WO2018033995A1 - Curable resin composition for forming easily strippable film, and process for producing same - Google Patents

Abstract

Disclosed is a curable resin composition which can be applied to a surface of a glass substrate to form a thin cured-resin film, which withstands 230°C burning and can be then easily stripped from the substrate. The curable resin composition comprises a crosslinking agent and a chain polymer which includes a side chain having an alcoholic secondary or tertiary hydroxyl group, wherein (a) the side chain contains 3-30 carbon atoms, contains at least one (un)saturated hydrocarbon group and optionally further contains at least one aromatic group, and can contain a bond selected from the group consisting of -COO-, -O-, and -CO-, the bond linking carbon atoms to each other, and (b) the crosslinking agent is selected from between a triazine-based crosslinking agent and a glycoluril-based crosslinking agent.

Description

Curable resin composition for forming easily peelable film and method for producing the same

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

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

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

Moreover, although the base film is required to be thinner year by year, the heat resistance of the base film decreases as the thickness is reduced. As a result, the upper limit of the heat treatment temperature has been reduced to about 100 ° C, and it is assumed that the upper limit of the temperature that can withstand the heat treatment of the base film will further decrease due to further demand for thinness in the future. There is a problem in that there is no base film material that can be fired at a possible temperature.

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

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

Here, the laminate must be easily peeled off from the substrate such as glass. Otherwise, a large strain is generated in the laminated body due to a load at the time of peeling, which causes disconnection of metal wiring and peeling of circuit connection, resulting in a significant deterioration of the product yield.

In particular, even if the substrate material itself is resistant to heat treatment at a higher temperature than the conventional one in the form of a thin film, if the firing in the process of forming the wiring thereon is performed at a higher temperature, the substrate material and it It becomes easy to adhere to the substrate surface. For this reason, it is not enough for the substrate material to withstand baking at a higher temperature than the conventional one in the form of a thin film, and it must be capable of being easily and easily peeled off from the substrate after such high temperature baking. Don't be.

Furthermore, since the base film is very thin as described above, the resin material for forming the base film is very thin and uniform without being struck by the substrate when applied to the substrate (glass substrate, etc.). It must be of a nature that can be expanded. On the other hand, such an affinity for the substrate is one of the factors that can cause the loss of easy peelability because it can cause the substrate to adhere to the substrate during the baking process.

WO2014 / 14205 Publication

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

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

1. A curable resin composition comprising a chain polymer having a side chain having an alcoholic secondary or tertiary hydroxyl group, and a crosslinking agent,
(A) the side chain comprises 3 to 30 carbon atoms and comprises at least one saturated or unsaturated hydrocarbon group, or in addition to at least one more An aromatic group and a bond selected from the group consisting of —COO—, —O—, and —CO— that connect carbon atoms;
(B) The crosslinking agent is selected from a triazine-based crosslinking agent or a glycoluril-based crosslinking agent.
Curable resin composition.
2. The chain polymer is a monomer unit having the side chain having an alcoholic secondary or tertiary hydroxyl group, a (meth) acrylate monomer, a vinyl ester monomer, a vinyl ether monomer, and others The curable resin composition according to 1 above, comprising at least one of the vinyl monomers as a monomer unit.
3. The chain polymer is CH ₂ ═CH—COO—R ¹ , CH ₂ ═C (CH ₃ ) —COO—R ² , CH ₂ ═CH—O—CO—R ³ , CH ₂ ═CH-0—R. ⁴ and CH ₂ ═CH—R ⁵ [where R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are independently of each other when each vinyl group is bonded via an ester bond] It has 3 to 30 carbon atoms including the carbon atoms constituting the ester bond, has an alcoholic secondary or tertiary hydroxyl group, and contains at least one saturated or unsaturated hydrocarbon group Or further comprising at least one aromatic group and having a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms. . ] The said curable resin composition of 1 or 2 which comprises the monomer unit chosen from the group which consists of a compound shown by these.
4). The chain polymer further has any one of (meth) acrylic monomer, vinyl ester monomer, vinyl ether monomer, and other vinyl monomers having no hydroxyl group and having 1 to 15 carbon atoms in the side chain. The curable resin composition according to any one of 1 to 3 above, which comprises at least one kind as an additional monomer unit.
5). The additional monomer units are CH ₂ ═CH—COO—R ⁶ , CH ₂ ═C (CH ₃ ) —COO—R ⁷ , CH ₂ ═CH—O—CO—R ⁸ , [where R ⁶ , R ⁷ and R ⁸ independently of one another have 1 to 15 carbon atoms, have no hydroxyl groups, comprise at least one saturated or unsaturated hydrocarbon group, or at least It comprises one aromatic group and can have a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms. The group group can have an amino group. ], CH ₂ = CH-0-R ⁹ , CH ₂ = CH-R ¹⁰ [wherein R ⁹ and R ¹⁰ independently of one another have 3 to 15 carbon atoms and have a hydroxyl group -COO-, -O-, and -CO, which contain at least one saturated or unsaturated hydrocarbon group, or further contain at least one aromatic group and connect carbon atoms A bond selected from the group consisting of — and the hydrocarbon group or aromatic group may have an amino group; ], C ₄ HO ₃ -R ¹¹ , and C ₄ H ₂ NO ₂ -R ¹² [where C ₄ HO _3- represents a maleic anhydride group, C ₄ H ₂ NO _2- represents a maleimide group, R ¹¹ and R ¹² are independently of each other a hydrogen atom or have 1 to 15 carbon atoms, have no hydroxyl group, and contain at least one saturated or unsaturated hydrocarbon group. Or further comprising at least one aromatic group and having a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms. The hydrocarbon group or aromatic group can have an amino group. The curable resin composition according to any one of 1 to 4 above, which is selected from the group consisting of compounds represented by the formula:
6). The curable resin composition according to any one of 1 to 5 above, wherein the proportion 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% .
7). The cross-linking agent is a group consisting of fully or partially alkoxymethylated melamine, fully or partially alkoxymethylated guanamine, fully or partially alkoxymethylated acetoguanamine, fully or partially alkoxymethylated benzoguanamine, and fully or partially alkoxymethylated glycoluril The curable resin composition according to any one of the above 1 to 6, which is selected from the above.
8). 8. The curable resin composition according to any one of 1 to 7 above, wherein the ratio of the weight of the linear polymer to the weight of the crosslinking agent in the composition is 1: 2 to 1: 0.05.
9. The curable resin composition according to any one of 1 to 8 above, which contains a solvent.
10. A cured resin film obtained by curing the curable resin composition according to any one of 1 to 9 above.
11. An easily peelable cured resin film obtained by curing the curable resin composition of any one of 1 to 9 on a substrate surface in a film shape.
12 A method for producing a cured resin film, comprising:
Providing a chain polymer with a side chain having an alcoholic secondary or tertiary hydroxyl group and a crosslinking agent;
Applying a composition comprising the chain polymer and the crosslinking agent on a substrate to form a curable resin composition coating;
Including a step of forming a cured resin film by performing a polymerization reaction in the coating film of the curable resin composition to be cured,
(A) the side chain comprises 3 to 30 carbon atoms and comprises at least one saturated or unsaturated hydrocarbon group, or in addition to at least one more An aromatic group, and a bond selected from the group consisting of —COO—, —O—, and —CO— that connect carbon atoms of adjacent groups among them. ,
(B) The crosslinking agent is selected from a triazine-based crosslinking agent or a glycoluril-based crosslinking agent.
Production method.
13. The chain polymer is a monomer unit having the side chain having an alcoholic secondary or tertiary hydroxyl group, a (meth) acrylate monomer, a vinyl ester monomer, a vinyl ether monomer, and others 13. The production method according to 12 above, comprising at least one of the vinyl monomers as a monomer unit.
14 The chain polymer is CH ₂ ═CH—COO—R ¹ , CH ₂ ═C (CH ₃ ) —COO—R ² , CH ₂ ═CH—O—CO—R ³ , CH ₂ ═CH-0—R. ⁴ and CH ₂ ═CH—R ⁵ [where R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are independently of each other when each vinyl group is bonded via an ester bond] It has 3 to 30 carbon atoms including the carbon atoms constituting the ester bond, has an alcoholic secondary or tertiary hydroxyl group, and contains at least one saturated or unsaturated hydrocarbon group Or further comprising at least one aromatic group and having a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms. . The manufacturing method of said 12 or 13 which comprises the monomer unit chosen from the group which consists of a compound shown by these.
15. The chain polymer further has any one of (meth) acrylic monomer, vinyl ester monomer, vinyl ether monomer, and other vinyl monomers having no hydroxyl group and having 1 to 15 carbon atoms in the side chain. 15. The production method according to any one of 12 to 14 above, which comprises at least one kind as an additional monomer unit.
16. The additional monomer units are CH ₂ ═CH—COO—R ⁶ , CH ₂ ═C (CH ₃ ) —COO—R ⁷ , CH ₂ ═CH—O—CO—R ⁸ , [where R ⁶ , R ⁷ and R ⁸ independently of one another have 1 to 15 carbon atoms, have no hydroxyl group, comprise at least one saturated or unsaturated hydrocarbon group, or at least It may contain a bond selected from the group consisting of —COO—, —O—, and —CO—, which contains one aromatic group and connects carbon atoms. ], CH ₂ = CH-0-R ⁹ , CH ₂ = CH-R ¹⁰ [wherein R ⁹ and R ¹⁰ independently of one another have 3 to 15 carbon atoms and have a hydroxyl group -COO-, -O-, and -CO, which contain at least one saturated or unsaturated hydrocarbon group, or further contain at least one aromatic group and connect carbon atoms A bond selected from the group consisting of: ], C ₄ HO ₃ -R ¹¹ , and C ₄ H ₂ NO ₂ -R ¹² [where C ₄ HO _3- represents a maleic anhydride group, C ₄ H ₂ NO _2- represents a maleimide group, R ¹¹ and R ¹² are independently of each other a hydrogen atom or have 1 to 15 carbon atoms, have no hydroxyl group, and contain at least one saturated or unsaturated hydrocarbon group. Or further comprising at least one aromatic group and having a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms. . The production method according to any one of 12 to 15 above, which is selected from the group consisting of compounds represented by the formula:
17. 17. The production method according to any one of 12 to 16 above, wherein the proportion 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%.
18. The cross-linking agent consists of fully or partially alkoxymethylated melamine, fully or partially alkoxymethylated guanamine, fully or partially alkoxymethylated acetoguanamine, or fully or partially alkoxymethylated benzoguanamine, and fully or partially alkoxymethylated glycoluril 18. The production method according to any one of 12 to 17 above, which is selected from the group.
19. 19. The production method according to any one of 12 to 18 above, 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.
20. 20. The production method according to any one of 12 to 19 above, wherein the composition contains a solvent.
21. 21. The method for producing a cured resin film according to any one of 12 to 20, further comprising a step of peeling the cured resin film formed on the substrate from the substrate.

The curable resin composition of the present invention can be applied to a glass substrate and cured to form a transparent thin film (for example, several hundred nm thick) that can be easily peeled off. In addition, the thin film formed on the substrate in this way can withstand heating up to 150 ° C., preferably withstands heating at 230 ° C., and further has resistance to the solvent used in the photoresist solution, Since it withstands an alkaline developing solution, it can be advantageously used as a resin base film for circuit fabrication by photolithography. In addition, the thin film formed from the curable resin composition of the present invention has easy peelability even after heating at such a temperature. Since it can be subjected to a circuit manufacturing process including a baking step, it is advantageous for maintaining the characteristics of the circuit and can be easily and easily peeled off from the substrate even after the circuit is manufactured. For this reason, as a base film having excellent characteristics, it can be widely used in the production of various sheet-like flexible electrical / electronic circuit components, for example, in the production of flexible display devices and touch sensors. .

In this specification, “heat resistance” means that a film obtained by curing a curable resin composition can withstand heating up to 150 ° C., and preferably withstands heating at 230 ° C. It means no degradation or other deterioration. The temperature of 230 ° C. is high enough to be used as a baking temperature in the production of an electronic circuit by a photolithography method.

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

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

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

The chain polymer which is one of the constituent elements of the curable resin composition of the present invention has a side chain having an alcoholic secondary or tertiary hydroxyl group. In this specification, the term “side chain” refers to a structural portion branched from a main chain, and “main chain” refers to atoms connected in a one-dimensional direction of repeating monomer units in the polymer structure. A chain consisting of Therefore, for example, when the polymer is a polymer of (meth) acrylate, “—COO—” which is a portion that contributes to the formation of an ester bond in each monomer is included in a part of the “side chain”. The table designation “(meth) acrylate” indicates acrylate and methacrylate without distinction.

In the present invention, the number of carbon atoms contained 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 can be one or more.

The above side chain comprises a saturated or unsaturated hydrocarbon group of at least one carbon atom, or further comprises at least one aromatic group. The side chain may contain one or more bonds selected from the group consisting of —COO—, —O—, and —CO—. The saturated or unsaturated hydrocarbon group constituting the side chain may occupy all carbon atoms of the side chain, for example, alone, or a plurality of saturated or unsaturated carbon groups may be —COO—, It may be linked via a bond selected from the group consisting of —O— and —CO—. When the side chain contains an aromatic group in addition to a saturated or unsaturated hydrocarbon group, the saturated or unsaturated hydrocarbon group and the aromatic group may be directly bonded, or —COO—, — They may be linked via a bond selected from the group consisting of O— and —CO—. In this specification, “—O—” and “—CO—” do not include the case where they are constituent parts of “—COO—”.

In the present invention, the alcoholic secondary and tertiary hydroxyl groups in the side chain are formed by curing the cured resin thin film formed by applying the curable resin composition of the present invention on a glass substrate and curing it. This is a decisive factor for maintaining easy peelability from the film. A chain polymer having such a side chain is a resin composition with an appropriate crosslinking agent, in particular, either a triazine-based crosslinking agent or a glycoluril-based crosslinking agent, and has a heat resistance when cured in the form of a thin film. An easily peelable film can be provided.

In the present invention, the chain polymer having the side chain having an alcoholic secondary or tertiary hydroxyl group is more preferably a (meth) acrylate monomer, a vinyl ester monomer, a vinyl ether monomer, other than the above. Vinyl monomers,
Any one of them is included as a monomer unit.

More preferably, the chain polymer in the present invention is CH ₂ ═CH—COO—R ¹ , CH ₂ ═C (CH ₃ ) —COO—R ² , CH ₂ ═CH—O—CO—R ³ , CH ₂ = CH-0-R ⁴ and CH ₂ = CH-R ⁵ [wherein R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are independently of each other via an ester bond to each vinyl group. In the case of bonding, it has 3 to 30 carbon atoms, more preferably 3 to 25 carbon atoms, still more preferably 3 to 20 carbon atoms including carbon atoms constituting the ester bond, -COO- having a secondary hydroxyl group and comprising at least one saturated or unsaturated hydrocarbon group, or further comprising at least one aromatic group, and connecting between carbon atoms, A bond selected from the group consisting of —O— and —CO—. Can have. A monomer unit selected from the group consisting of compounds represented by the formula:

In the above, examples of saturated or unsaturated hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, cyclohexyl, dicyclopentadienyl, decalinyl, adamantyl, butenyl, hexenyl, cyclohexenyl. , Decyl, and the like, and various linear, branched, monocyclic, and condensed cyclic groups within the limit of the carbon number of the side chain may be mentioned. When these groups are not located at the terminal, they may be divalent or higher groups depending on the bonding relationship with other groups. Examples of aromatic groups include monocyclic aromatic groups (monocyclic and condensed ring groups) such as phenyl, biphenylyl, naphthyl, and heteroaromatic groups (monocyclic, pyridinyl, quinolinyl, triazinyl, etc.) In the case where each aromatic group is not located at the terminal, it may be a divalent or higher valent group depending on the bonding relationship with other groups. In the present specification, a group having a saturated or unsaturated hydrocarbon chain part that forms a ring together with an aromatic ring part (for example, tetrahydronaphthyl or dihydronaphthyl) is an aromatic group and a saturated or unsaturated hydrocarbon group. Think of it as a combination.

In the present invention, the alcoholic secondary or tertiary hydroxyl group replaces a hydrogen atom on either the secondary or tertiary carbon atom of the saturated or unsaturated hydrocarbon group constituting the side chain. Hydroxyl group.

The preferred side chain having an alcoholic secondary or tertiary hydroxyl group of the chain polymer in the present invention includes the following, but since it is only necessary to have such a hydroxy group, the mentioned ones are not tired. It is an illustration and it is not limited to them.
(1a) AO-CO-type (A represents the remainder of the side chain, the same shall apply hereinafter) Side chain: 2-hydroxyethoxycarbonyl, 2-hydroxypropoxycarbonyl, 4- (hydroxymethyl) cyclohexylmethoxycarbonyl, 2 -Hydroxy-3- (cyclohexylcarbonyloxy) propoxycarbonyl, 3-benzoyloxy-2-hydroxypropoxycarbonyl, 4-benzoyloxy-3-hydroxycyclohexylmethoxycarbonyl, 3-hydroxy-1-adamantyloxycarbonyl, 2-hydroxycyclohexyl Oxycarbonyl, 4-undecanoyloxy-3-hydroxycyclohexylmethoxycarbonyl, 4-butanoyloxy-3-hydroxycyclohexylmethoxycarbonyl, and the like.
(2a) A-CO-O-type side chain: 2-hydroxypropylcarbonyloxy, 2-hydroxy-3- (cyclohexylcarbonyloxy) propylcarbonyloxy, 3-benzoyloxy-2-hydroxypropylcarbonyloxy, 4-benzoyl Oxy-3-hydroxycyclohexylmethylcarbonyloxy, 3-hydroxy-1-adamantylcarbonyloxy, 2-hydroxycyclohexyloxycarbonyloxy, 4-undecanoyloxy-3-hydroxycyclohexylmethylcarbonyloxy, 4-butanoyloxy- 3-hydroxycyclohexylmethylcarbonyloxy and the like.
(3a) AO-type side chain: 2-hydroxypropoxy, 2-hydroxy-3- (cyclohexylcarbonyloxy) propoxy, 3-benzoyloxy-2-hydroxypropoxy, 4-benzoyloxy-3-hydroxycyclohexylmethoxy, 3-hydroxy-1-adamantyloxy, 2-hydroxycyclohexyloxy, 4-undecanoyloxy-3-hydroxycyclohexylmethoxy, 4-butanoyloxy-3-hydroxycyclohexylmethoxy and the like.
(4a) 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 that gives these side chains to the chain polymer include, but are not limited to, the following.
(1b) 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3- (cyclohexylcarbonyloxy) propyl (meth) acrylate, 3-benzoyloxy-2-hydroxypropyl (meth) acrylate, 4-benzoyloxy-3- Hydroxycyclohexylmethyl (meth) acrylate, 1,3-adamantyl diol mono (meth) acrylate, and 2-hydroxycyclohexyl (meth) acrylate, 4-undecanoyloxy-3-hydroxycyclohexylmethyl (meth) acrylate, 4-buta (Meth) acrylates such as noyloxy-3-hydroxycyclohexylmethyl (meth) acrylate.
(2b) 2-hydroxybutanoic acid vinyl ester, 2-hydroxy-3- (cyclohexylcarbonyloxy) butanoic acid vinyl ester, 3-benzoyloxy-2-hydroxybutanoic acid vinyl ester, 4-benzoyloxy-3-hydroxycyclohexyl acetic acid Vinyl ester, 3-hydroxy-1-adamantylcarboxylic acid vinyl ester, 2-hydroxycyclohexyloxycarboxylic acid vinyl ester, 4-undecanoyloxy-3-hydroxycyclohexyl acetic acid vinyl ester, 4-butanoyloxy-3-hydroxy Vinyl esters such as cyclohexyl acetic acid vinyl ester.
(3b) 2-hydroxypropyl vinyl ether, 2-hydroxy-3- (cyclohexylcarbonyloxy) propyl vinyl ether, 3-benzoyloxy-2-hydroxypropyl vinyl ether, 4-benzoyloxy-3-hydroxycyclohexyl methyl vinyl ether, 3-hydroxy- Vinyl ethers such as 1-adamantyl vinyl ether, 2-hydroxycyclohexyl vinyl ether, 4-undecanoyloxy-3-hydroxycyclohexyl methyl ether, 4-butanoyloxy-3-hydroxycyclohexyl methyl ether.
(4b) 1-penten-4-ol, 4-hydroxy-5- (cyclohexylcarbonyloxy) -1-pentene, 5-benzoyloxy-4-hydroxy-1-pentene, 3- (4-benzoyloxy-3- Hydroxycyclohexyl) -1-propene, (3-hydroxy-1-adamantyl) ethene, (2-hydroxycyclohexyl) ethene, 3- (4-undecanoyloxy-3-hydroxycyclohexyl) -1-propene, 3- ( Vinyl monomers such as 4-butanoyloxy-3-hydroxycyclohexyl) -1-propene.
(5b) Maleic anhydride and maleimide each having the above (1a) to (4a) as substituents.

The chain polymer in the present invention is a (meth) acrylic polymer having no hydroxyl group and having 1 to 15 carbon atoms in the side chain in addition to the above-mentioned monomer having an alcoholic secondary or tertiary hydroxyl group. Any one of a monomer, a vinyl ester monomer, a vinyl ether monomer, and a vinyl monomer other than these monomers may be included as an additional monomer unit. Such additional monomer units are preferably CH ₂ ═CH—COO—R ⁶ , CH ₂ ═C (CH ₃ ) —COO—R ⁷ , CH ₂ ═CH—O—CO—R ⁸ , wherein In which R ⁶ , R ⁷ and R ⁸ independently of one another have 1 to 15 carbon atoms, have no hydroxyl groups and comprise at least one saturated or unsaturated hydrocarbon group , Or further comprising at least one aromatic group and having a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms. The hydrogen group or aromatic group can have an amino group. ], CH ₂ = CH-0-R ⁹ , CH ₂ = CH-R ¹⁰ [wherein R ⁹ and R ¹⁰ independently of one another have 3 to 15 carbon atoms and have a hydroxyl group -COO-, -O-, and -CO, which contain at least one saturated or unsaturated hydrocarbon group, or further contain at least one aromatic group and connect carbon atoms A bond selected from the group consisting of — and the hydrocarbon group or aromatic group may have an amino group; ], C ₄ HO ₃ -R ¹¹ , and C ₄ H ₂ NO ₂ -R ¹² [where C ₄ HO _3- represents a maleic anhydride group, C ₄ H ₂ NO _2- represents a maleimide group, R ¹¹ and R ¹² , independently of one another, are hydrogen atoms or have 1 to 15 carbon atoms, have no alcoholic secondary or tertiary hydroxyl groups, and are at least one saturated Or an unsaturated hydrocarbon group, or at least one aromatic group, and selected from the group consisting of —COO—, —O—, and —CO— that connect carbon atoms It can have a bond, and the hydrocarbon group or aromatic group can have an amino group. ] Can be selected from the group consisting of compounds represented by

Preferable examples of the monomer unit having no 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, tetrahydrofurfuryl (meth) acrylate, cyclohexyl ( (Meth) acrylate, phenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, octyl (meth) acrylate, benzyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylamino (Meth) acrylates such as propyl (meth) acrylate.
(2) Vinyl esters such as vinyl acetate, butanoic acid vinyl ester, pentanoic acid vinyl ester, hexanoic acid vinyl ester, cyclohexanecarboxylic acid vinyl ester, benzoic acid vinyl ester, cyclopentadienylcarboxylic acid vinyl ester, and nonanoic acid vinyl ester .
(3) Propyl vinyl ether, butyl vinyl ether, ethoxyethyl vinyl ether, glycidyl vinyl ether, pentyl vinyl ether, tetrahydrofurfuryl vinyl ether, cyclohexyl vinyl ether, phenyl vinyl ether, cyclopentadienyl vinyl ether, octyl vinyl ether, benzyl vinyl ether, 2- (vinyloxy) ethyldimethylamine , Vinyl ethers such as 3- (vinyloxy) propyldimethylamine.
(4) Vinyl derivatives such as 1-butene, 4-ethoxy-1-butene, 1-pentene, 1-hexene, vinylcyclohexane, styrene, vinyltoluene, 1-nonene and 3-phenylpropene.
(5) Maleic anhydride derivatives such as maleic anhydride, methylmaleic anhydride, butylmaleic anhydride, hexylmaleic anhydride, cyclohexylmaleic anhydride, phenylmaleic anhydride, octylmaleic anhydride .
(6) Maleimide derivatives such as maleimide, methylmaleimide, ethylmaleimide, butylmaleimide, hexylmaleimide, cyclohexylmaleimide, phenylmaleimide, benzylmaleimide and octylmaleimide.

The proportion of the monomer unit having an alcoholic secondary or tertiary hydroxyl group in the chain polymer in the present invention is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, more preferably 60 to It is 100 mol%, more preferably 80 to 100 mol%, particularly preferably 90 to 100 mol%.

In the present invention, the chain polymer is subjected to a polymerization reaction using a raw material monomer in a conventional manner, for example, using a conventional radical polymerization catalyst such as 2,2′-azobisisobutyronitrile (AIBN). Can be manufactured. The molecular weight of the chain polymer is usually preferably in the range of 10,000 to 100,000 (measured by gel filtration chromatography), but is not particularly limited to this range.

As the crosslinking agent in the curable resin composition of the present invention, a triazine-based crosslinking agent or a glycoluril-based crosslinking agent is preferable. Preferred examples of these cross-linking agents include fully or partially alkoxy (eg methoxy, ethoxy) methylated melamine, fully or partially alkoxy (eg methoxy, ethoxy) methylated guanamine, fully or partially alkoxy (eg methoxy, ethoxy) methyl. Acetoguanamine, fully or partially alkoxymethylated benzoguanamine, fully or partially alkoxy (eg methoxy, ethoxy) methylated glycoluril. Here, the “alkoxy” preferably has 1 to 4 carbon atoms. More specifically, as such a crosslinking agent, for example, hexamethoxymethyl melamine, hexaethoxymethyl melamine, tetramethoxymethyl methylol melamine, tetramethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl guanamine, tetramethoxymethyl acetoamine. Guanamine, tetramethoxymethylbenzoguanamine, trimethoxymethylbenzoguanamine, tetraethoxymethylbenzoguanamine, tetramethylolbenzoguanamine, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) Although glycoluril etc. are mentioned, it is not limited to these.

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

The mass ratio of the chain polymer to the crosslinking agent in the curable resin composition of the present invention is preferably 1: 0.05 to 1: 1, more preferably 1: 0.1 to 1: 0.5, Preferably, it is 1: 0.1 to 1: 0.3.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not intended to be limited to these examples.

1. Production of polymer as constituent of curable resin composition A polymer was produced as shown below as a constituent of the curable resin composition.

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

 

2-hydroxypropyl methacrylate was used as a monomer, and 100 parts by mass thereof was dissolved in propylene glycol monomethyl ether (PGME) so as to be 30% by mass. The resulting solution was heated to 80 ° C. while blowing nitrogen gas, and 5 mol% of 2,2′-azobisisobutyronitrile (AIBN) was added to the total amount of monomers, and then reacted at 80 ° C. for 8 hours. And polymer A-1 was obtained. It was 25000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.

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

 

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

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

 

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

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

 

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

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

 

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

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

 

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

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

 

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

[Production Example 8] Production of polymer A-8 Using 2-hydroxypropyl methacrylate and n-butyl acrylate of formula (1-1) as monomers, 50 parts by mass of each in total with propylene glycol monomethyl ether (PGME) To 30% by mass. The resulting solution was heated to 80 ° C. while blowing nitrogen gas, and 5 mol% of 2,2′-azobisisobutyronitrile (AIBN) was added to the total amount of monomers, and then reacted at 80 ° C. for 8 hours. And polymer A-8 was obtained. It was 18000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.

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

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

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

[Production Example 12] Production of polymer A-12 Polymer A- 12 was prepared in the same manner as in Example 8, except that 2-hydroxycyclohexyl methacrylate and dicyclopentadienyl methacrylate represented by the formula (1-5) were used as monomers. 12 was obtained. It was 25000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.

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

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

[Production Example 15] Production of polymer A-15 Polymer A- 15 was prepared in the same manner as in Example 8 except that 2-hydroxyethyl methacrylate and dicyclopentadienyl methacrylate represented by the formula (1-6) were used as monomers. 15 was obtained. When the average molecular weight (MW) of this polymer was measured by gel filtration chromatography, it was 39000.

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

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

 

Of 0.4 parts by mass of hexamethoxymethylmelamine (Nicarac MW-30, Sanwa Chemical Co., Ltd.) and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst were mixed with propylene glycol monomethyl ether (PGME). ) It was dissolved in 95 parts by mass. This solution was applied by spin coating on 0.7 mm thick soda glass and 0.5 mm non-alkali glass (EAGLE-XG, Corning), respectively, and heat-treated at 150 ° C. or higher for 30 minutes to obtain about 300 nm A film thickness was formed.

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

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

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

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

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

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

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

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

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

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

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

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

 

Of 1,3,4,6-tetrakis (methoxymethyl) glycoluril and 0.2 part by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst were added to propylene glycol monomethyl ether (PGME) 95 Dissolved in parts by mass. Using this solution, coating and heat treatment were performed on soda glass and non-alkali glass in the same manner as in Example 1 to form a film thickness of about 300 nm.

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

 

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

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

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

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

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

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

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

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

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

3. Evaluation of performance (1) Evaluation of peel force for cured resin thin film About the cured resin thin film prepared on the glass substrate in each of the above examples and comparative examples, the magnitude of the force required to peel them from the glass substrate (Peeling force) was quantitatively evaluated by the following method. In other words, TENSILON RTG-1310 (A & D Co., Ltd.) was used as the measuring device, and UR-100N-D type was used as the load cell. Nichiban tape (24 mm width) was applied to the cured resin thin film on the glass substrate. The measurement was performed by measuring the magnitude of the force (peeling force) required for peeling while pulling the glass substrate at a constant speed of 300 mm / min at a peeling angle of 90 °. The results are shown in Table 1.

 

As shown in Table 1, the peel strengths of the cured resin thin films of Comparative Examples 1 to 6 were 2.2 to 8.7 N / mm ² (soda glass substrate) and 3.2 to 9.2 (EAGLE-XG substrate). However, in Examples 1 to 16, it is 0.013 to 0.078 (soda glass substrate) and 0.028 to 0.085 ((EAGLE-XG substrate)), which is two orders of magnitude smaller. Actually, each cured resin thin film of the comparative example had a high peel force value, and thus the film and the substrate were destroyed. It could be easily removed without difficulty.
(2) Evaluation of peel strength for cured resin thin film after firing Assuming a firing process in circuit fabrication by patterning using photolithography method or printing method on cured resin thin film, when cured resin thin film is fired The peel force was measured. That is, for Examples 1 and 7 and Comparative Examples 1 and 2, the cured resin thin film formed on the soda glass substrate was baked at 230 ° C. for 1 hour or 3 hours, and the apparatus and method described in (1) above were used. The peel force was measured. The results are shown in Table 2 together with the values of the peel force before firing (initial peel force) in those examples and comparative examples.

 

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

The present invention can be applied to a substrate such as glass very thinly, and can be formed into a very thin cured resin thin film by drying and curing after coating, and baking at a temperature of 230 ° C. in the process of producing a circuit by patterning or the like thereon. As a curable resin composition that has durability at high temperatures and can be easily peeled off from a substrate even after being exposed to such high temperatures, it is useful for the production of film-type electrical / electronic circuit components.

Claims (21)

1. A curable resin composition comprising a chain polymer having a side chain having an alcoholic secondary or tertiary hydroxyl group, and a crosslinking agent,
   (A) the side chain comprises 3 to 30 carbon atoms and comprises at least one saturated or unsaturated hydrocarbon group, or in addition to at least one more An aromatic group and a bond selected from the group consisting of —COO—, —O—, and —CO— that connect carbon atoms;
   (B) The crosslinking agent is selected from a triazine-based crosslinking agent or a glycoluril-based crosslinking agent.
   Curable resin composition.
2. The chain polymer is a monomer unit having the side chain having an alcoholic secondary or tertiary hydroxyl group, a (meth) acrylate monomer, a vinyl ester monomer, a vinyl ether monomer, and others The curable resin composition according to claim 1, comprising at least one of the vinyl monomers as monomer units.
3. The chain polymer is CH ₂ ═CH—COO—R ¹ , CH ₂ ═C (CH ₃ ) —COO—R ² , CH ₂ ═CH—O—CO—R ³ , CH ₂ ═CH-0—R. ⁴ and CH ₂ ═CH—R ⁵ [where R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are independently of each other when each vinyl group is bonded via an ester bond] It has 3 to 30 carbon atoms including the carbon atoms constituting the ester bond, has an alcoholic secondary or tertiary hydroxyl group, and contains at least one saturated or unsaturated hydrocarbon group Or further comprising at least one aromatic group and having a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms. . ] The curable resin composition of Claim 1 or 2 which comprises the monomer unit chosen from the group which consists of a compound shown by these.
4. The chain polymer further has any one of (meth) acrylic monomer, vinyl ester monomer, vinyl ether monomer, and other vinyl monomers having no hydroxyl group and having 1 to 15 carbon atoms in the side chain. The curable resin composition according to any one of claims 1 to 3, comprising at least one kind as an additional monomer unit.
5. The additional monomer units are CH ₂ ═CH—COO—R ⁶ , CH ₂ ═C (CH ₃ ) —COO—R ⁷ , CH ₂ ═CH—O—CO—R ⁸ , [where R ⁶ , R ⁷ and R ⁸ independently of one another have 1 to 15 carbon atoms, have no hydroxyl groups, comprise at least one saturated or unsaturated hydrocarbon group, or at least It comprises one aromatic group and can have a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms. The group group can have an amino group. ], CH ₂ = CH-0-R ⁹ , CH ₂ = CH-R ¹⁰ [wherein R ⁹ and R ¹⁰ independently of one another have 3 to 15 carbon atoms and have a hydroxyl group -COO-, -O-, and -CO, which contain at least one saturated or unsaturated hydrocarbon group, or further contain at least one aromatic group and connect carbon atoms A bond selected from the group consisting of — and the hydrocarbon group or aromatic group may have an amino group; ], C ₄ HO ₃ -R ¹¹ , and C ₄ H ₂ NO ₂ -R ¹² [where C ₄ HO _3- represents a maleic anhydride group, C ₄ H ₂ NO _2- represents a maleimide group, R ¹¹ and R ¹² are independently of each other a hydrogen atom or have 1 to 15 carbon atoms, have no hydroxyl group, and contain at least one saturated or unsaturated hydrocarbon group. Or further comprising at least one aromatic group and having a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms. The hydrocarbon group or aromatic group can have an amino group. The curable resin composition according to any one of claims 1 to 4, which is selected from the group consisting of compounds represented by the formula:
6. 6. The curable resin composition according to claim 1, wherein the proportion 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%. object.
7. The cross-linking agent is a group consisting of fully or partially alkoxymethylated melamine, fully or partially alkoxymethylated guanamine, fully or partially alkoxymethylated acetoguanamine, fully or partially alkoxymethylated benzoguanamine, and fully or partially alkoxymethylated glycoluril The curable resin composition according to any one of claims 1 to 6, which is more selected.
8. The curable resin composition according to any one of claims 1 to 7, wherein a ratio of a mass of the linear polymer to a mass of the crosslinking agent in the composition is 1: 2 to 1: 0.05.
9. The curable resin composition according to any one of claims 1 to 8, which contains a solvent.
10. A cured resin film obtained by curing the curable resin composition according to any one of claims 1 to 9.
11. An easily peelable cured resin film obtained by curing the curable resin composition according to any one of claims 1 to 9 on the surface of a substrate.
12. A method for producing a cured resin film, comprising:
    Providing a chain polymer with a side chain having an alcoholic secondary or tertiary hydroxyl group and a crosslinking agent;
    Applying a composition comprising the chain polymer and the crosslinking agent on a substrate to form a curable resin composition coating;
    Including a step of forming a cured resin film by performing a polymerization reaction in the coating film of the curable resin composition to be cured,
    (A) the side chain comprises 3 to 30 carbon atoms and comprises at least one saturated or unsaturated hydrocarbon group, or in addition to at least one more An aromatic group, and a bond selected from the group consisting of —COO—, —O—, and —CO— that connect carbon atoms of adjacent groups among them. ,
    (B) The crosslinking agent is selected from a triazine-based crosslinking agent or a glycoluril-based crosslinking agent.
    Production method.
13. The chain polymer is a monomer unit having the side chain having an alcoholic secondary or tertiary hydroxyl group, a (meth) acrylate monomer, a vinyl ester monomer, a vinyl ether monomer, and others The production method according to claim 12, comprising at least one of the vinyl monomers as a monomer unit.
14. The chain polymer is CH ₂ ═CH—COO—R ¹ , CH ₂ ═C (CH ₃ ) —COO—R ² , CH ₂ ═CH—O—CO—R ³ , CH ₂ ═CH-0—R. ⁴ and CH ₂ ═CH—R ⁵ [where R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are independently of each other when each vinyl group is bonded via an ester bond] It has 3 to 30 carbon atoms including the carbon atoms constituting the ester bond, has an alcoholic secondary or tertiary hydroxyl group, and contains at least one saturated or unsaturated hydrocarbon group Or further comprising at least one aromatic group and having a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms. . The production method according to claim 12 or 13, comprising a monomer unit selected from the group consisting of compounds represented by the formula:
15. The chain polymer further has any one of (meth) acrylic monomer, vinyl ester monomer, vinyl ether monomer, and other vinyl monomers having no hydroxyl group and having 1 to 15 carbon atoms in the side chain. The production method according to any one of claims 12 to 14, comprising at least one kind as an additional monomer unit.
16. The additional monomer units are CH ₂ ═CH—COO—R ⁶ , CH ₂ ═C (CH ₃ ) —COO—R ⁷ , CH ₂ ═CH—O—CO—R ⁸ , [where R ⁶ , R ⁷ and R ⁸ independently of one another have 1 to 15 carbon atoms, have no hydroxyl group, comprise at least one saturated or unsaturated hydrocarbon group, or at least It may contain a bond selected from the group consisting of —COO—, —O—, and —CO—, which contains one aromatic group and connects carbon atoms. ], CH ₂ = CH-0-R ⁹ , CH ₂ = CH-R ¹⁰ [wherein R ⁹ and R ¹⁰ independently of one another have 3 to 15 carbon atoms and have a hydroxyl group -COO-, -O-, and -CO, which contain at least one saturated or unsaturated hydrocarbon group, or further contain at least one aromatic group and connect carbon atoms A bond selected from the group consisting of: ], C ₄ HO ₃ -R ¹¹ , and C ₄ H ₂ NO ₂ -R ¹² [where C ₄ HO _3- represents a maleic anhydride group, C ₄ H ₂ NO _2- represents a maleimide group, R ¹¹ and R ¹² are independently of each other a hydrogen atom or have 1 to 15 carbon atoms, have no hydroxyl group, and contain at least one saturated or unsaturated hydrocarbon group. Or further comprising at least one aromatic group and having a bond selected from the group consisting of —COO—, —O—, and —CO— connecting carbon atoms. . The production method according to any one of claims 12 to 15, which is selected from the group consisting of compounds represented by the formula:
17. The production method according to any one of claims 12 to 16, wherein the proportion 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%.
18. The cross-linking agent consists of fully or partially alkoxymethylated melamine, fully or partially alkoxymethylated guanamine, fully or partially alkoxymethylated acetoguanamine, or fully or partially alkoxymethylated benzoguanamine, and fully or partially alkoxymethylated glycoluril The production method according to any one of claims 12 to 17, which is selected from the group.
19. The production method according to any one of claims 12 to 18, wherein a ratio of a mass of the linear polymer to a mass of the crosslinking agent in the composition is 1: 2 to 1: 0.05.
20. The method according to any one of claims 12 to 19, wherein the composition contains a solvent.
21. 21. The method for producing a cured resin film according to claim 12, further comprising a step of peeling the cured resin film formed on the substrate from the substrate.