TW201428018A - Glycidyl ether compound, liquid crystal sealant, and method for producing glycidyl ether compound - Google Patents

Abstract

The present invention provides a glycidyl ether compound that scarcely affects liquid crystal molecular alignment and makes it possible for a liquid crystal sealant to adhere strongly and cure even when a liquid crystal sealant is applied in a narrow seal width and bonded to a base in a one-drop-fill method. The present invention also provides a liquid crystal sealant containing the glycidyl ether compound, and a method for producing the glycidyl ether compound.

Description

Method for producing epoxy propyl ether compound, liquid crystal sealing agent and epoxy propyl ether compound

The present invention relates to a method for producing a glycidyl ether compound, a liquid crystal sealing agent containing a glycidyl ether compound, and a glycidyl ether compound.

In the manufacture of a liquid crystal display device such as a liquid crystal panel, for example, a liquid crystal sealing agent is applied to any of the two substrates constituting the two substrates of the liquid crystal panel, and a specific amount of liquid crystal is dropped on any of the substrates, and is bonded under vacuum. After the base of the sheet is returned to the atmospheric pressure, the liquid crystal is filled, and the liquid crystal sealing agent which hardens the liquid crystal sealing agent is popularized.

In the liquid crystal dropping method, a radical polymerization compound having an epoxy group-containing compound as a main component is widely used as a liquid crystal sealing agent from the viewpoint of high-speed curing (for example, see JP-A-2007-297470).

[Summary of the Invention]

However, in recent years, with the popularization of smart phones or tablet terminals, the demand for small panels has increased, and by narrowing the design of the panel design, the thinning of the liquid crystal sealant is increasing. For example, it is required to halve the conventional seal width by 1.0 to 1.5 mm. With such a requirement, as the sealing width is narrowed and the adhesion area is reduced, it is necessary to maintain or improve the adhesion strength of the liquid crystal sealing agent from the viewpoint of durability.

In the liquid crystal dropping method, a sealing frame is applied to the substrate in a frame shape to form a sealing frame, a liquid crystal is dropped on the inside of the frame, a vacuum is applied to the panel, and the liquid crystal sealing agent is cured by UV irradiation to form a liquid crystal. The temperature above the Nematic Isotropic point is thermally cured, and the liquid crystal sealing agent is thermally hardened to align the liquid crystal.

When a large panel such as a TV is used, the panel has a large distance, and there is a certain distance from the liquid crystal dropping point to the sealing frame. After the liquid crystal is dropped and the panel is attached to the UV, the liquid crystal and the liquid crystal sealing agent are not in contact, so the liquid crystal sealing agent After photohardening, it is in contact with the liquid crystal. Alternatively, the contact time between the liquid crystal and the liquid crystal sealant in an uncured state is short.

Further, in the small panel, the distance from the liquid crystal dropping point to the sealing frame is short, so that the liquid crystal sealing agent is in contact with the liquid crystal in an uncured state (contact time is long) after the bonding. Therefore, conventionally, the liquid crystal sealant has a problem of liquid crystal contamination in an uncured state.

A free-polymerizable liquid crystal sealing agent containing an epoxy compound of a conventional epoxy/acrylic compound as a main component is not mentioned Pay such a request.

An object of the present invention is to provide a liquid crystal sealing agent which can be firmly adhered and hardened when a liquid crystal sealing agent is applied to a liquid crystal sealing agent with a narrow sealing width in a liquid crystal dropping method, and is not easily affected by liquid crystal alignment. An oxypropyl ether compound; a liquid crystal sealing agent containing a glycidyl ether compound; and a method for producing a glycidyl ether compound.

The present invention encompasses the following aspects.

[1] A glycidyl propyl ether compound which is represented by the following formula (1), [wherein, n ₁ is a number in the range of 2 to 30, m is a number in the range of 1 to 5, X is an oxygen atom (O), an alkyl group having 1 to 4 carbon atoms, or a carbon number of 2 to 4 The alkylene group, Y is a mutually independent alkyl group having 2 to 4 carbon atoms, and R is a hydrogen atom independently independent of each other, a glycidyl group, a methyl epoxy group, and a group 1:-CH ₂ - CH(OR ¹ )-CH ₂ -OR ² or base 2: -CH ₂ -C(CH ₃ )(OR ¹ )-CH ₂ -OR ² (wherein R ¹ is a hydrogen atom or (meth)acryloquinone a group, R ² is a (meth) propylene fluorenyl group, and R ′ is a hydrogen atom or a methyl group which are independent of each other, and in the above R, the epoxy propyl group, the methyl epoxide group, the group 1 and The average number x of the total of the base 2 is 2 or more, and when the R contains the base 1 or the base 2, the average number y of the total of the epoxy propyl group and the methyl epoxy group is the same as the above The ratio (y/z) of the average number z of the total of 1 and the aforementioned base 2 is 10/90 to 90/10].

[2] A liquid crystal sealing agent comprising the epoxy propyl ether compound according to the above [1].

[3] A method for producing a glycidyl propyl ether compound represented by the formula (1) of the above [1], which comprises the step of: (2): (wherein n ₂ is a number in the range of 2 to 30, and Y is independently an alkylene group having 2 to 4 carbon atoms, and R ¹¹ is independently a hydrogen atom, an epoxy propyl group or a methyl epoxy group, respectively. The compound C shown by propyl) and the following formula (3): [In the formula, X is an oxygen atom, an alkylene group having 1 to 4 carbon atoms or an alkylene group having 2 to 4 carbon atoms, and R ¹² is independently a hydrogen atom, an epoxy propyl group or a methyl epoxy group. Propyl, group 1: -CH ₂ -CH(OR ²¹ )-CH ₂ -OR ²² , or base 2: -CH ₂ -C(CH ₃ )(OR ²¹ )-CH ₂ -OR ²² (wherein R ²¹ is a step of reacting a compound D represented by a hydrogen atom or a (meth) acrylonitrile group and R ²² is a (meth) propylene fluorenyl group.

According to the present invention, in the liquid crystal dropping method, when the liquid crystal sealing agent is applied with a narrow sealing width and the substrate is bonded to the substrate, the liquid crystal sealing agent can be firmly adhered and hardened, and the liquid crystal alignment property is not easily affected. A method for producing a glycidyl propyl ether compound, a liquid crystal sealing agent containing a glycidyl propyl compound, and a glycidyl propyl compound.

Fig. 1 is a micrograph showing an example (compound A-3) in which the liquid crystal alignment property of the example is ○.

Fig. 2 is a micrograph showing an example (compound A-5) in which the liquid crystal alignment property of the example is ○.

Fig. 3 is a micrograph showing an example (Compound B) in which the liquid crystal alignment property of the example is ×.

Fig. 4 is a conceptual diagram showing an outline of a test method of adhesion strength.

[Formation for implementing the invention]

In the present specification, the term "step" is not an independent step, and even if it is not clearly distinguishable from other steps, the term is included if the intended purpose of the step is achieved. Use the value shown by "~" The range indicates the range in which the numerical values described before and after "~" are the minimum value and the maximum value, respectively. When the amount of each component in the composition is a plurality of substances corresponding to each component in the composition, unless otherwise stated, it means the total amount of the plural substances present in the composition.

Further, the (meth)acrylonitrile group means a methyl methacrylate group and/or an acryl fluorenyl group, and the (meth) acrylate type means a methacrylate and/or an acrylate.

[Compound A]

The glycopropyl ether compound (hereinafter also referred to as compound A) of the present invention is represented by the following formula (1).

In the formula, n ₁ is a number in the range of 2 to 30, and m is a number in the range of 1 to 5.

X is an oxygen atom (O), an alkylene group having 1 to 4 carbon atoms or an alkylene group having 2 to 4 carbon atoms. Y is an alkyl group having 2 to 4 carbon atoms independently of each other.

R is a hydrogen atom independently independent of each other, a glycidyl group, a methyl epoxy group, a group 1:-CH ₂ -CH(OR ¹ )-CH ₂ -OR ² or a group 2:-CH ₂ -C (CH) ₃ ) (OR ¹ )-CH ₂ -OR ² (wherein R ¹ is a hydrogen atom or a (meth)propenyl group, and R ² is a (meth)acryloyl group), and R' is a hydrogen independently of each other. Atom or methyl.

In the above R, the average number x of the total of the epoxy propyl group, the methyl epoxypropyl group, the base 1 and the base 2 is 2 or more, and when the R contains the base 1 or the base 2, The ratio (y/z) of the average number y of the total of the epoxy propyl group and the methyl epoxy group to the total number z of the total of the base 1 and the base 2 is 10/90 to 90/ 10.

In the compound A, in the liquid crystal dropping method, when the liquid crystal sealing agent is applied with a narrow sealing width to bond the substrate, the liquid crystal sealing agent can also be firmly adhered and hardened (hereinafter, also referred to as strong adhesion). From the viewpoint, n ₁ is a number in the range of 3 to 25, preferably in the range of 5 to 20, more preferably in the range of 5 to 15, and most preferably in the range of 7 to 10. Further, n ₁ is a number of repeating units of the compound (compound C) represented by the formula (2), that is, derived from n ₂ .

In the compound A, the adhesion to the liquid crystal sealing agent from the viewpoint of the coatability of the liquid crystal sealing agent (for example, the drawing speed of the dispenser and the production cycle are not lowered) (does not increase the viscosity of the compound A excessively) The viewpoint is that the number of the range of m to 1 to 5 is preferably in the range of 1 to 4, more preferably in the range of 1 to 3, and most preferably in the range of 1 to 2. The m system can be estimated from the reaction equivalent ratio (feed amount) of the compound C of the compound A and the compound D.

Further, n ₁ and m can also be measured by GPC.

Y is an alkyl group having 2 to 4 carbon atoms independently of each other, and is specifically an ethylene group, a propyl group, a trimethylene group, a tetramethylene group or the like. Y is preferably an ethylene group or a propyl group, more preferably an ethylene group.

In the R of the compound A, a glycidoxy group, a methyl epoxy group, The average number x of the total of the base 1 and the base 2 is 2 or more from the viewpoints of workability such as coating property affected by viscosity of the liquid crystal sealing agent, and physical properties such as strength after hardening affected by, for example, crosslinking density. It should be 2~2m+2, more preferably 2m~2m+2, and most preferably 2m+1~2m+2.

Further, the x-ray can be obtained by measuring the average molecular weight and molecular weight distribution of the compound A by high-speed liquid chromatography (HPLC) and liquid chromatography (LC-MS), and measuring n ₁ and m by GPC.

In the compound A, when the R includes the base 1 or the base 2, the average number y of the total of the epoxypropyl group and the methyl epoxy group is the average of the total of the base 1 and the base 2 The ratio of the number z (y/z) is 10/90~90/10, preferably 20/80~80/20, more preferably 30/70~70/30, and most preferably 40/60~60/40. .

In the compound A, from the viewpoint of strong adhesion, the R system is independently a hydrogen atom, a glycidyl group, a methyl epoxy group, a group 1 or a group 2, preferably a hydrogen atom, a glycidyl group or a group. 1. R' is preferably a hydrogen atom.

When Compound A is used for liquid crystal sealing agent, the viscosity of Compound A should be 1000~1000000mPa from the viewpoint of ensuring moderate viscosity of liquid crystal sealing agent. s, more preferably 3000~700000mPa. s, the most suitable is 5000~500000mPa. s, and the most suitable is 7000~250000mPa. s, especially suitable for 9000 ~ 200000mPa. s. Further, the viscosity was measured at 25 ° C using an E-type viscometer.

Further, the viscosity of the compound A can be adjusted by, for example, changing the ratio of n ₁ and m in the compound A and/or changing the ratio of the hydroxyl groups in the compound A.

When the compound A is used in a liquid crystal sealing agent, the epoxy equivalent is preferably from 100 to 3,000 g/eq, more preferably from 150 to 2,000 g/eq, from the viewpoint of strong adhesion.

Further, the epoxy equivalent of the compound A can be adjusted by the average molecular weight of the compound A and the number of epoxy groups per repeating unit. For example, it can be adjusted by the ratio of the epoxidation of the hydroxyl group of the compound P and the ratio of the (meth) acrylate modification of the epoxy group of the reactant Q.

When the compound A is in contact with a liquid crystal in an uncured state by a liquid crystal dropping method, it is difficult to affect the alignment of the liquid crystal (the change in the NI point is small), and it is difficult to hinder the alignment of the liquid crystal. Therefore, it is preferable as a liquid crystal sealing agent.

(Liquid Crystal Sealant Containing Compound A)

The liquid crystal sealing agent (hereinafter also referred to as "composition") containing the compound A is excellent in strong adhesion.

From the viewpoint of strong adhesion and liquid crystal alignment, the content of the compound A is preferably 10 to 100% by weight in the reaction-hardening component of the liquid crystal sealing agent (for example, a component which can be hardened by reaction by light and/or heating). More preferably 20 to 100% by weight, more preferably 30 to 100% by weight, more preferably 40 to 100% by weight, more preferably 50 to 100% by weight, more preferably 60 to 100% by weight, more preferably 70 It is preferably from 100 to 100% by weight, more preferably from 90 to 100% by weight, still more preferably 100% by weight.

For example, a compound B having an ethylenically unsaturated group and/or an epoxy group which is used as a main component of a liquid crystal sealing agent is blended (for example, a partial methyl group of an epoxy group of a bisphenol A type epoxy resin) Acrylate oligomer Further, when the liquid crystal sealing agent of the compound A is compared with the compound B alone, the strong adhesion is sufficiently improved. In other words, in addition to the liquid crystal sealant compound A, it is preferred to contain the compound B having an ethylenically unsaturated group and/or an epoxy group other than the compound A.

The compound B having an ethylenically unsaturated group may, for example, be a (meth) acrylate compound, an aliphatic acrylamide compound, an alicyclic acrylamide compound, an aromatic acrylamide compound or an N-substituted acrylamide. a compound.

Examples of the (meth) acrylate compound include p-isopropylphenylphenoxyethylene glycol (meth) acrylate, a third butyl (meth) acrylate, and an ethoxylated phenyl (methyl) group. An aliphatic (meth) acrylate represented by acrylate, benzyl (meth) acrylate or epoxy propyl (meth) acrylate, or a (meth) acrylate containing an aromatic ring.

The compound containing an ethylenically unsaturated group may, for example, be a monofunctional, difunctional, trifunctional or polyfunctional radically polymerizable unsaturated compound.

The monofunctional radically polymerizable unsaturated compound is preferably hydroxyethyl (meth) acrylate or benzyl (meth) acrylate from the viewpoint of ensuring viscosity of the composition, film hardness, and flexibility. Tetrahydrofuranmethyl (meth) acrylate, isooctyl (meth) acrylate, cyclohexyl (meth) acrylate, isomeric decyl (meth) acrylate, dicyclopentyl (meth) acrylate , cyclohexyloxyethyl (meth) acrylate, dicyclopentyl oxyethyl (meth) acrylate, isomyristyl (meth) acrylate, lauryl (meth) acrylate, third butyl Base (methyl) One or more selected from the group consisting of acrylate and diethylene glycol monoethyl ether (meth) acrylate, more preferably isodecyl (meth) acrylate or tetrahydrofuran methyl (A) One or more selected from the group consisting of acrylate, dicyclopentyl (meth) acrylate, and cyclohexyl (meth) acrylate.

The difunctional radically polymerizable unsaturated compound is preferably tricyclodecane dimethanol di(meth)acrylate or dimethylol bicyclic ring from the viewpoint of ensuring viscosity of the composition, film hardness, and flexibility. Pentane di(meth)acrylate, EO modified 1,6-hexanediol di(meth)acrylate, EO modified bisphenol A di(meth)acrylate, PO modified bisphenol A (Meth)acrylate, polyester di(meth)acrylate, polyethylene glycol di(meth)acrylate, polyoxydi(meth)acrylate and triethylene glycol di(meth)acrylic acid One or more compounds selected from the group consisting of esters are more preferably dimethylol dicyclopentane di(meth)acrylate and/or modified bisphenol A di(meth)acrylate. Among them, it is preferably a (meth) acrylate having a bisphenol A skeleton without a hydroxyl group, and a light Acrylate BP-4EAL (a bisphenol A EO adduct diacrylate) commercially available from Kyoeisha Chemical Co., Ltd. ), BP-4PA (PO adduct diacrylate of bisphenol A), and the like.

The trifunctional or higher radical polymerizable unsaturated compound is preferably modified by ECH to modify tris(meth)acrylate (trifunctional) and EO from the viewpoint of ensuring viscosity, film hardness, and flexibility of the composition. Triglyceride (trifunctional), PO modified tris (meth) acrylate (trifunctional), pentaerythritol tri (meth) acrylate (three One or more compounds selected from the group consisting of dipentaerythritol hexa(meth)acrylate (hexafunctional) and pentaerythritol tetra(meth)acrylate (tetrafunctional), more preferably EO-modified glycerol (Meth) acrylate and / or dipentaerythritol hexa (meth) acrylate.

The compound B having an epoxy group is preferably a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol AD type epoxy compound, a phenol novolac type epoxy compound, or a cresol novolac type epoxy compound. One or more compounds selected from the group consisting of a naphthalene type epoxy compound, such a hydrogenated compound and an alicyclic epoxy compound, more preferably a bisphenol A type epoxy compound or a bisphenol F type epoxy compound One or more compounds selected from the group consisting of naphthalene type epoxy compounds are most preferably bisphenol A type epoxy compounds.

Specific examples of the bisphenol A type epoxy compound include EPICLON 850S, 860, 1055, EPICLON 850CRP, and the like manufactured by DIC Corporation. Specific examples of the hydrogenated bisphenol A type epoxy compound include KRM-2408 manufactured by ADEKA Co., Ltd., and YX-8034 manufactured by JER Corporation. Specific examples of the bisphenol F-type epoxy compound include EPICLON 830S manufactured by DIC Corporation. Specific examples of the naphthalene type epoxy compound include HP-4032D and HP-7200H of EPICLON 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 type epoxy compound include EPICLON N-660 and N-670 manufactured by DIC Corporation. Specific examples of the alicyclic epoxy compound are 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate (Celoxide 2021P manufactured by Daicel), 1,2 :8,9-dicyclooxy limonene (Celoxide manufactured by Daicel) 3000), 1,2-epoxy-4-vinylcyclohexane (Celoxide 2000 manufactured by Daicel Co., Ltd.), 1,2-epoxy group of 2,2-bis(hydroxymethyl)-1-butanol- 4-(2-oxiranyl)cyclohexane adduct (EHPE 3150, manufactured by Daicel Co., Ltd.).

In the case of the compound B having an ethylenically unsaturated group and an epoxy group, a partial (meth) acrylate modified ring obtained by reacting an epoxy group-containing compound with a (meth) acrylate compound may also be used. The oxygen compound is more preferably a partially (meth)acrylated epoxy compound obtained by reacting a bisphenol A type epoxy compound with (meth)acrylic acid.

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

First, the bisphenol A type epoxy resin and (meth)acrylic acid are preferably equivalent to 1 equivalent of an epoxy group in the presence of a trivalent organic phosphate compound and/or an amine compound in a basic catalyst. ) Acrylic acid reacts 10 to 90 equivalent %. Then, the reaction product is purified by removing the basic catalyst by filtration, centrifugation, and/or washing. As the basic catalyst, a known basic catalyst used by the reaction of an epoxy resin with (meth)acrylic acid can be used. Further, an alkaline catalyst supporting a polymer which supports a basic catalyst to a polymer can also be used.

When the compound A does not contain an ethylenically unsaturated group, the above-mentioned ethylenically unsaturated group-containing compound which is a suitable example of the radical curable compound is preferably used as the compound B.

The liquid crystal sealing agent of the present invention may contain a photopolymerization initiator (a compound which is activated by absorption of light energy to generate a radical) as a source of radical generation when photopolymerizing Compound A and/or Compound B. The polymerization initiator is not particularly limited, and a known compound can be used as a polymerization initiator. The polymerization initiator may, for example, be a benzoin, an acetophenone, a benzophenone, a thioxanthone, an α-oxime ester, a phenylglyoxylic acid, a benzyl group or an azo system. The polymerization initiator of the compound, the diphenyl sulfide compound, the phosphorus oxide compound, the benzoin ether, and the onion ketone is preferably low in solubility in liquid crystal, and has a light irradiation by itself. The reactive base of the decomposition product is not gasified. Preferred polymerization initiators of the present invention are exemplified by the following: As shown, for example, EY resin KR-2 (manufactured by KSM Co., Ltd.) or the like.

The hardener is preferably an amine-based hardener such as an organic acid diterpene compound, imidazole and a derivative thereof, dicyandiamide, an aromatic amine, an epoxy-modified polyamine, or a polyamine group from the viewpoint of strong adhesion. Urea, etc., preferably VDH (1,3-bis(decylcarboethyl)-5-isopropylhydantoin), ADH (dioxamethane adipate), UDH (organic acid diterpene) 7,11-octadecadiene-1,18-dicarbenium) and LDH (octadecane-1,18-dicarboxylic acid dioxime). These hardeners may be used singly or in plural.

The photosensitizer may, for example, be a carbonyl compound, an organic sulfur compound, a persulfide compound, a redox compound, an azo or diazo compound, a halogen compound or a photoreducible dye, from the viewpoint of curability. Specific examples of the photosensitizer include benzoin methyl ether, benzoin isopropyl ether, benzoin derivative of α,α-dimethoxy-α-phenylethyl benzene; and diphenyl Ketone, 2,4-di Chlorobenzophenone, methyl phthalate benzoate, benzophenone derivative of 4,4'-bis(diethylamino)benzophenone; 2,4-diethyl thia a thioxanthone derivative of anthrone, 2-chlorothiazinone, 2-isopropylthioxanthone; 2-chloropurine, a 2-methyl onion-based onion derivative; N-methyl Acridinone, an acridone derivative of N-butylacridone; other, α,α-diethoxyethyl benzene, benzyl, anthrone, ketone, ureido compound, and the like. These light sensitizers may be used singly or in combination of two or more. A preferred photo sensitizer is 2,4-diethylthiaxanone (for example, DETX-S manufactured by Nippon Kayaku Co., Ltd.).

The liquid crystal sealing agent of the present invention may contain a curing accelerator from the viewpoint of promoting the curing reaction of the curable compound, and preferably, for example, 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methyl Imidazoles such as imidazole, 2-(dimethylaminomethyl)phenol, and amines of 1,8-diazocyclo[5.4.0]undec-7-ene (DBU) a phosphorus such as triphenylphosphine; a metal compound such as tin octylate;

The liquid crystal sealing agent of the present invention can be added with a filler from the viewpoints of viscosity control, greater strength improvement after hardening, adhesion reliability, and suppression of linear expansion. As the filler, an inorganic filler and an organic filler can be used. Examples of the inorganic filler include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum niobate, titanium oxide, aluminum oxide, zinc oxide, cerium oxide, kaolin, talc, glass beads, sericite-activated clay, bentonite, and nitrogen. Aluminum and tantalum nitride. The organic filler may, for example, be polymethyl methacrylate, polystyrene, a copolymer obtained by copolymerizing a monomer constituting these and other monomers, polyester fine particles, polyurethane fine particles, and Rubber particles.

The average particle diameter of the particles constituting the filler is 0.1 to 3 μm, more preferably 0.5 to 3 μm, from the viewpoint of blending the filler of the non-reactive component and further reducing the outgassing. Further, the average particle diameter of the filler was measured by a laser diffraction/scattering particle size distribution measuring apparatus (for example, HORIBA Partica LA-950V2) manufactured by HORIBA.

The liquid crystal sealing agent of the present invention may contain a decane coupling agent within the range in which the effects of the present invention are exerted.

From the viewpoint of the stability of the hardening strength of the liquid crystal sealing agent of the present invention, the decane coupling agent is preferably tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane, tetraisopropoxy decane or tetrabutoxy group. a tetraalkylnonane such as decane, dimethoxydiethoxydecane, dimethoxydiisopropoxydecane, diethoxydiisopropoxydecane or diethoxydibutoxydecane ; methyl trimethoxy decane, methyl triethoxy decane, methyl triisopropoxy decane, ethyl triethoxy decane, ethyl tributoxy decane, cyclohexyl triethoxy decane, benzene a trialkoxy decane such as triisopropoxy decane, vinyl trimethoxy decane, 3-epoxypropyl propyl trimethoxy decane, 3-methyl propylene oxy propyl trimethoxy decane And dimethyl dimethoxy decane, dimethyl diethoxy decane, diethyl diethoxy decane, diethyl dibutoxy decane, phenyl ethyl diethoxy decane, etc. At least one decane coupling agent selected from the group consisting of alkoxydecanes, more preferably methyltrimethoxydecane or methyltriethoxy Alkane, methyl triisopropoxy decane, ethyl triethoxy decane, ethyl tributoxy decane, cyclohexyl triethoxy decane, phenyl triisopropoxy decane, vinyl trimethoxy decane , 3-epoxypropylpropyltrimethoxydecane and 3-methylpropenyloxypropyltrimethoxy At least one of the trialkoxy decane decane coupling agents selected from the group consisting of decane is preferably 3-glycidylpropyltrimethoxydecane.

(Method for producing Compound A)

The method for producing the compound A of the present invention comprises the steps of: (2): (wherein n ₂ is a number in the range of 2 to 30, and Y is each independently an alkylene group having 2 to 4 carbon atoms, and R ¹¹ is independently a hydrogen atom, a propylene group or a methyl ring, respectively. The compound C represented by oxypropyl) and the following formula (3): [wherein, X is an oxygen atom (O), an alkylene group having 1 to 4 carbon atoms or an alkylene group having 2 to 4 carbon atoms, and R ¹² is independently a hydrogen atom, an epoxypropyl group, and an alkyl group. Epoxypropyl group, group 1: -CH ₂ -CH(OR ²¹ )-CH ₂ -OR ²² , or base 2: -CH ₂ -C(CH ₃ )(OR ²¹ )-CH ₂ -OR ²² (formula In the above, R ²¹ is a hydrogen atom or a (meth)acryl fluorenyl group, and R ²² is a step of reacting the compound D represented by (meth) acrylonitrile).

The n ₂ in the compound C is selected from the viewpoint of the strong adhesion of the compound A as long as the n _{1 of the} compound A falls within the above range, and is in the range of 3 to 25, preferably in the range of 5 to 20. The number is preferably in the range of 5 to 15, and is preferably in the range of 7 to 10. Further, the molecular weight (weight average molecular weight) of the compound C in which R ¹¹ is a hydrogen atom is preferably 2,000 or less.

In the compound C, Y is an alkylene group having 2 to 4 carbon atoms, and specifically, an ethylene group, a propyl group, a trimethylene group, a tetramethylene group or the like. Y is preferably an ethylene group or a propyl group, more preferably an ethylene group.

Compounds C and D are commercially available or can be readily prepared from commercially available compounds by well-known methods. For example, a compound C in which R ¹¹ is a hydrogen atom and Y is an ethylene group can be obtained as a polyethylene glycol having various repeating unit numbers (n ₂ ), and a compound having a desired range of n ₂ can be appropriately selected. . Further, the n ₂ system can also be calculated in the same manner as n ₁ . The molecular weight of the polyethylene glycol is preferably 2,000 or less.

Further, the compound C in which R ¹¹ is a hydrogen atom and Y is a propyl group can be obtained by using various kinds of repeating units as the poly(propyl ether glycol). For example, EXCENOL 420, EXCENOL 720, EXCENOL 1020, EXCENOL 2020 (above, manufactured by Asahi Glass Co., Ltd.) and the like can be mentioned. The molecular weight of the poly-propyl ether glycol is preferably 2,000 or less.

Further, the compound C in which R ¹¹ is a hydrogen atom and Y is a trimethylene group is produced, for example, by forming a polytrimethylene ether glycol having various repeating unit numbers according to the method described in JP-A-2013-515144. The molecular weight of the polytrimethylene ether glycol is preferably 2,000 or less.

Further, the compound C in which R ¹¹ is a hydrogen atom and Y is a tetramethylene group can be obtained as a polytetramethylene ether glycol having various repeating unit numbers. For example, PTMG650, PTMG850, PTMG1000, PTMG1300, PTMG1500, PTMG1800, PTMG2000 (above, manufactured by Mitsubishi Chemical Corporation) and the like can be mentioned. The molecular weight of the polytetramethylene ether glycol is preferably 2,000 or less.

Compound C, Compound D of R ¹¹ and R ¹² respectively, from the viewpoint of the adhesion strength of the compound A, should one of R ¹¹ and R ¹² is a hydrogen atom, the other is a glycidoxy group.

The compound C and the compound D are the compound A. For example, after reacting the compound C with the compound D in the presence of a base, the reactant of the compound C and the compound D can be introduced into the epichlorohydrin in the presence of a suitable catalyst. The reaction of a compound such as a glycidyl group or a methyl epoxy group. The above reaction is adjusted to a number in which the m in the compound A is from 1 to 5, preferably from 1 to 4, more preferably from 1 to 3, and most preferably from 1 to 2.

In the case of the number system of m, the synthesis of the intermediate P can be controlled as follows. For example, in Example 1-1, the equivalent ratio of the compound C1-1 to D1 is 1:2.5, but if the ratio is 1:2.0 or 1:1.5, the number of m increases. On the other hand, when forming 1:10 or 1:100, 1:1000, etc., it will not become less than 1. In the compound P, m = 0 is that the R of the compound D is a hydrogen atom, and X is an isopropylidene group (that is, bisphenol A itself).

Further, from the viewpoint of reactivity, it is preferred that one of R ¹¹ in the compound C and R ¹² in the compound D is a hydrogen atom, and the other is a glycidyl group.

The alkali is preferably an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkali metal carbonate such as sodium carbonate or potassium carbonate, or more preferably hydrogen, from the viewpoint of the rapid progress of the reaction and the cost of the synthesis. Sodium oxide. These bases are preferably used in the form of an aqueous solution, but it is also possible to add a powder or a solid base simultaneously or separately with water, as the case may be.

The amount of the base used is from the viewpoint of the rapid progress of the reaction and the cost of the synthesis. When R ¹¹ is a hydrogen atom and R ¹² is a propylene group, the base is preferably an equivalent of a hydroxyl group or more, and R ¹¹ is a propylene group. When R ¹² is a hydrogen atom, the amount of the catalyst may be 0.0001 to 0.1 equivalent of the hydroxyl group of the compound D, and more preferably 0.0001 to 0.01 equivalent. For example, in Example 1-1, bisphenol A is used in an amount of 2.5 equivalents of 5.0 equivalents of hydroxyl groups, and 1.5 g of 4% sodium hydroxide solution = 0.0015 equivalents of sodium hydroxide is used, so 1 equivalent of hydroxyl groups is used. The amount used is 0.0003 equivalents.

The amount of the compound such as epichlorohydrin is preferably from 0.5 to 20 equivalents, more preferably from 0.5 to 15 equivalents, from the viewpoint of the rapid progress of the reaction and the cost of the synthesis.

From the viewpoint of reaction time, catalyst cost, and catalyst activity, the catalyst is preferably a tertiary amine of trimethylamine, trioctylamine, tridecylamine, tetramethylammonium or methyltrioctylammonium. , methyltridecylammonium, benzyltrimethylammonium fourth-grade ammonium base, tetramethylammonium chloride, methyltrioctylammonium chloride, methyltridecylammonium chloride, chlorine The fourth ammonium salt of benzyltrimethylammonium is more preferably a fourth ammonium salt.

The amount of the catalyst used is preferably from 0.01 to 10% by weight, more preferably from 0.1 to 5, based on the total amount of the compound C, the compound D and the epichlorohydrin, from the viewpoint of suppressing the side reaction and appropriately ensuring the reaction rate. weight%.

The reaction with the above base is preferably carried out at 50 to 250 ° C, more preferably 70 to 200 ° C, most preferably 100 to 170 ° C, and the reaction with the above-mentioned epichlorohydrin or the like is preferably 25 to 100 ° C, more preferably It is 30~80 °C, and it is best to carry out 40~60 °C. In the reaction, an inert solvent may also be used in the reaction of a hydrocarbon, an ether or a ketone. However, when a compound such as epichlorohydrin is used excessively, even if a compound such as epichlorohydrin acts as a solvent, such a solvent is not required.

The purification of the compound A after completion of the reaction can be carried out according to a usual method. For example, a compound such as epichlorohydrin is distilled off, and if necessary, a water-insoluble solvent such as a hydrocarbon is added, and then the salt formed by washing with water is removed. Catalyst was used to obtain the intended compound A.

The method for producing the compound A of the present invention is from the viewpoint that a general-purpose raw material can be used as the compound C and the compound D, and the compound ¹¹ in the compound C is a glycidyl group C1 (polyalkylene glycol diol epoxide) When the propyl ether; for example, polyethylene glycol diepoxypropyl ether), the compound D1 (for example, bisphenol A) wherein R ¹² is a hydrogen atom in the compound D, preferably comprises: reacting the compound C1 with the compound D1; Step 1 of obtaining the reactant P of the compound C1 and the compound D1; and step 2 of epoxidizing the hydroxyl group of the reactant P to obtain a reactant Q in which a part or all of the hydroxyl group of the reactant P is epoxidized.

At this time, further, the reactant Q may be subjected to the step (3) of the (meth)acrylic acid reaction in the presence of a basic catalyst to obtain the compound A of the R group 1 or the group 2.

The alkaline catalyst can be used for the reaction of the reaction rate, the rapid reaction, and the catalyst cost, and the basic catalyst used for the reaction of the epoxy resin with (meth)acrylic acid can also be used. The polymer supporting the basic catalyst carries an alkaline catalyst. The basic catalyst is preferably a trivalent organic phosphorus compound and/or an amine compound. The basic atom of the basic catalyst is phosphorus and/or nitrogen.

For alkaline catalysts, epoxy resin and (meth) propylene can be used. A known basic catalyst used in the reaction of an acid. Further, it is also possible to use a polymer supported on a polymer to carry a basic catalyst. The basic catalyst is preferably a trivalent organic phosphorus compound and/or an amine compound. The basic atom of the basic catalyst is phosphorus and/or nitrogen.

Examples of the trivalent organic phosphorus compound include alkylphosphines such as triethylphosphine, tri-n-propylphosphine, and tri-n-butylphosphine, and salts thereof, triphenylphosphine, tri-m-tolylphosphorus, and ginseng. Arsenic triphosphates such as (2,6-dimethoxyphenyl)phosphorus and their salts, triphenyl phosphate, triethyl phosphate, decylphenyl phosphate Classes and their salts. The salt of the trivalent organic phosphorus compound may, for example, be triphenylphosphine/ethyl bromide, triphenylphosphine/butyl bromide, triphenylphosphine/octyl bromide, triphenylphosphine/decyl bromide. , triphenylphosphine/isobutyl bromide, triphenylphosphine/propyl chloride, triphenylphosphine/pentyl chloride, triphenylphosphine/hexyl bromide, and the like. Among them, triphenylphosphine is preferred.

The amine compound may, for example, be a tertiary amine such as a second-grade amine such as diethanolamine, triethanolamine, dimethylbenzylamine, dimethylaminomethylphenol or cis-diethylaminomethylphenol. 1,5,7-Trisazocyclo[4.4.0]non-5-ene (TBD), 7-methyl-1,5,7-trisazocyclo[4.4.0]癸-5 -ene (Me-TBD), 1,8-diazocyclo[5.4.0]undec-7-ene (DBU), 6-dibutylamino-1,8-diazocyclohexane [5.4.0] Undec-7-ene, 1,5-diazobicyclo[4.3.0]non-7-ene (DBN), 1,1,3,3-tetramethylguanamine, etc. Strong alkaline amine and its salts. Among them, 1,5,7-trisazocyclo[4.4.0]non-5-ene (TBD) is preferred. The salt of the amine compound may, for example, be benzyltrimethylammonium chloride or benzyltriethylammonium chloride.

The polymer supporting the basic catalyst is not particularly limited, and one type can be used. A polymer which is a polymer obtained by crosslinking polystyrene with divinylbenzene or a polymer obtained by crosslinking acrylic resin with divinylbenzene. These polymers are insoluble in a solvent (for example, methyl ethyl ketone or methyl isobutyl ketone) which can be used for the reaction of the epoxy resin obtained by the production method of the step 1 or the steps 1 and 2 with (meth)acrylic acid. Toluene, etc.) and raw materials and products.

The alkaline catalyst supporting the polymer is such that the basic catalyst is chemically bonded to the insoluble polymer, or the basic catalyst is introduced into the monomer to polymerize the monomer, and then the divinylbenzene or the like is blended. The monomer is crosslinked in a three-dimensional manner, and a basic catalyst for supporting a polymer which is insoluble in a solvent such as methyl ethyl ketone, methyl isobutyl ketone or toluene can be produced.

The basic catalyst for supporting the polymer may specifically be, for example, diphenylphosphinopolystyrene, 1,5,7-trisazocyclo[4.4.0]non-5-ene polystyrene, N, N-(diisopropyl)aminomethylpolystyrene, N-(methylpolystyrene)-4-(methylamino)pyridine, and the like. These basic catalysts for supporting the polymer may be used singly or in combination of two or more.

The alkaline catalyst system supporting the polymer can also be used by a commercially available person. Commercially available basic catalysts for supporting polymers include, for example, PS-PPh ₃ (diphenylphosphinopolystyrene, manufactured by BIOTAGE Co., Ltd.), and PS-TBD (1,5,7-trisazocyclobutane). [4.4.0] 癸-5-ene polystyrene, manufactured by BIOTAGE Co., Ltd.).

The use ratio of the basic catalyst for supporting the polymer is 1 equivalent to the epoxy of the epoxy resin obtained by the production method of the step 1 or 2, and the basic catalyst for supporting the polymer is 0.5 to 5.0. Milli equivalents, more preferably 1.0 to 3.0 milliequivalents. When the use ratio of the basic catalyst supporting the polymer is within the above range, it is preferable from the viewpoints of the reaction rate, the reaction time, and the catalyst cost.

In the production method of the present invention, the temperature of the reaction step of the epoxy resin and the (meth)acrylic acid obtained by the production method comprising the step 1 or the steps 1 and 2 is preferably 60 to 120 ° C, more preferably 80. ~120 ° C, the most suitable is 90 ~ 110 ° C.

In the presence of a catalyst, when the epoxy resin obtained by the production method of the step 1 or the steps 1 and 2 is reacted with (meth)acrylic acid, in order to prevent gelation, it is necessary to appropriately maintain the reaction system and the reaction system. The oxygen concentration in the gas phase. For example, when air is actively inhaled in the reaction system, it may cause oxidation of the catalyst and cause a decrease in activity, so care must be taken.

The reaction of the epoxy resin obtained by the production method of the step 1 or the steps 1 and 2 with the (meth)acrylic acid is carried out by partially reacting the epoxy resin obtained by the reaction, and is hardened by the active energy such as ultraviolet rays. The reaction is carried out in a container that shields the ultraviolet rays. Further, the reaction of the epoxy resin obtained by the production method comprising the step 1 or the steps 1 and 2 with (meth)acrylic acid is to prevent gas phase polymerization, and may also be a reflux solvent having a good solvent property for the epoxy resin. This is carried out, but at this time, it is necessary to remove the solvent after the termination of the reaction, so it is preferred to carry out the solvent. The reflux solvent may, for example, be acetone or methyl ethyl ketone.

In the production method of the present invention, after the epoxy resin obtained by the production method comprising the step 1 or the steps 1 and 2 is reacted with (meth)acrylic acid, the partially esterified epoxy resin can be removed by the supported polymer. Obtained by alkaline catalyst. The method of removing the basic catalyst for supporting the polymer is preferably filtration or centrifugation.

A method of filtering a basic catalyst for supporting a polymer is, for example, a network A 10 μm nylon network NY-10HC (manufactured by Swiss Sefar Co., Ltd.) was used to filter a basic catalyst for supporting a polymer.

The method of centrifuging and separating the alkaline catalyst which carries a polymer is a method of performing solid-liquid separation using a centrifugal separator, and removing the alkaline catalyst which carries a polymer.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples. Also, as long as there is no special statement, [%] is the weight basis.

[Comparative Example 1-2] (Compound B)

Mixed bisphenol A type epoxy resin (EXA850CRP, manufactured by DIC Co., Ltd.; also used as a compound of Comparative Example 1-1) 340 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 90.4 g, triphenylphosphine (Tokyo Chemical Co., Ltd.) 0.5 g, and 100 mg of BHT, and stirred at 100 ° C for 6 hours.

418 g of a compound B of a pale yellow transparent viscous material was obtained.

[Synthesis Example 1] (Compound C1-1)

200 g of polyethylene glycol #200 (2 equivalents/hydroxyl), epichlorohydrin 1110 g (6 equivalents), benzyltrimethylammonium chloride 37.1 g (0.1 equivalents) were placed in a mechanical mixer, thermometer, temperature adjustment 2 liter, three-neck round bottom flask with a condenser, a Dean-Stark trap, and a dropping funnel. Then, while stirring the mixture under a high vacuum of 70 torr Heat to about 50 or even 55 ° C and vigorously reflux epichlorohydrin. 300 g of the 48% NaOH solution was slowly added to the mixture over 2 hours. Immediately after the formation of the azeotrope, the epichlorohydrin was returned to the reaction system in the water/epichlorohydrin mixture while stirring was continued. After the addition was terminated, stirring was continued for 3 hours. Then, the reaction mixture was cooled to room temperature, 1 liter of chloroform was added, and the mixture was washed 6 times with 1 liter of water, and the solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 171 g of pale yellow transparent liquid compound C1-1. .

[Synthesis Example 2] (Compound C1-2)

In Synthesis Example 1, except that the polyethylene glycol #200 was 300 g of polyethylene glycol #300, the same procedure was carried out to obtain 222 g of a pale yellow transparent liquid compound C1-2.

[Synthesis Example 3] (Compound C1-4)

250 g of polyethylene glycol #1000 (0.5 eq/hydroxyl), epichlorohydrin 277 g (6 equivalents), benzyltrimethylammonium chloride 9.28 g (0.1 eq.) were placed in a mechanical mixer, thermometer, temperature adjustment A three-neck round bottom flask with a condenser, a condenser, a Dean-Stark trap, and a dropping funnel. Then, the mixture was heated to about 50 to 55 ° C while stirring under a high vacuum of 70 torr to vigorously reflux epichlorohydrin. 75 g of the 48% NaOH solution was slowly added to the mixture over 2 hours. Immediately after the formation of the azeotrope, the epichlorohydrin was returned to the reaction system in the water/epichlorohydrin mixture while stirring was continued. After the addition was terminated, stirring was continued for 3 hours. Then, the reaction mixture was allowed to cool to room temperature, and 500 ml of chloroform was added to 500 ml. Washed 6 times with water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to yield 138 g of Compound C 1-4 as a white solid.

[Example 1-1] (Compound A-1)

(1) Compound C1-1 (145 g (1 equivalent/epoxy group)) and bisphenol A (Compound D1) (570 g (2.5 equivalent)) were placed in an eggplant type flask, and the mixture was heated and stirred to a liquid temperature of 150. °C. 1.5 g of a 4% aqueous NaOH solution was added, and the mixture was stirred at 150 ° C for 2 hours. After cooling to a liquid temperature of 60 ° C or less, 500 ml of chloroform was added, and the mixture was washed 6 times with 1 liter of a 1% aqueous NaOH solution, and washed 3 times with 1 liter of water. Magnesium sulfate was added to the obtained organic phase, and after drying, the solid fraction was filtered by filtration, and the solvent of the obtained organic phase was distilled off under reduced pressure to obtain a reactant P- of 290 g of a synthetic intermediate of a yellow viscous material. 1.

(2) The reactant P-1 (170 g), epichlorohydrin (495 g), and benzyltrimethylammonium chloride (16.5 g) were placed in a mechanical mixer, a thermometer, a temperature regulator, a condenser, A 2-liter three-neck round bottom flask with a Dean-Stark trap and a dropping funnel. Then, the mixture was heated to about 50 to 55 ° C while stirring under a high vacuum of 70 torr to vigorously reflux epichlorohydrin. 133 g of a 48% NaOH solution was slowly added to the mixture over 2 hours. Immediately after the formation of the azeotrope, the epichlorohydrin was returned to the reaction system in the water/epichlorohydrin mixture while stirring was continued. After the addition was terminated, stirring was continued for 3 hours. Then, the reaction mixture was cooled to room temperature, and 1 liter of chloroform was added thereto, and the mixture was washed 6 times with 1 liter of water, and the solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 206 g of pale yellow viscous compound. A-1 (reactant Q-1).

[Example 1-2] (Compound A-2)

(1) The compound C1-2 (230 g (1 equivalent/epoxy group)) and bisphenol A (compound D1) (570 g (2.5 equivalent)) were placed in an eggplant type flask, and the mixture was heated and stirred to a liquid temperature of 150. °C. 1.5 g of a 4% aqueous NaOH solution was added, and the mixture was stirred at 150 ° C for 2 hours. After cooling to a liquid temperature of 60 ° C or less, 500 ml of chloroform was added, and the mixture was washed 6 times with 1 liter of a 1% aqueous NaOH solution, and washed 3 times with 1 liter of water. Magnesium sulfate was added to the obtained organic phase, and after drying, the solid fraction was filtered by filtration, and the solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 166 g of a reaction intermediate P-2 of a synthetic intermediate of a yellow viscous material. .

(2) The reactant P-2 (203 g), epichlorohydrin (495 g), and benzyltrimethylammonium chloride (16.5 g) were placed in a mechanical mixer, a thermometer, a temperature regulator, a condenser, A 2-liter three-neck round bottom flask with a Dean-Stark trap and a dropping funnel. Then, the mixture was heated to about 50 to 55 ° C while stirring under a high vacuum of 70 torr to vigorously reflux epichlorohydrin. 133 g of a 48% NaOH solution was slowly added to the mixture over 2 hours. Immediately after the formation of the azeotrope, the epichlorohydrin was returned to the reaction system in the water/epichlorohydrin mixture while stirring was continued.

After the addition was terminated, stirring was continued for 3 hours. Then, the reaction mixture was cooled to room temperature, 1 liter of chloroform was added, and the mixture was washed 6 times with 1 liter of water, and the solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 241 g of pale yellow viscous compound A-2. (Reaction Q-2).

[Example 1-3] (Compound A-3)

(1) Dynacoll EX-830 (Compound C1-3) (268 g (1 equivalent/epoxy group)) and bisphenol A (Compound D1) (570 g (2.5 equivalent)) manufactured by Nagase Chemtech Co., Ltd. The flask was heated and stirred to a liquid temperature of 150 °C. 1.5 g of a 4% aqueous NaOH solution was added, and the mixture was stirred at 150 ° C for 2 hours. After cooling to a liquid temperature of 60 ° C or less, 500 ml of chloroform was added, and the mixture was washed 6 times with 1 liter of a 1% aqueous NaOH solution, and washed 3 times with 1 liter of water. Magnesium sulfate was added to the obtained organic phase, and after drying, the solid fraction was filtered by filtration, and the solvent of the obtained organic phase was distilled off under reduced pressure to obtain a reactant P of 375 g of a synthetic intermediate of a yellow viscous material. -3.

(2) The reactant P-3 (200 g), epichlorohydrin (452 g), and benzyltrimethylammonium chloride (15.1 g) were placed in a mechanical mixer, a thermometer, a temperature regulator, a condenser, A 2-liter three-neck round bottom flask with a Dean-Stark trap and a dropping funnel. Then, the mixture was heated to about 50 to 55 ° C while stirring under a high vacuum of 70 torr to vigorously reflux epichlorohydrin. 122 g of the 48% NaOH solution was slowly added to the mixture over 2 hours. Immediately after the formation of the azeotrope, the epichlorohydrin was returned to the reaction system in the water/epichlorohydrin mixture while stirring was continued. After the addition was terminated, stirring was continued for 3 hours. Then, the reaction mixture was cooled to room temperature, and 1 liter of chloroform was added thereto, and the mixture was washed 6 times with 1 liter of water, and the solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 228 g of pale yellow viscous compound A-3. (Reaction Q-3).

[Example 1-4] (Compound A-4)

(1) The compound C1-4 (130 g (0.23 equivalent/epoxy group)) and bisphenol A (compound D1) (131 g (2.5 equivalent)) were placed in an eggplant type flask, and the mixture was heated and stirred to a liquid temperature of 150. °C. 0.3 g of a 4% aqueous NaOH solution was added, and the mixture was stirred at 150 ° C for 2 hours. After cooling to a liquid temperature of 60 ° C or less, 500 ml of chloroform was added, and the mixture was washed 6 times with 1 liter of a 1% aqueous NaOH solution, and washed 3 times with 1 liter of water. Magnesium sulfate was added to the obtained organic phase, and after drying, the solid fraction was filtered by filtration, and the solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain a reactant P-4 of a synthetic intermediate of 154 g of a yellow viscous material. .

(2) The reactant P-4 (140 g), epichlorohydrin (207 g), and benzyltrimethylammonium chloride (6.94 g) were placed in a mechanical mixer, a thermometer, a temperature regulator, a condenser, A 2-liter three-neck round bottom flask with a Dean-Stark trap and a dropping funnel. Then, the mixture was heated to about 50 to 55 ° C while stirring under a high vacuum of 70 torr to vigorously reflux epichlorohydrin. 56 g of the 48% NaOH solution was slowly added to the mixture over 2 hours. Immediately after the formation of the azeotrope, the epichlorohydrin was returned to the reaction system in the water/epichlorohydrin mixture while stirring was continued. After the addition was terminated, stirring was continued for 3 hours. Then, the reaction mixture was cooled to room temperature, 1 liter of chloroform was added, and the mixture was washed 6 times with 1 liter of water, and the solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 142 g of pale yellow viscous compound A-4. (Reaction Q-4).

[Example 1-5] (Compound A-5)

320 g of compound A-3 (reactant Q-3), 43.05 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.25 g of triphenylphosphine (basic catalyst, manufactured by Tokyo Chemical Industry Co., Ltd.), and 50 mg of BHT, and stirred at 100 ° C. After 8 hours, 357 g of a pale yellow viscous compound A-5 was obtained.

[Examples 2-1 to 9 and Comparative Example 2-1]

Each of the compounds A-1 to 5 (Examples 1-1 to 5) and the compound B (Comparative Example 1-2), EY resin KR-2 (manufactured by KSM Co., Ltd.), Zefiac F351 (manufactured by Gantz Chemical Co., Ltd.), Seahoster KE-C 50HG (manufactured by Nippon Shokubai Co., Ltd.), KBM-403 (decane coupling agent; manufactured by Shin-Etsu Chemical Co., Ltd.), and AJICURE VDH (1,3-bis(decylcarboethyl)-5-isopropyl After mixing with the blending amount (parts by weight) shown in Table 1, the mixture was thoroughly kneaded using three roller mills (C-43/4×10 manufactured by Inoue Co., Ltd.). The liquid crystal sealing agents of Examples 2-1 to 9 and Comparative Example 2-1 were obtained.

[Test conditions]

For the compounds A-1 to 5 (Examples 1-1 to 5), EPICRON 850 CRP (Comparative Example 1-1), and Compound B (Comparative Example 1-2), the viscosity and the epoxy equivalent were measured, and the alignment was evaluated. The change in the NI point was measured, and the adhesion of the liquid crystal sealing agent of Examples 2-1 to 9 and the liquid crystal sealing agent of Comparative Examples 2-1 to 3 was evaluated, and the change in the NI point was measured.

(1) Viscosity measurement

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

Select the rotator and the number of rotations as follows.

Compound A-1: 3° × R7.7 rotator, rotation number 5 rpm

Compound A-2: 3° × R7.7 rotator, rotation number 10 rpm

Compound A-3: 3° × R14 rotator, rotation number 5 rpm

Compound A-4: 3° × R14 rotator, rotation number 20 rpm

Compound A-5: 3° × R7.7 rotator, rotation number 5 rpm

EPICLON 850 CRP: 3° × R14 rotor, rotation number 20rpm

Compound B: 3° × R7.7 rotator, rotation number 10 rpm

(2) Determination of epoxy equivalent

JIS K 7236: Measured under the conditions described in 2001.

(3) NI point change measurement

Compounds A-1 to 5 (Examples 1-1 to 5), EPICRON 850 CRP (Comparative Example 1-1), Compound B (Comparative Example 1-2), and Liquid Crystal Sealants of Examples 2 to 9 were respectively used. 0.1 g of the liquid crystal sealing agent of Comparative Examples 2-1 to 3 was placed in an ampoule, and further, 1 g of liquid crystal (MLC-11900-080, manufactured by Merck) was added. The bottle was placed in an oven at 120 ° C for 1 hour, and after standing at room temperature and returned to room temperature (25 ° C), the liquid crystal portion was taken out and filtered through a 0.2 μm filter to obtain a liquid crystal sample for evaluation. The NI point was measured by a differential scanning calorimeter (DSC, manufactured by Perkin Elmer, PYRIS6), and 10 mg of the liquid crystal sample for evaluation was sealed in an aluminum sample plate. In the measurement, the measurement was carried out under the conditions of a temperature increase rate of 5 ° C /min. In addition, 10 mg of the liquid crystal was sealed in an aluminum sample pan, and the result of measurement at a temperature increase rate of 5 ° C /min was used as a blank group.

The difference TE-TB between the endothermic peak (phase transition temperature) TB of the blank group and the endothermic peak (phase transition temperature) TE of the liquid crystal for evaluation was changed as the NI point.

It is preferable to reduce the impurities, suppress the elution of the liquid crystal, ensure the alignment of the liquid crystal stably, and improve the display characteristics.

(4) Orientation assessment

The compound A-1 was applied to a single surface of an ITO glass substrate (60 mm × 70 mm × 0.7 mmt) provided with two rubbing treatment alignment films (Sunever SE-7492, manufactured by Nissan Chemical Industries, Ltd.) and sealed so as to be The diameter after the 15 mm gap bonding was 2 mm or less, and the other surface was bonded to each other. After the liquid crystal was injected, the panel was subjected to thermal curing in a hot air oven at 120 ° C for 1 hour to prepare an alignment evaluation panel.

Compound A-1 was replaced with Compounds A-2 to 5, EPICLON 850 CRP, and Compound B, respectively, to prepare a panel for evaluation of alignment.

The rubbing treatment was carried out as follows.

The TN6070 base plate (the ITO base plate manufactured by FPD Solutions) which was dried after washing with pure water was dropped into the alignment liquid SUNEVER SE-7492 (manufactured by Nissan Chemical Industries, Ltd.) (0.3 MPa, 5.3 sec) using an air dispenser. The applicator reaches 5000 rpm in 10 seconds, and the condition is maintained for 20 seconds (the film thickness is 7000 to 8000 angstroms). Coating Thereafter, it was prebaked on a hot plate (85 ° C, 1 minute) and baked in an oven (230 ° C, 60 minutes). The base was conveyed at a speed of 600 mm/min at a number of revolutions of 500 rpm using a rubbing cloth roller of cotton cloth, and rubbing treatment was performed with a pushing amount of 0.4 mm. The rubbing direction is defined in such a manner that the opposite base plate becomes a 90° twist (intersection). The rubbed substrate was immersed in pure water and subjected to ultrasonic cleaning. It was dried in an oven at 120 ° C as a friction-treated ITO glass substrate attached to the film.

With respect to the obtained panel, the alignment state of the liquid crystal at the time of sealing (dot coating portion) was confirmed. The confirmation was carried out by an optical microscope, and the polarizing plate was placed in the cross-Nicol state to hold the test cell to penetrate and observe, and the liquid crystal in the middle portion of the sealing and sealing (hereinafter, blank group liquid crystal) and the liquid crystal state at the time of sealing were compared. .

Part of the unevenness of the state of the blank group of liquid crystals seen when sealing,

○ when the seal is not observed at all, or when it is sealed, and from the time of sealing to less than 50 μm,

One part of the seal is evaluated as Δ from the time of sealing to 50 μm or more, or the entire circumference at the time of sealing, and from the time of sealing to less than 50 μm.

It was evaluated as × at the time of sealing and from the time of sealing to 50 μm or more.

Further, it is considered that a part of the above unevenness indicates that the liquid crystal alignment property is poor.

Figs. 1 and 2 show the liquid crystal alignment state during the sealing of the compound A-3 (Fig. 1) and A-5 (Fig. 2), which is different from the state of the blank group liquid crystal which is observed during sealing, and is sealed. When not observed at all, or part of the seal and from the time of sealing to less than 50 μm (○). Figure 3 is a compound The liquid crystal alignment state at the time of sealing of B is different from the state of the blank group liquid crystal which is observed at the time of sealing, and is partially the entire circumference at the time of sealing and is 50 μm or more (×) from the time of sealing.

(5) Evaluation of adhesion strength

An outline of the test method is shown in Fig. 4 .

The liquid crystal sealing agents of Examples 2-1 to 9 and Comparative Examples 2-1 to 3 were bonded to 15 mm × 3 mm and 15 mm × 21 mm on an ITO glass substrate (30 mm × 30 mm × 0.5 mmt) in which spacers of 6 μm were interposed. The diameter of the liquid crystal sealant after the position is separately coated into 1.5~2.5mm . Thereafter, the glass substrate (23 mm × 23 mm × 0.5 mmt) was bonded, and ultraviolet rays were irradiated with an illuminance of 3000 mJ/cm ² (UV irradiation apparatus: UVX-01224S1, manufactured by Ushio Electric Co., Ltd., 1000 mW/cm ² /365 nm for 30 seconds), and hardened. Thereafter, the film was thermally hardened in a hot air oven at 120 ° C for 1 hour to prepare a test piece for evaluation of adhesion strength. The glass substrate of the test piece was fixed using Autograph AGS-500 manufactured by Shimadzu Corporation, and the position of the ITO glass substrate at 15 mm × 25 mm was pulled at a speed of 5 mm/min, and the adhesion strength was evaluated. The evaluation results are shown in Table 1.

The disclosure of Japanese Patent Application No. 2012-227417 is hereby incorporated by reference in its entirety.

All documents, patent applications, and technical specifications contained in this specification are extracted from the specification, and the specifics and individual documents, patent applications, and technical specifications are hereby incorporated by reference. Into as a reference.

Claims (7)

A glycopropyl ether compound which is represented by the following formula (1), [wherein, n ₁ is a number in the range of 2 to 30, m is a number in the range of 1 to 5, and X is an oxygen atom, an alkylene group having 1 to 4 carbon atoms or an alkylene group having 2 to 4 carbon atoms; The group Y and the Y group are each independently an alkyl group having 2 to 4 carbon atoms, and the R groups are independently hydrogen atoms, epoxy propyl group, methyl epoxy group, and base 1: -CH ₂ -CH (OR). ¹ ) -CH ₂ -OR ² or a group 2: -CH ₂ -C(CH ₃ )(OR ¹ )-CH ₂ -OR ² (wherein R ¹ is a hydrogen atom or a (meth)acryl fluorenyl group, R ² is (meth)acryloyl), R' is a hydrogen atom or a methyl group which are independent of each other, and in the above R, the epoxy propyl group, the methyl epoxypropyl group, the above-mentioned group 1 and the aforementioned group 2 The total number x of the total is 2 or more, and when R includes the base 1 or the base 2, the average number y of the total of the epoxy propyl group and the methyl epoxy group is the same as the base 1 and the The ratio (y/z) of the average number z of the total of the bases 2 is 10/90 to 90/10]. A liquid crystal sealing agent containing a glycidyl propyl ether compound as in the first aspect of the patent application. The liquid crystal sealing agent of claim 2, wherein the content of the epoxy propyl ether compound in the liquid crystal sealing agent is 10 to 90 weight%. The liquid crystal sealing agent of claim 2, wherein the liquid crystal sealing agent further contains a compound B having an ethylenically unsaturated group and/or an epoxy group (excluding the above-mentioned epoxy propyl ether compound). A method for producing a glycidyl propyl ether compound represented by the formula (1) of the first application of the patent application, comprising the steps of: (2): (wherein n ₂ is a number in the range of 2 to 30, and Y is independently an alkylene group having 2 to 4 carbon atoms, and R ¹¹ is independently a hydrogen atom, an epoxy propyl group or a methyl epoxy group, respectively. The compound C shown by propyl) and the following formula (3): [In the formula, X is an oxygen atom, an alkylene group having 1 to 4 carbon atoms or an alkylene group having 2 to 4 carbon atoms, and R ¹² is independently a hydrogen atom, an epoxy propyl group or a methyl epoxy group. Propyl, group 1: -CH ₂ -CH(OR ²¹ )-CH ₂ -OR ²² , or base 2: -CH ₂ -C(CH ₃ )(OR ²¹ )-CH ₂ -OR ²² (wherein R ²¹ is a step of reacting a compound D represented by a hydrogen atom or a (meth) acrylonitrile group and R ²² is a (meth) propylene fluorenyl group. The patentable scope of application of the production method of item 5, wherein comprising: the compound C in the formula (2) R ¹¹ in a compound of the glycidyl group C1, D in the compound of the formula (3) R ¹² is a hydrogen atom In the case of the compound D1, the above step is a step 1 of reacting the compound C1 with the compound D1 to obtain a reactant P of the compound C1 and the compound D1; and epoxidizing the hydroxyl group of the reactant P to obtain the reactant Step 2 of the reactant Q in which a part or all of the hydroxyl group of P is epoxidized. The production method of claim 6, which further comprises the step 3 of reacting the reactant Q with (meth)acrylic acid in the presence of a basic catalyst.