TWI662055B - Curable resin, (meth) acrylic curable resin, and liquid crystal sealant composition having excellent softness after curing - Google Patents

Abstract

The present invention aims to provide a curable resin and a liquid crystal sealant composition containing the curable resin. The curable resin is capable of being formed without any problem even when the flexible liquid crystal display is bent, and the adhesive can be maintained. A hardened product in a state of softness and a low liquid crystal contamination property which hardly affects liquid crystal alignment.

The present invention is a curable resin represented by the following formula (1): (In the formula, X, R ¹ , R ² , Y, and A rings are predetermined bases, and m is a number in the range of 1 to 7).

Description

Curable resin, (meth) acrylic curable resin, and liquid crystal sealant composition having excellent softness after curing

The present invention relates to a curable resin and a (meth) acrylic curable resin used for a liquid crystal sealant that can exhibit excellent flexibility even after curing, and a liquid crystal sealant composition containing such a curable resin. .

For the manufacture of liquid crystal display devices such as liquid crystal panels, for example, a liquid crystal sealant is applied to the periphery of any one of the two substrates constituting the liquid crystal panel, a predetermined amount of liquid crystal is dropped on any of the substrates, and the two substrates are bonded under vacuum. The liquid crystal dropping method which returns to atmospheric pressure and further fills liquid crystals between the substrates and hardens the liquid crystal sealant is popular.

In the liquid crystal dropping method, from the viewpoint of high-speed curing, a radical polymerization reactive compound using an epoxy acrylate-based compound as a main agent can be widely used for a liquid crystal sealant (for example, refer to Patent Document 1).

[Advanced technical literature] [Patent Literature]

[Patent Document 1] JP 2007-297470

[Summary of Invention]

In the liquid crystal dropping method, a sealant is coated in a frame shape on any of two substrates, and then a frame seal is formed. The liquid crystal is dropped on any of the substrates, and the two substrates are bonded under vacuum, and irradiated with UV light. After the liquid crystal sealant is photocured, it is thermally cured at a temperature above the NImatic point of the liquid crystal (Nematic Isotropic point), and the liquid crystal sealant is thermally cured while aligning the liquid crystal.

For a large panel like a TV, because the panel is large, there is a certain distance from the liquid crystal dripping point to the frame seal. After the liquid crystal is bonded to the panel and irradiated with UV, the liquid crystal and the uncured liquid crystal sealant are combined. No contact, or the contact time is short, mainly because the liquid crystal sealant is first hardened by light and then contacted with the liquid crystal.

On the other hand, in recent years, small liquid crystal panels, which have increased demand due to the spread of smart phones or tablet-type terminals, have a shorter distance from the liquid crystal dripping point to the frame seal. The liquid crystal sealant is in contact with the liquid crystal in an uncured state, or the contact time is relatively long. Therefore, the liquid crystal contamination in the uncured state of the liquid crystal sealant becomes a problem more than in the past.

A radical polymerization reactive liquid crystal sealant using an epoxy compound containing a conventional epoxy / acrylic compound as a main agent is not completely satisfactory in terms of the requirements required to solve this problem.

In addition, in recent years, a market for a safe, lightweight, and freely foldable flexible liquid crystal display such as electronic paper is expected to develop. The flexible liquid crystal display is manufactured using a flexible substrate such as a plastic film instead of a rigid glass substrate in the past.

For liquid crystal sealants, the former was used to form a relatively rigid hardened material, so although it is suitable for the adhesion of substrates with less change in shape, such as glass, flexible displays made of flexible substrates such as films have traditionally been used in the past. In a product, a shape change caused by bending or shrinkage of a substrate may cause phenomena such as breakage or peeling, so it is not sufficiently suitable for this application.

From such a viewpoint, a liquid crystal sealant having sufficient flexibility is required as a sealant particularly suitable for a flexible liquid crystal display after curing.

From the above, it is known that the object of the present invention is to provide a hardened material with flexibility that can maintain the adhered state without any problem even when the flexible liquid crystal display is bent, and the liquid crystal has a low contamination property for the liquid crystal. A hardenable resin and a liquid crystal sealant composition containing the hardenable resin.

The present invention includes the following aspects.

(1) A curable resin represented by the following formula (1): [In the formula, m is a number in a range of 1 to 7, each of R ^{1 is} independently a hydrogen atom, glycidyl or methyl glycidyl, each of R ^{2 is} independently a hydrogen atom or methyl, and each of A rings is independent of each other Is a group having a total of 5 or more carbon atoms and a number of heteroatoms and containing one or more aromatic rings or heteroaromatic rings, and X is independently a hydrogen atom, a hydroxyl group, a glycidyloxy group, or a methylglycidyl group Oxygen, Y is the following formula (1a): (In the formula, Y ^{1 is} each independently an alkylene group having 2 to 5 carbon atoms, and n is a number in a range of 1 to 250), and the following formula (1b): (In the formula, each of Y ² is directly bonded or an alkylene group having 1 or 2 carbon atoms, R ^{3 is} independently a hydrogen atom or a methyl group, and p and q are each independently 0 or more, and these total the base structure is in the range of 1 to 200), or the formula (1b) unsaturated bonds in a part or all hydrogenated, For the R ¹ and X, glycidyl group or glycidyl group R & lt methyl ¹ The average number of the total of X with glycidyloxy or methylglycidyloxy x is 1 or more].

(2) The curable resin according to (1), wherein in the formula (1), the number of carbon atoms contained in ring A is 4 to 40, the number of oxygen atoms is 0 to 5, and 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 A ring is 1 to 5.

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

(4) A liquid crystal sealant composition containing the curable resin according to (1) or (2) and / or the (meth) acrylic curable resin according to (3).

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

(6) The liquid crystal sealant composition is (4) further containing a compound H having an ethylenically unsaturated group and / or an epoxy group (except for the curable resin and (meth) acrylic curable resin) ) Or the liquid crystal sealant composition according to (5).

According to the present invention, even in the case of a flexible flexible liquid crystal display, it is possible to form a hardened material with flexibility that can maintain an adhered state without problems, and the liquid crystal has low pollution, and it is difficult to create liquid crystal alignment. A curable resin and a liquid crystal sealant composition containing the curable resin.

[Form of Implementing Invention]

The present invention is explained in detail below. In this specification, (meth) acrylic acid means methacrylic acid and / or acrylic acid, and (meth) acrylate means methacrylate and / or acrylate.

[The 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 is a soft part formed by an ether site or a predetermined base Y having a block enclosed by an m-shaped bracket, and the cured product obtained by curing the curable resin of the present invention can be considered as this. The soft part can exhibit softness or rubber elasticity, and it has excellent softness. As shown in formula (1), the curable resin of the present invention has a flexible polymer structure, so that it can be considered that the crosslinked density of the cured product of the curable resin of the present invention can be moderately reduced, and the aforementioned flexibility can be exerted. .

In addition to having the aforementioned soft portion, the curable resin of the present invention has a structure containing an aromatic ring such as an A ring, and has such a predetermined structure. The curable resin of the present invention having a structure has a low liquid crystal contamination property.

(M related)

In the formula (1), m is a number in a range of 1 to 7, and from the viewpoint of the viscosity or handleability of the curable resin of the present invention, a number in a range of 1 to 5 is preferable, and a range of 1 to 3 is preferable. The number is better. The curable resin of the present invention can be produced, for example, by a production method described later, and in this case, it may be a mixture of plural kinds of compounds having different numbers of m.

(About X)

In the formula (1), each of X is independently 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, this part may cause a crosslinking reaction, and a (meth) acrylic group may be introduced into this part.

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

(About R ¹ )

In the above formula (1), each of R ^{1 is} independently a hydrogen atom, a glycidyl group, or a methyl glycidyl group. As described later, a group containing R ¹ may cause a crosslinking reaction, and a (meth) acrylic group may be introduced into this portion. When m is a number of 2 or more, R ¹ in the block enclosed by the parentheses in which m is described is also independent of each other and may be the same or different from each other.

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

For the curable resin of the present invention represented by the above formula (1), R ¹ of glycidyl or methyl glycidyl and X of glycidyloxy or methyl glycidyloxy (in other words, having an epoxy group) The average x of the total number of R ¹ and X) is 1 or more, and preferably 2 or more. In this way, the hardening resin has a certain number of crosslinkable groups, and by having the above-mentioned soft parts, the hardenability required for the liquid crystal sealant is secured. In terms of adhesiveness, excellent softness of the cured product is achieved (hereinafter also referred to as "flexibility after curing").

The above-mentioned x is from the viewpoint of the liquid crystal sealant composition containing the curable resin of the present invention described later, such as workability that affects viscosity, coating properties, and physical properties such as strength after curing that affects crosslink density. 2 or more is preferable, 2 to 16 is preferable, and 2 to 8 is more preferable.

For x, the average molecular weight and molecular weight of the hardening resin can be measured by high-speed liquid chromatography (HPLC) and liquid chromatography mass analysis (LC-MS) or gel filtration / permeation chromatography (GPC / GFC). Distribution, and after further measuring the epoxy equivalent of the curable resin, x in the above formula (1) was calculated from the measurement results.

(About R ² )

In the above formula (1), R ² are each independently a hydrogen atom or a methyl group. From the viewpoint of low liquid crystal contamination of the curable resin of the present invention, a hydrogen atom is preferred. When m is a number of 2 or more, R ² in the block enclosed by the parentheses in which m is recorded is also independent of each other and may be the same or different from each other.

(About A ring)

In the above formula (1), each of the A rings is independently a carbon number and a total number of hetero atoms of 5 or more, and contains one or more aromatic rings or heteroaromatic ring groups. When the total number of carbon atoms and heteroatoms is 5 or more, it means that if the carbon atoms and heteroatoms constituting the ring and the atoms constituting the ring bonded to the ring have a carbon atom or a heteroatom when viewed from the entire A ring, The total number of these carbon atoms and heteroatoms is 5 or more.

Regarding the A ring, from the viewpoint of the viscosity and handleability of the curable resin of the present invention and the liquid crystal sealant composition described later, the number of carbon atoms contained therein is 4 to 40, the number of oxygen atoms is 0 to 5, and 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 A ring is preferably 1 to 5.

The ring structure (aromatic ring and heteroaromatic ring) contained in the A ring may exist singly or in combination of two or more kinds. The aforementioned ring structure may be a single ring structure or a condensed ring structure. In addition, there may be a plurality of these ring structures bonded via a direct bond or a linking group.

Examples of the linking group include an alkylene group having 1 to 4 carbon atoms, an alkylene group having 2 to 4 carbon atoms, an ether group, an ester group, a keto group, a thioether group, and a sulfonyl group. The oxygen atom bonded to the A ring and the X and A rings in the formula (1) may be bonded via the linking group.

These ring structures may each independently have a substituent. Examples of such a substituent include alkyl, alkoxy, fluorenyl, and formamidine Group, carboxyl group, ester group, cyano group, nitro group, sulfonate group, amido group, hydroxyl group, mercapto group, silicon group and the like.

Examples of the ring structure contained in the A ring include benzene ring, naphthalene ring, fluorene ring, anthracene ring, furan ring, pyrrole ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, and thiazine Rings, and those in which the aforementioned substituents are bonded to the rings.

In addition, when m is a number of 2 or more, the A rings in the blocks enclosed by the parentheses in which m is described may be the same as or different from each other.

(About Y)

Next, Y in the formula (1) is a structural group in which part or all of the unsaturated bonds in the following formula (1a), (1b) or the unsaturated bond in the formula (1b) is hydrogenated. In addition, when m is a number of 2 or more, Y in the block enclosed by the parentheses in which m is described may be the same or different from each other or independently.

In the formula (1a), Y ^{1 is} independently an alkylene group having 2 to 5 carbon atoms, and n is a number in a range of 1 to 250. Examples of the above-mentioned alkylene group include ethylene, propyl, trimethyl, tetramethyl and neopentyl. From the viewpoints of the post-curing flexibility and liquid crystal contamination of the curable resin of the present invention, Y ¹ is preferably an ethylene or tetramethyl group. From the aforementioned flexibility and the handleability of the curable resin of the present invention, From a viewpoint, n is preferably a number in a range of 5 to 70, and more preferably a number in a range of 10 to 50.

In addition, when n is a number of 2 or more, Y ^{1 in} each of the repeating units enclosed by the parentheses describing n is also independent of each other and may be the same or different from each other.

And for formula (1b), Y ² are each independently bonded to each other or an alkylene group having 1 or 2 carbon atoms, R ^{3 is} each independently a hydrogen atom or a methyl group, and p and q are each independently 0 or more, And these totals are numbers in the range of 1 to 200. When p or q is 2 or more, the repeating units enclosed by the brackets in these words are plural, but R ^{3 in} each of these repeating units is also independent of each other and may be the same or different from each other. Moreover, if these repeating units are in the range of p or q mentioned above, they can be combined in a random manner.

The total number of P and q is from the viewpoint of the handleability of the curable resin of the present invention and the softness after curing, and is preferably a number in the range of 5 to 70, more preferably a number in the range of 10 to 50.

(Relevant m, n, p, q)

Regarding m in the formula (1) described above, the number m of the predetermined block (repeated unit) can be determined by the amount of the synthetic raw material of the curable resin of the present invention described later, or by the resin (or (A) described later). GPC measurement results of the base) acrylated curable resin) can be roughly estimated. n, and p, q The total value can be estimated from the GPC measurement result of the curable resin (or the (meth) acrylic curable resin described later), and these can also be estimated from the GPC measurement result of the synthetic material of the curable resin . And each value of p and q can be analyzed by IR and the like.

<Characteristics of hardening resin>

The viscosity of the curable resin of the present invention described above is generally 1000 to 2000000 mPa. s. As will be described later, the curable resin of the present invention is suitable for use in a liquid crystal sealant. However, when used in this application, the viscosity of the curable resin ranges from 3000 to 2000000 mPa from the viewpoint of ensuring that the liquid crystal sealant has a moderate viscosity. s is better. In addition, when the viscosity in this specification is 25 degreeC, the value measured using the E-type viscosity meter.

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

When a curable resin is used for a liquid crystal sealant, the epoxy equivalent is preferably from 400 to 10,000 g / eq, and more preferably from 500 to 5000 g / eq, from the viewpoint of having both adhesiveness and flexibility. In addition, the epoxy equivalent of the curable resin can be determined by the average molecular weight of the curable resin and the epoxy group (such as glycidol) per block (repeated unit) enclosed by the parentheses described by the m in the formula (1). The number of R ¹ ) is adjusted.

In addition, the NI point of the curable resin of the present invention is small. The aforementioned NI point is the temperature at which the liquid crystal undergoes phase transfer from the nematic phase to the isotropic phase (isotropic phase) (the phase transition temperature can be determined using a differential thermal analysis device). (Measured by the end of the endothermic absorption peak). The NI point of a liquid crystal is determined by the mixed composition of the liquid crystal components, and each compound has an intrinsic value. If the liquid crystal contamination-prone raw material or the sealant is mixed with the liquid crystal, it will cause a large change in the NI point. Conversely, if the liquid crystal contamination of the raw material or the sealant is low, the change in the NI point is small.

Specifically, the NI point change of the curable resin of the present invention is usually in a range of -5 ° C to + 5 ° C, and preferably in a range of -3 ° C to + 3 ° C. The details of the method for measuring the change in the NI point are described in the examples described later.

[(Meth) acrylic curable resin]

The curable resin of the present invention may be a (meth) acrylic curable resin obtained by reacting (meth) acrylic acid and / or (meth) acrylic anhydride. The (meth) acrylic-based olefin site may cause a cross-linking reaction, and the aforementioned (meth) acrylic hardening resin can achieve excellent flexibility while maintaining the adhesiveness required for a liquid crystal sealant.

The introduction of the (meth) acrylic group of the curable resin of the present invention is more specifically the epoxy group (for example, when R ¹ is a glycidyl group), a hydroxyl group, and an unsaturated bond (for example, Y is a formula ( 1b) caused by at least part of the time). In addition, the epoxy group may be ring-opened to generate a hydroxyl group by addition of a (meth) acrylic group or the like, but a (meth) acrylic group may be further introduced into the hydroxyl group.

In addition, the (meth) acrylic acid group can be introduced into the (meth) acrylic compound such as acrylic acid, methacrylic acid, and these anhydrous substances, ester compounds, or acids by the hardening resin of the present invention. And the like.

<Characteristics of (meth) acrylic hardening resin>

Like the curable resin of the present invention, the (meth) acrylic curable resin of the present invention shows preferable characteristics for use in a liquid crystal sealant.

That is, the viscosity of the (meth) acrylic hardening resin of the present invention is usually 1000 ~ 2000000mPa. s, from the viewpoint of ensuring moderate viscosity of the liquid crystal sealant, 3000 ~ 2000000mPa. s is better.

In addition, the change in the NI point of the (meth) acrylic curable resin of the present invention is small. The change in the NI point is usually in a range of -5 ° C to + 5 ° C, and preferably in a range of -3 ° C to + 3 ° C.

[Manufacturing method of hardening resin]

Next, the manufacturing method of the curable resin of this invention is demonstrated.

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

For formulae (2) and (3), Y ¹ , n, Y ² , R ³ , p, and q are as defined above, and R ^{4 is} each independently a hydrogen atom, a glycidyl group, or a methyl glycidyl group. Further, in the formula (3), a part or all of the unsaturated bonds in the repeating unit enclosed by the parentheses describing the word p or q may be hydrogenated.

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

For example, when -OR ⁴ existing at the molecular end of the compound E is a glycidyloxy group or a methyl glycidyloxy group, at least one of -OR ⁵ or X in the compound F is a hydroxyl group. The ring-opening reaction between glyceryl or methylglycidyl and hydroxyl group will connect compound F at the end of compound E. If necessary, free hydroxyl groups (for example, newly generated by ring-opening reaction) in the obtained compound (synthesis intermediate G described later, which is a hardening resin of the present invention when it has more than one epoxy group in the molecule) At least a part of the hydroxyl group is adjusted by glycidyl etherification as described later, and x is adjusted to 1 or more to obtain a curable resin of the present invention when m in Formula (1) is 1.

When compound F is a group obtained by ring-opening an epoxy group such as -OR ⁵ and X as a hydroxyl group, any one of -OR ⁵ and X may be a glycidyloxy group or a methyl group of compound E. Glycidyloxy. With respect to the compound thus obtained, if necessary, a free hydroxyl group is etherified with a glycidyl group as described later to obtain a curable resin of the present invention where m in the formula (1) is 2 or more. In addition, m can be adjusted by the loadings of compounds E and F. Even when -OR ⁵ and X are simultaneously ring-opened epoxy groups, m can be obtained by adjusting the loadings. The curable resin of the present invention.

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 addition, the molecular weight in this specification is a number average molecular weight equivalent to standard polystyrene measured by GPC.

Although the compounds E and F may be commercial products, or they can be easily prepared from known compounds by known methods. For example, R ⁴ is a hydrogen atom, and Y ¹ is an ethylidene compound of formula (2). E can be obtained as a polyethylene glycol having various repeating unit numbers (n). A compound having n in a desired range is appropriately selected. Just fine. In addition, n can be roughly calculated from the GPC measurement results of polyethylene glycol.

In addition, polyethylene glycol can be introduced into the end of polyethylene glycol by carrying out a reaction with a compound (hereinafter also referred to as an "epoxidized compound") capable of introducing a glycidyl group or a methyl glycidyl group such as epichlorohydrin. This can easily convert R ⁴ from a hydrogen atom to a glycidyl group or the like. The explanation is as follows. This is another example of compounds E and F in which R ⁴ or R ⁵ is a hydrogen atom.

Further, a compound of the formula (2) wherein R ⁴ is a hydrogen atom and Y ¹ is a propyl group can be obtained as a polyether ether glycol having various repeating unit numbers (n). Examples include EXCENOL420, EXCENOL720, EXCENOL1020, and EXCENOL2020 (the above are manufactured by Asahi Glass Co., Ltd.).

In addition, the compound E of the formula (2) in which R ⁴ is a hydrogen atom and Y ¹ is a trimethyl group can be produced, for example, according to the method described in Japanese Patent Application Publication No. 2013-515144. Dimethyl ether glycol.

Further, a compound E of the formula (2) wherein R ⁴ is a hydrogen atom and Y ¹ is a tetramethylene group is obtained as a polytetramethylene ether glycol having various repeating unit numbers (n). Examples include PTMG650, PTMG850, PTMG1000, PTMG1300, PTMG1500, PTMG1800, and PTMG2000 (manufactured by Mitsubishi Chemical Corporation).

In addition, a compound E of the formula (3) wherein R ³ is a hydrogen atom and R ⁴ is a hydrogen atom can be obtained as polybutadiene introduced as a terminal hydroxyl group having various repeating unit numbers (p, q). Examples include NISSO PB G-1000, G-2000 (manufactured by Soda Corporation, Japan), Poly bd R-45HT (manufactured by Idemitsu Kosan Co., Ltd.), and the like.

In addition, R ³ is a hydrogen atom, R ⁴ is a hydrogen atom, and the compound E of the formula (3) in which a part or all of the unsaturated bonds in the repeating unit enclosed by the brackets in which the word p or q is described is obtained as The polyhydric hydride introduced with a terminal hydroxyl group has various repeating units (p, q). Examples include NISSO-PB GI-1000, GI-2000 (manufactured by Soda Corporation, Japan), and the like.

Further, the compound E of the formula (3) in which R ³ is a methyl group and R ⁴ is a hydrogen atom can be obtained as a polyisoprene introduced as a terminal hydroxyl group having various repeating unit numbers (p, q). Examples include Poly ip (manufactured by Idemitsu Kosan Co., Ltd.).

It can be obtained that 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 included in the parentheses describing the letter p or q are hydrogenated. The compound E of the formula (3) is a terminal hydroxyl group. Polyisoprene-introduced hydrides have various repeating unit numbers (p, q). Examples include EPOL (manufactured by Idemitsu Kosan Co., Ltd.).

R ⁵ is a hydrogen atom, X is a hydroxyl group, and ring A is a compound F that satisfies a predetermined number of atoms and ring structure. Examples include resorcinol, 2- (4-hydroxyphenyl) ethanol, and bisphenol A. , Bisphenol M, bisphenol P, 1,6-naphthalenediol, 2-ethyl-9,10-anthracenediol, 3,4-thiophenediol, 9,9-bis (4-hydroxy-3- Methylphenyl) fluorene and the like.

In addition, as R ⁵ is a hydrogen atom, X is a hydrogen atom, and ring A is a compound F that satisfies a predetermined number of atoms and ring structure, examples of which include phenol, 4-α-cumol, 4-methoxyphenol, and 4 -Hydroxyquinoline and the like. .

Compound E, Compound F of R ⁴ and R ⁵ in each of the resulting hardened resin hardening the viewpoint of flexibility and low liquid crystal contamination point of view, to one of R ⁴ and R ⁵ is a hydrogen atom, the other is Glycidyl is preferred.

Compound E and compound F are intended to form the curable resin of the present invention. For example, after reacting compound E and compound F in the presence of a base, if necessary, the obtained synthetic intermediate G is epoxidized with a suitable catalyst in the presence of a suitable catalyst. The compounds are reacted. In the above reaction, it is desired to make m in the curable resin 1 to 7, preferably 1 to 5, and more preferably 1 to 3, and the loading amount can be adjusted. These compounds may be used alone or in combination of two or more.

The number of m can be controlled as follows when synthesizing the synthetic intermediate G in the case of Examples described later. For example, although the equivalent ratio of epoxy group to bisphenol A (equivalent to compound F) in compound E-1 in Synthesis Example 1 is 1.0: 2.5, if the ratio is 1.0: 2.0 or 1.0: 1.5, the number of m Will increase. Conversely, if it is 1.0: 10, 1.0: 100, 1.0: 1000, etc., it will not become less than 1.

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

From the viewpoint of the rapid progress of the reaction and the cost of the synthesis, the alkali includes alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, tetramethylammonium chloride, and chlorine. Quaternary ammonium salts such as methyltrioctylammonium chloride, methyltridecylammonium chloride, benzyltrimethylammonium chloride are preferred, and sodium hydroxide or a fourth-order ammonium salt is preferred. These bases are preferably used as an aqueous solution, but powder or solid bases may be added simultaneously or separately with water, as appropriate. These bases may be used alone or in combination of two or more.

The amount of base used is from the viewpoint of the rapid progress of the reaction and the cost of the synthesis. When R ⁴ is a hydrogen atom and R ⁵ is a glycidyl group, the base is equivalent to a hydroxyl group or more, and R ⁴ is a glycidyl group or a methyl glycidyl group. The glyceryl group and the case where R ⁵ is a hydrogen atom may be a catalyst amount, and 0.0001 to 0.1 equivalents of the hydroxyl group of the compound F may be sufficient.

The epoxidized compound is used in an amount of 0.05 to 20 equivalents, preferably 0.05 to 15 equivalents, for the hydroxyl group contained in the raw material compound. This amount can be adjusted by the average number x of epoxy groups in the intended curable resin, and even if a large excess is used for the hydroxyl group, the average number of hydroxyl groups of the raw material compound of x will not be increased.

As a catalyst, from the viewpoints of reaction time, cost, and reactivity, tertiary amines such as trimethylamine, trioctylamine, and tridecylamine, tetramethylammonium chloride, and methyl chloride Quaternary ammonium salts such as trioctylammonium, methyltridecylammonium chloride and benzyltrimethylammonium chloride are preferred, and the fourth-order ammonium salt is more preferred. These may be used individually by 1 type, and may be used in combination of 2 or more type.

From the viewpoint of ensuring an appropriate reaction rate while suppressing side reactions, the amount of catalyst used is preferably 0.0001 to 0.5 equivalents, and more preferably 0.01 to 0.1 equivalents for the hydroxyl group contained in the raw material compound.

The reaction with the above-mentioned base is preferably performed at 50 to 250 ° C, preferably 70 to 200 ° C, more preferably 100 to 170 ° C, and the reaction with the above-mentioned epoxidized compound is preferably 25 to 100 ° C, more preferably The temperature is 30 to 80 ° C, and more preferably 40 to 60 ° C. In the reaction, a solvent inert to the reaction such as a hydrocarbon, an ether, or a ketone can be used. However, when an excessive amount of an epoxidized compound is used, the compound Because the substance can function as a solvent, these solvents are required separately.

Purification of the hardening resin after the reaction can be performed according to a conventional method. For example, after distilling off the excess epoxidized compound, if necessary, adding a water-insoluble solvent such as hydrocarbon, and then removing the salt and catalyst produced by washing with water, The intended curable resin of the present invention was obtained.

In the method for producing a curable resin of the present invention, from the viewpoint that a general-purpose raw material can be used as the compound E and the compound F, the compound E1 in which compound R ⁴ is a glycidyl group (the diglycidyl ether of the compound E) Compound (for example, polyethylene glycol diglycidyl ether), and compound F1 (for example, bisphenol A) in which R ^{5 in} compound F is a hydrogen atom, the aforementioned compound E1 is reacted with the aforementioned compound F1 to obtain the aforementioned compound Step 1 of synthesizing intermediate G of E1 and the aforementioned compound F1, and step 2 of epoxidizing the hydroxyl groups of synthetic intermediate G to obtain a hardening resin in which a part or all of the hydroxyl groups of synthetic intermediate G are epoxidized Better.

<Manufacturing method of (meth) acrylic hardening resin>

Further, step 3 of reacting a curable resin with a (meth) acrylic compound in the presence of a basic catalyst, introducing a (meth) acrylic group into at least a part of the epoxy group, the hydroxyl group, and the unsaturated bond. The (meth) acrylic curable resin of the present invention was obtained.

As the basic catalyst, a known basic catalyst used in the reaction between epoxy resin and (meth) acrylic acid can be used. Alternatively, a polymer-supported basic catalyst in which a basic catalyst is supported on a polymer may be used. As alkaline The catalyst is preferably a trivalent organic phosphorus compound, a salt thereof, an amine compound, and a salt thereof. These alkaline catalysts may be used individually by 1 type, and may be used in combination of 2 or more type. The basic atom of the basic catalyst is phosphorus and / or nitrogen.

Examples of the trivalent organic phosphorus compound include triethylphosphine, tri-n-propylphosphine, alkylphosphines of tri-n-butylphosphine, and salts thereof, triphenylphosphine, Arylphosphines such as tri-m-tolylphosphine, ginseng (2,6-dimethoxyphenyl) phosphine and their salts, triphenylphosphites, triethylphosphites, ginseng ( Nonylphenyl) phosphites such as phosphites and their salts. Of these, triphenylphosphine is also preferred.

Examples of the salt of a trivalent organic phosphorus compound include triphenylphosphine. Ethyl bromide, triphenylphosphine. Butyl bromide, triphenylphosphine. Octyl bromide, triphenylphosphine. Decyl bromide, triphenylphosphine. Isobutyl bromide, triphenylphosphine. Propyl chloride, triphenylphosphine. Amyl chloride, triphenylphosphine. Hexyl bromide, etc.

Examples of the amine compound include secondary amines such as diethanolamine, triethanolamine, dimethylbenzylamine, tertiary dimethylaminomethylphenol, and tertiary amines such as diethylaminomethylphenol. , 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5 -Ene (Me-TBD), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), 6-dibutylamino-1,8-diazabicyclo [5.4. 0] Strongly basic amines such as undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene (DBN), 1,1,3,3-tetramethyl vein. Among them, 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD) is also preferable.

Examples of the salt of the amine compound include benzyltrimethyl chloride Ammonium chloride, benzyltriethylammonium chloride, and salts of the aforementioned strong basic amines.

The polymer supporting the basic catalyst is not particularly limited, and a polymer in which polystyrene is crosslinked with divinylbenzene or a polymer in which acrylic resin is crosslinked with divinylbenzene can be used. These polymers are insoluble to the following solvents, raw materials, and products. The solvents are used for the reaction between the curable resin obtained by the production method containing step 1 or steps 1 and 2 and the (meth) acrylic compound. Solvents (for example, methyl ethyl ketone, methyl isobutyl ketone, toluene, etc.), raw materials, and products. These polymers may be used alone or in combination of two or more.

The polymer-supported basic catalyst can be chemically bonded to the insoluble polymer by introducing the basic catalyst, or the basic catalyst can be introduced into the monomer, and the monomer can be cross-linked with divinylbenzene after polymerizing the monomer. The monomer is produced by three-dimensional cross-linking. By such cross-linking, it becomes a polymer-supported basic catalyst that is insoluble in solvents such as methyl ethyl ketone, methyl isobutyl ketone, and toluene.

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

As the polymer-supported alkaline catalyst, a commercial product can be used. Examples of commercially supported polymer-supported basic catalysts include PS-PPh ₃ (diphenylphosphine polystyrene, manufactured by Biotage), PS-TBD (1,5,7-triazabicyclo [4.4.0] dec-5-ene polystyrene, manufactured by Biotage) and the like.

In the method for producing a (meth) acrylic curable resin of the present invention, the temperature in the reaction step of the curable resin and the (meth) acrylic compound obtained by the production method containing step 1 or steps 1 and 2 is adjusted to 60 to 120 ° C is preferred, 80 to 120 ° C is more preferred, and 90 to 110 ° C is more preferred.

When the curable resin obtained by the manufacturing method containing step 1 or steps 1 and 2 is reacted with a (meth) acrylic compound in the presence of a catalyst, it is necessary to prevent gelation in the reaction system and the reaction system. The gas phase oxygen concentration on the system is maintained at an appropriate amount. For example, when the air is actively blown into the reaction system, the catalyst will be oxidized and the activity will be reduced, so it must be paid attention to.

For the reaction between the curable resin obtained by the manufacturing method containing step 1 or steps 1 and 2 and the (meth) acrylic compound, the (meth) acrylic curable resin obtained by the reaction can be subjected to ultraviolet rays. It is hardened by active energy rays, so it is better to react in a container that can block ultraviolet rays. In addition, the reaction between the curable resin obtained by the manufacturing method containing Step 1 or Steps 1 and 2 and the (meth) acrylic compound can prevent gas-phase polymerization, although it is possible to show good solvent-based reflux for the curable resin. It is performed in the presence of a solvent, but in this case, it is necessary to remove the solvent after completion of the reaction. Therefore, the aforementioned reaction is preferably performed without a solvent. Examples of the reflux solvent include acetone, methyl ethyl ketone, and toluene.

[Liquid crystal sealant composition]

Curable resin and (meth) acrylic curable resin of the present invention (Hereinafter, these are also collectively referred to as "curable resins of the present invention.") It has all the characteristics described above, has a good viscosity for use as a liquid crystal sealant, low liquid crystal contamination, and excellent softness after curing.

Therefore, the liquid crystal sealant composition using the curable resin or the like of the present invention has excellent handleability. In the liquid crystal dropping method, even in the case of contact with the liquid crystal in an uncured state, it is difficult to affect the alignment of the liquid crystal. Therefore, it is difficult to hinder the alignment of the liquid crystal. When used in a flexible device such as a flexible liquid crystal display, even when a flexible substrate sandwiching a cured liquid crystal sealant is bent, the excellent flexibility or stress is caused. The mitigating effect makes it difficult for cracks in the liquid crystal sealing portion or peeling from the substrate to occur.

Specifically, the viscosity of the liquid crystal sealant composition of the present invention is usually 1000 to 2000000 mPa. s, with 10000 ~ 1000000mPa. s is better. The viscosity of the liquid crystal sealant composition can be adjusted by the structure of the curable resin or the like of the present invention, or by adding a component or a solvent to the components contained in the liquid crystal sealant composition described below.

In the liquid crystal sealant composition of the present invention containing the curable resin of the present invention as such, the storage elasticity of the cured liquid crystal sealant hardened product is generally 1.0 × at room temperature (25 ° C) from the viewpoint of flexibility. 10 ³ to 3.0 × 10 ⁹ Pa, preferably 1.0 × 10 ³ to 1.0 × 10 ⁹ Pa. The method for measuring the storage elastic modulus is described in detail in the items of the examples described later.

The glass transition temperature (Tg) of the cured liquid crystal sealant obtained by curing the liquid crystal sealant composition of the present invention is usually 80 ° C or lower, preferably 40 ° C or lower, and more preferably Below 30 ° C, more preferably below room temperature (25 ° C), particularly preferably -80 ~ 25 ° C.

The liquid crystal sealant composition of the present invention contains the curable resin and the like of the present invention, but the content of the curable resin and the like in the liquid crystal sealant composition is usually 5 to 95% by weight, and it is aligned with respect to flexibility, adhesion and liquid crystal. From the viewpoint of the influence of sex, it is preferably 10 to 95% by weight.

In addition, the liquid crystal sealant composition of the present invention may contain various characteristics required for the application, and the various components described below may be further contained within a range that does not impair the effects of the present invention.

<Compound H>

The liquid crystal sealant composition of the present invention may contain other hardening components such as the curable resin of the present invention. For example, the compound H has a conventional ethylenically unsaturated group and / or epoxy group used as the main agent of the liquid crystal sealant. (E.g., an oligomer in which a part of the epoxy group of the bisphenol A epoxy resin is (meth) acrylated), the liquid crystal sealant composition such as the curable resin of the present invention is added simultaneously, and only the compound is added Compared with the case of H, the flexibility of the hardened | cured material of a liquid-crystal sealing compound is greatly improved.

Examples of the compound H having an ethylenically unsaturated group include a (meth) acrylate compound, an aliphatic propylene fluorenyl compound, an alicyclic propylene fluorenyl compound, an aromatic propylene fluorenyl compound, or N-substituted propylene. Fluorenyl compounds.

Examples of the (meth) acrylate compound include p-cumylphenoxyethylene glycol (meth) acrylate, t-butyl (methyl Acrylate), ethoxylated phenyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, aliphatic (meth) acrylate, aromatic The ring contains a (meth) acrylate.

Examples of the compound H having an ethylenically unsaturated group include monofunctional, difunctional, trifunctional, and polyfunctional radically polymerizable unsaturated compounds.

As the monofunctional radically polymerizable unsaturated compound, from the viewpoint of ensuring the viscosity and flexibility of the liquid crystal sealant composition, it is selected from the group consisting of hydroxyethyl (meth) acrylate, benzyl (methyl) Base) acrylate, tetrahydrofurfuryl (meth) acrylate, isooctyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentyl ( (Meth) acrylate, cyclohexyloxyethyl (meth) acrylate, dicyclopentyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, different meat 1 or more compounds in the group of cardamom (meth) acrylate, lauryl (meth) acrylate, tert-butyl (meth) acrylate, and diethylene glycol monoethyl ether (meth) acrylate Preferably, it is selected from the group consisting of isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopentyl (meth) acrylate, and dicyclopentenyloxyethyl (methyl) One or more compounds in the group of acrylate and cyclohexyl (meth) acrylate are preferred.

The difunctional radically polymerizable unsaturated compound is selected from the group consisting of tricyclodecane dimethanol di (meth) acrylate, dihydroxy, from the viewpoint of ensuring the viscosity and flexibility of the liquid crystal sealant composition. Methyldicyclopentane di (meth) acrylate, EO modified 1,6-hexanediol di (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modified bis Phenol A di (meth) acrylate, polyester di (meth) acrylate (e.g. ARONIX M-6100, manufactured by Toa Synthetic Corporation), polyethylene glycol di (meth) acrylate (e.g. 4G, Shin Nakamura Chemical Industrial company) and silicon di (meth) acrylate (e.g., EBECRYL 350, Daicel Orunekusu company) group of one or more compounds are preferred, and dimethyloldicyclopentanedi (methyl) ) Acrylate and / or EO or PO modified bisphenol A di (meth) acrylate is preferred. Among them, a (meth) acrylate having a bisphenol A skeleton without a hydroxyl group is preferred. As such a (meth) acrylate, a light acrylate BP-4EAL (bis EO adduct diacrylate of phenol A), BP-4PA (PO adduct diacrylate of bisphenol A) and the like are sold.

The trifunctional or polyfunctional radically polymerizable unsaturated compound is selected from the group consisting of EO modified glycerol tri (meth) acrylate (from the viewpoint of ensuring the viscosity and flexibility of the liquid crystal sealant composition). Trifunctional), PO modified glycerol tri (meth) acrylate (trifunctional), pentaerythritol tri (meth) acrylate (trifunctional), dipentaerythritol hexa (meth) acrylate (hexafunctional), and pentaerythritol tetra ( One or more compounds grouped by meth) acrylate (tetrafunctional) are preferred, and EO-modified glycerol tri (meth) acrylate is preferred.

Next, as the compound H having an epoxy group, it is selected from the group consisting of a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, and a bisphenol AD type. Epoxy compounds, phenol novolac epoxy compounds, cresol novolac epoxy compounds, naphthalene epoxy compounds, resorcinol epoxy compounds, these hydrogenated compounds and alicyclic epoxy compounds At least one compound is preferred, and at least one compound selected from the group consisting of a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a naphthalene type epoxy compound, and a resorcinol type epoxy compound is preferred. , More preferably a bisphenol A epoxy compound.

Specific examples of the bisphenol A type epoxy compound include EPICLON850S, 860, 1055, EXA-850CRP, etc., manufactured by DIC Corporation.

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

Specific examples of the bisphenol F-type epoxy compound include EPICLON830S manufactured by DIC Corporation.

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

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 novolac 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 Chemtex.

Specific examples of the alicyclic epoxy compound include 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate (CELLOXIDE 2021P manufactured by Daicel Chemical Industries, Ltd.), 1,2: 8,9-diepoxy limonene (manufactured by Daicel Chemical Industries, Ltd. CELLOXIDE3000), 1,2-epoxy-4-vinylcyclohexane (CELLOXIDE2000 manufactured by Daicel Chemical Industries, Ltd.), 1,2-epoxy of 2,2-bis (hydroxymethyl) -1-butanol 4- (2-oxiranyl) cyclohexane adduct (EHPE3150 manufactured by Daicel Chemical Industries, Ltd.) and the like.

Examples of the compound H having an ethylenically unsaturated group and an epoxy group include a partial (meth) acrylate-modified epoxy compound obtained by reacting an epoxy-containing compound with a (meth) acrylic compound. This compound is preferably a partially (meth) acrylated epoxy compound obtained by reacting a bisphenol A type epoxy resin with (meth) acrylic acid.

Part of the (meth) acrylated epoxy compound obtained by reacting the bisphenol A type epoxy resin with (meth) acrylic acid can be obtained, for example, as follows.

First, the bisphenol A epoxy resin and (meth) acrylic acid are reacted in the presence of a basic catalyst, preferably in the presence of a trivalent organic phosphate compound and / or an amine compound. The reaction ratio at this time is a ratio of 10 to 90 equivalent% of (meth) acrylic acid for 1 equivalent of epoxy group. Next, the reaction product is filtered, centrifuged, and / or washed with water to remove the alkaline catalyst and purified. As said basic catalyst, the well-known basic catalyst used for the reaction of an epoxy resin and (meth) acrylic acid can be used. Alternatively, a polymer-supported basic catalyst in which a basic catalyst is supported on a polymer may be used.

As described above, the liquid crystal sealant composition of the present invention may contain various compounds H, and the curable resin of the present invention does not contain ethyl. In the case of an ethylenically unsaturated group, a compound having the aforementioned ethylenically unsaturated group as the compound H is preferably a radically polymerizable compound.

The compound H described above may be used alone or in combination of two or more.

<Photopolymerization initiator>

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

Examples of the photopolymerization initiator include benzoin, acetophenone, benzophenone, thioxanthone, α-hydroxamate, phenylglyoxylic acid, benzyl, and azo Compounds, diphenyl sulfide compounds, fluorenylphosphine oxide compounds, benzoin ethers and anthraquinones, etc., preferably have low solubility in liquid crystals, and have reactive groups upon light irradiation Without decomposing the decomposition products.

<Photosensitizer>

The liquid crystal sealant composition of the present invention is generally used for photo-hardening, and if it is desired to improve the sensitivity to light at this time, it may have a photosensitizer. As the photosensitizer, various conventionally known compounds can be used without particular limitation, and the photosensitizer can be used alone or in combination of two or more.

As the aforementioned photosensitizer, from the viewpoint of hardenability, for example Examples include carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreducible pigments.

Specific examples of the photosensitizer include acridinone derivatives such as N-methylacridone and N-butylacridone; others include α, α-diethoxyacetophenone and benzyl , Fluorenone, xanthone, uranium and thorium compounds, etc., which are also cited as examples of the above-mentioned photopolymerization initiators can also function as photosensitizers.

<Hardener>

From the viewpoint of improving the adhesiveness of the liquid crystal sealant composition of the present invention, a hardener may be contained in the liquid crystal sealant composition. The said hardening | curing agent is not specifically limited, A well-known compound can be used.

As the hardener, there are amine-based hardeners from the viewpoint of adhesiveness, and examples include organic acid dihydrazine compounds, imidazole and its derivatives, dicyandiamide, aromatic amines, epoxy-modified polyamines, and polyamines. Aminourea and the like are preferred. These hardeners may be used individually by 1 type, and may be used in combination of 2 or more type.

<Hardening accelerator>

The liquid crystal sealant composition of the present invention may contain a hardening accelerator from the viewpoint of accelerating the hardening reaction of the hardening component (the hardening resin of the present invention or the compound H described above), and the hardening accelerator may be used alone. Or two or more of them.

Examples of such preferable examples include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole; 2- (dimethylaminomethyl) phenol; and 1, Tertiary amines such as 8-diazabicyclo [5.4.0] undec-7-ene (DBU); phosphines such as triphenylphosphine; metal compounds such as tin octylate.

<Filler>

The liquid crystal sealant composition of the present invention may contain a filler from the viewpoint of viscosity control, subsequent reliability, and suppression of linear expansion. As said filler, an inorganic filler and an organic filler can be used, These can be used individually by 1 type, and can also be used in combination of 2 or more type.

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

Examples of the organic filler include polymethyl methacrylate, polystyrene, copolymers obtained by copolymerizing the monomers constituting these with other monomers, polyester microparticles, polyurethane microparticles, and rubber. Microparticles and core-shell type particles composed of a shell containing a copolymer having a high glass transition temperature and a core containing a copolymer having a low glass transition temperature. Examples of the core-shell type particles include Zefi ACK series (F351, etc.) manufactured by Ganz Kasei Corporation.

By adding a non-reactive component to the filler, the average particle size of the particles constituting the filler can be reduced from the viewpoint of air leakage from the liquid crystal sealant. The diameter is usually 0.1 to 3 μm, and preferably 0.5 to 3 μm. The average particle diameter of the filler can be measured by a laser diffraction / scattered particle diameter distribution measuring device (for example, Partica LA-950V2, manufactured by HORIBA).

<Silane coupling agent>

The liquid crystal sealant composition of the present invention may contain a silane coupling agent within a range that achieves the effects of the present invention. Silane coupling agents can be used singly or in combination of two or more kinds.

From the standpoint of adhesiveness and flexibility of a liquid crystal sealant hardened product obtained by merging and curing the liquid crystal sealant composition of the present invention, examples of the silane coupling agent include those selected from tetramethoxysilane and tetraethoxy Silane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane, dimethoxydiisopropoxysilane, diethoxydiisopropoxide Tetraalkoxysilanes such as methylsilane, diethoxydibutoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltriethoxy Silane, ethyltributoxysilane, cyclohexyltriethoxysilane, phenyltriisopropoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Trialkoxysilanes such as methacryloxypropyltrimethoxysilane; and dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, diethyl At least one silane coupling agent grouped by dialkoxysilanes such as dibutoxysilane and phenylethyldiethoxysilane Jia, in their been drawn selected from the group consisting of methyl trimethoxy Silane, methyl triethoxy silicon Alkane, methyltriisopropoxysilane, ethyltriethoxysilane, ethyltributoxysilane, cyclohexyltriethoxysilane, phenyltriisopropoxysilane, vinyltrimethoxysilane At least one type of trialkoxysilane-based silane coupling agent grouped by 1,3-glycidoxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane is preferred. 3-Glycidoxypropyltrimethoxysilane is more preferred.

[Example]

Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited to these examples. The compounds used in the examples and comparative examples were produced as described below.

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

340.0 g of mixed bisphenol A epoxy resin (EXA850CRP, manufactured by DIC Corporation), 90.4 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.5 g of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.), and BHT (two 100 mg of butylhydroxytoluene) was stirred at 100 ° C for 6 hours. 418.0 g of partially methacrylated bisphenol A epoxy resin was obtained as a pale yellow transparent viscous substance.

[Synthesis Example 1] Methacrylic hardening resin 1

(1) Polyethylene glycol # 1000 (manufactured by LION) 2000.0 g (4.0 equivalents / hydroxyl), epichlorohydrin 2220.0 g (6.0 equivalents), benzyl 74.3 g (0.10 equivalents) of trimethylammonium chloride was placed in a 5-liter three-necked round-bottomed flask equipped with a mechanical stirrer, thermometer, temperature regulator, condenser, Dean-Stark trap, and dropping funnel.

Next, while stirring the mixture under a high vacuum of 50 torr, the mixture was heated to about 50 to 60 ° C and the epichlorohydrin was vigorously refluxed. 600.0 g of a 48% NaOH aqueous solution was slowly added to the mixture over 2 hours. When an azeotrope is formed, the epichlorohydrin is returned to the reaction system in the water / epichlorohydrin mixture while stirring is continued.

After the end of the addition, stirring was continued for 3 hours. Next, the reaction mixture was cooled to room temperature, 3 L of chloroform was added, and washed 6 times with 3 L of water. The obtained organic phase solvent was distilled off under reduced pressure to obtain 1150.0 g of compound E-1 as a white waxy solid.

(2) Put compound E-1 (950.0 g (1.7 equivalents / epoxy group)) and bisphenol A (988.0 g (2.5 equivalents)) into an eggplant-shaped flask, and heat and stir until the liquid temperature reaches 150 ° C. 2.9 g of 4% NaOH aqueous solution was added, and it stirred at 150 degreeC for 6 hours.

The temperature of the cooling liquid was lower than 60 ° C., 2 L of chloroform was added, and washed 6 times with 2 L of a 1% NaOH aqueous solution, and washed 6 times with 2 L of water.

Magnesium sulfate was added to the obtained organic phase, and after drying, solid components were filtered off by filtration, etc., and the obtained organic phase solvent was distilled off under reduced pressure to obtain 997.0 g of a pale yellow transparent viscous synthetic intermediate.物 G-1.

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

Next, the mixture was heated to about 50 to 60 ° C. while stirring under a high vacuum of 50 torr, and the epichlorohydrin was vigorously refluxed. 384.0 g of a 48% NaOH aqueous solution was slowly added to the mixture over 2 hours. When an azeotrope is generated, in the water / epichlorohydrin mixture, the epichlorohydrin is continuously stirred while being returned to the reaction system. After the addition was completed, stirring was continued for 3 hours.

Next, the reaction mixture was cooled to room temperature, 2 L of chloroform was added, and washed 6 times with 2 L of water. The obtained organic phase solvent was distilled off under reduced pressure to obtain 982.0 g of a resin 1 having 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 ° C for 5 hours. 107.0 g of a light yellow viscous methacrylic curable resin 1 was obtained.

[Synthesis Example 2] Methacrylic hardening resin 2

(1) 500.0 g (1.0 equivalent / hydroxyl) of polytetramethylene methyl ether glycol (PTMG) 1000 (manufactured by Mitsubishi Chemical Corporation), 555.0 g of epichlorohydrin (6.0 equivalent), benzyltrimethylammonium chloride 18.6 g (0.10 equivalent) of the compound was placed in a 2-liter three-necked round-bottomed flask with a mechanical stirrer, thermometer, temperature regulator, condenser, Dean-Stark trap, and dropping funnel.

Next, while stirring the mixture under a high vacuum of 50 Torr, heat the mixture to about 50 to 60 ° C and vigorously reflux the ring. Oxychloropropane. 150.0 g of a 48% NaOH aqueous solution was slowly added to the mixture over 2 hours. When an azeotrope is generated, in the water / epichlorohydrin mixture, the epichlorohydrin is continuously stirred while being returned to the reaction system. After the addition was completed, stirring was continued for 3 hours.

Next, the reaction mixture was cooled to room temperature, and then chloroform was added, followed by washing 4 times with 1 L of water. The obtained organic phase solvent was distilled off under reduced pressure to obtain 459.0 g of compound E-2 as a white waxy solid.

(2) The compound E-2 (132.0 g (0.20 equivalents / epoxy group)) and bisphenol A (114.0 g (2.5 equivalents)) were placed in an eggplant-shaped flask, and heated and stirred until the liquid temperature became 150 ° C. 0.3 g of 4% NaOH aqueous solution was added, and it stirred at 150 degreeC for 6 hours. After cooling to a liquid temperature of 60 ° C. or lower, 500 mL of chloroform was added, and washed three times with 1 L of a 1% NaOH aqueous solution and three times with 1 L of water.

Magnesium sulfate was added to the obtained organic phase, and after drying, solid components were filtered off by filtration, etc., and the obtained organic phase solvent was removed by distillation under reduced pressure to obtain 140.0 g of a pale yellow transparent viscous synthetic intermediate reactant. G-2.

(3) Put reactant G-2 (140.0g), epichlorohydrin (195.0g), and benzyltrimethylammonium chloride (6.5g) in a mechanical stirrer, thermometer, and temperature regulator , Condenser, Dean-Stark trap and dropping funnel 1 liter three-neck round bottom flask.

Next, the mixture was heated to about 50 to 60 ° C. while being stirred under a high vacuum of 50 Torr, and epichlorohydrin was vigorously refluxed. 53.0g of 48% NaOH solution slowly over 2 hours Add to the mixture. When an azeotrope is generated, in the water / epichlorohydrin mixture, the epichlorohydrin is continuously stirred while being returned to the reaction system. After the addition was completed, stirring was continued for 3 hours. After the reaction mixture was cooled to room temperature, 500 mL of chloroform was added, and the reaction mixture was washed 4 times with 500 mL of water. The obtained organic phase solvent was distilled off under reduced pressure to obtain 129.0 g of resin 2 as a pale yellow viscous substance.

(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 pale yellow viscous methacrylic curable resin 2 was obtained.

[Synthesis Example 3] Methacrylic hardening resin 3

(1) 350.0 g (0.50 equivalent / hydroxyl) of NISSO-PB G-1000 (manufactured by Soda, Japan), 370.0 g (8.0 equivalent) of epichlorohydrin, 9.3 g (0.10 equivalent) of benzyltrimethylammonium chloride ) Put into a 2-liter three-necked round-bottomed flask with a mechanical stirrer, thermometer, thermostat, condenser, Dean-Stark trap, and dropping funnel.

Next, the mixture was heated to about 50 to 60 ° C. while being stirred under a high vacuum of 50 Torr, and epichlorohydrin was vigorously refluxed. 75.0 g of a 48% NaOH aqueous solution was slowly added to the mixture over 2 hours. When an azeotrope is generated, in the water / epichlorohydrin mixture, the epichlorohydrin is continuously stirred while being returned to the reaction system. After the addition was completed, stirring was continued for 3 hours.

Next, the reaction mixture was cooled to room temperature, and chlorine was added After imitation of 500 mL, it was washed 6 times with 500 mL of water. The obtained organic phase solvent was distilled off under reduced pressure, and 298.0 g of compound E-3 as a transparent viscous substance was obtained.

(2) Compound E-3 (96.5g (0.10 equivalent / epoxy)), bisphenol A (68.5g (3.0 equivalent)), benzyltrimethylammonium chloride 0.9g (0.050 equivalent), and formazan 100.0 g of methyl isobutyl ketone was put into an eggplant-shaped flask, and stirred while heating to reflux to a liquid temperature of 120 ° C for 20 hours. The liquid temperature was cooled below 60 ° C., 300 mL of chloroform was added, and washed 5 times with 300 mL of a 1% NaOH aqueous solution, and washed 5 times with 300 mL of water.

Magnesium sulfate was added to the obtained organic phase, and after drying, solid components were filtered off by filtration, etc., and the obtained organic phase solvent was distilled off under reduced pressure to remove 75.5 g of a pale yellow transparent viscous synthetic intermediate reactant. G-3.

(3) Put the reactant G-3 (75.5g), epichlorohydrin (112.5g), and benzyltrimethylammonium chloride (2.8g) into a mechanical stirrer, thermometer, and temperature regulator. , Condenser, Dean-Stark trap, and a 500 mL three-necked round bottom flask with a dropping funnel.

Next, the mixture was heated to about 50 to 60 ° C. while being stirred under a high vacuum of 50 torr, and epichlorohydrin was vigorously refluxed. 23.0 g of a 48% NaOH aqueous solution was slowly added to the mixture over 2 hours. When an azeotrope is generated, in the water / epichlorohydrin mixture, the epichlorohydrin is continuously stirred while being returned to the reaction system. After the addition was completed, stirring was continued for 3 hours.

Next, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and washed with 300 mL of water 6 times. The obtained organic phase solvent was distilled off under reduced pressure, and 54.4 g of a pale yellow viscous resin 3 was obtained.

(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 ° C. for 5 hours. 47.0 g of a light yellow viscous methacrylic curable resin 3 was obtained.

[Synthesis Example 4] Methacrylic hardening resin 4

(1) NISSO-PB GI-1000 (manufactured by Soda Co., Ltd.) 300.0 g (0.40 equivalent / hydroxyl), epichlorohydrin 296.0 g (8.0 equivalent), benzyltrimethylammonium chloride 7.4 g (0.10 equivalent) ) Put into a 2-liter three-necked round-bottomed flask with a mechanical stirrer, thermometer, thermostat, condenser, Dean-Stark trap, and dropping funnel.

Next, the mixture was heated to about 50 to 60 ° C. while being stirred under a high vacuum of 50 torr, and the epichlorohydrin was vigorously refluxed. 60.0 g of a 48% NaOH aqueous solution was slowly added to the mixture over 2 hours. When an azeotrope is generated, in the water / epichlorohydrin mixture, the epichlorohydrin is continuously stirred while being returned to the reaction system. After the addition was completed, stirring was continued for 3 hours.

Herein, the reaction mixture was cooled to room temperature, 500 mL of chloroform was added, and washed with 500 mL of water six times. The obtained organic phase solvent was distilled off under reduced pressure to obtain 264.0 g of a transparent viscous compound. 物 E-4.

(2) Compound E-4 (80.0 g (0.060 equivalents / epoxy)), bisphenol A (57.1 g (4.0 equivalents)), benzyltrimethylammonium chloride 0.9 g (0.080 equivalents), and formazan 100.0 g of methyl isobutyl ketone was put into an eggplant-shaped flask, and stirred for 20 hours while heating under reflux to a liquid temperature of 120 ° C. The liquid temperature was cooled below 60 ° C., 300 mL of chloroform was added, and washed 5 times with 300 mL of a 1% NaOH aqueous solution, and washed 5 times with 300 mL of water.

Magnesium sulfate was added to the obtained organic phase, and after drying, the solid content was filtered off by filtration, etc., and the obtained organic phase solvent was removed by distillation under reduced pressure to obtain a reaction of 80.0 g of a pale yellow viscous synthetic intermediate.物 G-4.

(3) Put the reactant G-4 (80.0g), epichlorohydrin (88.8g), and benzyltrimethylammonium chloride (3.0g) in a mechanical stirrer, thermometer, and temperature regulator. 500 mL three-neck round bottom flask with a condenser, Dean-Stark trap and a dropping funnel.

Next, the mixture was heated to about 50 to 60 ° C. while being stirred under a high vacuum of 50 torr, and the epichlorohydrin was vigorously refluxed. 24.0 g of a 48% NaOH aqueous solution was slowly added to the mixture over 2 hours. When an azeotrope is generated, in the water / epichlorohydrin mixture, the epichlorohydrin is continuously stirred while being returned to the reaction system. After the addition was completed, stirring was continued for 3 hours.

Next, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and then washed 6 times with 300 mL of water. Organic phase The solvent was distilled off under reduced pressure to obtain 56.0 g of resin 4 as a pale yellow viscous substance.

(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 ° C. for 12 hours. 47.0 g of a light yellow viscous methacrylic curable resin 4 was obtained.

[Synthesis Example 5] Methacrylic hardening resin 5

(1) Compound E-2 (96.0 g (0.15 equivalents / epoxy)), 4-α-cumol (30.0 g (1.0 equivalents)), benzyltrimethylammonium chloride 1.4 g (0.050 equivalents) ) Put into an eggplant-type flask, and stir for 30 hours while heating and refluxing to a liquid temperature of 120 ° C. The liquid temperature was cooled below 60 ° C., and 125.0 g of a pale yellow viscous synthetic intermediate G-5 was obtained.

(2) Put reactant G-5 (125.0g), epichlorohydrin (150.0g), and benzyltrimethylammonium chloride (2.8g) into a mechanical stirrer, thermometer, and temperature regulator. 500 mL three-neck round bottom flask with condenser, Dean-Stark trap and dropping funnel.

Next, the mixture was heated to about 50 to 60 ° C. while being stirred under a high vacuum of 50 torr, and the epichlorohydrin was vigorously refluxed. 30.0 g of a 48% NaOH aqueous solution was slowly added to the mixture over 2 hours. When an azeotrope is generated, in the water / epichlorohydrin mixture, the epichlorohydrin is continuously stirred while being returned to the reaction system. After the addition was completed, stirring was continued for 3 hours.

Herein, the reaction mixture was cooled to room temperature, 500 mL of chloroform was added, and washed with 500 mL of water six times. The obtained organic phase solvent was distilled off under reduced pressure, and 130.0 g of a pale yellow viscous resin 5 was obtained.

(3) After mixing 63.5 g of resin 5, 4.3 g of methacrylic acid, 0.1 g of triphenylphosphine, and 13 mg of BHT, the mixture was stirred at 100 ° C. for 6 hours. 66.0 g of a light yellow viscous methacrylic curable resin 5 was obtained.

[Synthesis Example 6] Methacrylic hardening resin 6

(1) The compound E-2 (64.0 g (0.10 equivalents / epoxy group)) and resorcinol (27.5 g (2.5 equivalents)) were placed in an eggplant-shaped flask, and heated to a liquid temperature of 120 ° C. 0.2 g of 4% NaOH aqueous solution was added, and it stirred at 120 degreeC for 24 hours. After cooling to a liquid temperature of 60 ° C. or lower, 300 mL of chloroform was added and washed 4 times with 300 mL of water.

Magnesium sulfate was added to the obtained organic phase, and after drying, the solid content was filtered off by filtration, etc., and the obtained organic phase solvent was removed by distillation under reduced pressure to obtain 60.5 g of a pale yellow transparent viscous synthetic intermediate reactant. G-6.

(2) Put the reactant G-6 (60.5g), epichlorohydrin (102.0g), and benzyltrimethylammonium chloride (3.4g) into a mechanical stirrer, thermometer, and temperature regulator. , Condenser, Dean-Stark trap and a 500 mL three-necked round bottom flask with a dropping funnel.

Secondly, the mixture is subjected to a high of 50 torr Stir under vacuum, heat to about 50 to 60 ° C, and vigorously reflux epichlorohydrin. 28.0 g of a 48% NaOH aqueous solution was slowly added to the mixture over 2 hours. When an azeotrope is generated, in the water / epichlorohydrin mixture, the epichlorohydrin is continuously stirred while being returned to the reaction system. After the addition was completed, stirring was continued for 3 hours. Next, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and washed 6 times with 300 mL of water. The obtained organic phase solvent was distilled off under reduced pressure to obtain 48.0 g of resin 6 as a pale yellow viscous substance.

(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. 42.8 g of a light yellow viscous methacrylic curable resin 6 was obtained.

[Synthesis Example 7] Methacrylic hardening resin 7

(1) Put compound E-2 (53.0 g (0.080 equivalents / epoxy group)) and 2- (4-hydroxyphenyl) ethanol (11.1 g (1.0 equivalents)) in an eggplant-shaped flask, and heat to The liquid temperature was 120 ° C. A benzyltrimethylammonium chloride (3.0 g (0.20 equivalent)) was added, and the mixture was stirred at 120 ° C for 24 hours. After cooling to a liquid temperature of 60 ° C. or lower, 300 mL of chloroform was added, washed once with 300 mL of a 1% NaOH aqueous solution, and washed five times with 300 mL of water.

Magnesium sulfate was added to the obtained organic phase, and after drying, the solid content was filtered off by filtration, etc., and the obtained organic phase solvent was removed by distillation under reduced pressure to obtain 59.0 g of a pale yellow transparent viscous synthetic intermediate. It should be G-7.

(2) Put reactant G-7 (59.0g), epichlorohydrin (93.3g), and benzyltrimethylammonium chloride (3.1g) into a mechanical stirrer, thermometer, and temperature regulator. , 500 mL three-necked round bottom flask with condenser, Dean-Stark trap and dropping funnel.

Next, the mixture was heated to about 50 to 60 ° C. while being stirred under a high vacuum of 50 torr, and the epichlorohydrin was vigorously refluxed. 25.2 g of a 48% NaOH aqueous solution was slowly added to the mixture over 2 hours. When an azeotrope is generated, in the water / epichlorohydrin mixture, the epichlorohydrin is continuously stirred while being returned to the reaction system. After the addition was completed, stirring was continued for 3 hours. Next, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and washed 6 times with 300 mL of water. The obtained organic phase solvent was distilled off under reduced pressure to obtain 50.5 g of resin 7 as a pale yellow viscous substance.

(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 ° C. for 7 hours. 51.0 g of a light yellow viscous methacrylic curable resin 7 was obtained.

[Synthesis Example 8] Methacrylic hardening resin 8

(1) The compound E-2 (94.0 g (0.15 equivalents / epoxy group)) and phenol (21.2 g (1.5 equivalents)) were placed in an eggplant-shaped flask, and heated to a liquid temperature of 120 ° C. A benzyltrimethylammonium chloride (2.8 g (0.10 equivalent)) was added, and the mixture was stirred at 120 ° C for 24 hours. Cool the liquid To 60 ° C or lower, 300 mL of methyl isobutyl ketone was added, washed twice with 300 mL of a 1% NaOH aqueous solution, and washed four times with 300 mL of water.

Magnesium sulfate was added to the obtained organic phase, and after drying, solid components were filtered off by filtration, etc., and the obtained organic phase solvent was removed by distillation under reduced pressure to obtain 90.0 g of a pale yellow transparent viscous synthetic intermediate. Reaction G-8.

(2) Put the reactants G-8 (90.0g), epichlorohydrin (130.0g), and benzyltrimethylammonium chloride (2.6g) into a mechanical stirrer, thermometer, and temperature regulator. 500 mL three-neck round bottom flask with a condenser, Dean-Stark trap and a dropping funnel.

Next, the mixture was heated to about 50 to 60 ° C. while being stirred under a high vacuum of 50 torr, and the epichlorohydrin was vigorously refluxed. 21.0 g of a 48% NaOH aqueous solution was slowly added to the mixture over 2 hours. When an azeotrope is generated, in the water / epichlorohydrin mixture, the epichlorohydrin is continuously stirred while being returned to the reaction system. After the addition was completed, stirring was continued for 3 hours. Next, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and washed 6 times with 300 mL of water. The obtained organic phase solvent was distilled off under reduced pressure, and 80 g of a pale yellow viscous resin 8 was obtained.

(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 ° C for 13 hours. 59.2 g of a pale yellow viscous methacrylic curable resin 8 was obtained.

[Synthesis Example 9] Methacrylic hardening resin 9

(1) Compound E-2 (63.0 g (0.10 equivalents / epoxy group)) and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (95.0 g (2.5 equivalents)), 1 -Butanol (80.0 g) was placed in an eggplant-shaped flask and heated to reflux at 120 ° C. A benzyltrimethylammonium chloride (0.9 g (0.050 equivalent)) was added, and the mixture was stirred at 120 ° C for 20 hours. After cooling to a liquid temperature of 60 ° C. or lower, 300 mL of chloroform was added, washed 14 times with 300 mL of a 1% NaOH aqueous solution, and washed 5 times with 300 mL of water.

Magnesium sulfate was added to the obtained organic phase, and after drying, solid components were filtered off by filtration, etc., and the obtained organic phase solvent was removed by distillation under reduced pressure to obtain 56.0 g of a pale yellow transparent viscous synthetic intermediate reactant. G-9.

(2) Put reactant G-9 (56.0g), epichlorohydrin (111.0g), and benzyltrimethylammonium chloride (2.2g) into a mechanical stirrer, thermometer, and temperature regulator. 500 mL three-neck round bottom flask with a condenser, Dean-Stark trap and a dropping funnel.

Next, the mixture was heated to about 50 to 60 ° C. while being stirred under a high vacuum of 50 torr, and the epichlorohydrin was vigorously refluxed. 18.0 g of a 48% NaOH aqueous solution was slowly added to the mixture over 2 hours. When an azeotrope is generated, in the water / epichlorohydrin mixture, the epichlorohydrin is continuously stirred while being returned to the reaction system. After the addition was completed, stirring was continued for 3 hours. Next, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and washed 6 times with 300 mL of water. The obtained organic phase solvent was distilled off under reduced pressure to obtain 54.0 g of pale yellow Viscous resin 9.

(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 ° C for 9 hours. 49.8 g of a light yellow viscous methacrylic curable resin 9 was obtained.

[Synthesis Example 10] Methacrylic hardening resin 10

(1) Put 1000.0 g (1.0 equivalent / hydroxy) of PEG-2000 (manufactured by Toho Chemical Industry Co., Ltd.), 925.0 g of epichlorohydrin (10 equivalent), and 18.6 g (0.10 equivalent) of benzyltrimethylammonium chloride In a 5-liter three-neck round bottom flask with a mechanical stirrer, thermometer, thermostat, condenser, Dean-Stark trap, and dropping funnel.

Next, the mixture was heated to about 50 to 60 ° C. while being stirred under a high vacuum of 50 torr, and the epichlorohydrin was vigorously refluxed. 150.0 g of a 48% NaOH aqueous solution was slowly added to the mixture over 2 hours. When an azeotrope is generated, in the water / epichlorohydrin mixture, the epichlorohydrin is continuously stirred while being returned to the reaction system.

After the addition was completed, stirring was continued for 3 hours. Next, the reaction mixture was cooled to room temperature, and then chloroform was added, followed by washing three times with 1 L of water. The obtained organic phase solvent was distilled off under reduced pressure to obtain 760.0 g of compound E-5 as a white waxy solid.

(2) Put compound E-5 (220.0 g (0.20 equivalents / epoxy group)) and bisphenol A (31.0 g (1.4 equivalents)) in an eggplant-shaped flask, and heat and stir until the liquid temperature is 110 ° C. Add benzyltrimethylammonium chloride 1.9 g, and stirred at 110 ° C for 20 hours.

After cooling to a liquid temperature of 60 ° C. or lower, 300 mL of chloroform was added, washed 3 times with 300 mL of a 1% NaOH aqueous solution, and washed 6 times with 300 mL of water.

Magnesium sulfate was added to the obtained organic phase, and after drying, solid components were filtered off by filtration, etc., and the obtained organic phase solvent was removed by distillation under reduced pressure to obtain 110.0 g of a pale yellow transparent viscous synthetic intermediate reactant G-10.

(3) Put reactant G-10 (108.0g), epichlorohydrin (175.0g), and benzyltrimethylammonium chloride (2.3g) into a mechanical stirrer, thermometer, and temperature regulator. , Condenser, Dean-Stark trap and dropping funnel 1 liter three-neck round bottom flask.

Next, the mixture was heated to about 50 to 60 ° C. while being stirred under a high vacuum of 50 torr, and the epichlorohydrin was vigorously refluxed. 19.0 g of a 48% NaOH aqueous solution was slowly added to the mixture over 2 hours. When an azeotrope is generated, in the water / epichlorohydrin mixture, the epichlorohydrin is continuously stirred while being returned to the reaction system. After the addition was completed, stirring was continued for 3 hours.

Next, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and washed 6 times with 300 mL of water. The obtained organic phase solvent was distilled off under reduced pressure to obtain 92.0 g of a resin 10 as a white waxy solid.

(4) 21.7 g of resin 10, 1.1 g of methacrylic acid, 0.1 g of benzyl trimethyl ammonium chloride, 50.0 g of toluene, and 15 mg of BHT Mix and stir at 100 ° C for 7 hours. Next, the reaction mixture was cooled to room temperature, 100 mL of chloroform was added, and the reaction mixture was washed three times with 100 mL of water. The obtained organic phase solvent was distilled off under reduced pressure, and 17.0 g of a white waxy solid methacrylic hardening resin 10 was obtained.

[Synthesis Example 11] Methacrylic hardening resin 11

(1) 500.0 g (0.50 equivalent / hydroxyl) of polytetramethylene methyl ether glycol (PTMG) 2000 (manufactured by Mitsubishi Chemical Corporation), 463.0 g (10 equivalent) of epichlorohydrin, benzyltrimethylammonium chloride 9.3 g (0.10 equivalents) of the compound was placed in a 2-liter three-necked round-bottomed flask equipped with a mechanical stirrer, thermometer, thermostat, condenser, Dean-Stark trap, and dropping funnel.

Next, the mixture was heated to about 50 to 60 ° C. while being stirred under a high vacuum of 50 torr, and the epichlorohydrin was vigorously refluxed. 75.0 g of a 48% NaOH aqueous solution was slowly added to the mixture over 2 hours. When an azeotrope is generated, in the water / epichlorohydrin mixture, the epichlorohydrin is continuously stirred while being returned to the reaction system.

After the addition was completed, stirring was continued for 3 hours. Next, the reaction mixture was cooled to room temperature, and then chloroform was added, followed by washing three times with 1 L of water. The obtained organic phase solvent was distilled off under reduced pressure to obtain 450.0 g of compound E-6 as a white waxy solid.

(2) The compound E-6 (127.0 g (0.10 equivalents / epoxy group)) and bisphenol A (15.0 g (1.4 equivalents)) were placed in an eggplant-shaped flask, and heated to a liquid temperature of 110 ° C. 0.9 g of benzyltrimethylammonium chloride was added, and it stirred at 110 degreeC for 20 hours.

After cooling to a liquid temperature of 60 ° C. or lower, 300 mL of chloroform was added, washed 3 times with 300 mL of a 1% NaOH aqueous solution, and washed 6 times with 300 mL of water.

Magnesium sulfate was added to the obtained organic phase, and after drying, solid components were filtered off by filtration, etc., and the obtained organic phase solvent was removed by distillation under reduced pressure to obtain 120.0 g of a pale yellow transparent viscous synthetic intermediate reactant. G-11.

(3) Put reactant G-11 (117.0g), epichlorohydrin (125.0g), and benzyltrimethylammonium chloride (2.5g) into a mechanical stirrer, thermometer, and temperature regulator. , 1-liter three-neck round-bottomed flask with condenser, Dean-Stark trap, and dropping funnel.

Next, the mixture was heated to about 50 to 60 ° C. while being stirred under a high vacuum of 50 torr, and the epichlorohydrin was vigorously refluxed. 20.0 g of a 48% NaOH aqueous solution was slowly added to the mixture over 2 hours. When an azeotrope is generated, in the water / epichlorohydrin mixture, the epichlorohydrin is continuously stirred while being returned to the reaction system. After the addition was completed, stirring was continued for 3 hours.

Next, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and washed 6 times with 300 mL of water. The obtained organic phase solvent was removed by distillation under reduced pressure to obtain 92.0 g of resin 11 as a pale yellow viscous substance.

(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 ° C. for 7 hours. 54.0 g of a light yellow viscous methacrylic curable resin 11 was obtained.

[Manufacture of photopolymerization initiator]

The photopolymerization initiators used in the examples and comparative examples were produced as follows.

<Manufacture of Photopolymerization Initiator 1>

DenacolEX-830 (manufactured by Nagase Chemtex, a diglycidyl ether of PEG400) 26.8 g (0.10 equivalent / epoxy group), 16.5 g (1.0 equivalent) of 4-dimethylaminobenzoic acid, benzyltrimethyl 3.7 g (0.20 equivalents) of ammonium chloride and 25.0 g of MIBK (methyl isobutyl ketone) were placed in a flask, and stirred at 110 ° C. for 24 hours. The reaction mixture was cooled to room temperature, dissolved in 50 g of chloroform, and washed 6 times with 100 ml of water. The organic phase solvent was distilled off under reduced pressure to obtain 35.3 g of a photopolymerization initiator 1.

<Manufacture of Photopolymerization Initiator 2>

DenacolEX-830 (manufactured by Nagase Chemtex, a diglycidyl ether of PEG400) 26.8 g (0.10 equivalent / epoxy group), 22.8 g (1.0 equivalent) of 2-hydroxy-9H-thioxan-9-one, benzyl 3.7 g (0.20 equivalents) of trimethylammonium chloride and 40.0 g of MIBK were placed in a flask and stirred at 110 ° C. for 72 hours. The reaction mixture was cooled to room temperature, dissolved in 50 g of chloroform, and washed 6 times with 100 ml of water. The organic phase solvent was distilled off under reduced pressure, and 36.2 g of a photopolymerization initiator 2 was obtained.

[Examples 1 to 11 and Comparative Example 1]

The methacrylated bisphenol A epoxy resin, methacrylic hardening resins 1 to 11, the photopolymerization initiators 1 and 2 and EH of the hardener were prepared in the synthesis examples and comparative synthesis examples. -5030S (manufactured by ADEKA (polyamine compound)), after mixing at the compounding amount (parts by weight) as shown in Table 1 below, use a three-roller mixer (C-43 / 4 × 10 by Inoue Seisakusho) to fully mix After kneading, the liquid crystal sealant compositions of Examples 1 to 11 and Comparative Example 1 were obtained.

Each compound produced in the synthesis example and the comparative synthesis example, and the liquid crystal sealant composition of these compounds were evaluated by the following tests.

[Test conditions]

For partial methacrylated bisphenol A epoxy resin, methacrylate hardening resins 1-9, and 1, the epoxy equivalent, viscosity, and NI point changes were measured, and for methacrylate hardening resin 10, the ring was measured. Oxygen equivalent and NI point change, viscosity and NI point change were measured for photopolymerization initiators 1 and 2, NI point change was measured for hardener (EH-5030S), and for liquid crystals manufactured in Examples 1 to 11 and Comparative Example 1 The hardened product of the sealant composition was measured for Tg and storage elasticity at various temperatures.

(1) Determination of epoxy equivalent

The measurement was performed under the conditions described in JISK7236: 2001.

(2) Viscosity measurement

The measurement was performed at 25 ° C using an E-type viscometer (RE105U, manufactured by Toki Sangyo Co., Ltd.).

Select the rotor and number of revolutions as follows.

Partially methacrylic bisphenol A epoxy resin: 3 ° × R7.7 rotor, 10rpm

Methacrylic hardening resin 1: 3 ° × R7.7 rotor, 15rpm

Methacrylic hardening resin 2: 3 ° × R7.7 rotor, 15rpm

Methacrylic hardening resin 3: 3 ° × R7.7 rotor, 0.5 rpm

Methacrylic hardening resin 4: 3 ° × R7.7 rotor, 0.2rpm

Methacrylic hardening resin 5: 1 ° 34 ′ × R24 rotor, revolutions 2.0 rpm

Methacrylic hardening resin 6: 3 ° × R14 rotor, 5.0 rpm

Methacrylic hardening resin 7: 1 ° 34 ′ × R24 rotor, 5.0 rpm

Methacrylic hardening resin 8: 1 ° 34 ′ × R24 rotor, revolutions 2.0 rpm

Methacrylic hardening resin 9: 3 ° × R7.7 rotor, revolutions 2.0 rpm

Methacrylic hardening resin 11: 3 ° × R7.7 rotor, 15 rpm

(3) NI point change measurement

Partially methacrylated bisphenol A epoxy resin, methacrylic hardening resins 1 to 11, photopolymerization initiators 1 and 2, and hardener (EH-5030S) were added to each sample bottle, and then 0.1 g was added. 1 g of liquid crystal (MLC-11900-080, manufactured by Merck) was added. This bottle was left in an oven at 120 ° C. for 1 hour, and then left at room temperature to return to room temperature (25 ° C.). Then, the liquid crystal portion was taken out and filtered through a 0.2 μm filter as a liquid crystal test sample for evaluation.

The measurement of the NI point was performed using a differential scanning calorimeter (DSC, manufactured by PerkinElmer, PYRIS6), and 10 mg of the liquid crystal sample for evaluation was sealed in an aluminum sample pan, and the temperature was raised at a temperature of 5 ° C / min. . In addition, 10 mg of the above-mentioned liquid crystal was sealed in an aluminum sample pan, and the measurement result was performed under the condition of a temperature increase rate of 5 ° C./min as a control group.

The difference TE-TB between the endothermic absorption peak top (phase transition temperature) TB of the control group and the endothermic absorption peak top (phase transition temperature) TE of the liquid crystal for evaluation was taken as the NI point change. From the viewpoint of suppressing the dissolution of the liquid crystal sealant-containing components from the liquid crystal, stably ensuring the alignment of the liquid crystal, and improving the display characteristics, the smaller the absolute value of the NI point change, the better.

(4) Tg measurement

The liquid crystal sealant compositions manufactured in Examples 1 to 11 and Comparative Example 1 were injected into a mold having a length of 5 cm, a width of 5 mm, and a thickness of 0.5 mm. Ultraviolet rays (using a UV irradiation device: UVX-01224S1, manufactured by USHIO Electric Corporation) , 100mW / cm ² / 365nm for 30 seconds) after the integral light amount of 3000mJ / cm ² irradiated and cured, thermally cured for 1 hour in a hot air oven of 120 deg.] C, thereby to obtain a cured test sheet.

The obtained hardened test piece was stretched in a deformation mode using a dynamic viscoelasticity measuring device (DMA, DMS6100 manufactured by Seiko Instruments Inc.) at a frequency of 1.0 Hz and a range of -50 ° C to 100 ° C at 2 ° C / The measurement was performed while increasing the temperature. The loss of the obtained result was taken as the Tg of the absorption peak temperature in tanδ.

(5) Determination of storage elasticity

For the liquid crystal sealant compositions manufactured in Examples 1 to 11 and Comparative Example 1, a hardened test piece was produced under the same conditions as Tg and a dynamic viscoelasticity measuring device (DMA, manufactured by Seiko Instruments Inc.) was used. DMS6100). From the obtained results, the storage elasticity values at each temperature were taken out.

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

Claims (5)

A method for producing (meth) acrylic curable resin, characterized in that the curable resin represented by the following formula (1) is selected from (meth) acrylic acid, (meth) acrylic anhydride, One or more (meth) acrylic compounds composed of acrylate compound and (meth) acrylic acid halide reacted:

[In the formula, m is a number in the range of 1 to 7, X is independently a hydrogen atom, a hydroxyl group, a glycidyloxy group, or a methyl glycidyloxy group, and R ^{1 is} each independently a hydrogen atom, a glycidyl group, or A methyl glycidyl group, each R ^{2 is} independently a hydrogen atom or a methyl group, and each A ring is independently a total of 5 or more carbon atoms and hetero atoms, and a group containing more than one aromatic ring or heteroaromatic ring , Y is the following formula (1a):

(In the formula, 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). The following formula (1b):

(In the formula, Y ^{2 is} each independently a direct bond or an alkylene group having 1 or 2 carbon atoms, R ^{3 is} independently a hydrogen atom or a methyl group, p and q are each independently a number of 0 or more, and these The total number is in the range of 1 to 200) or the radical of a part or all of the hydrogenated structure of the unsaturated bond in the aforementioned formula (1b), and R in relation to the aforementioned R ¹ and X, glycidyl group or methyl glycidyl group ¹ The average number x of the total number of X with glycidyloxy or methylglycidyloxy is 1 or more]. The method for producing a (meth) acrylic curable resin according to claim 1, wherein for the aforementioned formula (1), the number of carbon atoms contained in the A ring is 4 to 40, the number of oxygen atoms is 0 to 5, and the nitrogen atom The number is 0 ~ 5, the number of sulfur atoms is 0 ~ 5, and the number of ring structures contained in the A ring is 1 ~ 5. A method for manufacturing a liquid crystal sealant composition, which is characterized by containing a combination of a curable resin as shown in formula (1) of claim 1 and a (meth) acrylated curable resin of claim 1 or 2, or as The step of claim 1 or 2 (meth) acrylate hardenable resin, photopolymerization initiator and / or hardener. The method for producing a liquid crystal sealant composition according to claim 3, wherein the content of the curable resin and / or (meth) acrylated curable resin in the liquid crystal sealant composition is 5 to 95% by weight. The method for producing a liquid crystal sealant composition according to claim 3 or 4, which further contains a compound H having an ethylenically unsaturated group and / or an epoxy group (however, except for the aforementioned curable resin and (meth) acrylation Steps other than curable resin).