KR102442826B1 - Curable resin composition for easy release film formation and manufacturing method thereof - Google Patents

Abstract

Disclosed is a curable resin composition that can be applied to the surface of a glass substrate to form a thin film of a cured resin, can withstand firing at 230°C, and can be easily peeled off the substrate without unreasonableness. The present composition is 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 contains 3 to 30 carbon atoms, and at least one a saturated or unsaturated hydrocarbon group, or at least one aromatic group in addition thereto, provided that the linkage between carbon atoms may include 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-based compound and/or a condensate thereof, a glycoruryl-based compound and/or a condensate thereof, an imidazolidinone-based compound and/or a condensate thereof.

Description

Curable resin composition for easy release film formation and manufacturing method thereof

The present invention relates to a curable resin composition, and more particularly, to a curable resin composition for forming an easy release film, particularly for forming a thin film that can be easily peeled off from the substrate by coating it on a substrate such as glass and curing it to form a thin film It relates to a curable resin composition. In particular, it relates to a curable resin composition that is difficult to modify even during heat treatment and easily forms a thin film by maintaining easy peelability.

BACKGROUND ART A display device such as a liquid crystal display device is widely used in a vending machine, a portable terminal such as an ATM smart phone, a computer, and other various electric and electronic devices. The screen of the display device is generally a high-strength flat panel type.

In response to this, development of a flexible display device having a screen capable of being deformed to a certain degree is being developed by reflecting the expansion of potential uses of the display device. Although there is a resin base film as a substrate constituting the curved circuit, when it is used in the screen of a display device, it is impossible to produce a fine circuit, so a transparent and as thin and light film as possible is required.

The production of various micro electric/electronic circuits on a resin base film uses, for example, photolithography, and is used for forming a metal film on the base film, coating a photoresist film, pre-baking, exposing the circuit pattern, and dissolving the resist. Processes such as development, rinsing, firing, etching, and photoresist removal are combined and repeated depending on the purpose and method to produce a circuit. In addition, a necessary anisotropic conductive film (ACF) is disposed between and on the layers produced in this way, and a printed wiring board is disposed on the required portion thereon, and between the printed circuit board and the metal wiring through the anisotropic conductive film by heating and pressing A circuit connection is made.

In order to fabricate the entire circuit as such a laminate, several firing steps are generally required. For circuit performance, it is preferable to perform firing at a sufficiently high temperature (around 230° C.), but the upper limit of the firing temperature is limited depending on the level of heat resistance of the base film. That is, firing is possible only in a low-temperature region below the heat resistance limit of the base film. Although it is possible to use other materials (silver nanoparticles, etc.) as metal wiring that can be fired at such a low temperature, wiring produced by low-temperature firing using this is technically undesirable because the characteristics are lowered compared to conventional wiring using ITO. .

Moreover, although thinning of the base film is required every year, the heat resistance of the base film decreases with the thinning. As a result, the upper limit of the heat treatment temperature is currently lowered to about 100 ° C. Assuming that the upper limit of the temperature that can withstand the heat treatment of the base film is further reduced according to the request for further thinning in the future, the performance of the circuit can be maintained. There is a problem in that the base film material that can cope with this is not conspicuous.

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

In addition, according to the thin film, it is preferable to use a very thin film of about 300 nm for the base film. that is required It is formed by sequentially depositing circuit components such as metal wiring on a very thin base film formed on a substrate such as glass, installing an anisotropic conductive film, laminating printed circuit board wiring, circuit connection, etc. , glass or the like, and each layer formed thereon with a base film is peeled off as an integral laminate to obtain a laminate as a circuit component.

Here, it should be easy to peel the laminate from the substrate such as glass. Otherwise, a large distortion is generated in the laminate by the load at the time of pulling and peeling, thereby causing disconnection of metal wiring and peeling of circuit connections, resulting in a significant deterioration in yield of the product.

In particular, even if the substrate material itself can withstand heat treatment at a higher temperature than before in the form of a thin film, if the firing in the process of fabricating wiring thereon is performed at that high temperature, the substrate material and the surface of the substrate laminated thereon are easily adhered. Therefore, it is insufficient for the substrate material to withstand firing at a higher temperature than before in the form of a thin film, and it should be able to be easily peeled off from the substrate even after such high temperature firing.

Furthermore, since the base film is very thin as described above, the resin material for forming it should be very thin and uniformly expandable without repulsion to the substrate when applied to a substrate (eg, glass substrate). On the other hand, this affinity to the substrate may cause adhesion to the substrate in the firing process, and thus may be a factor hindering easy peelability.

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

An object of the present invention under the above background is to deposit a thin film of a cured resin by coating a very thin film on the surface of a substrate (glass, etc.) and curing it to produce a circuit by patterning, etc., and then withstand a high temperature of 230°C in the firing process In addition, it is to provide a curable resin composition that can be easily peeled off from a substrate even after being exposed to high temperatures.

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 crosslinking agent within a specific range.

Hereinafter, 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 contains 3 to 30 carbon atoms and contains at least one saturated or unsaturated hydrocarbon group or at least one aromatic group in addition thereto, provided that the linkage between carbon atoms is -COO-, - may comprise a bond selected from the group consisting of O- and -CO-,

(b) the cross-linking agent is a triazine-based cross-linking agent or a curable resin composition selected from a glycoluril-based cross-linking agent.

(Item A2) The chain polymer is a monomer unit having a side chain having an alcoholic secondary or tertiary hydroxyl group, and at least among (meth)acrylic monomers, vinyl ester monomers, vinyl ether monomers and other vinyl monomers. The curable resin composition of the above item, characterized in that it contains one monomer unit.

(Item A3) The above _- mentioned chain polymer is CH2 ₌ CH _- ^C O ^- R ¹ , C H ₂ = C (COH ₃ ) - H = H - H = H O-R ⁴ and C H ₂ = C H-R ⁵ [In the above formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a carbon atom constituting the ester bond when bonded to each vinyl group through an ester bond. It has 3 to 30 carbon atoms including may have a bond selected from the group consisting of -COO-, -O- and -CO-].

(Item A4) The chain polymer does not have a hydroxyl group and contains at least one (meth)acrylic monomer having 1 to 15 carbon atoms in the side chain, a vinyl ester-based monomer, a vinyl ether-based monomer, and other vinyl-based monomers as an additional monomer unit The curable resin composition of any one of the above, characterized in that it comprises a.

(Item A5) ^The additional monomer unit is CH2 = COH _{-COP-R6 , CH 2 = CH (CH 3 ) -COH =} ^{H -} R above, ＣＯＯ ^- R R ⁷ and R ⁸ independently of each other have 1 to 15 carbon atoms, do not contain a hydroxy group, contain at least one saturated or unsaturated hydrocarbon group, or further contain at least one aromatic group, and the linkage between carbon atoms is -COO may have a bond selected from the group consisting _{of -} , ^-O- and ^-CO- , and the hydrocarbon group or aromatic group may have an amino group], wherein R ⁹ and R ¹⁰ independently of each other have 3 to 15 carbon atoms, no hydroxyl group, at least one saturated or unsaturated hydrocarbon group, or additionally at least one aromatic group, and the link between carbon atoms is _-COO- , ^-O- and _-CO- may have _a bond selected from the group consisting _of , _and the hydrocarbon group or aromatic group may have an amino group], ¹² [In the above formula, C ₄ H O ₃ - represents a maleic anhydride group, C ₄ H ₂ N O- represents a maleimide group, and R ¹¹ and R ¹² are each independently a hydrogen atom or have 1 to 15 carbon atoms and a hydroxyl group. and contains at least one saturated or unsaturated hydrocarbon group, or further contains at least one aromatic group, wherein the linkage between carbon atoms may have a bond selected from the group consisting of -COO-, -O- and -CO-; The curable resin composition according to any one of the above, characterized in that it is selected from the group consisting of compounds represented by [the hydrocarbon group or the aromatic group may have an amino group].

(Item A6) The curable resin composition of any one of the above items, characterized in that the monomer unit having an alcoholic secondary or tertiary hydroxyl group occupies 30 to 100 mol% of the monomer unit constituting the chain polymer. .

(Item A7) said crosslinking agent is 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 glycouryl The curable resin composition of any one of the above, characterized in that it is selected from.

(Item A8) The curable resin composition according to any one of the above items, wherein in the composition, the mass ratio of the linear polymer to the crosslinking agent is 1:2 to 1:0.05.

(Item A9) The curable resin composition according to any one of the above items, characterized in that it contains a solvent.

(Item A10) A cured resin film, characterized in that it is formed by curing the curable resin composition according to any one of the above items.

(Item A11) An easily peelable cured resin film, characterized in that it is obtained by curing the curable resin composition according to any one of the above items in the form of a film on the surface of a substrate.

(Item A12) A 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 crosslinking agent;

forming a curable resin composition coating film by applying a composition including the chain polymer and a crosslinking agent to a substrate;

Comprising the step of obtaining a cured resin film by curing by advancing a polymerization reaction in the curable resin composition coating film,

Here

(a) the side chain has 3 to 30 carbon atoms and contains at least one saturated or unsaturated hydrocarbon group or additionally contains at least one aromatic group, provided that the linkage between the carbon atoms of adjacent groups of them is -COO- , may have a bond selected from the group consisting of -O- and -CO-,

(b) the cross-linking agent is a manufacturing method, characterized in that selected from a triazine-based cross-linking agent or a glycoruryl-based cross-linking agent.

(Item A13) The chain polymer is a monomer unit having a side chain having an alcoholic secondary or tertiary hydroxyl group, and at least among (meth)acrylic monomers, vinyl ester monomers, vinyl ether monomers and other vinyl monomers. A method for producing the yield, characterized in that it comprises one monomer unit.

(Item A14) The above _- mentioned chain polymer is CH2 ₌ CH _- ^C O ^- R ¹ , C H ₂ = C (COH ₃ ) - H = H O-R ⁴ and CH ₂ = H-R ⁵ [In the above formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a carbon atom constituting the ester bond when bonded to each vinyl group through an ester bond. It has 3 to 30 carbon atoms including may have a bond selected from the group consisting of -COO-, -O- and -CO-]

(Item A15) The chain polymer does not contain a hydroxyl group and contains at least one of a (meth)acrylic monomer, a vinyl ester-based monomer, a vinyl ether-based monomer, and other vinyl-based monomers having 1 to 15 carbon atoms in the side chain as an additional monomer unit The manufacturing method of any one of the above items, characterized in that it comprises a.

(Item A16) The additional monomer unit is CH2 = COH ^- COP _- R6 , CH2 ₌ CH _{(CH 3 )} ^-COH = H ^- R above, ＣＯＯ ^- R R ⁷ and R ⁸ independently of each other have 1 to 15 carbon atoms, no hydroxyl group, at least one saturated or unsaturated hydrocarbon group, or additionally at least one aromatic group, and the linkage between carbon atoms is -COO It may have a bond selected from the group consisting of -, -O- and -CO-], CH2 = CH _- O _- ^R9 , CH2 = H ^- R10 [wherein R9 and R10 are each independently a carbon atom It has 3 to 15 atoms, does not contain a hydroxy group, contains at least one saturated or unsaturated hydrocarbon group or further contains at least one aromatic group, and the linkage between carbon atoms consists of -COO-, -O- and -CO- may have a bond selected from the group], C 4 H O ₃ －R ¹¹ and C ₄ H ₂ N ₂ － R ¹² [In the above formula, C ₄ HO ₃ - represents a maleic anhydride group, and C ₄ H ₂ NO ₂ - is maleic anhydride _. represents a mid group, and R ¹¹ and R ¹² are each independently a hydrogen atom or have 1 to 15 carbon atoms, do not contain a hydroxy group, contain at least one saturated or unsaturated hydrocarbon group, or further contain at least one aromatic group, The connection between carbon atoms may have a bond selected from the group consisting of -COO-, -O- and -CO-].

(Item A17) The method for producing any one of the above items, characterized in that the occupied ratio of the monomer units having an alcoholic secondary or tertiary hydroxyl group in the monomer units constituting the chain polymer is 30 to 100 mol%.

(Item A18) said crosslinking agent is 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 glycouryl Any one of the above items, characterized in that selected from the manufacturing method.

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

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

(Item A21) The method for producing a cured resin film according to any one of the above items, further comprising the step of peeling the cured resin film formed on the substrate from the substrate.

The present invention also provides the following items.

(Item B1) A curable resin composition comprising a chain polymer having a side chain having an alcoholic secondary or tertiary hydroxyl group and a crosslinking agent,

(a) the side chain contains 3 to 30 carbon atoms, contains at least one saturated or unsaturated hydrocarbon group, or additionally contains at least one aromatic group, and the linkage between carbon atoms is -COO-, - may comprise a bond selected from the group consisting of O- and -CO-,

(b) the crosslinking agent is selected from the group consisting of a triazine-based compound and/or a condensate thereof, a glycoruryl-based compound and/or a condensate thereof, and an imidazolidinone-based compound and/or a condensate thereof. Curable resin, characterized in that composition.

(Item B2) The chain polymer is a monomer unit having a side chain having an alcoholic secondary or tertiary hydroxyl group, an unsubstituted or α-position substituted (meth)acrylic monomer, an unsubstituted or α-position substituted vinyl ester-based monomer, The curable resin composition comprising at least one of an unsubstituted or α-position-substituted vinyl ether-based monomer and other unsubstituted or α-position-substituted vinyl-based monomers as a monomer unit.

(Item B3) The above-mentioned chain polymer is CH2 ₌ ^C (R ^１ａ ) _{-COH2 ＝} CH (Ｒ ^１＼ ) ^－Ｏ －ＣＯ, ^Ｒ3 R 1 , R ^{3 , R 4 and R 5 In the above formula, R 1 , R 3 , R 4 and R 5 are} _each ^{independently of each other when} bonded to each vinyl group through an ester bond, including a carbon atom constituting an ester bond. has 3 to 30 carbon atoms, has an alcoholic secondary or tertiary hydroxyl group, contains one or more saturated or unsaturated hydrocarbon groups, or contains at least one aromatic group in addition thereto, and the link between carbon atoms is -COO It may have a bond selected from the group consisting of -, -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]. The curable resin composition of any one of the above, characterized in that it comprises a monomer unit selected from.

(Item B4) The chain polymer is of formula A1:

[Formula 1]

[In the above formula, R ^1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group, and L ¹ is a single bond, a substituted or unsubstituted alkylene group and a substituted or unsubstituted alkenylene group. and R ^2a , R ^3a and R ^4a are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted hydrocarbon radical, 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.] The curable resin composition according to any one of the above, characterized in that it contains a monomer unit represented by

(Item B5) The chain polymer is of formula A2:

[Formula 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, and L ¹ is a single bond, a substituted or unsubstituted alkylene group and a substituted or unsubstituted alkenylene group. is selected, and R ^5a to R ^14a are each independently hydrogen, a hydroxy group and

[Formula 3]

is selected from the group consisting of or together form a ring. with the proviso that R ^5a to R ^14a are at least one of the above ring substituents a hydroxyl group, and R ^15a is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or It is selected from the group consisting of an unsubstituted aromatic group and a substituted or unsubstituted heteroaromatic group.] The curable resin composition according to any one of the above, characterized in that it contains a monomer unit represented by

(Item B6) The chain polymer is of formula A3:

[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 hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted It is selected from the group consisting of an alkynyl group.] The curable resin composition of any one of the above, characterized in that it contains a monomer unit represented by

(Item B7) The chain polymer is of formula A4:

[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, and L ¹ is a single bond, a substituted or unsubstituted alkylene group and a substituted or unsubstituted alkenylene group. selected, and R ^18a is an adamantyl group substituted with at least one hydroxy group.] The curable resin composition according to any one of the above, characterized in that it comprises a monomer unit represented by

(Item B8) The chain polymer is of formula A5:

[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, and L ¹ is a single bond, a substituted or unsubstituted alkylene group and a substituted or unsubstituted alkenylene group. selected, 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.] The curable resin composition according to any one of the above items.

(Item B9) The curable resin composition according to any one of the above items, wherein R ^19a is a substituted or unsubstituted adamantyl group.

(Item B10) A curable resin composition comprising a chain polymer having a side chain having an alcoholic secondary or tertiary hydroxyl group and a crosslinking agent,

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

(b) the cross-linking agent is a curable resin composition, characterized in that selected from a triazine-based cross-linking agent or a glycorulyl-based cross-linking agent.

(Item B11) The chain polymer is a monomer unit having the side chain having an alcoholic secondary or tertiary hydroxyl group, and among (meth)acrylic monomers, vinyl ester monomers, vinyl ether monomers and other vinyl monomers. The curable resin composition of any one of the above, characterized in that it contains at least one as a monomer unit.

(Item B12) The above-mentioned chain polymer is CH2 = CH _- COP ^- R ¹ , CH _{2 =} C (COH ₃ )-COH ^- R ₂ O-R ⁴ and C H ₂ = H-R ⁵ [In the above formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently each other, when bonding to each vinyl group through an ester bond, the carbon atom constituting the ester bond is formed. having 3 to 30 carbon atoms, including alcoholic secondary or tertiary hydroxyl groups, containing at least one saturated or unsaturated hydrocarbon group, or in addition thereto, at least one aromatic group, and the linkage between carbon atoms is - It may have a bond selected from the group consisting of COO-, -O- and -CO-.] The curable resin of any one of the above, characterized in that it contains a monomer unit selected from the group consisting of compounds represented by composition.

(Item B13) The curable resin composition according to any one of the above items, wherein the monomer unit is a (meth)acrylic monomer.

(Item B14) The curable resin composition according to any one of the above items, wherein R ^1a is hydrogen or methyl.

(Item B15) The chain polymer contains or does not contain a hydroxy group and is an unsubstituted or α-position-substituted (meth)acrylic monomer having 1 to 15 carbon atoms in the side chain, an unsubstituted or α-position-substituted vinyl ester-based monomer, an unsubstituted or The curable resin composition according to any one of the above, characterized in that it contains at least one of an α-position-substituted vinyl ether-based monomer and other unsubstituted or α-position-substituted vinyl-based monomers as an additional monomer unit.

(Item B16) ^The above additional monomer units are CH2 ₌ C(R1A) ^-COH2 ₌ CH (R1A ) ^{-OR is independently of each other in the formula 6 and O -} R It has 1 to 15 carbon atoms, contains or does not contain a hydroxy group, contains at least one saturated or unsaturated hydrocarbon group or further contains at least one aromatic group, and the linkage between carbon atoms is -COO-, -O- and -CO - may have a bond selected from the group consisting of, the hydrocarbon group or aromatic group may have an amino group, and R1a 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 1b} ) ^{-O - R 9} comprising at least one saturated or unsaturated hydrocarbon group or further comprising at least one aromatic group therein, and the linkage between carbon atoms may have a bond selected from the group consisting of -COO- -O- and -CO-, wherein 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],

C ₄ (R ^1a ) O ₃ －R ¹¹ and _{C 4} （ R ¹ a ） ^HN ₂ － R ¹² [ _{In the} above formula, ^１ａ ）HNO ₂ - represents an unsubstituted or substituted maleimide group, R ¹¹ and R ¹² are each independently a hydrogen atom, or have 1 to 15 carbon atoms, with or without a hydroxy group, and at least one saturated or unsaturated hydrocarbon group comprising or additionally comprising at least one aromatic group and the linkage between carbon atoms may have a bond selected from the group consisting of -COO-, -O- and -CO-, wherein the hydrocarbon group or aromatic group may have an amino group and R ^1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group.] The curable resin composition of any one of the above items, characterized in that it is selected from the group consisting of compounds represented by .

(Item B17) The chain polymer does not contain a hydroxyl group and contains at least one of (meth)acrylic monomers, vinyl ester monomers, vinyl ether monomers, and other vinyl monomers having 1 to 15 carbon atoms in the side chain, additional monomer units The curable resin composition of any one of the above, characterized in that it comprises a.

(Item B18) ^The above additional monomer units are CH2 = CH _- COP _- R6 , CH2 ₌ CH _{(HCH 3} ^{) -COH} = H ^- R above, R ⁷ and R ⁸ independently of each other have 1 to 15 carbon atoms, no hydroxyl group, at least one saturated or unsaturated hydrocarbon group, or additionally at least one aromatic group, and the linkage between carbon atoms is -COO It may have a bond selected from the group consisting of -, -O- and -CO-, and the hydrocarbon group or aromatic group may have an amino group.],

H2 = CH _- O-R ⁹ , H ₂ = H-R ¹⁰ [wherein R ⁹ and R ¹⁰ each independently represent 3 to 15 carbon atoms, no hydroxyl group, and at least one saturated or unsaturated hydrocarbon group, or It further includes at least one aromatic group, and the linkage between 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 H O ₃ -R ¹¹ and _{C 4} H ₁₂ [ ^In the above formula, C ₄ H ^O ₃ - represents maleic anhydride, C ₄ and R ¹² , _{2 9} R are maleimide groups. independently of each other a hydrogen atom or having 1 to 15 carbon atoms, no hydroxyl group, at least one saturated or unsaturated hydrocarbon group, or additionally at least one aromatic group, and the link between carbon atoms is -COO-, It may have a bond selected from the group consisting of -O- and -CO-, and the hydrocarbon group or aromatic group may have an amino group.] Curable resin composition.

(Item B19) The curable resin composition according to any one of the above, characterized in that the ratio of the monomer unit having an alcoholic secondary or tertiary hydroxyl group in the monomer unit constituting the chain polymer is 30 to 100 mol%. .

(Item B20) The crosslinking agent is fully or partially alkoxymethylated melamine and/or its condensates, fully or partially alkoxymethylated guanamines and/or its condensates, fully or partially alkoxymethylated acetoguanamines and/or its condensates, fully or partially alkoxymethylated benzoguanamines and/or condensates thereof, fully or partially alkoxymethylated glycouryl and/or condensates thereof and fully or partially alkoxymethylated imidazolidinones and/or condensates thereof, characterized in that The curable resin composition of any one of the above items.

(Item B21) The crosslinking agent is of formula B1:

[Formula 7]

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

[Formula 8]

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

Formula B2:

[Formula 9]

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

Formula B3:

[Formula 10]

[In the above formula, R ^12b and R ^13b are each independently having 1 to 10 carbon atoms, and are selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group, and R ^14b and R ^15b are each independently hydrogen or It has 1 to 10 carbon atoms and is selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group.] 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, trimer or higher polymer of the compound represented by formula B1, formula B2 or formula 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, formula B2 or formula B3, respectively.

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

[Formula 11]

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

(Item B26) The curable resin composition according to any one of the above items, wherein in the composition, the mass ratio of the linear polymer to the mass of the crosslinking agent is 1:2 to 1:0.03.

(Item B27) The curable resin composition according to any one of the above, 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 Sunade SI-100L (Samshin Chemical Industry Co., Ltd.) or a salt thereof, or The curable resin composition according to any one of the above, characterized in that it is a solvate thereof.

(Item B29) 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 the curable resin composition according to any one of the above items.

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

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

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

(Item B34) A method for producing a cured resin film from the curable resin composition according to any one of the above items,

(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 including the chain polymer and a crosslinking agent on a substrate and forming a cured resin composition coating film;

(iii) forming a cured resin film by curing the polymerization reaction in the curable resin composition coating film.

(Item B35) (iv) The method for producing the above item, further comprising the step of peeling the cured resin film formed on the substrate from the substrate.

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

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

(ii) forming a curable resin composition coating film by applying a composition including the chain polymer and a crosslinking agent to a substrate;

(iii) forming a cured resin film by curing the polymerization reaction in the curable resin composition coating film,

in the above step

(a) the side chain contains 3 to 30 carbon atoms, contains at least one saturated or unsaturated hydrocarbon group, or further contains at least one aromatic group, and the link between carbon atoms is -COO-, may comprise a bond selected from the group consisting of -O- and -CO-,

(b) the cross-linking agent is a manufacturing method, characterized in that selected from a triazine-based cross-linking agent or a glycoruryl-based cross-linking 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. The method according to any one of the preceding claims, characterized in that it comprises at least one monomer unit.

(Item B38) The above _- mentioned chain polymer is CH2 ₌ CH _- ^C O ^- R ¹ , C H ₂ = C (COH ₃ ) - H = H-H O-R ⁴ and CH ₂ = H-R ⁵ [In the above formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently of each other, when bonding to each vinyl group through an ester bond, the carbon atoms constituting the ester bond having 3 to 30 carbon atoms, including alcoholic secondary or tertiary hydroxyl groups, containing at least one saturated or unsaturated hydrocarbon group or further containing at least one aromatic group, It may have a bond selected from the group consisting of -COO-, -O- and -CO-.] Preparation of any one of the above items, characterized in that it contains a monomer unit selected from the group consisting of compounds represented by Way.

(Item B39) The chain polymer does not contain a hydroxyl group and has 1 to 15 carbon atoms in the side chain. At least one additional monomer unit selected from (meth)acrylic monomers, vinyl ester monomers, vinyl ether monomers, and other vinyl monomers. The manufacturing method of any one of the above items, characterized in that it comprises a.

(Item B40) The additional monomer unit is CH2 = COH ^- COP _- R6 , CH2 ₌ CH _{(CH 3 )} ^-COH = H ^- R above, ＣＯＯ ^- R R ⁷ and R ⁸ independently of each other have 1 to 15 carbon atoms, no hydroxyl group, at least one saturated or unsaturated hydrocarbon group, or additionally at least one aromatic group, and the linkage between carbon atoms is -COO may have a bond selected from the group consisting of -, -O- and -CO-],

H2 = CH _- O-R ⁹ , H ₂ = H-R ¹⁰ [wherein R ⁹ and R ¹⁰ each independently represent 3 to 15 carbon atoms, no hydroxyl group, and at least one saturated or unsaturated hydrocarbon group, or It further comprises at least one aromatic group and the linkage between carbon atoms may have a bond selected from the group consisting of -COO-, -O- and -CO-],

C ₄ H O ₃ －R ¹¹ and C ₄ H _{2 2} N O ₂ － R ¹² [In the above formula, C ₄ H O ₃ - represents maleic anhydride, R ₁₁ and R ^{12 O} ₂ independently of each other, has a hydrogen atom or 1 to 15 carbon atoms, does not contain a hydroxy group, contains at least one saturated or unsaturated hydrocarbon group, or additionally contains at least one aromatic group, and the link between carbon atoms is -COO-, It may have a bond selected from the group consisting of -O- and -CO-.] The method for producing any one of the above items, characterized in that it is selected from the group consisting of compounds represented by

(Item B41) The method for producing any one of the above items, characterized in that the occupied ratio of the monomer unit having an alcoholic secondary or tertiary hydroxyl group as the monomer unit constituting the chain polymer is 30 to 100 mol%.

(Item B42) said crosslinking agent is 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 glycouryl Any one of the above items, characterized in that selected from the manufacturing method.

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

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

(Item B45) The process according to any one of the preceding items, wherein the composition comprises an acid catalyst.

(Item B46) (iv) The method for producing a cured resin film according to any one of the above items, further comprising the step of peeling the cured resin film formed on the substrate from the substrate.

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

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

(Item B49) A synthetic resin, pellet, film, plate, fiber, foaming agent, tube, rubber, elastomer, etc. comprising the curable resin composition or cured resin film of any one of the above items, used for two-wheeled vehicles (bicycles, motorcycles, etc.), automobiles , airplanes, trains, ships, rockets, spacecraft, transport, leisure, furniture (eg tables, chairs, desks, shelves, etc.), bedding (eg beds, hammocks, etc.), clothing, protective clothing, sporting goods, bathtubs , kitchen, tableware, cooking utensils, containers and packaging materials (food containers, cosmetic containers, cargo containers, trash cans, etc.), construction (buildings, roads, construction parts, etc.), agricultural films, industrial films, water and sewage, paints, cosmetics, electricity Industrial and electronic industries (electronic products, computer parts, printed circuit boards, insulators, conductors, wiring coating materials, power generation elements, speakers, microphones, noise cancellers, transducers, etc.), optical communication cables, medical materials and instruments (catheters, Manufacture of guide wires, artificial blood vessels, artificial muscles, artificial organs, dialysis membranes, endoscopes, etc.), small pumps, actuators, robotic materials (sensors used in industrial robots, etc.), energy generating devices and plants (solar power generation, wind power generation, etc.) composition for

(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 the curable resin composition or the cured resin film according to any one of the above items.

(Item B51) A composition for manufacturing a material, such as a catheter, guide wire, pharmaceutical container or tube, comprising the curable resin composition or the cured resin film according to any one of the above items.

(Item B52) Automobile parts (body panels, bumper belts, rocker panels, side moles, engine parts, driving parts, conducting parts, steering system parts, ballast parts, A composition for the production of suspension/braking device parts, brake parts, shaft parts, pipes, tanks, wheels, seats, seat belts, etc.).

(Item B53) A composition for manufacturing a vibration-proof material for automobiles, a paint for automobiles, and a synthetic resin for automobiles comprising the curable resin composition or cured resin film according to any one of the above items.

(Item B54) Use of the curable resin composition or the cured resin film according to any one of the above for the manufacture of a circuit by a photolithography method.

(Item B55) Use of the curable resin composition or the cured resin film according to any one of the above for the manufacture of sheet-like flexible electric/electronic circuit components or flexible display devices.

(Item B56) Used in synthetic resins, pellets, films, plates, fibers, foaming agents, tubes, rubber, elastomers, etc. Furniture (e.g. tables, chairs, desks, shelves, etc.), bedding (e.g. beds, hammocks, etc.), clothing, protective clothing, sporting goods, bathtubs, kitchens, cutlery, cookware, containers and packaging (food containers) , cosmetic containers, cargo containers, trash cans, etc.), construction (buildings, roads, construction parts, etc.), agricultural films, industrial films, water and sewage, paints, cosmetics, electrical and electronic industries (electronic products, computer parts, printed circuits, etc.) Substrates, insulators, conductors, wiring coating materials, power generation elements, speaker microphones, noise cancellers, transducers, etc.), optical communication cables, medical materials and instruments (catheters, guide wires, artificial blood vessels, artificial muscles, artificial organs, dialysis membranes, endoscopes, etc.) etc.), small pumps, actuators, robot materials (sensors used in industrial robots, etc.), energy generating devices and plants (solar power generation, wind power generation, etc.) use.

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

(Item B58) Use of the curable resin composition or the cured resin film according to any one of the above for the manufacture of materials such as catheters, guide wires, pharmaceutical containers or tubes.

(Item B59) Automobile parts (body panels, bumper belts, rocker panels, side moles, engine parts, driving parts, conduction parts, steering system parts, stabilizer parts, suspension/brake system parts, brake parts, shaft parts, pipes, Use of the curable resin composition or the cured resin film of any one of the above for the manufacture of tanks, wheels, seats, seat belts, etc.).

(Item B60) Use of the curable resin composition or cured resin film according to any one of the above items for the production of a vibration-proof material for automobiles, automobile paints, and synthetic resins for automobiles.

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

(Item B62) A method for manufacturing a sheet-like flexible electric/electronic circuit component or flexible display device, comprising the step of forming the curable resin composition or the cured resin film according to any one of the above items by conducting a polymerization reaction.

(Item B63) Used in synthetic resins, pellets, films, plates, fibers, foaming agents, tubes, rubber, elastomers, etc. Furniture (e.g. tables, chairs, desks, shelves, etc.), bedding (e.g. beds, hammocks, etc.), clothing, protective clothing, sporting goods, bathtubs, kitchens, cutlery, cookware, containers and packaging (food containers) , cosmetic containers, cargo containers, trash cans, etc.), construction (buildings, roads, construction parts, etc.), agricultural films, industrial films, water and sewage, paints, cosmetics, electrical and electronic industries (electronic products, computer parts, printed circuits, etc.) Substrates, insulators, conductors, wiring coating materials, power generation elements, speaker microphones, noise cancellers, transducers, etc.), optical communication cables, medical materials and instruments (catheters, guide wires, artificial blood vessels, artificial muscles, artificial organs, dialysis membranes, endoscopes, etc.) etc.), small pumps, actuators, robot materials (sensors used in industrial robots, etc.), energy generating devices and methods of manufacturing plants (solar power generation, wind power generation, etc.), by performing a polymerization reaction in any one of the above items A method comprising the step of forming a curable resin composition or a cured resin film of

(Item B64) A method for manufacturing an electronic material, a medical material, a health care material, a life science material, or a robot material, comprising the step of forming the curable resin composition or the cured resin film according to any one of the above items by performing a polymerization reaction How to include.

(Item B65) A method for manufacturing a material such as a catheter, guide wire, pharmaceutical container or tube, comprising the step of forming the curable resin composition or the cured resin film according to any one of the above items by conducting a polymerization reaction.

(Item B66) Automobile parts (body panels, bumper belts, rocker panels, side moles, engine parts, driving parts, conduction parts, steering system parts, stabilizer parts, suspension/brake system parts, brake parts, shaft parts, pipes, A method for manufacturing tanks, wheels, seats, seat belts, etc.), comprising the step of forming the curable resin composition or the cured resin film according to any one of the above items by performing a polymerization reaction.

(Item B67) A method for producing an automobile dustproof material, automobile paint, and automobile synthetic resin, comprising the step of forming the curable resin composition or cured resin film according to any one of the above items by conducting a polymerization reaction.

[1] Definition of terms

As used herein, "heat resistance" means that the film obtained by curing the curable resin composition does not substantially decompose or otherwise deteriorate which can withstand heating up to 150° C. and preferably can withstand heating at 230° C. The temperature of 230 DEG C is high enough to be used as a firing temperature in the production of an electronic circuit by a photolithography method.

As used herein, "easy peeling film" means that a film formed by coating and curing on a substrate, particularly a glass substrate, can be easily peeled off from the substrate without damaging the film (that is, without unreasonableness). means character. As a glass substrate, suitable glass substrates, such as a soda glass substrate and an alkali free glass substrate, are mentioned, for example. A soda glass substrate is one 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 manufacturing, the preferred thickness is 200 to 400 nm, for example, about 300 nm, which corresponds to the current thinning request for 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 this specification, "cured resin thin film" is used synonymously with "cured resin film".

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

References herein to "-O-" and "CO-" include cases where they are a constituent part of "COO-". Incidentally, "-COO-" is a description showing the ester when both groups of the ester are not fixed, and includes both '-COO-' and '-O-CO-'. However, when both ends of the ester are fixed, '-COO-' and '-O-CO-' are used separately.

As used herein, "alkyl" refers to a monovalent group formed by the loss of one hydrogen atom from an aliphatic hydrocarbon (alkane) such as methane, ethane, and propane, and is generally represented by C _n H _2n+1 - (where n is an amount) is an integer of). Alkyl may be straight-chain or branched. As the C1-C4 alkyl group (C1-4 alkyl group), for example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group and the like, but the present invention is not limited to these examples.

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

As used herein, the term "alkenyl group" refers to a monovalent group formed by the loss of one hydrogen atom in an aliphatic hydrocarbon (alkene) containing at least one double bond such as ethene, propene, and butene, and generally C _m H _2m-1 (where m is an integer greater than or equal to 2). The alkenyl group may be straight-chain or branched.

Examples of the alkenyl group having 2 to 6 carbon atoms include an ethenyl group, 1-propenyl group, 2-propenyl group, butenyl group, pentenyl group, and hexenyl group, but 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. .

As used herein, the term "alkynyl group" refers to a monovalent group formed by the loss of one hydrogen atom in an aliphatic hydrocarbon (alkyne) containing at least one triple bond such as ethyne (acetylene), propyne, and butyne, generally C _m H It is expressed as _2m-3 (where m is an integer greater than or equal to 2). The alkynyl group may be straight-chain or branched. Examples of the alkynyl group having 2 to 6 carbon atoms include an ethynyl group, 1-propynyl group, 2-propynyl group, butynyl group, pentynyl group, and hexynyl group, but the present invention is not limited to these examples. . Examples of the alkynyl group having 2 to 10 carbon atoms include an alkynyl group having 2 to 6 carbon atoms, heptynyl group, octynyl group, noninyl group, and decynyl group, but the present invention is not limited to these examples. .

As used herein, the term "alkylene group" refers to a divalent group formed by the loss of two hydrogen atoms from an aliphatic hydrocarbon (alkane) such as methane, ethane, and propane, and is generally represented by -(C _m H _2m )- (where m is a positive integer). The alkyl group may be straight-chain or branched. Examples of the alkylene group having 1 to 10 carbon atoms include methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, tert-butylene group, n-pentene group, n- A hexylene group, an isohexylene group, etc. may be mentioned, but the present invention is not limited to these examples. A C1-C6 alkylene group is preferable and a C1-C4 alkylene group is more preferable. A methylene group and an ethylene group are more preferable, and an ethylene group is even more preferable.

As used herein, the term "alkenylene group" refers to a divalent group formed by the loss of two hydrogen atoms in an aliphatic hydrocarbon (alkene) containing at least one double bond such as ethenylene, propenylene, and butenylene, and is generally -(C _m H _2m-2 )- (where m is an integer greater than or equal to 2). The alkenylene group may be straight-chain or branched. Examples of the alkenylene group having 2 to 10 carbon atoms include ethenylene group, n-propenylene group, isophenylene group, n-butenylene group, isobutenylene group, n-pentenylene group, n-hexenylene group, isohexenylene group, and the like, but the present invention is not limited to these examples. A C2-C6 alkenylene group is preferable, and a C2-C4 alkenylene group is more preferable. An ethenylene group and an n-propenylene group are more preferable, and an ethenylene group is still more preferable.

As used herein, "alkoxy" refers to a monovalent group formed by loss of a hydrogen atom of a hydroxyl group of an alcohol, and is 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 group, ethoxy group, n-propyloxy group, isopropyloxy group, n-propyloxy group, isobutyloxy group, tert-butyloxy group, sec-butyl group oxy group, n-pentyloxy group, isoamyloxy group, n-hexyloxy group, isohexyloxy group, etc. may be mentioned, but the present invention is not limited to these examples.

As used herein, the term “haloalkyl group” refers to an alkyl group in which one or more hydrogen atoms of the alkyl group are substituted with halogen atoms. Also, "perhaloalkyl" refers to an alkyl group in which all hydrogen atoms of the alkyl group are substituted with halogen atoms. Examples of the haloalkyl group having 1 to 6 carbon atoms include trifluoromethyl group, trifluoroethyl group, perfluoroethyl group, trifluoron-propyl group, perfluoron-propyl group, trifluoroisopropyl group, purple Luoroisopropyl group, trifluoron-butyl group, perfluoron-butyl group, trifluoroisobutyl group, perfluoroisobutyl group, trifluorotert-butyl group, perfluorotert-butyl group group, trifluoro n-pentyl group, perfluoro n-pentyl group, trifluoro n-hexyl group, perfluoro n-hexyl group, and the like, but the present invention is not limited to these examples.

As used herein, the term "cycloalkyl group" refers to a monocyclic or polycyclic saturated hydrocarbon group, and also includes 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, an isobornyl group, and the like. In the case of "C _3-12 cycloalkyl group", a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a C _6-12 cycloalkyl group, and the like can be mentioned. Preferably, a "C _6-12 cycloalkyl group is mentioned.

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

As used herein, the term "hydrocarbon group" refers to a monovalent group formed by the loss of one hydrogen atom in a compound composed of only carbon and hydrogen. Hydrocarbon radical includes the above "alkyl group", "alkenyl group", "alkylene group", "alkenylene group", "cycloalkyl group" and "cycloalkenyl group" and the following "aromatic group" and "alicyclic group", etc. . The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group is classified into a chain hydrocarbon group and a cyclic hydrocarbon group according to 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, cyclohexyl. Various straight-chain, branched-chain, mono-cyclic, and condensed-cyclic groups such as cenyl and decyl within the limit of the number of carbon atoms in the side chain may be mentioned, but are not limited thereto. When each group is not located at the terminal, it may be a divalent or higher group depending on a bonding relationship with other groups.

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

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

As used herein, the term "alicyclic (group)" refers to a portion (or group) formed by leaving one hydrogen atom bonded to a ring having no aromatic properties composed of only carbon and hydrogen. The alicyclic group includes the above "cycloalkyl group" and "cycloalkenyl group". The alicyclic group may be saturated or unsaturated. Examples of the saturated or unsaturated alicyclic group include, but are not limited to, various monocyclic and condensed cyclic groups within the limit of the number of carbon atoms in the side chain, such as cyclohexyl, dicyclopentadienyl, decarinyl, adamantyl, and cyclohexenyl. does not When each group is not located at the terminal, it may be a divalent or higher group depending on a bonding relationship with other groups.

In general, the term "substituted (which/is)" means that one or more hydrogen radicals in a given structure have been substituted, depending on the radical of the particular substituent. In the present specification, the number of substituents in the group defined using "substituting (which/is)" is not particularly limited as long as it is substitutable and is 1 or more. In addition, the description of each group, except where specifically stated, also applies to the case where the group is a part or a substituent of another group. Also, in this specification, a substituent that does not specifically specify the term "substituted (which is/are)" means an "unsubstituted" substituent. In addition, it is recognized that the term "substituted or unsubstituted" is used interchangeably with the term "may be substituted" in this specification.

"Substituted alkyl group", "substituted alkyl group", "substituted alkenyl group", "substituted alkynyl group", "substituted cycloalkyl group", "substituted cycloalkenyl group", "substituted hydrocarbon group", "substituted aromatic group", "substituted hetero Substituents of the groups described herein, including "aromatic groups", "substituted alkylene groups", "substituted alkenylene groups", "substituted or unsubstituted secondary or tertiary OH-containing groups" and "substituted adamantyl groups" Examples of the halogen, hydroxyl group, C _1-10 alkyl group, C _1-10 alkoxy group, C _2-10 alkenyl group, C _6-12 cycloalkyl group, C _6-12 cycloalkenyl group, C _1-10 halo group, C _2-10 haloalkenyl group, C _6-18 hydrocarbon group, C _6-18 aromatic group, C _6-18 heteroaromatic group, C _6-12 aromatic group substituted C _1-10 alkyl group, C _6-12 hydrocarbon group C _1-10 alkyl group, C _6-12 aromatic group substituted C _2-10 alkenyl group, C _6-12 hydrocarbon group substituted C _2-10 alkenyl group, -CN, oxo group (=O), -O ( CH ₂ ) ₂ O-, -OC(CH ₃ ) ₂ O-, -OCH ₂ O-, -O-, ester group (-COO- or -O-CO-), ester substituted with C _6-12 hydrocarbon group group, C _6-12 ester group substituted with aromatic group, C _6-18 hydrocarbon group substituted with ester group, C _1-10 alkyl group substituted with ester group, C _1-6 alkylene group, C _2-6 alkenylene group, etc. However, the present invention is not limited to these examples.

Preferred examples of the substituent include a hydroxy group, a C _6-18 hydrocarbon group, a C _1-10 alkyl group, a C _1-10 alkyl group substituted with a C _6-12 aromatic group, a C _1-10 alkyl group substituted with a C _6-12 hydrocarbon group, an ester C _6-18 hydrocarbon group substituted with a group, C _1-10 alkyl group substituted with an ester group, an ester group (-COO- or -O-CO-), an ester group substituted with a C _6-12 hydrocarbon group, C _6-12 aromatic an ester group substituted with a group, a C _2-10 alkenyl group, a C _6-12 alkenyl group substituted with a C _6-12 aromatic group, a C _2-10 alkenyl group substituted with a C _6-12 hydrocarbon group, a C _1-10 alkoxy group, A C _6-12 cycloalkyl group, a C _6-12 cycloalkenyl group may be mentioned, and more specific examples include a benzoyloxy group, a phenyl group, a cyclohexyl group, a cyclohexenyl group, an adamantyl group, an adamantyl group substituted with a hydroxy group. can

In the present specification, "α-position-substituted (meth)acrylic monomer" forms a double bond immediately next to (α-position) of the ester group -COO- carbon as shown by CH2 ₌ C(R1a) ^-COC - ^R1 means an acrylic monomer in which carbon is substituted. Similarly, the "α-position-substituted vinyl ester-based monomer" is a double next to the oxygen (α-position) of the ester group -O-CO-, as ^shown by CH2 ₌ C(R1a)-O ^- COC-R3 It means an ^acryl _- based monomer ⁱⁿ which the carbon forming a bond is substituted. “α-position-substituted vinyl ether-based monomer” means immediately It refers to an acrylic monomer in which carbon forming a double bond at the side (α position) is substituted. “α-position-substituted vinyl-based monomer” refers to an acryl-based monomer in which an internal carbon other than the terminal carbon of a vinyl group is substituted, 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 curable resin composition of the preferred embodiment (2-1) to be described later.

As used herein, "secondary or tertiary OH-containing group" refers to a group containing one or two or more secondary or tertiary hydroxy (OH) groups. Thus, "secondary or tertiary OH-containing group" also includes the secondary or tertiary hydroxyl group itself. In "a substituted or unsubstituted secondary or tertiary OH-containing group", "substituted or unsubstituted" refers to a group containing one or two or more secondary or tertiary hydroxy (OH) groups other than the corresponding hydroxy group. It indicates that the group moiety of is substituted or unsubstituted, and does not indicate that the hydroxy group is substituted or unsubstituted.

As used herein, "solvate" refers to a compound or a salt thereof further comprising a solvent in an amount bound by non-covalent intermolecular forces unless otherwise specified. If the solvent is water, the solvate is a hydrate.

In this specification, "or" is used when adopting "at least one or more" of the items listed in the sentence. The same goes for "or". In this specification, when "within two numerical ranges" is specified, the range includes the two numerical values themselves. Therefore, 'X to Y' representing a range means 'X or more and Y or less'. Also, unless otherwise specified, 'weight' and 'mass', 'weight %' or 'wt %' and 'mass %' The expression 'about' means the whole range of numerical values obtained by rounding up significant figures or the number to the nearest one in the case of a measurement, with a tolerance of 10%, unless otherwise specified. .

[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 modify within the scope of the present invention in consideration of the description of the present specification. It is also understood that the following embodiments of the present invention can be used alone or in combination.

(2-1) Curable resin composition

In one aspect the invention

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 contains 3 to 30 carbon atoms, contains at least one saturated or unsaturated hydrocarbon group, or further contains at least one aromatic group, and the link between carbon atoms is -COO-, - may comprise a bond selected from the group consisting of O- and -CO-,

The crosslinking agent is a triazine-based compound and/or its condensate, a glycouryl-based compound and/or its condensate, and an imidazolidinone-based compound and/or its condensate.

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

It can be said that the curable resin composition of this invention is a thermosetting resin composition hardened|cured by heat processing.

The chain polymer, which is one of the components 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 included in the side chain having an 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 two or more.

The side chain contains at least one saturated or unsaturated hydrocarbon group of carbon atoms or further contains at least one aromatic group. The side chain may include one or two or more bonds selected from the group consisting of -COO-, -O- and -CO-. One saturated or unsaturated hydrocarbon group constituting the side chain may occupy all carbon atoms of the side chain alone, for example, and a plurality of saturated or unsaturated carbon groups are mutually the group consisting of -COO-, -O- and -CO- It may be connected through a bond selected from When the side chain contains an aromatic group other than a 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 is substantially decisive because the cured resin film formed by coating and curing the curable resin composition of the present invention on a glass substrate can maintain easy peelability from the substrate even after firing. is an element In addition, it is more preferable that the alcoholic secondary or tertiary hydroxyl group of the side chain is bonded to the alicyclic part of the side chain, and the alicyclic part of the side chain can also maintain easy peelability of the cured resin film, so it is a substantially decisive factor.

The chain polymer having such a side chain is a suitable crosslinking agent, in particular, a triazine-based compound and/or a condensate thereof, a glycouryl-based compound and/or a condensate thereof, or an imidazolidinone-based compound and/or a condensate thereof. As the resin composition, it is possible to provide an easily peelable film having heat resistance when cured in the form of a thin film.

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

In the present invention, the chain polymer having the side chain having an alcoholic secondary or tertiary hydroxyl group is more preferably a (meth)acrylic monomer, a vinyl ester monomer, a vinyl ether monomer, and other vinyl monomers. At least one is included as a monomer unit. Preferably, the monomer unit is a (meth)acrylic monomer, and more preferably, the monomer unit is a methacrylic monomer.

Preferably, the chain polymer of the present invention is CH ₂ =C(R ^1a )-COO-R ¹ CH ₂ =C(R ^1a )-O-CO-R ³ , CH ₂ =C(R ^1a )-OR ⁴ and CH ₂ =C(R ^1a )-R ⁵ [wherein R ¹ , R ³ , R ⁴ and R ⁵ are each independently of each other when bonded to each vinyl group through an ester bond, including carbon atoms constituting the ester bond It has 3 to 30 carbon atoms, more preferably 3 to 25 carbon atoms, most preferably 3 to 20 carbon atoms, contains alcoholic secondary or tertiary hydroxyl groups, and contains or adds to one or more saturated or unsaturated hydrocarbon groups. contains at least one aromatic group and the linkage between carbon atoms may have a bond selected from the group consisting of -COO-, -O- and -CO-. 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 present invention is CH2=CH _- COP _- ^R1 , CH2 ₌ ^C (COH ₃ )-COH- _R2 , ^-2 =H-H ^H4 and CH2 ₌ HH- ⁵ [ ^In the above formula, ^R1 , ^R2 , R3, ^R4 , and ^carbonR5 are each independently bonded to each other through an ester bond to each vinyl group through an ester bond. 3 to 30 carbon atoms, including atoms, more preferably 3 to 25 carbon atoms, most preferably 3 to 20 carbon atoms, bearing an alcoholic secondary or tertiary hydroxyl group, and at least one saturated or unsaturated hydrocarbon a group comprising or further comprising at least one aromatic group, and the linkage between carbon atoms may have a bond selected from the group consisting of -COO-, -O- and -CO-.] It contains a monomer unit selected from.

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

Examples of the aromatic group include carbocyclic aromatic groups (monocyclic and condensed cyclic groups) such as phenyl, biphenyl, and naphthyl, and heteroaromatic groups (monocyclic and condensed cyclic groups) such as pyridyl, pyrimidinyl, quinolinyl, and triazinyl. ), and if it is not located at the terminal for each aromatic group, it may be a divalent or higher group depending on the bonding relationship with other groups. Also herein, a group having a saturated or unsaturated hydrocarbon chain moiety (eg, tetrahydronaphthyl or dihydronaphthyl) that forms a ring with the aromatic ring moiety is understood as a bond between an aromatic group and a saturated or unsaturated hydrocarbon group. .

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

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

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

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

More preferably, the chain polymer of the present invention is in Formula A1

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, provided that at least one of R ^2a , R ^3a and R ^4a is a secondary or tertiary hydroxyl group and a substituted or and a monomer unit selected from the group consisting of unsubstituted secondary or tertiary OH-containing hydrocarbon groups.

More preferably, the chain polymer of the present invention is in Formula A1

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

L ¹ is selected from the group consisting of a single bond, an 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, provided that at least one of R ^2a , R ^3a and R ^4a is secondary or tertiary hydroxy and substituted or an unsubstituted secondary or tertiary OH-containing hydrocarbon group, and the other two independently include a monomer unit selected from the group consisting of hydrogen, a substituted or unsubstituted hydrocarbon group.

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

[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, a substituted or unsubstituted alkenylene group, and R ^5a to R ^14a are each independently hydrogen, a hydroxy group and

[Formula 14]

is selected from the group consisting of or forms a ring integrally, with the proviso that at least one of R ^5a to R ^14a or a substituent of the ring is a hydroxyl group,

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

More preferably, the chain polymer of the present invention is in 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 are each independently hydrogen, a hydroxyl group and

[Formula 15]

is selected from the group consisting of or forms a ring integrally, with the proviso that at least one of R ^5a to R ^14a or a substituent of the ring is a hydroxyl 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 is in Formula A2,

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

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

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

[Formula 16]

and, other than that, hydrogen, or R ^5a to R ^14a form a ring substituted with one hydroxyl group,

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

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

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

[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 a substituted or unsubstituted alkylene group, 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, 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.]

More preferably, in the present invention, the chain polymer is in 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 includes a monomer unit, characterized in that it is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group.

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

[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,

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

More preferably, the chain polymer of the present invention is in 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,

R ^18a includes a monomer unit characterized in that it is an adamantyl group substituted with at least one hydroxyl group.

The chain polymer is of formula A5:

[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,

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 is in 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 includes a monomer unit, characterized in that it 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, R ^19a 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.

Preferred side chains having a chain polymeric alcoholic secondary or tertiary hydroxyl group of the present invention include the following. In addition, it is preferable to have such a hydroxyl group, and what is disclosed is merely an example and not limited thereto.

(1a) A-O-CO-type (A represents the residue portion 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-undecanoyloxy-3-hydroxycyclohexylmethoxycarbonyl,

4-butanoyloxy-3-hydroxycyclohexylmethoxycarbonyl and the like.

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

2-hydroxypropylcarbonyloxy,

2-hydroxy-3-(cyclohexylcarbonyloxy)propylcarbonyloxy;

3-benzoyloxy-2-hydroxypropylcarbonyloxy,

4-benzoyloxy-3-hydroxycyclohexylmethylcarbonyloxy,

3-hydroxy-1-adamantylcarbonyloxy,

2-hydroxycyclohexyloxycarbonyloxy,

4-undecanoyloxy-3-hydroxycyclohexylmethylcarbonyloxy,

4-butanoyloxy-3-hydroxycyclohexylmethylcarbonyloxy and the like.

(3a) A-O-type side chains:

2-hydroxypropoxy,

2-hydroxy-3-(cyclohexylcarbonyloxy)propoxy,

3-benzoyloxy-2-hydroxypropoxy,

4-benzoyloxy-3-hydroxycyclohexylmethoxy,

3-hydroxy-1-adamantyloxy,

2-hydroxycyclohexyloxy,

4-undecanoyloxy-3-hydroxycyclohexylmethoxy,

4-butanoyloxy-3-hydroxycyclohexylmethoxy and the like.

(4a) Other:

2-hydroxypropyl,

2-hydroxy-3-(cyclohexylcarbonyloxy)propyl,

3-benzoyloxy-2-hydroxypropyl,

4-benzoyloxy-3-hydroxycyclohexylmethyl,

3-hydroxy-1-adamantyl;

2-hydroxycyclohexyl,

4-undecanoyloxy-3-hydroxycyclohexylmethyl,

4-butanoyloxy-3-hydroxycyclohexylmethyl and the like.

Preferred examples of the monomer providing such a side chain to the chain polymer include, but are not limited to, the following.

(1b)

2-hydroxypropyl (meth) acrylate,

2-hydroxy-3-(cyclohexylcarbonyloxy)propyl (meth)acrylate;

3-benzoyloxy-2-hydroxypropyl (meth) acrylate,

4-benzoyloxy-3-hydroxycyclohexylmethyl (meth)acrylate,

1,3-adamantyldiol mono (meth) acrylate;

2-hydroxycyclohexyl (meth) acrylate,

4-undecanoyloxy-3-hydroxycyclohexylmethyl (meth) acrylate;

(meth)acrylates, such as 4-butanoyloxy-3-hydroxycyclohexylmethyl (meth)acrylate.

(2b)

2-hydroxybutanoic acid vinyl ester;

2-hydroxy-3-(cyclohexylcarbonyloxy)butanoate vinyl ester;

3-benzoyloxy-2-hydroxybutanoate vinyl ester;

4-benzoyloxy-3-hydroxycyclohexyl acetate vinyl ester;

3-hydroxy-1-adamantyl carboxylic acid vinyl ester;

2-hydroxycyclohexyl carboxyl carboxylic acid vinyl ester;

4-undecanoyloxy-3-hydroxycyclohexyl acetate vinyl ester;

Vinyl esters, such as 4-butanoyloxy-3-hydroxycyclohexyl acetate vinyl ester.

(3b)

2-hydroxypropyl vinyl ether;

2-hydroxy-3-(cyclohexylcarbonyloxy)propyl vinyl ether;

3-benzoyloxy-2-hydroxypropyl vinyl ether;

4-benzoyloxy-3-hydroxycyclohexylmethylvinyl ether;

3-hydroxy-1-adamantyl vinyl ether;

2-hydroxycyclohexyl vinyl ether;

4-undecanoyloxy-3-hydroxycyclohexylmethyl ether;

4-Butanoyloxy-3-hydroxycyclohexylmethyl ether

vinyl ethers, etc.

(4b)

1-pentene-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;

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

(5b)

Maleic anhydride and maleimide each having the above (1a) to (4a) as a substituent.

The chain polymer of the present invention is an unsubstituted or α-position-substituted (meth)acrylic monomer having 1 to 15 carbon atoms in the side chain containing or not containing a hydroxyl group in addition to the monomer having an alcoholic secondary or tertiary hydroxyl group. Alternatively, it may include at least one of an α-position substituted vinyl ester-based monomer, an unsubstituted or α-position substituted vinyl ether-based monomer, and other unsubstituted or α-position substituted vinyl-based monomers as an additional monomer unit.

These additional monomer units are preferably CH2 ₌ C(R1a) ^-COH2 ₌ CH( ^R1A ) ^{-O -} O ^- R in the above ^formulas independently of each other [R] having 1 to 15 carbon atoms, with or without hydroxy groups, containing at least one saturated or unsaturated hydrocarbon group, or further containing at least one aromatic group, the linkages between carbon atoms being -COO-, -O- and It may have a bond selected from the group consisting of -CO-, the hydrocarbon group or aromatic group may have an amino group, and R ^1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted alkenyl group.] ,

CH ₂ = C (R ^1a ) - O - R ⁹ , C H ₂ = C (R ^1a ) - R ¹⁰ [In the above formula, R ⁹ and R ¹⁰ each independently contain 3 to 15 carbon atoms and include or not include a hydroxy group. and contains at least one saturated or unsaturated hydrocarbon group or further contains at least one aromatic group, and the linkage between 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 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 , C ₄ (R ^1a ) HN O ₂ －R ¹² [In the above formula, C ₄ (R ^1a )O ₃ - represents maleic anhydride, C ₄ (R ^1a )H ₂ ( - represents a maleimide group, R ¹¹ and R ¹² are each independently a hydrogen atom or having 1 to 15 carbon atoms, with or without alcoholic secondary or tertiary hydroxy groups, and at least one saturated or unsaturated hydrocarbon group comprising or additionally comprising at least one aromatic group, and the linkage between carbon atoms may have a bond selected from the group consisting of -COO-, -O- and -CO-, wherein the hydrocarbon group or aromatic group is 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.]

It may be selected from the group consisting of compounds represented by

The chain polymer of the present invention does not contain a hydroxyl group other than the monomer having an alcoholic secondary or tertiary hydroxyl group and has 1 to 15 carbon atoms in the side chain, a (meth)acrylic monomer, a vinyl ester-based monomer, a vinyl ether-based monomer, At least one of other vinyl-based monomers may be included as an additional monomer unit.

^In the formula, R ² = CH ₂ = C H O _- R , C H ₂ = C ( H ₃ ) - C H O - ^{R above} [ R ⁷ and R ⁸ independently of each other have 1 to 15 carbon atoms, have a hydroxyl group, contain at least one saturated or unsaturated hydrocarbon group, or further contain at least one aromatic group, and the link between carbon atoms is It 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],

H2 = CH _- O _- R ⁹ , H2 = H-R ¹⁰ [wherein R ₉ and R ₁₀ are each independently of each other having 3 to 15 carbon atoms, a hydroxyl group, and at least one saturated or unsaturated hydrocarbon group. comprising or additionally comprising at least one aromatic group, the linkage between carbon atoms may have a bond selected from the group consisting of -COO-, -O-, and -CO-, wherein the hydrocarbon group or aromatic group may have an amino group.],

C ₄ H O ₃ －R ¹¹ and C ₄ H ₂ N ₂ － R ¹² [ ^In the above formula, C ₄ H O ₃ - represents maleic anhydride, and C ₄ H ₂ N ^O ₂ - represents maleimide. independently of each other, hydrogen atoms or having 1 to 15 carbon atoms, alcoholic secondary or tertiary hydroxyl groups, containing at least one saturated or unsaturated hydrocarbon group, or further containing at least one aromatic group, and containing between 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]

It may be selected from the group consisting of compounds represented by

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

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

(2) vinyl acetate ester, butanoic acid vinyl ester, pentanoic acid vinyl ester, hexanoic acid vinyl ester, cyclohexanecarboxylic acid vinyl ester, benzoic acid vinyl ester, cyclopentadienyl carboxylate vinyl ester, nonanoic acid vinyl ester, etc. 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) ethyl dimethylamine, and 3-(vinyloxy) propyl dimethylamine.

(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 monomer units, or may be a copolymer including two or three or more types of monomer units, but at least one of the monomer units of the copolymer is an alcoholic secondary or It is a monomer unit having a side chain having a tertiary hydroxyl group. Preferably the copolymer comprises a monomer unit having a side chain bearing at least one alcoholic secondary or tertiary hydroxyl group and a further monomer unit having no at least one hydroxyl group.

The proportion of the monomer unit 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%, more preferably 60 to 100 mol%. mol%, more preferably 80-100 mol%, most preferably 90-100 mol%.

In the present invention, the chain polymer is prepared by performing a polymerization reaction using a conventional radical polymerization catalyst such as 2,2'-azobisisobutyronitrile (AIBN) in a conventional manner using the raw material monomer. can do. The molecular weight of the chain polymer is preferably in the range of 10000 to 100000 (measured by gel filtration chromatography), but is not particularly limited to this range.

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

Preferred specific examples of such crosslinking agents are fully or partially alkoxy (eg methoxy, ethoxy)methylated melamine and/or condensates thereof, fully or partially alkoxy (eg methoxy, ethoxy)methylated guanamine and/or Condensates thereof, fully or partially alkoxy (eg methoxy, ethoxy)methylated acetoguanamine and/or condensates thereof, fully or partially alkoxy methylated benzoguanamines and/or condensates thereof, fully or partially alkoxy (eg For example, methoxy, ethoxy) methylated glycouryl and/or its condensates, fully or partially alkoxymethylated imidazolidinones and/or its condensates are mentioned.

In the above formula, "alkoxy" preferably has 1 to 4 carbon atoms. Preferred compounds as such crosslinking agents are specifically, for example,

hexamethoxymethylmelamine,

hexaethoxymethylmelamine,

tetramethoxymethylmethylolmelamine,

tetramethoxymethylmelamine,

hexabutoxymethylmelamine,

tetramethoxymethylguanamine,

tetramethoxymethylacetguanamine,

tetramethoxymethylbenzoguanamine,

trimethoxymethylbenzoguanamine,

tetraethoxymethylbenzoguanamine,

tetramethylolbenzoguanamine,

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

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

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

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

and the like, but are not limited thereto.

In one embodiment preferably said crosslinking agent is of formula B1:

[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, and

[Formula 21]

is selected from the group consisting of disubstituted amines represented by

R ^2b to R ^7b are each 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.]

It is selected from the group consisting of a compound represented by and / or a condensate thereof.

More preferably, the crosslinking agent of the present invention is in Formula B1,

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

[Formula 22]

is selected from the group consisting of disubstituted amines represented by

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

compounds and/or condensates thereof.

In each embodiment, the crosslinking agent is of formula B2:

[Formula 23]

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

Preferably, the crosslinking agent of the present invention in Formula B2, R ^8b to R ^11b are each independently a compound selected from a substituted or unsubstituted alkyl group and/or a condensate thereof.

In particular in each embodiment, the preferred cross-linking agent is of formula B3:

[Formula 24]

[In the above formula, R ^12b and R ^13b are each independently having 1 to 10 carbon atoms, and are selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group, and R ^14b and R ^15b are each independently hydrogen or It has 1 to 10 carbon atoms and is selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group.] and/or a condensate thereof.

Preferably, in the crosslinking agent of the present invention, in Formula B3, R ^12b to R ^13b are each independently selected from a substituted or unsubstituted alkyl group, and R ^14b to R ^15b are each independently selected from hydrogen, a substituted or unsubstituted alkyl group. a compound selected from the group and/or a condensate thereof.

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

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

[Formula 25]

hexamethoxymethylmelamine;

hexabutoxymethylmelamine;

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

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

tetramethoxymethylbenzoguanamine;

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

The condensate is preferably a polymer of the compound represented above, and more preferably a dimer, trimer or higher polymer of the compound.

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 of the above compound (ie, a dimer, trimer, or higher polymer).

In another aspect, the crosslinking agent preferably has a weight average degree of polymerization of 1 to 3 or higher in the compound. It is preferably from 1 to 1.8, more preferably from 1.3 to 1.8, and more preferably from 1.5 to a weight average degree of polymerization without being limited thereto. In addition, when the weight average degree of polymerization of the condensate of the compound is 1, it means that the condensate is the compound itself. The weight average degree of polymerization is any value within the above range, and is preferably 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 3, 4 or larger. More preferably, it is 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, Especially preferably, it is 1.5.

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

In the present invention, the curable resin composition contains an acid catalyst. The acid catalyst is optionally included as a polymerization catalyst for the reaction between the monomer unit and the crosslinking agent. The acid catalyst can be appropriately selected and used as a polymerization catalyst.

The acid catalyst may be a compound selected from Bronsted acid and/or Lewis acid, or a salt thereof, or a solvate thereof. Examples of the acid catalyst include protic acids such as dinonylnaphthalenedisulfonic acid, dinonylnaphthalene(mono)sulfonic acid, dodecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfonic acid (PTS), phosphoric acid, sulfuric acid and acetic acid; and a compound selected from the group consisting of thermal acid generators such as Sun-Aid SI-100L, SI-150L, SI-110L, SI-60L and SI-80L (Samshin Hoehak Industrial Co., Ltd.), a salt thereof, or a solvate thereof , but 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 Sunade SI-100L (Samshin Chemical Industry Co., Ltd.), or a salt thereof, or a salt thereof It is a solvate. More preferably, the acid catalyst is pyridinium-p-toluenesulfonic acid, p-toluenesulfonic acid, or a hydrate thereof.

When the curable resin composition of the present invention further contains an acid catalyst, the amount of the acid catalyst may be appropriately determined according to the ratio of the mass of the chain polymer of the curable resin composition to the crosslinking agent, and preferably the chain polymer of the curable resin composition, the crosslinking agent and 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 this invention, curable resin composition contains a solvent further. A conventional aprotic solvent can be appropriately selected and used within a range capable of forming a uniform coating film by drying after applying the curable resin composition to a substrate such as glass because the boiling point is not too low or too high.

For example, propylene glycol monomethyl ether is a suitable solvent, but is not limited thereto. Since the dilution with a solvent is for convenience during polymerization of monomers and when applying the curable resin composition to which a crosslinking agent and catalyst are added, there is no particular upper or lower limit on the degree of dilution.

(2-2) Cured resin film

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

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

The cured resin film formed by the curable resin composition of the present invention is heat resistant in the sense of "heat resistance", and at the same time has easy peelability even after heat treatment in a heat resistant temperature range.

The curable resin composition of the present invention is typically prepared by applying a solution obtained by dissolving a chain polymer, a crosslinking agent and, if necessary, an acid catalyst in a solvent on a glass substrate (preferably soda-lime glass), and heat treatment (100° C. to 230° C., 1 minute). By curing the above), an easily peelable cured resin film having a thickness of several hundred nm (preferably a thickness of about 200 nm to about 300 nm) can be formed as a transparent thin film. Without being limited by theory, as a mechanism, the hydroxyl group of the side chain of a chain polymer and a crosslinking agent are a film which can be peeled by curing shrinkage at the time of crosslinking by heating.

[Formula 26]

A well-known coating method can be used as a method of apply|coating to the said glass substrate. Examples thereof include spin coating, spinless coating, die coating, spray coating, roll coating, screen coating, slit coating, dip coating, and gravure coating. Preferably it is spin coating.

The thin film deposited on the substrate in this way can withstand heating up to 150° C., and preferably can also withstand heating (sintering) of 230° C. In addition, it has resistance to solvents used in photoresist solutions and can withstand alkaline developing solutions, so it can be advantageously used as a resin base film for circuit fabrication by photolithography.

In addition, since the thin film formed by the curable resin composition of the present invention has easy peelability even after heating at such a temperature, even though it is a thin film, it can be attached in a circuit manufacturing process including a firing step at a higher temperature than in the prior art. It is advantageous for maintaining properties.

In addition, it can be easily peeled off from the substrate even after circuit fabrication. Therefore, as a base film with excellent properties, it can be widely used in the manufacture of various flexible electric/electronic circuit components in the form of a sheet, and for example, it can be used in the manufacture of flexible display devices or touch sensors.

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

The peeling force of the cured resin film of the present invention can be measured, for example, by the following measuring method. The curable resin composition of the present invention is typically prepared as a solution in which a chain polymer crosslinking agent and, if necessary, an acid catalyst are dissolved in a solvent, applied to a glass substrate (preferably soda lime glass), and heat treated (100°C to 230°C, 1 minute) above) to prepare a cured resin film on the glass substrate by curing. As a measuring device, for example, TENSILON RTG-1310 (A&D) type UR-100N-D is used as a load cell.

Attach a Nichiban tape (24 mm width) to the cured resin film on the glass substrate, pull it at an angle of 90° to the glass substrate at a constant speed of 300 mm/min, and measure the magnitude of the force (peel force) required for peeling with the device. .

The cured resin film of the present invention preferably has a peeling force of 0.5 N/mm ² or less to a soda glass substrate or an alkali-free glass substrate. More preferably, the cured resin film of the present invention has a peeling force with respect to a soda glass substrate or an alkali-free glass substrate of 0.1 N/mm ² or less. More preferably, the cured resin film of the present invention has a peeling force with respect to a soda glass substrate or an alkali-free glass substrate of 0.09 N/mm ² or less.

Preferred values of the peeling force for the soda glass substrate are 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.

Preferred values of the peeling force with respect to the alkali-free glass substrate are 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 or less. /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 with respect to the soda glass substrate or the alkali-free glass substrate is 0.5 N/mm ² or less, the cured resin film may be regarded as easily peelable.

[3] Manufacturing method of cured resin film

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

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

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

(iii) to obtain a cured resin film by curing the polymerization reaction in the curable resin composition coating film,

A manufacturing method is provided.

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 method disclosed in the following examples and/or the same method known to those skilled in the art.

In one embodiment, the manufacturing method further comprises the step of (i') polymerizing at least one raw material monomer before step (i) to prepare a chain 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, the bulk polymerization method and the solution polymerization method are preferable.

In addition, the polymerization of the monomer can be performed by, for example, a radical polymerization method, a living radical polymerization method, an anionic polymerization method, a cationic polymerization method, an addition polymerization method, a polycondensation method, or the like.

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

A chain transfer agent may be used to adjust the molecular weight when polymerizing the monomers. 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, and methyl2-(dodecylthiocarbono). Thioylthio)-2-methylpropionate, 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid 3-azide-1-propanol ester, 2-(dodecylthiocarbonothioylthio) )-2-methylpropionic acid pentafluorophenyl ester, lauryl mercaptan, dodecyl mercaptan, mercaptan group-containing compounds such as thioglycerol, and inorganic salts such as sodium hypophosphite and sodium hydrogen sulfite. is not limited to these examples.

These chain transfer agents may be used individually, respectively, or 2 or more types may be used together. The amount of the chain transfer agent is not particularly limited, but is generally about 0.01 to 10 parts by weight per 100 parts by weight of the total monomer.

It is preferable to use a polymerization initiator when polymerizing the monomer. Polymerization initiators include, for example, thermal polymerization initiators, photopolymerization initiators, redox polymerization initiators, ATRP (atom transfer radical polymerization) initiators, ICAR ATRP initiators, ARGET ATRP initiators, RAFT agents (reversible addition-cleavage chain transfer polymerization), NMP agents (polymerization via nitroxide), a polymer polymerization initiator, and the like. These polymerization initiators may be used independently, respectively, and may use 2 or more types together.

Examples of the thermal polymerization initiator include azo polymerization initiators such as azoisobutyronitrile, methyl azoisobutyrate, and azobisdimethylvaleronitrile, and peroxide 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 independently, respectively, and may use 2 or more types together.

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

Examples of the photopolymerization initiator include 2-oxoglutaric acid, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl[4-(methylthio) Phenyl]-2-morpholinopropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, benzophenone, 1-[4-(2-hydroxyethoxy)phenyl] -2-hydroxy-2-methyl 1-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, bis (2,6-dimethoxybenzoyl) )-2,4,4-trimethylpentylphosphine oxide, and the like, but the present invention is not limited to these examples. These polymerization initiators may be used independently, respectively, and may use 2 or more types together.

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

Other polymerization initiators usable in the present invention include, for example, redox polymerization initiators such as hydrogen peroxide and iron (II) salts, persulfates and sodium hydrogen sulfite, and ATRP (atom transfer radical polymerization) using an alkyl halide under a metal catalyst. ) initiator, ICAR ATRP initiator and ARGET ATRP initiator using metal and nitrogen-containing ligands, RAFT agent (reversible addition-cleavage chain transfer polymerization), NMP agent (polymerization via nitroxide), polymer azo polymerization containing polydimethylsiloxane units polymer polymerization initiators such as initiators and polyethylene glycol unit-containing polymer azo polymerization initiators, but the present invention is not limited to these examples. These polymerization initiators may be used independently, respectively, and may use 2 or more types together.

In the case of using the usable polymerization initiator as the polymerization initiator, it is preferable that the amount of the polymerization initiator is generally about 0.01 parts by weight to 20 parts by weight per 100 parts by weight of the total monomer.

In one embodiment, electron beam polymerization advances by irradiating an electron beam to a monomer.

There is no particular limitation on the polymerization reaction temperature and atmosphere at the time of polymerizing the monomer. Generally, the polymerization reaction temperature is from about 50°C to about 120°C. It is preferable that the atmosphere at the time of a polymerization reaction is an inert gas atmosphere, such as nitrogen gas, for example. In addition, the polymerization reaction time of the monomer cannot be determined uniformly because it varies depending on the polymerization reaction temperature and the like, but is generally about 3 to 20 hours.

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

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

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

In another embodiment, in the manufacturing method, step (iii) further includes the step of heat-treating the curable resin composition coating film. 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 longer, more preferably 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, etc. can, but is not limited thereto. A particularly preferred heat treatment time is 10 minutes to 2 hours.

The cured resin film prepared by the above production method has the cured resin properties of (2-2) above and is obtained as an easily peelable film.

[4] Usage

The curable resin composition or cured resin film of the present invention is used for plastic pellets, films, plates, fibers, foaming agents, tubes, rubbers, elastomers, etc. Transportation, leisure, furniture (eg tables, chairs, desks, shelves, etc.), bedding (eg beds, hammocks, etc.), clothing, protective clothing, sporting goods, bathtubs, kitchens, tableware, cooking utensils, containers and packaging (food containers, cosmetic containers, cargo containers, trash cans, etc.), construction (buildings, roads, construction parts, etc.), agricultural films, industrial films, water and sewage, paints, cosmetics, electrical and electronic industries (electronic products, computer parts, etc.) , printed circuit boards, insulators, conductors, wiring coating materials, power generation elements, speakers, microphones, noise cancellers, transducers, etc.), optical communication cables, medical materials and devices (catheters, guide wires, artificial blood vessels, artificial muscles, artificial muscles, etc.) Organs, dialysis membranes, endoscopes, etc.), small pumps, actuators, robot materials (sensors used in industrial robots, etc.), energy generating devices and plants (solar power generation, wind power generation, etc.) can be applied to various fields.

The curable resin composition or the cured resin film of the present invention can be used for electronic materials, medical materials, healthcare materials, life science materials, robot materials, and the like. The curable resin composition or the cured resin film of the present invention can be used, for example, as a material for catheters, guide wires, pharmaceutical containers, tubes, and the like.

The curable resin composition or cured resin film of the present invention can be used in automobile parts (body panels, bumper belts, rocker panels, side moles, engine parts, driving parts, conduction parts, steering system parts, stabilizer parts, suspension/braking system parts, brake parts, Shaft parts, pipes, tanks, wheels, seats, seat belts, etc.) can be used. The polymer of the present invention may be used in vibration-proofing materials for automobiles, automobile paints, synthetic resins for automobiles, and the like.

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

In the above, preferred embodiments of the present invention have been shown and described for ease of understanding. The present invention is illustrated by the following examples, but the foregoing description and the following examples are provided for illustrative purposes only and not for the purpose of limiting the present invention. Accordingly, the scope of the present invention is not limited by the examples specifically described herein, but 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 the embodiment obtained by appropriately combining the technical means disclosed in each embodiment is 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) Preparation of Polymer A-1

Formula (1-1)

[Formula 27]

Using 2-hydroxypropyl methacrylate as a monomer, 100 parts by weight of propylene glycol monomethyl ether (PGME) was dissolved to 30% by weight. After blowing nitrogen gas into the obtained solution, the temperature was raised to 80° C., 5 mol% of 2,2′-azobisisobutyronitrile (AIBN) was added based on the total amount of monomers, and then the reaction was performed at 80° C. for 8 hours to perform a polymer. A-1 was obtained. The average molecular weight (MW) of this polymer was determined by gel filtration chromatography to be 25,000.

(Preparation Example 2) Preparation of Polymer A-2

Formula (1-2)

[Formula 28]

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

(Production Example 3) Preparation of Polymer A-3

Formula (1-3)

[Formula 29]

Polymer A-3 was obtained in the same manner as in Preparation Example 1 except that 4-benzoyloxy-3-hydroxycyclohexylmethylmethacrylate was used as a monomer. The average molecular weight (MW) of this polymer was determined by gel filtration chromatography to be 32,000.

(Preparation Example 4) Preparation of polymer A-4

Formula (1-4)

[Formula 30]

Polymer A-4 was obtained in the same manner as in Preparation Example 1 except that 1,3-adamantyldiol monomethacrylate was used as a monomer. The average molecular weight (MW) of this polymer was determined by gel filtration chromatography to be 18,000.

(Preparation Example 5) Preparation of polymer A-5

Formula (1-5)

[Formula 31]

Polymer A-5 was obtained in the same manner as in Preparation 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

Formula (1-6)

[Formula 32]

Polymer A-6 was obtained in the same manner as in Preparation 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

Formula (1-7)

[Formula 33]

Polymer A-7 was obtained in the same manner as in Preparation Example 1 except that 4-(hydroxymethyl)cyclohexylmethylacrylate was used as a monomer. The average molecular weight (MW) of this polymer was determined by gel filtration chromatography to be 18,000.

(Preparation Example 8) Preparation of Polymer A-8

Using 2-hydroxypropyl methacrylate and n-butyl acrylate of the formula (1-1) as monomers, 50 parts by mass thereof were dissolved in propylene glycol monomethyl ether (PGME) in a total amount of 30 mass %. The obtained solution was heated to 80° C. while blowing nitrogen gas, and 5 mol% of 2,2'-azobisisobutyronitrile (AIBN) was added based on the total amount of monomers, followed by reaction at 80° C. for 8 hours to perform a polymer A-8 was obtained. The average molecular weight (MW) of this polymer was determined by gel filtration chromatography to be 18,000.

(Preparation Example 9) Preparation of Polymer A-9

Polymer A-9 was obtained in the same manner as in Preparation Example 8 except that 2-hydroxypropyl methacrylate and methyl methacrylate of 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.

(Preparation Example 10) Preparation of Polymer A-10

Polymer A-10 was obtained in the same manner as in Preparation Example 8 except that 2-hydroxypropyl methacrylate and styrene of Formula (1-1) were used as monomers. The average molecular weight (MW) of this polymer was determined by gel filtration chromatography to be 22,000.

(Production Example 11) Preparation 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. did. The average molecular weight (MW) of this polymer was determined by gel filtration chromatography to be 35,000.

(Preparation Example 12) Preparation of Polymer A-12

Polymer A-12 was obtained in the same manner as in Preparation Example 8 except that 2-hydroxycyclohexyl methacrylate and dicyclopentadienyl methacrylate of 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.

(Preparation Example 13] Preparation of Polymer A-13

Polymer A-13 was obtained in the same manner as in Preparation Example 8 except that 2-hydroxyethyl methacrylate and butyl acrylate of 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.

(Preparation Example 14) Preparation of Polymer A-14

Polymer A-14 was obtained in the same manner as in Preparation 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) Preparation of Polymer A-15

Polymer A-15 was obtained in the same manner as in Preparation 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 determined by gel filtration chromatography to be 39,000.

(Production Example 16) Preparation of Polymer A-16

Formula (1-8)

[Formula 34]

Polymer A-16 in the same manner as in Preparation Example 1 except that 4-(4-methoxyphenylpropenoyl)oxy-3-hydroxycyclohexylmethylmethacrylate was used as a monomer

[Formula 35]

was obtained. 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

Formula (1-9)

[Formula 36]

Polymer A-17 in the same manner as in Preparation Example 1 except that 4-adamantanecarboxyoxy-3-hydroxycyclohexylmethyl methacrylate was used as a monomer.

[Formula 37]

was obtained. The average molecular weight (MW) of this polymer was determined by gel filtration chromatography to be 31,700.

(Production Example 18) Preparation of Polymer A-18

Polymer A-18 in the same manner as in Preparation Example 8 except that 2-hydroxycyclohexyl methacrylate and methyl methacrylate of Formula (1-5) were used as monomers

[Formula 38]

was obtained. The average molecular weight (MW) of this polymer was determined by gel filtration chromatography and was 25,500.

(Production Example 19) Preparation of Polymer A-19

Formula (1-10)

[Formula 39]

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

[Formula 40]

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

(Preparation Example 20) Preparation of Polymer A-20

Formula (1-11)

[Formula 41]

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

[Formula 42]

was obtained. 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

Formula (1-12)

[Formula 43]

Polymer A-21 in the same manner as in Preparation Example 1 except that 4-(2-cyclohexylacetyl)oxy-3-hydroxycyclohexanemethyl2-methacrylate was used as a monomer.

[Formula 44]

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

(Production Example 22) Preparation of Polymer A-22

Polymer A-22 was carried out in the same manner as in Preparation Example 8 except that 2-hydroxycyclohexyl methacrylate and benzyl methacrylate of Formula (1-5) were used as monomers.

[Formula 45]

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

(Production Example 23) Preparation of Polymer A-23

4-(4-methoxyphenylpropenoyl)oxy-3-hydroxycyclohexylmethylmethacrylate of formula (1-8) and formula (1-13)

[Formula 46]

Using 3,4-epoxycyclohexylmethyl methacrylate as a monomer, 100 parts by weight of propylene glycol monomethyl ether (PGME) was dissolved to 20% by weight. The obtained solution was heated to 80° C. while blowing nitrogen gas, 4 mol% of 2,2'-azobisisobutyronitrile (AIBN) was added based on the total amount of monomers, and the reaction was performed at 80° C. for 8 hours to perform a polymer. was obtained.

After that, 99 parts by mass and 1 part by mass of 4-methoxycinnamic acid and 1 part by mass of methacrylic acid, respectively, or 3 mol% of tetraethylammonium bromide was added, the temperature was raised to 100° C. while blowing air, and the reaction was carried out for 38 hours to perform a reaction for polymer A- 23

[Formula 47]

was obtained. The average molecular weight (MW) of this polymer was determined by gel filtration chromatography to be 42,900.

(Production Example 24) Preparation of Polymer A-24

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

[Formula 48]

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

2. Preparation of curable resin composition

Various curable resin compositions of the present invention were coated on two types of glass substrates prepared as shown below, and cured by heating to form a film.

(Example 1)

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

[Formula 49]

0.4 parts by mass of hexamethoxymethylmelamine (Nikaraku MW-30 Samhwa Chemical Co., Ltd.) and 0.2 parts 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 0.7 mm thick soda glass and 0.5 mm thick alkali-free glass (EAGLE-XG, Corning Corporation) by spin coating, respectively, and heat-treated at 150° C. or higher for 30 minutes to form a film to a thickness of about 300 nm.

(Example 2)

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

(Example 3)

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

(Example 4)

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

(Example 5)

4.4 parts by mass of polymer A-3, 0.4 parts 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 propylene glycol monomethyl ether (PGME) It was dissolved in 95 parts by mass. This solution was applied to soda glass and alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film to a thickness of about 300 nm.

(Example 6)

4.4 parts by mass of polymer A-4, 0.4 parts 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 propylene glycol monomethyl ether (PGME) It was dissolved in 95 parts by mass. This solution was applied to soda glass and alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film to a thickness of about 300 nm.

(Example 7)

4.4 parts by mass of polymer A-5, 0.4 parts 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 propylene glycol monomethyl ether (PGME) It was dissolved in 95 parts by mass. This solution was applied to soda glass and alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film to a thickness of about 300 nm.

(Example 8)

4.4 parts by mass of polymer A-8, 0.4 parts 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 propylene glycol monomethyl ether (PGME) It was dissolved in 95 parts by mass. This solution was applied to soda glass and alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film to a thickness of about 300 nm.

(Example 9)

4.4 parts by mass of polymer A-9, 0.4 parts 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 propylene glycol monomethyl ether (PGME) It was dissolved in 95 parts by mass. This solution was applied to soda glass and alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film to a thickness of about 300 nm.

(Example 10)

4.4 parts by mass of polymer A-3, 0.4 parts 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 propylene glycol monomethyl ether (PGME) It was dissolved in 95 parts by mass. This solution was applied to soda glass and alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film to a thickness of about 300 nm.

(Example 11)

4.4 parts by mass of polymer A-11, 0.4 parts 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 propylene glycol monomethyl ether (PGME) It was dissolved in 95 parts by mass. This solution was applied to soda glass and alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film to a thickness of about 300 nm.

(Example 12)

4.4 parts by mass of polymer A-12, 0.4 parts 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 propylene glycol monomethyl ether (PGME) It was dissolved in 95 parts by mass. This solution was applied to soda glass and alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film to a thickness of about 300 nm.

(Example 13)

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

[Formula 50]

0.4 parts by mass of 1,3,4,6-tetrakis(methoxymethyl)glycoluryl (Nicaraku MW-270, Samhwa Chemical Co., Ltd.), 0.2 parts by mass of pyridinium-p-toluenesulfonate as a polymerization catalyst propylene glycol It was dissolved in 95 parts by mass of monomethyl ether (PGME). This solution was applied to soda glass and alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film to 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

[Formula 51]

0.4 parts by mass of tetramethoxymethylbenzoguanamine and 0.2 parts 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 alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film to a thickness of about 300 nm.

(Example 15)

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

(Example 16)

4.4 parts by mass of polymer A-1, 0.4 parts by weight of hexamethoxymethylmelamine (formula (B-1)) as a crosslinking agent, and 0.2 parts by mass of Saneido SI-100L (Samshin Chemical Industry Co., Ltd.), which is a thermal acid generator as a polymerization catalyst Part was dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME). This solution was applied to soda glass and alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film to a thickness of about 300 nm.

(Comparative Example 1)

4.4 parts by weight of polymer A-6, 0.4 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 propylene glycol monomethyl ether (PGME) It was dissolved in 95 parts by weight. This solution was applied to soda glass and alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film to a thickness of about 300 nm.

(Comparative Example 2)

4.4 parts by weight of polymer A-7, 0.4 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 propylene glycol monomethyl ether (PGME) It was dissolved in 95 parts by weight. This solution was applied to soda glass and alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film to a thickness of about 300 nm.

(Comparative Example 3)

4.4 parts by weight of polymer A-13, 0.4 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 propylene glycol monomethyl ether (PGME) It was dissolved in 95 parts by weight. This solution was applied to soda glass and alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film to a thickness of about 300 nm.

(Comparative Example 4)

4.4 parts by weight of polymer A-14, 0.4 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 propylene glycol monomethyl ether (PGME) It was dissolved in 95 parts by weight. This solution was applied to soda glass and alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film to a thickness of about 300 nm.

(Comparative Example 5)

4.4 parts by weight of polymer A-15, 0.4 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 propylene glycol monomethyl ether (PGME) It was dissolved in 95 parts by weight. This solution was applied to soda glass and alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film to a thickness of about 300 nm.

(Comparative Example 6)

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

(Example 17)

3.2 parts by weight of polymer A-16, 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 propylene glycol monomethyl ether (PGME) It was dissolved in 95 parts by weight. This solution was applied to soda glass and alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film to 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 propylene glycol monomethyl ether (PGME) It was dissolved in 95 parts by weight. This solution was applied to soda glass and alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film to a thickness of about 300 nm.

(Example 19)

3.2 parts by weight of polymer A-18, 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 propylene glycol monomethyl ether (PGME) It was dissolved in 95 parts by weight. This solution was applied to soda glass and alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film to 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 propylene glycol monomethyl ether (PGME) It was dissolved in 95 parts by weight. This solution was applied to soda glass and alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film to 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 propylene glycol monomethyl ether (PGME) It was dissolved in 95 parts by weight. This solution was applied to soda glass and alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film to 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 propylene glycol monomethyl ether (PGME) It was dissolved in 95 parts by weight. This solution was applied to soda glass and alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film to a thickness of about 300 nm.

(Example 23)

3.2 parts by weight of polymer A-22, 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 propylene glycol monomethyl ether (PGME) It was dissolved in 95 parts by weight. This solution was applied to soda glass and alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film to 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 propylene glycol monomethyl ether (PGME) It was dissolved in 95 parts by weight. This solution was applied to soda glass and alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film to a thickness of about 300 nm.

(Comparative Example 7)

3.2 parts by weight of polymer A-24, 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 propylene glycol monomethyl ether (PGME) It was dissolved in 95 parts by weight. This solution was applied to soda glass and alkali-free glass in the same manner as in Example 1, respectively, and heat-treated to form a film to a thickness of about 300 nm.

3. Performance evaluation

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

For each of the cured resin thin films prepared on the glass substrates of Examples and Comparative Examples, the magnitude of the force required to peel them from the glass substrate (peel force) was quantitatively evaluated in the following manner. That is, TENSILON RTG-1310 (A&Day Co., Ltd.) is used as a measuring device, and UR-100N-D type is used as a load cell. Nichiban tape (24mm width) is attached to a thin film of cured resin on a glass substrate for measurement. It was carried out by measuring the magnitude of the force (peel force) required for peeling by pulling at a constant speed of 300 mm/min at a peeling angle of 90° with the above device.

The results are shown in Table 1. Peel force for Examples 1 to 16 in Tables 1 and 2 was expressed in 3 decimal places. In principle, other measured values and calculated values are displayed to two decimal places.

As shown in Table 1, the peeling force of the cured resin thin film of Comparative Examples 1 to 6 was 2.2 to 8.7 N/mm ² (soda glass substrate) and 3.2 to 9.2 N/mm ² (EAGLE-XG substrate), whereas Example Peeling forces of 1 to 16 were 0.013 to 0.078 N/mm ² (soda glass substrate) and 0.028 to 0.085 N/mm ² ((EAGLE-XG substrate), which were found to be as small as two orders of magnitude. Substantially, each cured resin of Comparative Example It was observed that the film and the substrate were destroyed due to the high peel force value of the thin film, whereas each of the cured resin thin films of the Examples could be easily peeled off without any problem in any case.

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

Assuming the baking process in circuit manufacture by the patterning using the photolithography method or the printing method on the cured resin thin film, the peeling force at the time of baking the cured resin thin film was performed. That is, for Examples 1, 7, and Comparative Examples 1 and 2, the cured resin thin film formed on the soda glass substrate was fired at 230° C. for 1 hour or 3 hours, and each peeling force was obtained according to the apparatus and method described in (1) above. was measured. The results are shown in Table 2 together with the values of the peel force (initial peel force) 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 before firing after firing at 230°C for 1 hour or 3 hours, and could be easily peeled off without difficulty. The cured resin thin films of Comparative Examples 1 and 2 were adhered to the glass substrate more strongly than before firing.

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

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

(3) In the case of changing the crosslinking agent and mixing ratio, it is applied to the cured resin thin film after firing.

Peel force evaluation for

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

<Evaluation criteria>

Substrate: soda glass (coated on tinned surface)

Film formation: Spin coating > Baking at 150℃ or 230℃ for 30 minutes ※ Finishing film thickness

50-200nm

Peel test conditions: A peel test is performed with a Nichiban 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, Samhwa Chemical Co., Ltd.) of the formula (B-1), and MW-30LF is hexamethoxymethylmelamine (low free formaldehyde product). ) (Nikaraku MW-30LF, Samhwa Chemical Co., Ltd.), and MX-270 is 1,3,4,6-tetrakis(methoxymethyl)glycoluryl (Nicaraku MW-) of the above formula (B-2) 270, Samhwa Chemical Co., Ltd.).

The results are shown in Table 5. MW-30 was used as a reference compound to examine peel strength and peel properties by changing the mixing ratio of other compounds (Examples 25 to 27 and Comparative Examples 8 to 10). In Table 5, in the peel test item, "○" indicates that the formed cured resin film can be easily peeled off without unreasonableness and has easy peelability, and "x" indicates that it cannot be easily peeled and does not have easy peelability.

As shown in Table 5, in the case of using MW-30, the peeling force was low as 0.02 at the mixing ratio of the polymer/crosslinking agent of 45/50, and easily peelable, and in the case of 90/10, the peeling force was 7.5, which was 2 digits. It was large or large and did not have easy peelability. When MX-270 is used, it has low peeling force and easy peelability at both 45/50 and 90/10 mixing ratios. On the other hand, MW-30LF had high peel strength at both the mixing ratio of 45/50 and 90/10 and did not have easy peelability. This result is thought to be because MW-30LF has less formaldehyde and thus lacks a methylol moiety (reaction point of thermal crosslinking) compared to MW-30.

(4) Review of the limit of the peeling force of the cured resin thin film

When the weight ratio (wt %) of the polymer, the crosslinking agent, and the acid catalyst was changed, the peel force of the prepared cured resin thin film was measured. That is, with respect to Examples 28 to 38 and Comparative Examples 11 to 15, a solution prepared using a polymer, a crosslinking agent, and an acid catalyst in the weight ratios shown in Table 6 was applied on a soda glass substrate and calcined at 230° C. for 20 minutes. A cured resin film was formed in the same manner as in Example 1, and each peeling force was 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, crosslinking agent B-1 exhibited easy peelability at 10 wt% or more based on the total amount of polymer, crosslinking agent, and acid catalyst (Examples 28 to 30), and crosslinking agent B-2 was 3 wt% As mentioned above, easy peelability was expressed (Examples 33-38). Also, in Comparative Example 8 of Table 5, easy peelability was not expressed at a polymer/crosslinking agent mixing ratio of 90/10, but easily peelability was expressed in 85/10 of Example 29 of Table 6, which is almost the same mixing ratio using an acid catalyst. Therefore, it can be said that expression of easy peelability becomes easy by injecting|throwing-in an acid catalyst.

As described above, the present invention has been exemplified using preferred embodiments of the present invention, but the scope of the present invention should be interpreted only by the claims. It is understood that patents, patent applications, and other documents cited herein are hereby incorporated by reference in their entirety as if specifically set forth herein in their entirety. 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. is used as

According to the present invention, a very thin cured resin film can be formed by applying very thinly to a substrate such as glass and drying and curing after application, and has a high temperature durability of 230 ° C. It is a curable resin composition which can be peeled off from a board|substrate without unreasonableness even after being exposed to high temperature, and is useful for manufacture of a film type electric/electronic circuit component.

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 contains 3 to 30 carbon atoms, may include at least one saturated or unsaturated hydrocarbon group, and may further include at least one aromatic group, wherein the linkage between carbon atoms is -COO It may contain a bond selected from the group consisting of -, -O- and -CO-,
(b) the crosslinking agent is selected from the group consisting of a triazine-based compound and/or a condensate thereof, a glycoruryl-based compound and/or a condensate thereof, and an imidazolidinone-based compound and/or a condensate thereof,
The chain polymer is of formula A5:
[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.]
and a monomer unit represented by
The crosslinking agent is of formula B1:
[Formula 7]

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

It is selected from the group consisting of divalent substituted amines represented by , and R ^2b to R ^7b are each 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. ]
A compound represented by and / or a condensate thereof,
Formula B2:
[Formula 9]

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

[In the above formula, R ^12b and R ^13b are each independently having 1 to 10 carbon atoms, and are selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group, and R ^14b and R ^15b are each independently hydrogen or having 1 to 10 carbon atoms and is selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group.]
A compound represented by and / or a condensate thereof
As selected from the group consisting of
In this case, when the chain polymer includes a monomer unit represented by Formula A2 in which L ¹ is a single bond, R ^5a is a hydroxyl group, and R ^6a to R ^14a are hydrogen, the crosslinking agent is a compound represented by Formula B1 and / or characterized in that it is not a condensate thereof
Curable resin composition.
delete The curable resin composition according to claim 1, wherein R ^19a is a substituted or unsubstituted adamantyl group.
4. The curable resin composition according to claim 1 or 3, wherein R ^1a is hydrogen or methyl.
The method according to claim 1 or 3, wherein the chain polymer contains or does not contain a hydroxyl group, the side chain has 1 to 15 carbon atoms, an unsubstituted or α-position substituted (meth)acrylic monomer, an unsubstituted or α-position substituted A curable resin composition comprising as an additional monomer unit at least one of a vinyl ester-based monomer, an unsubstituted or α-position substituted vinyl ether-based monomer, and other unsubstituted or α-position substituted vinyl-based monomers.
6. The method of claim 5,
The additional monomer units are
ＣＨ _２ = Ｃ（ ^Ｒ１ａ ） ^{－ＣＯＯ－Ｒ６ , ＣＨ ２ ＝Ｃ（Ｒ１ａ ）} _－Ｏ -ＣＯ- ^R８
[ ^In the above formula, R6 and ^R8 each independently have 1 to 15 carbon atoms, and may or may not contain a hydroxyl group, may include at least one saturated or unsaturated hydrocarbon group, and may further include at least one aromatic group. In this case, the link between 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 ^R1b is hydrogen, substituted or It is selected from the group consisting of an unsubstituted alkyl group and a substituted or unsubstituted alkenyl group.],
ＣＨ _２ = Ｃ（ ^Ｒ１ａ ）－Ｏ ^－ Ｒ９ , ＣＨ2 _＝ Ｃ（ ^Ｒ１ａ ） ^－R10
[ ^In the above formula, R9 and R10 are each independently having ³ to 15 carbon atoms, with or without a hydroxyl group, and may include at least one saturated or unsaturated hydrocarbon group, and may further include at least one aromatic group. In this case, the link between 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 R1a is hydrogen, a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group.],
Ｃ _４ （ ^{Ｒ １} ） Ｏ _{３ －} ^{Ｒ 11} and Ｃ _４
[In the above formula, C ₄ (R ^1a ) O ₃ - represents an unsubstituted or substituted maleic anhydride group, C ₄ (R ^1a ) HN O ₂ - represents an unsubstituted or substituted maleimide group, and R ¹¹ and R ² - represent an unsubstituted or substituted maleimide group. is a hydrogen atom or has 1 to 15 carbon atoms, contains or does not contain a hydroxy group, may contain at least one saturated or unsaturated hydrocarbon group, and may further contain at least one aromatic group, wherein between carbon atoms The linkage 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 ^R1b is hydrogen, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted It is selected from the group consisting of an alkenyl group.]
A curable resin composition, characterized in that it is selected from the group consisting of compounds represented by.
The method according to claim 1 or 3, wherein the chain polymer does not contain a hydroxyl group and contains 1 to 15 carbon atoms in a side chain of (meth)acrylic monomers, vinyl ester monomers, vinyl ether monomers, and other vinyl monomers. Curable resin composition comprising at least one as an additional monomer unit.
6. The method of claim 5,
The additional monomer units are
ＣＨ _２ = ＣＨ _- ＣＯＯ-Ｒ６ , ＣＨ ^２ ＝Ｃ（ＣＨ ₃ ）－ＣＯＯ ^- Ｒ７ , ^ＣＯＨ _２ ＝Ｃ
[ ^In the above formula, R6, R7, and ^R8 each independently have ¹ to 15 carbon atoms, do not include a hydroxy group, and may include at least one saturated or unsaturated hydrocarbon group, and may further include at least one aromatic group. In this case, the link between 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],
ＣH ₂ = ＣＨ _- O ^- R ⁹
[ ^In the above formula, R9 and R10 each independently have 3 to ¹⁵ carbon atoms, do not include a hydroxy group, may include at least one saturated or unsaturated hydrocarbon group, and may further include at least one aromatic group, wherein The linkage between 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
[In the above formula, C ₄ H O ₃ - represents a maleic anhydride group, C ₄ H ₂ N O ₂ - represents a maleimide group, and R ¹¹ and R ¹² are each independently a hydrogen atom or have 1 to 15 carbon atoms and a hydroxyl group. and may contain at least one saturated or unsaturated hydrocarbon group, and may further contain at least one aromatic group, wherein the linkage between carbon atoms is selected from the group consisting of -COO-, -O- and -CO- It may have a selected bond and the hydrocarbon group or aromatic group may have an amino group.]
A curable resin composition, characterized in that it is selected from the group consisting of compounds represented by.
The curable resin composition according to claim 1 or 3, wherein the monomer unit constituting the chain polymer is occupied by a monomer unit having an alcoholic secondary or tertiary hydroxyl group in a ratio of 30 to 100 mol%. .
4. The curable resin composition according to claim 1 or 3, wherein the condensate contains a polymer of the compound represented by the formula B1, formula B2 or formula B3.
The curable resin composition according to claim 1 or 3, wherein the condensate comprises a dimer, a trimer or a higher polymer of the compound represented by Formula B1, Formula B2 or Formula B3.
The curable resin composition according to claim 1 or 3, wherein the crosslinking agent has a weight average degree of polymerization of 1.3 to 1.8 with respect to the compound represented by Formula B1, Formula B2 or Formula B3, respectively.
According to claim 1 or 3, R ^1b is a substituted or unsubstituted aromatic group and
[Formula 11]

Curable resin composition, characterized in that selected from the group consisting of divalent substituted amines represented by, R ^2b to R ^13b are each independently a substituted or unsubstituted alkyl group, and R ^14b and R ^15b are each independently hydrogen.
The curable resin composition according to claim 1 or 3, wherein a ratio of the mass of the linear polymer to the mass of the crosslinking agent in the composition is 1:2 to 1:0.03.
The curable resin composition according to claim 1 or 3, further comprising an acid catalyst.
16. The method of claim 15, wherein the acid catalyst is selected from the group consisting of p-toluenesulfonic acid (PTS), dodecylbenzenesulfonic acid, and the thermal acid generator '4-hydroxyphenylbenzylmethylsulfonium hexafluoroantimonate' A curable resin composition, characterized in that it is a compound or a salt thereof or a solvate thereof.
The curable resin composition according to claim 1 or 3, further comprising a solvent.
A cured resin film obtained by curing the curable resin composition of claim 1.
An easily peelable cured resin film obtained by curing a curable resin composition comprising a crosslinking agent and a chain polymer having a side chain having an alcoholic secondary or tertiary hydroxyl group represented by the following formula in the form of a film on the surface of a substrate, ,
(a) the side chain contains 3 to 30 carbon atoms, may include at least one saturated or unsaturated hydrocarbon group, and may further include at least one aromatic group, wherein the linkage between carbon atoms is -COO It may contain a bond selected from the group consisting of -, -O- and -CO-,
(b) the crosslinking agent is selected from the group consisting of a triazine-based compound and/or a condensate thereof, a glycoruryl-based compound and/or a condensate thereof, and an imidazolidinone-based compound and/or a condensate thereof,
The chain polymer is of formula A2:
[Formula 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 are each independently hydrogen, a hydroxyl group and
[Formula 3]

selected from the group consisting of or form a ring together,
However, R ^5a to R ^14a or at least one of the substituents of the ring is a hydroxyl 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 .]
and a monomer unit represented by
The crosslinking agent is of formula B1:
[Formula 7]

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

It is selected from the group consisting of divalent substituted amines represented by , and R ^2b to R ^7b are each 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. ]
A compound represented by and / or a condensate thereof,
Formula B2:
[Formula 9]

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

[In the above formula, R ^12b and R ^13b are each independently having 1 to 10 carbon atoms, and are selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group, and R ^14b and R ^15b are each independently hydrogen or having 1 to 10 carbon atoms and is selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group.]
A compound represented by and / or a condensate thereof
As selected from the group consisting of
In this case, when the chain polymer includes a monomer unit represented by Formula A2 in which L ¹ is a single bond, R ^5a is a hydroxyl group, and R ^6a to R ^14a are hydrogen, the crosslinking agent is a compound represented by Formula B1 and / or characterized in that it is not a condensate thereof
Easily peelable cured resin film.
20. The cured resin film according to claim 18 or 19, wherein the cured resin film has peeling force on a soda glass substrate or an alkali-free glass substrate of 0.5 N/mm ² or less.
21. The cured resin film according to claim 20, wherein the cured resin film has peeling force in a soda glass substrate or an alkali-free glass substrate of 0.1 N/mm ² or less.
In the method for producing a cured resin film from the curable resin composition of claim 1 or 3,
(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 including the chain polymer and a crosslinking agent on a substrate and forming 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;
A manufacturing method comprising a.
23. The method according to claim 22, further comprising the step of (iv) peeling the cured resin film formed on the substrate from the substrate.
(i) preparing a chain polymer having a side chain having an alcoholic secondary or tertiary hydroxyl group and a crosslinking agent;
(ii) forming a curable resin composition coating film by applying a composition including the chain polymer and a crosslinking agent to a substrate; and
(iii) forming a cured resin film by curing the polymerization reaction in the curable resin composition coating film;
In the method for producing a cured resin film comprising:
(a) the side chain contains 3 to 30 carbon atoms, may contain at least one saturated or unsaturated hydrocarbon group, and may further contain at least one aromatic group, wherein the linkage between carbon atoms is - may comprise a bond selected from the group consisting of COO-, -O- and -CO-,
(b) the cross-linking agent is selected from a triazine-based cross-linking agent or a glycoruryl-based cross-linking agent,
The chain polymer is of formula A5:
[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.]
and a monomer unit represented by
The crosslinking agent is of formula B1:
[Formula 7]

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

It is selected from the group consisting of divalent substituted amines represented by , and R ^2b to R ^7b are each 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. ]
A compound represented by and / or a condensate thereof,
Formula B2:
[Formula 9]

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

[Wherein, R ^12b and R ^13b are each independently selected from the group consisting of 1 to 10 carbon atoms and a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group,
R ^14b and R ^15b are each independently hydrogen or having 1 to 10 carbon atoms, and are selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group.]
A compound represented by and / or a condensate thereof
As selected from the group consisting of
In this case, when L ¹ is a single bond, R ^5a is a hydroxyl group, and R ^6a to R ^14a are hydrogen, the crosslinking agent is not a compound represented by Formula B1 and/or a condensate thereof.
manufacturing method.
25. The method of claim 24, wherein the chain polymer does not contain a hydroxyl group and has 1 to 15 carbon atoms in the side chain. At least one of a (meth)acrylic monomer, a vinyl ester-based monomer, a vinyl ether-based monomer, and other vinyl-based monomers is added A manufacturing method, characterized in that it comprises a monomer unit.
26. The method of claim 25, wherein the additional monomer units are
ＣＨ _２ = ＣＨ _- ＣＯＯ-Ｒ６ , ＣＨ ^２ ＝Ｃ（ＣＨ ₃ ）－ＣＯＯ ^- Ｒ７ , ^ＣＯＨ _２ ＝Ｃ
[ ^In the above formula, R6, R7 and ^R8 each independently have ¹ to 15 carbon atoms, do not include a hydroxy group, and may include at least one saturated or unsaturated hydrocarbon group, and may further include at least one aromatic group. wherein the linkage between carbon atoms may have a bond selected from the group consisting of -COO-, -O- and -CO-],
ＣH ₂ = ＣＨ _- O ^- R ⁹
[ ^In the above formula, R9 and R10 each independently have 3 to ¹⁵ carbon atoms, do not contain a hydroxy group, and may include at least one saturated or unsaturated hydrocarbon group, and may further include at least one aromatic group, wherein The linkage between 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
[In the above formula, C ₄ H O ₃ - represents a maleic anhydride group, C ₄ H ₂ N O ₂ - represents a maleimide group, and R ¹¹ and R ¹² each independently represent a hydrogen atom or 1 to 15 carbon atoms and a hydroxyl group. and may contain at least one saturated or unsaturated hydrocarbon group, and may further contain at least one aromatic group, wherein the linkage between carbon atoms is selected from the group consisting of -COO-, -O- and -CO- may have selected bonds.]
A manufacturing method, characterized in that it is selected from the group consisting of compounds represented by.
27. The method according to any one of claims 24 to 26, characterized in that the occupied ratio of the monomer unit having an alcoholic secondary or tertiary hydroxyl group as the monomer unit constituting the chain polymer is 30 to 100 mol%. manufacturing method.
The method according to any one of claims 24 to 26, wherein the mass ratio of the linear polymer of the composition to the mass of the crosslinking agent is 1:2 to 1:0.03.
27. The method according to any one of claims 24 to 26, wherein the composition comprises a solvent.
27. The method of any one of claims 24-26, wherein the composition comprises an acid catalyst.
The method for producing a cured resin film according to any one of claims 24 to 26, further comprising the step of (iv) peeling the cured resin film formed on the substrate from the substrate. delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete