KR20170057460A - Curable resin having excellent post-curing flexibility, methacrylated curable resin, and liquid crystal sealing agent composition - Google Patents

Abstract

(식 중, X, R¹, R², Y, A환은 소정의 기이고, m은, 1 내지 7의 범위의 수이다)The present invention relates to a curable resin composition which forms a cured product having flexibility capable of maintaining an adhesive state even when the flexible liquid crystal display is bent and has a low liquid stain resistance and hardly affects liquid crystal alignability, And a liquid crystal encapsulating composition. The present invention is a curable resin represented by the following formula (1):

(Wherein X, R ¹ , R ² , Y, A ring is a predetermined group and m is a number in the range of 1 to 7)

Description

TECHNICAL FIELD [0001] The present invention relates to a curable resin, a (meth) acryl-curable resin, and a liquid crystal encapsulant composition having excellent flexibility after curing,

The present invention relates to a curable resin and a (meth) acrylated curable resin suitable for liquid crystal encapsulants exhibiting excellent flexibility even after curing, and a liquid crystal encapsulant composition comprising these curable resins.

In the production of a liquid crystal display device such as a liquid crystal panel, for example, a liquid crystal sealing agent is applied to the outer periphery of any one of two substrates constituting a liquid crystal panel, and a predetermined amount of liquid crystal is dropped A liquid crystal dropping method in which two substrates are bonded under vacuum and then returned to the atmospheric pressure to fill the space between the substrates with each other to cure the liquid crystal sealing agent has been popular.

In the liquid crystal dropping method, a radical polymerization reactive compound based on an epoxy acrylate compound is widely used as a liquid crystal sealing agent from the viewpoint of high-speed curing (see, for example, Patent Document 1).

Japanese Patent Application Laid-Open No. 2007-297470

In the liquid crystal dropping method, a sealant is applied to one of two substrates in a frame shape to form a frame seal, liquid crystal is dropped on any one of the substrates, both substrates are bonded under vacuum, After the curing agent is photo-cured, it is thermally cured at a temperature higher than the NI point (Nematic Isotropic point) of the liquid crystal, thereby thermally curing the liquid crystal sealing agent and aligning the liquid crystal.

In the case of a large panel such as a TV, since the panel is large, there is a distance of a certain distance or more from the dropping point of the liquid crystal drop to the frame seal, the liquid crystal is sealed and the liquid crystal sealing agent Or the contact time is short, mainly the liquid crystal sealing agent is photo-cured and then contacted with the liquid crystal.

On the other hand, in a small liquid crystal panel whose demand is increasing recently due to the spread of smart phones and tablet-type terminals, since the distance from the liquid drop drop point to the frame seal is short, until the liquid crystal sealing agent is UV- It is in contact with the liquid crystal in the cured state, or the contact time is long. Therefore, the liquid crystal staining property in the uncured state of the liquid crystal sealing agent becomes more problematic than the conventional one.

It is difficult to say that the liquid crystal encapsulant reactive with radical polymerization based on an epoxy compound containing a conventional epoxy / acrylic compound sufficiently meets the request for solving such a problem.

In addition, a flexible, lightweight and freely bendable flexible liquid crystal display, such as electronic paper, is expected to be developed on the market. The flexible liquid crystal display is manufactured using a flexible substrate such as a plastic film in place of the conventional rigid glass substrate.

As for the liquid crystal encapsulant, conventionally, since it forms a relatively rigid cured product, it is suitable for adhering a substrate having little change in shape such as glass. However, in a flexible display including a flexible substrate such as a film, It is difficult to say that it is sufficiently suitable for the application because breakage or peeling occurs due to the shape change caused by shrinkage of the substrate.

From this point of view, a liquid crystal sealing material having sufficient flexibility even after curing is demanded as a sealing material particularly suitable for a flexible liquid crystal display.

In view of the above, it is an object of the present invention to provide a curable resin composition which is capable of forming a cured product having flexibility capable of maintaining an adhesive state even when the flexible liquid crystal display is bent and also has a curable resin hardly affected by liquid crystal orientation, And a liquid crystal encapsulant composition comprising a curable resin.

The present invention includes the following aspects.

(1) a curable resin represented by the following formula (1):

Wherein m is a number in the range of 1 to 7, R ¹ is each independently a hydrogen atom, a glycidyl group or a methyl glycidyl group, R ² are each independently of one another a hydrogen atom or a methyl group, Each independently represents an aromatic ring or a heteroaromatic ring containing at least one carbon atom and the number of heteroatoms of at least 5, and X is independently selected from the group consisting of a hydrogen atom, a hydroxyl group, a glycidyloxy group, Or methylglycidyloxy group, and Y is a group represented by the following formula (1a):

(Wherein Y ¹ is each independently an alkylene group having 2 to 5 carbon atoms and n is a number in the range of 1 to 250)

(Wherein Y ² is independently a direct bond or an alkylene group having 1 or 2 carbon atoms, R ³ is each independently a hydrogen atom or a methyl group, p and q are each independently 0 or more, And the sum of them is a number in the range of 1 to 200), or a group having a structure in which some or all of unsaturated bonds in the formula (1b) are hydrogenated, and in R ¹ and X, a glycidyl group or methyl glycidyl The mean x of the total number of R ¹ and the X as the glycidyloxy group or the methylglycidyloxy group is 1 or more.

(2) The polyimide resin composition according to the above (1), wherein the number of carbon atoms contained in the A ring is 4 to 40, the number of oxygen atoms is 0 to 5, the number of nitrogen atoms is 0 to 5, the number of sulfur atoms is 0 to 5, Wherein the number of ring structures contained in the curing resin is 1 to 5.

(3) A (meth) acrylated curable resin obtained by reacting at least a part of an epoxy group, a hydroxyl group and an unsaturated bond of the curable resin according to (1) or (2) with (meth) acrylic acid and / or (meth) acrylic acid anhydride.

(4) A liquid crystal sealing composition comprising the curable resin according to (1) or (2) and / or the (meth) acryl-curable resin according to (3)

(5) The liquid crystal sealing composition according to (4), wherein the content of the curable resin and / or the (meth) acryl-curable resin in the liquid crystal sealing composition is from 5 to 95% by weight.

(6) The liquid crystal sealing composition according to (4) or (5), further comprising a compound H having an ethylenic unsaturated group and / or an epoxy group (excluding the above-mentioned curable resin and (meth) And a liquid crystal polymer.

According to the present invention, a cured product having flexibility capable of maintaining an adhesive state even when the flexible liquid crystal display is bent is formed, and a curable resin and a curable resin having low liquid stain resistance and hardly influencing the liquid crystal orientation property are included Is provided.

Hereinafter, the present invention will be described in detail. In the present specification, (meth) acryl means methacryl and / or acryl, and (meth) acrylate means methacrylate and / or acrylate.

[Curable resin of the present invention]

The curable resin of the present invention is represented by the following formula (1).

The curable resin of the present invention has a flexible portion including an ether portion of a block parenthesized with the suffix of m and a predetermined group Y. The cured product obtained by curing the curable resin of the present invention has flexibility It is considered to exhibit rubber elasticity and is excellent in flexibility. As shown by the formula (1), the curable resin of the present invention has a flexible polymer structure, whereby the cross-linking density of the cured product of the curable resin of the present invention is suitably decreased, .

In addition, the curable resin of the present invention has an aromatic ring-containing structure called the A ring, and the curable resin of the present invention having such a predetermined structure has low liquid stain resistance.

(for m)

In the formula (1), m is a number in the range of 1 to 7, and preferably in the range of 1 to 5, and more preferably in the range of 1 to 3, from the viewpoints of viscosity and handleability of the curable resin of the present invention desirable. The curable resin of the present invention can be produced, for example, by a production method described later, and in that case, a mixture of a plurality of kinds of compounds having different numbers of m may be obtained.

(For X)

In the formula (1), each X independently represents a hydrogen atom, a hydroxyl group, a glycidyloxy group or a methylglycidyloxy group. When X is a hydroxyl group, a glycidyloxy group or a methylglycidyloxy group, as described later, the moiety may cause a crosslinking reaction, and (meth) acrylic group may be introduced into the moiety.

From the viewpoint of low liquid crystal staining property, such X is preferably a hydroxyl group and a glycidyloxy group.

(For R ¹ )

In the formula (1), R ¹ is each independently a hydrogen atom, a glycidyl group or a methyl glycidyl group. As described later, the group containing R ¹ can cause a cross-linking reaction, and (meth) acryl groups can also be introduced into the part. When m is a number of 2 or more, R ^{1 in} each block enclosed in parentheses suffixed with m is also independent and may be the same or different from each other.

From the viewpoint of low liquid crystal contamination, such R ¹ is preferably a hydrogen atom and a glycidyl group.

In the curable resin of the present invention represented by the above formula (1), R ¹ which is a glycidyl group or methylglycidyl group, X which is a glycidyloxy group or methylglycidyloxy group (that is, R ¹ having an epoxy group and X) is 1 or more, preferably 2 or more. As described above, since the curable resin has a number of crosslinkable groups of a certain number or more and has the above-mentioned flexible portion, the flexibility (hereinafter also referred to as "flexibility after curing") of the cured product is also ensured while securing the curability and adhesiveness required for the liquid crystal sealing agent ) Can also be achieved.

X represents a physical property of the liquid crystal encapsulant composition containing the curable resin of the present invention, which will be described later, such as workability such as coating properties that affect viscosity, for example, strength after curing, , It is preferably 2 or more, more preferably 2 to 16, still more preferably 2 to 8, as described above.

The average molecular weight and the molecular weight distribution of the curable resin were measured by high performance liquid chromatography (HPLC) and liquid chromatography mass spectrometry (LC-MS) or gel filtration / permeation chromatography (GPC / GFC) , And the epoxy equivalent of the curable resin is further measured. From this measurement result, x in the above formula (1) can be calculated.

(For R ² )

In the above formula (1), R ² is each independently a hydrogen atom or a methyl group, and is preferably a hydrogen atom in view of the low liquid crystal contamination of the curable resin of the present invention. When m is a number of 2 or more, R ^{2 in} each block enclosed in parentheses suffixed with m is also independent and may be the same or different from each other.

(For A circle)

In the above formula (1), each A ring is independently an aromatic ring having 5 or more carbon atoms and a total number of hetero atoms, or one or more aromatic rings, or a group containing a heteroaromatic ring. When the sum of the number of carbon atoms and the number of hetero atoms is 5 or more, when the whole ring A is a carbon atom and a hetero atom constituting the ring, or a group having a carbon atom or a hetero atom in the ring constituting atom, And the total number of carbon atoms and the number of hetero atoms including the group is 5 or more.

As to the A ring, it is preferable that the number of carbon atoms contained therein is 4 to 40, the number of oxygen atoms is 0 to 5, the number of nitrogen atoms is 0 to 3, and the number of oxygen atoms is 0 to 5, from the viewpoints of viscosity and handling property of the curable resin of the present invention and a liquid crystal sealing composition, 5, the number of sulfur atoms is 0 to 5, and the number of the ring structures contained in the ring A is 1 to 5.

The ring structures (aromatic rings and heteroaromatic rings) contained in the A ring may be either singly or in combination of two or more, and the ring structure may be a monocyclic structure or a condensed ring structure. These ring structures may be bonded to each other via a direct bond or a linking group.

Examples of the linking group include an alkylene group having 1 to 4 carbon atoms, an alkylidene group having 2 to 4 carbon atoms, an ether group, an ester group, a keto group, a sulfide group and a sulfonyl group. In the above formula (1), the oxygen atom bonded to the A ring and the ring structure of X and the A ring may be bonded via this connecting group.

Each of these ring structures may independently have a substituent. Examples of such a substituent include an alkyl group, an alkoxy group, an acyl group, a formyl group, a carboxyl group, an ester group, a cyano group, a nitro group, a sulfo group, an amide group, a hydroxyl group, a mercapto group and a silyl group.

Examples of the ring structure included in the A ring include a benzene ring, a naphthalene ring, a fluorene ring, an anthracene ring, a furan ring, a pyrrole ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, And those in which the substituent is bonded to the ring thereof.

When m is a number of 2 or more, the A rings in the individual blocks enclosed in parentheses suffixed with m are also independent and may be the same or different from each other.

(For Y)

Subsequently, Y in the formula (1) is a group having a structure obtained by hydrogenating a part or all of the unsaturated bonds in the following formulas (1a) and (1b) or formula (1b) When m is a number of 2 or more, the Y groups in the individual blocks enclosed in parentheses suffixed with m are also independent and may be the same or different from each other.

In formula (1a), Y ¹ is each independently an alkylene group having 2 to 5 carbon atoms, and n is a number in the range of 1 to 250. Examples of the alkylene group include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group and a neopentyl group. From the viewpoints of flexibility and liquid crystal staining property of the curable resin of the present invention, Y ¹ is preferably an ethylene group or a tetramethylene group, and from the viewpoint of flexibility and handleability of the curable resin of the present invention, n is preferably 5 To 70, and more preferably in the range of 10 to 50. < RTI ID = 0.0 >

When n is a number of 2 or more, Y ^{1 s in} each repeat unit parenthesized by subscripts of n are also independent and may be the same or different from each other.

In formula (1b), Y ² is independently a direct bond or an alkylene group having 1 or 2 carbon atoms, R ³ is each independently a hydrogen atom or a methyl group, p and q are each independently 0 or more And their sum is a number in the range of 1 to 200. When p or q is 2 or more, there are a plurality of repeating units bound in parentheses attached with these subscripts, but R ^{3 in} each repeating unit may also be independent of one another and may be different from each other. These repeating units can be bonded at random in the range of p or q.

The total number of p and q is preferably a number in the range of 5 to 70, more preferably in the range of 10 to 50, from the viewpoints of handling properties of the curable resin of the present invention and flexibility after curing.

(for m, n, p, q)

M representing the number of predetermined blocks (repeating units) relating to the above-described formula (1) is determined by the amount of the starting material of the curable resin of the present invention to be described later, or the GPC measurement of the resin (or a (meth) Can be estimated from the results. The total value of n and p and q can be estimated from the GPC measurement results of the curable resin (or (meth) acrylated curable resin to be described later), and they can also be estimated from the GPC measurement results of the curable resin synthesis raw material. The values of p and q can be analyzed by IR or the like.

≪ Properties of curable resin &

The viscosity of the curable resin of the present invention described above is usually 1,000 to 2,000,000 mPa · s. As will be described later, the curable resin of the present invention is suitable for use as a liquid crystal sealing agent. However, when used in this application, the viscosity of the curable resin is preferably from 3,000 to 2,000,000 mPa · S. In the present specification, the viscosity is a value measured at 25 캜 using an E-type viscometer.

The viscosity of the curable resin can be adjusted by, for example, changing m or the like in the formula (1) and / or changing the ratio of the hydroxyl groups in the curable resin (for example, when R ¹ is a hydrogen atom) .

When the curable resin is used as a liquid crystal sealing agent, the epoxy equivalent is preferably 400 to 10,000 g / eq, more preferably 500 to 5,000 g / eq, from the viewpoint of achieving both adhesion and flexibility. The epoxy equivalent of the curable resin is determined by the average molecular weight of the curable resin and the number of epoxy groups (R ¹ , for example, a glycidyl group) per block (repeating unit) parenthesized with the subscript of m in the formula (1) Can be adjusted.

Also, the curable resin of the present invention has a small NI point change. The NI point is a temperature at which the liquid crystal transitions from a nematic phase to an isotropic phase (isotropic phase) (the phase transition temperature can be measured from an endothermic peak top using a differential thermal analyzer). The NI point of the liquid crystal is determined by the mixed composition of each component of the liquid crystal, and each value is a unique value. When the raw material or sealant having high stain of liquid crystal contamination is mixed with the liquid crystal, the NI point greatly changes. Conversely, when the raw material or the sealant has low liquid stain resistance, the change in NI point is small.

Specifically, in the curable resin of the present invention, the NI point change is usually in the range of -5 占 폚 to + 5 占 폚, and preferably in the range of -3 占 폚 to + 3 占 폚. The details of the method of measuring the NI point change will be described in the following embodiments.

[(Meth) acrylated curable resin]

The curable resin of the present invention can be made into a (meth) acryl-curable resin by reacting (meth) acrylic acid and / or (meth) acrylic acid anhydride. The olefin moiety of the (meth) acryl group can cause a crosslinking reaction, and even in the (meth) acrylated curable resin, excellent flexibility can be achieved while securing the adhesiveness required for the liquid crystal sealing agent.

More specifically, the introduction of the (meth) acrylic group into the curable resin of the present invention can be carried out by using an epoxy group (for example, when R ¹ is a glycidyl group), a hydroxyl group and an unsaturated bond (for example, (1b). ≪ / RTI > When the epoxy group is opened by the addition of a (meth) acryl group or the like, a hydroxyl group is generated, but a (meth) acryl group may be further introduced into the hydroxyl group.

The introduction of the (meth) acrylic group can be carried out by reacting the curable resin of the present invention with a (meth) acrylic acid-based compound such as acrylic acid, methacrylic acid, an anhydride thereof, an ester compound or an acid halide .

<Properties of (meth) acrylated curable resin>

The (meth) acrylated curable resin of the present invention exhibits preferable characteristics for use in a liquid crystal encapsulant like the curable resin of the present invention.

That is, the viscosity of the (meth) acrylated curable resin of the present invention is usually 1,000 to 2,000,000 mPa · s, and preferably 3,000 to 2,000,000 mPa · s from the viewpoint of securing a suitable viscosity for the liquid crystal sealing agent.

Further, the (meth) acrylated curable resin of the present invention has a small NI point change, and its NI point change is usually in the range of -5 ° C to + 5 ° C, and preferably in the range of -3 ° C to + 3 ° C.

[Production method of curable resin]

Next, the production method of the curable resin of the present invention will be described.

The production method of the curable resin includes a step of reacting the compound E represented by the following formula (2) or (3) with the compound F represented by the following formula (4).

In the formulas (2) and (3), Y ¹ , n, Y ² , R ³ , p and q are as defined above, and R ⁴ each independently represent a hydrogen atom, a glycidyl group, It is a scheduler. In the formula (3), part or all of the unsaturated bonds in the repeating units parenthesized with p or q suffixes may be hydrogenated.

In the formula (4), X and A ring are as defined above, and R ⁵ is a hydrogen atom, a glycidyl group or a methyl glycidyl group.

For example, when -OR ⁴ present at the molecular end of the compound E is a glycidyloxy group or a methylglycidyloxy group, at least one of -OR ⁵ and X in the compound F is a hydroxyl group, The compound F is linked to the terminal of the compound E by a ring-opening reaction between a hydroxyl group and a methyl group or a methyl group. If necessary, a hydroxyl group (for example, a hydroxyl group which is newly generated by a ring-opening reaction) in the resulting compound (synthetic intermediate G to be described later, which is a curable resin of the present invention when the compound has at least one epoxy group in the molecule) Hydroxyl group) is adjusted to be not less than 1 by making glycidyl ether as described below to obtain the curable resin of the present invention in which m in the formula (1) is 1.

In addition, in the compound F, when -OR ⁵ and X are groups capable of opening an epoxy group such as a hydroxyl group, both of -OR ⁵ and X may react with a glycidyloxy group or a methylglycidyloxy group of the compound E can do. In the thus obtained compound, the curable resin of the present invention in which m is 2 or more in the formula (1) can be obtained by glycidyl etherating the hydroxyl group which is liberated as necessary, as described later. Further, m can be controlled according to the amount of the compounds E and F, and even when -OR ⁵ and X are groups capable of opening the epoxy group, the curable resin of the invention having m = 1 can be obtained by adjusting the amount of the compound .

Each of the compounds E and F may be used alone or in combination of two or more.

The molecular weight of the compound E represented by the formula (2) or (3) is preferably 500 to 10,000. In the present specification, the molecular weight is the number average molecular weight in terms of standard polystyrene measured by GPC.

Compounds E and F can be readily prepared from commercially available or commercially available compounds according to known methods. For example, compound E of formula (2) wherein R ⁴ is a hydrogen atom and Y ¹ is an ethylene group is available as polyethylene glycol having a number of repeating units (n) of various numbers, and a compound having n in a desired range is appropriately Select it. Also, n may be estimated from the results of GPC measurement of polyethylene glycol.

The polyethylene glycol is reacted with a glycidyl group such as epichlorohydrin or a compound capable of introducing a methyl glycidyl group (hereinafter also referred to as &quot; epoxidized compound &quot;) to introduce a glycidyl group or the like into the terminal of the polyethylene glycol Which can easily convert R ⁴ from a hydrogen atom to a glycidyl group or the like. This also applies to the other examples of compounds E and F in which R ⁴ or R ⁵ is a hydrogen atom, which will be described below.

Compound E of formula (2) in which R ⁴ is a hydrogen atom and Y ¹ is a propylene group is available as polypropylene ether glycol having various repeating unit numbers (n). EXCENOL 420, EXCENOL 720, EXCENOL 1020, EXCENOL 2020 (manufactured by Asahi Glass Co., Ltd.), and the like.

The compound E of the formula (2) in which R ⁴ is a hydrogen atom and Y ¹ is a trimethylene group can be produced, for example, in accordance with the method described in Japanese Patent Publication No. 2013-515144, Lt; RTI ID = 0.0 &gt; polytrimethylene &lt; / RTI &gt;

Compound E of formula (2) in which R ⁴ is a hydrogen atom and Y ¹ is a tetramethylene group is available as polytetramethylene ether glycol having various repeating unit numbers (n). For example, PTMG650, PTMG850, PTMG1000, PTMG1300, PTMG1500, PTMG1800, PTMG2000 (manufactured by Mitsubishi Chemical Corporation) and the like.

Compound E of the formula (3) in which R ³ is a hydrogen atom and R ⁴ is a hydrogen atom is available as having a number of repeating units (p, q) as a terminal hydroxyl-introduced polybutadiene. For example, NISSO PB G-1000, G-2000 (manufactured by Nippon Bossa Co., Ltd.) and Poly bd R-45HT (manufactured by Idemitsu Kosan Co., Ltd.).

Compound (E) of the formula (3) in which R ³ is a hydrogen atom, R ⁴ is a hydrogen atom and part or all of the unsaturated bond in the repeating unit in parentheses attached with the suffix p or q is hydrogenated, As the hydride of the terminal hydroxyl group-introduced polybutadiene, it is possible to have various repeating unit numbers (p, q). For example, NISSO-PB GI-1000 and GI-2000 (manufactured by Nissan Chemical Industries, Ltd.) and the like can be given.

Compound E of formula (3) in which R ³ is a methyl group and R ⁴ is a hydrogen atom is available as having a number of repeating units (p, q) as terminal hydroxyl-introduced polyisoprene. For example, Poly ip (manufactured by Idemitsu Kosan Co., Ltd.).

The compound E of the formula (3) in which R ³ is a methyl group, R ⁴ is a hydrogen atom, and a part or all of the unsaturated bonds in the repeating unit in parentheses suffixed with p or q is hydrogenated, (P, q) as a hydride of a hydroxyl-introduced polyisoprene is available. For example, EPOL (manufactured by Idemitsu Kosan Co., Ltd.) and the like.

Examples of the compound F in which R ⁵ is a hydrogen atom, X is a hydroxyl group, and the ring A satisfies the specified number of atoms and the number of ring structures includes resorcinol, 2- (4-hydroxyphenyl) ethanol, bisphenol A, M, bisphenol P, 1,6-naphthalenediol, 2-ethyl-9,10-anthracenediol, 3,4-thiophenediol, 9,9-bis (4-hydroxy- .

Examples of the compound F in which R ⁵ is a hydrogen atom, X is a hydrogen atom, and the ring A satisfies the specified number of atoms and the number of ring structures include phenol, 4-α-cumylphenol, 4- Hydroxyquinoline, and the like.

R ⁴ in the compound E and R ⁵ in the compound F are each a hydrogen atom in one of R ⁴ and R ⁵ from the viewpoints of the flexibility after curing and the stain on the low liquid crystal of the obtained curable resin, It is desirable to be a syllable.

The compound E and the compound F can be produced by reacting the compound E and the compound F in the presence of an alkali, for example, to produce the curable resin of the present invention, and then, if necessary, the resulting synthetic intermediate G in a suitable epoxidization To react with the compound. The above-mentioned reaction is carried out so that the amount of m is 1 to 7, preferably 1 to 5, and more preferably 1 to 3 in the curable resin. These compounds may be used alone or in combination of two or more.

As to the number of m, the synthesis intermediate G can be controlled in the following manner in the case of the later-described examples. For example, in Synthesis Example 1, the equivalent ratio of the epoxy group to the bisphenol A (corresponding to the compound F) in the compound E-1 is 1.0: 2.5. When this ratio is 1.0: 2.0 or 1.0: 1.5, m . Conversely, even when the ratio is set at 1.0: 10, 1.0: 100, 1.0: 1000, etc., it is not less than 1.

From the viewpoint of reactivity, it is preferable that one of R ⁴ in the compound E and R ^{5 in} the compound F is a hydrogen atom and the other is a glycidyl group or a methylglycidyl group.

Examples of the alkali include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, tetramethylammonium chloride, methyltrioctylammonium chloride, methyl chloride Quaternary ammonium salts such as tridecylammonium chloride and benzyltrimethylammonium chloride are preferable, and sodium hydroxide or quaternary ammonium salt is more preferable. These alkalis are preferably used as an aqueous solution, but in some cases, powders or solid alkalis may be added simultaneously or separately with water. These alkalis may be used singly or in combination of two or more.

When the R ⁴ is a hydrogen atom and R ⁵ is a glycidyl group, the alkali may be an equivalent of a hydroxyl group or more, and R ⁴ is preferably a glycidyl group or a methyl group, for example, A glycidyl group, and when R ⁵ is a hydrogen atom, it may be a catalytic amount, and is 0.0001 to 0.1 equivalent of the hydroxyl group of the compound F.

The amount of the epoxidized compound to be used is preferably 0.05 to 20 equivalents, more preferably 0.05 to 15 equivalents relative to the hydroxyl groups contained in the starting compound. This amount is adjusted by the average number x of epoxy groups in the objective curable resin, but even if a large excess amount is used for the hydroxyl group, x does not exceed the average number of hydroxyl groups of the starting compound.

As the catalyst, from the viewpoints of reaction time, cost and reaction activity, a tertiary amine such as trimethylamine, trioctylamine and tridecylamine, tetramethylammonium chloride, methyltrioctylammonium chloride, methyltridecylammonium chloride, benzyltrimethyl chloride Quaternary ammonium salts such as ammonium are preferred, and quaternary ammonium salts are more preferred. These may be used alone or in combination of two or more.

The amount of the catalyst to be used is preferably 0.0001 to 0.5 equivalents, more preferably 0.01 to 0.1 equivalents, based on the hydroxyl groups contained in the raw material compound from the viewpoint of appropriately securing the reaction rate while suppressing side reactions.

The reaction with the above-described alkali is carried out preferably at 50 to 250 ° C, more preferably at 70 to 200 ° C, further preferably at 100 to 170 ° C, and the reaction with the above-mentioned epoxidized compound is preferably carried out at 25 Deg.] C to 100 [deg.] C, more preferably 30 to 80 [deg.] C, and more preferably 40 to 60 [deg.] C. In the reaction, a solvent inert to the reaction such as hydrocarbon, ether or ketone may be used. However, when the epoxidized compound is used excessively, the compound also functions as a solvent, and therefore these solvents are not essential.

After completion of the reaction, the curable resin can be purified by a conventional method. For example, the excess epoxidized compound is distilled off, and if necessary, a salt or a salt formed by adding a non-aqueous solvent such as a hydrocarbon, The objective curable resin of the present invention can be obtained by removing the catalyst.

From the viewpoint that a general purpose raw material can be used as the compound E and the compound F, the production method of the curable resin of the present invention is preferably a method wherein the compound E1 in which R ⁴ in the compound E is a glycidyl group (diglycidyl etherified product of the compound E (For example, polyethylene glycol diglycidyl ether), and the compound F is a compound F1 (for example, bisphenol A) in which R ⁵ is a hydrogen atom, the compound E1 is reacted with the compound F1, A step 1 of obtaining the compound E1 and a synthetic intermediate G of the compound F1, and a step 2 of epoxidizing the hydroxyl group of the synthetic intermediate G to obtain a curable resin in which part or all of the hydroxyl groups of the synthetic intermediate G are epoxidized .

<Process for producing (meth) acrylated curable resin>

The (meth) acrylated curable resin of the present invention in which (meth) acrylic group is introduced into at least a part of the epoxy group, the hydroxyl group and the unsaturated bond is obtained through Step 3 in which the curable resin is reacted with the (meth) acrylic acid compound in the presence of the basic catalyst Can be obtained.

As the basic catalyst, a known basic catalyst used for the reaction of an epoxy resin with (meth) acrylic acid can be used. A polymer-supported basic catalyst in which a basic catalyst is supported on a polymer may also be used. As the basic catalyst, trivalent organic phosphorus compounds, salts thereof, amine compounds and salts thereof are preferable. These basic catalysts may be used alone or in combination of two or more. Further, the basic atom of the basic catalyst is phosphorus and / or nitrogen.

Examples of the trivalent organic phosphorus compound include alkylphosphines such as triethylphosphine, tri-n-propylphosphine and tri-n-butylphosphine and salts thereof, triphenylphosphine, tri-m-tolylphosphine, tris (2,6-dimethoxyphenyl) phosphine, and salts thereof, phosphorous acid triesters such as triphenyl phosphite, triethyl phosphite, and tris (nonylphenyl) phosphite, and salts thereof have. Among them, triphenylphosphine is preferable.

Examples of the trivalent organic phosphorus compound salt include triphenylphosphine · ethyl bromide, triphenylphosphine · butyl bromide, triphenylphosphine · octyl bromide, triphenylphosphine · decyl bromide, triphenylphosphine · isobutyl bromide, tri Phenylphosphine · propyl chloride, triphenylphosphine · pentyl chloride, triphenylphosphine · hexyl bromide and the like.

Examples of the amine compound include secondary amines such as diethanolamine, tertiary amines such as triethanolamine, dimethylbenzylamine, trisdimethylaminomethylphenol and trisethylaminomethylphenol, 1,5,7-triazabicyclo [4.4 (TBD), 7-methyl-1,5,7-triazabicyclo [4.4.0] deca-5-ene (Me-TBD), 1,8-diazabicyclo [5.4 (DBU), 6-dibutylamino-1,8-diazabicyclo [5.4.0] undeca-7-ene, 1,5-diazabicyclo [4.3.0] 5-ene (DBN), 1,1,3,3-tetramethylguanidine, and the like. Among them, 1,5,7-triazabicyclo [4.4.0] deca-5-ene (TBD) is preferred.

Examples of salts of amine compounds include benzyltrimethylammonium chloride, benzyltriethylammonium chloride, salts of strongly basic amines, and the like.

The polymer for supporting the basic catalyst is not particularly limited and a polymer obtained by crosslinking polystyrene with divinylbenzene or a polymer obtained by crosslinking an acrylic resin with divinylbenzene is used. These polymers may be used in a solvent (for example, methyl ethyl ketone, methyl isobutyl ketone, toluene, etc.) used for the reaction of the (meth) acrylic acid compound with the curable resin obtained by the production method including Step 1 or Steps 1 and 2, And insoluble in raw materials and products. These polymers may be used alone or in combination of two or more.

The polymer-supported basic catalyst can be prepared by chemically bonding a basic catalyst to an insoluble polymer, or by introducing a basic catalyst into a monomer, polymerizing the monomer, and then three-dimensionally crosslinking the polymer with a crosslinking monomer such as divinylbenzene By such crosslinking, it is insoluble in a solvent such as methyl ethyl ketone, methyl isobutyl ketone, or toluene, or becomes a polymer supported basic catalyst.

Specific examples of the polymer-supported basic catalyst include diphenylphosphino polystyrene, 1,5,7-triazabicyclo [4.4.0] deca-5-ene polystyrene, N, N- (diisopropyl) aminomethyl polystyrene, N- (methylpolystyrene) -4- (methylamino) pyridine, and the like. These polymer-supported basic catalysts may be used singly or in combination of two or more.

A commercially available polymer-supported basic catalyst may be used. Examples of commercially available polymer-supported basic catalysts include PS-PPh ₃ (diphenylphosphino polystyrene, manufactured by Biotage Corp.), PS-TBD (1,5,7-triazabicyclo [4.4.0] deca- Polystyrene, manufactured by Biotage), and the like.

In the method for producing a (meth) acrylated curable resin of the present invention, the temperature in the reaction step between the curable resin and the (meth) acrylic acid-based compound obtained by the production method comprising Step 1 or Steps 1 and 2 is preferably 60 to 120 캜, more preferably 80 to 120 캜, and further preferably 90 to 110 캜.

When a curable resin obtained by the production method including Step 1 or Steps 1 and 2 is reacted with a (meth) acrylic acid-based compound in the presence of a catalyst, the gaseous oxygen concentration in the reaction system and the gaseous phase on the reaction system are appropriately Need to keep. For example, when air is actively blown into the reaction system, oxidation of the catalyst may occur, which may result in lowering of the activity.

Regarding the reaction between the curable resin and the (meth) acrylic acid-based compound obtained by the production method including the step 1 or the steps 1 and 2, the (meth) acrylated curable resin obtained by this reaction is cured , It is preferable to carry out the reaction in a vessel shielding ultraviolet rays. The reaction between the curable resin and the (meth) acrylic acid-based compound obtained by the production method including the step 1 or the steps 1 and 2 is carried out in the presence of a reflux solvent exhibiting both solubility in the curable resin In this case, however, it is necessary to remove the solvent after completion of the reaction. Therefore, it is preferable that the reaction is carried out in the absence of a solvent. Examples of the reflux solvent include acetone, methyl ethyl ketone, and toluene.

[Liquid crystal sealing composition]

The curable resin and the (meth) acrylated curable resin of the present invention (hereinafter also referred to as "the curable resin etc. of the present invention") have various properties as described above, and have a viscosity suitable for use as a liquid crystal sealing agent, And excellent flexibility after curing.

Therefore, the liquid crystal encapsulant composition using the curable resin or the like of the present invention is excellent in handleability, and even when brought into contact with the liquid crystal in an uncured state by the liquid crystal dropping method, it is difficult to affect the orientation of the liquid crystal It is difficult to inhibit the orientation of the liquid crystal. When the flexible substrate is used in a flexible device such as a flexible liquid crystal display, even if the flexible substrate sandwiching the cured liquid crystal sealing agent is bent, due to its excellent flexibility and stress relaxation effect, Cracking, separation from the substrate, and the like are less likely to occur.

Specifically, the viscosity of the liquid crystal sealing composition of the present invention is usually 1000 to 2000000 mPa · s, preferably 10000 to 1000000 mPa · s. The viscosity of the liquid crystal encapsulant composition can be controlled by the structure of the curable resin or the like of the present invention or by the addition of a component that can be a component of the liquid crystal encapsulant composition as described below and a solvent.

The liquid crystal encapsulant composition of the present invention including the curable resin of the present invention, such as the liquid crystal encapsulant composition of the present invention, generally has a storage elastic modulus at room temperature (25 캜) of 1.0 × 10 ³ to 3.0 × 10 ⁹ Pa, and preferably 1.0 × 10 ³ to 1.0 × 10 ⁹ Pa. The method of measuring the storage elastic modulus will be described in detail in the section of Examples to be described later.

The glass transition temperature (Tg) of the liquid crystal encapsulating material cured product obtained by curing the liquid crystal encapsulating composition of the present invention is usually 80 占 폚 or lower, preferably 40 占 폚 or lower, more preferably 30 占 폚 or lower , More preferably room temperature (25 캜) or lower, and particularly preferably -80 to 25 캜.

The liquid crystal encapsulant composition of the present invention includes the curable resin of the present invention. The content of the curable resin and the like in the liquid crystal encapsulant composition is usually 5 to 95% by weight, and the content of the curable resin, From the viewpoint of the effect, it is preferably 10 to 95% by weight.

The liquid crystal sealing composition of the present invention may further contain various components described below in a range that does not impair the effects of the present invention, depending on various properties required for the application.

<Compound H>

The liquid crystal sealing composition of the present invention may contain a curing component in addition to the curable resin of the present invention. For example, a conventional ethylenically unsaturated group and / or an epoxy group-containing compound H ( For example, a liquid crystal encapsulant composition containing the curable resin of the present invention together with an oligomer (meth) acrylate of a part of the epoxy group of a bisphenol A type epoxy resin is more preferable than the liquid crystal encapsulant Flexibility is greatly improved.

 Examples of the compound H having an ethylenically unsaturated group include an acrylamide compound and an N-substituted acrylamide compound including a (meth) acrylate compound, an aliphatic acrylamide compound, an alicyclic acrylamide compound, and an aromatic compound.

Examples of the (meth) acrylate compound include para-cumylphenoxy ethylene glycol (meth) acrylate, t-butyl (meth) acrylate, ethoxylated phenyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (Meth) acrylate, and an aromatic ring-containing (meth) acrylate.

As the compound H having an ethylenic unsaturated group, a monofunctional, bifunctional, trifunctional or multifunctional radically polymerizable unsaturated compound may also be mentioned.

The monofunctional radically polymerizable unsaturated compound is preferably at least one compound selected from the group consisting of hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate (Meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isomyristyl (meth) acrylate, lauryl (meth) acrylate, tert- butyl (meth) acrylate, and diethylene glycol monoethyl ether (Meth) acrylate, and at least one compound selected from the group consisting of isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate Relate, dicyclopentanyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate and cyclohexyl (meth) at least one compound selected the group consisting of the acrylate is more preferable.

Examples of the bifunctional radically polymerizable unsaturated compound include tricyclodecane dimethanol di (meth) acrylate, dimethylol dicyclopentanedi (meth) acrylate, EO-modified (meth) acrylate, and the like, from the viewpoint of ensuring viscosity and flexibility of the liquid crystal encapsulating composition (Meth) acrylates such as 1,6-hexanediol di (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modified bisphenol A di (For example, 4G manufactured by Shin-Nakamura Chemical Co.) and silicone di (meth) acrylate (for example, EBECRYL 350, manufactured by Daicel Chemical Industries, Ltd.), polyethylene glycol di (meth) acrylate (Meth) acrylate and / or EO or PO-modified bisphenol A di (meth) acrylate is preferably used as the compound of the formula It is. Among them, (meth) acrylate having no hydroxyl group and having a bisphenol A skeleton is preferable, and as such (meth) acrylate, light acrylate BP-4EAL (EO of bisphenol A Adduct diacrylate), BP-4PA (PO adduct of bisphenol A diacrylate) and the like are commercially available.

Examples of the trifunctional or multifunctional radically polymerizable unsaturated compound include EO-modified glycerol tri (meth) acrylate (trifunctional), PO-modified glycerol tri (meth) acrylate Acrylate (trifunctional), pentaerythritol tetra (meth) acrylate (trifunctional), dipentaerythritol hexa (meth) acrylate (hexafunctional) and pentaerythritol tetra Is preferred, and EO-modified glycerol tri (meth) acrylate is more preferable.

Subsequently, the compound H having an epoxy group is preferably a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol AD type epoxy compound, a phenol novolak type epoxy compound, a cresol novolak type epoxy compound, a naphthalene type epoxy compound, At least one compound selected from the group consisting of a ricinole type epoxy compound, a hydrogenated compound thereof and an alicyclic epoxy compound, more preferably a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a naphthalene type epoxy compound, And a ricinole type epoxy compound, and more preferably a bisphenol A type epoxy compound.

Specific examples of the bisphenol A type epoxy compound include EPICLON 850S, 860, 1055, and EXA-850CRP manufactured by DIC Corporation.

Specific examples of the hydrogenated bisphenol A type epoxy compound include KRM-2408 manufactured by ADEKA, and YX-8034 manufactured by JER.

Specific examples of the bisphenol F type epoxy compound include EPICLON 830S manufactured by DIC Corporation.

Specific examples of the naphthalene type epoxy compound include EPICLON HP-4032D and HP-7200H manufactured by DIC.

Specific examples of the phenol novolak type epoxy compound include EPICLON N-740 and N-770 manufactured by DIC Corporation.

Specific examples of the cresol novolak-type epoxy compound include EPICLON N-660 and N-670 manufactured by DIC Corporation.

Specific examples of the resorcinol-type epoxy compound include Denacol EX-201 manufactured by Nagase Chemtech.

Specific examples of the alicyclic epoxy compounds include 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate (Celloxide 2021P, manufactured by Dai-ichi), 1,2: 8,9-diepoxy 1,2-epoxy-4-vinylcyclohexane (Cellocide 2000, manufactured by Daicel Chemical Industries, Ltd.) and 1,2-epoxy (2,2-bis (hydroxymethyl) (2-oxiranyl) cyclohexane adduct (EHPE3150, manufactured by Daicel Chemical Industries, Ltd.).

Examples of the compound H having an ethylenic unsaturated group and an epoxy group include a partial (meth) acrylate-modified epoxy compound obtained by reacting an epoxy group-containing compound with a (meth) acrylic acid-based compound. As the compound, a bisphenol A- (Meth) acrylated epoxy compound obtained by reacting (meth) acrylic acid.

The (meth) acrylated epoxy compound obtained by reacting the bisphenol A type epoxy resin with (meth) acrylic acid is obtained, for example, as follows.

First, the bisphenol A type epoxy resin is reacted with (meth) acrylic acid in the presence of a basic catalyst, preferably a trivalent organic phosphoric acid compound and / or an amine compound. The reaction ratio at this time is in a ratio of 10 to 90 equivalent% of (meth) acrylic acid to 1 equivalent of epoxy group. Subsequently, the reaction product is purified by removing the basic catalyst by treatment such as filtration, centrifugation and / or water washing. As the basic catalyst, a known basic catalyst used for the reaction of an epoxy resin with (meth) acrylic acid can be used. A polymer-supported basic catalyst in which a basic catalyst is supported on a polymer may also be used.

As described above, the liquid crystal sealing composition of the present invention can contain various compounds H, but when the ethylenic unsaturated group is not contained in the curable resin of the present invention, the compound Compounds having one ethylenically unsaturated group are preferred.

The compounds H described above can be used singly or in combination of two or more kinds.

<Photopolymerization initiator>

The liquid crystal sealing composition of the present invention may contain a photopolymerization initiator as a radical generating source when the curable resin of the present invention and the like, and when contained, the compound H are photopolymerized. The photopolymerization initiator is not particularly limited, and known compounds may be used, and they may be used alone or in combination of two or more.

As the photopolymerization initiator, there may be mentioned a photopolymerization initiator such as benzoin, acetophenone, benzophenone, thioxanthone,? -Acyloxime ester, phenylglyoxylate, benzyl, azo, diphenyl sulfide, Based compounds, benzoin ethers and anthraquinones, and preferably have a low solubility in a liquid crystal and also have a reactive group which itself does not gasify decomposition products upon irradiation with light.

<Optical sensitizer>

The liquid crystal sealing composition of the present invention is usually photo-cured, but may contain a photosensitizer in order to increase the sensitivity to light at that time. As the photosensitizer, various conventionally known compounds may be used without particular limitation, and the photosensitizer may be used alone or in combination of two or more.

Examples of the photosensitizer include a carbonyl compound, an organic sulfur compound, a persulfate, a redox compound, an azo compound and a diazo compound, a halogen compound, and a light reducing pigment from the viewpoint of curability.

Specific examples of the photosensitizer include acridone derivatives such as N-methyl acridone and N-butyl acridone; Other examples include?,? - diethoxyacetophenone, benzyl, fluorenone, xanthone and uranyl compounds, and also examples of the photopolymerization initiator that function as a photosensitizer.

<Curing agent>

From the viewpoint of enhancing the adhesiveness of the liquid crystal sealing composition of the present invention, the liquid crystal sealing composition may contain a curing agent. The curing agent is not particularly limited, and known compounds may be used.

As the curing agent, an amine-based curing agent such as an organic acid dihydrazide compound, imidazole and derivatives thereof, dicyandiamide, aromatic amine, epoxy-modified polyamine, polyaminourea and the like are preferable from the viewpoint of adhesiveness. These curing agents may be used alone or in combination of two or more.

<Curing accelerator>

The liquid crystal sealing composition of the present invention may contain a curing accelerator from the viewpoint of accelerating the curing reaction of the curing component (the curable resin of the present invention or the compound H described above), and the curing accelerator may be used alone And can be used in combination of two or more.

Preferable examples thereof include imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol and 1,8-diazabicyclo [5.4.0] undeca-7-ene (DBU); Phosphines such as triphenylphosphine; And metal compounds such as tin octylate.

<Filler>

The liquid crystal sealing composition of the present invention may contain a filler in view of viscosity control, adhesion reliability, and suppression of linear expansion. As the filler, inorganic fillers and organic fillers can be used. These fillers can be used singly or in combination of two or more kinds.

Examples of the inorganic filler include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, titanium oxide, alumina, zinc oxide, silicon dioxide, kaolin, talc, glass beads, cericite activated clay, bentonite, aluminum nitride and silicon nitride .

Examples of the organic filler include copolymers obtained by copolymerizing methyl polymethacrylate, polystyrene, monomers constituting these, and other monomers, polyester fine particles, polyurethane fine particles, rubber fine particles, and copolymers having a high glass transition temperature Core shell type particles composed of a shell and a core of a copolymer having a low glass transition temperature. Examples of the core-shell type particles include Zephyr series (such as F351) manufactured by Gansu Chemical Industry Co., Ltd. and the like.

The average particle diameter of the particles constituting the filler is usually from 0.1 to 3 탆, more preferably from 0.5 to 3 탆, from the viewpoint of reducing the out gas from the liquid crystal sealing agent by blending the filler which is a non-reactive component. The average particle diameter of the filler was measured by a laser diffraction / scattering type particle diameter distribution measuring apparatus (for example, Paverica LA-950V2 manufactured by HORIBA) manufactured by HORIBA.

<Silane coupling agent>

The liquid crystal sealing composition of the present invention may contain a silane coupling agent within the range of exhibiting the effect of the present invention. The silane coupling agent may be used alone or in combination of two or more.

From the viewpoint of achieving both the adhesiveness and flexibility of the liquid crystal encapsulant cured by curing the liquid crystal encapsulant composition of the present invention, examples of the silane coupling agent include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane , Tetraalkoxysilanes such as tetrabutoxysilane, dimethoxydiethoxysilane, dimethoxydiisopropoxysilane, diethoxydiisopropoxysilane, and diethoxydiboxysilane; Methyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltriethoxysilane, ethyltributoxysilane, cyclohexyltriethoxysilane, phenyltriisopropoxysilane, vinyltrimethoxysilane Trialkoxysilanes such as 3-glycidoxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; And at least one silane coupling agent selected from the group consisting of dialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, diethyldibutoxysilane and phenylethyldiethoxysilane is preferable ,

Among these, preferred are methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltriethoxysilane, ethyltributoxysilane, cyclohexyltriethoxysilane, phenyltriisopropoxysilane, vinyltri More preferably at least one trialkoxysilane silane coupling agent selected from the group consisting of methoxysilane, 3-glycidoxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane,

More preferred is 3-glycidoxypropyltrimethoxysilane.

Example

Hereinafter, the present invention will be described concretely with reference to Examples, but the present invention is not limited to these Examples. The compounds used in Examples and Comparative Examples were prepared as follows.

[Comparative Synthesis Example 1] Partial methacrylated bisphenol A type epoxy resin

, 340.0 g of bisphenol A type epoxy resin (EXA850CRP, manufactured by DIC Kabushiki Kaisha), 90.4 g of methacrylic acid (manufactured by Tokyo Kasei Kasei), 0.5 g of triphenylphosphine (manufactured by Tokyo Kasei Kasei) and 0.5 g of BHT (dibutylhydroxytoluene) And the mixture was stirred at 100 占 폚 for 6 hours. 418.0 g of a partially methacrylated bisphenol A type epoxy resin obtained as a pale yellow transparent dots was obtained.

[Synthesis Example 1] Synthesis of methacrylic curable resin 1

(1) 2000.0 g (4.0 equivalent / hydroxyl group) of polyethylene glycol # 1000 (manufactured by LION), 2220.0 g (6.0 equivalent) of epichlorohydrin and 74.3 g (0.10 equivalent) of benzyltrimethylammonium chloride were placed in a mechanical stirrer, Was placed in a 5-liter three-necked round bottom flask equipped with a stirrer, condenser, Dean Stark trap and a dropping funnel.

Subsequently, the mixture was heated to about 50 to 60 DEG C with stirring under a high vacuum of 50 torr to reflux epichlorohydrin. 600.0 g of 48% NaOH aqueous solution was slowly added to the mixture over 2 hours. As the azeotropic water was produced, the stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture.

After completion of the addition, stirring was continued for 3 hours. Subsequently, the reaction mixture was cooled to room temperature, 3 L of chloroform was added, and the mixture was washed 6 times with 3 L of water. The obtained organic phase solvent was removed by distillation under reduced pressure to obtain 1150.0 g of Compound E-1 as a white solid.

(2) Compound E-1 (950.0 g (1.7 eq. / Epoxy group)) and bisphenol A (988.0 g (2.5 eq.)) Were placed in an eggplant-shaped flask and heated and stirred at 150 ° C. 2.9 g of a 4% NaOH aqueous solution was added, and the mixture was stirred at 150 占 폚 for 6 hours.

The mixture was cooled until the liquid temperature became 60 DEG C or less, 2 L of chloroform was added, and the mixture was washed 6 times with 2 L of 1% aqueous NaOH solution and 6 L of water.

The resulting organic phase was subjected to distillation to remove the solvent of the organic phase by distillation to obtain 997.0 g of the reaction product G-1 as a synthetic yellow transparent spot compound .

(3) Reaction product G-1 (997.0 g), epichlorohydrin (1423.0 g) and benzyltrimethylammonium chloride (47.5 g) were placed in a flask equipped with a mechanical stirrer, thermometer, thermostat, condenser, Dean Stark trap and dropping funnel 5-liter three-necked round bottom flask.

Subsequently, the mixture was heated to about 50 to 60 DEG C with stirring under a high vacuum of 50 torr to reflux epichlorohydrin. 384.0 g of 48% aqueous NaOH solution was slowly added to the mixture over 2 hours. As the azeotropic water was produced, the stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. After completion of the addition, stirring was continued for 3 hours.

Subsequently, the reaction mixture was cooled to room temperature, 2 L of chloroform was added, and the mixture was washed 6 times with 2 L of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 982.0 g of Resin 1 as a pale yellow viscous substance.

(4) 100.0 g of Resin 1, 8.6 g of methacrylic acid, 0.5 g of triphenylphosphine and 20 mg of BHT were mixed and stirred at 100 占 폚 for 5 hours. To obtain 107.0 g of methacrylic curable resin 1 having a light yellow dot structure.

[Synthesis Example 2] Synthesis of methacrylic curable resin 2

(1 equivalent) of polytetramethylene ether glycol (PTMG) 1000 (manufactured by Mitsubishi Chemical Co., Ltd.), 555.0 g (6.0 equivalent) of epichlorohydrin, 18.6 g (0.10 equivalent) of benzyltrimethylammonium chloride, Was placed in a 2 liter three-neck round bottom flask equipped with a mechanical stirrer, thermometer, thermostat, condenser, Dean Stark trap and dropping funnel.

Subsequently, the mixture was heated to about 50 to 60 DEG C with stirring under a high vacuum of 50 torr to reflux epichlorohydrin. 150.0 g of 48% aqueous NaOH solution was slowly added to the mixture over 2 hours. As the azeotropic water was produced, the stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. After completion of the addition, stirring was continued for 3 hours.

Subsequently, the reaction mixture was cooled to room temperature, 1 L of chloroform was added, and the mixture was washed 4 times with 1 L of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 459.0 g of Compound E-2 as a white solid.

(2) Compound E-2 (132.0 g (0.20 eq / epoxy group)) and bisphenol A (114.0 g (2.5 eq.)) Were placed in an eggplant-shaped flask and heated and stirred at 150 ° C. 0.3 g of a 4% NaOH aqueous solution was added, and the mixture was stirred at 150 占 폚 for 6 hours. The mixture was cooled until the liquid temperature became 60 DEG C or less, 500 mL of chloroform was added, and the mixture was washed three times with 1 L of 1% NaOH aqueous solution and three times with 1 L of water.

To the obtained organic phase, magnesium sulfate was added, and after drying, the solid component was filtered off by filtration and the solvent of the obtained organic phase was distilled off under reduced pressure to obtain 140.0 g of the reaction product G-2 as a light yellow transparent dots, .

(3) Reaction Product G-2 (140.0 g), epichlorohydrin (195.0 g) and benzyltrimethylammonium chloride (6.5 g) were added to a reaction vessel equipped with a mechanical stirrer, thermometer, temperature controller, condenser, Dean Stark trap and dropping funnel Lt; RTI ID = 0.0 &gt; 1-liter &lt; / RTI &gt; round bottom flask.

Subsequently, the mixture was heated to about 50 to 60 DEG C with stirring under a high vacuum of 50 torr to reflux epichlorohydrin. 53.0 g of 48% NaOH aqueous solution was slowly added to the mixture over 2 hours. As the azeotropic water was produced, the stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. After completion of the addition, stirring was continued for 3 hours. Subsequently, the reaction mixture was cooled to room temperature, 500 mL of chloroform was added, and the mixture was washed with 500 mL of water four times. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 129.0 g of Resin 2 as a pale yellow viscous material.

(4) 48.6 g of Resin 2, 4.3 g of methacrylic acid, 0.3 g of triphenylphosphine and 10 mg of BHT were mixed and stirred at 100 ° C for 6 hours. 50.6 g of a methacrylic curable resin 2 having a light yellow dot structure was obtained.

[Synthesis Example 3] Synthesis of methacrylic curable resin 3

(1) 350.0 g (0.50 equivalents / hydroxyl group) of NISSO-PB G-1000 (manufactured by Nippon Bossa), 370.0 g (8.0 equivalents) of epichlorohydrin, and 9.3 g (0.10 equivalents) of benzyltrimethylammonium chloride were mixed on a mechanical stirrer, Was placed in a 2-liter three-neck round bottom flask equipped with a thermometer, thermostat, condenser, Dean Stark trap and dropping funnel.

Subsequently, the mixture was heated to about 50 to 60 DEG C with stirring under a high vacuum of 50 torr to reflux epichlorohydrin. 75.0 g of a 48% aqueous NaOH solution was slowly added to the mixture over 2 hours. As the azeotropic water was produced, the stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. After completion of the addition, stirring was continued for 3 hours.

Subsequently, the reaction mixture was cooled to room temperature, 500 mL of chloroform was added, and the mixture was washed six times with 500 mL of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 298.0 g of Compound E-3 as a transparent spot-forming compound.

(2) A mixture of Compound E-3 (96.5 g (0.10 eq. / Epoxy group)), bisphenol A (68.5 g (3.0 eq.)), Benzyltrimethylammonium chloride 0.9 g (0.050 eq.) And methyl isobutyl ketone And the mixture was stirred for 20 hours while being heated to reflux so that the liquid temperature was 120 占 폚. The mixture was cooled until the liquid temperature became 60 DEG C or less, 300 mL of chloroform was added, and the mixture was washed 5 times with 300 mL of 1% aqueous NaOH solution and then with 5 times with 300 mL of water.

To the obtained organic phase, magnesium sulfate was added, and after drying, the solid was separated by filtration and the solvent of the obtained organic phase was distilled off by distillation under reduced pressure to obtain 75.5 g of the reaction intermediate G-3 .

(3) Reaction G-3 (75.5 g), epichlorohydrin (112.5 g) and benzyltrimethylammonium chloride (2.8 g) were added to a reaction vessel equipped with a mechanical stirrer, thermometer, thermostat, condenser, Dean Stark trap and dropping funnel And placed in a 500 milliliter three-neck round bottom flask.

Subsequently, the mixture was heated to about 50 to 60 DEG C with stirring under a high vacuum of 50 torr to reflux epichlorohydrin. 23.0 g of 48% aqueous NaOH solution was slowly added to the mixture over 2 hours. As the azeotropic water was produced, the stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. After completion of the addition, stirring was continued for 3 hours.

Subsequently, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and the mixture was washed six times with 300 mL of water. The obtained organic phase solvent was removed by distillation under reduced pressure to obtain 54.4 g of Resin 3 as a pale yellow viscous material.

(4) 50.0 g of Resin 3, 3.3 g of methacrylic acid, 0.2 g of triphenylphosphine and 10 mg of BHT were mixed and stirred at 100 占 폚 for 5 hours. To obtain 47.0 g of methacrylic curable resin 3 having a light yellow dot structure.

[Synthesis Example 4] Synthesis of methacrylic curable resin 4

(1) 300.0 g (0.40 eq. / Hydroxyl group) of NISSO-PB GI-1000 (manufactured by Nippon Bonding Co.), 296.0 g (8.0 eq.) Of epichlorohydrin and 7.4 g (0.10 eq.) Of benzyltrimethylammonium chloride were placed on a mechanical stirrer, Was placed in a 2-liter three-neck round bottom flask equipped with a thermometer, thermostat, condenser, Dean Stark trap and dropping funnel.

Subsequently, the mixture was heated to about 50 to 60 DEG C with stirring under a high vacuum of 50 torr to reflux epichlorohydrin. 60.0 g of 48% aqueous NaOH solution was slowly added to the mixture over 2 hours. As the azeotropic water was produced, the stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. After completion of the addition, stirring was continued for 3 hours.

Subsequently, the reaction mixture was cooled to room temperature, 500 mL of chloroform was added, and the mixture was washed six times with 500 mL of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 264.0 g of Compound E-4 as a transparent spot-forming compound.

(2) A mixture of Compound E-4 (80.0 g (0.060 eq. / Epoxy group)), bisphenol A (57.1 g (4.0 eq.)), Benzyltrimethylammonium chloride 0.9 g (0.080 eq.) And methyl isobutylketone And the mixture was stirred for 20 hours while being heated to reflux so that the liquid temperature was 120 占 폚. The mixture was cooled until the liquid temperature became 60 DEG C or less, 300 mL of chloroform was added, and the mixture was washed 5 times with 300 mL of 1% aqueous NaOH solution and then with 5 times with 300 mL of water.

Magnesium sulfate was added to the obtained organic phase, and after drying, the solid was separated by filtration and the solvent of the obtained organic phase was distilled off under reduced pressure to obtain 80.0 g of a reaction intermediate G-4 as a light yellow viscous material .

(3) Reaction product G-4 (80.0 g), epichlorohydrin (88.8 g) and benzyltrimethylammonium chloride (3.0 g) were added to a reaction vessel equipped with a mechanical stirrer, thermometer, temperature controller, condenser, Dean Stark trap and dropping funnel And placed in a 500 milliliter three-neck round bottom flask.

Subsequently, the mixture was heated to about 50 to 60 DEG C with stirring under a high vacuum of 50 torr to reflux epichlorohydrin. 24.0 g of 48% NaOH aqueous solution was slowly added to the mixture over 2 hours. As the azeotropic water was produced, the stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. After completion of the addition, stirring was continued for 3 hours.

Subsequently, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and the mixture was washed six times with 300 mL of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 56.0 g of Resin 4 as a pale yellow viscous material.

(4) 50.0 g of Resin 4, 3.0 g of methacrylic acid, 0.2 g of triphenylphosphine and 10 mg of BHT were mixed and stirred at 100 占 폚 for 12 hours. To obtain 47.0 g of methacrylic curable resin 4 having a light yellow dot structure.

[Synthesis Example 5] Synthesis of methacrylic curable resin 5

(1) Compound E-2 (96.0 g (0.15 eq. / Epoxy group)), 4-a-cumylphenol (30.0 g (1.0 eq.)) And benzyltrimethylammonium chloride 1.4 g (0.050 eq. And the mixture was stirred for 30 hours while heating and refluxing so that the liquid temperature was 120 占 폚. The reaction solution was cooled until the liquid temperature became 60 캜 or lower to obtain 125.0 g of the reaction product G-5 as a synthetic yellow intermediate.

(2) Reaction Product G-5 (125.0 g), epichlorohydrin (150.0 g) and benzyltrimethylammonium chloride (2.8 g) were placed in a reaction vessel equipped with a mechanical stirrer, thermometer, thermostat, condenser, Dean Stark trap and dropping funnel And placed in a 500 milliliter three-neck round bottom flask.

Subsequently, the mixture was heated to about 50 to 60 DEG C with stirring under a high vacuum of 50 torr to reflux epichlorohydrin. 30.0 g of a 48% aqueous NaOH solution was slowly added to the mixture over 2 hours. As the azeotropic water was produced, the stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. After completion of the addition, stirring was continued for 3 hours.

Subsequently, the reaction mixture was cooled to room temperature, 500 mL of chloroform was added, and the mixture was washed six times with 500 mL of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 130.0 g of Resin 5 as a pale yellow viscous material.

(3) 63.5 g of Resin 5, 4.3 g of methacrylic acid, 0.1 g of triphenylphosphine and 13 mg of BHT were mixed and stirred at 100 ° C for 6 hours. To obtain 66.0 g of a methacrylic curable resin 5 having a light yellow dot structure.

[Synthesis Example 6] Synthesis of methacrylated curable resin 6

(1) Compound E-2 (64.0 g (0.10 eq / epoxy group)) and resorcinol (27.5 g (2.5 eq.)) Were placed in an eggplant-shaped flask and heated and stirred so that the liquid temperature was 120 캜. And 0.2 g of a 4% NaOH aqueous solution was added, followed by stirring at 120 캜 for 24 hours. The mixture was cooled until the liquid temperature became 60 DEG C or less, 300 mL of chloroform was added, and the mixture was washed with 300 mL of water four times.

To the obtained organic phase, magnesium sulfate was added, and after drying, the solid was separated by filtration and the solvent of the obtained organic phase was distilled off by distillation under reduced pressure to obtain 60.5 g of the reaction intermediate G-6 as a light yellow transparent dots .

(2) Reaction G-6 (60.5 g), epichlorohydrin (102.0 g) and benzyltrimethylammonium chloride (3.4 g) were added to a reaction vessel equipped with a mechanical stirrer, a thermometer, a temperature controller, a condenser, a Dean Stark trap and a dropping funnel And placed in a 500 milliliter three-neck round bottom flask.

Subsequently, the mixture was heated to about 50 to 60 DEG C with stirring under a high vacuum of 50 torr to reflux epichlorohydrin. 28.0 g of 48% NaOH aqueous solution was slowly added to the mixture over 2 hours. As the azeotropic water was produced, the stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. After completion of the addition, stirring was continued for 3 hours. Subsequently, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and the mixture was washed six times with 300 mL of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 48.0 g of Resin 6 as a pale yellow viscous material.

(3) 44.6 g of Resin 6, 4.3 g of methacrylic acid, 0.1 g of triphenylphosphine and 10 mg of BHT were mixed and stirred at 100 ° C for 14 hours. To obtain 42.8 g of a methacrylic curable resin 6 having a light yellow dot structure.

[Synthesis Example 7] Synthesis of methacrylated curable resin 7

(1) Compound E-2 (53.0 g (0.080 eq / epoxy group)) and 2- (4-hydroxyphenyl) ethanol (11.1 g (1.0 eq.)) Were placed in an eggplant type flask and heated Lt; / RTI &gt; Benzyltrimethylammonium chloride (3.0 g (0.20 eq.)) Was added, and the mixture was stirred at 120 占 폚 for 24 hours. The mixture was cooled until the liquid temperature became 60 DEG C or less, 300 mL of chloroform was added, and the mixture was washed once with 300 mL of 1% NaOH aqueous solution and then washed with 300 mL of water five times.

To the obtained organic phase, magnesium sulfate was added, and after drying, the solid was separated by filtration and the solvent of the obtained organic phase was distilled off under reduced pressure to obtain 59.0 g of a reaction intermediate G-7 as a light yellow transparent dots, .

(2) Reaction product G-7 (59.0 g), epichlorohydrin (93.3 g) and benzyltrimethylammonium chloride (3.1 g) were added to a reaction vessel equipped with a mechanical stirrer, thermometer, temperature controller, condenser, Dean Stark trap and dropping funnel And placed in a 500 milliliter three-neck round bottom flask.

Subsequently, the mixture was heated to about 50 to 60 DEG C with stirring under a high vacuum of 50 torr to reflux epichlorohydrin. 25.2 g of 48% NaOH aqueous solution was slowly added to the mixture over 2 hours. As the azeotropic water was produced, the stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. After completion of the addition, stirring was continued for 3 hours. Subsequently, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and the mixture was washed six times with 300 mL of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 50.5 g of Resin 7 as a pale yellow viscous material.

(3) 47.3 g of Resin 7, 5.2 g of methacrylic acid, 0.1 g of triphenylphosphine and 10 mg of BHT were mixed and stirred at 100 占 폚 for 7 hours. 51.0 g of a methacrylic curable resin 7 having a light yellow dot structure was obtained.

[Synthesis Example 8] Synthesis of methacrylic curable resin 8

(1) Compound E-2 (94.0 g (0.15 eq / epoxy group)) and phenol (21.2 g (1.5 eq.)) Were placed in an eggplant-shaped flask and heated and stirred so that the liquid temperature was 120 占 폚. Benzyltrimethylammonium chloride (2.8 g (0.10 eq.)) Was added, and the mixture was stirred at 120 占 폚 for 24 hours. The mixture was cooled until the liquid temperature became 60 DEG C or lower, 300 mL of methyl isobutyl ketone was added, and the mixture was washed twice with 300 mL of 1% NaOH aqueous solution and then with 300 mL of water four times.

To the obtained organic phase, magnesium sulfate was added, and after drying, the solid was separated by filtration and the solvent of the obtained organic phase was distilled off under reduced pressure to give 90.0 g of a reaction intermediate G-8 .

(2) Reaction Product G-8 (90.0 g), epichlorohydrin (130.0 g) and benzyltrimethylammonium chloride (2.6 g) were placed in a flask equipped with a mechanical stirrer, thermometer, thermostat, condenser, Dean Stark trap and dropping funnel And placed in a 500 milliliter three-neck round bottom flask.

Subsequently, the mixture was heated to about 50 to 60 DEG C with stirring under a high vacuum of 50 torr to reflux epichlorohydrin. 21.0 g of 48% aqueous NaOH solution was slowly added to the mixture over 2 hours. As the azeotropic water was produced, the stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. After completion of the addition, stirring was continued for 3 hours. Subsequently, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and the mixture was washed six times with 300 mL of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 80 g of resin 8 as a pale yellow viscous material.

(3) 57.6 g of Resin 8, 3.5 g of methacrylic acid, 0.1 g of triphenylphosphine and 10 mg of BHT were mixed and stirred at 100 占 폚 for 13 hours. To obtain 59.2 g of a methacrylic curable resin 8 having a light yellow dot structure.

[Synthesis Example 9] Methacrylated curable resin 9

(1) Synthesis of Compound E-2 (63.0 g (0.10 eq. / Epoxy group)) and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (95.0 g ) Were placed in a eggplant-shaped flask, and the mixture was heated to reflux at 120 ° C. Benzyltrimethylammonium chloride (0.9 g (0.050 eq.)) Was added, and the mixture was stirred at 120 占 폚 for 20 hours. The mixture was cooled until the liquid temperature became 60 DEG C or less, 300 mL of chloroform was added, and the mixture was washed 14 times with 300 mL of 1% NaOH aqueous solution and washed with 300 mL of water five times.

After drying, the solid matter was separated by filtration by filtration and the solvent of the obtained organic phase was distilled off by distillation under reduced pressure to obtain 56.0 g of a reaction intermediate G-9 as a light yellow transparent dots, .

(2) Reaction product G-9 (56.0 g), epichlorohydrin (111.0 g) and benzyltrimethylammonium chloride (2.2 g) were added to a reaction vessel equipped with a mechanical stirrer, thermometer, temperature controller, condenser, Dean Stark trap and dropping funnel And placed in a 500 milliliter three-neck round bottom flask.

Subsequently, the mixture was heated to about 50 to 60 DEG C with stirring under a high vacuum of 50 torr to reflux epichlorohydrin. 18.0 g of 48% aqueous NaOH solution was slowly added to the mixture over 2 hours. As the azeotropic water was produced, the stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. After completion of the addition, stirring was continued for 3 hours. Subsequently, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and the mixture was washed six times with 300 mL of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 54.0 g of Resin 9 as a pale yellow viscous material.

(3) 51.0 g of Resin 9, 4.3 g of methacrylic acid, 0.1 g of triphenylphosphine and 10 mg of BHT were mixed and stirred at 100 占 폚 for 9 hours. To obtain 49.8 g of a methacrylic curable resin 9 having a light yellow dot structure.

[Synthesis Example 10] Synthesis of methacrylic curable resin 10

(1) 1000.0 g (1.0 equivalent / hydroxyl group) of PEG-2000 (manufactured by Toho Chemical Industry Co., Ltd.), 925.0 g (10 equivalents) of epichlorohydrin and 18.6 g (0.10 equivalent) of benzyltrimethylammonium chloride were placed on a mechanical stirrer, Was placed in a 5-liter three-neck round bottom flask equipped with a thermostat, condenser, Dean Stark trap and dropping funnel.

Subsequently, the mixture was heated to about 50 to 60 DEG C with stirring under a high vacuum of 50 torr to reflux epichlorohydrin. 150.0 g of 48% aqueous NaOH solution was slowly added to the mixture over 2 hours. As the azeotropic water was produced, the stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture.

 After completion of the addition, stirring was continued for 3 hours. Subsequently, the reaction mixture was cooled to room temperature, 1 L of chloroform was added, and the mixture was washed three times with 1 L of water. The obtained organic phase solvent was removed by distillation under reduced pressure to obtain 760.0 g of Compound E-5 as a white solid.

(2) Compound E-5 (220.0 g (0.20 eq. / Epoxy group)) and bisphenol A (31.0 g (1.4 eq.)) Were placed in an eggplant type flask and heated and stirred so that the liquid temperature reached 110 占 폚. Benzyltrimethylammonium chloride (1.9 g), and the mixture was stirred at 110 占 폚 for 20 hours.

The mixture was cooled until the liquid temperature became 60 DEG C or less, and 300 mL of chloroform was added. The mixture was washed three times with 300 mL of 1% aqueous NaOH solution and then washed six times with 300 mL of water.

To the obtained organic phase, magnesium sulfate was added, and after drying, the solid was separated by filtration and the solvent of the obtained organic phase was distilled off by distillation under reduced pressure to obtain 110.0 g of the reaction product G-10 as a light yellow transparent dots, .

(3) Reaction Product G-10 (108.0 g), epichlorohydrin (175.0 g) and benzyltrimethylammonium chloride (2.3 g) were placed in a reaction vessel equipped with a mechanical stirrer, thermometer, temperature controller, condenser, Dean Stark trap and dropping funnel Lt; RTI ID = 0.0 &gt; 1-liter &lt; / RTI &gt; round bottom flask.

Subsequently, the mixture was heated to about 50 to 60 DEG C with stirring under a high vacuum of 50 torr to reflux epichlorohydrin. 19.0 g of 48% aqueous NaOH solution was slowly added to the mixture over 2 hours. As the azeotropic water was produced, the stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. After completion of the addition, stirring was continued for 3 hours.

Subsequently, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and the mixture was washed six times with 300 mL of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 92.0 g of a resin 10 having a white copper solid.

(4) 21.7 g of Resin 10, 1.1 g of methacrylic acid, 0.1 g of benzyltrimethylammonium chloride, 50.0 g of toluene and 15 mg of BHT were mixed and stirred at 100 占 폚 for 7 hours. Subsequently, the reaction mixture was cooled to room temperature, 100 mL of chloroform was added, and the mixture was washed three times with 100 mL of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 17.0 g of a methacrylated curable resin 10 having a white pale solid.

[Synthesis Example 11] Synthesis of methacrylic curable resin 11

(1 equivalent) of polytetramethylene ether glycol (PTMG) 2000 (manufactured by Mitsubishi Chemical Corporation), 463.0 g (10 equivalents) of epichlorohydrin, 9.3 g (0.10 equivalent) of benzyltrimethylammonium chloride, Was placed in a 2 liter three-neck round bottom flask equipped with a mechanical stirrer, thermometer, thermostat, condenser, Dean Stark trap and dropping funnel.

Subsequently, the mixture was heated to about 50 to 60 DEG C with stirring under a high vacuum of 50 torr to reflux epichlorohydrin. 75.0 g of a 48% aqueous NaOH solution was slowly added to the mixture over 2 hours. As the azeotropic water was produced, the stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture.

After completion of the addition, stirring was continued for 3 hours. Subsequently, the reaction mixture was cooled to room temperature, 1 L of chloroform was added, and the mixture was washed three times with 1 L of water. The obtained organic phase solvent was removed by distillation under reduced pressure to obtain 450.0 g of Compound E-6 as a white solid.

(2) Compound E-6 (127.0 g (0.10 eq. / Epoxy group)) and bisphenol A (15.0 g (1.4 eq.)) Were placed in an eggplant type flask and heated and stirred so that the liquid temperature was 110 占 폚. Benzyltrimethylammonium chloride (0.9 g), and the mixture was stirred at 110 占 폚 for 20 hours.

The mixture was cooled until the liquid temperature became 60 DEG C or less, and 300 mL of chloroform was added. The mixture was washed three times with 300 mL of 1% aqueous NaOH solution and then washed six times with 300 mL of water.

To the obtained organic phase, magnesium sulfate was added, and after drying, the solid was separated by filtration and the solvent of the obtained organic phase was distilled off by distillation under reduced pressure to obtain 120.0 g of the reaction product G-11 .

(3) Reaction The reaction product G-11 (117.0 g), epichlorohydrin (125.0 g) and benzyltrimethylammonium chloride (2.5 g) were placed in a flask equipped with a mechanical stirrer, thermometer, temperature controller, condenser, Dean Stark trap and dropping funnel Lt; RTI ID = 0.0 &gt; 1-liter &lt; / RTI &gt; round bottom flask.

Subsequently, the mixture was heated to about 50 to 60 DEG C with stirring under a high vacuum of 50 torr to reflux epichlorohydrin. 20.0 g of a 48% aqueous NaOH solution was slowly added to the mixture over 2 hours. As the azeotropic product was produced, the stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. After completion of the addition, stirring was continued for 3 hours.

Subsequently, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and the mixture was washed six times with 300 mL of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 92.0 g of Resin 11 as a light yellow spot-formed product.

(4) 55.0 g of Resin 11, 2.6 g of methacrylic acid, 0.1 g of triphenylphosphine and 10 mg of BHT were mixed and stirred at 100 占 폚 for 7 hours. To obtain 54.0 g of methacrylic curable resin 11 having a light yellow dot structure.

[Production of Photopolymerization Initiator]

The photopolymerization initiators used in Examples and Comparative Examples were prepared as follows.

&Lt; Preparation of photopolymerization initiator 1 >

(0.1 equivalent / epoxy group), 4-dimethylaminobenzoic acid (16.5 g, 1.0 equivalent) and benzyltrimethylammonium chloride (3.7 g, 0.20 equivalents) were added to a solution of 10 g of DENARCOL EX-830 (diglycidyl ether of Nagase- And 25.0 g of MIBK (methyl isobutyl ketone) were placed in a flask and stirred at 110 DEG C for 24 hours. The reaction mixture was cooled to room temperature, dissolved in 50 g of chloroform, and washed six times in 100 ml of water. The organic phase solvent was distilled off under reduced pressure to obtain 35.3 g of Photopolymerization Initiator 1.

&Lt; Preparation of photopolymerization initiator 2 >

22.8 g (1.0 eq.) Of 2-hydroxy-9H-thioxanthen-9-one, 26.8 g (0.10 eq. / Epoxy group) of Denacol EX-830 (diglycidyl ether of Nagase Chemtech, 3.7 g (0.20 eq.) Of trimethyl ammonium chloride and 40.0 g of MIBK were placed in a flask and stirred at 110 DEG C for 72 hours. The reaction mixture was cooled to room temperature, dissolved in 50 g of chloroform, and washed six times in 100 ml of water. The organic phase solvent was distilled off under reduced pressure to obtain 36.2 g of the photopolymerization initiator 2.

[Examples 1 to 11 and Comparative Example 1]

Each of the partially methacrylated bisphenol A epoxy resin, methacrylic curable resins 1 to 11, the photopolymerization initiators 1 and 2, and the curing agent EH-5030S (produced by ADEKA (a polyamine-based compound ) Were mixed in the blending amounts (parts by weight) shown in the following Table 1 and sufficiently kneaded using a three-roll mill (C-43/4 x 10, manufactured by Inoue Seisakusho) 1 &lt; / RTI &gt;

Each of the compounds prepared in Synthesis Examples and Comparative Synthesis Examples and each of these liquid crystal encapsulant compositions was evaluated by the following test.

[Exam conditions]

The epoxy equivalent weight, viscosity and NI point change of the partially methacrylated bisphenol A type epoxy resin and the methacrylic curable resins 1 to 9 and 11 were measured,

The epoxy equivalent and the NI point change were measured for the methacrylic curable resin 10,

The photopolymerization initiators 1 and 2 were measured for viscosity and NI point change,

For the curing agent (EH-5030S), the NI point change was measured,

The cured product Tg and the storage modulus at various temperatures of the liquid crystal encapsulant compositions prepared in Examples 1 to 11 and Comparative Example 1 were measured.

(1) Measurement of epoxy equivalence

JIS K 7236: 2001.

(2) Viscosity measurement

The measurement was carried out at 25 占 폚 using an E-type viscometer (RE105U manufactured by Ohtsuka Kogyo Co., Ltd.).

The rotor and the number of revolutions were selected as follows.

Partially methacrylated bisphenol A type epoxy resin: 3 占 R7.7 rotor, number of revolutions 10 rpm

Methacrylated curable resin 1: 3 占 폚 R7.7 rotor, number of revolutions 15 rpm

Methacrylated curable resin 2: 3 占 폚 R7.7 rotor, number of revolutions 15 rpm

Methacrylated curable resin 3: 3 占 폚 R7.7 rotor, revolution number 0.5 rpm

Methacrylated curable resin 4: 3 占 R7.7 rotor, rotation number 0.2 rpm

Methacrylic curable resin 5: 1 占 34 占 R24 rotor, revolutions 2.0 rpm

Methacrylated curable resin 6: 3 占 폚 R14 rotor, revolution speed 5.0 rpm

Methacrylated curable resin 7: 1 占 34 占 R24 rotor, revolution number 5.0 rpm

Methacrylated curable resin 8: 1 占 34 占 R24 rotor, revolutions 2.0 rpm

Methacrylated curable resin 9: 3 占 폚 R7.7 rotor, revolutions 2.0 rpm

Methacrylated curable resin 11: 3 占 폚 R7.7 rotor, rotation number 15 rpm

(3) NI point change measurement

0.1 g of each of the partially methacrylated bisphenol A type epoxy resin, the methacrylic curable resin 1 to 11, the photopolymerization initiator 1 and 2 and the curing agent (EH-5030S) was placed in an ampule bottle, and liquid crystal (MLC-11900-080, Ltd.) was further added. The bottle was placed in an oven at 120 deg. C for 1 hour, then allowed to stand at room temperature, returned to room temperature (25 deg. C) and then taken out of the liquid crystal portion and filtered through a 0.2 mu m filter to obtain a liquid crystal sample for evaluation.

The NI point was measured using a differential scanning calorimeter (DSC, manufactured by Perkin Elmer Co., Ltd., PYRIS6), and 10 mg of a liquid crystal sample for evaluation was sealed in an aluminum sample pan at a temperature raising rate of 5 deg. C / min. Further, 10 mg of the above liquid crystal was sealed in an aluminum sample pan, and the measurement was carried out under the condition of a heating rate of 5 캜 / min.

The difference TE-TB between the endothermic peak top (phase transition temperature) TB of the blank and the endothermic peak top (phase transition temperature) TE of the evaluation liquid crystal was referred to as NI point change. From the standpoint of suppressing the elution of the component contained in the liquid crystal encapsulant into the liquid crystal, stably securing the alignment of the liquid crystal, and improving display characteristics, the absolute value of the NI point change is preferably as small as possible.

(4) Tg measurement

The liquid crystal encapsulant compositions prepared in Examples 1 to 11 and Comparative Example 1 were molded into a mold having a length of 5 cm, a width of 5 mm and a thickness of 0.5 mm, and ultraviolet rays (UV irradiation device: UVX-01224S1, , 30 sec at 100 mW / cm 2/365 nm) was cured by irradiation with an accumulated light quantity of 3000 mJ / cm 2, and then thermosetting was performed in a hot air oven at 120 ° C for 1 hour to prepare a hardened test piece.

The obtained cured product specimen was measured at a frequency of 1.0 Hz at a rate of 2 DEG C / min in a range of -50 DEG C to 100 DEG C while measuring a strain mode in a dynamic viscoelasticity measuring apparatus (DMA, DMS6100, manufactured by Seiko Instruments Inc.) . The peak top temperature at the loss tangent tan? Of the obtained result was Tg.

(5) Measurement of storage modulus

The liquid crystal encapsulant compositions prepared in Examples 1 to 11 and Comparative Example 1 were subjected to measurement with a dynamic viscoelasticity measuring device (DMA, manufactured by Seiko Instruments Inc., DMS6100) under the same conditions as in the case of Tg . The values of storage modulus at each temperature were extracted from the obtained results.

The results of the above evaluation are shown in Table 1 together with the composition of the liquid crystal sealing composition of Examples 1 to 11 and Comparative Example 1.

Claims (11)

A curable resin represented by the following formula (1): &quot;

Wherein m is a number ranging from 1 to 7,
X is, independently from each other, a hydrogen atom, a hydroxyl group, a glycidyloxy group, or a methylglycidyloxy group,
R ¹ are each independently a hydrogen atom, a glycidyl group or a methyl glycidyl group,
R ² are each independently a hydrogen atom or a methyl group,
The A rings each independently represent a group including a ring structure in which the sum of the number of carbon atoms and the number of hetero atoms is 5 or more and is one or more aromatic rings or heteroaromatic rings,
Y represents an oxygen atom bonded to the A ring when at least one of X is a hydrogen atom and X and A ring structure are directly bonded to each other, X is independently a hydroxyl group, a glycidyloxy group or a methylglycidyloxy group, And X are bonded to each other via a linking group and / or when X is a condensed ring or a heteroaromatic ring of an aromatic ring having at least one A-ring ring structure, the following formula (1a ):

(Wherein Y ¹ is each independently an alkylene group having 2 to 5 carbon atoms and n is a number in the range of 1 to 250)

(Wherein Y ² is independently a direct bond or an alkylene group having 1 or 2 carbon atoms, R ³ is each independently a hydrogen atom or a methyl group, p and q are each independently a number of 0 or more, (1b) or the above formula (1b) is a group in which a part or all of the unsaturated bonds in the formula (1b) are hydrogenated, 1b), wherein the linking group is selected from the group consisting of an alkylene group having 1 to 4 carbon atoms, an alkylidene group having 2 to 4 carbon atoms, an ether group, an ester group, a keto group, a sulfide group A sulfonyl group, and a sulfonyl group,
Wherein the average number x of the total number of R ¹ , which is a glycidyl group or a methyl glycidyl group, and X, which is a glycidyloxy group or a methylglycidyloxy group, in R ¹ and X is 1 or more, Sealant composition. A curable resin represented by the following formula (1): &quot;

Wherein m is a number ranging from 1 to 7,
X is, independently from each other, a hydrogen atom, a hydroxyl group, a glycidyloxy group, or a methylglycidyloxy group,
R ¹ are each independently a hydrogen atom, a glycidyl group or a methyl glycidyl group,
R ² are each independently a hydrogen atom or a methyl group,
The A rings each independently represent an aromatic ring having a total of 5 or more carbon atoms and the number of heteroatoms and at least one aromatic ring or a ring containing a heteroaromatic ring,
Y represents an oxygen atom bonded to the A ring when at least one of X is a hydrogen atom and X and A ring structure are directly bonded to each other, X is independently a hydroxyl group, a glycidyloxy group or a methylglycidyloxy group, And X are bonded to each other via a linking group and / or when X is a condensed ring or a heteroaromatic ring of an aromatic ring having at least one A-ring ring structure, the following formula (1a ):

(Wherein Y ¹ is each independently an alkylene group having 2 to 5 carbon atoms and n is a number in the range of 1 to 250)

(Wherein Y ² is independently a direct bond or an alkylene group having 1 or 2 carbon atoms, R ³ is each independently a hydrogen atom or a methyl group, p and q are each independently 0 or more, (1b) or the above formula (1b) is a group in which a part or all of the unsaturated bonds in the formula (1b) are hydrogenated, 1b), wherein the linking group is selected from the group consisting of an alkylene group having 1 to 4 carbon atoms, an alkylidene group having 2 to 4 carbon atoms, an ether group, an ester group, a keto group, a sulfide group A sulfonyl group, and a sulfonyl group,
An epoxy group, a hydroxyl group and an epoxy group of R ¹ and X in which the average of x of the total number of R ¹ , which is a glycidyl group or a methyl glycidyl group, and X, which is a glycidyloxy group or a methylglycidyloxy group, (Meth) acrylate curable resin having a (meth) acryl group introduced into at least a part of the unsaturated bond. The curable resin composition according to claim 1, wherein the curable resin represented by the following formula (1)

Wherein m is a number ranging from 1 to 7,
X is, independently from each other, a hydrogen atom, a hydroxyl group, a glycidyloxy group, or a methylglycidyloxy group,
R ¹ are each independently a hydrogen atom, a glycidyl group or a methyl glycidyl group,
R ² are each independently a hydrogen atom or a methyl group,
A rings each independently represent a group containing a ring structure which is an aromatic ring or a heteroaromatic ring in which the sum of the number of carbon atoms and the number of hetero atoms is 5 or more,
Y represents an oxygen atom bonded to the A ring when at least one of X is a hydrogen atom and X and A ring structure are directly bonded to each other, X is independently a hydroxyl group, a glycidyloxy group or a methylglycidyloxy group, And X are bonded to each other via a linking group and / or when X is a condensed ring or a heteroaromatic ring of an aromatic ring having at least one A-ring ring structure, the following formula (1a ):

(Wherein Y ¹ is each independently an alkylene group having 2 to 5 carbon atoms and n is a number in the range of 1 to 250)

(Wherein Y ² is independently a direct bond or an alkylene group having 1 or 2 carbon atoms, R ³ is each independently a hydrogen atom or a methyl group, p and q are each independently 0 or more, (1b) or the above formula (1b) is a group in which a part or all of the unsaturated bonds in the formula (1b) are hydrogenated, 1b), wherein the linking group is selected from the group consisting of an alkylene group having 1 to 4 carbon atoms, an alkylidene group having 2 to 4 carbon atoms, an ether group, an ester group, a keto group, a sulfide group A sulfonyl group, and a sulfonyl group,
An epoxy group, a hydroxyl group and an epoxy group of R ¹ and X in which the average of x of the total number of R ¹ , which is a glycidyl group or a methyl glycidyl group, and X, which is a glycidyloxy group or a methylglycidyloxy group, (Meth) acrylate curable resin having a (meth) acryl group introduced into at least a part of the unsaturated bond. 4. The compound according to any one of claims 1 to 3, wherein in the formula (1), the number of carbon atoms contained in the ring A is 4 to 40, the number of oxygen atoms is 0 to 5, the number of nitrogen atoms is 0 to 5 , The number of sulfur atoms is 0 to 5, and the number of ring structures contained in the ring A is 1 to 5. [ The liquid crystal sealing composition according to any one of claims 1 to 3, wherein the content of the curable resin and / or the (meth) acryl-curable resin in the liquid crystal sealing composition is 5 to 95% by weight. The liquid crystal display according to any one of claims 1 to 3, wherein the liquid crystal sealing composition comprises a compound H having an ethylenic unsaturated group and / or an epoxy group (excluding the curable resin and the (meth) acryl-curable resin) Further comprising a liquid crystal polymer. The liquid crystal sealing composition according to any one of claims 1 to 3, which is for a liquid crystal dropping process. The liquid crystal encapsulant composition according to any one of claims 1 to 3, which is for a flexible liquid crystal display. A curable resin represented by the following formula (1): &quot;

Wherein m is a number ranging from 1 to 7,
X is, independently from each other, a hydrogen atom, a hydroxyl group, a glycidyloxy group, or a methylglycidyloxy group,
R ¹ are each independently a hydrogen atom, a glycidyl group or a methyl glycidyl group,
R ² are each independently a hydrogen atom or a methyl group,
A rings each independently represent a group containing a ring structure which is an aromatic ring or a heteroaromatic ring in which the sum of the number of carbon atoms and the number of hetero atoms is 5 or more,
Y represents an oxygen atom bonded to the A ring when at least one of X is a hydrogen atom and X and A ring structure are directly bonded to each other, X is independently a hydroxyl group, a glycidyloxy group or a methylglycidyloxy group, And X are bonded to each other via a linking group and / or when X is a condensed ring or a heteroaromatic ring of an aromatic ring having at least one A-ring ring structure, the following formula (1a ):

(Wherein Y ¹ is each independently an alkylene group having 2 to 5 carbon atoms and n is a number in the range of 1 to 250)

(Wherein Y ² is independently a direct bond or an alkylene group having 1 or 2 carbon atoms, R ³ is each independently a hydrogen atom or a methyl group, p and q are each independently 0 or more, (1b) or the above formula (1b) is a group in which a part or all of the unsaturated bonds in the formula (1b) are hydrogenated, 1b), wherein the linking group is selected from the group consisting of an alkylene group having 1 to 4 carbon atoms, an alkylidene group having 2 to 4 carbon atoms, an ether group, an ester group, a keto group, a sulfide group A sulfonyl group, and a sulfonyl group,
In the above R ¹ and X, the average x of the total number of R ¹ , which is a glycidyl group or a methyl glycidyl group, and X, which is a glycidyloxy group or a methylglycidyloxy group, is 1 or more. 10. The compound according to claim 9, wherein the number of carbon atoms contained in the ring A is 4 to 40, the number of oxygen atoms is 0 to 5, the number of nitrogen atoms is 0 to 5, the number of sulfur atoms is 0 to 5 , And the number of ring structures contained in the ring A is 1 to 5. A (meth) acrylated curable resin having a (meth) acryl group introduced into at least a part of an epoxy group, a hydroxyl group and an unsaturated bond of the curable resin according to claim 9 or 10.