KR102337215B1 - Thermosetting resin composition - Google Patents

Abstract

The present invention satisfies the properties required in the prior art as a protective film by including an isocyanuric acid derivative as a crosslinking agent together with a copolymer containing a carboxyl group or an epoxy group, and at the same time effectively improves the crosslinking density to have excellent mechanical properties and heat resistance, It relates to a thermosetting resin composition capable of providing a cured film without yellowing at a high temperature.

Description

Thermosetting resin composition {Thermosetting resin composition}

The present invention relates to a thermosetting resin composition. More specifically, (a1) a copolymer of an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride, (a2) an epoxy group-containing unsaturated compound, (a3) an olefinically unsaturated compound other than the above (a1) or (a2) [A]; And to provide a thermosetting resin composition comprising a compound [B] or isocyanuric acid derivative [B] having a polyfunctional thiol group.

The thermosetting resin composition of the present invention provides a thermosetting resin composition suitable as a material for a protective film for an optical device having excellent mechanical properties and heat resistance.

Optical devices such as liquid crystal display devices (LCDs) are immersed in organic solvents, acid, alkali solutions, etc. during the manufacturing process, or when the wiring electrode layer is formed, subjected to severe treatment such as local high temperature heating by sputtering. do. Therefore, in some cases, an overcoat is provided on the surface of these devices to prevent deterioration during manufacturing.

The protective film withstands the above treatment and at the same time has excellent adhesion to the substrate or lower layer, high smoothness and surface hardness, excellent transparency, and excellent heat resistance and light resistance to prevent deterioration such as coloring, yellowing, and whitening over a long period of time, solvent resistance It is required to have excellent chemical resistance such as acid resistance and alkali resistance, water resistance, and the like. In addition, when such a protective film is applied to a color filter of a color liquid crystal display, it is preferable that the level difference of a general color filter can be flattened as a base substrate.

The protective film is composed of a cured film of a curable resin composition, wherein the curable resin composition may be largely divided into thermosetting and photocuring properties (photosensitivity). When pattern formation of a protective film is required, a photosensitive resin composition is required, but in other cases, a thermosetting resin composition is used. This is because the thermosetting resin composition is more convenient in process than the photosensitive resin composition, and can increase the crosslinking density, and thus has excellent mechanical properties and heat resistance.

In such a thermosetting resin composition, Korean Patent Registration No. 10-1485186 (thermosetting resin composition) contains a vinyl compound containing an isocyanate group or a blocked isocyanate group together with an acrylic resin containing a carboxyl group or an epoxy group as a crosslinking agent. It is possible to provide a cured film having excellent mechanical properties and heat resistance and no yellowing at high temperature by improving the crosslinking density. Korean Patent Registration No. 10-1351767 (thermosetting resin composition and protective film made of this composition) is a material for forming a protective film used in color filters for optical devices. (a1) unsaturated carboxylic acid or its anhydride, (a2) epoxy group-containing unsaturated a copolymer [A] of the compound, (a3) a trialkoxysilane-based unsaturated compound, and (a4) an olefin-based unsaturated compound. Korean Patent Registration No. 10-1309374 (thermosetting resin composition) relates to a thermosetting composition preferable as a material for forming a protective film used in color filters for optical devices and a protective film made of the composition, (a1) unsaturated carboxylic acid or anhydride thereof , (a2) an epoxy group-containing unsaturated compound, and (a3) a copolymer [A] of an olefinically unsaturated compound. Korea Patent Publication No. 2015-20853 (thermosetting resin composition) relates to a thermosetting composition preferable as a material for forming a protective film used in color filters for optical devices and a protective film made of the composition, (a1) unsaturated carboxylic acid or anhydride thereof , (a2) an epoxy group-containing unsaturated compound, and (a3) a copolymer [A] of an olefinically unsaturated compound. In the thermosetting resin composition, the curable compound [B] contains an alicyclic epoxy compound. Korea Patent Publication No. 2010-103033 (thermosetting resin composition, thermosetting protective film and liquid crystal display device) relates to a thermosetting resin composition suitable for forming a protective film installed to prevent deterioration of a substrate generated during the manufacturing process of an optical device such as a liquid crystal display device (a-1) unsaturated carboxylic acid or unsaturated carboxylic acid anhydride (hereinafter referred to as compound a-1), (a-2) an unsaturated compound containing an epoxy group, and (a-3) above (a-1), (a-2) ) is a thermosetting resin composition containing a copolymer of an olefinically unsaturated compound other than Korea Patent Publication No. 2009-63985 (thermosetting resin composition) is a material for forming a protective film used in color filters for optical devices, unsaturated carboxylic acid or its anhydride (a1), epoxy group-containing unsaturated compound (a2), olefinically unsaturated compound The thermosetting resin composition containing the polymer [A] of (a3) WHEREIN: It is a thermosetting resin composition containing a bismaleimide compound as a curable compound [B]. In addition, the prior art related to such a protective film includes Japanese Laid-Open Patent Publication Nos. 2000-103937, 2000-119472, and 2000-143772.

However, the conventional thermosetting resin composition having such a composition does not have excellent mechanical properties and, in particular, has poor heat resistance at high temperatures, and often exhibits yellowing. As part of preventing this phenomenon, an excessive amount of a polyfunctional monomer containing an ethylenically unsaturated group may be used, but such excessive use has a problem of exacerbating the yellowing phenomenon at high temperature.

Korean Patent Registration No. 10-1062250 (thermosetting resin composition)

The object of the present invention is to consider the problems of the prior art as described above, and at the same time satisfy the characteristics required from the prior art, and at the same time effectively improve the crosslinking density, thereby providing excellent mechanical properties and heat resistance, and is very suitable as a material for forming a protective film for optical devices. , to provide a thermosetting resin composition without yellowing at high temperature.

Conventionally, as an example of a thermosetting resin composition used to form a protective film, an acrylic resin containing a carboxyl group or an epoxy group, a polyfunctional monomer containing an ethylenically unsaturated group serving as a crosslinking agent, and a composition containing a thermal polymerization initiator are mainly used. However, the conventional thermosetting resin composition having such a composition does not have excellent mechanical properties and, in particular, has poor heat resistance at high temperatures, and thus yellowing occurs in many cases. In order to prevent this phenomenon, an excessive amount of a polyfunctional monomer containing an ethylenically unsaturated group is used, but there is a problem of exacerbating the yellowing phenomenon at high temperature when excessively used. Therefore, the protective film withstands the harsh treatment as described above, and at the same time has excellent adhesion to the substrate or the lower layer, high smoothness and surface hardness, and excellent transparency. It is calculated|required that it is excellent in agent resistance, acid resistance, alkali resistance, etc.

The thermosetting resin composition provided to solve the above-mentioned first technical problem of the present invention is (a1) an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride, (a2) an unsaturated compound containing an epoxy group, (a3) an olefin other than (a1) or (a2) copolymers of systemically unsaturated compounds [A]; And it may be a thermosetting resin composition comprising a compound [B] or an isocyanuric acid derivative [B] having a polyfunctional thiol group.

According to an embodiment of the present invention, the compound [B] having a polyfunctional thiol group may be any one or more selected from the following formula (1) compounds.

[Formula 1]

A is a compound represented by the following [Formula 2], and n is an integer of 1 to 4 repeating units in the main chain.

[Formula 2]

The * represents a bond other than C, wherein R ₁ is a linear or cyclic alkyl group having 1 to 6 carbon atoms, a linear or cyclic alkylene group having 2 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 20 carbon atoms. It may be at least one selected from the group consisting of arylene groups or a compound represented by the following formula (3).

[Formula 3]

The R ₃ to R ₅ may each independently be at least one selected from the group consisting of C, N, O, Si, P and S bonded to the A.

The compound [B] having the polyfunctional thiol group according to another embodiment of the present invention may be included in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the copolymer [A].

According to another embodiment of the present invention, the thermosetting resin composition may contain 150 parts by weight or less of the polymerizable compound having an ethylenically unsaturated bond with respect to 100 parts by weight of the copolymer [A].

According to another embodiment of the present invention, the thermosetting resin composition may contain 20 parts by weight or less of a thermal radical polymerization initiator based on 100 parts by weight of the copolymer [A].

In addition, the isocyanuric acid derivative is a compound represented by the following [Formula 4].

[Formula 4]

wherein R ₆ to R ₈ are a linear or cyclic alkyl group having 1 to 6 carbon atoms, a linear or cyclic alkylene group having 2 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylene group having 7 to 20 carbon atoms, or the following [Formula 5 It is selected from the compounds represented by ].

[Formula 5]

According to another embodiment of the present invention, the thermosetting resin composition may contain 150 parts by weight or less of the polymerizable compound having an ethylenically unsaturated bond with respect to 100 parts by weight of the copolymer [A].

According to another embodiment of the present invention, the thermosetting resin composition may contain 20 parts by weight or less of a thermal radical polymerization initiator based on 100 parts by weight of the copolymer [A].

In addition, the present invention may include a cured film prepared from the thermosetting resin composition.

According to another embodiment of the present invention, the cured film may be a color filter protective film of an optical device.

The thermosetting resin composition according to the present invention contains an isocyanuric acid derivative serving as a crosslinking agent together with a copolymer containing a carboxyl group or an epoxy group, and thus the cured film prepared using the thermosetting resin composition is a protective film. It is to provide a cured film for an optical device that satisfies these requirements, effectively improves the crosslinking density, has excellent mechanical properties and heat resistance, and has no yellowing at high temperature.

Hereinafter, the thermosetting resin composition according to the present invention and a cured film for an optical device using the same will be described in detail. However, the following descriptions are merely exemplary descriptions of the present invention, and the technical spirit of the present invention is not limited by the following descriptions, and those of ordinary skill in the art to which the present invention pertains from this It will be understood that various modifications and equivalent other embodiments are possible. Therefore, the true technical protection scope of the present invention should be determined by the technical spirit of the appended claims.

According to one embodiment of the present invention, [A] (a1) unsaturated carboxylic acid or unsaturated carboxylic acid anhydride (hereinafter referred to as compound (a1)), (a2) an epoxy group-containing unsaturated compound (hereinafter referred to as compound (a2)), (a3) ) a copolymer of an olefinically unsaturated compound other than (a1) or (a2) (hereinafter referred to as compound (a3)); Compound [B] or isocyanuric acid derivative [B] having a polyfunctional thiol group It is to provide a thermosetting resin composition comprising.

First, copolymer [A] is obtained by a known polymerization method, that is, compound (a1), compound (a2), and compound (a3) can be synthesized by radical polymerization in a solvent in the presence of a polymerization initiator.

The copolymer [A] may contain the compound (a1) in an amount of 5 to 40% by weight, preferably 10 to 30% by weight, which is based on the heat resistance, chemical resistance, surface hardness, and preservation of the resulting cured film. It may be determined in consideration of stability.

Examples of the compound (a1) include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; and dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid, or anhydrides of these dicarboxylic acids. Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferably used from the point of copolymerization reactivity, heat resistance, and easy availability. These compounds may be used alone or in combination.

In addition, the copolymer [A] may contain 10 to 70% by weight of compound (a2), preferably 20 to 60% by weight, which takes into account the heat resistance and surface hardness of the resulting cured film or the storage stability of the copolymer. can be determined by

Examples of the compound (a2) include glycidyl acrylate, glycidyl methacrylate, glycidyl αethyl acrylate, glycidyl αnpropyl acrylate, glycidyl αnbutyl acrylate, 3,4 epoxybutyl acrylate, 3,4 epoxy butyl methacrylic acid, 6,7 epoxy heptyl acrylic acid, 6,7 epoxy heptyl methacrylic acid, 6,7 epoxy heptyl αethyl acrylic acid, ovinyl benzyl glycidyl ether, mvinyl benzyl glycidyl ether, pvinyl benzyl glycidyl ether and the like can be preferably used in view of increasing copolymerization reactivity and heat resistance and hardness of the resulting protective film. These compounds may be selected and used alone or in combination.

The copolymer [A] may contain 10 to 70% by weight of compound (a3), preferably 20 to 50% by weight, which may be determined in consideration of the storage stability of the copolymer and the heat resistance and surface hardness of the cured film. have.

As said compound (a3), For example, methacrylic acid alkyl esters, such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec butyl methacrylate, and t-butyl methacrylate; acrylic acid alkyl esters such as methyl acrylate and isopropyl acrylate; methacrylic acid cycloalkyl esters such as cyclohexyl methacrylate, 2methyl cyclohexyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, and isoboronyl methacrylate; acrylic acid cycloalkyl esters such as cyclohexyl acrylate, 2methyl cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, and isoboronyl acrylate; methacrylic acid aryl esters such as ethyl methacrylate and benzyl methacrylate; acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid; hydroxyalkyl esters such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; and styrene, omethyl styrene, mmethyl styrene, pmethyl styrene, vinyl toluene, p methoxy styrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1 and 3-butadiene, isoprene, and 2,3-dimethyl 1,3-butadiene. Among them, styrene, t-butyl methacrylate, dicyclopentenyl methacrylate, p-methoxy styrene, 2methyl cyclohexyl acrylate, 1,3-butadiene, etc. may be preferable in terms of copolymerization reactivity and heat resistance. These compounds may be used alone or in combination.

Such copolymer [A] has a carboxyl group, a carboxylic acid anhydride group or an epoxy group, and can be easily cured by heating without using a special curing agent in combination.

Examples of the solvent that can be used in the synthesis of the copolymer [A] include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether; and propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and propylene glycol butyl ether acetate.

As a polymerization initiator that can be used in the synthesis of the copolymer [A], a commonly known radical polymerization initiator can be used. For example, 2,2' azobis isobutyronitrile, 2,2' azobis (2,4 dimethylvaleronitrile), 2,2' azobis (4 methoxy 2,4 dimethylvaleronitrile), etc. azo compounds; organic peroxides such as benzoyl peroxide, t-butyl peroxy fivalate, and 1,1'bis(tbutyl peroxy)cyclohexane; and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to be used as a redox initiator.

The thermosetting resin composition of the present invention contains a compound [B] or an isocyanuric acid derivative [B] having a polyfunctional thiol group together with the copolymer [A], and these compounds [B] are added to the copolymer [A]. It can act as a curing agent for

The isocyanuric acid derivative has excellent reactivity, and the cured film obtained therefrom can secure a higher curing density, and as a result, it is possible to prevent deterioration of heat resistance, UV resistance, and chemical resistance of the cured film.

According to an embodiment of the present invention, the compound [B] having the polyfunctional thiol group may be any one or more selected from the following formula (1) compounds.

[Formula 1]

A is a compound represented by the following [Formula 2], and n is an integer of 1 to 4 repeating units in the main chain.

[Formula 2]

The * represents a bond other than C, wherein R ₁ is a linear or cyclic alkyl group having 1 to 6 carbon atoms, a linear or cyclic alkylene group having 2 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 20 carbon atoms. It may be at least one selected from the group consisting of arylene groups or a compound represented by the following formula (3).

[Formula 3]

The R ₃ to R ₅ may each independently be at least one selected from the group consisting of C, N, O, Si, P and S bonded to the A.

In addition, R ₃ to R ₅ may be present in a form that is not bound to A.

The content of the compound [B] having a polyfunctional thiol group is 0.1 to 50 parts by weight, preferably 0.1 to 40 parts by weight, based on 100 parts by weight of the copolymer [A] to form a cured film with high crosslinking density or various kinds of cured films It may be advantageous in terms of satisfying the tolerance and in preventing the problem of destabilizing the properties of the cured film or reducing adhesion by preventing the residual of the compound [B] having a polyfunctional thiol group inside the cured film.

Examples of the polyfunctional thiol group include 1,4,bis(3-mercaptobutyryloxy)butane), 1,3,5-tris(3-mercaptoburyloxetyl)-1,3,5-triazine-2 ,4,6(1H,3H,5H)-trione, pentaerythritone dedrakis (3-mercaptobutylate), etc. are mentioned.

Meanwhile, in another embodiment of the present invention, the copolymer [A] and the compound [B] having a polyfunctional thiol group or an isocyanuric acid derivative [B] may be included.

In addition, the isocyanuric acid derivative is a compound represented by the following [Formula 4].

[Formula 4]

wherein R ₆ to R ₈ are a linear or cyclic alkyl group having 1 to 6 carbon atoms, a linear or cyclic alkylene group having 2 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylene group having 7 to 20 carbon atoms, or the following [Formula 5 It is selected from the compounds represented by ].

[Formula 5]

The content of the isocyanuric acid derivative [B] is 0.1 to 50 parts by weight, preferably 0.1 to 40 parts by weight, based on 100 parts by weight of the copolymer [A] to form a cured film having a high crosslinking density or to exhibit various resistances of the cured film It may be advantageous in terms of preventing the problem of destabilizing the properties of the cured film or reducing adhesion by preventing the remaining of the isocyanuric acid derivative [B] inside the cured film.

Examples of the isocyanuric acid derivative include TEPIC-L, TEPIC-PAS, TEPIC-VL, TEPIC-UC of Nissan Chemical Industries, MeDAIC, DA-MGIC, MA-DGIC, MeDHIC, MACIC-1, and the like of Shikoku Chemical Corporation. can be heard

On the other hand, in another embodiment of the present invention, in addition to the copolymer [A] and the isocyanuric acid derivative [B], [C] a polymerizable compound having an ethylenically unsaturated bond (hereinafter referred to as a polymerizable compound [C]), [D] A thermal radical polymerization initiator (hereinafter referred to as thermal radical polymerization initiator [D]) may be contained.

In addition, [C] a polymerizable compound having an ethylenically unsaturated bond (hereinafter referred to as polymerizable compound [C]) and [D] a thermal radical polymerization initiator (hereinafter referred to as thermal radical polymerization initiator [D]) may be contained. . As the polymerizable compound [C], a monofunctional, bifunctional, or trifunctional or higher (meth)acrylate may have good polymerizability, and may be preferable in terms of improving heat resistance and surface hardness of the resulting cured film. Examples of the monofunctional (meth)acrylate include 1,4,bis(3-mercaptobutyryloxy)butane), 2-hydroxyethyl (meth)acrylate, carbitol (meth)acrylate, isobornyl (meth)acrylate, 3methoxy butyl (meth)acrylate, 2(meth)acryloyloxyethyl 2-hydroxypropyl phthalate, etc. are mentioned.

Examples of the bifunctional (meth)acrylate include 1,3,5-trine (3-mercaptoburyloxetyl)-1,3,5-triazine-2,4,6(1H,3H, 5H)-trione, ethylene glycol (meth) acrylate, 1,6 hexanediol (meth) acrylate, 1,9 nonanediol (meth) acrylate, propylene glycol (meth) acrylate, tetraethylene glycol (meth) ) acrylate, bisphenoxy ethyl alcohol fluorene diacrylate, and the like.

As said trifunctional or more than trifunctional (meth)acrylate, for example, pentaerythritol dedrakis (3-mercaptobutylate), trishydroxyethyl isocyanurate tri(meth)acrylate, trimethylpropane tri(meth) Acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are mentioned.

It can be used alone or in combination by selecting from these monofunctional, bifunctional, or trifunctional or more (meth)acrylates.

When the polymerizable compound [C] is included in the thermosetting resin composition, the content is 150 parts by weight or less, preferably 120 parts by weight or less, more preferably 0.1 to 100 parts by weight based on 100 parts by weight of the copolymer [A]. It may be advantageous in terms of adhesion of the cured film.

Examples of the thermal radical polymerization initiator [D] include 2,2'azobisisobutyronitrile, 2,2'azobis(2,4dimethylvaleronitrile), 2,2'azobis(4methoxy2) Azo compounds, such as 4 dimethylvaleronitrile) and 1,1' azobis 1-cyclohexyl nitrile; and organic peroxides such as benzoyl peroxide, t-butyl peroxide, and 1,1'bis(tbutylperoxy)cyclohexane.

The content of the thermal radical polymerization initiator [D] is 20 parts by weight or less, preferably 15 parts by weight or less, and more preferably 0.1 to 12 parts by weight based on 100 parts by weight of the copolymer [A]. It can be advantageous in terms of

The thermosetting resin composition of the present invention is prepared by uniformly mixing each component of the copolymer [A] and the compound [B] having a polyfunctional thiol group, as needed, the polymerizable compound [C] and the thermal radical polymerization initiator [D]. can be manufactured. Usually, the thermosetting resin composition of the present invention is dissolved in a suitable solvent and used in a solution state. That is, the copolymer [A], the compound [B] having a polyfunctional thiol group, the polymerizable compound [C], the thermal radical polymerization initiator [D] and other additives are mixed in a predetermined ratio to form a thermosetting resin composition in a solution state will be prepared The composition of the present invention must contain the copolymer [A] and the compound [B] having a polyfunctional thiol group.

As a solvent used for the preparation of the thermosetting resin composition of the present invention, each component of the copolymer [A], the compound having a polyfunctional thiol group [B], the polymerizable compound [C], and the thermal radical polymerization initiator [D] was uniformly It can be dissolved easily, and it is ok as long as it does not react with any one component. Specifically, For example, Alcohol, such as methanol and ethanol; ethers such as tetrahydrofuran, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether; and propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and propylene glycol butyl ether acetate. Among these solvents, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and propylene glycol methyl ether acetate may be preferable in terms of solubility, reactivity with each component, and convenience of forming a coating film.

Moreover, it is also possible to use a high boiling point solvent together with the said solvent. As a high boiling point solvent which can be used together, for example, Nmethyl formamide, N,N dimethyl formamide, Nmethyl acetamide, N,N dimethyl acetamide, Nmethyl pyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, etc. can be heard

The thermosetting resin composition of this invention may contain other components other than the above as needed in the range which does not impair the objective of this invention. Here, as another component, surfactant for improving applicability|paintability is mentioned. Examples of the surfactant include fluorine and silicone-based surfactants, such as FC129, FC170C, and FC430 manufactured by 3M, KP322, KP323, KP340, and KP341 manufactured by Shin-Etsu Silicone. These surfactants are used in an amount of 5 parts by weight or less, preferably 2 parts by weight or less, and more preferably 0.1 to 1.5 parts by weight based on 100 parts by weight of the copolymer [A] to prevent foaming during application of the thermosetting resin composition. It may be advantageous in terms of prevention.

The composition solution prepared as described above can be used after filtration using a filter having a pore diameter of about 0.1 to 5 μm.

The target protective film can be obtained by apply|coating the thermosetting resin composition of this invention to a base substrate, and processing it at 150-300 degreeC in oven for 10-100 minutes.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to these Examples.

<Production Example>

2,2'azobis as a polymerization initiator based on 100 parts by weight of a total content of monomers (compound (al), compound (a2), compound (a3)) used in the synthesis of the copolymer in a reaction vessel equipped with a cooling tube and a stirrer 5 parts by weight of isobutyronitrile was dissolved in 200 parts by weight of diethylene glycol dimethyl ether as a solvent. Subsequently, 20% by weight of styrene, 30% by weight of methacrylic acid, 40% by weight of glycidyl methacrylate and 10% by weight of dicyclopentenyloxyethyl methacrylate were added, and after nitrogen substitution, gently stirring was started.

The temperature of the solution was raised to 80° C. and this temperature was maintained for 4 hours to obtain a polymer solution including copolymer [A1]. The solid content concentration of the obtained polymer solution was 33 weight%.

<Example 1>

100 parts by weight of the copolymer [A1] obtained in Preparation Example (based on solid content) and 100 parts by weight of the copolymer [A1] as a compound [B] having a polyfunctional thiol group as 1,4,bis(3-mer) 20 parts by weight of captobutyryloxy)butane (Showa Denko's Karenz MT BD1) and 0.1 parts by weight of 3M's FC430 (fluorine-based surfactant) as a surfactant are mixed, and diethylene glycol dimethyl ether and Nmethyl pyrrolidone mixed solvent (weight ratio 80) : 20), and the solid content concentration was 25% by weight. Then, it filtered with a filter with a pore diameter of 0.45 micrometers, and the thermosetting resin composition solution (S1) was prepared.

<Example 2>

1,3,5-tris ( 3-Mercaptoburyloxetyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (Showa Denko Karenz MT NR1) 20 parts by weight, as a surfactant, Shin-Etsu Silicone After mixing 0.1 parts by weight of KP341 (silicone-based surfactant) and dissolving it in a mixed solvent of diethylene glycol dimethyl ether and Nmethyl pyrrolidone (weight ratio 80:20), the solid content concentration was 25% by weight. Then, it filtered with a filter with a pore diameter of 0.45 micrometers, and the thermosetting resin composition solution (S2) was prepared.

<Example 3>

100 parts by weight of the copolymer [A1] obtained in Preparation Example (based on the solid content) and 100 parts by weight of the copolymer [A1] as a compound [B] having a polyfunctional thiol group, pentaerythritone dedrakis (3 20 parts by weight of the compound represented by mercaptobutylate) (Showa Denko Karenz MT PE1), 100 parts by weight of trimethylpropane trimethacrylate as the polymerizable compound [C], 5 benzoyl peroxide as the thermal radical polymerization initiator [D] 3M's FC430 (0.1 parts by weight of a fluorine-based surfactant was mixed and dissolved in a mixed solvent of diethylene glycol dimethyl ether and Nmethyl pyrrolidone (weight ratio 80:20) as parts by weight and surfactant so that the solid content concentration was 25% by weight Then, it filtered with a filter with a pore diameter of 0.45 micrometers, and the thermosetting resin composition solution (S3) was prepared.

<Example 4>

100 parts by weight of the copolymer [A1] obtained in Preparation Example (based on the solid content) and 100 parts by weight of the copolymer [A1] as a compound [B] having a polyfunctional thiol group as 1,4,bis(3-mer) 10 parts by weight of captobutyryloxy)butane (Showa Denko Karenz MT BD1), 100 parts by weight of pentaerythritol tetramethacrylate as polymerizable compound [C], 1,1' azobis1 as thermal radical polymerization initiator [D] 5 parts by weight of cyclohexylnitrile and 0.1 parts by weight of Shin-Etsu Silicone KP341 (silicone-based surfactant) as a surfactant were mixed and dissolved in a mixed solvent of diethylene glycol dimethyl ether and Nmethyl pyrrolidone (weight ratio 80:20), and then the solid content concentration was made to be 25% by weight. Then, it filtered with a filter with a pore diameter of 0.45 micrometers, and the thermosetting resin composition solution (S4) was prepared.

<Example 5>

1,3,5-tris ( 3-Mercaptoburyloxetyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (Showa Denko Karenz MT NR1) 10 parts by weight, polymerizable compound [C] Mix 100 parts by weight of dipentaerythritol pentamethacrylate as a thermal radical polymerization initiator [D] 5 parts by weight of 1,1'azobis 1 cyclohexylnitrile as a surfactant, 0.1 parts by weight of Shin-Etsu Silicone KP341 (silicone-based surfactant) as a surfactant After dissolving in a mixed solvent of diethylene glycol dimethyl ether and Nmethyl pyrrolidone (weight ratio 80:20), the solid content concentration was 25% by weight. Then, it filtered with a filter with a pore diameter of 0.45 micrometers, and the thermosetting resin composition solution (S5) was prepared.

<Comparative Example 1>

A thermosetting resin composition solution was prepared in the same manner as in Example 1, except that compound [B] having a polyfunctional thiol group was not added.

<Comparative Example 2>

A thermosetting resin composition solution was prepared in the same manner as in Example 3, except that compound [B] having a polyfunctional thiol group was not added.

<Comparative Example 3>

A thermosetting resin composition solution was prepared in the same manner as in Comparative Example 2, except that the content of the polymerizable compound [C] was 200 parts by weight.

<Formation of cured film>

The thermosetting resin composition was applied to a film thickness of 2 μm on a glass substrate using a spin coater, and baked in a clean oven at 220° C. for 30 minutes to form a cured film on the glass substrate.

The evaluation methods for the Examples and Comparative Examples are as follows.

(1) Adhesion

Using a cutter knife on the cured film according to the checkered tape method, 11 rows of 1 mm apart cuts are made to the depth of the top surface of the glass substrate, and 11 rows of 1 mm spacing are made to the depth of the top surface of the glass substrate again in the vertical direction. After forming the checkerboard pattern, an adhesive tape (Elcometer, Part Number K0001539M001) was attached to the checkerboard pattern and peeled off by performing an adhesion test, the number of peeled checkerboard patterns was measured, and the adhesiveness of the cured film was evaluated according to the following criteria.

○: The number of peeled checkerboard patterns 5 or less

△: 6 to 49 pieces of peeled checkerboard patterns

×: 50 or more of peeled checkerboard patterns

(2) Surface hardness

For the cured film, the surface hardness was evaluated by performing a pencil hardness test method according to the pencil hardness method (test standard: ASTM D3363).

(3) Transparency

The transmittance of the cured film in a wavelength range of 400 to 700 nm was measured using a spectrophotometer (UV-3101PC, manufactured by Shimatsu Corporation), and the transparency of the cured film was evaluated according to the following criteria.

○: Minimum transmittance of 95% or more

△: minimum transmittance of 90% or more, less than 95%

×: Minimum transmittance less than 90%

(4) flatness

The surface unevenness of the cured film was irradiated using α-step (manufacturer: KLA Tencor, equipment name: AS-500), and the step difference of the substrate was measured.

(5) UV resistance

The transmittance of the protective film was measured at 400 to 700 nm using a spectrophotometer (UV-3101PC, manufactured by Shimatsu Corporation). Separately, the cured film was irradiated with UV (wavelength 254 nm, irradiation amount 200 mJ/cm 2 ), and transmittance was measured in the same manner. From each transmittance, the UV resistance of the protective film was evaluated according to the following criteria.

○: Transmission spectrum change within 1%

×: change in transmission spectrum exceeds 1%

(6) Heat resistance (degree of yellowing)

The transmittance of the protective film was measured at 400 to 700 nm using a spectrophotometer (UV-3101PC, manufactured by Shimatsu Corporation). Separately, the cured film was heated in a clean oven at 240° C. for 60 minutes, and transmittance was measured in the same manner. From each transmittance, the heat resistance of the protective film was evaluated according to the following criteria.

○: Transmission spectrum change within 1%

×: change in transmission spectrum exceeds 1%

(7) acid resistance

After the glass substrate on which the cured film was formed was immersed in 25 wt% hydrochloric acid aqueous solution at 30° C. for 20 minutes, the change in appearance of the cured film was observed to evaluate acid resistance.

(8) alkali resistance

After the glass substrate on which the cured film was formed was immersed in 10 wt% sodium hydroxide aqueous solution at 30° C. for 60 minutes, the change in appearance of the cured film was observed to evaluate alkali resistance.

The evaluation results are shown in Table 1 below.

division Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 adhesion ○ ○ ○ ○ ○ ○ ○ ○ surface hardness 5H 5H 5H 5H 5H 3H 3H 5H Transparency ○ ○ ○ ○ ○ ○ ○ ○ planarity 0.1㎛
Below 0.1㎛
Below 0.1㎛
Below 0.1㎛
Below 0.1㎛
Below 0.3㎛
Below 0.3㎛
Below 0.1㎛
Below UV resistance ○ ○ ○ ○ ○ × × × heat resistance
(degree of yellowing) ○ ○ ○ ○ ○ × × × acid resistance no change no change no change no change no change no change no change no change alkali resistance no change no change no change no change no change no change no change no change

From the results of Table 1, it can be seen that when a compound having a polyfunctional thiol group is included as the curable compound, the surface hardness is improved and planarity is improved as the crosslinking density is effectively increased, and UV resistance and heat resistance are also improved. have.

When the compound having a polyfunctional ethylenically unsaturated group as in Comparative Example 3 is used in excess, the formation of a cured film having a surface hardness of about 5H can be equalized, but the heat resistance is poor and the yellowing phenomenon is worsened.

<Example 1-1>

Nissan Chemical Industries, among the compounds represented by Formula 1 as an isocyanuric acid derivative [B], using 100 parts by weight of the copolymer [A1] obtained in Preparation Example (based on the solid content) and 100 parts by weight of the copolymer [A1] 20 parts by weight of TEPIC-L and 0.1 parts by weight of 3M's FC430 (fluorine-based surfactant) as a surfactant were mixed and dissolved in a mixed solvent of diethylene glycol dimethyl ether and Nmethyl pyrrolidone (weight ratio 80:20), and the solid content was It was made to be 25 weight%. Then, it filtered with a filter with a pore diameter of 0.45 micrometers, and the thermosetting resin composition solution (S1) was prepared.

<Example 2-1>

Nisan Chemical Industries, among the compounds represented by Formula 1 as an isocyanuric acid derivative [B], with 100 parts by weight of the copolymer [A1] obtained in Preparation Example (based on the solid content) and 100 parts by weight of the copolymer [A1] 20 parts by weight of TEPIC-PAS, 0.1 parts by weight of Shin-Etsu Silicone's KP341 (silicone-based surfactant) as a surfactant, and dissolved in a mixed solvent of diethylene glycol dimethyl ether and Nmethyl pyrrolidone (weight ratio 80:20) The concentration was set to 25% by weight. Then, it filtered with a filter with a pore diameter of 0.45 micrometers, and the thermosetting resin composition solution (S2) was prepared.

<Example 3-1>

Nissan Chemical Industries, among the compounds represented by Formula 1 as an isocyanuric acid derivative [B], using 100 parts by weight of the copolymer [A1] obtained in Preparation Example (based on the solid content) and 100 parts by weight of the copolymer [A1] 20 parts by weight of TEPIC-VL, 100 parts by weight of trimethylpropane trimethacrylate as a polymerizable compound [C], 5 parts by weight of benzoyl peroxide as a thermal radical polymerization initiator [D], and 3M FC430 (fluorosurfactant) as a surfactant After mixing 0.1 parts by weight and dissolving in a mixed solvent of diethylene glycol dimethyl ether and Nmethyl pyrrolidone (weight ratio 80:20), the solid content concentration was 25% by weight, and then filtered through a filter having a pore diameter of 0.45 μm A thermosetting resin composition solution (S3) was prepared.

<Example 4-1>

100 parts by weight of the copolymer [A1] obtained in Preparation Example (based on the solid content) and 100 parts by weight of the copolymer [A1] as an isocyanuric acid derivative [B] among the compounds represented by Formula 1, Shikoku Chemical Corporation 10 parts by weight of DA-MGIC, 100 parts by weight of pentaerythritol tetramethacrylate as a polymerizable compound [C], 5 parts by weight of 1,1' azobis 1 cyclohexylnitrile as a surfactant [D], as a surfactant 0.1 parts by weight of Shin-Etsu Silicone KP341 (silicone-based surfactant) was mixed and dissolved in a mixed solvent of diethylene glycol dimethyl ether and Nmethyl pyrrolidone (weight ratio 80:20) so that the solid content concentration was 25% by weight. Then, it filtered with a filter with a pore diameter of 0.45 micrometers, and the thermosetting resin composition solution (S4) was prepared.

<Example 5-1>

100 parts by weight of the copolymer [A1] obtained in Preparation Example (based on the solid content) and 100 parts by weight of the copolymer [A1] as an isocyanuric acid derivative [B] among the compounds represented by Formula 1, Shikoku Chemical Corporation 10 parts by weight of MA-DGIC, 100 parts by weight of dipentaerythritol pentamethacrylate as polymerizable compound [C], 5 parts by weight of 1,1' azobis 1 cyclohexylnitrile as thermal radical polymerization initiator [D], surfactant 0.1 parts by weight of Shin-Etsu Silicone KP341 (silicone-based surfactant) was mixed and dissolved in a mixed solvent of diethylene glycol dimethyl ether and Nmethyl pyrrolidone (weight ratio 80:20), and the solid content concentration was 25% by weight. Then, it filtered with a filter with a pore diameter of 0.45 micrometers, and the thermosetting resin composition solution (S5) was prepared.

<Comparative Example 1-1>

A thermosetting resin composition solution was prepared in the same manner as in Example 1, except that the isocyanuric acid derivative [B] was not added.

<Comparative Example 2-1>

A thermosetting resin composition solution was prepared in the same manner as in Example 3, except that the isocyanuric acid derivative [B] was not added.

<Comparative Example 3-1>

A thermosetting resin composition solution was prepared in the same manner as in Comparative Example 2, except that the content of the polymerizable compound [C] was 200 parts by weight.

<Formation of cured film>

The thermosetting resin composition was applied to a film thickness of 2 μm on a glass substrate using a spin coater, and baked in a clean oven at 220° C. for 30 minutes to form a cured film on the glass substrate.

The evaluation methods for the Examples and Comparative Examples are as follows.

(1) Adhesion

Using a cutter knife on the cured film according to the checkered tape method, 11 rows of 1 mm apart cuts are made to the depth of the top surface of the glass substrate, and 11 rows of 1 mm spacing are made to the depth of the top surface of the glass substrate again in the vertical direction. After forming the checkerboard pattern, an adhesive tape (Elcometer, Part Number K0001539M001) was attached to the checkerboard pattern and peeled off by performing an adhesion test, the number of peeled checkerboard patterns was measured, and the adhesiveness of the cured film was evaluated according to the following criteria.

○: Number of peeled checkerboard patterns 5 or less

△: Number of peeled checkerboard patterns 6 to 49

×: 50 or more of the number of peeled checkerboard patterns

(2) Surface hardness

The surface hardness of the cured film was evaluated by performing a pencil hardness test method according to the pencil hardness method (test standard: ASTM D3363).

(3) Transparency

The transmittance of the cured film in a wavelength range of 400 to 700 nm was measured using a spectrophotometer (UV-3101PC, manufactured by Shimatsu Corporation), and the transparency of the cured film was evaluated according to the following criteria.

○: Minimum transmittance of 95% or more

△: minimum transmittance of 90% or more, less than 95%

×: Minimum transmittance less than 90%

(4) flatness

The surface unevenness of the cured film was irradiated using α-step (manufacturer: KLA Tencor, equipment name: AS-500), and the step difference of the substrate was measured.

(5) UV resistance

The transmittance of the protective film was measured at 400 to 700 nm using a spectrophotometer (UV-3101PC, manufactured by Shimatsu Corporation). Separately, the cured film was irradiated with UV (wavelength 254 nm, irradiation amount 200 mJ/cm 2 ), and transmittance was measured in the same manner. From each transmittance, UV resistance of the protective film was evaluated according to the following criteria.

○: Transmission spectrum change within 1%

×: change in transmission spectrum exceeds 1%

(6) Heat resistance (degree of yellowing)

The transmittance of the protective film was measured at 400 to 700 nm using a spectrophotometer (UV-3101PC, manufactured by Shimatsu Corporation). Separately, the cured film was heated in a clean oven at 240° C. for 60 minutes, and transmittance was measured in the same manner. From each transmittance, the heat resistance of the protective film was evaluated according to the following criteria.

○: Transmission spectrum change within 1%

×: change in transmission spectrum exceeds 1%

(7) acid resistance

After the glass substrate on which the cured film was formed was immersed in 25 wt% hydrochloric acid aqueous solution at 30° C. for 20 minutes, the change in appearance of the cured film was observed to evaluate acid resistance.

(8) alkali resistance

After the glass substrate on which the cured film was formed was immersed in 10 wt% sodium hydroxide aqueous solution at 30° C. for 60 minutes, the change in appearance of the cured film was observed to evaluate alkali resistance.

The evaluation results are shown in Table 2 below.

division Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 adhesion ○ ○ ○ ○ ○ ○ ○ ○ surface hardness 5H 5H 5H 5H 5H 3H 3H 5H Transparency ○ ○ ○ ○ ○ ○ ○ ○ planarity 0.1㎛
Below 0.1㎛
Below 0.1㎛
Below 0.1㎛
Below 0.1㎛
Below 0.3㎛
Below 0.3㎛
Below 0.1㎛
Below UV resistance ○ ○ ○ ○ ○ × × × heat resistance
(degree of yellowing) ○ ○ ○ ○ ○ × × × acid resistance no change no change no change no change no change no change no change no change alkali resistance no change no change no change no change no change no change no change no change

From the results of Table 2, when a compound having an isocyanuric acid derivative is included as the curable compound, the surface hardness is improved and planarity is improved as the crosslinking density is effectively increased, and UV resistance and heat resistance are also improved. Able to know.

When the compound having a polyfunctional ethylenically unsaturated group as in Comparative Example 3 is used in excess, the formation of a cured film having a surface hardness of about 5H can be equalized, but the heat resistance is poor and the yellowing phenomenon is worsened.

Claims (9)

(a1) a copolymer [A] of an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride, (a2) an epoxy group-containing unsaturated compound, (a3) an olefinically unsaturated compound other than the above (a1) or (a2); and an isocyanuric acid derivative [B],
The isocyanuric acid derivative [B] is included in an amount of 0.1 to 40 parts by weight based on 100 parts by weight of the copolymer [A],
The isocyanuric acid derivative [B] is a thermosetting resin composition comprising a compound represented by the following [Formula 4]:
Formula (4)

wherein R ₆ to R ₈ are a linear or cyclic alkyl group having 1 to 6 carbon atoms, a linear or cyclic alkylene group having 2 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylene group having 7 to 20 carbon atoms, or the following [Formula 5 It is selected from the compounds represented by ].
Formula (5)

. delete delete delete delete According to claim 1,
The thermosetting resin composition is a thermosetting resin composition, characterized in that it further comprises 150 parts by weight or less of a polymerizable compound having an ethylenically unsaturated bond with respect to 100 parts by weight of the copolymer [A]. According to claim 1,
The thermosetting resin composition is a thermosetting resin composition, characterized in that it further comprises 20 parts by weight or less of a thermal radical polymerization initiator based on 100 parts by weight of the copolymer [A]. A cured film made of the thermosetting resin composition according to any one of claims 1, 6 and 7. The cured film according to claim 8, wherein the cured film is a color filter protective film of an optical device.