, robot materials (industrial) It can be applied to a wide range of fields such as sensors used for industrial robots), energy generators and plants (solar power generation, wind power generation, etc.).

The curable resin composition or cured resin film of the present invention can be used for electronic materials, medical materials, healthcare 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 for, for example, a catheter, a guide wire, a pharmaceutical container, a tube and the like.

The curable resin composition or cured resin film of the present invention is used for automobile parts (body panels, bumper bands, rocker panels, side moldings, engine parts, drive parts, conductive parts, steering device parts, stabilizer parts, suspension / brake device parts. Brake parts, shaft parts, pipes, tanks, wheels, seats, seat belts, etc.). The polymer of the present invention can be used for an anti-vibration material for automobiles, paints for automobiles, synthetic resins for automobiles, and the like.

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

Display devices such as liquid crystal display devices are widely used in ticket machines, ATMs, portable terminals such as smartphones, computers, and other various electric and electronic devices. The screens of these display devices are generally rigid flat plates. On the other hand, a flexible display device having a screen that can be deformed to some extent has been developed to reflect the expansion of potential uses of the display device. As a substrate constituting a circuit that can be bent, there is a resin base film. However, when it is used in a screen of a display device, it is required to be able to produce a fine circuit and be transparent and as thin and light as possible.

In the production of various fine electric and electronic circuits on a resin base film, for example, a photolithography method is used to form a metal film on the base film, coating a photoresist film, pre-baking, circuit pattern exposure, resist Processes such as development by development, rinsing, baking, etching, and photoresist removal are combined according to the purpose and method, and repeated to produce a circuit. Further, an anisotropic conductive film (ACF) is disposed between and on the layers thus produced, if necessary, and a printed wiring board is disposed on a necessary portion thereon, and is heated and pressurized. Thus, the circuit connection between the printed wiring board and the metal wiring is made through the anisotropic conductive film. In order to produce the entire circuit as a laminated body in this manner, generally, several firing steps are included. For circuit performance, firing is desirably performed at a sufficiently high temperature (around 230 ° C.), but the upper limit of the firing temperature is limited by the heat resistance level of the base film. In other words, the baking in each step cannot be performed unless the region is on the low-temperature side below the limit that the base film can withstand. Although it is possible to use other materials (silver nanoparticles, etc.) as the metal wiring that can be fired in such a low temperature region, the wiring produced by low-temperature firing using them is a conventional one using ITO. Since the characteristics are inferior to those of the wiring, it is not technically preferable.

Moreover, although the base film is required to be thinner year by year, the heat resistance of the base film decreases as the thickness is reduced. As a result, the upper limit of the heat treatment temperature is currently reduced to about 100 ° C, and the circuit performance is maintained assuming that the upper limit of the temperature that can withstand the heat treatment of the base film is further lowered due to further thinning demand in the future. There is a problem that there is no base film material that can be fired at a possible temperature.

Therefore, there is a demand for a base film material that can withstand higher temperatures.

Furthermore, since the base film is very thin as described above, the resin material for forming the base film is very thin and uniform without being bounced to the substrate when applied to the substrate (glass substrate, etc.). It must be of a nature that allows it to spread (eg, has wettability). On the other hand, such an affinity for the substrate is one of the factors that can cause easy adhesion to the substrate in the firing step, and thus can easily lose the peelability.

In the present invention, a curable resin thin film can be formed by applying an extremely thin curable resin composition to the surface of a substrate (glass, etc.) and cured by heating, and a circuit is formed thereon by patterning or the like. By providing a curable resin composition and a cured resin film that can withstand high temperatures of 230 ° C. to 300 ° C. in firing and can be easily and easily peeled off from a substrate even after being exposed to such high temperatures, It can be applied to a wide range of fields such as those listed above.

References such as scientific literature, patents, and patent applications cited in this specification are incorporated herein by reference in their entirety to the same extent as if they were specifically described.

As described above, the present invention has been described by showing preferred embodiments for easy understanding. Hereinafter, the present invention will be described based on examples. However, the above description and the following examples are provided for illustrative purposes only and are not provided for the purpose of limiting the present invention. Accordingly, the scope of the invention is not limited to the embodiments or examples specifically described herein, but is limited only by the claims.

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

<Method and Material>
The methods and materials used in the examples, test examples and comparative examples were as follows unless otherwise specified.
<Gel permeation chromatography>
A mixture containing the polymer was diluted with tetrahydrofuran so that the solid content of the mixture was 0.1% by mass to prepare a sample, and a gel permeation chromatography column (TSK GEL 5000HXL, TSK GEL A total of 3000 HXL (manufactured by Tosoh Corporation; trade name) were injected in this order in series (5000 HXL upstream)). Next, the eluent containing the polymer is extracted by pouring tetrahydrofuran as an eluent at 1 ml / min into the gel permeation chromatography column into which the diluent has been injected. The molecular weight was measured.
<Crosslinking agent>
MW-30: Hexamethoxymethylmelamine, trade name Nicarak MW-30, Sanwa Chemical Co., Ltd. MX-270: 1,3,4,6-tetrakis (methoxymethyl) glycoluril, trade name Nicalac MW-270, ( Sanwa Chemical Co., Ltd. BX-4500: Tetramethoxymethyl benzoguanamine, trade name Nicalac BX-4500, Sanwa Chemical Co., Ltd. <acid catalyst> pyridinium p-toluenesulfonate, Tokyo Chemical Industry Co., Ltd. <solvent> propylene glycol monomethyl Ether (PGME) / ethanol = 90/10

<Polymer>
The polymer forming the constituent elements of the curable resin composition was produced as described in the following production examples.

[Production Example 1] Production of polymer A-1 The following formula (1-1):

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

Got. When the weight average molecular weight (MW) of this polymer was measured by gel permeation chromatography, it was 25,000.

[Production Example 2] Production of polymer A-2 The following formula (1-2):

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

Got. When the weight average molecular weight (MW) of this polymer was measured by gel permeation chromatography, it was 22,000.

[Production Example 3] Production of polymer A-3 The following formula (1-3):

Polymer A-3 was prepared in the same manner as in Production Example 1 except that 4-benzoyloxy-3-hydroxycyclohexylmethyl methacrylate was used as a monomer.

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

[Production Example 4] Production of polymer A-4 The following formula (1-4):

A polymer A-4 was prepared in the same manner as in Example 1 except that 1,3-adamantyldiol monomethacrylate was used as a monomer.

Got. When the weight average molecular weight (MW) of this polymer was measured by gel permeation chromatography, it was 18,000.

[Production Example 5] Production of polymer A-5 The following formula (1-5):

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

Got. When the weight average molecular weight (MW) of this polymer was measured by gel permeation chromatography, it was 36,000.

[Production Example 6] Production of polymer A-6 The following formula (1-6):

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

Got. When the weight average molecular weight (MW) of this polymer was measured by gel permeation chromatography, it was 33,000.

[Production Example 7] Production of polymer A-7 The following formula (1-7):

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

Got. When the weight average molecular weight (MW) of this polymer was measured by gel permeation chromatography, it was 30,000.

[Production Example 8] Production of polymer A-8 The following formula (1-8):

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

Got. When the weight average molecular weight (MW) of this polymer was measured by gel permeation chromatography, it was 27,700.

[Production Example 9] Production of polymer A-9 The following formula (1-9):

Polymer A-9 was prepared in the same manner as in Production Example 1 except that 4-adamantanecarboxycarboxy-3-hydroxycyclohexylmethyl methacrylate was used as a monomer.

Got. When the weight average molecular weight (MW) of this polymer was measured by gel permeation chromatography, it was 31,700.

[Production Example 10] Production of polymer A-10 The following formula (1-10):

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

Got. When the weight average molecular weight (MW) of this polymer was measured by gel permeation chromatography, it was 42,000.

[Production Example 11] Production of polymer A-11 The following formula (1-11):

Polymer A-11 was prepared in the same manner as in Production Example 1 except that 4- (hydroxymethyl) cyclohexylmethyl acrylate was used as a monomer.

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

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

50 parts by mass of hexamethoxymethylmelamine (Nicarac MW-30, Sanwa Chemical Co., Ltd.) and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst, propylene glycol monomethyl ether (PGME) / ethanol = 90 The composition was obtained as a solution (NV = 5%).

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

50 parts by mass of 1,3,4,6-tetrakis (methoxymethyl) glycoluril (Nicarac MX-270, Sanwa Chemical Co., Ltd.) and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst, It was dissolved in a solution of propylene glycol monomethyl ether (PGME) / ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

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

Of tetramethoxymethyl benzoguanamine (Nicarac BX-4500, Sanwa Chemical Co., Ltd.) and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst, propylene glycol monomethyl ether (PGME) / ethanol = 90 The composition was obtained as a solution (NV = 5%).

[Example 4]
45 parts by mass of the polymer A-2, 50 parts by mass of the cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether ( It was dissolved in a solution of (PGME) / ethanol = 90/10 to obtain a 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 pyridinium p-toluenesulfonate as a polymerization catalyst 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 the polymer A-2, 50 parts by mass of the cross-linking agent tetramethoxymethylbenzoguanamine (formula (B-3)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether ( It was dissolved in a solution of (PGME) / ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

[Example 7]
45 parts by mass of polymer A-3, 50 parts by mass of the cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether ( It was dissolved in a solution of (PGME) / ethanol = 90/10 to obtain a 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 pyridinium p-toluenesulfonate as a polymerization catalyst 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 the cross-linking agent tetramethoxymethylbenzoguanamine (formula (B-3)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether ( It was dissolved in a solution of (PGME) / ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

[Example 10]
45 parts by mass of polymer A-4, 50 parts by mass of the cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether ( It was dissolved in a solution of (PGME) / ethanol = 90/10 to obtain a 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 pyridinium p-toluenesulfonate as a polymerization catalyst 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 the cross-linking agent tetramethoxymethylbenzoguanamine (formula (B-3)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether ( It was dissolved in a solution of (PGME) / ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

[Example 13]
45 parts by mass of polymer A-5, 50 parts by mass of the cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether ( It was dissolved in a solution of (PGME) / ethanol = 90/10 to obtain a 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 pyridinium p-toluenesulfonate as a polymerization catalyst 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 the cross-linking agent tetramethoxymethylbenzoguanamine (formula (B-3)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether ( It was dissolved in a solution of (PGME) / ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

[Example 16]
45 parts by mass of polymer A-6, 50 parts by mass of the cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether ( It was dissolved in a solution of (PGME) / ethanol = 90/10 to obtain a 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 pyridinium p-toluenesulfonate as a polymerization catalyst 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 the cross-linking agent tetramethoxymethylbenzoguanamine (formula (B-3)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether ( It was dissolved in a solution of (PGME) / ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

[Example 19]
45 parts by mass of polymer A-7, 50 parts by mass of the cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether ( It was dissolved in a solution of (PGME) / ethanol = 90/10 to obtain a 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 pyridinium p-toluenesulfonate as a polymerization catalyst 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 the cross-linking agent tetramethoxymethylbenzoguanamine (formula (B-3)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether ( It was dissolved in a solution of (PGME) / ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

[Example 22]
45 parts by mass of polymer A-8, 50 parts by mass of the cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether ( It was dissolved in a solution of (PGME) / ethanol = 90/10 to obtain a 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 pyridinium p-toluenesulfonate as a polymerization catalyst 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 the cross-linking agent tetramethoxymethylbenzoguanamine (formula (B-3)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether ( It was dissolved in a solution of (PGME) / ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

[Example 25]
45 parts by mass of polymer A-9, 50 parts by mass of the cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether ( It was dissolved in a solution of (PGME) / ethanol = 90/10 to obtain a 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 pyridinium p-toluenesulfonate as a polymerization catalyst 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 the cross-linking agent tetramethoxymethylbenzoguanamine (formula (B-3)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether ( It was dissolved in a solution of (PGME) / ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

[Example 28]
30 parts by mass of the polymer A-1, 65 parts by mass of the cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether ( It was dissolved in a solution of (PGME) / ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

[Example 29]
70 parts by mass of the polymer A-1, 25 parts by mass of the cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether ( It was dissolved in a solution of (PGME) / ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

[Example 30]
30 parts by mass of polymer A-1, 65 parts by mass of crosslinking agent 1,3,4,6-tetrakis (methoxymethyl) glycoluril (formula (B-2)), and pyridinium p-toluenesulfonate as a polymerization catalyst 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 pyridinium p-toluenesulfonate as a polymerization catalyst 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]
30 parts by mass of polymer A-2, 65 parts by mass of the cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether ( It was dissolved in a solution of (PGME) / ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

[Example 33]
70 parts by mass of polymer A-2, 25 parts by mass of the cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether ( It was dissolved in a solution of (PGME) / ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

[Example 34]
30 parts by mass of polymer A-2, 65 parts by mass of crosslinking agent 1,3,4,6-tetrakis (methoxymethyl) glycoluril (formula (B-2)), and pyridinium p-toluenesulfonate as a polymerization catalyst 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 pyridinium p-toluenesulfonate as a polymerization catalyst 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 the cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether ( It was dissolved in a solution of (PGME) / ethanol = 90/10 to obtain a 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 pyridinium p-toluenesulfonate as a polymerization catalyst 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 the cross-linking agent tetramethoxymethylbenzoguanamine (formula (B-3)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether ( It was dissolved in a solution of (PGME) / ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

[Comparative Example 4]
45 parts by mass of polymer A-11, 50 parts by mass of the cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether ( It was dissolved in a solution of (PGME) / ethanol = 90/10 to obtain a 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 pyridinium p-toluenesulfonate as a polymerization catalyst 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 the cross-linking agent tetramethoxymethylbenzoguanamine (formula (B-3)), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether ( It was dissolved in a solution of (PGME) / ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

[Comparative Example 7]
45 parts by mass of polymer A-1, 50 parts by mass of cross-linking agent toluene diisocyanate (TDI, Mitsui Chemicals), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether ( It was dissolved in a solution of (PGME) / ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

[Comparative Example 8]
45 parts by mass of polymer A-1, 50 parts by mass of cross-linking agent isophorone diisocyanate (IPDI, Mitsui Chemicals), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether (PGME). ) / Ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

[Comparative Example 9]
45 parts by mass of polymer A-1, 50 parts by mass of cross-linking agent hexamethylene diisocyanate (HDI, Mitsui Chemicals), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether ( It was dissolved in a solution of (PGME) / ethanol = 90/10 to obtain a 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 (isocyanatemethyl) benzene (Takenate 500, Mitsui Chemicals), and 5 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst A part was dissolved in a solution of propylene glycol monomethyl ether (PGME) / ethanol = 90/10 to obtain a composition as a solution (NV = 5%).

[Measurement Example 1] Evaluation of Peeling Force and Transmittance After the compositions of the above Examples and Comparative Examples were each applied by spin coating on 0.7 mm soda glass and heated at 100 ° C. for 2 minutes. The film was heated at 150 ° C. for 5 minutes, and heat-treated at 230 ° C. for 2 hours, 230 ° C. for 8 hours, 260 ° C. for 2 hours, or 300 ° C. for 30 minutes to form a film having a thickness of about 300 nm. Alternatively, the compositions of the above Examples and Comparative Examples were each applied by spin coating on 0.7 mm soda glass and heated at 100 ° C. for 30 seconds to form a film thickness of about 300 nm. And about the cured resin thin film produced on the glass substrate in each, the transmittance | permeability ((lambda) = 400nm) and the peeling force and the transmittance | permeability which evaluated about the magnitude | size (peeling force) required to peel them from a glass substrate The measurement method is shown below, and the measurement results of peel strength and transmittance are shown in Tables 1 to 3.

Peeling force (N / mm ² ): TENSILON RTG-1310 (A & D Co., Ltd.) as a measuring device and UR-100N-D type as a load cell. Measurement is performed on a cured resin thin film on a glass substrate by Nichiban A tape (24 mm width) was affixed, and the magnitude of the force required for peeling (peeling force) was measured with the above apparatus while pulling at a constant speed of 300 mm / min at a peeling angle of 90 ° with respect to the glass substrate. In each example and each comparative example, the transmittance was not measured for those not peeled off from the glass substrate.

Transmittance (%): V-660 (JASCO Corporation) was used as a measuring device, and the light transmittance of 400 to 700 nm wavelength light with respect to an equivalent glass substrate was measured.

Table 1 to Table 3 show the following.

The curable resin films containing chain polymers having side chains having alcoholic secondary or tertiary OH-containing groups or phenolic OH-containing groups shown in Examples 1 to 35 are shown in Comparative Examples 1 to 6. Compared to a curable resin film that does not contain a chain polymer with a side chain having an alcoholic secondary or tertiary OH-containing group or phenolic OH-containing group, it has high peel resistance and high-speed curability. I understand.

In Examples 1 to 35 in which the crosslinking agent is selected from the group consisting of triazine compounds and / or condensates thereof, and glycoluril compounds and / or condensates thereof, isocyanate was used as the crosslinking agent. Compared with Comparative Examples 7 to 10, it can be seen that the heat resistance to easy peeling is high. In particular, when Examples 1 to 3 and Comparative Examples 7 to 10 containing the same chain polymer and different crosslinking agents are compared, the crosslinking agent is a triazine compound and / or a condensate thereof, and a glycoluril compound and / or It can be seen that those selected from the group consisting of the condensates have high easy-to-peel heat resistance and high-speed curability.

As described above, the present invention has been exemplified by using the preferred embodiments of the present invention, but it is understood that the scope of the present invention should be interpreted only by the scope of the claims. Patents, patent applications, and other references cited herein should be incorporated by reference in their entirety, as if the contents themselves were specifically described herein. It is understood.

The present invention can be applied to a substrate such as glass very thinly, and can be formed into a very thin cured resin thin film by drying and curing after coating. As a curable resin composition that has durability at a high temperature of 300 ° C. and can be easily peeled off from a substrate even after being exposed to such a high temperature, it is useful for the production of film-type electrical / electronic circuit components. is there.

Claims

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 represented by the formula A1:

[Wherein 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 independently selected from the group consisting of hydrogen and substituted or unsubstituted hydrocarbon groups, provided that at least one of R 2a , R 3a , and R 4a is A substituted or unsubstituted alcoholic secondary or tertiary OH-containing group or phenolic OH-containing group, or at least two of R 2a , R 3a , and R 4a taken together to form an alcohol A substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted heteroaromatic group, which contains a secondary or tertiary OH or phenolic OH, Or the polycycle containing these is formed. ]
Comprising a monomer unit represented by
(B) The crosslinking agent is selected from the group consisting of triazine compounds and / or condensates thereof, glycoluril compounds and / or condensates thereof, and imidazolidinone compounds and / or condensates thereof. ,
Curable resin composition.
The chain polymer is represented by the formula A2:

[Wherein R 1a and L 1 are as defined in claim 1;
R 5a to R 14a are independently of each other hydrogen, a hydroxy group, and

Selected from the group consisting of or together 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 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 Selected from the group consisting of ]
The curable resin composition of Claim 1 which comprises the monomer unit shown by these.
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 chain polymer is represented by formula A5:

[Wherein R 1a and L 1 are as defined 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. ]
The curable resin composition according to any one of claims 1 to 5, which comprises a monomer unit represented by:
The curable resin composition according to claim 6, wherein L 1 is a substituted or unsubstituted alkylene group.
L 1 is a methylene group, according to claim 6 or 7 curable resin composition.
The curable resin composition according to any one of claims 6 to 8, wherein R 19a is a phenyl group.
10. The curable resin composition according to claim 1, wherein the crosslinking agent is a triazine compound and / or a condensate thereof.
The cross-linking agent

The curable resin composition according to any one of claims 1 to 10, wherein
L 1 is a single bond, The curable resin composition of Claim 1 or 2.
The curable resin composition according to any one of claims 2 to 5 or 12, wherein any two or more of R 5a to R 14a are hydroxy groups and the other is hydrogen.
13. The curable resin composition according to claim 2, wherein any one of R 5a to R 14a is a hydroxy group and the other is hydrogen.
The curable resin composition according to claim 2, 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 compound and / or a condensate thereof.
The cross-linking agent

The curable resin composition according to claim 1 to 9 or 12 to 15.
The cross-linking agent

The curable resin composition according to claim 1 to 10 or 12 to 15.
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 comprises a primary alcohol.
The curable resin composition according to 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 based on the total amount of the solvent.
The cross-linking agent is a fully or partially alkoxymethylated melamine and / or its condensate, a fully or partially alkoxymethylated guanamine and / or its condensate, a complete or partially alkoxymethylated acetoguanamine and / or its condensate, fully or One selected from the group consisting of partially alkoxymethylated benzoguanamine and / or its condensate, fully or partially alkoxymethylated glycoluril and / or its condensate, and fully or partially alkoxymethylated imidazolidinone and / or its condensate The curable resin composition according to any one of claims 1 to 23.
The crosslinking agent is of formula B1:

[Wherein 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

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. ]
And / or a condensate thereof,
Formula B2:

[R 8b to R 11b are independently selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group having 1 to 10 carbon atoms. ]
And / or a condensate thereof, and Formula B3:

[Wherein R 12b and R 13b are independently selected from the group consisting of 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted alkenyl group;
R 14b and R 15b are independently of each other hydrogen or selected from the group consisting of substituted or unsubstituted alkyl groups and substituted or unsubstituted alkenyl groups having 1 to 10 carbon atoms. ]
The curable resin composition according to any one of claims 1 to 24, which is selected from the group consisting of a compound represented by the formula (1) and / or a condensate thereof.
The curable resin composition according to any one of claims 1 to 25, wherein the condensate comprises a polymer of the compound represented by formula B1, formula B2, or formula B3.
The condensate comprises at least one of a dimer, trimer, and higher order polymer of the compound represented by formula B1, formula B2, or formula B3. Curable resin composition.
The crosslinking agent according to any one of claims 1 to 27, wherein the crosslinking agent has a weight average degree of polymerization of 1.3 to 1.8 for the compound represented by formula B1, formula B2, or formula B3, respectively. Curable resin composition.
R 1b is a substituted or unsubstituted aromatic group, and

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 25 to 28.
The curable resin composition according to any one of claims 1 to 29, wherein a ratio of a mass of the linear polymer to a 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.
32. 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 claim 1, further comprising a foaming agent.
The curable resin composition according to any one of claims 1 to 35, which has a 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 according to claim 37, wherein the cured resin film has a transmittance (% T) of 99% or more at 400 nm and a b * of 0.1 or less.
The cured resin film according to claim 37, having heat resistance of 230 ° C to 300 ° C.
40. The cured resin film according to claim 39, which has heat resistance at 230 ° C. to 260 ° C. for 1 to 2 hours.
The cured resin film according to claim 39, which has heat resistance at 230 ° C for 8 hours or more.
The cured resin film according to claim 39, which has 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 on the surface of a substrate.
The cured resin film according to any one of claims 37 to 43, which has a peeling force on a soda glass substrate or a non-alkali glass substrate of 0.5 N / mm 2 or less.
The cured resin film according to any one of claims 37 to 44, which has a peeling force on a soda glass substrate or a non-alkali glass substrate of 0.1 N / mm 2 or less.
A method for producing a cured resin film from the curable resin composition according to any one of claims 1 to 36, comprising:
(I) providing the chain polymer with a side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group and the crosslinking agent;
(Ii) applying the curable resin composition containing the chain polymer and the crosslinking agent on a substrate to form a curable resin composition coating film;
(Iii) performing a polymerization reaction in the curable resin composition coating film and curing it to form a cured resin film,
Production method.
(Iv) The manufacturing method according to claim 46, further comprising a step of peeling the cured resin film formed on the substrate from the substrate.
The proportion of the monomer unit having an alcoholic secondary or tertiary OH-containing group or phenolic OH-containing group in the monomer unit constituting the chain polymer is 30 to 100 mol%. Production method.
The cross-linking agent consists of fully or partially alkoxymethylated melamine, fully or partially alkoxymethylated guanamine, fully or partially alkoxymethylated acetoguanamine, or fully or partially alkoxymethylated benzoguanamine, and fully or partially alkoxymethylated glycoluril. The production method according to any one of claims 46 to 48, which is selected from the group.
The production method according to any one of claims 46 to 49, wherein the ratio of the mass of the linear polymer to the mass of the crosslinking agent in the composition is 1: 2 to 1: 0.05.