WO2018034342A1

WO2018034342A1 - Curable resin composition for forming easily-peelable film, and method for producing same

Info

Publication number: WO2018034342A1
Application number: PCT/JP2017/029635
Authority: WO
Inventors: 幸樹椿; 恵百本; 茂樹阿波; 裕貴大浦
Original assignee: 大阪有機化学工業株式会社
Priority date: 2016-08-19
Filing date: 2017-08-18
Publication date: 2018-02-22
Also published as: TWI852902B; KR20190044062A; JP7008627B2; JPWO2018034342A1; KR102442826B1; TW201825531A

Abstract

Disclosed is a curable resin composition which can be applied to the surface of a glass substrate to form a cured resin thin film that can withstand firing at 230°C and can be easily peeled off from the substrate without difficulty. The composition is a curable resin composition comprising a crosslinking agent and a chain polymer having a side chain having an alcoholic secondary or tertiary hydroxy group, wherein (a) the side chain, which contains 3-30 carbon atoms, comprises at least one saturated or unsaturated hydrocarbon group or comprises the at least one saturated or unsaturated hydrocarbon group while further comprising at least one aromatic group, and may contain a bond which connects carbon atoms with each other, the bond being selected from the group consisting of -COO-, -O-, and -CO-, and (b) the crosslinking agent is selected from the group consisting of a triazine-based compound and/or a condensate thereof, a glycoluril-based compound and/or a condensate thereof, and an imidazolidinone-based compound and/or a condensate thereof.

Description

Curable resin composition for forming easily peelable 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 film, and in particular, it can be applied to a substrate such as glass and cured to form a thin film, and then from the substrate without difficulty. The present invention relates to a curable resin composition that provides a thin film that can be easily peeled, and more particularly, to a curable resin composition that provides a thin film that is not easily denatured even when subjected to a heat treatment and that maintains easy peelability.

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 than conventional ones.

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.

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 can be expanded. 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.

International Publication No. 2015/016532

In the above background, the present invention is a process in which a film can be formed by applying a very thin surface to a substrate (glass or the like), a cured resin thin film can be formed by curing, and a circuit is formed thereon by patterning or the like. An object of the present invention is to provide a curable resin composition that can withstand a high temperature of 230 ° C. in baking and can be easily and easily peeled off from a substrate even after being exposed to such a high temperature.

The present inventor has found that the above object can be achieved by a curable resin composition comprising a polymer having a side chain having a specific range of structural characteristics and a specific range of a crosslinking agent. That is, the present invention provides the following items.

Item A1. A curable resin composition comprising a chain polymer having a side chain having an alcoholic secondary or tertiary hydroxy group, and a crosslinking agent,
(A) the side chain comprises 3 to 30 carbon atoms and comprises at least one saturated or unsaturated hydrocarbon group or in addition to at least one more An aromatic group, and a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms,
(B) The crosslinking agent is selected from a triazine-based crosslinking agent or a glycoluril-based crosslinking agent.
Curable resin composition.
Item A2. The chain polymer is a monomer unit having the side chain having an alcoholic secondary or tertiary hydroxy group, and is a (meth) acrylic monomer, a vinyl ester monomer, a vinyl ether monomer, and others The curable resin composition according to the above item, comprising at least one of the vinyl monomers as a monomer unit.
Item A3. The chain polymer is CH ₂ ═CH—COO—R ¹ , CH ₂ ═C (CH ₃ ) —COO—R ² , CH ₂ ═CH—O—CO—R ³ , CH ₂ ═CH—O—R. ⁴ and CH ₂ ═CH—R ⁵ [wherein R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are independently of each other when each vinyl group is bonded via an ester bond] It has 3 to 30 carbon atoms including the carbon atom constituting the ester bond, has an alcoholic secondary or tertiary hydroxy group, and contains at least one saturated or unsaturated hydrocarbon group. Or further comprising at least one aromatic group and having a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms. . The curable resin composition according to any one of the above items, which comprises a monomer unit selected from the group consisting of compounds represented by:
Item A4. The chain polymer further has (meth) acrylic monomers, vinyl ester monomers, vinyl ether monomers, and other vinyl monomers having no hydroxy group and having 1 to 15 carbon atoms in the side chain. The curable resin composition according to any one of the above items, comprising at least one of these as an additional monomer unit.
Item A5. The additional monomer units are CH ₂ ═CH—COO—R ⁶ , CH ₂ ═C (CH ₃ ) —COO—R ⁷ , CH ₂ ═CH—O—CO—R ⁸ , wherein R ⁶ , R ⁷ and R ⁸ independently of one another have 1 to 15 carbon atoms, have no hydroxy group, comprise at least one saturated or unsaturated hydrocarbon group, or at least It comprises one aromatic group and can have a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms, and the hydrocarbon group or aromatic The group group can have an amino group. ], CH ₂ ═CH—O—R ⁹ , CH ₂ ═CH—R ^10, wherein R ⁹ and R ¹⁰ independently of one another have 3 to 15 carbon atoms and have a hydroxy group And at least one saturated or unsaturated hydrocarbon group, or further comprising at least one aromatic group and connecting between carbon atoms —COO—, —O—, and —CO -It may have a bond selected from the group consisting of-and the hydrocarbon group or aromatic group may have an amino group. ], C ₄ HO ₃ —R ¹¹ , and C ₄ H ₂ NO ₂ —R ¹² [where C ₄ HO ₃ — represents a maleic anhydride group, C ₄ H ₂ NO ₂ — represents a maleimide group, ¹¹ and R ¹² are each independently a hydrogen atom or have 1 to 15 carbon atoms, have no hydroxy group, and contain at least one saturated or unsaturated hydrocarbon group. Or further comprising at least one aromatic group and having a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms. The hydrocarbon group or aromatic group may have an amino group. ] The curable resin composition in any one of the said item which is chosen from the group which consists of a compound shown by these.
Item A6. The curable resin composition according to any one of the above items, wherein the proportion of the monomer unit having an alcoholic secondary or tertiary hydroxy group in the monomer unit constituting the chain polymer is 30 to 100 mol%.
Item A7. The cross-linking agent is a group consisting of fully or partially alkoxymethylated melamine, fully or partially alkoxymethylated guanamine, fully or partially alkoxymethylated acetoguanamine, fully or partially alkoxymethylated benzoguanamine, and fully or partially alkoxymethylated glycoluril. The curable resin composition according to any one of the above items, which is selected from the above.
Item A8. 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 A9. The curable resin composition according to any one of the above items, comprising a solvent.
Item A10. A cured resin film obtained by curing the curable resin composition of any of the above items.
Item A11. 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 A12. A method for producing a cured resin film, comprising:
Providing a chain polymer with a side chain having an alcoholic secondary or tertiary hydroxy group and a crosslinking agent;
Applying a composition containing the chain polymer and the crosslinking agent on a substrate to form a curable resin composition coating film;
And a step of forming a cured resin film by performing a polymerization reaction in the curable resin composition coating film and curing it,
(A) the side chain comprises 3 to 30 carbon atoms and comprises at least one saturated or unsaturated hydrocarbon group or in addition to at least one more An aromatic group, and a bond selected from the group consisting of —COO—, —O—, and —CO— that connect the carbon atoms of adjacent groups among them. ,
(B) The crosslinking agent is selected from a triazine-based crosslinking agent or a glycoluril-based crosslinking agent.
Production method.
Item A13. The chain polymer is a monomer unit having the side chain having an alcoholic secondary or tertiary hydroxy group, and is a (meth) acrylic monomer, a vinyl ester monomer, a vinyl ether monomer, and others The production method of the above item, comprising at least one of the vinyl monomers as a monomer unit.
Item A14. The chain polymer is CH ₂ ═CH—COO—R ¹ , CH ₂ ═C (CH ₃ ) —COO—R ² , CH ₂ ═CH—O—CO—R ³ , CH ₂ ═CH—O—R. ⁴ and CH ₂ ═CH—R ⁵ [wherein R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are independently of each other when each vinyl group is bonded via an ester bond] It has 3 to 30 carbon atoms including the carbon atom constituting the ester bond, has an alcoholic secondary or tertiary hydroxy group, and contains at least one saturated or unsaturated hydrocarbon group. Or further comprising at least one aromatic group and having a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms. . ] The manufacturing method in any one of the said item which is what comprises the monomer unit chosen from the group which consists of a compound shown by these.
Item A15. The chain polymer further has (meth) acrylic monomers, vinyl ester monomers, vinyl ether monomers, and other vinyl monomers having no hydroxy group and having 1 to 15 carbon atoms in the side chain. The production method according to any one of the above items, comprising at least one of any of these as an additional monomer unit.
Item A16. The additional monomer units are CH ₂ ═CH—COO—R ⁶ , CH ₂ ═C (CH ₃ ) —COO—R ⁷ , CH ₂ ═CH—O—CO—R ⁸ , wherein R ⁶ , R ⁷ and R ⁸ independently of one another have 1 to 15 carbon atoms, have no hydroxy group, comprise at least one saturated or unsaturated hydrocarbon group, or at least It may contain a bond selected from the group consisting of —COO—, —O—, and —CO—, which contains one aromatic group and connects carbon atoms. ], CH ₂ ═CH—O—R ⁹ , CH ₂ ═CH—R ^10, wherein R ⁹ and R ¹⁰ independently of one another have 3 to 15 carbon atoms and have a hydroxy group And at least one saturated or unsaturated hydrocarbon group, or further comprising at least one aromatic group and connecting between carbon atoms —COO—, —O—, and —CO A bond selected from the group consisting of: ], C ₄ HO ₃ —R ¹¹ , and C ₄ H ₂ NO ₂ —R ¹² [where C ₄ HO ₃ — represents a maleic anhydride group, C ₄ H ₂ NO ₂ — represents a maleimide group, ¹¹ and R ¹² are each independently a hydrogen atom or have 1 to 15 carbon atoms, have no hydroxy group, and contain at least one saturated or unsaturated hydrocarbon group. Or further comprising at least one aromatic group and having a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms. . ] The manufacturing method in any one of the said item which is selected from the group which consists of a compound shown by these.
Item A17. The method according to any one of the above items, wherein the proportion of the monomer unit having an alcoholic secondary or tertiary hydroxy group in the monomer unit constituting the chain polymer is 30 to 100 mol%.
Item A18. 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 A19. 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 A20. The production method of any of the above items, wherein the composition comprises a solvent.
Item A21. The method for producing a cured resin film according to any one of the above items, further comprising a step of peeling the cured resin film formed on the substrate from the substrate.

The present invention also provides the following items.
Item B1. A curable resin composition comprising a chain polymer having a side chain having an alcoholic secondary or tertiary hydroxy group, and a crosslinking agent,
(A) the side chain comprises 3 to 30 carbon atoms and comprises at least one saturated or unsaturated hydrocarbon group or in addition to at least one more An aromatic group, and a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms,
(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.
Item B2. The chain polymer is a monomer unit having the side chain having an alcoholic secondary or tertiary hydroxy group, and is an unsubstituted or α-substituted (meth) acrylic monomer, unsubstituted or α-substituted Curability of the above item comprising at least one of vinyl ester monomers, unsubstituted or α-substituted vinyl ether monomers, and other unsubstituted or α-substituted vinyl monomers as monomer units. Resin composition.
Item B3. The chain polymer is CH ₂ ═C (R ^1a ) —COO—R ¹ , CH ₂ ═C (R ^1a ) —O—CO—R ³ , CH ₂ ═C (R ^1a ) —O—R ⁴ , And CH ₂ ═C (R ^1a ) —R ⁵ [wherein R ¹ , R ³ , R ⁴ , and R ⁵ are independent of each other when each vinyl group is bonded via an ester bond] It has 3 to 30 carbon atoms including the ester bond constituent carbon atom, has an alcoholic secondary or tertiary hydroxy group, and contains at least one saturated or unsaturated hydrocarbon group. Or further comprising at least one aromatic group and having a bond selected from the group consisting of —COO—, —O—, and —CO— that connect carbon atoms, R ^1a is hydrogen, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted alkenyl It is selected from the group consisting of. The curable resin composition according to any one of the above items, which comprises a monomer unit selected from the group consisting of compounds represented by:
Item B4. 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;
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 It is a substituted or unsubstituted secondary or tertiary OH-containing group. ]
A curable resin composition according to any one of the above items, comprising a monomer unit represented by:
Item B5. The chain polymer is represented by the formula A2:

[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;
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 B6. The chain polymer is represented by formula A3:

[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 ² is selected from the group consisting of a substituted or unsubstituted alkylene group and a substituted or unsubstituted alkenylene group,
R ^16a is selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted alkynyl group;
R ^17a is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, and substituted or unsubstituted alkynyl groups. ]
A curable resin composition according to any one of the above items, comprising a monomer unit represented by:
Item B7. The chain polymer is represented by formula A4:

[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;
R ^18a is an adamantyl group substituted with at least one hydroxy group. ]
A curable resin composition according to any one of the above items, comprising a monomer unit represented by:
Item B8. The chain polymer is represented by formula A5:

[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;
R ^19a is selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted cycloalkenyl group. ]
A curable resin composition according to any one of the above items, comprising a monomer unit represented by:
Item B9. The curable resin composition according to any one of the above items, wherein R ^19a is a substituted or unsubstituted adamantyl group.
Item B10. A curable resin composition comprising a chain polymer having a side chain having an alcoholic secondary or tertiary hydroxy group, and a crosslinking agent,
(A) the side chain comprises 3 to 30 carbon atoms and comprises at least one saturated or unsaturated hydrocarbon group or in addition to at least one more An aromatic group, and a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms,
(B) The crosslinking agent is selected from a triazine-based crosslinking agent or a glycoluril-based crosslinking agent.
Curable resin composition.
Item B11. The chain polymer is a monomer unit having the side chain having an alcoholic secondary or tertiary hydroxy group, and is a (meth) acrylic monomer, a vinyl ester monomer, a vinyl ether monomer, and others The curable resin composition according to any one of the above items, comprising at least one of the vinyl monomers as a monomer unit.
Item B12. The chain polymer is CH ₂ ═CH—COO—R ¹ , CH ₂ ═C (CH ₃ ) —COO—R ² , CH ₂ ═CH—O—CO—R ³ , CH ₂ ═CH—O—R. ⁴ and CH ₂ ═CH—R ⁵ [wherein R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are independently of each other when each vinyl group is bonded via an ester bond] It has 3 to 30 carbon atoms including the carbon atom constituting the ester bond, has an alcoholic secondary or tertiary hydroxy group, and contains at least one saturated or unsaturated hydrocarbon group. Or further comprising at least one aromatic group and having a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms. . The curable resin composition according to any one of the above items, which comprises a monomer unit selected from the group consisting of compounds represented by:
Item B13. The curable resin composition according to any one of the above items, wherein the monomer unit is a (meth) acrylic monomer.
Item B14. The curable resin composition according to any one of the above items, wherein R ^1a is hydrogen or methyl.
Item B15. The chain polymer may further have a hydroxy group or may have an unsubstituted or α-substituted (meth) acrylic monomer having 1 to 15 carbon atoms in the side chain, unsubstituted or It comprises at least one of α-substituted vinyl ester monomers, unsubstituted or α-substituted vinyl ether monomers, and other unsubstituted or α-substituted vinyl monomers as additional monomer units. The curable resin composition of any of the above items.
Item B16. The additional monomer units are CH ₂ ═C (R ^1a ) —COO—R ⁶ , CH ₂ ═C (R ^1a ) —O—CO—R ⁸ [where R ⁶ and R ⁸ are independent of each other. Having 1 to 15 carbon atoms, with or without hydroxy groups, comprising at least one saturated or unsaturated hydrocarbon group, or at least one more The hydrocarbon group or aromatic group may have a bond selected from the group consisting of —COO—, —O—, and —CO—, which includes an aromatic group and connects carbon atoms. It can have an amino group and R ^1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted alkenyl group. CH ₂ ═C (R ^1a ) —O—R ⁹ , CH ₂ ═C (R ^1a ) —R ^10, wherein R ⁹ and R ¹⁰ independently of one another have 3 to 15 carbon atoms With or without a hydroxy group, comprising at least one saturated or unsaturated hydrocarbon group, or further comprising at least one aromatic group, carbon It may have a bond selected from the group consisting of —COO—, —O—, and —CO— that connect the atoms, and the hydrocarbon group or aromatic group may have an amino group, and R ^1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted alkenyl group. C ₄ (R ^1a ) O ₃ —R ¹¹ , and C ₄ (R ^1a ) HNO ₂ —R ^12, wherein C ₄ (R ^1a ) O ₃ — represents an unsubstituted or substituted maleic anhydride group, C ₄ (R ^1a ) HNO ₂ — represents an unsubstituted or substituted maleimide group, and R ¹¹ and R ¹² are each independently a hydrogen atom or a group having 1 to 15 carbon atoms, May or may not have a group, and includes at least one saturated or unsaturated hydrocarbon group, or further includes at least one aromatic group, and connects carbon atoms. It may have a bond selected from the group consisting of —COO—, —O—, and —CO—, the hydrocarbon group or aromatic group may have an amino group, and R ^1a is hydrogen, Substituted or unsubstituted alkyl group and substituted or unsubstituted alkenyl It is selected from the group consisting of. ] The curable resin composition in any one of the said item which is chosen from the group which consists of a compound shown by these.
Item B17. The chain polymer further has (meth) acrylic monomers, vinyl ester monomers, vinyl ether monomers, and other vinyl monomers having no hydroxy group and having 1 to 15 carbon atoms in the side chain. The curable resin composition according to any one of the above items, comprising at least one of these as an additional monomer unit.
Item B18. The additional monomer units are CH ₂ ═CH—COO—R ⁶ , CH ₂ ═C (CH ₃ ) —COO—R ⁷ , CH ₂ ═CH—O—CO—R ⁸ , wherein R ⁶ , R ⁷ and R ⁸ independently of one another have 1 to 15 carbon atoms, have no hydroxy group, comprise at least one saturated or unsaturated hydrocarbon group, or at least It comprises one aromatic group and can have a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms, and the hydrocarbon group or aromatic The group group can have an amino group. ], CH ₂ ═CH—O—R ⁹ , CH ₂ ═CH—R ^10, wherein R ⁹ and R ¹⁰ independently of one another have 3 to 15 carbon atoms and have a hydroxy group And at least one saturated or unsaturated hydrocarbon group, or further comprising at least one aromatic group and connecting between carbon atoms —COO—, —O—, and —CO -It may have a bond selected from the group consisting of-and the hydrocarbon group or aromatic group may have an amino group. ], C ₄ HO ₃ —R ¹¹ , and C ₄ H ₂ NO ₂ —R ¹² [where C ₄ HO ₃ — represents a maleic anhydride group, C ₄ H ₂ NO ₂ — represents a maleimide group, ¹¹ and R ¹² are each independently a hydrogen atom or have 1 to 15 carbon atoms, have no hydroxy group, and contain at least one saturated or unsaturated hydrocarbon group. Or further comprising at least one aromatic group and having a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms. The hydrocarbon group or aromatic group may have an amino group. ] The curable resin composition in any one of the said item which is chosen from the group which consists of a compound shown by these.
Item B19. The curable resin composition according to any one of the above items, wherein the proportion of the monomer unit having an alcoholic secondary or tertiary hydroxy group in the monomer unit constituting the chain polymer is 30 to 100 mol%.
Item B20. 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 B21. 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 B22. 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 B23. The curable resin composition of any of the above items, wherein the condensate comprises a dimer, trimer or higher order polymer of the compound represented by formula B1, formula B2 or formula B3.
Item B24. 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 B25. 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 B26. The curable resin composition according to any one of the above items, wherein the ratio of the weight of the linear polymer to the weight of the crosslinking agent in the composition is 1: 2 to 1: 0.03.
Item B27. The curable resin composition according to any one of the above items, further comprising an acid catalyst.
Item B28. 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 thereof; The curable resin composition according to any one of the above items, which is a solvate thereof.
Item B29. The curable resin composition according to any one of the above items, comprising a solvent.
Item B30. A cured resin film obtained by curing the curable resin composition of any of the above items.
Item B31. 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 B32. 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 B33. 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 B34. A method for producing a cured resin film from the curable resin composition of any of the above items,
(I) providing a chain polymer with a side chain having an alcoholic secondary or tertiary hydroxy 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,
Production method.
Item B35. (Iv) The method according to the above item, further comprising the step of peeling the cured resin film formed on the substrate from the substrate.
Item B36. A method for producing a cured resin film, comprising:
(I) providing a chain polymer with a side chain having an alcoholic secondary or tertiary hydroxy group and a crosslinking agent;
(Ii) applying a 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 to form a cured resin film,
(A) the side chain comprises 3 to 30 carbon atoms and comprises at least one saturated or unsaturated hydrocarbon group or in addition to at least one more An aromatic group, and a bond selected from the group consisting of —COO—, —O—, and —CO— that connect the carbon atoms of adjacent groups among them. ,
(B) The crosslinking agent is selected from a triazine-based crosslinking agent or a glycoluril-based crosslinking agent.
Production method.
Item B37. The chain polymer is a monomer unit having the side chain having an alcoholic secondary or tertiary hydroxy group, and is a (meth) acrylic monomer, a vinyl ester monomer, a vinyl ether monomer, and others The production method according to any one of the above items, comprising at least one of the vinyl monomers as a monomer unit.
Item B38. The chain polymer is CH ₂ ═CH—COO—R ¹ , CH ₂ ═C (CH ₃ ) —COO—R ² , CH ₂ ═CH—O—CO—R ³ , CH ₂ ═CH—O—R. ⁴ and CH ₂ ═CH—R ⁵ [wherein R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are independently of each other when each vinyl group is bonded via an ester bond] It has 3 to 30 carbon atoms including the carbon atom constituting the ester bond, has an alcoholic secondary or tertiary hydroxy group, and contains at least one saturated or unsaturated hydrocarbon group. Or further comprising at least one aromatic group and having a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms. . ] The manufacturing method in any one of the said item which is what comprises the monomer unit chosen from the group which consists of a compound shown by these.
Item B39. The chain polymer further has (meth) acrylic monomers, vinyl ester monomers, vinyl ether monomers, and other vinyl monomers having no hydroxy group and having 1 to 15 carbon atoms in the side chain. The production method according to any one of the above items, comprising at least one of any of these as an additional monomer unit.
Item B40. The additional monomer units are CH ₂ ═CH—COO—R ⁶ , CH ₂ ═C (CH ₃ ) —COO—R ⁷ , CH ₂ ═CH—O—CO—R ⁸ , wherein R ⁶ , R ⁷ and R ⁸ independently of one another have 1 to 15 carbon atoms, have no hydroxy group, comprise at least one saturated or unsaturated hydrocarbon group, or at least It may contain a bond selected from the group consisting of —COO—, —O—, and —CO—, which contains one aromatic group and connects carbon atoms. ], CH ₂ ═CH—O—R ⁹ , CH ₂ ═CH—R ^10, wherein R ⁹ and R ¹⁰ independently of one another have 3 to 15 carbon atoms and have a hydroxy group And at least one saturated or unsaturated hydrocarbon group, or further comprising at least one aromatic group and connecting between carbon atoms —COO—, —O—, and —CO A bond selected from the group consisting of: ], C ₄ HO ₃ —R ¹¹ , and C ₄ H ₂ NO ₂ —R ¹² [where C ₄ HO ₃ — represents a maleic anhydride group, C ₄ H ₂ NO ₂ — represents a maleimide group, ¹¹ and R ¹² are each independently a hydrogen atom or have 1 to 15 carbon atoms, have no hydroxy group, and contain at least one saturated or unsaturated hydrocarbon group. Or further comprising at least one aromatic group and having a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms. . ] The manufacturing method in any one of the said item which is selected from the group which consists of a compound shown by these.
Item B41. The method according to any one of the above items, wherein the proportion of the monomer unit having an alcoholic secondary or tertiary hydroxy group in the monomer unit constituting the chain polymer is 30 to 100 mol%.
Item B42. 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 B43. 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: 0.03.
Item B44. The production method of any of the above items, wherein the composition comprises a solvent.
Item B45. The production method of any of the above items, wherein the composition further comprises an acid catalyst.
Item B46. (Iv) The method for producing a cured resin film 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 B47. 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 B48. 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 B49. Used for synthetic resins, pellets, films, plates, fibers, foaming agents, tubes, rubber, elastomers, etc., including curable resin compositions or cured resin films of any of the above items, 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, bathtubs , 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, Paints, cosmetics, electrical industry and electronics industry (electric appliances, computer parts, printed circuit boards, insulators, conductors, wiring coating materials, power generation elements, speakers , Microphones, noise cancellers, transducers, etc.), optical communication cables, medical materials and instruments (catheters, guide wires, artificial blood vessels, artificial muscles, artificial organs, dialysis membranes, endoscopes, etc.), small pumps, actuators, robot materials ( Sensors used in industrial robots, etc.), energy generators and compositions for producing plants (solar power, wind power, etc.).
Item B50. 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 B51. The composition for preparation of materials, such as a catheter, a guide wire, a pharmaceutical container, or a tube containing the curable resin composition or cured resin film in any one of the said items.
Item B52. Automotive parts (body panels, bumper bands, rocker panels, side moldings, engine parts, drive parts, transmission parts, steering device parts, stabilizer parts, suspensions, including the curable resin composition or cured resin film of any of the above items -Compositions for the production of braking device parts, brake parts, shaft parts, pipes, tanks, wheels, seats, seat belts, etc.
Item B53. The composition for preparation of the vibration isolator for motor vehicles, the coating material for motor vehicles, and the synthetic resin for motor vehicles containing the curable resin composition or cured resin film in any one of the said item.
Item B54. 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 B55. 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 B56. Used for plastics, pellets, films, plates, fibers, foaming agents, tubes, rubber, elastomers, 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, cosmetics) Containers, freight containers, waste bins, etc.), architecture (buildings, roads, building parts, etc.), agricultural films, industrial films, water and sewage, paints, cosmetics, electrical and electronics industries (electrical appliances, computer parts) , Printed circuit boards, insulators, conductors, wiring coating materials, power generation elements, speakers, microphones, noise cancellers, transducers, etc. ), Optical communication cables, medical materials and instruments (catheters, guide wires, artificial blood vessels, artificial muscles, artificial organs, dialysis membranes, endoscopes, etc.), small pumps, actuators, robot materials (industrial robots, etc.) Use of the curable resin composition or cured resin film of any of the above items for the production of a sensor), an energy generation device and a plant (solar power generation, wind power generation, etc.).
Item B57. Use of the curable resin composition or cured resin film of any of the above items for the production of electronic materials, medical materials, healthcare materials, life science materials, or robot materials.
Item B58. 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 B59. Automobile parts (body panels, bumper bands, rocker panels, side moldings, engine parts, drive parts, transmission parts, steering parts, stabilizer parts, suspension / brake equipment parts, brake parts, shaft parts, pipes, tanks, wheels Use of the curable resin composition or cured resin film of any of the above items for the production of a sheet, a seat belt, etc.).
Item B60. 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, an automotive paint, and a synthetic resin for automobiles.
Item B61. 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 performing a polymerization reaction.
Item B62. A method for producing a sheet-like flexible electrical / electronic circuit component or a flexible display device, comprising a step of forming a curable resin composition or a cured resin film of any of the above items by performing a polymerization reaction. Including.
Item B63. Used for plastics, pellets, films, plates, fibers, foaming agents, tubes, rubber, elastomers, 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, cosmetics) Containers, freight containers, waste bins, etc.), architecture (buildings, roads, building parts, etc.), agricultural films, industrial films, water and sewage, paints, cosmetics, electrical and electronics industries (electrical appliances, computer parts) , Printed circuit boards, insulators, conductors, wiring coating materials, power generation elements, speakers, microphones, noise cancellers, transducers, etc. ), Optical communication cables, medical materials and 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.), and a curable resin composition or cured resin film of any of the above items is formed by performing a polymerization reaction. A method comprising the steps of:
Item B64. A method for producing an electronic material, a medical material, a health care material, a life science material, or a robot material, 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.
Item B65. A method for producing a material such as a catheter, a guide wire, a pharmaceutical container, or a tube, comprising a step of forming a curable resin composition or a cured resin film of any of the above items by causing a polymerization reaction. ,Method.
Item B66. Automobile parts (body panels, bumper bands, rocker panels, side moldings, engine parts, drive parts, transmission parts, steering parts, stabilizer parts, suspension / brake equipment parts, brake parts, shaft parts, pipes, tanks, wheels , Sheet, seat belt, etc.), which comprises 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 B67. An anti-vibration material for automobiles, a paint for automobiles, and a synthetic resin for automobiles, comprising a step of forming a curable resin composition or a cured resin film of any of the above items by performing a polymerization reaction. ,Method.

[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. It means no degradation or other deterioration. The temperature of 230 ° C. is high enough to be used as a baking temperature in the production of an electronic circuit by a photolithography method.

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, the 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 this specification, “—O—” and “—CO—” do not include the case where they are constituent parts of “—COO—”. Note that “—COO—” is a description showing an ester when groups at both ends of the ester are not fixed, and includes both “—COO—” and “—O—CO—”. However, when the groups at both ends of the ester are fixed, “—COO—” and “—O—CO—” are used separately.

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 “alkynyl group” means a monovalent hydrogen atom generated by loss of one hydrogen atom from an aliphatic hydrocarbon (alkyne) containing at least one triple bond such as ethyne (acetylene), propyne, and butyne. This group is generally represented by C _m H _2m-3 (where m is an integer of 2 or more). An alkynyl group can be straight or branched. Examples of the alkynyl group having 2 to 6 carbon atoms include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a butynyl group, a pentynyl group, a hexynyl group, and the like. Is not to be done. Examples of the alkynyl group having 2 to 10 carbon atoms include an alkynyl group having 2 to 6 carbon atoms, a heptynyl group, an octynyl group, a noninyl group, and a decynyl group, 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. Or it contains one or more hetero atoms (for example, 1 to 4). 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 alkyl group”, “substituted alkenyl group”, “substituted alkynyl group”, “substituted cycloalkyl group”, “substituted cycloalkenyl group”, “substituted hydrocarbon group”, “substituted aromatic group” , “Substituted heteroaromatic group”, “substituted alkylene group”, “substituted alkenylene group”, “substituted or unsubstituted secondary or tertiary OH-containing group” and “substituted adamantyl group” Examples of substituents on the groups described therein include 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 6 ~ 12} Aromatic In substituted _{C 1 ~ 10} alkyl _{group, C 6 ~ 12} hydrocarbons _{C 1 ~ 10} alkyl group substituted with a _{group, C 6 ~ 12} aromatic _{C 2 ~ 10} alkenyl group substituted with a group, _{C 6 ~} C _2-10 alkenyl group substituted with ₁₂ hydrocarbon groups, —CN, oxo group (═O), —O (CH ₂ ) ₂ O—, —OC (CH ₃ ) ₂ O—, —OCH ₂ O— , -O-, ester (-COO- or _{-O-CO -), C 6} ~ 12 -substituted ester group with a hydrocarbon _{group, C 6 ~ 12} aromatic-substituted ester group with a group, an ester group substituted _{C 6 ~ 18} hydrocarbon 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 provides such exemplary only It is not limited to. 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, the “α-substituted (meth) acrylic monomer” refers to the carbon atom of the ester group —COO— (α-position) as represented by CH ₂ ═C (R ^1a ) —COO—R ^1. ) Refers to an acrylic monomer substituted with carbon forming a double bond. Similarly, the “α-position substituted vinyl ester monomer” refers to an oxygen atom immediately adjacent to the ester group —O—CO— (CH ₂ ═C (R ^1a ) —O—CO—R ³ (α Is an acrylic monomer substituted with carbon forming a double bond at the position), and the “α-substituted vinyl ether monomer” is represented by CH ₂ ═C (R ^1a ) —O—R ^4. As described above, it refers to an acrylic monomer in which a carbon that forms a double bond (α-position) immediately adjacent to the oxygen of the ether group —O— is substituted, and the “α-substituted vinyl monomer” is CH _As shown by ₂ ═C (R ^1a ) —R ⁵ , it refers to an acrylic monomer in which an internal carbon that is not a terminal carbon of a vinyl group is substituted. R ¹ , R ³ , R ⁴ , R ⁵ and R ^1a are as defined in the preferred embodiment (2-1) curable resin composition described below.

In the present specification, the “secondary or tertiary OH-containing group” refers to a group containing one or more secondary or tertiary hydroxy (OH) groups. Accordingly, the “secondary or tertiary OH-containing group” includes a secondary or tertiary hydroxy group itself. “Substituted or unsubstituted” in “substituted or unsubstituted secondary or tertiary OH-containing group” refers to a group containing one or more secondary or tertiary hydroxy (OH) groups. It means that a part of the group other than the hydroxy group is substituted or unsubstituted, and does not indicate that the hydroxy group is substituted 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, “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 one aspect, the present invention provides:
A curable resin composition comprising a chain polymer having a side chain having an alcoholic secondary or tertiary hydroxy group, and a crosslinking agent,
(A) the side chain comprises 3 to 30 carbon atoms and comprises at least one saturated or unsaturated hydrocarbon group or in addition to at least one more An aromatic group, and a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms,
(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.

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 has side chains having alcoholic secondary or tertiary hydroxy groups.

In the present invention, the number of carbon atoms contained in the side chain having an alcoholic secondary or tertiary hydroxy group of the chain polymer is preferably 3 to 30. The number of hydroxy groups in the side chain having an alcoholic secondary or tertiary hydroxy group can be one or more.

The above side chain comprises a saturated or unsaturated hydrocarbon group of at least one carbon atom, or further comprises at least one aromatic group. The side chain may contain one or more bonds selected from the group consisting of —COO—, —O—, and —CO—. Saturated or unsaturated hydrocarbon groups constituting the side chain may occupy all carbon atoms of the side chain, for example, alone, or a plurality of saturated or unsaturated carbon groups may be —COO—, It may be linked via a bond selected from the group consisting of —O— and —CO—. When the side chain contains an aromatic group in addition to a saturated or unsaturated hydrocarbon group, the saturated or unsaturated hydrocarbon group and the aromatic group may be directly bonded, and —COO—, — They may be linked via a bond selected from the group consisting of O— and —CO—.

In the present invention, the alcoholic secondary and tertiary hydroxy groups in the side chain are formed on the cured resin thin film formed by applying the curable resin composition of the present invention on a glass substrate and curing it. This is a decisive factor for maintaining easy peelability from the film. Furthermore, it is more preferable that the alcoholic secondary and tertiary hydroxy groups in the side chain are bonded to the alicyclic part of the side chain, and the alicyclic part of the side chain also maintains the easy peelability of the cured resin thin film. It's a decisive factor for doing it. 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.

In the present invention, the chain polymer having the side chain having an alcoholic secondary or tertiary hydroxy group is more preferably an unsubstituted or α-substituted (meth) acrylic monomer, unsubstituted or α-substituted. It comprises at least one of a vinyl ester monomer, an unsubstituted or α-substituted vinyl ether monomer, and an unsubstituted or α-substituted vinyl monomer other than the above as a monomer unit.

In the present invention, the chain polymer having the side chain having an alcoholic secondary or tertiary hydroxy group is more preferably a (meth) acrylic monomer, a vinyl ester monomer, a vinyl ether monomer, or other than the above. It comprises at least one vinyl monomer as a monomer unit. Preferably, the monomer unit is a (meth) acrylic monomer, and more preferably, the monomer unit is a methacrylic monomer.

Preferably, the chain polymer in the present invention is CH ₂ ═C (R ^1a ) —COO—R ¹ CH ₂ ═C (R ^1a ) —O—CO—R ³ , CH ₂ ═C (R ^1a ) —O. —R ⁴ , and CH ₂ ═C (R ^1a ) —R ⁵ [where R ¹ , R ³ , R ⁴ , and R ⁵ are independently bonded to each vinyl group via an ester bond. In the case of having 3 to 30 carbon atoms, more preferably 3 to 25 carbon atoms, still more preferably 3 to 20 carbon atoms including the carbon atoms constituting the ester bond, and an alcoholic secondary or tertiary hydroxy group. And comprises at least one saturated or unsaturated hydrocarbon group, or further comprises at least one aromatic group, and connects —COO—, —O— And a bond selected from the group consisting of —CO—. R ^1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted alkenyl group. A monomer unit selected from the group consisting of compounds represented by the formula:

More preferably, the chain polymer in the present invention is CH ₂ ═CH—COO—R ¹ , CH ₂ ═C (CH ₃ ) —COO—R ² , CH ₂ ═CH—O—CO—R ³ , CH ₂ ═CH—O—R ⁴ and CH ₂ ═CH—R ⁵ [wherein R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are independently of each other via an ester bond to each vinyl group In the case of bonding, it has 3 to 30 carbon atoms, more preferably 3 to 25 carbon atoms, and still more preferably 3 to 20 carbon atoms including the carbon atoms constituting the ester bond. -COO- having a secondary hydroxy group and comprising at least one saturated or unsaturated hydrocarbon group, or further comprising at least one aromatic group and connecting between carbon atoms, Has a bond selected from the group consisting of —O— and —CO—. Can be. A monomer unit selected from the group consisting of compounds represented by the formula:

In the above, examples of the saturated or unsaturated hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, cyclohexyl, dicyclopentadienyl, decalinyl, adamantyl, butenyl, hexenyl, cyclohexenyl , Decyl and the like, and various linear, branched, monocyclic, and condensed cyclic groups within the limit range of the number of carbon atoms in the side chain may be mentioned. When these groups are not located at the terminal, they may be divalent or higher groups depending on the bonding relationship with other groups. 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 condensed ring group), and each aromatic group may be a divalent or higher valent group depending on the bonding relationship with other groups, when it is not located at the terminal. 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.

In the present invention, the alcoholic secondary or tertiary hydroxy group replaces a hydrogen atom on a secondary or tertiary carbon atom of any of the saturated or unsaturated hydrocarbon groups constituting the side chain. Hydroxy group.

The alcoholic hydroxy group in the side chain of the chain polymer is preferably a secondary hydroxy group or a tertiary hydroxy group, and further bonded to an alicyclic group constituting a part or all of the side chain. preferable.

More preferably, the chain polymer in the present invention has 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;
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 It is a substituted or unsubstituted secondary or tertiary OH-containing group. ]
The monomer unit shown by these is comprised.

More preferably, the chain polymer in the present invention is represented by the formula A1,
R ^1a is selected from the group consisting of hydrogen and substituted or unsubstituted alkyl groups;
L ¹ is selected from the group consisting of a single bond and a substituted or unsubstituted alkylene group,
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 It comprises monomer units selected from the group consisting of secondary or tertiary hydroxy groups and substituted or unsubstituted secondary or tertiary OH-containing hydrocarbon groups.

Even more preferably, the chain polymer in the present invention is represented by the formula A1:
R ^1a is selected from the group consisting of hydrogen and an unsubstituted alkyl group;
L ¹ is selected from the group consisting of a single bond and an unsubstituted alkylene group,
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 Selected from the group consisting of secondary or tertiary hydroxy groups and substituted or unsubstituted secondary or tertiary OH-containing hydrocarbon groups, the other two being independently of each other hydrogen and substituted or non-substituted It comprises monomer units selected from the group consisting of substituted hydrocarbon groups.

More preferably, the chain polymer in the present invention has the 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 ]
The monomer unit shown by these is comprised.

More preferably, the chain polymer in the present invention is represented by the formula A2:
R ^1a is selected from the group consisting of hydrogen and substituted or unsubstituted alkyl groups;
L ¹ is selected from the group consisting of a single bond and a substituted or unsubstituted alkylene group,
R ^5a to R ^14a are independently of each other hydrogen, 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 selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, and a substituted or unsubstituted aromatic group,
Comprising monomer units.

Even more preferably, the chain polymer in the present invention is represented by the formula A2:
R ^1a is selected from the group consisting of hydrogen and an unsubstituted alkyl group;
L ¹ is selected from the group consisting of a single bond and an unsubstituted alkylene group,
Of R ^5a to R ^14a , R ^7a is a hydroxy group, and R ^9a is

And the others are hydrogen, or R ^5a to R ^14a together form a ring substituted with at least one hydroxy group,
R ^15a is selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, and a substituted or unsubstituted phenyl,
Comprising monomer units.
Even more preferably, the ring substituted with at least one hydroxy group is adamantane substituted with at least one hydroxy group.

More preferably, the chain polymer in the present invention has the formula A3:

[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 ² is selected from the group consisting of a substituted or unsubstituted alkylene group and a substituted or unsubstituted alkenylene group,
R ^16a is selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted alkynyl group;
R ^17a is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, and substituted or unsubstituted alkynyl groups. ]
It comprises a monomer unit represented by

More preferably, the chain polymer in the present invention is represented by the formula A2:
R ^1a is selected from the group consisting of hydrogen and substituted or unsubstituted alkyl groups;
L ² is selected from a substituted or unsubstituted alkylene group,
R ^16a is selected from a substituted or unsubstituted alkyl group;
R ^17a is selected from the group consisting of hydrogen and substituted or unsubstituted alkyl groups,
Comprising monomer units.

More preferably, the chain polymer in the present invention has the formula A4:

[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;
R ^18a is an adamantyl group substituted with at least one hydroxy group. ]
The monomer unit shown by these is comprised.

More preferably, the chain polymer in the present invention is represented by the formula A4:
R ^1a is selected from the group consisting of hydrogen and substituted or unsubstituted alkyl groups;
L ¹ is selected from the group consisting of a single bond and a substituted or unsubstituted alkylene group,
R ^18a is an adamantyl group substituted with at least one hydroxy group,
Comprising monomer units.

The chain polymer is represented by formula A5:

[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;
R ^19a is selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted cycloalkenyl group. ]
It comprises a monomer unit represented by

More preferably, the chain polymer in the present invention is represented by the formula A5:
R ^1a is selected from the group consisting of hydrogen and substituted or unsubstituted alkyl groups;
L ¹ is selected from the group consisting of a single bond and a substituted or unsubstituted alkylene group,
R ^19a is selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted cycloalkenyl group,
Comprising monomer units.
Even more preferably, in formula A5, R ^19a is a substituted or unsubstituted adamantyl group.

Preferably, in the monomer unit, R ^1a is hydrogen or methyl, and more preferably, in the monomer unit, R ^1a is methyl.

Preferred side chains having an alcoholic secondary or tertiary hydroxy group of the chain polymer in the present invention include the following, but since it is only necessary to have such a hydroxy group, the mentioned ones are not tired. It is an illustration and it is not limited to them.
(1a) AO-CO-type (A represents the remainder of the side chain; the same shall apply hereinafter) Side chain: 2-hydroxyethoxycarbonyl, 2-hydroxypropoxycarbonyl, 4- (hydroxymethyl) cyclohexylmethoxycarbonyl, 2 -Hydroxy-3- (cyclohexylcarbonyloxy) propoxycarbonyl, 3-benzoyloxy-2-hydroxypropoxycarbonyl, 4-benzoyloxy-3-hydroxycyclohexylmethoxycarbonyl, 3-hydroxy-1-adamantyloxycarbonyl, 2-hydroxycyclohexyl Oxycarbonyl, 4-undecanoyloxy-3-hydroxycyclohexylmethoxycarbonyl, 4-butanoyloxy-3-hydroxycyclohexylmethoxycarbonyl, and the like.
(2a) A-CO-O-type side chain: 2-hydroxypropylcarbonyloxy, 2-hydroxy-3- (cyclohexylcarbonyloxy) propylcarbonyloxy, 3-benzoyloxy-2-hydroxypropylcarbonyloxy, 4-benzoyl Oxy-3-hydroxycyclohexylmethylcarbonyloxy, 3-hydroxy-1-adamantylcarbonyloxy, 2-hydroxycyclohexyloxycarbonyloxy, 4-undecanoyloxy-3-hydroxycyclohexylmethylcarbonyloxy, 4-butanoyloxy- 3-hydroxycyclohexylmethylcarbonyloxy and the like.
(3a) AO-type side chain: 2-hydroxypropoxy, 2-hydroxy-3- (cyclohexylcarbonyloxy) propoxy, 3-benzoyloxy-2-hydroxypropoxy, 4-benzoyloxy-3-hydroxycyclohexylmethoxy, 3-hydroxy-1-adamantyloxy, 2-hydroxycyclohexyloxy, 4-undecanoyloxy-3-hydroxycyclohexylmethoxy, 4-butanoyloxy-3-hydroxycyclohexylmethoxy and the like.
(4a) Others: 2-hydroxypropyl, 2-hydroxy-3- (cyclohexylcarbonyloxy) propyl, 3-benzoyloxy-2-hydroxypropyl, 4-benzoyloxy-3-hydroxycyclohexylmethyl, 3-hydroxy-1- Adamantyl, 2-hydroxycyclohexyl, 4-undecanoyloxy-3-hydroxycyclohexylmethyl, 4-butanoyloxy-3-hydroxycyclohexylmethyl, and the like.

Preferred examples of the monomer that gives these side chains to the chain polymer include, but are not limited to, the following.
(1b) 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, 2-hydroxycyclohexyl (meth) acrylate, 4-undecanoyloxy-3-hydroxycyclohexylmethyl (meth) acrylate, 4-buta (Meth) acrylates such as noyloxy-3-hydroxycyclohexylmethyl (meth) acrylate.
(2b) 2-hydroxybutanoic acid vinyl ester, 2-hydroxy-3- (cyclohexylcarbonyloxy) butanoic acid vinyl ester, 3-benzoyloxy-2-hydroxybutanoic acid vinyl ester, 4-benzoyloxy-3-hydroxycyclohexyl acetic acid Vinyl ester, 3-hydroxy-1-adamantylcarboxylic acid vinyl ester, 2-hydroxycyclohexyloxycarboxylic acid vinyl ester, 4-undecanoyloxy-3-hydroxycyclohexyl acetic acid vinyl ester, 4-butanoyloxy-3-hydroxy Vinyl esters such as cyclohexyl acetic acid vinyl ester.
(3b) 2-hydroxypropyl vinyl ether, 2-hydroxy-3- (cyclohexylcarbonyloxy) propyl vinyl ether, 3-benzoyloxy-2-hydroxypropyl vinyl ether, 4-benzoyloxy-3-hydroxycyclohexyl methyl vinyl ether, 3-hydroxy- Vinyl ethers such as 1-adamantyl vinyl ether, 2-hydroxycyclohexyl vinyl ether, 4-undecanoyloxy-3-hydroxycyclohexyl methyl ether, 4-butanoyloxy-3-hydroxycyclohexyl methyl ether.
(4b) 1-penten-4-ol, 4-hydroxy-5- (cyclohexylcarbonyloxy) -1-pentene, 5-benzoyloxy-4-hydroxy-1-pentene, 3- (4-benzoyloxy-3- Hydroxycyclohexyl) -1-propene, (3-hydroxy-1-adamantyl) ethene, (2-hydroxycyclohexyl) ethene, 3- (4-undecanoyloxy-3-hydroxycyclohexyl) -1-propene, 3- ( Vinyl monomers such as 4-butanoyloxy-3-hydroxycyclohexyl) -1-propene.
(5b) Maleic anhydride and maleimide each having the above (1a) to (4a) as substituents.

The chain polymer in the present invention may have a hydroxy group in addition to the above-mentioned monomer having an alcoholic secondary or tertiary hydroxy group, and the side chain has 1 carbon atom. -15, unsubstituted or α-substituted (meth) acrylic monomers, unsubstituted or α-substituted vinyl ester monomers, unsubstituted or α-substituted vinyl ether monomers, and other unsubstituted or α-substituted vinyls Any at least one type of monomer may be included as an additional monomer unit. Such additional monomer units are preferably CH ₂ ═C (R ^1a ) —COO—R ⁶ , CH ₂ ═C (R ^1a ) —O—CO—R ⁸ wherein R ⁶ , and R ⁸ Independently of one another, have 1 to 15 carbon atoms, may or may not have a hydroxy group, and comprise at least one saturated or unsaturated hydrocarbon group, or The hydrocarbon group may further include at least one aromatic group, and may have a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms. Alternatively, the aromatic group can have an amino group, and R ^1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted alkenyl group. CH ₂ ═C (R ^1a ) —O—R ⁹ , CH ₂ ═C (R ^1a ) —R ^10, wherein R ⁹ and R ¹⁰ independently of one another have 3 to 15 carbon atoms With or without a hydroxy group, comprising at least one saturated or unsaturated hydrocarbon group, or further comprising at least one aromatic group, carbon It may have a bond selected from the group consisting of —COO—, —O—, and —CO— that connect the atoms, and the hydrocarbon group or aromatic group may have an amino group, and R ^1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted alkenyl group. _{^{_{], C 4 (R 1a) O}}} 3 -R 11, and _{^{_{C 4 (R 1a) HNO 2}}} -R 12 _[C 4 herein ^(R 1a) _{O 3} - represents a maleic anhydride _{group, C} 4 (R ^1a ) HNO ₂ — represents a maleimide group, R ¹¹ and R ¹² independently of one another are hydrogen atoms or have 1 to 15 carbon atoms, and are alcoholic secondary or tertiary With or without hydroxy groups, comprising at least one saturated or unsaturated hydrocarbon group or further comprising at least one aromatic group, A bond selected from the group consisting of —COO—, —O—, and —CO—, which has a bond selected from the group consisting of —COO—, —O—, and —CO—, the hydrocarbon group or aromatic group may have an amino group, and R ^1a represents hydrogen; Substituted or unsubstituted alkyl groups and substituted or unsubstituted alkenyl It is selected from the group consisting of. ] Can be selected from the group consisting of compounds represented by

The chain polymer according to the present invention has, in addition to the above-mentioned monomer having an alcoholic secondary or tertiary hydroxy group, a hydroxyl group and a side chain having 1 to 15 carbon atoms (meth) At least one of acrylic monomers, vinyl ester monomers, vinyl ether monomers, and other vinyl monomers may be included as an additional monomer unit. Such additional monomer units are preferably CH ₂ ═CH—COO—R ⁶ , CH ₂ ═C (CH ₃ ) —COO—R ⁷ , CH ₂ ═CH—O—CO—R ⁸ , wherein Each of R ⁶ , R ⁷ and R ⁸ independently of one another has 1 to 15 carbon atoms, has no hydroxy group, and comprises at least one saturated or unsaturated hydrocarbon group Or further comprising at least one aromatic group and having a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms. The hydrogen group or aromatic group can have an amino group. ], CH ₂ ═CH—O—R ⁹ , CH ₂ ═CH—R ^10, wherein R ⁹ and R ¹⁰ independently of one another have 3 to 15 carbon atoms and have a hydroxy group And at least one saturated or unsaturated hydrocarbon group, or further comprising at least one aromatic group and connecting between carbon atoms —COO—, —O—, and —CO -It may have a bond selected from the group consisting of-and the hydrocarbon group or aromatic group may have an amino group. ], C ₄ HO ₃ —R ¹¹ , and C ₄ H ₂ NO ₂ —R ¹² [where C ₄ HO ₃ — represents a maleic anhydride group, C ₄ H ₂ NO ₂ — represents a maleimide group, ¹¹ and R ¹² , independently of one another, are hydrogen atoms or have 1 to 15 carbon atoms, have no alcoholic secondary or tertiary hydroxy group, and are at least one saturated Or an unsaturated hydrocarbon group, or at least one aromatic group, and selected from the group consisting of —COO—, —O—, and —CO— that connect carbon atoms. It can have a bond, and the hydrocarbon group or aromatic group can have an amino group. ] Can be selected from the group consisting of compounds represented by

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 of the coalescence is a monomer unit having a side chain having an alcoholic secondary or tertiary hydroxy group. Preferably, the copolymer comprises monomer units with side chains having at least one alcoholic secondary or tertiary hydroxy group and additional monomer units not having at least one hydroxy group. Including.

The proportion of the monomer unit having an alcoholic secondary or tertiary hydroxy group in the chain polymer in the present invention is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, more preferably 60 to It is 100 mol%, more preferably 80 to 100 mol%, particularly preferably 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 molecular weight of the chain polymer is usually preferably in the range of 10,000 to 100,000 (measured by gel filtration chromatography), but is not particularly limited to this range.

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-dimeth Examples thereof include, but are not limited to, xylmethyl-2-imidazolidinone.

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). 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.

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.

(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 by the curable resin composition of the present invention is heat-resistant in the meaning of the above “heat resistance”, and has easy peelability after heat treatment in a temperature range that is heat-resistant.

In the curable resin composition of the present invention, a solution obtained by dissolving a chain polymer, a crosslinking agent, and, if necessary, an acid catalyst in a solvent is typically applied on a glass substrate (preferably soda lime glass). Then, by curing by heat treatment (100 ° C. to 230 ° C., 1 minute or longer), an easily peelable cured resin film having a film thickness of several hundred nm (preferably, a film thickness of about 200 nm to about 300 nm) is made into a transparent thin film Can be formed. 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., and preferably withstand heating (firing) at 230 ° C. Furthermore, since it is resistant to the solvent used in the photoresist solution and is resistant to an alkaline developing solution, it can be advantageously used as a resin base film for circuit production by photolithography. 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 electric and electronic circuit components, and can be used for the production of flexible display devices, touch sensors and the like. .

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 a measuring device, and UR-100N-D type is used as a 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 an alkali-free glass substrate of 0.5 N / mm ² or less. The cured resin film of the present invention more preferably has a peeling force 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.

[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 hydroxy 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 polymerization initiators include thermal polymerization initiators, photopolymerization initiators, redox polymerization initiators, ATRP (atom transfer radical polymerization) initiators, ICAR ATRP initiators, ARGET ATRP initiators, RAFT (reversible addition-cleavage). Chain transfer polymerization) agents, NMP (polymerization via nitroxide) agents, polymer polymerization initiators and the like. These polymerization initiators may be used alone or in combination of two or more.

Examples of thermal polymerization initiators include azo 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 and 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 230 ° C., more preferably 150 ° C. to 230 ° 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.

[4] Applications The curable resin composition or cured resin film of the present invention is used for synthetic resins, pellets, films, plates, fibers, foaming agents, tubes, rubber, elastomers, etc., 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, bathtubs , 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, Paints, cosmetics, electrical industry and electronics industry (electric appliances, computer parts, printed circuit boards, insulators, conductors, wiring coating materials, power generation elements, speakers, Microphones, noise cancellers, transducers, etc.), optical communication cables, medical materials and 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, automobile paints, automobile synthetic resins, and the like.

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.

1. Production of Polymer as Component of Curable Resin Composition As a component of curable resin composition, a polymer was produced as shown below.

[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. And polymer A-1 was obtained. When the average molecular weight (MW) of this polymer was measured by gel filtration chromatography, it was 25,000.

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

Polymer A-2 was obtained in the same manner as in Production Example 1 except that 3-benzoyloxy-2-hydroxypropyl methacrylate was used as a monomer. When the average molecular weight (MW) of this polymer was measured by gel filtration chromatography, it was 22,000.

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

Polymer A-3 was obtained in the same manner as in Production Example 1 except that 4-benzoyloxy-3-hydroxycyclohexylmethyl methacrylate was used as a monomer. When the average molecular weight (MW) of this polymer was measured by gel filtration chromatography, it was 32,000.

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

Polymer A-4 was obtained in the same manner as in Production Example 1 except that 1,3-adamantyldiol monomethacrylate was used as a monomer. It was 18000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.

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

Polymer A-5 was obtained in the same manner as in Production Example 1 except that 2-hydroxycyclohexyl methacrylate was used as a monomer. When the average molecular weight (MW) of this polymer was measured by gel filtration chromatography, it was 36000.

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

Polymer A-6 was obtained in the same manner as in Production Example 1 except that 2-hydroxyethyl methacrylate was used as a monomer. When the average molecular weight (MW) of this polymer was measured by gel filtration chromatography, it was 42,000.

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

Polymer A-7 was obtained in the same manner as in Production Example 1 except that 4- (hydroxymethyl) cyclohexylmethyl acrylate was used as a monomer. It was 18000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.

[Production Example 8] Production of polymer A-8 Using 2-hydroxypropyl methacrylate and n-butyl acrylate represented by formula (1-1) as monomers, 50 parts by mass of each were added to propylene glycol monomethyl ether (PGME). To 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. And polymer A-8 was obtained. It was 18000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.

[Production Example 9] Production of polymer A-9 Polymer A-9 was obtained in the same manner as in Production Example 8 except that 2-hydroxypropyl methacrylate and methyl methacrylate represented by formula (1-1) were used as monomers. . It was 25000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.

[Production Example 10] Production of polymer A-10 Polymer A-10 was obtained in the same manner as in Production Example 8 except that 2-hydroxypropyl methacrylate of formula (1-1) and styrene were used as monomers. When the average molecular weight (MW) of this polymer was measured by gel filtration chromatography, it was 22,000.

[Production Example 11] Production of polymer A-11 As in Production Example 8, except that 4-benzoyloxy-3-hydroxycyclohexylmethyl methacrylate and dicyclopentadienyl methacrylate of the formula (1-3) were used as monomers. Thus, a polymer A-11 was obtained. It was 35000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.

[Production Example 12] Production of polymer A-12 A polymer A- 12 was obtained. It was 25000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.

[Production Example 13] Production of polymer A-13 Polymer A-13 was obtained in the same manner as in Production Example 8 except that 2-hydroxyethyl methacrylate and butyl acrylate of formula (1-6) were used as monomers. . When the average molecular weight (MW) of this polymer was measured by gel filtration chromatography, it was 38000.

[Production Example 14] Production of polymer A-14 Polymer A-14 was obtained in the same manner as in Production Example 8 except that 2-hydroxyethyl methacrylate and methyl methacrylate represented by the formula (1-6) were used as monomers. . When the average molecular weight (MW) of this polymer was measured by gel filtration chromatography, it was 36000.

[Production Example 15] Production of polymer A-15 Polymer A- 15 was obtained. When the average molecular weight (MW) of this polymer was measured by gel filtration chromatography, it was 39000.

[Production Example 16] Production of polymer A-16 The following formula (1-8),

Polymer A-16 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 average molecular weight (MW) of this polymer was measured by gel filtration chromatography, it was 27,700.

[Production Example 17] Production of polymer A-17 The following formula (1-9),

Polymer A-17 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 average molecular weight (MW) of this polymer was measured by gel filtration chromatography, it was 31,700.

[Production Example 18] Production of polymer A-18 Polymer A-18 was produced in the same manner as in Production Example 8 except that 2-hydroxycyclohexyl methacrylate and methyl methacrylate represented by the formula (1-5) were used as monomers.

Got. When the average molecular weight (MW) of this polymer was measured by gel filtration chromatography, it was 25,500.

[Production Example 19] Production of polymer A-19 The following formula (1-10):

Polymer A-19 was prepared in the same manner as in Production Example 1, except that 3-hydroxyadamantylmethyl-2-methacrylate was used as a monomer.

Got. When the average molecular weight (MW) of this polymer was measured by gel filtration chromatography, it was 35,700.

[Production Example 20] Production of polymer A-20 The following formula (1-11):

Polymer A-20 was prepared in the same manner as in Production Example 1 except that 2-hydroxy-4-methacryloxymethyl-cyclohexyl-3-cyclohexene-1-carboxylate was used as a monomer.

Got. When the average molecular weight (MW) of this polymer was measured by gel filtration chromatography, it was 26,700.

[Production Example 21] Production of polymer A-21 The following formula (1-12):

Polymer A-21 in the same manner as in Production Example 1 except that 4- (2-cyclohexylacetyl) oxy-3-hydroxycyclohexanemethyl 2-methacrylate was used as a monomer.

Got. When the average molecular weight (MW) of this polymer was measured by gel filtration chromatography, it was 30,700.

[Production Example 22] Production of polymer A-22 Polymer A-22 was produced in the same manner as in Production Example 8 except that 2-hydroxycyclohexyl methacrylate and benzyl methacrylate represented by the formula (1-5) were used as monomers.

Got. When the average molecular weight (MW) of this polymer was measured by gel filtration chromatography, it was 32,700.

[Production Example 23] Production of polymer A-23 4- (4-methoxyphenylpropenoyl) oxy-3-hydroxycyclohexylmethyl methacrylate of formula (1-8) and formula (1-13)

3,4-epoxycyclohexylmethyl methacrylate was used as a monomer, and 100 parts by mass thereof was dissolved in propylene glycol monomethyl ether (PGME) so as to be 20% by mass. The resulting solution was heated to 80 ° C. while blowing nitrogen gas, 4 mol% of 2,2′-azobisisobutyronitrile (AIBN) was added to the total amount of monomers, and then reacted at 80 ° C. for 8 hours. To obtain a polymer. Thereafter, 99 parts by mass and 1 part by mass of 4-methoxycinnamic acid and methacrylic acid, respectively, and 3 mol% of tetraethylammonium bromide were added, the temperature was raised to 100 ° C. while blowing air, and the reaction was carried out for 38 hours. A-23

Got. When the average molecular weight (MW) of this polymer was measured by gel filtration chromatography, it was 42,900.

[Production Example 24] Production of polymer A-24 Polymer A-24 was produced in the same manner as in Production Example 8 except that methyl methacrylate, glycidyl methacrylate and dicyclopentadienyl methacrylate were used as monomers.

2. Production of Curable Resin Composition Various curable resin compositions of the present invention were produced as described below, applied onto two types of glass substrates, and cured by heating to form a film.

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

Of 0.4 parts by mass of hexamethoxymethylmelamine (Nicarac MW-30, Sanwa Chemical Co., Ltd.) and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst were mixed with propylene glycol monomethyl ether (PGME). ) It was dissolved in 95 parts by mass. This solution was applied by spin coating on 0.7 mm thick soda glass and 0.5 mm non-alkali glass (EAGLE-XG, Corning), respectively, and heat-treated at 150 ° C. or higher for 30 minutes, A film thickness was formed.

[Example 2]
3.2 parts by weight of polymer A-1, 0.8 parts by weight of the cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 0.2 parts by weight of pyridinium-p-toluenesulfonic acid as a polymerization catalyst Was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

Example 3
2.4 parts by mass of polymer A-1, 2.4 parts by mass of cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst Was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

Example 4
4.4 parts by mass of polymer A-2, 0.4 parts by mass of the cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst Was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

Example 5
4.4 parts by mass of polymer A-3, 0.4 parts by mass of cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst Was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

Example 6
4.4 parts by mass of polymer A-4, 0.4 parts by mass of cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst Was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

Example 7
4.4 parts by mass of polymer A-5, 0.4 parts by mass of cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst Was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

Example 8
4.4 parts by mass of polymer A-8, 0.4 parts by mass of cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst Was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

Example 9
4.4 parts by mass of polymer A-9, 0.4 parts by mass of cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst Was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

Example 10
4.4 parts by mass of polymer A-10, 0.4 parts by mass of cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst Was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

Example 11
4.4 parts by mass of polymer A-11, 0.4 parts by mass of cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst Was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

Example 12
4.4 parts by mass of polymer A-12, 0.4 parts by mass of cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst Was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

Example 13
4.4 parts by mass of the polymer A-1, the following formula (B-2) as a crosslinking agent:

Of 1,3,4,6-tetrakis (methoxymethyl) glycoluril (Nicalac MW-270, Sanwa Chemical Co., Ltd.), and 0. 0 of pyridinium-p-toluenesulfonic acid as a polymerization catalyst. 2 parts by mass was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

Example 14
4.4 parts by mass of the polymer A-1, the following formula (B-3) as a crosslinking agent:

0.4 parts by mass of tetramethoxymethylbenzoguanamine and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst were dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

Example 15
4.4 parts by mass of the polymer A-1, 0.4 parts by mass of the cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 0.2 parts by mass of dodecylbenzenesulfonic acid as a polymerization catalyst It was dissolved in 95 parts by mass of glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

Example 16
4.4 parts by mass of polymer A-1, 0.4 parts by mass of cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and thermal acid generator Sun-Aid SI-100L (Sanshin Chemical) as a polymerization catalyst 0.2 part by mass of (Co., Ltd.) was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

[Comparative Example 1]
4.4 parts by mass of polymer A-6, 0.4 parts by mass of cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst Was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

[Comparative Example 2]
4.4 parts by mass of polymer A-7, 0.4 parts by mass of cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst Was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

[Comparative Example 3]
4.4 parts by mass of polymer A-13, 0.4 parts by mass of cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst Was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

[Comparative Example 4]
4.4 parts by mass of polymer A-14, 0.4 parts by mass of cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst Was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

[Comparative Example 5]
4.4 parts by mass of polymer A-15, 0.4 parts by mass of cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst Was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

[Comparative Example 6]
4.4 parts by mass of Polymer A-1, 0.4 parts by mass of Duranate TPA-100 (Asahi Kasei Co., Ltd.) as the isocyanurate-based crosslinking agent, and 0.2 parts of pyridinium-p-toluenesulfonic acid as the polymerization catalyst A part by mass was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

Example 17
3.2 parts by weight of polymer A-16, 0.8 parts by weight of the cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 0.2 parts by weight of pyridinium-p-toluenesulfonic acid as a polymerization catalyst Was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

Example 18
3.2 parts by mass of polymer A-17, 0.8 parts by mass of cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst Was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

Example 19
3.2 parts by weight of polymer A-18, 0.8 parts by weight of the cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 0.2 parts by weight of pyridinium-p-toluenesulfonic acid as a polymerization catalyst Was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

Example 20
3.2 parts by weight of polymer A-19, 0.8 parts by weight of the cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 0.2 parts by weight of pyridinium-p-toluenesulfonic acid as a polymerization catalyst Was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

Example 21
3.2 parts by weight of polymer A-20, 0.8 parts by weight of the cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 0.2 parts by weight of pyridinium-p-toluenesulfonic acid as a polymerization catalyst Was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

[Example 22]
3.2 parts by weight of polymer A-21, 0.8 parts by weight of the cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 0.2 parts by weight of pyridinium-p-toluenesulfonic acid as a polymerization catalyst Was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

Example 23
3.2 parts by weight of polymer A-22, 0.8 parts by weight of the cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 0.2 parts by weight of pyridinium-p-toluenesulfonic acid as a polymerization catalyst Was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

Example 24
3.2 parts by weight of polymer A-23, 0.8 parts by weight of the cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 0.2 parts by weight of pyridinium-p-toluenesulfonic acid as a polymerization catalyst Was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

[Comparative Example 7]
3.2 parts by weight of polymer A-24, 0.8 parts by weight of the cross-linking agent hexamethoxymethylmelamine (formula (B-1)), and 0.2 parts by weight of pyridinium-p-toluenesulfonic acid as a polymerization catalyst Was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film having a thickness of about 300 nm.

3. Evaluation of performance (1) Evaluation of peel force for cured resin thin film About the cured resin thin film prepared on the glass substrate in each of the above examples and comparative examples, the magnitude of force required to peel them from the glass substrate (Peeling force) was quantitatively evaluated by the following method. In other words, TENSILON RTG-1310 (A & D Co., Ltd.) was used as the measuring device, and UR-100N-D type was used as the load cell. The measurement was performed by measuring the magnitude of the force (peeling force) required for peeling while pulling at a constant speed of 300 mm / min with respect to the glass substrate at a peeling angle of 90 °. The results are shown in Table 1. The peel strengths for Examples 1 to 16 in Table 1 and Table 2 are indicated by 3 digits after the decimal point. Other measured values and calculated values are displayed in principle up to two decimal places.

As shown in Table 1, the peel strengths of the cured resin thin films of Comparative Examples 1 to 6 were 2.2 to 8.7 N / mm ² (soda glass substrate) and 3.2 to 9.2 N / mm ² (EAGLE- Whereas in Examples 1 to 16, it was 0.013 to 0.078 N / mm ² (soda glass substrate) and 0.028 to 0.085 N / mm ² ((EAGLE-XG substrate). In fact, each cured resin thin film of the comparative example has a high peeling force value, and thus the film and the substrate are broken, whereas Each of the cured resin thin films could be easily removed without difficulty.

(2) Evaluation of peel strength for cured resin thin film after firing Assuming a firing process in circuit fabrication by patterning using a photolithographic method or a printing method on the cured resin thin film, when the cured resin thin film is fired The peel force was measured. That is, for Examples 1 and 7 and Comparative Examples 1 and 2, the cured resin thin film formed on the soda glass substrate was baked at 230 ° C. for 1 hour or 3 hours, respectively, by the apparatus and method described in (1) above. The peel force was measured. A result is shown in Table 2 with the value of the peeling force (initial peeling force) before baking in those Examples and comparative examples.

As seen in Table 2, the cured resin thin films of Examples 1 and 7 remained at a level two orders of magnitude lower than those of Comparative Examples 1 and 2 before firing even after firing at 230 ° C. for 1 hour or 3 hours. It could be easily removed without difficulty. The cured resin thin films of Comparative Examples 1 and 2 were more strongly bonded to the glass substrate than before firing.

Assuming a firing process in circuit fabrication by patterning using a photolithographic method or printing method on a cured resin thin film by the same means as in (2) above, the peeling force when the cured resin thin film is fired is measured. went. That is, for Examples 12, 16 to 22, and Comparative Example 7, the cured resin thin film formed on the soda glass substrate was baked at 230 ° C. for 20 minutes, and the peeling force was determined by the apparatus and method described in (1) above. Was measured. A result is shown in Table 3 with the value of the peeling force (initial peeling force) before baking in those Examples and comparative examples.

As can be seen in Table 3, the cured resin thin films of Examples 12 to 24 remained at a level two orders of magnitude lower than that of Comparative Example 7 before firing after firing at 230 ° C. for 20 minutes, as before firing. It was easy and easy to remove. On the other hand, the cured resin thin film of Comparative Example 7 had a high peeling force as before firing and could not be easily peeled off.

(3) Evaluation of peel force for cured resin thin film after firing when cross-linking agent and mixing ratio are changed When cross-linking agent and polymer / cross-linking agent mixing ratio are changed to those shown in Table 5 below The peel strengths of the cured resin thin films prepared for Examples 25 to 27 and Comparative Examples 8 to 10 were measured. Various conditions are as follows.
<Evaluation conditions>
・ Substrate: Soda glass (coated on tin-treated surface)
・ Filming: Spin coating> Bake for 30 minutes at 150 ° C or 230 ° C * Finished film thickness 50-200nm
-Peel test conditions: Perform a peel test with Nichiban tape (24 mm width).
The polymer used is polymer A-3.
Table 4 shows the crosslinking agents used. In Table 4, MW-30 is hexamethoxymethylmelamine (Nikalac MW-30, Sanwa Chemical Co., Ltd.) of the above formula (B-1), and MW-30LF is hexamethoxymethylmelamine (low free formaldehyde product). MX-270 is 1,3,4,6-tetrakis (methoxymethyl) glycoluril (Nicarak MW-270, (Ncarac MW-30LF, Sanwa Chemical Co., Ltd.) Sanwa Chemical Co., Ltd.).

The results are shown in Table 5. Using MW-30 as a reference compound, the peeling force and peeling characteristics were examined by changing the mixing ratio of other compounds (Examples 25 to 27 and Comparative Examples 8 to 10). In Table 5, “◯” in the column of the peel test indicates that the formed cured resin film can be easily and easily peeled off and has easy peelability, and “×” can be easily peeled off. It means that it did not have easy peelability.

As can be seen from Table 5, when MW-30 was used, when the polymer / crosslinking agent mixing ratio was 45/50, the peel force was as low as 0.02 and had easy peelability, but in the case of 90/10 Had a peel strength as large as 7.5 and double digits, and did not have easy peelability. When MX-270 was used, it had low peel strength and easy peelability at both mixing ratios of 45/50 and 90/10. On the other hand, MW-30LF had a high peeling force at both mixing ratios of 45/50 and 90/10, and was not easily peelable. This result seems to be because MW-30LF has less formaldehyde and less methylol portion (reaction point for thermal crosslinking) than MW-30.

(4) Examination of threshold value of peel force of cured resin thin film The peel force of the produced cured resin thin film was measured when the weight ratio (wt%) of the polymer, the crosslinking agent, and the acid catalyst was changed. That is, for Examples 28 to 38 and Comparative Examples 11 to 15, a solution prepared using a polymer, a cross-linking agent, and an acid catalyst at a weight ratio shown in Table 6 below was applied onto a soda glass substrate, and was heated to 230 ° C. A cured resin film was formed in the same manner as in Example 1 except that baking was carried out for 20 minutes, and the respective peeling forces were measured and compared by the apparatus and method described in (1) above. The results are shown in Table 6.

As can be seen from Table 6, with regard to the cross-linking agent B-1, easy release was exhibited at 10 wt% or more based on the total amount of the polymer, the cross-linking agent, and the acid catalyst (Examples 28 to 30). Regarding B-2, easy peelability was exhibited at 3 wt% or more (Examples 33 to 38). In Comparative Example 8 of Table 5, the polymer / crosslinking agent mixing ratio of 90/10 did not exhibit easy peeling, but the 85 / of Example 29 of Table 6 having almost the same mixing ratio using an acid catalyst. No. 10 exhibits easy peelability. Therefore, it can be said that easy peelability is easily developed by adding an acid catalyst.

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. This application claims priority to international patent application PCT / JP2016 / 074180 (filed on August 19, 2016) and Taiwan patent application No. 105126494 (filed on August 19, 2016), and their contents. The entirety is incorporated herein by reference.

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 high temperatures and can be easily peeled off from a substrate even after being exposed to such high temperatures, it is useful in the production of film-type electrical / electronic circuit components.

Claims

A curable resin composition comprising a chain polymer having a side chain having an alcoholic secondary or tertiary hydroxy group, and a crosslinking agent,
(A) the side chain comprises 3 to 30 carbon atoms and comprises at least one saturated or unsaturated hydrocarbon group or in addition to at least one more An aromatic group, and a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms,
(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.
The chain polymer is a monomer unit having the side chain having an alcoholic secondary or tertiary hydroxy group, and is an unsubstituted or α-substituted (meth) acrylic monomer, unsubstituted or α-substituted The curing according to claim 1, comprising at least one of a vinyl ester monomer, an unsubstituted or α-substituted vinyl ether monomer, and other unsubstituted or α-substituted vinyl monomers as monomer units. Resin composition.
The chain polymer is CH 2 ═C (R 1a ) —COO—R 1 , CH 2 ═C (R 1a ) —O—CO—R 3 , CH 2 ═C (R 1a ) —O—R 4 , And CH 2 ═C (R 1a ) —R 5 [wherein R 1 , R 3 , R 4 , and R 5 are independent of each other when each vinyl group is bonded via an ester bond] It has 3 to 30 carbon atoms including the ester bond constituent carbon atom, has an alcoholic secondary or tertiary hydroxy group, and contains at least one saturated or unsaturated hydrocarbon group. Or further comprising at least one aromatic group and having a bond selected from the group consisting of —COO—, —O—, and —CO— that connect carbon atoms, R 1a is hydrogen, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted alkenyl It is selected from the group consisting of. The curable resin composition of Claim 1 or 2 which comprises the monomer unit chosen from the group which consists of a compound shown by these.
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;
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 It is a substituted or unsubstituted secondary or tertiary OH-containing group. ]
The curable resin composition according to any one of claims 1 to 3, which comprises a monomer unit represented by:
The chain polymer is represented by the formula A2:

[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;
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 according to any one of claims 1 to 4, which comprises a monomer unit represented by:
The chain polymer is represented by formula A3:

[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 2 is selected from the group consisting of a substituted or unsubstituted alkylene group and a substituted or unsubstituted alkenylene group,
R 16a is selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted alkynyl group;
R 17a is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, and substituted or unsubstituted alkynyl groups. ]
The curable resin composition according to any one of claims 1 to 4, which comprises a monomer unit represented by:
The chain polymer is represented by formula A4:

[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;
R 18a is an adamantyl group substituted with at least one hydroxy group. ]
The curable resin composition according to any one of claims 1 to 4, which comprises a monomer unit represented by:
The chain polymer is represented by formula A5:

[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;
R 19a is selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted cycloalkenyl 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 8, wherein R 19a is a substituted or unsubstituted adamantyl group.
A curable resin composition comprising a chain polymer having a side chain having an alcoholic secondary or tertiary hydroxy group, and a crosslinking agent,
(A) the side chain comprises 3 to 30 carbon atoms and comprises at least one saturated or unsaturated hydrocarbon group or in addition to at least one more An aromatic group, and a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms,
(B) The crosslinking agent is selected from a triazine-based crosslinking agent or a glycoluril-based crosslinking agent.
Curable resin composition.
The chain polymer is a monomer unit having the side chain having an alcoholic secondary or tertiary hydroxy group, and is a (meth) acrylic monomer, a vinyl ester monomer, a vinyl ether monomer, and others The curable resin composition according to claim 1, 2 or 10, comprising at least one of the vinyl monomers as monomer units.
The chain polymer is CH 2 ═CH—COO—R 1 , CH 2 ═C (CH 3 ) —COO—R 2 , CH 2 ═CH—O—CO—R 3 , CH 2 ═CH—O—R. 4 and CH 2 ═CH—R 5 [wherein R 1 , R 2 , R 3 , R 4 , and R 5 are independently of each other when each vinyl group is bonded via an ester bond] It has 3 to 30 carbon atoms including the carbon atom constituting the ester bond, has an alcoholic secondary or tertiary hydroxy group, and contains at least one saturated or unsaturated hydrocarbon group. Or further comprising at least one aromatic group and having a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms. . A curable resin composition according to any one of claims 1 to 3 or 10 to 11, which comprises a monomer unit selected from the group consisting of compounds represented by the formula:
The curable resin composition according to any one of claims 2 to 12, wherein the monomer unit is a (meth) acrylic monomer.
The curable resin composition according to any one of claims 3 to 9, wherein R 1a is hydrogen or methyl.
The chain polymer may further have a hydroxy group or may have an unsubstituted or α-substituted (meth) acrylic monomer having 1 to 15 carbon atoms in the side chain, unsubstituted or It comprises at least one of α-substituted vinyl ester monomers, unsubstituted or α-substituted vinyl ether monomers, and other unsubstituted or α-substituted vinyl monomers as additional monomer units. The curable resin composition according to any one of claims 1 to 14.
The additional monomer units are CH 2 ═C (R 1a ) —COO—R 6 , CH 2 ═C (R 1a ) —O—CO—R 8 [where R 6 and R 8 are independent of each other. Having 1 to 15 carbon atoms, with or without hydroxy groups, comprising at least one saturated or unsaturated hydrocarbon group, or at least one more The hydrocarbon group or aromatic group may have a bond selected from the group consisting of —COO—, —O—, and —CO—, which includes an aromatic group and connects carbon atoms. It can have an amino group and R 1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted alkenyl group. CH 2 ═C (R 1a ) —O—R 9 , CH 2 ═C (R 1a ) —R 10, wherein R 9 and R 10 independently of one another have 3 to 15 carbon atoms With or without a hydroxy group, comprising at least one saturated or unsaturated hydrocarbon group, or further comprising at least one aromatic group, carbon It may have a bond selected from the group consisting of —COO—, —O—, and —CO— that connect the atoms, and the hydrocarbon group or aromatic group may have an amino group, and R 1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted alkenyl group. C 4 (R 1a ) O 3 —R 11 , and C 4 (R 1a ) HNO 2 —R 12, wherein C 4 (R 1a ) O 3 — represents an unsubstituted or substituted maleic anhydride group, C 4 (R 1a ) HNO 2 — represents an unsubstituted or substituted maleimide group, and R 11 and R 12 are each independently a hydrogen atom or a group having 1 to 15 carbon atoms, May or may not have a group, and includes at least one saturated or unsaturated hydrocarbon group, or further includes at least one aromatic group, and connects carbon atoms. It may have a bond selected from the group consisting of —COO—, —O—, and —CO—, the hydrocarbon group or aromatic group may have an amino group, and R 1a is hydrogen, Substituted or unsubstituted alkyl group and substituted or unsubstituted alkenyl It is selected from the group consisting of. The curable resin composition according to any one of claims 1 to 15, which is selected from the group consisting of compounds represented by the formula:
The chain polymer further has (meth) acrylic monomers, vinyl ester monomers, vinyl ether monomers, and other vinyl monomers having no hydroxy group and having 1 to 15 carbon atoms in the side chain. The curable resin composition according to any one of claims 1 to 16, which comprises at least one of them as an additional monomer unit.
The additional monomer units are CH 2 ═CH—COO—R 6 , CH 2 ═C (CH 3 ) —COO—R 7 , CH 2 ═CH—O—CO—R 8 , wherein R 6 , R 7 and R 8 independently of one another have 1 to 15 carbon atoms, have no hydroxy group, comprise at least one saturated or unsaturated hydrocarbon group, or at least It comprises one aromatic group and can have a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms, and the hydrocarbon group or aromatic The group group can have an amino group. ], CH 2 ═CH—O—R 9 , CH 2 ═CH—R 10, wherein R 9 and R 10 independently of one another have 3 to 15 carbon atoms and have a hydroxy group And at least one saturated or unsaturated hydrocarbon group, or further comprising at least one aromatic group and connecting between carbon atoms —COO—, —O—, and —CO -It may have a bond selected from the group consisting of-and the hydrocarbon group or aromatic group may have an amino group. ], C 4 HO 3 —R 11 , and C 4 H 2 NO 2 —R 12 [where C 4 HO 3 — represents a maleic anhydride group, C 4 H 2 NO 2 — represents a maleimide group, 11 and R 12 are each independently a hydrogen atom or have 1 to 15 carbon atoms, have no hydroxy group, and contain at least one saturated or unsaturated hydrocarbon group. Or further comprising at least one aromatic group and having a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms. The hydrocarbon group or aromatic group may have an amino group. The curable resin composition according to any one of claims 1 to 17, which is selected from the group consisting of compounds represented by the formula:
The curable resin composition according to any one of claims 1 to 18, wherein a proportion of the monomer unit having an alcoholic secondary or tertiary hydroxy group in the monomer unit constituting the chain polymer is 30 to 100 mol%. object.
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 19, wherein
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 20, wherein the curable resin composition is selected from the group consisting of a compound represented by formula (1) and / or a condensate thereof.
The curable resin composition according to any one of claims 1 to 21, wherein the condensate includes a polymer of the compound represented by formula B1, formula B2, or formula B3.
The curable resin composition according to any one of claims 1 to 22, wherein the condensate comprises a dimer, trimer or higher order polymer of the compound represented by formula B1, formula B2 or formula B3. object.
The crosslinking agent according to any one of claims 1 to 23, 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 1 to 24.
The curable resin composition according to any one of claims 1 to 25, 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: 0.03.
The curable resin composition according to any one of claims 1 to 26, further comprising an acid catalyst.
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 thereof; 28. The curable resin composition of claim 27, which is a solvate thereof.
The curable resin composition according to any one of claims 1 to 28, comprising a solvent.
A cured resin film obtained by curing the curable resin composition according to any one of claims 1 to 29.
An easily peelable cured resin film obtained by curing the curable resin composition according to any one of claims 1 to 29 on a substrate surface in a film shape.
The cured resin film of Claim 30 or 31 which has the peeling force in the board | substrate made from a soda glass of 0.5 N / mm < 2 > or less, or a board | substrate made from an alkali free glass.
The cured resin film according to any one of claims 30 to 32, 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 29, comprising:
(I) providing a chain polymer with a side chain having an alcoholic secondary or tertiary hydroxy 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,
Production method.
(Iv) The method according to claim 34, further comprising the step of peeling the cured resin film formed on the substrate from the substrate.
A method for producing a cured resin film, comprising:
(I) providing a chain polymer with a side chain having an alcoholic secondary or tertiary hydroxy group and a crosslinking agent;
(Ii) applying a 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 to form a cured resin film,
(A) the side chain comprises 3 to 30 carbon atoms and comprises at least one saturated or unsaturated hydrocarbon group or in addition to at least one more An aromatic group, and a bond selected from the group consisting of —COO—, —O—, and —CO— that connect the carbon atoms of adjacent groups among them. ,
(B) The crosslinking agent is selected from a triazine-based crosslinking agent or a glycoluril-based crosslinking agent.
Production method.
The chain polymer is a monomer unit having the side chain having an alcoholic secondary or tertiary hydroxy group, and is a (meth) acrylic monomer, a vinyl ester monomer, a vinyl ether monomer, and others The production method according to claim 36, comprising at least one of the vinyl monomers as a monomer unit.
The chain polymer is CH 2 ═CH—COO—R 1 , CH 2 ═C (CH 3 ) —COO—R 2 , CH 2 ═CH—O—CO—R 3 , CH 2 ═CH—O—R. 4 and CH 2 ═CH—R 5 [wherein R 1 , R 2 , R 3 , R 4 , and R 5 are independently of each other when each vinyl group is bonded via an ester bond] It has 3 to 30 carbon atoms including the carbon atom constituting the ester bond, has an alcoholic secondary or tertiary hydroxy group, and contains at least one saturated or unsaturated hydrocarbon group. Or further comprising at least one aromatic group and having a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms. . 38. The method according to claim 36 or 37, comprising a monomer unit selected from the group consisting of compounds represented by the formula:
The chain polymer further has (meth) acrylic monomers, vinyl ester monomers, vinyl ether monomers, and other vinyl monomers having no hydroxy group and having 1 to 15 carbon atoms in the side chain. The production method according to any one of claims 36 to 38, comprising at least one of them as an additional monomer unit.
The additional monomer units are CH 2 ═CH—COO—R 6 , CH 2 ═C (CH 3 ) —COO—R 7 , CH 2 ═CH—O—CO—R 8 , wherein R 6 , R 7 and R 8 independently of one another have 1 to 15 carbon atoms, have no hydroxy group, comprise at least one saturated or unsaturated hydrocarbon group, or at least It may contain a bond selected from the group consisting of —COO—, —O—, and —CO—, which contains one aromatic group and connects carbon atoms. ], CH 2 ═CH—O—R 9 , CH 2 ═CH—R 10, wherein R 9 and R 10 independently of one another have 3 to 15 carbon atoms and have a hydroxy group And at least one saturated or unsaturated hydrocarbon group, or further comprising at least one aromatic group and connecting between carbon atoms —COO—, —O—, and —CO A bond selected from the group consisting of: ], C 4 HO 3 —R 11 , and C 4 H 2 NO 2 —R 12 [where C 4 HO 3 — represents a maleic anhydride group, C 4 H 2 NO 2 — represents a maleimide group, 11 and R 12 are each independently a hydrogen atom or have 1 to 15 carbon atoms, have no hydroxy group, and contain at least one saturated or unsaturated hydrocarbon group. Or further comprising at least one aromatic group and having a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms. . The production method according to any one of claims 36 to 40, which is selected from the group consisting of compounds represented by the formula:
The production method according to any one of claims 36 to 40, wherein the proportion of the monomer unit having an alcoholic secondary or tertiary hydroxy group in the monomer unit constituting the chain polymer is 30 to 100 mol%.
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 36 to 41, which is selected from the group.
The production method according to any one of claims 36 to 42, 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: 0.03.
44. The production method according to claim 36, wherein the composition contains a solvent.
The method according to any one of claims 36 to 44, wherein the composition further comprises an acid catalyst.
(Iv) The method for producing a cured resin film according to any one of claims 34 to 45, further comprising the step of peeling the cured resin film formed on the substrate from the substrate.