KR20190044062A - Curable resin composition for forming a peelable film and method for producing the same - Google Patents

Abstract

Discloses a curable resin composition which can be applied to the surface of a glass substrate to form a thin film of a cured resin and which can withstand firing at 230 캜 and easily peel off from the substrate without difficulty. The present invention provides a curable resin composition comprising a chain polymer having a side chain having an alcoholic secondary or tertiary hydroxyl group and a cross-linking agent, wherein the side chain comprises 3 to 30 carbon atoms and at least one A saturated or unsaturated hydrocarbon group or further comprises at least one aromatic group, with the proviso that the linkage between the carbon atoms may comprise a bond selected from the group consisting of -COO-, -O- and -CO-, b) The crosslinking agent is a curable resin composition selected from the group consisting of a triazine compound and / or a condensate thereof, a glycoluril compound and / or a condensate thereof, an imidazolidinone compound and / or a condensate thereof.

Description

Curable resin composition for forming a 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 easy peelable film. More particularly, the present invention relates to a curable resin composition for forming a peelable film, To a curable resin composition. The present invention relates to a curable resin composition which is difficult to modify even during heat treatment and maintains easy releasability to easily form a thin film.

2. Description of the Related Art Display devices such as liquid crystal display devices and the like are widely used in portable terminals such as ticket machines, ATM smart phones, and computers and various other electric and electronic devices. The screen of the display device is generally of a high-strength plate type.

On the other hand, a flexible display device having a screen capable of some degree of deformation is being developed in response to the expansion of the potential use of the display device. A resin base film is used as a substrate constituting the curved circuit, but when it is used in a screen of a display device, a minute circuit can not be produced, and a transparent film which is as thin and light as possible is required.

Various microelectronic and electronic circuits are manufactured on a resin base film. For example, a photolithography method is used, and a metal film is formed on a base film, coating of a photoresist film, prebaking, exposure of a circuit pattern, A process of rinsing, baking, etching, photoresist removal, and the like are repeatedly combined with each other in accordance with the object and method to produce a circuit. In addition, an anisotropic conductive film (ACF) necessary for the layers and layers to be manufactured in this way is disposed, a printed wiring board is disposed at a necessary position, and the printed wiring board is heated and pressurized to form an anisotropic conductive film Circuit connection is made.

In general, a plurality of sintering steps are required to fabricate the entire circuit as such a laminate. For the performance of the circuit, firing is preferably performed at a sufficiently high temperature (around 230 캜), but the upper limit of the firing possible temperature is restricted depending on the level of the heat resistance of the base film. That is, firing can be performed only at a low temperature region below the heat resistance limit of the base film. Although it is possible to use other materials (such as silver nanoparticles) as the metal wiring that can be fired at such a low temperature, the wiring formed by the low-temperature firing using this material is technically undesirable because the characteristics are lowered compared with the conventional wiring using ITO .

Furthermore, although the base film is required to be thinned every year, the heat resistance of the base film is deteriorated by the thin film. As a result, since the upper limit of the heat treatment temperature is lowered to about 100 ° C, it is assumed that the upper limit of the temperature that can withstand the heat treatment of the base film is further reduced in accordance with the demand for further thinning in the future. There is a problem in that the base film material that can cope with this problem is not conspicuous.

Therefore, there is a demand for a base film material that can withstand a higher temperature than the conventional one.

Further, it is preferable to use a very thin film having a thickness of about 300 nm according to the thinning of the base film. For this purpose, a base film is manufactured by curing a resin composition, which is a base film material, on another substrate . A circuit element such as a metal wiring is sequentially deposited on a very thin base film formed on a substrate such as a glass substrate, and an anisotropic conductive film, lamination of printed wiring boards, circuit connection, etc. are also carried out according to purposes, , A laminate as a circuit component can be obtained by peeling the base film together with the respective layers on which the base film is formed on the substrate as an integral laminate.

Here, it is easy to peel the laminate from the substrate such as glass. Otherwise, a large strain is generated in the laminate due to the load at the time of pulling off, thereby causing disconnection of the metal wiring and peeling of the circuit connection, resulting in a marked deterioration of the yield of the product.

In particular, although the substrate material itself can withstand a heat treatment at a higher temperature than the conventional one in a thin film form, if the firing in the process of manufacturing the wiring thereon is performed at such a high temperature, the substrate material and the substrate surface stacked thereon are likely to be fixed. Therefore, the substrate material is insufficient to withstand the firing at a higher temperature than the conventional one in the form of a thin film, and it must be easy to peel off easily from the substrate even after such a high-temperature firing.

Furthermore, since the base film is very thin as described above, the resin material for forming the base film must be very thin and uniformly magnified without repulsion on the substrate (glass substrate or the like). This affinity to the substrate may be a factor that interferes with the ease of peeling since it may cause sticking to the substrate in the baking process.

[Patent Document 1] International Publication No. 2015/016532

Under the circumstances, the object of the present invention is to deposit a thin film of a cured resin by depositing very thinly on the surface of a substrate (glass or the like) and curing it, and then forming a circuit thereon by patterning, etc., The present invention also provides a curable resin composition which can easily peel off from a substrate even after exposure to a high temperature.

The present inventors have determined that the above object is 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 cross-linking agent.

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 hydroxyl group and a crosslinking agent,

(a) the side chain comprises from 3 to 30 carbon atoms and comprises at least one saturated or unsaturated hydrocarbon group or further comprises at least one aromatic group, with the proviso that the linkage between the carbon atoms is -COO-, - O-, and -CO-,

(b) the crosslinking agent is selected from a triazine crosslinking agent or a glycoluril crosslinking agent.

(Item A2) The chain polymer is a monomer unit having a side chain having an alcoholic secondary or tertiary hydroxyl group, and is at least one of a (meth) acrylic monomer, a vinyl ester monomer, a vinyl ether monomer and other vinyl monomers Wherein the curable resin composition comprises one monomer unit.

(Item A3) The polymer chain 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 independently represent an ester bond-forming carbon atom Containing at least one saturated or unsaturated hydrocarbon group or further containing at least one aromatic group and having a carbon atom-to-carbon number of 3 to 30 inclusive and having an alcoholic secondary or tertiary hydroxyl group and containing at least one saturated or unsaturated hydrocarbon group, May have a bond selected from the group consisting of -COO-, -O- and -CO-. Curable resin composition according to any one of < RTI ID = 0.0 >

(Item A4) The chain polymer comprises at least one of a (meth) acrylic monomer having no hydroxy group and having 1 to 15 carbon atoms in its side chain, a vinyl ester monomer, a vinyl ether monomer, and other vinyl monomer, Wherein the curable resin composition is a curable resin composition.

(Item A5) The additional monomer units include ^{_{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 from 1 to 15 carbon atoms, do not contain a hydroxy group and contain at least one saturated or unsaturated hydrocarbon group or additionally contain at least one aromatic group and the linkage between the carbon atoms is -COO -, -O- and -CO-, and the hydrocarbon group or the aromatic group may have an amino group], CH ₂ ═CH-O-R ⁹ , CH ₂ ═CH-R ¹⁰ [ wherein R ⁹ and R ¹⁰ are each independently have 3 to 15 carbon atoms, not including the hydroxy group, and at least one in addition to including or where groups of at least one saturated or unsaturated hydrocarbon It comprises an aromatic group and the connection between the carbon atoms is -COO-, may have a bond selected from the group consisting of -O- and -CO-, and may have a hydrocarbon group or the aromatic group is an amino _group], C 4 _HO 3 -R ¹¹ and C ₄ H ₂ NO ₂ -R ¹² wherein C ₄ HO ₃ - represents a maleic anhydride group, C ₄ H ₂ NO- represents a maleimide group, R ¹¹ and R ¹² independently represent a hydrogen atom or Containing from 1 to 15 carbon atoms and containing no hydroxy group and containing at least one saturated or unsaturated hydrocarbon group or further containing at least one aromatic group and the link between the carbon atoms is selected from the group consisting of -COO-, -O- and -CO- And the hydrocarbon group or the aromatic group may have an amino group] Any of the documents that the selected item, characterized in a curable resin composition.

(Item A6) The curable resin composition according to any one of the above items, wherein the proportion occupied by the monomer unit having the alcoholic secondary or tertiary hydroxyl group of the monomer unit constituting the chain polymer is 30 to 100 mol% .

(Item A7) The cross-linking agent is selected from the group consisting of complete or partial alkoxymethylated melamine, complete or partial alkoxymethylated guanamine, complete or partial alkoxymethylated acetoguanamine, complete or partial alkoxymethylated benzoguanamine and complete or partial alkoxymethylated glyceryl And the curable resin composition according to any one of the above items.

(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 ratio of the crosslinking agent in the composition is 1: 2 to 1: 0.05.

(Item A9) A curable resin composition according to any one of the above items, which contains a solvent.

(Item A10) A cured resin film obtained by curing any one of the above items.

(Item A11) A readily releasable cured resin film characterized in that any one of the above-mentioned curable resin compositions is cured on the substrate surface in a film form.

(Item A12) In the method for producing a cured resin film,

Preparing a chain polymer having a side chain having an alcohol secondary or tertiary hydroxyl group and a cross-linking agent;

Applying a composition comprising the chain polymer and a cross-linking agent to a substrate to form a curable resin composition coat;

And curing the polymerization reaction in the curable resin composition coating film to obtain a cured resin film,

Here

(a) the side chain has from 3 to 30 carbon atoms and comprises at least one saturated or unsaturated hydrocarbon group or additionally contains at least one aromatic group, with the proviso that the linkage between the carbon atoms of adjacent groups is -COO- , -O-, and -CO-,

(b) the crosslinking agent is selected from a triazine crosslinking agent or a glycoluril crosslinking agent.

(Item A13) The chain polymer is a monomer unit having a side chain having an alcoholic secondary or tertiary hydroxyl group, and may be a (meth) acrylic monomer, a vinyl ester monomer, a vinyl ether monomer and other vinyl monomers ≪ / RTI > wherein the polymer comprises one monomer unit.

(Item A14) The polymer chain 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 independently represent an ester bond-forming carbon atom Containing at least one saturated or unsaturated hydrocarbon group or further containing at least one aromatic group and having a carbon atom-to-carbon number of 3 to 30 inclusive and having an alcoholic secondary or tertiary hydroxyl group and containing at least one saturated or unsaturated hydrocarbon group, May have a bond selected from the group consisting of -COO-, -O- and -CO-]. How my production.

(Item A15) The chain polymer comprises at least one of a (meth) acrylic monomer, a vinyl ester monomer, a vinyl ether monomer and other vinyl monomer having no hydroxy group and having 1 to 15 carbon atoms in the side chain, Wherein the method comprises the steps of:

(Item A16) The additional monomer units include ^{_{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 from 1 to 15 carbon atoms, do not contain a hydroxy group and contain at least one saturated or unsaturated hydrocarbon group or additionally contain at least one aromatic group and the linkage between the carbon atoms is -COO -, -O- and -CO-, CH ₂ ═CH-O-R ⁹ , CH ₂ ═CH-R ¹⁰ [wherein R 9 and R ¹⁰ are independently of each other a carbon atom Containing from 3 to 15 carbon atoms and containing no hydroxy group and containing at least one saturated or unsaturated hydrocarbon group or further containing at least one aromatic group, the linking between the carbon atoms being --COO--, --O-- and --CO -, C ₄ HO ₃ -R ¹¹ and C ₄ H ₂ NO ₂ -R ¹² wherein C ₄ HO ₃ - represents a maleic anhydride group and C ₄ H ₂ NO ₂ - represents a maleimide group, R ¹¹ and R ¹² independently of one another are a hydrogen atom or contain from 1 to 15 carbon atoms, do not contain a hydroxy group and contain at least one saturated or unsaturated hydrocarbon group or further comprise at least one aromatic And the linkage between the carbon atoms may be a bond selected from the group consisting of -COO-, -O- and -CO-. Gt;

(Item A17), wherein the proportion of the monomer units constituting the chain polymer is occupied by monomer units having an alcoholic secondary or tertiary hydroxyl group of 30 to 100 mol%.

(Item A18) The cross-linking agent is selected from the group consisting of complete or partial alkoxymethylated melamines, fully or partially alkoxymethylated guanamines, fully or partially alkoxymethylated acetoguanamines, fully or partially alkoxymethylated benzoguanamines and fully or partially alkoxymethylated glycourilyls , And a method of manufacturing the same.

 (Item A19) The method of any one of the above items, wherein the mass ratio of the linear polymer to the crosslinking agent in the composition is 1: 2 to 1: 0.05.

(Item A20) The method of any one of the above items, wherein the composition comprises a solvent.

(Item A21) The method of manufacturing a cured resin film according to any one of the items above, further comprising peeling off 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-like polymer having a side chain having an alcoholic secondary or tertiary hydroxyl group and a crosslinking agent,

(a) the side chain comprises from 3 to 30 carbon atoms and contains at least one saturated or unsaturated hydrocarbon group or further contains at least one aromatic group, and the linkage between the carbon atoms is -COO-, - O-, and -CO-,

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

(Item B2) The chain polymer is a monomer unit having a side chain having an alcoholic secondary or tertiary hydroxyl group, and may be an unsubstituted or? -Substituted (meth) acrylic monomer, an unsubstituted or? -Substituted vinyl ester monomer, Position-substituted vinyl ether monomer, an unsubstituted or alpha-substituted vinyl ether monomer, and other unsubstituted or alpha-substituted vinyl monomer as monomer units.

(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 independently represent an ester bond-forming carbon atom when bonded to each vinyl group through an ester bond] Containing from 3 to 30 carbon atoms and having an alcoholic secondary or tertiary hydroxyl group and containing at least one saturated or unsaturated hydrocarbon group or further containing at least one aromatic group and the linkage between the carbon atoms being -COO -, -O-, and -CO-, and R1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted alkenyl group. From the group consisting of water and any of the above items, it characterized in that it comprises a monomer unit selected one of the curable resin composition.

 (Item B4) The chain polymer is represented by the formula A1:

[Chemical Formula 1]

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 a group 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, substituted or unsubstituted hydrocarbon radicals, provided that at least one of R ^2a , R ^3a and R ^4a is a substituted or unsubstituted secondary Or a tertiary OH-containing group], wherein the curable resin composition contains a monomer unit represented by the following formula (1):

(Item B5) The chain polymer is represented by the formula A2:

(2)

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 a group selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group and a substituted or unsubstituted alkenylene group And R < ^5a > to R < ^14a > independently from each other are hydrogen,

(3)

≪ / RTI > or together form a ring. However R ^5a ~ R ^14a is at least one hydroxy group of the ring substituents, R ^15a is substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkenyl group, a substituted or An unsubstituted aromatic group, and a substituted or unsubstituted heteroaromatic group. The curable resin composition according to any one of the above items, wherein the curable resin composition comprises a monomer unit represented by the following formula

 (Item B6) The chain polymer is represented by the formula A3:

[Chemical Formula 4]

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, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, An alkenyl group, an alkynyl group, and an alkynyl group.

(Item B7) The chain polymer is represented by Formula A4:

[Chemical Formula 5]

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 a group selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group and a substituted or unsubstituted alkenylene group , And R < ^18a > is an adamantyl group substituted with at least one hydroxy group. [5] The curable resin composition according to any one of the above items,

(Item B8) The chain polymer is represented by Formula A5:

[Chemical Formula 6]

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 a group selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group and a substituted or unsubstituted alkenylene group And 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. Wherein the curable resin composition is a curable resin composition.

(Item B9) The curable resin composition according to any one of the above items, wherein ^R19a 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 hydroxyl group and a crosslinking agent,

(a) the side chain comprises from 3 to 30 carbon atoms and contains at least one saturated or unsaturated hydrocarbon group or further contains at least one aromatic group and the linkage between the carbon atoms is -COO-, -O - and -CO-, < / RTI >

(b) the crosslinking agent is selected from a triazine crosslinking agent or a glycoluril crosslinking agent.

(Item B11) The chain polymer is a monomer unit having the side chain having an alcoholic secondary or tertiary hydroxyl group, and the (meth) acrylic monomer, the vinyl ester monomer, the vinyl ether monomer and the vinyl monomer And at least one of them is contained as a monomer unit.

(Item B12) wherein the polymer chain 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 independently represent an ester bond constituent carbon atom when they are bonded to each vinyl group through an ester bond, Containing from 3 to 30 carbon atoms and having an alcoholic secondary or tertiary hydroxyl group and containing at least one saturated or unsaturated hydrocarbon group or further containing at least one aromatic group and the connection between the carbon atoms is - COO-, -O-, and -CO-. [0043] The above-mentioned < RTI ID = 0.0 > Any one of the curable resin composition of the.

(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 of any one of the above items, wherein R ^1a is hydrogen or methyl.

(Item B15) The chain polymer includes an unsubstituted or? -Substituted (meth) acrylic monomer having a carbon number of 1 to 15 in the side chain, an unsubstituted or? -Substituted vinyl ester monomer, an unsubstituted or? position-substituted vinyl ether-based monomer, and other unsubstituted or? -substituted vinyl-based monomer as additional monomer units. The curable resin composition according to any one of the above items,

(Item B16) wherein the additional monomer unit is selected from the group consisting of CH ₂ ═C (R ^1a ) -COO-R ⁶ , CH ₂ ═C (R ^1a ) -O-CO-R ⁸ wherein R ⁶ and R ⁸ are independently of each other Containing at least one saturated or unsaturated hydrocarbon group or further containing at least one aromatic group and having a carbon number of 1 to 15 and containing or not containing a hydroxy group and the link between the carbon atoms is selected from the group consisting of -COO-, -O- and -CO -, the hydrocarbon group or the 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,

^{_{CH 2 = C (R 1a)}} -O-R 9, CH 2 = C (R 1a) -R 10 [ wherein R ⁹ and R ¹⁰ are independently has a carbon number of 3-15 with each other with or without a hydroxyl group, and Containing at least one saturated or unsaturated hydrocarbon group or further containing at least one aromatic group and the linkage between the carbon atoms may have a bond selected from the group consisting of -COO- -O- and -CO-, and the hydrocarbon group Or an 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 R ₄ C ^(R 1a) _{O 3} - represents an unsubstituted or substituted maleic acid, _C 4 (R ¹ ) HNO ₂ - represents an unsubstituted or substituted maleimide group, R ¹¹ and R ¹² independently of one another are a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, with or without a hydroxy group, and at least one saturated or unsaturated hydrocarbon group Or further include at least one aromatic group and the linkage between the carbon atoms may have a bond selected from the group consisting of -COO-, -O- and -CO-, and the hydrocarbon group or the aromatic group may have an amino group and, R ^1a is selected from the group consisting of hydrogen, substituted or unsubstituted alkenyl group and a substituted or unsubstituted al.] the compound represented by Any one of the curable resin composition of the item, characterized in that the member selected from the group consisting of.

(Item B17) The chain polymer comprises at least one of a (meth) acrylic monomer, a vinyl ester monomer, a vinyl ether monomer and other vinyl monomer having no carbon atoms and having 1 to 15 carbon atoms in the side chain, Wherein the curable resin composition is a curable resin composition.

(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 from 1 to 15 carbon atoms, do not contain a hydroxy group and contain at least one saturated or unsaturated hydrocarbon group or additionally contain at least one aromatic group and the linkage between the carbon atoms is -COO -, -O-, and -CO-, and the hydrocarbon group or the aromatic group may 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 from 3 to 15 carbon atoms and do not contain a hydroxy group and contain at least one saturated or unsaturated hydrocarbon group Further including at least one aromatic group, and the linkage between the carbon atoms may have a bond selected from the group consisting of -COO-, -O- and -CO-, 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 wherein C ₄ HO ₃ - represents a maleic anhydride group, C ₄ H ₂ NO ₂ - represents a maleimide group, and R ¹¹ and R ¹² represent Independently of each other, a hydrogen atom, or from 1 to 15 carbon atoms, which does not contain a hydroxy group and which contains at least one saturated or unsaturated hydrocarbon group or which additionally contains at least one aromatic group, the connection between the carbon atoms being --COO--, -O-, and -CO-, and the hydrocarbon group or the aromatic group may have an amino group], wherein the compound is selected from the group consisting of Curable resin composition.

(Item B19) The curable resin composition according to any one of the above items, wherein the proportion occupied by monomer units having an alcoholic secondary or tertiary hydroxyl group of the monomer units constituting the chain polymer is from 30 to 100 mol% .

(Item B20) The crosslinking agent may be a complete or partial alkoxymethylated melamine and / or its condensate, a complete or partial alkoxymethylated guanamine and / or its condensates, a complete or partial alkoxymethylated acetoguanamine and / or its condensates, Or a partial alkoxymethylated benzoguanamine and / or a condensate thereof, a complete or partial alkoxymethylated glyceryl and / or its condensate and a complete or partial alkoxymethylated imidazolidinone and / or a condensate thereof. Wherein the curable resin composition is a curable resin composition.

 (Item B21) The crosslinking agent is represented by the formula B1:

(7)

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

[Chemical Formula 8]

And R ^2b to R ^7b are independently selected from the group consisting of substituted or unsubstituted alkyl groups and substituted or unsubstituted alkenyl groups each having 1 to 10 carbon atoms. And / or a condensate thereof,

Expression B2:

[Chemical Formula 9]

[Wherein R ^8b to R ^11b each independently represent a group 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 /

Expression B3:

[Chemical formula 10]

Wherein R ^12b and R ^13b 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 R ^14b and R ^15b are each independently selected from the group consisting of hydrogen or A substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group having 1 to 10 carbon atoms, and / or a condensate thereof. Any one of the curable resin compositions.

(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 according to any one of the above items, wherein the condensate comprises a dimer, a trimer or a higher-order polymer of the compound represented by the formula B1, B2 or B3.

(Item B24) The curable resin composition 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 with respect to the compound represented by the formula B1, B2 or B3, respectively.

(Item B25) R ^1b is a substituted or unsubstituted aromatic group and

(11)

, R ^2b to R ^13b are independently of each other a substituted or unsubstituted alkyl group, and R ^14b and R ^15b are each independently a hydrogen atom. Resin composition.

(Item B26) 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 ratio of the crosslinking agent is 1: 2 to 1: 0.03.

(Item B27) an acid catalyst. The curable resin composition of 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-100L (Samsin Chemical Industry Co., Ltd.) Wherein the curable resin composition is a solvate thereof.

(Item B29). ≪ / RTI > The curable resin composition according to any one of the above items, further comprising a solvent.

(Item B30) A cured resin film obtained by curing any one of the above items.

(Item B31) A readily releasable cured resin film obtained by curing a curable resin composition of any one of the above items in a film form on the surface of a substrate.

(Item B32) A cured resin film having any one of the above items having a peeling force in a soda-glass substrate or an alkali-free glass substrate of 0.5 N / mm ² or less.

(Item B33) A cured resin film having any one of the above items having a peeling force in a soda-glass substrate or an alkali-free glass substrate of 0.1 N / mm ² or less.

(Item B34) In the method for producing a cured resin film from any one of the above-mentioned curable resin compositions,

(I) preparing a chain polymer having a side chain having an alcoholic secondary or tertiary hydroxyl group and a crosslinking agent;

(Ii) applying the curable resin composition comprising the chain polymer and the cross-linking agent on a substrate to form a cured resin composition coating film;

(Iii) a step of forming a cured resin film by causing a polymerization reaction to proceed in the coating film of the curable resin composition.

(Item B35). (Iv) The method of manufacturing the item further comprising peeling the cured resin film formed on the substrate from the substrate.

(Item B36) In the method for producing a cured resin film,

(I) preparing a chain polymer having a side chain having an alcoholic secondary or tertiary hydroxyl group and a crosslinking agent;

(Ii) applying a composition comprising the chain polymer and a cross-linking agent to a substrate to form a curable resin composition coating film;

(Iii) forming a cured resin film by causing a polymerization reaction to proceed in the curable resin composition coating film,

In this step

(a) the side chain comprises from 3 to 30 carbon atoms and contains at least one saturated or unsaturated hydrocarbon group or further contains at least one aromatic group, and the linkage between the carbon atoms is -COO-, -O- and -CO-, < / RTI >

(b) the crosslinking agent is selected from a triazine crosslinking agent or a glycoluril crosslinking agent.

(Item B37) The chain polymer is a monomer unit having a side chain having an alcoholic secondary or tertiary hydroxyl group and is selected from among (meth) acrylic monomers, vinyl ester monomers, vinyl ether monomers and other vinyl monomers A process according to any one of the preceding claims characterized in that it comprises at least one monomer unit.

(Item B38) wherein the polymer chain 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 independently represent an ester bond constituent carbon atom when they are bonded to each vinyl group through an ester bond, Containing 3 to 30 carbon atoms and having an alcoholic secondary or tertiary hydroxyl group and containing at least one saturated or unsaturated hydrocarbon group or additionally containing at least one aromatic group, -COO-, -O-, and -CO-], and a compound represented by the following formula Either in the production process.

(Item B39) The chain polymer comprises at least one additional monomer unit of a (meth) acrylic monomer, a vinyl ester monomer, a vinyl ether monomer, and other vinyl monomers having no carbon atoms and having 1 to 15 carbon atoms in the side chain The method comprising the steps of:

(Item B40) wherein 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 from 1 to 15 carbon atoms, do not contain a hydroxy group and contain at least one saturated or unsaturated hydrocarbon group or additionally contain at least one aromatic group and the linkage between the carbon atoms is -COO -, -O-, and -CO-,

CH ₂ ═CH-O-R ⁹ , CH ₂ ═CH-R ¹⁰ wherein R ⁹ and R ¹⁰ independently of one another have from 3 to 15 carbon atoms and do not contain a hydroxy group and contain at least one saturated or unsaturated hydrocarbon group Further including at least one aromatic group and the linkage between the carbon atoms may have a bond selected from the group consisting of -COO-, -O- and -CO-,

C ₄ HO ₃ -R ¹¹ and C ₄ H ₂ NO ₂ -R ¹² wherein C ₄ HO ₃ - represents a maleic anhydride group, C ₄ H ₂ NO ₂ - represents a maleimide group, and R ¹¹ and R ¹² represent Independently of each other, a hydrogen atom or from 1 to 15 carbon atoms, which does not contain a hydroxy group and which contains at least one saturated or unsaturated hydrocarbon group or which additionally contains at least one aromatic group, the connection between the carbon atoms being --COO--, -O-, and -CO-, and the compound represented by the formula (1) is selected from the group consisting of compounds represented by the following formulas.

(Item B41) The production method of any one of the above items, wherein the proportion of the monomer units constituting the chain type polymer occupied by monomer units having an alcoholic secondary or tertiary hydroxyl group is 30 to 100 mol%.

(Item B42) The cross-linking agent is selected from the group consisting of complete or partial alkoxymethylated melamine, fully or partially alkoxymethylated guanamine, fully or partially alkoxymethylated acetoguanamine, fully or partially alkoxymethylated benzoguanamine and fully or partially alkoxymethylated glycourilyl , And a method of manufacturing the same.

(Item B43) The method of any one of the above items, wherein the mass ratio of the linear polymer to the crosslinking agent in the composition is 1: 2 to 1: 0.03.

(Item B44) The method of any one of the above items, wherein the composition comprises a solvent.

(Item B45) The method of any one of the above items, wherein the composition comprises an acid catalyst.

(Item B46). (Iv) A method of producing a cured resin film according to any one of the items above, further comprising peeling off the cured resin film formed on the substrate from the substrate.

(Item B47) A composition for producing a circuit by a photolithography method comprising a curable resin composition or a cured resin film of any one of the above items.

(Item B48) A composition for the production of a flexible electric or electronic circuit component or a flexible display device in the form of a sheet comprising a curable resin composition or a cured resin film of any one of the above items.

(Item B49) It is used in a synthetic resin, a pellet, a film, a plate, a fiber, a foaming agent, a tube, a rubber, and an elastomer including a curable resin composition or a cured resin film of any one of the above items, (Such as a table, a chair, a desk, a shelf), a bedding (such as a bed, a hammock, etc.), a clothes, a protective clothing, a sporting goods, a bathtub (Kitchen, kitchen, tableware, cooking utensil, containers and packaging materials) (food containers, cosmetics containers, cargo containers, trash cans, etc.) (Electronic products, computer parts, printed circuit boards, insulators, conductors, wiring film materials, power generation devices, speakers, microphones, noise suppressors, transducers, etc.), optical communication cables, medical materials and devices (Sensors used in industrial robots, etc.), energy generation devices and plants (solar power generation, wind power generation, etc.), small pumps, actuators, robot materials ). ≪ / RTI >

(Item B50) A composition for the production of an electronic material, a medical material, a health care material, a life science material, or a robot material comprising a curable resin composition or a cured resin film of any one of the items.

(Item B51) A composition for producing a material such as a catheter, a guide wire, a medicine container or a tube, which comprises a curable resin composition or a cured resin film of any one of the above items.

(Item B52) An automobile part (including a body panel, a bumper belt, a rocker panel, a side mall, an engine part, a driving part, a conduction part, a steering part, a ballast part, Suspension parts, brake parts, brake parts, shaft parts, pipes, tanks, wheels, seats, seat belts, etc.).

(Item B53) A composition for the manufacture of a vehicle dustproof material, an automotive coating material, and a synthetic resin for automobiles, which comprises a curable resin composition or a cured resin film of any one of the above items.

(Item B54) Use of a curable resin composition or a cured resin film of any one of the above items for the production of a circuit by photolithography.

(Item B55) Use of a curable resin composition or a cured resin film of any of the above items for the production of sheet-like flexible electric or electronic circuit components or flexible display devices.

(Item B56) It is used in a synthetic resin, a pellet, a film, a plate, a fiber, a foaming agent, a tube, a rubber and an elastomer and is used for a motorcycle (a bicycle, a motorcycle), an automobile, an airplane, a train, a ship, a rocket, (Such as a table, a chair, a desk, a shelf, etc.), a bedding (such as a bed, a hammock, etc.), a garment, a protective clothing, a sporting goods, a bathtub, a kitchenware, (Building, road, building parts, etc.), agricultural film, industrial film, water and sewage, paints, cosmetics, electrical industry and electronics industry (electronic products, computer parts, printed circuit (Catheter, guide wire, artificial blood vessel, artificial muscle, artificial organ, dialysis membrane, endoscope, etc.), optical communication cable, medical material and apparatusThe use of a curable resin composition or a cured resin film of any one of the above items for the production of a small pump, an actuator, a robot material (a sensor used for industrial robots and the like), an energy generating device and a plant (solar power generation, wind power generation, .

(Item B57) Use of a curable resin composition or a cured resin film of any of the above items for the production of an electronic material, a medical material, a health care material, a life science material, or a robot material.

(Item B58) Use of a curable resin composition or a cured resin film of any one of the above items for the production of a material such as a catheter, a guide wire, a medicine container or a tube.

(Item B59) Automobile parts (body panels, bumper belts, rocker panels, side malls, engine parts, drive parts, conduction parts, control parts, ballast parts, suspension and braking parts, brake parts, shaft parts, Tires, wheels, seats, seat belts, etc.). The use of the curable resin composition or the cured resin film of any of the above items.

(Item B60) Use of a curable resin composition or a cured resin film of any one of the above items for the production of an automotive dustproof material, an automotive coating material, or an automotive synthetic resin.

(Item B61) A method for producing a circuit by photolithography, comprising the step of forming a curable resin composition or a cured resin film of any one of the items by performing a polymerization reaction.

(Item B62) A method for producing a sheet-like flexible electric / electronic circuit component or a flexible display device, which comprises a step of forming a curable resin composition or a cured resin film of any one of the items by performing polymerization reaction.

(Item B63) It is used in a synthetic resin, a pellet, a film, a plate, a fiber, a foaming agent, a tube, a rubber and an elastomer and is used for a motorcycle (a bicycle, a motorcycle), an automobile, an airplane, a train, a ship, a rocket, (Such as a table, a chair, a desk, a shelf, etc.), a bedding (such as a bed, a hammock, etc.), a garment, a protective clothing, a sporting goods, a bathtub, a kitchenware, (Building, road, building parts, etc.), agricultural film, industrial film, water and sewage, paints, cosmetics, electrical industry and electronics industry (electronic products, computer parts, printed circuit (Catheter, guide wire, artificial blood vessel, artificial muscle, artificial organ, dialysis membrane, endoscope, etc.), optical communication cable, medical material and apparatus), A small pump, an actuator, a robot material (a sensor used for industrial robots and the like), an energy generating device and a plant (solar power generation, wind power generation, etc.) And a step of forming a curable resin composition or a cured resin film.

(Item B64) A process for producing an electronic material, a medical material, a health care material, a life science material, or a robot material, wherein a polymerization reaction is carried out to form a curable resin composition or a cured resin film of any one of the items Methods of inclusion.

(Item B65) A method for producing a material such as a catheter, a guide wire, a medicine container or a tube, comprising the step of forming a curable resin composition or a cured resin film of any one of the items by performing a polymerization reaction.

(Item B66) Automobile parts (body panels, bumper belts, rocker panels, side malls, engine parts, drive parts, conduction parts, control parts, ballast parts, suspension / braking parts, brake parts, shaft parts, A tire, a tire, a wheel, a seat, a seat belt, or the like), comprising the step of forming a curable resin composition or a cured resin film of any one of the items by performing a polymerization reaction.

 (Item B67) A method for producing an automotive dustproof material, an automotive coating material, or an automotive synthetic resin, comprising the step of forming a curable resin composition or a cured resin film of any one of the items by performing a polymerization reaction.

 [1] Definition of Terms

As used herein, the term " heat resistance " means that the film obtained by curing the curable resin composition does not cause substantial decomposition or other deterioration, which is capable of withstanding heating up to 150 캜, preferably capable of withstanding heating at 230 캜. The temperature of 230 占 폚 is high enough to be used as a firing temperature in the production of an electronic circuit by photolithography.

In the present specification, the term "peelable film" means that a film formed by coating and curing on a substrate, particularly a glass substrate, can easily peel off the film on the substrate without damaging it (that is, without difficulty) It means nature. Examples of the glass substrate include a suitable glass substrate such as a soda glass substrate and an alkali-free glass substrate. A soda glass substrate is a particularly preferred example.

In the present specification, the thickness of the " cured resin film " is not limited. When used as a base film for circuit fabrication, a preferable thickness is 200 to 400 nm, for example, about 300 nm, which corresponds to the current demand for thinning of electronic components and the performance of the cured resin film itself is limited to the thickness range The thickness of the cured resin film is optional. In the present specification, the term "cured resin thin film" is used in the same sense as "cured resin film".

In the present specification, the term " side chain " in the chain polymer means a structural portion branched at the main chain, and " main chain " means a chain composed of atoms connected in a one-dimensional direction of the repeating monomer unit in the polymer structure. Thus, for example, when the polymer is a (meth) acrylate polymer, it is a moiety that forms an ester bond in each monomer. &Quot; -COO- " is included in a part of " side chain ". The notation of " (meth) acrylate " indicates acrylate and methacrylate without distinction. Similarly, the notation " (meth) acrylic " indicates acrylic and methacrylic indiscriminately. The term " (meth) acrylate " indicates acrylic acid and methacrylic acid.

Described herein as " -O- " " CO- " include those where they are part of " COO- ". In addition, " -COO- " is a description showing an ester when both end groups of the ester are not fixed, and includes both '-COO-' and '-O-CO-'. However, when both end groups of the ester are fixed, '-COO-' and '-O-CO-' are used separately.

As used herein, "alkyl" means a monovalent group resulting from the elimination of one hydrogen atom from an aliphatic hydrocarbon (alkane) such as methane, ethane, propane, and is generally represented by C _n H _{2n + 1} - Lt; / RTI > Alkyl can be linear or branched. Examples of the alkyl group (C1-4 alkyl group) having 1 to 4 carbon atoms include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, But the present invention is not limited to these examples.

Examples of the alkyl group having 1 to 6 carbon atoms (C _1-6 alkyl) include an alkyl group having 1 to 4 carbon atoms, a tert-butyl group, a sec-butyl group, an n-pentyl group, - hexyl group, isohexyl group, cyclohexyl group and the like, but the present invention is not limited to these examples. Examples of the alkyl group (C _1-10 alkyl group) having _{1 to 10} carbon atoms include an alkyl group having 1 to 6 carbon atoms, an n-octyl group, a n-nonyl group and an n-decanyl group, The invention is not limited to these examples.

Of the terms "alkenyl groups" are ethene, propene, means a monovalent group generated is one hydrogen atom is lost from aliphatic hydrocarbon (alkene) containing at least one double bond, such as butene, and, in general, C _m H _2m-1 (Where m is an integer of 2 or more). The alkenyl group may be straight-chain or branched.

Examples of the alkenyl group having 2 to 6 carbon atoms include an ethynyl group, a 1-propenyl group, a 2-propenyl group, a butenyl group, a pentenyl group and a hexenyl group. However, the invention is not limited to these examples. Examples of the alkenyl group having 2 to 10 carbon atoms include an alkenyl group having 2 to 6 carbon atoms, a heptenyl group, an octenyl group, a nonenyl group and a decenyl group, but the present invention is not limited to these examples .

In this specification, "alkynyl group" are ethynyl (acetylene), propyne, in an aliphatic hydrocarbon (alkyne) containing at least one triple bond, such as butyne; means a monovalent group a hydrogen atom is produced is lost, generally C _m H _2m-3 (where m is an integer of 2 or more). The alkynyl group may be straight-chain 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 and a hexynyl group, but the present invention is not limited thereto . Examples of the alkynyl group having 2 to 10 carbon atoms include an alkynyl group, a heptynyl group, an octynyl group, a nonynyl group and a decynyl group having 2 to 6 carbon atoms, but the present invention is not limited to these examples .

In the present specification, the term "alkylene group" means a divalent group formed by eliminating two hydrogen atoms from an aliphatic hydrocarbon (alkane) such as methane, ethane or propane and is generally represented by - (C _m H _2m ) - Is a positive integer). The alkyl group may be linear or branched. Examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, A hexylene group, and an isohexylene group, but the present invention is not limited to these examples. An alkylene group having 1 to 6 carbon atoms is preferable and an alkylene group having 1 to 4 carbon atoms is more preferable. More preferably a methylene group and an ethylene group, and still more preferably an ethylene group.

The term " alkenylene group " as used herein means a divalent group formed by eliminating two hydrogen atoms from an aliphatic hydrocarbon (alkene) containing at least one double bond such as ethenylene, propenylene or butenylene, _m H _2m-2 ) - (where m is an integer of 2 or more). The alkenylene group may be straight-chain or branched. Examples of the alkenylene group having 2 to 10 carbon atoms include an ethenylene group, an n-propenylene group, an isophenylene group, an n-butenylene group, an isobuthenylene group, an n- An isohexenylene group and the like, but the present invention is not limited to these examples. An alkenylene group having 2 to 6 carbon atoms is preferable, and an alkenylene group having 2 to 4 carbon atoms is more preferable. More preferably an ethenylene group and an n-prophenylene group, and still more preferably an ethenylene group.

As used herein, " alkoxy " means a monovalent group formed by elimination of a hydrogen atom of a hydroxyl group of an alcohol, generally represented by C _n H _{2n + 1} O- (where n is an integer of 1 or more). Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-propyloxy, isobutyloxy, N-pentyloxy group, isoamyloxy group, n-hexyloxy group, isohexyloxy group and the like, but the present invention is not limited to these examples.

As used herein, the term " haloalkyl group " means an alkyl group in which one or more hydrogen atoms of the alkyl group are substituted with halogen atoms. &Quot; Perhaloalkyl " means an alkyl group in which all the hydrogen atoms of the alkyl group are substituted with halogen atoms. Examples of the haloalkyl group having 1 to 6 carbon atoms include a trifluoromethyl group, a trifluoroethyl group, a perfluoroethyl group, a trifluoro n-propyl group, a perfluoro n-propyl group, a trifluoro isopropyl group, Butyl group, a trifluoro isobutyl group, a perfluoroisobutyl group, a trifluoro tert-butyl group, a perfluoro tert-butyl group, a perfluorohexyl group, N-pentyl group, trifluoro n-pentyl group, perfluoro n-pentyl group, trifluoro n-hexyl group, and perfluoro n-hexyl group, but the present invention is not limited to these examples.

As used herein, the term " cycloalkyl group " means a monocyclic or polycyclic saturated hydrocarbon group, and includes those having a crosslinked 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 and an isobornyl group. _{Examples of the} "C _3-12 cycloalkyl group" include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a C _6-12 cycloalkyl group. Preferably a " C _6-12 cycloalkyl group ".

As used herein, the term " cycloalkenyl group " means a monocyclic or polycyclic unsaturated hydrocarbon group containing a double bond, including those having a crosslinked structure. And one or more double bonds of the carbon-carbon bond of the above-mentioned " cycloalkyl group ". For example, the "C _3-12 cycloalkenyl group" means a cyclic alkenyl group having 3 to 12 carbon atoms. Specific examples thereof include a 1-cyclohexenyl group, a 2-cyclohexenyl group, a 3-cyclohexenyl group, a cycloheptenyl group, a cyclooctenyl group, a cyclononenyl group and the like in the case of the "C _6-12 cycloalkenyl group" . _{Examples of the} "C _3-12 cycloalkyl group" include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a C _6-12 cycloalkenyl group. Preferably a " C _6-12 cycloalkenyl group ".

In the present specification, the term "hydrocarbon group" refers to a monovalent group formed by eliminating one hydrogen atom from a compound consisting solely of carbon and hydrogen. The hydrocarbon radical includes the above-mentioned "alkyl group", "alkenyl group", "alkylene group", "alkenylene group", "cycloalkyl group" and "cycloalkenyl group" and the following "aromatic group" and " . The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group is classified into a chain type hydrocarbon group and a cyclic hydrocarbon group depending on the bonding method of carbon, and the cyclic hydrocarbon group is also classified into an alicyclic hydrocarbon group and an aromatic hydrocarbon group. Examples of saturated or unsaturated hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, cyclohexyl, dicyclopentadienyl, decarinyl, adamantyl, butenyl, hexenyl, Decyl, etc., and various straight chain, branched chain, monocyclic and condensed cyclic groups within the limit of the number of carbon atoms in the side chain. When each group is not located at the terminal, it may be a divalent or higher group depending on the bonding relationship with other groups.

As used herein, the term " aromatic group " means a group formed by leaving one hydrogen atom bonded to an aromatic hydrocarbon ring. (C ₃ H ₅ -) in benzene, a tolyl group (CH ₃ C ₆ H ₄ -) in toluene, a xylyl group ((CH ₃ ) ₂ C ₆ H ₃ -) in xylene, a naphthyl group (C ₁₀ H ₈ -). The term " heteroaromatic group " as used herein refers to a monocyclic or polycyclic heteroatom-containing aromatic group, and the group includes one or more heteroatoms selected from a nitrogen atom, a sulfur atom and an oxygen atom, 1 to 4).

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

In the present specification, the term "alicyclic group" means a moiety (or group) formed by leaving one hydrogen atom bonded to a ring having no aromatic property composed only of carbon and hydrogen. The cycloaliphatic group includes the above-mentioned "cycloalkyl group" and "cycloalkenyl group". The alicyclic group may be saturated or unsaturated. Examples of the saturated or unsaturated alicyclic group include various monocyclic and condensed cyclic groups within the limit of the number of carbon atoms of the side chain such as cyclohexyl, dicyclopentadienyl, decarinyl, adamantyl, cyclohexenyl and the like, but are not limited thereto Do not. When each group is not located at the terminal, it may be a divalent or higher group depending on the bonding relationship with other groups.

In general, the term " substituted " means that at least one hydrogen radical is substituted in a given structure depending on the radical of the particular substituent. In the present specification, the number of substituents of the groups defined by using "substituted / unsubstituted" is not particularly limited as long as it is substitutable, and is 1 or more. Unless otherwise stated, the description of each group applies even if the group is a part or substituent of another group. Also, a substituent that does not specifically specify the term " substituted " in the present specification means an "unsubstituted" substituent. In addition, the term " substituted or unsubstituted " is used herein interchangeably with the term " may be substituted ".

Substituted alkyl group, a substituted alkyl group, a substituted alkenyl group, a substituted alkynyl group, a substituted cycloalkyl group, a substituted cycloalkenyl group, a substituted hydrocarbon group, a substituted aromatic group, A substituent of a group described in this specification including an aromatic group, a substituted alkylene group, a substituted alkenylene group, a substituted or unsubstituted secondary or tertiary OH containing group, and a substituted adamantyl group. Examples of the substituent include a halogen, a hydroxy group, a C _1-10 alkyl group, a C _1-10 alkoxy group, a C _2-10 alkenyl group, a C _6-12 cycloalkyl group, a C _6-12 cycloalkenyl group, a C _1-10 halo group, a C Substituted with a C _1-10 alkyl group or a C _6-12 hydrocarbon group substituted with a _2-10 haloalkenyl group, a C _6-18 hydrocarbon group, a C _6-18 aromatic group, a C _6-18 heteroaromatic group, a C _6-12 aromatic group, a C _{1 ~ 10} alkyl group, C _{6 ~} C ₁₂ aromatic of _2-10 alkenyl group, C _{6 ~ 12} hydrocarbon group substituted C _2-10 alkenyl group, -CN, an oxo group (= O) substituted by a group, -O ( CH ₂ ) ₂ O-, -OC (CH ₃ ) ₂ O-, -OCH ₂ O-, -O-, Encircling (-COO- or -O-CO-), C _{6 ~ 12} hydrocarbon-substituted ester groups, C _{6 ~ 12} aromatic group substituted by an ester group, a C _{6 ~ 18} hydrocarbon group substituted by an ester, substituted with ester A C _1-10 alkyl group, a C _1-6 alkylene group, a C _2-6 alkenylene group and the like, but the present invention is not limited to these examples.

Preferred examples of the substituent include a hydroxy group, C _{6 ~ 18} hydrocarbon groups, C _{1 ~ 10} alkyl group, C _{6 ~ 12} aromatic group-substituted C _{1 ~ 10} alkyl group, C _{6 ~ 12} hydrocarbons of C _{1 ~ 10} alkyl, the ester substituted with a groups substituted by C _{6 ~ 18} hydrocarbon group, a C _{1 ~ 10} alkyl group substituted by an ester, an ester group (-COO- or -O-CO-), an ester group substituted with a C _{6 ~ 12} hydrocarbons, aromatic C _{6 ~ 12} group substituted with an ester group, a C _2-10 alkenyl group, C _{6 ~ 12} aromatic group-substituted C _2-10 alkenyl group, C _{6 ~ 12} hydrocarbon group substituted by a C _2-10 alkenyl group, C _{1 ~ 10} alkoxy group, A C _6-12 cycloalkyl group, and a C _6-12 cycloalkenyl group. More specific examples include an adamantyl group substituted by a benzoyloxy group, a phenyl group, a cyclohexyl group, a cyclohexenyl group, an adamantyl group, or a hydroxy group .

"Α-substituted (meth) acrylic monomer" herein is to form a double bond of CH ₂ = ^C (R 1a), as represented by ^{-COO-R 1,} an ester group -COO- right side of the carbon (α position) Quot; refers to a carbon-substituted acrylic monomer. Similarly, the "α-substituted vinyl ester-based monomer" is CH ₂ = ^C (R 1a), as represented by ^{-O-CO-R 3,} an ester group -O-CO- next (α position) of the oxygen double Position-substituted vinyl ether monomer "means an acrylic monomer substituted with carbon which forms a bond. As shown by CH ₂ = C (R ^1a ) -O-R ⁴ , Means a carbon-substituted acrylic monomer forming a double bond at the side (? Position). "α-position substituted vinyl-based monomer" means an acrylic monomer substituted with an internal carbon which is not a terminal carbon of a vinyl group, as represented by CH ₂ ═C (R ^1a ) -R ⁵ . R ¹ , R ³ , R ⁴ , R ⁵ and R ^1a are as defined in the following Preferred Embodiment (2-1) Curable Resin Composition.

The term "a secondary or tertiary OH-containing group" in the present specification refers to a group containing one or more secondary or tertiary hydroxy (OH) groups. Accordingly, the " second or tertiary OH-containing group " also includes a secondary or tertiary hydroxyl group itself. In the "substituted or unsubstituted secondary or tertiary OH containing group", "substituted or unsubstituted" means a group containing one or more secondary or tertiary hydroxy (OH) groups other than the corresponding hydroxy group Represents a substituted or unsubstituted group, and does not mean that the hydroxy group is substituted or unsubstituted.

As used herein, " solvate " means a compound or a salt thereof, which further includes a solvent in a constant or non-constant ratio, bound by a non-covalent intermolecular force, unless otherwise specified. When the solvent is water, the solvate is a hydrate.

In this specification, " or " is used when adopting " at least one " of the matters listed in the sentence. "Or" is the same. In the specification, " within two numerical ranges ", the range includes two numerical values themselves. Therefore, 'X to Y' representing the range means' not less than X and not more than Y '. Unless otherwise specified,' weight ',' mass', 'weight%', or 'wt%' and ' Is used as a synonym. The term "about" means a range of values obtained by rounding off to one or more significant digits or digits to the right of the displayed number, unless otherwise stated, with a tolerance of 10% .

[2] Description of the Preferred Embodiment

Hereinafter, preferred embodiments of the present invention will be described. It is understood that the embodiments provided below are provided for a better understanding of the present invention and that the scope of the present invention is not limited by the following description. Therefore, it is apparent that those skilled in the art can appropriately make modifications within the scope of the present invention by taking the description of this specification into consideration. It is also understood that the following embodiments of the present invention can be used singly or in combination.

(2-1) Curable resin composition

In one aspect,

A curable resin composition comprising a chain polymer having a side chain having an alcoholic secondary or tertiary hydroxyl group and a crosslinking agent,

(a) the side chain comprises from 3 to 30 carbon atoms and comprises at least one saturated or unsaturated hydrocarbon group or further comprising at least one aromatic group, the linking between the carbon atoms is --COO--, - O-, and -CO-,

The crosslinking agent may be a triazine-based compound and / or a condensate thereof, a glycoluril compound and / or a condensate thereof, and an imidazolidinone compound and /

≪ / RTI > is selected from the group consisting of < RTI ID = 0.0 >

The curable resin composition of the present invention is a thermosetting resin composition which is cured by heat treatment.

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

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

Said side chain comprising at least one saturated or unsaturated hydrocarbon group of carbon atoms or further comprising at least one aromatic group. The side chain may contain one or two or more bonds selected from the group consisting of -COO-, -O- and -CO-. The saturated or unsaturated hydrocarbon group constituting the side chain may include, for example, one carbon atom of the entire side chain or a plurality of saturated or unsaturated carbon groups constituted by -COO-, -O- and -CO-, May be connected through a bond selected from the group consisting of When the side chain contains an aromatic group other than the saturated or unsaturated hydrocarbon group, the saturated or unsaturated hydrocarbon group and the aromatic group may be directly connected or may be connected through a bond selected from the group consisting of -COO-, -O- and -CO-.

In the present invention, the alcoholic secondary or tertiary hydroxyl group of the side chain can be used as the alcoholic secondary or tertiary hydroxyl group because the cured resin film formed by applying and curing the curable resin composition of the present invention on the glass substrate can maintain easy releasability on the substrate even after firing, Element. Further, it is more preferable that the alcoholic secondary or tertiary hydroxyl group of the side chain is bonded to the alicyclic moiety of the side chain, and the alicyclic moiety of the side chain is also a substantially decisive factor because the easy releasability of the cured resin film can be maintained.

The chain polymer having such a side chain may comprise any suitable cross-linking agent, especially a triazine-based compound and / or a condensate thereof, a glycoluril-based compound and / or a condensate thereof, or an imidazolidinone-based compound and / When the resin composition is cured in the form of a thin film, an easy peeling film having heat resistance can be provided.

In the present invention, the chain polymer having the side chain having the alcoholic secondary or tertiary hydroxyl group is more preferably an unsubstituted or? -Substituted (meth) acrylic monomer, an unsubstituted or? -Substituted vinyl ester monomer, An unsubstituted or? -Substituted vinyl ether monomer, and an unsubstituted or? -Substituted vinyl monomer other than the above, as a monomer unit.

In the present invention, the chain polymer having the side chain having the alcoholic secondary or tertiary hydroxyl group is more preferably a (meth) acrylic monomer, a vinyl ester monomer, a vinyl ether monomer, a vinyl monomer other than the above At least one 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 of the invention is ^{_{CH 2 = C (R 1a)}} -COO-R 1 CH 2 = C (R 1a) -O-CO-R 3, CH 2 = C (R 1a) -OR 4 and ^{_{CH 2 = C (R 1a)}} -R 5 [ wherein R and R ^1, R ^3, R ⁴ and R ⁵ are independently from each other, including the configuration of carbon atom bonded to the art if the ester is bonded to each of the vinyl through an ester bond Having from 3 to 30 carbon atoms, more preferably from 3 to 25 carbon atoms, most preferably from 3 to 20 carbon atoms and having an alcoholic secondary or tertiary hydroxyl group and containing or containing at least one saturated or unsaturated hydrocarbon group Includes at least one aromatic group and the linkage between the carbon atoms may have a bond selected from the group consisting of -COO-, -O- and -CO-. And R ^{< 1a} > is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted alkenyl group.

More preferably the chain polymer of the 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 bonded to each vinyl group through an ester bond, Having 3 to 30 carbon atoms, more preferably 3 to 25 carbon atoms, most preferably 3 to 20 carbon atoms including an atom, and having an alcoholic secondary or tertiary hydroxyl group, and at least one saturated or unsaturated hydrocarbon Group, or further contains at least one aromatic group, and the linkage between the carbon atoms may have a bond selected from the group consisting of -COO-, -O- and -CO-. Lt; RTI ID = 0.0 > a < / RTI > group.

Examples of the saturated or unsaturated hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, cyclohexyl, dicyclopentadienyl, decanyl, adamantyl, butenyl, hexenyl, But are not limited to, various linear, branched, monocyclic, condensed cyclic groups within the limit of the number of carbon atoms of the side chain such as hexenyl, decyl, and the like. When each group is not located at the terminal, it may be a divalent or higher group depending on the bonding relationship with other groups.

Examples of the aromatic group include carbocyclic aromatic groups (monocyclic group and condensed ring group) such as phenyl, biphenyl, naphthyl and the like, and heteroaromatic groups such as pyridyl, pyrimidinyl, quinolinyl and triazinyl ). When the aromatic group is not located at the terminal, it may be a group of two or more depending on the bonding relationship with other groups. Also, in the present specification, a group having a saturated or unsaturated hydrocarbon chain moiety (for example, tetrahydronaphthyl or dihydronaphthyl) which forms a ring together with an aromatic ring moiety is understood as a combination of an aromatic group and a saturated or unsaturated hydrocarbon group .

In the present invention, the alcoholic secondary or tertiary hydroxyl group is a hydroxy group substituted with a hydrogen atom at the secondary or tertiary carbon atom of any of the saturated or unsaturated hydrocarbon groups constituting the side chain.

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

More preferably, the chain polymer of the present invention has the formula A1:

[Chemical Formula 12]

[In the above formula

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

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

R ^2a , R ^3a and R ^4a are independently selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon groups, with the proviso that at least one of R ^2a , R ^3a and R ^4a is a substituted or unsubstituted secondary or tertiary An OH-containing group].

More preferably, the chain polymer of the present invention has the formula

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

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

R ^2a , R ^3a and R ^4a are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted hydrocarbon group, with the proviso that at least one of R ^2a , R ^3a and R ^4a is a secondary or tertiary hydroxyl group, And an unsubstituted secondary or tertiary OH-containing hydrocarbon group.

More preferably, the chain polymer of the present invention has the formula

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

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 each independently selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon groups, with the proviso that at least one of R ^2a , R ^3a and R ^4a is a secondary or tertiary hydroxy and substitution Or an unsubstituted secondary or tertiary OH containing hydrocarbon group, and the other two independently of one another include a monomer unit selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon groups.

More preferably, the chain polymer of the present invention has the formula A2:

[Chemical Formula 13]

Wherein R ^1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, and L ¹ is a single bond, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted alkenylene group And R < ^5a > to R < ^14a > independently of one another are hydrogen,

[Chemical Formula 14]

, Provided that at least one of R ^5a to R ^14a or a substituent of the ring is a hydroxy group,

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

More preferably, the chain polymer of the present invention has the formula A2,

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

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

R ^5a to R ^14a independently represent hydrogen, a hydroxyl group,

[Chemical Formula 15]

, 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. do.

More preferably, the chain polymer of the present invention has a structure represented by the formula A2,

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

L < ¹ > is selected from the group consisting of a single bond and an unsubstituted alkylene group,

Among R ^5a to R ^14a , R ^7a is a hydroxy group and R ^9a is

[Chemical Formula 16]

, And the other is hydrogen, or R ^5a to R ^14a form a ring in which one hydroxy group is substituted with one

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 group .

Also more preferably, the ring substituted with at least one hydroxy group is adamantane substituted with a hydroxy group

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

[Chemical Formula 17]

[In the above formula

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

L ² is selected from the group consisting of substituted or unsubstituted alkylene groups, substituted or unsubstituted alkenylene groups,

R ^16a is selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group,

And R ^17a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted alkynyl group.

More preferably, in the present invention, the chain polymer is represented by the formula A3,

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

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, substituted or unsubstituted alkyl groups, and the like.

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

[Chemical Formula 18]

[In the above formula

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

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

And R ^18a is an adamantyl group substituted with at least one hydroxy group.

More preferably, the chain polymer of the present invention has a structure represented by the formula (A4)

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

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

And R ^18a is an adamantyl group substituted with at least one hydroxy group.

The chain polymer may be represented by the formula A5:

[Chemical Formula 19]

[In the above formula

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

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

And 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.

More preferably, the chain polymer of the present invention has a structure represented by the formula A5,

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

L ¹ is selected from the group consisting of a single bond, 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.

More preferably, in formula A5, ^R19a is a substituted or unsubstituted adamantyl group.

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

Preferable side chains having a polymeric alcoholic secondary or tertiary hydroxyl group in the chain of the present invention include the following. It is also preferred that such a hydroxyl group be present and that the disclosure is illustrative only and is not limited thereto.

(1a) A-O-CO- (A represents the remaining part of the side chain, the same applies 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-hydroxycyclohexyloxycarbonyl,

4-undecane oil oxy-3-hydroxycyclohexylmethoxycarbonyl,

4-butanedioxy-3-hydroxycyclohexylmethoxycarbonyl and the like.

(2a) A-CO-O- type side chain:

2-hydroxypropylcarbonyloxy,

2-hydroxy-3- (cyclohexylcarbonyloxy) propylcarbonyloxy,

3-benzoyloxy-2-hydroxypropylcarbonyloxy,

4-benzoyloxy-3-hydroxycyclohexylmethylcarbonyloxy,

3-hydroxy-1-adamantylcarbonyloxy,

2-hydroxycyclohexyloxycarbonyloxy,

4-undecane oil oxy-3-hydroxycyclohexylmethylcarbonyloxy,

4-butanedioxy-3-hydroxycyclohexylmethylcarbonyloxy, and the like.

(3a) A-O-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-undecane oil oxy-3-hydroxycyclohexylmethoxy,

4-butanedioxy-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-undecane oil oxy-3-hydroxycyclohexylmethyl,

3-hydroxycyclohexylmethyl, and the like.

Preferable examples of monomers that provide such side chains to the chain-like 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-adamantyl diol mono (meth) acrylate,

2-hydroxycyclohexyl (meth) acrylate,

4-undecane oil oxy-3-hydroxycyclohexylmethyl (meth) acrylate,

(Meth) acrylate such as 4-butanedioxy-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-undecane oil oxy-3-hydroxycyclohexyl acetic acid vinyl ester,

And vinyl esters such as 4-butanedioxy-3-hydroxycyclohexyl 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-hydroxycyclohexylmethyl vinyl ether,

3-hydroxy-1-adamantyl vinyl ether,

2-hydroxycyclohexyl vinyl ether,

4-undecane oil oxy-3-hydroxycyclohexylmethyl ether,

4-butanedioxy-3-hydroxycyclohexylmethyl ether

Such as vinyl 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,

And vinyl monomers such as 3- (4-butanyloxy-3-hydroxycyclohexyl) -1-propene.

(5b)

Maleic anhydride and maleimide having (1a) to (4a) as substituents, respectively.

The chain polymer of the present invention may contain, in addition to the monomer having the alcoholic secondary or tertiary hydroxyl group, an unsubstituted or alpha-substituted (meth) acrylic monomer having 1 to 15 carbon atoms in the side chain containing or not having a hydroxy group, Or an α-substituted vinyl ester monomer, an unsubstituted or α-substituted vinyl ether monomer, and other unsubstituted or α-substituted vinyl monomer as additional monomer units.

These additional monomer units are preferably selected from the group consisting of CH ₂ ═C (R ^1a ) -COO-R ⁶ , CH ₂ ═C (R ^1a ) -O-CO-R ⁸ wherein R ⁶ and R ⁸ are independently of each other Containing at least one saturated or unsaturated hydrocarbon group or further comprising at least one aromatic group, with the proviso that the linkage between the carbon atoms is selected from the group consisting of -COO-, -O-, -CO-, the hydrocarbon group or the aromatic group may have an amino group, and R &^lt; ^{1a >} is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, 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 are each independently have 3 to 15 carbon atoms with or without a hydroxyl group And includes at least one saturated or unsaturated hydrocarbon group or further contains at least one aromatic group, and the linkage between the carbon atoms may have a bond selected from the group consisting of -COO-, -O- and -CO-, The hydrocarbon group or the aromatic group may have an amino group and R &^lt; ^{1a >} is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group,

^{_{C 4 (R 1a) O 3}} -R 11, C 4 (R 1a) HNO 2 -R 12 [ wherein R ₄ C (R ^1a) O ₃ - represents a maleic acid ^{_{group, C 4 (R 1a) HNO}} 2 - represents a maleimide group, R ¹¹ and R ¹² independently of one another are a hydrogen atom or contain 1 to 15 carbon atoms, with or without an alcoholic secondary or tertiary hydroxyl group, and at least one saturated or unsaturated hydrocarbon group And further includes at least one aromatic group, and the linkage between the carbon atoms may have a bond selected from the group consisting of -COO-, -O- and -CO-, and the hydrocarbon group or the aromatic group may be an amino group And R &^lt; ^{1a >} is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted alkenyl group.

≪ / RTI >

The chain polymer of the present invention may contain, in addition to the monomer having the alcoholic secondary or tertiary hydroxyl group, a (meth) acrylic monomer, a vinyl ester monomer, a vinyl ether monomer, and a vinyl ether monomer having no hydroxy group and having 1 to 15 carbon atoms in the side chain. Based monomer may include at least one of the other vinyl-based monomers as an additional monomer unit.

Monomer units of these more preferably ^{_{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 from 1 to 15 carbon atoms and have a hydroxyl group and comprise at least one saturated or unsaturated hydrocarbon group or further comprise at least one aromatic group, -COO-, -O- and -CO-, and the hydrocarbon group or the aromatic group may 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 from 3 to 15 carbon atoms and have a hydroxy group and at least one saturated or unsaturated hydrocarbon group And wherein the linkage between the carbon atoms may comprise a bond selected from the group consisting of -COO-, -O-, and -CO-, wherein the hydrocarbon or aromatic group is optionally substituted with one or more substituents selected from the group consisting of An amino group,

C ₄ HO ₃ -R ¹¹ and C ₄ H ₂ NO ₂ -R ¹² wherein C ₄ HO ₃ - represents a maleic anhydride group, C ₄ H ₂ NO ₂ - represents a maleimide group, and R ¹¹ and R ¹² represent Independently of one another, a hydrogen atom or an alkyl group having from 1 to 15 carbon atoms and containing an alcoholic secondary or tertiary hydroxyl group and containing at least one saturated or unsaturated hydrocarbon group or further containing at least one aromatic group, May have a bond selected from the group consisting of -COO-, -O- and -CO-, and the hydrocarbon group or the aromatic group may have an amino group]

≪ / RTI >

Preferable examples of the monomer unit having no hydroxy group include, but are not limited to, the following.

 (Meth) acrylates such as methyl (meth) acrylate, propyl (meth) acrylate, glycidyl (meth) acrylate, butyl (meth) acrylate, ethoxyethyl (Meth) acrylate, benzyl (meth) acrylate, N (meth) acrylate, dicyclopentadienyl (meth) acrylate, (Meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate and glycidyl Methacrylate.

(2) vinyl esters such as vinyl acetate, vinyl butanoate, vinyl pentanoate, vinyl hexanoate, cyclohexanecarboxylic acid vinyl ester, benzoic acid vinyl ester, cyclopentadienyl carboxylic acid vinyl ester and nonanoic acid vinyl ester Vinyl esters.

 (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 ether, octyl Vinyl ethers such as vinyl ether, benzyl vinyl ether, 2- (vinyloxy) ethyldimethylamine and 3- (vinyloxy) propyldimethylamine.

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

(5) Maleic anhydride derivatives such as maleic anhydride, methyl maleic anhydride, butyl maleic anhydride, hexyl maleic anhydride, cyclohexyl maleic anhydride, phenyl maleic anhydride, and octyl maleic anhydride.

 (6) Maleimide derivatives such as maleimide, methylmaleimide, ethylmaleimide, butylmaleimide, hexylmaleimide, cyclohexylmaleimide, phenylmaleimide, benzylmaleimide and octylmaleimide.

The chain polymer of the present invention may be a homopolymer of a monomer unit or a copolymer containing two or three or more types of monomer units, but at least one of the monomer units of the copolymer may be an alcoholic And a monomer unit having a side chain having a tertiary hydroxyl group. Preferably, the copolymer comprises a monomer unit having a side chain having at least one alcoholic secondary or tertiary hydroxyl group and an additional monomer unit having at least one hydroxy group.

The ratio of the monomer units having an alcoholic secondary or tertiary hydroxyl group in the chain polymer of the present invention is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, still more preferably 60 to 100 mol% Mol%, more preferably 80 to 100 mol%, and most preferably 90 to 100 mol%.

In the present invention, the chain polymer is produced by carrying out polymerization reaction using a conventional radical polymerization catalyst such as, for example, 2,2'-azobisisobutyronitrile (AIBN) can do. The molecular weight of the chain-like polymer is preferably in the range of 10,000 to 100,000 (measured by gel filtration chromatography), but is not limited to this range.

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

Specific examples of such cross-linking agents include, but are not limited to, fully or partially alkoxy (e.g. methoxy, ethoxy) methylated melamine and / or its condensates, fully or partially alkoxy (e.g. methoxy, ethoxy) methylated guanamine and / (For example methoxy, ethoxy) methylated acetoguanamine and / or its condensates, complete or partial alkoxymethylated benzoguanamine and / or its condensates, complete or partial alkoxy For example methoxy, ethoxy) methylated glyceryl and / or its condensates, fully or partially alkoxymethylated imidazolidinones and / or their condensates.

In the above formula, " alkoxy " preferably has 1 to 4 carbon atoms. As such a crosslinking agent, preferred compounds are specifically exemplified by

Hexamethoxymethyl melamine,

Hexaethoxymethyl melamine,

Tetramethoxymethyl methylol melamine,

Tetramethoxymethyl melamine,

Hexabutoxymethyl melamine,

Tetramethoxymethylguanamine,

Tetramethoxymethylacetoguanamine,

Tetramethoxymethylbenzoguanamine,

Trimethoxymethylbenzoguanamine,

Tetraethoxymethylbenzoguanamine,

Tetramethylolbenzoguanamine,

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

1,3,4,6-tetrakis (butoxymethyl) glycoryl,

4,5-dihydroxy-1,3-methoxymethyl-2-imidazolidinone,

4,5-dimethoxy-1,3-dimethoxymethyl-2-imidazolidinone

But are not limited thereto.

In one embodiment, the cross-linking agent preferably has the formula B1:

[Chemical Formula 20]

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

[Chemical Formula 21]

Lt; / RTI > is selected from the group consisting of < RTI ID = 0.0 >

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

And / or a condensate thereof.

More preferably, the cross-linking agent of the present invention is a cross-

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

[Chemical Formula 22]

Lt; / RTI > is selected from the group consisting of < RTI ID = 0.0 >

R ^2b to R ^7b are each independently selected from substituted or unsubstituted alkyl groups

Compound and / or a condensate thereof.

In each embodiment, the cross-linking agent is represented by the formula B2:

(23)

[Wherein R ^8b to R ^11b each independently represent a group 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 It is selected from the group.

Preferably, the crosslinking agent of the present invention is a compound represented by the formula B2 wherein R ^8b to R ^11b are independently selected from a substituted or unsubstituted alkyl group and / or a condensate thereof.

Particularly, in each embodiment, the preferred crosslinking agent is represented by the formula B3:

≪ EMI ID =

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

Preferably, the crosslinking agent of the present invention is a crosslinking agent of the formula B3, wherein R ^12b to R ^13b are independently selected from substituted or unsubstituted alkyl groups, and R ^14b to R ^15b are independently selected from hydrogen, a substituted or unsubstituted alkyl group And / or a condensate thereof.

More preferably, in the above-mentioned crosslinking agent of the present invention, R ^14b to R ^15b in the formula B3 are each independently hydrogen.

In the curable resin composition of the present invention, the crosslinking agent preferably includes the following compounds and / or condensates specifically represented by the following structural formulas.

(25)

Hexamethoxymethylmelamine;

Hexabutoxymethylmelamine;

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

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

Tetramethoxymethylbenzoguanamine;

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

As the condensate, polymers of the compounds shown above are preferably exemplified, and more preferred are dimers, trimers or higher polymers of the above compounds.

The crosslinking agent of the curable resin composition of the present invention may be the above compound and its condensate, and may be a mixture of the above compound and a polymer (i.e., dimer, trimer, or higher polymer) of the above compound.

In another aspect, the crosslinking agent preferably has a weight average degree of polymerization of 1 to 3 or more in the compound. Preferably from 1 to 1.8, more preferably from 1.3 to 1.8, and even more preferably 1.5, weight average degree of polymerization. When the weight average degree of polymerization of the condensate of the compound is 1, it means that the condensate itself is the compound itself. The weight average degree of polymerization may be any value within the above range and is preferably a value of 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, and particularly preferably 1.5.

The ratio of the mass ratio of the chain polymer to the crosslinking agent in the curable resin composition is preferably from 1: 0.03 to 1: 2, more preferably from 1: 0.05 to 1: 2, from 1: 0.05 to 1: More preferably from 1: 0.09 to 1: 0.3 and from 1: 0.1 to 1: 0.3, more preferably from 1: 0.09 to 1: 1,

In the present invention, the curable resin composition comprises an acid catalyst. The acid catalyst is included as necessary as a polymerization catalyst for the reaction with the monomer unit and the crosslinking agent. The acid catalyst may be appropriately selected as a polymerization catalyst.

The acid catalyst may be a compound selected from Bronsted acid and / or Lewis acid, or a salt thereof, or a solvate thereof. Examples of the acid catalyst include acids such as dinonylnaphthalene disulfonic acid, dinonylnaphthalene (mono) sulfonic acid, dodecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfonic acid (PTS), phosphoric acid, sulfuric acid, And a thermal acid generator such as Sun Aid SI-100L, SI-150L, SI-110L, SI-60L and SI-80L (Samsin Dairy Industry Co., Ltd.), its salt or its solvate And the present invention is not limited thereto. Preferably, the acid catalyst is a compound selected from the group consisting of p-toluenesulfonic acid (PTS), dodecylbenzenesulfonic acid and thermal acid generator Sun-100L (Samsin Chemical Industry Co., Ltd.) Lt; / RTI > 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 comprises an acid catalyst, the amount of the acid catalyst can be appropriately determined according to the ratio of the mass of the chain polymer of the curable resin composition and the cross-linking agent, and preferably the chain polymer, The ratio of the mass of the acid catalyst is 1: 0.03: 0.05 to 1: 2: 0.1, 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 may be diluted to an appropriate concentration depending on the solvent. That is, in the present invention, the curable resin composition further includes a solvent. The boiling point is not excessively low or high and it is possible to appropriately select and use a conventional proprietary solvent within a range capable of forming a uniform coating film by drying after the curable resin composition is applied to a substrate such as glass or the like.

For example, propylene glycol monomethyl ether is a suitable solvent and is not limited thereto. Since dilution with a solvent is convenient for the polymerization reaction of the monomer and for the application of the curable resin composition to which the crosslinking agent and the catalyst are added, there is no particular upper limit lower limit for 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 still another aspect, the present invention provides a readily releasable cured resin film obtained by curing the curable resin composition of (2-1) above in the form of a film on a substrate surface.

The cured resin film formed by the curable resin composition of the present invention has heat resistance in the above-mentioned " heat resistance " as well as easy releasability even after heat treatment in a heat resistant temperature range.

Typically, the curable resin composition of the present invention is prepared by applying a solution prepared by dissolving a chain polymer, a crosslinking agent and, if necessary, a further acid catalyst in a solvent onto a glass substrate (preferably soda lime glass) (Preferably about 200 nm to about 300 nm) can be formed as a transparent thin film by curing the resin composition of the present invention. Without being limited by theory, the mechanism is a film in which the hydroxy group of the side chains of the chain polymer and the cross-linking agent can be peeled off by curing shrinkage upon crosslinking by heating.

(26)

A known coating method can be used as a method of applying the coating liquid to the glass substrate. For example, spin coating, spinless coating, die coating, spray coating, roll coating, screen coating, slit coating, dip coating and gravure coating. It is preferably spin-coated.

The thin film thus deposited on the substrate is able to withstand heating up to 150 DEG C and preferably withstand 230 DEG C (sintering). It is also resistant to a solvent used in a photoresist solution and can withstand an alkaline developing solution. Thus, it can be advantageously used as a resin base film for producing circuits by photolithography.

In addition, since the thin film formed by the curable resin composition of the present invention has easy releasability even after heating at such a temperature, it can be adhered in a circuit manufacturing process including a baking step at a higher temperature than a conventional thin film, It is advantageous to maintain the characteristics.

In addition, after the circuit is formed, the substrate can easily be peeled off easily. Therefore, it can be widely used for manufacturing a variety of sheet-shaped flexible electric / electronic circuit parts with excellent characteristics and can be used, for example, in the manufacture of flexible display devices and touch sensors.

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

The peeling force of the cured resin film of the present invention can be measured by the following measuring method, for example. Typically, the curable resin composition of the present invention is prepared by preparing a solution in which a chain polymer crosslinking agent and, if necessary, an acid catalyst are dissolved in a solvent, applying the solution to a glass substrate (preferably soda lime glass) Or more) and curing it to produce a cured resin film on a glass substrate. For example, TENSILON RTG-1310 (A & D) load cell UR-100N-D type is used as a measuring device.

The size of the force (peeling force) necessary for peeling is measured in the apparatus by attaching a nitrate half tape (24 mm width) to the cured resin film on the glass substrate and pulling the glass substrate at a constant rate of 300 mm / min at an angle of 90 ° to the glass substrate .

The cured resin film of the present invention preferably has a peeling force against 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 against 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 peeling force against a soda-glass substrate or an alkali-free glass substrate of 0.09 N / mm ² or less.

Preferred levels of release force for a soda glass substrate is 0.5 N / mm ² or less, 0.4 N / mm ² or less, 0.3 N / mm ² or less, 0.2 N / mm ² or less, 0.1 N / mm ² or less, 0.09 N / mm ² or less, 0.08 N / mm ² or less, 0 .07 N / mm ² or less, 0.06 N / mm ² or less, 0.05 N / mm ² or less, 0.04 N / mm ² or less, 0.03 N / mm ² or less, N 0.02 / mm ² or less and 0.01 N / mm ² or less.

Preferred levels of release force for the alkali-free glass substrate is 0.5 N / mm ² or less, 0.4 N / mm ² or less, 0.3 N / mm ² or less, 0.2 N / mm ² or less, 0.1 N / mm ² or less, 0.09 N / mm ² or less, 0.08 N / mm ² or less, 0.07 N / mm ² or less, 0.06 N / mm ² or less, 0.05 N / mm ² or less, 0.04 N / mm ² or less, 0.03 N / mm ² or less, 0 .02 N / mm ² or less, 0.01 N / mm ² or less.

When the peeling force against a soda-glass substrate or an alkali-free glass substrate is 0.5 N / mm ² or less, the cured resin film can be regarded as easily peelable.

 [3] Process for producing a cured resin film

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

(I) preparing a chain polymer having a side chain having an alcoholic secondary or tertiary hydroxyl group and a crosslinking agent;

(Ii) applying the curable resin composition comprising the chain polymer and the crosslinking agent on a substrate to form a curable resin composition coating film;

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

And a manufacturing method thereof.

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

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

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

Examples of the method for polymerizing the monomer include a bulk polymerization method, a solution polymerization method, an emulsion polymerization method and a suspension polymerization method, but the present invention is not limited to these examples. Among these polymerization methods, a bulk polymerization method and a solution polymerization method are preferable.

The polymerization of the monomer can be carried out by, for example, radical polymerization, living radical polymerization, anion polymerization, cationic polymerization, addition polymerization, polycondensation or the like.

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

A chain transfer agent can be used to adjust the molecular weight when polymerizing the monomer. The chain transfer agent can be generally used in combination with a monomer. Examples of the chain transfer agent include 2- (dodecylthiocarbonothioylthio) -2-methylpropionic acid, 2- (dodecylthiocarbonothioylthio) propionic acid, methyl 2- (dodecylthiocarbono 2-methylpropionic acid 3-azido-1-propanol ester, 2- (dodecylthiocarbonothioylthio) -2-methylpropionic acid 3- ) -2-methylpropionic acid pentafluorophenyl ester, lauryl mercaptan, dodecyl mercaptan, thioglycerol and the like, inorganic salts such as sodium hypophosphite and sodium hydrogen sulfite, The present invention is not limited to these examples.

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 generally about 0.01 to 10 parts by weight per 100 parts by weight of the total monomer.

It is preferable to use a polymerization initiator when the monomers are polymerized. Examples of the polymerization initiator include thermal polymerization initiators, photopolymerization initiators, redox polymerization initiators, ATRP (atom transfer radical polymerization) initiators, ICAR ATRP initiators, ARGET ATRP initiators, RAFT agents (reversible addition- (Polymerization through nitroxide), a polymeric polymerization initiator, and the like. These polymerization initiators may be used alone or in combination of two or more.

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

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

Examples of the photopolymerization initiator include 2-oxoglutaric acid, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan- Phenyl] -2-morpholinopropane-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, benzophenone, 1- [4- (2-hydroxyethoxy) Propane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, bis (2,6-dimethoxybenzoyl ) -2,4,4-trimethylpentylphosphine oxide, but the present invention is not limited to these examples. These polymerization initiators may be used alone or in combination of two or more.

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

Examples of other polymerization initiators that can be used in the present invention include redox polymerization initiators such as hydrogen peroxide and iron (II) salts, persulfate and sodium hydrogen sulfite, ATRP (atom transfer radical polymerization ) Initiators, ICAR ATRP initiators with metal and nitrogen containing ligands, ARGET ATRP initiators, RAFT agents (reversible addition-cleavage chain transfer polymerization), NMP agents (polymerization via nitroxides), polymeric azo polymerization with polydimethylsiloxane units A polymerization initiator such as an initiator and a polymeric azo polymerization initiator containing a polyethylene glycol unit, but the present invention is not limited to these examples. These polymerization initiators may be used alone or in combination of two or more.

When the above-mentioned polymerization initiator is used as the polymerization initiator, the amount of the polymerization initiator is preferably about 0.01 to 20 parts by weight per 100 parts by weight of the total monomer.

In one embodiment, electron beam polymerization is carried out by irradiating the monomer with electron beams.

The polymerization reaction temperature and atmosphere at the time of polymerizing the monomer are not particularly limited. Generally, the polymerization temperature is from about 50 캜 to about 120 캜. The atmosphere during the polymerization reaction is preferably an inert gas atmosphere such as nitrogen gas. Since the polymerization reaction time of the monomer varies depending on the polymerization reaction temperature and the like, it can not be uniformly determined but is generally about 3 to 20 hours.

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

In one embodiment, the method of applying the curable resin composition to the substrate in the step (ii) of the production method may be a known coating method. 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 by spin coating.

In another embodiment, in the step (ii) of the production method, the composition preferably further comprises an acid catalyst. Without being limited to theory, the curable resin composition coating film includes an acid catalyst, so that the acid catalyst can act as a polymerization catalyst in the polymerization reaction of step (iii) and can promote the reaction. Accordingly, in another embodiment, step (i) of the production method further comprises the step of providing an acid catalyst.

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

The cured resin film produced by the above production method has the cured resin characteristics of (2-2) and can be obtained as an easy peeling film.

[4] Usage

The curable resin composition or the cured resin film of the present invention can be used as a plastic pellet, a film, a plate, a fiber, a foaming agent, a tube, a rubber, an elastomer, (Eg, bed, hammock, etc.), clothing, protective clothing, sporting goods, bathtubs, kitchenware, tableware, cooking utensils, containers and packaging materials (Such as food containers, cosmetics containers, cargo containers, trash cans), construction (buildings, roads, construction parts, etc.), agricultural films, industrial films, water and sewage, paints, cosmetics, (Catheter, guidewire, artificial blood vessel, etc.), optical communication cable, medical material and apparatus (catheter, guide wire, artificial blood vessel, Ball muscles, artificial organs, dialysis membrane, an endoscope, etc.), a small pump, the sensor used in the actuator, the robot material (industrial robot), the energy generating device and a plant (photovoltaic power generation, wind power generation, etc.), etc. can be applied to various fields.

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

The curable resin composition or the cured resin film of the present invention can be applied to automobile parts (body panels, bumper belts, rocker panels, side malls, engine parts, driving parts, conduction parts, steering parts, ballast parts, Shaft parts, pipes, tanks, wheels, seats, seat belts, etc.). The polymer of the present invention can be used for automotive dustproof materials, automotive paints, automobile synthetic resins, and the like.

References to scientific literature, patents, and patent applications cited herein are hereby incorporated by reference in their entirety to the same extent as if each is specifically indicated.

Hereinafter, preferred embodiments of the present invention are shown and described for ease of understanding. The present invention is illustrated by the following examples, but the description and the following examples are provided for illustrative purposes only and are not intended to be limiting of the present invention. Accordingly, the scope of the present invention is not limited by the embodiments specifically described herein but is limited only by the claims.

 (Example)

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not intended to be limited to these Examples. And embodiments obtained by suitably combining the technical means disclosed in each embodiment are also included in the scope of the present invention.

1. Preparation of Polymer as a Component of Curable Resin Composition

As a component of the curable resin composition, a polymer was prepared as follows.

(Production Example 1) Production of polymer A-1

The following formula (1-1)

(27)

100 parts by weight of 2-hydroxypropyl methacrylate as a monomer was dissolved so as to be 30% by weight of propylene glycol monomethyl ether (PGME). A solution of 2,2'-azobisisobutyronitrile (AIBN) in an amount of 5 mol% based on the total amount of the monomers was added to the obtained solution, and the reaction was carried out at 80 DEG C for 8 hours to obtain a polymer A-1 was obtained. The average molecular weight (MW) of this polymer was determined by gel filtration chromatography to be 25,000.

(Production Example 2) Production of polymer A-2

The following formula (1-2)

(28)

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. The average molecular weight (MW) of this polymer was measured by gel filtration chromatography and found to be 22,000.

(Production Example 3) Production of Polymer A-3

(1-3)

[Chemical Formula 29]

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. The average molecular weight (MW) of this polymer was determined by gel filtration chromatography to be 32,000.

(Production Example 4) Production of Polymer A-4

(1-4)

(30)

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. The average molecular weight (MW) of this polymer was measured by gel filtration chromatography and found to be 18,000.

(Production Example 5) Production of polymer A-5

(1-5)

(31)

Polymer A-5 was obtained in the same manner as in Production Example 1 except that 2-hydroxycyclohexyl methacrylate was used as a monomer. The average molecular weight (MW) of this polymer was determined by gel filtration chromatography to be 36,000.

(Preparation Example 6) Preparation of polymer A-6

The following formula (1-6)

(32)

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

(Preparation Example 7) Preparation of polymer A-7

The following formula (1-7)

(33)

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. The average molecular weight (MW) of this polymer was measured by gel filtration chromatography and found to be 18,000.

(Production Example 8) Production of polymer A-8

50 parts by mass of the 2-hydroxypropyl methacrylate and n-butyl acrylate of the formula (1-1) were dissolved in propylene glycol monomethyl ether (PGME) in a total amount of 30% by mass. Azobisisobutyronitrile (AIBN) was added in an amount of 5 mol% based on the total amount of the monomers, and the reaction was carried out at 80 DEG C for 8 hours to obtain a polymer A-8 was obtained. The average molecular weight (MW) of this polymer was measured by gel filtration chromatography and found to be 18,000.

(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 of the formula (1-1) were used as monomers. The average molecular weight (MW) of this polymer was determined by gel filtration chromatography to be 25,000.

(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. The average molecular weight (MW) of this polymer was measured by gel filtration chromatography and found to be 22,000.

(Production Example 11) Production of polymer A-11

Polymer A-11 was obtained in the same manner as in Production Example 8 except that 4-benzoyloxy-3-hydroxycyclohexylmethyl methacrylate and dicyclopentadienyl methacrylate of the formula (1-3) were used as monomers Respectively. The average molecular weight (MW) of this polymer was determined by gel filtration chromatography and found to be 35,000.

(Production Example 12) Production of polymer A-12

Polymer A-12 was obtained in the same manner as in Production Example 8 except that 2-hydroxycyclohexyl methacrylate and dicyclopentadienyl methacrylate of the formula (1-5) were used as monomers. The average molecular weight (MW) of this polymer was determined by gel filtration chromatography to be 25,000.

(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 the formula (1-6) were used as monomers. The average molecular weight (MW) of this polymer was determined by gel filtration chromatography to be 38,000.

(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 of the formula (1-6) were used as monomers. The average molecular weight (MW) of this polymer was determined by gel filtration chromatography to be 36,000.

(Production Example 15) Production of polymer A-15

Polymer A-15 was obtained in the same manner as in Production Example 8 except that 2-hydroxyethyl methacrylate and dicyclopentadienyl methacrylate of the formula (1-6) were used as monomers. The average molecular weight (MW) of this polymer was measured by gel filtration chromatography and found to be 39,000.

(Production Example 16) Production of polymer A-16

The following formula (1-8)

(34)

Except that 4- (4-methoxyphenylpropenoyl) oxy-3-hydroxycyclohexylmethyl methacrylate was used as a monomer, Polymer A-16

(35)

≪ / RTI > The average molecular weight (MW) of this polymer was determined by gel filtration chromatography to be 27,700.

(Preparation Example 17) Preparation of polymer A-17

The following formula (1-9)

(36)

Adamantanecarboxyoxy-3-hydroxycyclohexylmethyl methacrylate was used as a monomer, a polymer A-17

(37)

≪ / RTI > The average molecular weight (MW) of this polymer was determined by gel filtration chromatography to be 31,700

(Production Example 18) Production of polymer A-18

Except that 2-hydroxycyclohexyl methacrylate and methyl methacrylate of the formula (1-5) were used as monomers, Polymer A-18

(38)

≪ / RTI > The average molecular weight (MW) of this polymer was determined by gel filtration chromatography to be 25,500

(Preparation Example 19) Preparation of polymer A-19

(1-10)

[Chemical Formula 39]

Except that 3-hydroxyadamantylmethyl-2-methacrylate was used as a monomer, Polymer A-19

(40)

≪ / RTI > The average molecular weight (MW) of this polymer was determined by gel filtration chromatography to be 35,700

(Production Example 20) Production of polymer A-20

The following formula (1-11)

(41)

Except that 2-hydroxy-4-methacryloxymethyl-cyclohexyl-3-cyclohexene-1-carboxylate was used as a monomer, Polymer A-20

(42)

≪ / RTI > The average molecular weight (MW) of this polymer was determined by gel filtration chromatography to be 26,700.

(Preparation Example 21) Preparation of polymer A-21

(1-12)

(43)

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

(44)

≪ / RTI > The average molecular weight (MW) of this polymer was determined by gel filtration chromatography to be 30,700.

(Production Example 22) Production of polymer A-22

Except that 2-hydroxycyclohexyl methacrylate and benzyl methacrylate of the formula (1-5) were used as monomers, Polymer A-22

[Chemical Formula 45]

≪ / RTI > The average molecular weight (MW) of this polymer was determined by gel filtration chromatography to be 32,700.

(Production Example 23) Production of polymer A-23

4- (4-methoxyphenylpropenoyl) oxy-3-hydroxycyclohexylmethyl methacrylate of the formula (1-8) and the formula (1-13)

(46)

100 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate as a monomer was dissolved in 20 wt% of propylene glycol monomethyl ether (PGME). Azobisisobutyronitrile (AIBN) was added in an amount of 4 mol% based on the total amount of the monomers, and the reaction was carried out at 80 DEG C for 8 hours to obtain a polymer ≪ / RTI >

Thereafter, 99 mass parts and 1 mass part of 4-methoxy cinnamic acid and methacrylic acid, respectively, or 3 mole% of tetraethyl ammonium bromide were added and the temperature was raised to 100 ° C while blowing air and the reaction was carried out for 38 hours to obtain polymer A- 23

(47)

≪ / RTI > The average molecular weight (MW) of the polymer was determined to be 42,900 by gel filtration chromatography.

(Production Example 24) Production of polymer A-24

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

(48)

≪ / RTI > The average molecular weight (MW) of this polymer was determined by gel filtration chromatography to be 35,700.

2. Preparation of Curable Resin Composition

The various curable resin compositions of the present invention were coated on two kinds of glass substrates prepared as described below and formed by heat curing.

(Example 1)

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

(49)

0.4 part by mass of hexamethoxymethylmelamine (NIKARAKU MW-30 manufactured by Samwha Chemical Co., Ltd.) and 0.2 part by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were dissolved in 95 parts by weight of propylene glycol monomethyl ether (PGME). This solution was applied to soda glass of 0.7 mm thickness and non-alkali glass of 0.5 mm thickness (EAGLE-XG, Corning) by spin coating, respectively, and heat treated at 150 ° C or higher for 30 minutes to form a film with a thickness of about 300 nm.

(Example 2)

3.2 parts by mass of the polymer A-1, 0.8 parts by mass of a crosslinking agent hexamethoxymethylmelamine (formula (B-1)) and 0.2 parts by mass of pyridinium-p-toluenesulfonate as a polymerization catalyst were dissolved in propylene glycol monomethyl ether (PGME) 95 Mass part. This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film having a thickness of about 300 nm.

(Example 3)

2.4 parts by mass of a polymer A-1, 2.4 parts by mass of a crosslinking agent hexamethoxymethylmelamine (formula (B-1)) and 0.2 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were dissolved in propylene glycol monomethyl ether (PGME) 95 Mass part. This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film having a thickness of about 300 nm.

(Example 4)

4.4 parts by mass of Polymer A-2, 0.4 part by mass of crosslinking agent hexamethoxymethylmelamine (Formula (B-1)) and 0.2 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were dissolved in propylene glycol monomethyl ether (PGME) 95 Mass part. This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, and heat-treated to form a film having a thickness of about 300 nm

(Example 5)

4.4 parts by mass of Polymer A-3, 0.4 part by mass of hexamethoxymethylmelamine (formula (B-1)) as a crosslinking agent, and 0.2 part by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were dissolved in propylene glycol monomethyl ether (PGME) 95 parts by mass. This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film having a thickness of about 300 nm.

(Example 6)

4.4 parts by mass of Polymer A-4, 0.4 part by mass of hexamethoxymethylmelamine (formula (B-1)) as a crosslinking agent, and 0.2 part by mass of pyridinium-p-toluenesulfonate as a polymerization catalyst were dissolved in propylene glycol monomethyl ether (PGME) 95 parts by mass. This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film having a thickness of about 300 nm.

(Example 7)

4.4 parts by mass of Polymer A-5, 0.4 part by mass of hexamethoxymethylmelamine (formula (B-1)) as a crosslinking agent, and 0.2 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were dissolved in propylene glycol monomethyl ether (PGME) 95 parts by mass. This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film having a thickness of about 300 nm.

(Example 8)

4.4 parts by mass of Polymer A-8, 0.4 part by mass of hexamethoxymethylmelamine (formula (B-1)) as a crosslinking agent, and 0.2 parts by mass of pyridinium-p-toluenesulfonate as a polymerization catalyst were dissolved in propylene glycol monomethyl ether (PGME) 95 parts by mass. This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film having a thickness of about 300 nm.

(Example 9)

4.4 parts by mass of Polymer A-9, 0.4 part by mass of hexamethoxymethylmelamine (formula (B-1)) as a crosslinking agent, and 0.2 parts by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were dissolved in propylene glycol monomethyl ether (PGME) 95 parts by mass. This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film having a thickness of about 300 nm.

(Example 10)

4.4 parts by mass of Polymer A-3, 0.4 part by mass of hexamethoxymethylmelamine (formula (B-1)) as a crosslinking agent, and 0.2 part by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were dissolved in propylene glycol monomethyl ether (PGME) 95 parts by mass. This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film having a thickness of about 300 nm.

(Example 11)

4.4 parts by mass of Polymer A-11, 0.4 part by mass of hexamethoxymethylmelamine (formula (B-1)) as a crosslinking agent, and 0.2 part by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were dissolved in propylene glycol monomethyl ether (PGME) 95 parts by mass. This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film having a thickness of about 300 nm.

(Example 12)

4.4 parts by mass of Polymer A-12, 0.4 part by mass of hexamethoxymethylmelamine (formula (B-1)) as a crosslinking agent, and 0.2 part by mass of pyridinium-p-toluenesulfonate as a polymerization catalyst were dissolved in propylene glycol monomethyl ether (PGME) 95 parts by mass. This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, respectively, and heat-treated 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,

(50)

0.4 part by mass of 1,3,4,6-tetrakis (methoxymethyl) glycoluril (NIKARAKU MW-270, manufactured by SAMHWA CHEMICAL Co., Ltd.) and 0.2 part by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were dissolved in propylene glycol And dissolved in 95 parts by mass of monomethyl ether (PGME). This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film having a thickness of about 300 nm.

(Example 14)

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

(51)

0.4 part by mass of tetramethoxymethylbenzoguanamine and 0.2 part by mass of pyridinium p-toluenesulfonate as a polymerization catalyst were dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film having a thickness of about 300 nm.

(Example 15)

4.4 parts by mass of Polymer A-1, 0.4 part by mass of hexamethoxymethylmelamine (formula (B-1)) as a crosslinking agent, and 0.2 part by mass of pyridinium-p-toluenesulfonate as a polymerization catalyst were dissolved in propylene glycol monomethyl ether (PGME) 95 parts by mass. This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film having a thickness of about 300 nm.

(Example 16)

, 4.4 parts by mass of Polymer A-1, 0.4 part by mass of hexamethoxymethylmelamine (formula (B-1)) as a crosslinking agent, 0.2 mass of a thermal acid generator, Sanyo SD-100L (Samsin Chemical Industry Co., Ltd.) Was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film having a thickness of about 300 nm.

(Comparative Example 1)

4.4 parts by weight of Polymer A-6, 0.4 part by weight of hexamethoxymethylmelamine (Formula (B-1)) as a crosslinking agent, and 0.2 part by weight of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether (PGME) 95 parts by weight. This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film having a thickness of about 300 nm.

(Comparative Example 2)

4.4 parts by weight of Polymer A-7, 0.4 part by weight of hexamethoxymethylmelamine (Formula (B-1)) as a crosslinking agent, and 0.2 part by weight of pyridinium-p-toluenesulfonate as a polymerization catalyst were dissolved in propylene glycol monomethyl ether (PGME) 95 parts by weight. This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film having a thickness of about 300 nm.

(Comparative Example 3)

4.4 parts by weight of Polymer A-13, 0.4 part by weight of hexamethoxymethylmelamine (Formula (B-1)) as a crosslinking agent and 0.2 part by weight of pyridinium-p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether (PGME) 95 parts by weight. This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film having a thickness of about 300 nm.

(Comparative Example 4)

, 4.4 parts by weight of Polymer A-14, 0.4 part by weight of hexamethoxymethylmelamine (Formula (B-1)) as a crosslinking agent, and 0.2 part by weight of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether (PGME) 95 parts by weight. This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film having a thickness of about 300 nm.

(Comparative Example 5)

4.4 parts by weight of Polymer A-15, 0.4 part by weight of hexamethoxymethylmelamine (Formula (B-1)) as a crosslinking agent, and 0.2 part by weight of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether (PGME) 95 parts by weight. This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film having a thickness of about 300 nm.

(Comparative Example 6)

4.4 parts by weight of Polymer A-1, 0.4 part by weight of an isocyanurate crosslinking agent Duraneto TPA-100 (Asahi Chemical Industry Co., Ltd.), 0.2 part by weight of pyridinium p-toluenesulfonate as a polymerization catalyst, And dissolved in 95 parts by weight of methyl ether (PGME). This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film having a thickness of about 300 nm.

(Example 17)

, 3.2 parts by weight of Polymer A-16, 0.8 part by weight of hexamethoxymethylmelamine (Formula (B-1)) as a crosslinking agent, and 0.2 part by weight of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether (PGME) 95 parts by weight. This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film having a thickness of about 300 nm.

(Example 18)

, 3.2 parts by weight of Polymer A-17, 0.8 parts by weight of hexamethoxymethylmelamine (Formula (B-1)) as a crosslinking agent and 0.2 parts by weight of pyridinium-p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether (PGME) 95 parts by weight. This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film having a thickness of about 300 nm.

(Example 19)

, 3.2 parts by weight of Polymer A-18, 0.8 part by weight of hexamethoxymethylmelamine (Formula (B-1)) as a crosslinking agent, and 0.2 part by weight of pyridinium-p-toluenesulfonate as a polymerization catalyst with propylene glycol monomethyl ether (PGME) 95 parts by weight. This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, respectively, and heat-treated 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 hexamethoxymethylmelamine (Formula (B-1)) as a crosslinking agent and 0.2 parts by weight of pyridinium-p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether (PGME) 95 parts by weight. This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, respectively, and heat-treated 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 hexamethoxymethylmelamine (Formula (B-1)) as a crosslinking agent and 0.2 parts by weight of pyridinium-p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether (PGME) 95 parts by weight. This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, respectively, and heat-treated 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 hexamethoxymethylmelamine (Formula (B-1)) as a crosslinking agent and 0.2 parts by weight of pyridinium-p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether (PGME) 95 parts by weight. This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film having a thickness of about 300 nm.

(Example 23)

, 0.8 part by weight of polymer A-22, 0.8 part by weight of hexamethoxymethylmelamine (formula (B-1)) as a crosslinking agent, and 0.2 part by weight of pyridinium p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether (PGME) 95 parts by weight. This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, respectively, and heat-treated 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 hexamethoxymethylmelamine (Formula (B-1)) as a crosslinking agent and 0.2 parts by weight of pyridinium-p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether (PGME) 95 parts by weight. This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, respectively, and heat-treated 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 part by weight of hexamethoxymethylmelamine (Formula (B-1)) as a crosslinking agent and 0.2 part by weight of pyridinium-p-toluenesulfonate as a polymerization catalyst were mixed with propylene glycol monomethyl ether (PGME) 95 parts by weight. This solution was applied to soda glass and an alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film having a thickness of about 300 nm.

3. Performance Evaluation

(1) Evaluation of peel strength for cured resin thin film

The force (peeling force) required to peel the cured resin thin films from the glass substrate on each of the glass substrates of the examples and comparative examples was quantitatively evaluated by the following method. For the measurements, use a TENSILON RTG-1310 (A & D) as a measuring instrument and UR-100N-D as a load cell. Measurements were made by placing a Nichiban tape (24 mm width) on a glass substrate (Peeling force) required for peeling by pulling at a constant speed of 300 mm / min at a peeling angle of 90 deg.

The results are shown in Table 1. The peel forces for Examples 1 to 16 in Table 1 and Table 2 are indicated by three decimal places. Other measured values and calculated values are shown to two decimal places in principle.

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-XG substrate) The peeling strengths of 1 to 16 were found to be as small as two digits by 0.013 to 0.078 N / mm ² (soda glass substrate) and 0.028 to 0.085 N / mm ² (EAGLE-XG substrate) It was observed that the film and the substrate were broken due to the high peeling force of the thin film. On the other hand, each of the cured resin thin films of the examples could easily be easily peeled off in any case.

(2) Evaluation of peel force on the cured resin thin film after firing

The peeling force was measured on the cured resin thin film in the case where the cured resin thin film was baked on the assumption of the baking step in the circuit manufacturing by patterning using the photolithography method or the printing method. That is, the cured resin thin film formed on the soda glass substrate was baked at 230 ° C for 1 hour or 3 hours for Examples 1, 7, and Comparative Examples 1 and 2, and the peeling force Were measured. The results are shown in Table 2 together with the peel strength (initial peel strength) values before firing in the Examples and Comparative Examples.

As shown in Table 2, the cured resin thin films of Examples 1 and 7 were two orders of magnitude lower than those of Comparative Examples 1 and 2 after firing at 230 ° C for 1 hour or 3 hours, and were easily peeled off easily. The cured resin thin films of Comparative Examples 1 and 2 were bonded to the glass substrate more strongly than before the firing.

The peeling force was measured in the same manner as in the above (2) in the case where the cured resin thin film was fired on a cured resin thin film on the assumption of a firing step in circuit manufacturing by patterning using a photolithography method or a printing method. That is, the cured resin thin film formed on the soda glass substrate was baked at 230 ° C for 20 minutes for Examples 12, 16 to 22 and Comparative Example 7, and the peeling force was measured according to the apparatus and method described in the above (1). The results are shown in Table 3 together with the peeling force (initial peeling force) value before firing in the examples and the comparative examples.

As shown in Table 3, the cured resin thin films of Examples 12 to 24 were two orders of magnitude lower than those of Comparative Examples 1 and 2 before sintering after sintering at 230 ° C for 20 minutes, and they were easily peeled off easily. On the other hand, the cured resin thin film of Comparative Example 7 had a high peeling force and could not be peeled off.

(3) The cured resin thin film after sintering when the crosslinking agent and the mixing ratio are changed

    Evaluation of peel strength

The peel strengths of the cured resin thin films prepared for Examples 25 to 27 and Comparative Examples 8 to 10 when the mixing ratio of the crosslinking agent and the polymer / crosslinking agent were changed to those shown in Table 5 were measured. The various conditions are as follows.

<Evaluation Criteria>

Substrate: Soda glass (coated on tin treated surface)

Coating: Spin coating> Baking at 150 ° C or 230 ° C for 30 minutes Finish coat thickness

        50 to 200 nm

Peel test conditions: A peel test is carried out on a Niche half tape (24 mm width).

The polymer used is polymer A-3.

The crosslinking agents used are shown in Table 4. In Table 4, MW-30 is hexamethoxymethylmelamine (NIKARAKU MW-30, manufactured by Samhwa Chemical Co., Ltd.) of the formula (B-1) and MW-30LF is hexamethoxymethylmelamine (low glass formaldehyde product MX-270 is 1,3,4,6-tetrakis (methoxymethyl) glycoluril (NIKARAKU MW-30LF, manufactured by Sankyo Chemical Co., Ltd.) of the formula (B- 270, and Samhwa Chemical Co., Ltd.).

The results are shown in Table 5. MW-30 was used as a reference compound to change the mixing ratio of other compounds to examine the peeling force and peeling properties (Examples 25 to 27 and Comparative Examples 8 to 10). In Table 5, " o " in the item of peeling test indicates that the formed cured resin film can be easily peeled off easily and has easy releasability, and " x "

As shown in Table 5, when the MW-30 is used, the peeling force is low at 0.02 as the mixing ratio of the polymer / crosslinking agent is 45/50. Thus, in the case of 90/10, the peeling force is 7.5, The number was too large and the dragon had no peelability. When MX-270 is used, it has low peel force 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 did not have easy peelability. These results suggest that MW-30LF is less formaldehyde and is inferior to MW-30 in terms of methylol moiety (reaction point of thermal crosslinking).

(4) Limitations of peel strength of cured resin thin film

When the weight ratio (wt%) of the polymer, the crosslinking agent and the acid catalyst was changed, the peeling force of the prepared cured resin thin film was measured. Specifically, except that the solutions prepared in Examples 28 to 38 and Comparative Examples 11 to 15 using the polymer, crosslinking agent and acid catalyst in the weight ratios shown in Table 6 below were applied on a soda glass substrate and fired at 230 ° C for 20 minutes A cured resin film was formed in the same manner as in Example 1, and the respective peeling forces were measured and compared according to the apparatus and method described in (1) above. The results are shown in Table 6.

As shown in Table 6, the crosslinking agent B-1 exhibited easy peelability of 10% by weight or more based on the total amount of polymer, crosslinking agent and acid catalyst (Examples 28 to 30) (Example 33 to 38). &Lt; tb &gt; &lt; TABLE &gt; In Comparative Example 8 of Table 5, the ease of peeling property was not exhibited at a mixing ratio of polymer / crosslinking agent of 90/10. However, 85/10 of Example 29 in Table 6, which is an almost same mixing ratio using an acid catalyst, It can be said that the release of the easy peeling property is facilitated by the introduction of the acid catalyst.

Although the preferred embodiments of the present invention have been described for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims. The patents, patent applications and other documents cited in this specification are to be understood as being incorporated herein by reference in its entirety, such as the contents of which are expressly incorporated herein by reference. This application claims priority to International Patent Application No. PCT / JP2016 / 074180 (filed on August 19, 2016) and Taiwan Patent Application No. 105126494 (filed on August 19, 2016), the contents of which are incorporated herein by reference in their entirety .

 [Industrial applicability]

The present invention has a high temperature durability of 230 deg. C in a firing step in which a very thin thin film of a cured resin can be formed by applying a very thin layer on a glass substrate or the like, applying and drying and curing, and forming a circuit thereon by patterning or the like And can be peeled off from the substrate without any difficulty even after exposure to high temperatures. The curable resin composition is useful for the production of film-type electric / electronic circuit components.

Claims (46)

A curable resin composition comprising a chain polymer having a side chain having an alcoholic secondary or tertiary hydroxyl group and a crosslinking agent,
(a) the side chain comprises from 3 to 30 carbon atoms and contains at least one saturated or unsaturated hydrocarbon group or further contains at least one aromatic group, and the linkage between the carbon atoms is -COO-, - O-, and -CO-,
(b) the crosslinking agent is selected from the group consisting of a triazine compound and / or a condensate thereof, a glycoluril compound and / or a condensate thereof, and an imidazolidinone compound and / or a condensate thereof Composition.
The polymer according to claim 1, wherein the chain polymer is a monomer unit having a side chain having an alcoholic secondary or tertiary hydroxyl group, and is an unsubstituted or? -Substituted (meth) acrylic monomer, an unsubstituted or? And at least one of monomers, unsubstituted or? -Positionally substituted vinyl ether monomers, and other unsubstituted or? -Substituted vinyl monomers as a monomer unit.
According to claim 1 or 2, wherein the polymer chain 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
[In the above formula
When R ¹ , R ³ , R ⁴ and R ⁵ are bonded to each vinyl group through an ester bond, they have 3 to 30 carbon atoms including an ester bond constituting carbon atom, and an alcoholic secondary or tertiary Containing a hydroxy group and containing at least one saturated or unsaturated hydrocarbon group or further containing at least one aromatic group and the linkage between the carbon atoms is a bond selected from the group consisting of -COO-, -O- and -CO-, And,
R ^1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted alkenyl group.
And a monomer unit selected from the group consisting of a compound represented by the following formula (1).
The method according to any one of claims 1 to 3, wherein the chain polymer is
Expression A1:
[Chemical Formula 1]

[In the above formula
R ^1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group,
L ¹ is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group and a substituted or unsubstituted alkenylene group,
R ^2a , R ^3a and R ^4a are each independently selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon radicals,
Provided that at least one of R ^2a , R ^3a and R ^4a is a substituted or unsubstituted secondary or tertiary OH containing group.
&Lt; / RTI &gt; and a monomer unit represented by the following formula (1).
5. The polymer according to any one of claims 1 to 4, wherein the chain polymer is
Expression A2:
(2)

[In the above formula
R ^1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group,
L ¹ is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group and a substituted or unsubstituted alkenylene group,
R ^5a to R ^14a independently represent hydrogen, a hydroxyl group,
(3)

&Lt; / RTI &gt; or together form a ring.
Only ~ R ^5a R ^14a is at least one hydroxy group of the ring substituents,
R ^15a is selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted heteroaromatic group .]
&Lt; / RTI &gt; and a monomer unit represented by the following formula (1).
5. The polymer according to any one of claims 1 to 4, wherein the chain polymer is
Formula A3:
[Chemical Formula 4]

[In the above formula
R ^1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group,
L 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, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted alkynyl group.
&Lt; / RTI &gt; and a monomer unit represented by the following formula (1).
5. The polymer according to any one of claims 1 to 4, wherein the chain polymer is
Expression A4:
[Chemical Formula 5]

[In the above formula
R ^1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group,
L ¹ is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group and a substituted or unsubstituted alkenylene group,
R ^18a is an adamantyl group substituted with at least one hydroxy group.
&Lt; / RTI &gt; and a monomer unit represented by the following formula (1).
The method of any one of claims 1 to 5, wherein the chain polymer is
Formula A5:
[Chemical Formula 6]

[In the above formula
R ^1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group,
L ¹ is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group and a substituted or unsubstituted alkenylene group,
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.
&Lt; / RTI &gt; wherein the curable resin composition comprises a monomer unit represented by the following formula (1).
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 hydroxyl group and a crosslinking agent,
(a) the side chain comprises from 3 to 30 carbon atoms and contains at least one saturated or unsaturated hydrocarbon group or further contains at least one aromatic group and the linkage between the carbon atoms is -COO-, -O - and -CO-, &lt; / RTI &gt;
(b) the crosslinking agent is selected from a triazine crosslinking agent or a glycoluril crosslinking agent.
The positive resist composition according to any one of claims 1, 2, and 10, wherein the chain polymer is a monomer unit having the side chain having an alcoholic secondary or tertiary hydroxyl group, and the (meth) acrylic monomer, the vinyl ester monomer, An ether-based monomer, and a vinyl-based monomer other than these, as a monomer unit.
The method according to any one of claims 1 to 3, 10 to 11,
The polymer chain 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 independently represent an alkyl group having from 3 to 30 carbon atoms including an ester bond constituting carbon atom when they are bonded to each vinyl group through an ester bond, Secondary or tertiary hydroxyl groups, containing one or more saturated or unsaturated hydrocarbon groups or additionally containing at least one aromatic group and the linkage between the carbon atoms being comprised of -COO-, -O- and -CO-, Lt; RTI ID = 0.0 &gt; and / or &lt; / RTI &gt;
And a monomer unit selected from the group consisting of compounds represented by the following formula (1).
13. The curable resin composition according to any one of claims 2 to 12, wherein the monomer unit is a (meth) acrylic monomer.
10. The curable resin composition according to any one of claims 3 to 9, wherein R &^lt; ^{1a &gt;} is hydrogen or methyl.
The polymer according to any one of claims 1 to 14, wherein the chain polymer comprises an unsubstituted or? -Substituted (meth) acrylic monomer having 1 to 15 carbon atoms in the side chain, with or without a hydroxy group, Position-substituted vinyl ester-based monomer, an unsubstituted or? -Substituted vinyl ether-based monomer, and other unsubstituted or? -Substituted vinyl-based monomer as additional monomer units.
16. The method according to any one of claims 1 to 15,
The additional monomer unit
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 from 1 to 15 carbon atoms, contain or contain no hydroxy groups, contain at least one saturated or unsaturated hydrocarbon group or additionally contain at least one aromatic group, The linkage may have a bond selected from the group consisting of -COO-, -O- and -CO-, and the hydrocarbon group or the aromatic group may have an amino group. R ^1a is hydrogen, a substituted or unsubstituted alkyl group, An 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 from 3 to 15 carbon atoms, contain or contain no hydroxy groups, contain at least one saturated or unsaturated hydrocarbon group or additionally contain at least one aromatic group, The linkage may have a bond selected from the group consisting of -COO- -O- and -CO-, and the hydrocarbon group or the aromatic group may have an amino group, and R1a is hydrogen, a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl Group, &lt; / RTI &gt;
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 ^{_{acid, C 4 (R 1a) HNO}} 2 - represents an unsubstituted or substituted maleimide, ^{R 11} and R ¹² are independently of each other Containing at least one saturated or unsaturated hydrocarbon group or containing at least one aromatic group and having a carbon number of 1 to 15 and containing or not having a hydroxy group and the link between the carbon atoms being -COO-, -O- and -CO-, the hydrocarbon group or the aromatic group may have an amino group, and R &^lt; ^{1a &gt;} is hydrogen, a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group Selected.]
And a compound represented by the following formula (1).
The polymer according to any one of claims 1 to 16, wherein the chain polymer is a copolymer of a (meth) acrylic monomer, a vinyl ester monomer, a vinyl ether monomer, and a monomer having no carbon atoms and having 1 to 15 carbon atoms in the side chain Vinyl-based monomer as an additional monomer unit.
18. The method according to any one of claims 1 to 17,
The additional monomer unit
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 from 1 to 15 carbon atoms, do not contain a hydroxy group and contain at least one saturated or unsaturated hydrocarbon group or further contain at least one aromatic group, May have a bond selected from the group consisting of -COO-, -O- and -CO-, and the hydrocarbon group or the aromatic group may 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 from 3 to 15 carbon atoms, do not contain a hydroxy group and contain at least one saturated or unsaturated hydrocarbon group or additionally contain at least one aromatic group, -COO-, -O-, and -CO-, and the hydrocarbon group or the aromatic group may have an amino group.
C ₄ HO ₃ -R ¹¹ and C ₄ H ₂ NO ₂ -R ¹²
Wherein C ₄ HO ₃ - represents a maleic anhydride group, C ₄ H ₂ NO ₂ - represents a maleimide group, R ¹¹ and R ¹² independently represent a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, Containing at least one saturated or unsaturated hydrocarbon group or further comprising at least one aromatic group and the linkage between the carbon atoms 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 a compound represented by the following formula (1).
19. The polymer electrolyte fuel cell according to any one of claims 1 to 18, wherein the proportion of the monomer unit constituting the chain polymer occupied by the monomer unit having an alcoholic secondary or tertiary hydroxyl group is 30 to 100 mol% .
20. The process according to any one of claims 1 to 19, wherein the cross-linking agent is selected from the group consisting of complete or partial alkoxymethylated melamine and / or its condensates, fully or partially alkoxymethylated guanamine and / or its condensates, And / or its condensates, fully or partially alkoxymethylated benzoguanamine and / or its condensates, fully or partially alkoxymethylated glyceryl and / or its condensates and fully or partially alkoxymethylated imidazolidinones and / or And condensates thereof. &Lt; RTI ID = 0.0 &gt; 21. &lt; / RTI &gt;
21. The coating composition according to any one of claims 1 to 20, wherein the crosslinking agent is
Expression B1:
(7)

Wherein R ^1b is a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted heteroaromatic group,
[Chemical Formula 8]

And R ^2b to R ^7b are independently selected from the group consisting of substituted or unsubstituted alkyl groups and substituted or unsubstituted alkenyl groups each having 1 to 10 carbon atoms.
And / or a condensate thereof,
Expression B2:
[Chemical Formula 9]

[Wherein R ^8b to R ^11b independently of each other are 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
Expression B3:
[Chemical formula 10]

Wherein R ^12b and R ^13b 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 R ^14b and R ^15b are each independently selected from the group consisting of hydrogen or A substituted or unsubstituted alkyl group, and a substituted or unsubstituted alkenyl group having 1 to 10 carbon atoms.
And / or a condensate thereof
&Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt;
22. The curable resin composition according to any one of claims 1 to 21, wherein the condensate comprises a polymer of the compound represented by formula B1, formula B2 or formula B3.
23. 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 the formula B1, B2 or B3 Composition.
24. The curable resin composition according to any one of claims 1 to 23, wherein the crosslinking agent has a weight average degree of polymerization of from 1.3 to 1.8 with respect to the compound represented by the formula B1, formula B2 or formula B3, respectively .
25. The compound according to any one of claims 1 to 24, wherein R &lt; ^{1b &gt;} is a substituted or unsubstituted aromatic group and /
(11)

, R ^2b to R ^13b are independently a substituted or unsubstituted alkyl group, and R ^14b and R ^15b are independently of each other hydrogen.
26. The curable resin composition according to any one of claims 1 to 25, wherein the mass ratio of the linear polymer and the crosslinking agent in the composition is 1: 2 to 1: 0.03.
27. The curable resin composition according to any one of claims 1 to 26, further comprising an acid catalyst.
28. The method according to claim 27, wherein the acid catalyst is a compound selected from the group consisting of p-toluenesulfonic acid (PTS), dodecylbenzenesulfonic acid, and a thermal acid generator Sun-100L (Samsin Chemical Industries, Salt or a solvate thereof.
29. The curable resin composition according to any one of claims 1 to 28, further comprising a solvent.
A cured resin film obtained by curing the curable resin composition of any one of claims 1 to 29.
A readily releasable cured resin film obtained by curing a curable resin composition of any one of claims 1 to 29 in a film form on the surface of a substrate.
31. The cured resin film according to claim 30 or 31, wherein the cured resin film has a peeling force in a soda-glass substrate or an alkali-free glass substrate of 0.5 N / mm ² or less.
32. The cured resin film according to any one of claims 30 to 32, wherein the cured resin film has a peeling force in a soda-glass substrate or an alkali-free glass substrate of 0.1 N / mm ² or less.
A method for producing a cured resin film from the curable resin composition of any one of claims 1 to 29,
(I) preparing a chain polymer having a side chain having an alcoholic secondary or tertiary hydroxyl group and a crosslinking agent;
(Ii) applying the curable resin composition comprising the chain polymer and the cross-linking agent on a substrate to form a cured resin composition coating film; And
(Iii) forming a cured resin film by curing the polymerization reaction in the curable resin composition coating film;
&Lt; / RTI &gt;
35. The method of claim 34, further comprising: (iv) peeling the cured resin film formed on the substrate from the substrate.
In the method for producing a cured resin film,
(I) preparing a chain polymer having a side chain having an alcoholic secondary or tertiary hydroxyl group and a crosslinking agent;
(Ii) applying a composition comprising the chain polymer and a cross-linking agent to a substrate to form a curable resin composition coating film; And
(Iii) forming a cured resin film by curing the polymerization reaction in the curable resin composition coating film;
Lt; / RTI &gt;
In this step
(a) the side chain comprises from 3 to 30 carbon atoms and contains at least one saturated or unsaturated hydrocarbon group or further contains at least one aromatic group, and the linkage between the carbon atoms is -COO-, -O- and -CO-, &lt; / RTI &gt;
(b) the crosslinking agent is selected from a triazine crosslinking agent or a glycoluril crosslinking agent.
37. The method of claim 36, wherein the chain polymer is a monomer unit having a side chain having an alcoholic secondary or tertiary hydroxyl group, wherein the (meth) acrylic monomer, the vinyl ester monomer, the vinyl ether monomer, &Lt; / RTI &gt; wherein the polymer comprises at least one monomer unit selected from the group consisting of: &lt; RTI ID = 0.0 &gt;
37. The method of claim 36 or claim 37, wherein the polymer chain 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 independently represent an alkyl group having 3 to 30 carbon atoms including the ester bond constituent carbon atoms when they are bonded to each vinyl group through an ester bond, A secondary or tertiary hydroxyl group and contains at least one saturated or unsaturated hydrocarbon group or further contains at least one aromatic group and the linkage between the carbon atoms is --COO--, --O-- and --CO-- May have a bond selected from the group consisting of:
And a monomer unit selected from the group consisting of a compound represented by the following formula (1).
39. The polymer according to any one of claims 36 to 38, wherein the chain polymer is selected from the group consisting of (meth) acrylic monomers, vinyl ester monomers, vinyl ether monomers, Vinyl-based monomer and at least one additional monomer unit of the vinyl-based monomer.
40. The process of any one of claims 36 to 39,
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 from 1 to 15 carbon atoms, do not contain a hydroxy group and contain at least one saturated or unsaturated hydrocarbon group or further contain at least one aromatic group, May have a bond selected from the group consisting of -COO-, -O- and -CO-,
CH ₂ = CH-O-R ⁹ , CH ₂ = CH-R ¹⁰
Wherein R ⁹ and R ¹⁰ independently of one another have from 3 to 15 carbon atoms, do not contain a hydroxy group and contain at least one saturated or unsaturated hydrocarbon group or additionally contain at least one aromatic group, -COO-, -O-, and -CO-,
C ₄ HO ₃ -R ¹¹ and C ₄ H ₂ NO ₂ -R ¹²
Wherein C ₄ HO ₃ - represents a maleic anhydride group, C ₄ H ₂ NO ₂ - represents a maleimide group, R ¹¹ and R ¹² independently represent a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, and a hydroxy group Containing at least one saturated or unsaturated hydrocarbon group or additionally containing at least one aromatic group and the linkage between the carbon atoms may have a bond selected from the group consisting of -COO-, -O- and -CO- .]
Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt;
40. The polymer electrolyte fuel cell according to any one of claims 36 to 40, wherein the proportion of the monomer unit constituting the chain polymer occupied by the monomer unit having an alcoholic secondary or tertiary hydroxyl group is 30 to 100 mol% .
45. The composition of any one of claims 36 to 41, wherein the cross-linking agent is selected from the 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 glycerol. &Lt; RTI ID = 0.0 &gt; 8. &lt; / RTI &gt;
43. The method according to any one of claims 36 to 42, wherein the mass ratio of the linear polymer to the crosslinking agent in the composition is 1: 2 to 1: 0.03.
44. The method of any one of claims 36 to 43, wherein the composition comprises a solvent.
45. The process according to any one of claims 36 to 44, wherein the composition comprises an acid catalyst.
The method of manufacturing a cured resin film according to any one of claims 34 to 45, further comprising (iv) peeling the cured resin film formed on the substrate from the substrate.