JP2019151682A - Anion polymerization initiator and polymerizable composition containing the anion polymerization initiator - Google Patents

Abstract

To provide an anion polymerization initiator that is characterized by high reactivity and few by-products, a high molecular weight of a polymer resulting from the reaction, and a narrow molecular weight distribution and little coloration, and a polymerizable composition containing the anion polymerization initiator.SOLUTION: The present invention provides an anion polymerization initiator that contains at least one ionic phosphide compound. The ionic phosphide compound is preferably a compound represented by general formula (I) (where Rand Rindependently represent a hydrogen atom, a C1 to 10 alkyl group, a C6 to 20 aryl group or a C7 to 20 arylalkyl group, Mis an alkali metal ion, an alkaline earth metal ion, another metal ion or a cationic organic ion, n is a number of 1-5).SELECTED DRAWING: None

Description

  The present invention relates to an anionic polymerization initiator containing an ionic phosphide compound and a polymerizable composition containing the anionic polymerization initiator.

  Polymerizable compositions containing an anionic polymerization initiator are used in the fields of inks, paints, various coating agents, adhesives, optical members and the like.

  For example, the following Patent Documents 1 to 4 disclose various anionic polymerization initiators, and the following Patent Document 5 introduces a metallated organic phosphine into a monomer containing a conjugated diene monomer to produce a reactive polymer. Methods for preparing such polymers are disclosed.

JP-A-8-100014 JP 2008-088435 A JP2013-023570A International Publication No. 2014/987924 JP-T-2015-512461

However, when these known anionic polymerization initiators are used, problems such as a broad molecular weight distribution of the obtained polymer and coloring of the obtained polymer may occur.
An object of the present invention is to provide an anionic polymerization initiator having a high reactivity, a small amount of by-products, a high molecular weight of the polymer obtained as a result of the reaction, a narrow molecular weight distribution and a small coloration, and a polymerization property containing the anionic polymerization initiator. It is to provide a composition.

  The present invention achieves the above object by providing an anionic polymerization initiator containing at least one ionic phosphide compound.

  The present invention also provides a polymerizable composition containing the anionic polymerization initiator (A) and the anionic polymerizable organic substance (B).

  The anionic polymerization initiator of the present invention has high reactivity. Therefore, the polymerizable composition containing the anionic polymerization initiator has high curability. In addition, the polymer obtained using the anionic polymerization initiator of the present invention is less colored. Therefore, the anionic polymerization initiator of the present invention and the polymerizable composition containing the anionic polymerization initiator are useful in various applications such as adhesives and various coating materials.

  Hereinafter, the anionic polymerization initiator, the polymerizable composition and the polymer thereof according to the present invention will be described in detail.

The anionic polymerization initiator of the present invention contains at least one ionic phosphide compound. An ionic phosphide compound is a phosphorus compound that can act as an anionic polymerization initiating species in a polymerizable composition.

  Although it does not restrict | limit especially as said ionic phosphide compound, A well-known compound can be used, For example, what is represented with the following general formula (I) is mentioned.

（式中、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、炭素原子数１〜１０のアルキル基、炭素原子数６〜２０のアリール基又は炭素原子数７〜２０のアリールアルキル基を表し、Ｍ^ｎ＋は、アルカリ金属イオン、アルカリ土類金属イオン、その他の金属イオンもしくはカチオン性を示す有機イオンを表し、ｎは１〜５の数である。）

Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. , M ^{n +} represents an alkali metal ion, an alkaline earth metal ion, another metal ion or an organic ion exhibiting a cationic property, and n is a number of 1 to 5.)

In the general formula (I), the alkyl group having 1 to 10 carbon atoms represented by R ¹ and R ² includes methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso -Butyl, amyl, iso-amyl, tert-amyl, hexyl, heptyl, isoheptyl, t-heptyl, n-octyl, isooctyl, t-octyl, 2-ethylhexyl, n-nonyl, n-decyl, trifluoromethyl, difluoro Methyl, monofluoromethyl, pentafluoroethyl, tetrafluoroethyl, trifluoroethyl, difluoroethyl, heptafluoropropyl, hexafluoropropyl, pentafluoropropyl, tetrafluoropropyl, trifluoropropyl, perfluorobutyl, cyclopropyl, cyclobuty , Cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc. cyclononyl and cyclodecyl and the like,
Examples of the aryl group having 6 to 20 carbon atoms represented by R ¹ and R ² include phenyl, naphthyl, anthracen-1-yl, phenanthren-1-yl, o-tolyl, m-tolyl, p-tolyl, 4 -Vinylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-t-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2 -Ethylhexyl) phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4 -Di-t-butylphenyl, 2,5-di-t-butylphenyl, 2,6-di-t-butylphenyl 2,4-di-t-pentylphenyl, 2,5-di-t-amylphenyl, cyclohexylphenyl, biphenyl, 2,4,5-trimethylphenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 4-tri Chlorophenyl, 4-trifluorophenyl, perfluorophenyl, etc.
Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R ¹ and R ² include benzyl, phenethyl, 2-phenylpropyl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl, 4-chlorophenylmethyl and the like. .
R ¹ and R ² are preferably an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an arylalkyl group having 7 to 10 carbon atoms.

Examples of the alkali metal ion represented by M ^{n +} in the general formula (I) include Li ⁺ , Na ⁺ and K ^+, and examples of the alkaline earth metal ion include Mg ²⁺ , Ba ²⁺ , Ca ²⁺ and Sr. ^{2+ and the} like. Other metal ions include Ag ⁺ , Cu ⁺ , Zn ²⁺ , Fe ²⁺ , Cu ²⁺ , Fe ³⁺ , Al ^{3+ and the} like.

  Examples of organic ions exhibiting cationic properties in the general formula (I) include quaternary ammonium ions such as tetramethylammonium ion and tetrabutylammonium ion, quaternary ions such as tetramethylphosphonium ion, tetrabutylphosphonium ion and tetraphenylphosphonium ion. And tertiary sulfonium ions such as phosphonium ions and tetraphenylsulfonium.

  Examples of the ionic phosphide compound represented by the general formula (I) include the following compound No. 1-No. 22 is mentioned.

  The ionic phosphide compound represented by the general formula (I) can be produced by a conventionally known method. For example, an organic metal such as a metal alkoxide and a metal phenoxide is mixed with an organic phosphine at −78 to 100 ° C. It is obtained by reacting for 1 minute to 10 hours. Further, for example, it can also be obtained by ion exchange of alkali metal ions of alkali metal phosphide with organic ions having cationic properties such as tetrabutylammonium ions.

  The anionic polymerization initiator (A) according to the present invention contains at least one ionic phosphide compound represented by the above general formula (I) and can be used in combination with other known anionic polymerization initiators. When used in combination with another anionic polymerization initiator, the ionic phosphide compound represented by the general formula (I) is 50 to 90 parts by mass in 100 parts by mass of the anionic polymerization initiator (A). It is preferable because of its high properties.

  The polymerizable composition of the present invention contains the anionic polymerization initiator (A) and the anionic polymerizable organic substance (B).

  The proportion of the anionic polymerization initiator (A) used with respect to the anionic polymerizable organic substance (B) described below is not particularly limited, and there is no problem if it is used at an ordinary proportion within the range not impairing the object of the present invention. For example, the anionic polymerization initiator (A) may be 0.1 to 20 mol%, preferably 1 to 15 mol%, relative to 100 mol% of the anionic polymerizable organic substance (B). If the amount is too small, curing tends to be insufficient, and if the amount is too large, various physical properties such as water absorption of the polymer and polymer strength may be adversely affected.

  The anionic polymerizable organic substance (B) used in the present invention is a compound that is polymerized or crosslinked by an anionic polymerization initiator activated by heating, and is an epoxy compound, episulfide compound, oxetane compound, vinyl ether compound. In addition to ethylenically unsaturated compounds such as styrene and acrylic compounds, styrene compounds and lactone compounds, reaction products of epoxy compounds and acid anhydrides, reaction products of epoxy compounds and thiols, reaction products of epoxy compounds and phenols, and epoxy compounds Examples thereof include a reaction product of carboxylic acid and a reaction product of an acrylic compound and a thiol. Among them, an epoxy compound is preferable because the obtained polymer has a large molecular weight and a narrow molecular weight distribution.

  As said epoxy compound, an alicyclic epoxy compound (B1), an aliphatic epoxy compound (B2), an aromatic epoxy compound (B3), etc. are mentioned.

Specific examples of the alicyclic epoxy compound (B1) are obtained by epoxidizing a polyglycidyl etherified product of a polyhydric alcohol having at least one alicyclic ring or a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent. And cyclopentene oxide-containing compounds. For example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexane Ruboxylate, methylenebis (3,4-epoxycyclohexane), propane-2,2-diyl-bis (3,4-epoxycyclohexane), 2,2-bis (3,4-epoxycyclohexyl) propane, dicyclopentadiene diepoxide , Ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy 2-epoxyethylcyclohexane, 7-oxabicyclo [4.1.0] heptane, poly [oxy- (1-oxo-1,6-hexanediyl)]] derivative, hexanedioic acid bis [(7-oxabicyclo [ 4.1.0] Heptane-3-yl) methi ], Alpha-pinene oxide and limonene dioxide, and the like. These may be used as a mixture of one or two or more.
Examples of the alicyclic epoxy compound (B1) include hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, or 3,4-epoxy-1-methylcyclohexyl-3,4. -Epoxy-1-methylhexanecarboxylate is preferable from the viewpoint of improving adhesion.

  A commercially available product can be used as the alicyclic epoxy compound (B1). For example, Celoxide 2021P, Celoxide 2081, Celoxide 2000, Celoxide 3000 and Cyclomer M100 (manufactured by Daicel); CYRACURE UVR-6128 (manufactured by Dow Chemical Company) and the like can be mentioned.

  In the polymerizable composition of the present invention, the alicyclic epoxy compound (B1) is 0 to 70% by mass, particularly 20 to 65% by mass with respect to 100% by mass of the anionic polymerizable organic substance (B). , Because viscosity, coating property and reactivity are improved.

The aliphatic epoxy compound (B2) refers to an epoxy compound that is not classified into the alicyclic epoxy compound (B1) or the aromatic epoxy compound (B3) described later. Specific examples of the aliphatic epoxy compound include fatty acids. Monofunctional epoxy compounds such as glycidyl ethers of aliphatic alcohols, glycidyl esters of alkyl carboxylic acids, polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and polyglycidyl esters of aliphatic long-chain polybasic acids A polyfunctional epoxy compound is mentioned. As representative compounds, allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin Triglycidyl ether, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, hydrogenated bisphenol diglycidyl ether, dicyclopentadiene dimethanol diglycidyl ether and polypropylene And glycidyl ethers of polyhydric alcohols such as diglycidyl ether of glycol. Polyglycidyl etherified products of polyether polyols and aliphatic long-chain dibasic acids obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane and glycerin A diglycidyl ester is mentioned. Furthermore, monoglycidyl ethers of higher aliphatic alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxy stearate, butyl epoxy stearate, epoxidized soybean oil, and epoxidized polybutadiene, etc. A mixture of seeds or more can be used.
As the aliphatic epoxy compound (B2), a glycidyl etherified product of an aliphatic alcohol and a polyglycidyl etherified product of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof are preferable because the viscosity, coating property and reactivity are improved. . Furthermore, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether and 1,6-hexanediol diglycidyl ether are preferred.

  A commercially available product can be used as the aliphatic epoxy compound (B2). For example, Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX-313, Denacol EX-314, Denacol EX-411, Denacol EX-411, Denacol EX- 421, Denacol EX-512, Denacol EX-521, Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX- 851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-861, Denacol EX-911, Denacol EX-941, Denacol X-920 and Denacol EX-931 (manufactured by Nagase ChemteX); Epolite M-1230, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF And Epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.); Adeka Resin EP-4088S, Adekaglycilol ED-503, Adekaglycilol ED-503G, Adekaglycilol ED-506, Adekaglycilol ED-523T (manufactured by ADEKA) and the like It is done.

  In the polymerizable composition of the present invention, the aliphatic epoxy compound (B2) is 0 to 70% by mass, particularly 20 to 65% by mass with respect to 100% by mass of the anionic polymerizable organic substance (B). Viscosity, coatability and reactivity are improved, which is preferable.

The aromatic epoxy compound (B3) refers to an epoxy compound having a plurality of epoxy groups and containing an aromatic ring. Specific examples of such polyfunctional aromatic epoxy compounds include monohydric / polyglycidyl etherified products of monohydric phenols having at least one aromatic ring, such as phenol, cresol, butylphenol, or alkylene oxide adducts thereof, such as Bisphenol A, bisphenol F, or a glycidyl etherified compound or a phenol novolac type epoxy compound obtained by further adding an alkylene oxide to these; a glycidyl ether of an aromatic compound having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone or catechol; Polyglycidyl etherified products of aromatic compounds having two or more alcoholic hydroxyl groups such as benzenedimethanol, benzenediethanol and benzenedibutanol; phthalic acid, terephthalic acid, trimelli Polyglycidyl esters of polybasic aromatic compounds having two or more carboxylic acids such as toic acid; polyglycidyl esters and glycidyl esters of benzoic acids such as benzoic acid, toluic acid and naphthoic acid; epoxy of styrene oxide and divinylbenzene The compound etc. are mentioned, These can be used 1 type or in mixture of 2 or more types.
Among them, polyglycidyl ethers of phenols, polyglycidyl ethers of aromatic compounds having two or more alcoholic hydroxyl groups, polyglycidyl ethers of polyphenols, polyglycidyl esters of benzoic acids, polyglycidyl esters of polybasic acids It is preferable from a viewpoint of viscosity reduction of polymeric composition to contain at least 1 type chosen from these groups.
As the aromatic epoxy compound, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol E type epoxy compound and a phenol novolac type epoxy compound are preferable because of excellent curability.

  The polymerizable composition of the present invention is cured such that the aromatic epoxy compound (B3) is 0 to 70% by mass, particularly 20 to 65% by mass with respect to 100% by mass of the anionic polymerizable organic substance (B). From the viewpoint of improving the property.

  Examples of the ethylenically unsaturated compound include a monomer represented by the following formula (II) and a monomer represented by the following formula (III).

（式中、Ｘは、炭素原子数１〜７のアルキル基、炭素原子数１〜７のアルコキシ基、炭素原子数６〜１２のアリール基、炭素原子数６〜１２のアリールオキシ基もしくは炭素原子数６〜１０の脂環式炭化水素基、またはこれらの基中の水素原子が、エポキシ基、オキセタン基、水酸基およびカルボキシル基からなる群より選択される１種以上の基で置換されたものである。）

(In the formula, X is an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, or a carbon atom. The alicyclic hydrocarbon group of several 6 to 10 or a hydrogen atom in these groups is substituted with one or more groups selected from the group consisting of epoxy group, oxetane group, hydroxyl group and carboxyl group is there.)

（式中、Ｒ¹⁹¹は、水素原子、メチル基又はハロゲン原子を表し、Ｘ’は、炭素原子数１〜７のアルキル基、炭素原子数６〜１２のアリール基若しくは炭素原子数６〜１０の脂環式炭化水素基、又はこれらの基中の水素原子が、エポキシ基、オキセタン基、水酸基およびカルボキシル基からなる群より選択される１種以上の基で置換されたものである。)

(In the formula, R ¹⁹¹ represents a hydrogen atom, a methyl group, or a halogen atom, and X ′ represents an alkyl group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, or 6 to 10 carbon atoms. An alicyclic hydrocarbon group or a hydrogen atom in these groups is substituted with one or more groups selected from the group consisting of an epoxy group, an oxetane group, a hydroxyl group and a carboxyl group.)

  Examples of the alkyl group having 1 to 7 carbon atoms represented by X in the formula (II) include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, Examples include iso-amyl, tert-amyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl and tert-heptyl. Among these, the C1-C4 partially substituted by the 1 or more types of group chosen from the group which consists of a C1-C4 alkyl group or an epoxy group, an oxetane group, a hydroxyl group, and a carboxyl group. These alkyl groups are preferred from the viewpoint of curability.

  Examples of the alkoxy group having 1 to 7 carbon atoms represented by X in the formula (II) include methoxy, ethoxy, propyloxy, iso-propyloxy, butyloxy, sec-butyloxy, tert-butyloxy, iso-butyloxy, Amyloxy, iso-amyloxy, tert-amyloxy, hexyloxy, 2-hexyloxy, 3-hexyloxy, cyclohexyloxy, 4-methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, iso-heptyloxy and and tert-heptyloxy. Among these, the C1-C4 partially substituted by the 1 or more types of group chosen from the group which consists of a C1-C4 alkyl group or an epoxy group, an oxetane group, a hydroxyl group, and a carboxyl group. These alkoxy groups are preferred from the viewpoint of curability.

  Examples of the aryl group having 6 to 12 carbon atoms represented by X in the formula (II) include phenyl, methylphenyl and naphthyl.

  Examples of the aryloxy group having 6 to 12 carbon atoms represented by X in the formula (II) include phenyloxy, methylphenyloxy and naphthyloxy.

  Examples of the alicyclic hydrocarbon group having 6 to 10 carbon atoms represented by X in the above formula (II) include cyclohexyl, methylcyclohexyl, norbornyl, bicyclopentyl, bicyclooctyl, trimethylbicycloheptyl, tricyclooctyl. , Tricyclodecanyl, spirooctyl, spirobicyclopentyl, adamantyl and isobornyl.

In the above formula (II), when a part of X is substituted with an epoxy group or an oxetane group, examples of the monomer represented by formula (II) include the following formulas (1) to (3): The monomer represented by these is mentioned.

（式中、Ｒ¹⁹²は、水素原子または炭素原子数１〜６のアルキル基を表し、ｍは、１〜６の整数である。）

(Wherein R ¹⁹² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and m is an integer of 1 to 6)

（式中、Ｒ¹⁹³は、水素原子または炭素原子数１〜６のアルキル基を表し、ｎは、１〜６の整数である。）

(In the formula, R ¹⁹³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 6).

（式中、Ｒ¹⁹⁴は、水素原子または炭素原子数１〜６のアルキル基を表し、ｓは、１〜６の整数である。）。

(In the formula, R ¹⁹⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and s is an integer of 1 to 6).

In the above formula (III), examples of the halogen atom represented by R ¹⁹¹ include fluorine, chlorine, bromine and iodine.

  In the above formula (III), when a part of X ′ is substituted with an epoxy group or an oxetane group, the monomer represented by formula (III) is represented by the following formulas (4) to (6): What is represented.

（式中、Ｒ¹⁹¹は、上記式（ＩＩ）と同じであり、Ｒ¹⁹⁵は、水素原子または炭素原子数１〜６のアルキル基を表し、ｔは、１〜６の整数である。）

(In the formula, R ¹⁹¹ is the same as the above formula (II), R ¹⁹⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and t is an integer of 1 to 6).

（式中、Ｒ¹⁹¹は、上記式（ＩＩ）と同じであり、Ｒ¹⁹⁶は、水素原子または炭素原子数１〜６のアルキル基を表し、ｑは、１〜６の整数である。）

(In the formula, R ¹⁹¹ is the same as the above formula (II), R ¹⁹⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and q is an integer of 1 to 6).

（式中、Ｒ¹⁹¹は、上記式（ＩＩ）と同じであり、Ｒ¹⁹⁷は、水素原子または炭素原子数１〜６のアルキル基を表し、ｙは、１〜６の整数である。）。

(In the formula, R ¹⁹¹ is the same as in the above formula (II), R ¹⁹⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and y is an integer of 1 to 6).

  In the above polymer, the proportion of the monomer constituting the polymer is such that X is the number of carbon atoms substituted with one or more groups selected from the group consisting of an epoxy group, an oxetane group, a hydroxyl group and a carboxyl group. The monomer represented by the above (II) or (III) in the case of an alkyl group having 1 to 7, an aryl group having 6 to 12 carbon atoms, or an alicyclic hydrocarbon group having 6 to 10 carbon atoms Is preferably 10 to 100% by mass because the adhesiveness is improved.

  A known curing agent can be further added to the polymerizable composition of the present invention. As the curing agent, conventionally known ones can be appropriately used. Examples thereof include imidazole compounds, amine compounds, amide compounds, acid anhydride compounds, phenol compounds, thiol compounds, latent thermosetting agents, onium salts, and the like. It is done.

Examples of the imidazole compound include 2-undecylimidazole and compounds described in JP-A-2015-017059.
Examples of the amine compound include aliphatic amine compounds such as ethylenediamine, diethylenetriamine and hexamethylenediamine; arylaliphatic amine compounds such as N-methylaniline, m-xylenediamine, p-xylenediamine, diphenylamine and hydroxyphenylglycine; 1 , 3-bisaminomethylcyclohexane, N-methylpiperazine, morpholine, piperidine, isophoronediamine and cyclic aliphatic amine compounds such as 4,4-methylenebiscyclohexaneamine, etc.
Examples of the amide compound include dicyandiamide,
Examples of the acid anhydride compound include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, hydrogenated methylnadic acid anhydride, and trialkyltetrahydroanhydride. Phthalic acid, methylcyclohexene tetracarboxylic dianhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, ethylene glycol bisanhydro trimellitate, glycerin bis (anhydro trimelli Tate) Monoacetate, dodecenyl succinic anhydride, aliphatic dibasic polyanhydride, chlorendic anhydride, methylbutenyl tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, methyl hymic anhydride, al Succinic anhydride substituted with a sulfonyl group, and glutaric anhydride and the like,
Examples of the phenol compound include phenol novolak and cresol novolak.

Examples of the onium salt include cation and anion salts represented by [A] ^{m +} [B] ^m− , and specific examples include sulfonium salts and iodonium salts.

  In the polymerizable composition of the present invention, the content of the curing agent is preferably 0.001 to 50% because the reactivity becomes high.

  A curing accelerator can be added to the polymerizable composition of the present invention. Curing accelerators include tertiary amine compounds such as imidazole and dimethylaminopyridine; phosphorus compounds such as triphenylphosphine; boron trifluoride amine complexes such as boron trifluoride and boron trifluoride monoethylamine complex; thiodipropion Organic acid compounds such as acids; benzoxazine compounds such as thiodiphenol benzoxazine and sulfonyl benzoxazine; sulfonyl compounds and the like. These may be used alone or in combination of two or more. It is preferable that the addition amount of these catalysts is 0.001-15 mass parts in 100 mass parts of thermopolymerizable compositions.

  The use ratio of the known curing agent to the anionic polymerization initiator (A) of the present invention is 0 to 10 parts by mass of the known curing agent with respect to 100 parts by mass of the anionic polymerization initiator (A).

  A silane coupling agent can be further added to the polymerizable composition of the present invention. As the silane coupling agent, for example, an epoxy-functional alkoxysilane can be used, and typical compounds include γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropyltriethoxysilane, and γ-glycidyloxypropyl. Examples include methyldimethoxysilane, γ-glycidyloxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

  Commercially available products can also be used as the epoxy functional alkoxysilane, such as D2632, G0261, G0210 and T2675 (manufactured by Tokyo Chemical Industry Co., Ltd.); KBM-303, KBM-402, KBM-403, KBE-402 and KBE-403. (Manufactured by Shin-Etsu Silicone) and the like.

  The properties of the polymer can be improved by adding a thermoplastic organic polymer to the polymerizable composition of the present invention as necessary. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid- Examples include methyl methacrylate copolymer, glycidyl (meth) acrylate-polymethyl (meth) acrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, and saturated polyester.

  A solvent that dissolves or disperses each component of the anionic polymerization initiator (A) and the anionic polymerizable organic substance (B) can be added to the polymerizable composition of the present invention. For example, ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-di Ether solvents such as ethoxyethane, propylene glycol monomethyl ether and dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, texanol, etc. Ester solvents of: Cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; methanol, ethanol, iso-propyl Alcohol solvents such as panol, n-propanol, iso-butanol, n-butanol and amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene Ether ester solvents such as glycol monomethyl ether acetate, 3-methoxybutyl acetate and ethoxyethyl propionate; BTX solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; Terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; mineral spirits, Swazol # 310 (manufactured by Cosmo Matsuyama Oil Co., Ltd.) and Solvesso # 100 ( Paraffinic solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride and 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; Propylene carbonate, carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water, and the like. These solvents can be used as one or a mixture of two or more.

  In the polymerizable composition of the present invention, the concentration of the anionic polymerization initiator (A) in the solvent is 0.005 to 5 mol / l.

  The polymerizable composition of the present invention can be applied onto a support substrate by a known means such as a roll coater, a curtain coater, various printings, or dipping. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.

The material for the support substrate is not particularly limited, and a commonly used material can be used. For example, inorganic materials such as glass; cellulose esters such as diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose and nitrocellulose; polyamides; polyimides; polyurethanes; epoxy resins; polycarbonates; Polyesters such as polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate and polybutylene terephthalate; polystyrene; polyethylene, polypropylene And polyolefins such as polymethylpentene; vinylids such as polyvinyl acetate, polyvinyl chloride and polyvinyl fluoride Acrylic resins such as polymethyl methacrylate and polyacrylic acid ester; Polycarbonate; Polysulfone; Polyethersulfone; Polyetherketone; Polyetherimide; Polymer such as polyoxyethylene, norbornene resin and cycloolefin polymer (COP) Materials.
The support substrate may be subjected to surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment.

  In addition, as long as the effects of the present invention are not impaired, other monomers, energy ray-sensitive polymerization initiators, inorganic fillers, organic fillers, pigments, dyes and other colorants, antifoaming agents, thickeners, surface active agents Agent, leveling agent, flame retardant, thixotropic agent, diluent, plasticizer, stabilizer, polymerization inhibitor, ultraviolet absorber, antioxidant, antistatic agent, flow regulator, adhesion promoter and randomizing agent Various resin additives such as can be added.

The conditions for curing the polymerizable composition of the present invention by heating are 70 to 250 ° C. and 1 to 100 minutes. After pre-baking (PAB), pressurization and post-baking (PEB) can be performed, and baking can be performed at several different temperatures.
The heating conditions vary depending on the type and mixing ratio of each component. For example, the heating conditions are 70 to 180 ° C., 5 to 15 minutes for an oven, 1 to 5 minutes for a hot plate, and then 180 to 250 ° C., preferably 200 to It can be cured by heat treatment at 250 ° C. for 30 to 90 minutes for an oven and 5 to 30 minutes for a hot plate.

  Specific applications of the polymerizable composition of the present invention include antistatic agents, optical films, polarizing plates, adhesives, glasses, optical materials represented by imaging lenses, paints, coating agents, automotive interior and exterior materials, Lining agent, ink, resist, liquid resist, printing plate, insulating varnish, insulating sheet, laminate, printed circuit board, for semiconductor devices, for LED packages, for liquid crystal injection ports, for organic EL, for optical elements, for electrical insulation, Sealants for electronic parts and separation membranes, molding materials, putty, glass fiber impregnating agents, sealants, passivation films for semiconductors and solar cells, interlayer insulating films, protective films, backs of liquid crystal display devices Prism lens sheet used for light, lens sheet such as Fresnel lens sheet used for screen of projection TV, lenticular lens sheet, etc. 'S part, or a backlight using such a sheet can include an optical lens such as a micro lens, an optical element, an optical connector, an optical waveguide, casting agent for optical molding, rubber, tires and the like.

  For example, when applied as an optical film, a metal, wood, rubber, plastic, glass, ceramic product or the like is used as a substrate, and the polymerizable composition of the present invention is applied to the substrate by the above-mentioned means, Heat and cure by means. As a typical configuration of the optical film, a transparent support provided with various layers such as an undercoat layer, an antireflection layer, a hard coat layer, a gas barrier layer, a lubricating layer, and an adhesive layer as necessary may be mentioned. .

In addition, as a supporting substrate, an inorganic material is used for the substrate, and a film coated by the above method, or a vacuum deposition method, an ion plating method, a plasma CVD method, an ion assist method, a reactive sputtering method, and a chemical vapor phase It is also possible to use a laminate of films prepared by various vapor deposition methods such as a growth method.
When laminating a film by a vapor deposition method, it is preferable to use glass as the substrate, and the film thickness is, for example, 5 to 300 nm, although it varies depending on the type of inorganic material used. The vapor deposition film can be formed only on one side of the substrate, or can be formed on both sides of the substrate.
Examples of the inorganic material include silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), indium (In), sodium (Na), boron ( B), oxides such as titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) and antimony (Sb); indium-tin composite oxide (abbreviated as ITO) and antimony-tin composite oxide A composite oxide such as a product (abbreviated as ATO) can be used.

  Although it does not restrict | limit especially as a polymer of the polymeric composition of this invention, For example, the polymer which is a structure represented by the following general formula (IV) is mentioned.

（式中、Ｙはヒドロキシル基又は−ＰＲ¹¹Ｒ¹²を表し、Ｒ¹¹及びＲ¹²は、それぞれ独立に、水素原子、炭素原子数１〜１０のアルキル基、炭素原子数６〜２０のアリール基又は炭素原子数７〜２０のアリールアルキル基を表す。αはポリマー鎖であり、βは水素原子又は重合停止末端基を表す。

(In the formula, Y represents a hydroxyl group or —PR ¹¹ R ¹² , and R ¹¹ and R ¹² are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Alternatively, it represents an arylalkyl group having 7 to 20 carbon atoms, α represents a polymer chain, and β represents a hydrogen atom or a polymerization termination terminal group.

In the general formula (IV), as the alkyl group having 1 to 10 carbon atoms, the aryl group having 6 to 20 carbon atoms and the arylalkyl group having 7 to 20 carbon atoms represented by R ¹¹ and R ¹² , The same thing as what was mentioned by the said general formula (I) is mentioned, A polyether, polyester, polyamide, polyurethane, polyolefin etc. are mentioned as a polymer chain represented by (alpha).
As the polymerization termination terminal group represented by β, amino groups such as n-butylamino group and di-n-butylamino group, ethoxy, n-propyloxy group, 1-hydroxy-2-methyl-propyloxy group and Examples include alkoxy groups such as 2-hydroxypropyloxy group.

  The molecular weight of the polymer is preferably 500 to 10,000 because the curability of the polymer is increased.

  EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated further in detail, this invention is not limited to these Examples.

  Hereinafter, the polymerizable composition of the present invention and the polymer obtained by curing the polymerizable composition will be specifically described with reference to examples, evaluation examples, and comparative examples.

[Synthesis Example 1] Compound No. 1 Synthesis of 5 A 100 mL four-necked flask was dried under reduced pressure and subjected to a nitrogen flow, and then bis (4-methoxyphenyl) phosphine and THF were added and stirred at 5 ° C. Thereto, 1.03 equivalent of potassium t-butoxide was added dropwise as a THF (tetrahydrofuran) solution with respect to bis (4-methoxyphenyl) phosphine. After completion of the dropwise addition, the mixture was stirred at room temperature for 4 hours. Concentrated and dried under reduced pressure at 20 ° C. using an evaporator. Nitrogen was introduced to return to normal pressure, and a white powder was obtained in a yield of 86%. Formation of the target product was confirmed by ¹ H-NMR, ³¹ P-NMR and mass spectrum.

[Synthesis Example 2] Compound No. Synthesis of 16 A 100 mL three-necked flask was dried under reduced pressure and subjected to a nitrogen flow, and then tetrabutylammonium chloride and dehydrated acetonitrile were added and stirred at 5 ° C. Thereto, 1.1 equivalent of potassium diphenylphosphine was added dropwise as a THF solution with respect to tetrabutylammonium chloride. After completion of the dropwise addition, the mixture was stirred and filtered at 5 ° C. for 5 hours and at room temperature for 1 hour to remove white powder (KCl). The filtrate was concentrated under reduced pressure at 30 ° C. using an evaporator. Further, vacuum drying was performed to obtain a yellow oily substance with a yield of 28%. The production of the target product was confirmed by ¹ H-NMR.

[Examples 1-1 to 1-2 and Comparative Examples 1-1 to 1-4] Preparation and Polymerization 1 of Polymerizable Composition
A 50 mL three-necked flask equipped with a septum was subjected to a nitrogen flow (20 mL / min), and then glycidyl phenyl ether was added thereto and stirred at 5 ° C. Thereto, 0.05 equivalent of the anionic polymerization initiator shown in Table 1 with respect to glycidyl phenyl ether was added dropwise as a THF solution. After completion of dropping, the mixture was heated and stirred at 70 ° C. for 6 hours to obtain a polymer. The molecular weight of the obtained polymer was measured by GPC in terms of polystyrene. The results are shown in Table 1.

  From Table 1, the polymer of the polymerizable composition of the present application containing the compound represented by the general formula (I) as an anionic polymerization initiator has a large molecular weight and a narrow molecular weight distribution, but other anionic polymerization initiators. It is clear that the polymer obtained by using has a low molecular weight or a wide molecular weight distribution.

[Examples 2-1 to 2-2 and Comparative Examples 2-1 to 2-2] Preparation of Polymerizable Composition and Polymerization 2
Adeka Resin EP-4100E (bisphenol A polyfunctional epoxy: manufactured by ADEKA) was added to a 100 mL three-necked flask that had been vacuum degassed, and after reducing the pressure and replacing with nitrogen (flow: 20 mL / min), 5 mL of dehydrated THF was added. Stirring was performed at 5 ° C. Thereto was added dropwise 0.10 equivalent of the THF solution of the anionic polymerization initiator shown in Table 2 with respect to Adeka Resin EP-4100E while paying attention to heat generation. After completion of dropping, the mixture was stirred at 65 ° C. for 5 hours. The appearance of the obtained polymer was confirmed. The yellowed one was indicated by “X”, the pale yellow one was indicated by “Δ”, and the white one was indicated by “◯”. Moreover, the thermogravimetric decrease of the polymer was measured, and the physical properties of the polymer were compared. The results are shown in Table 2.

  From Table 2, the polymer of the polymerizable composition of the present application containing the compound represented by the above general formula (I) as an anionic polymerization initiator has high heat resistance because it is less colored and highly reactive. It is clear that the polymer obtained using the anionic polymerization initiator is inferior in heat resistance because it is colored and has low reactivity.

[Examples 3-1 to 3-2 and Comparative examples 3-1 to 3-2] Preparation of polymerizable composition and polymerization 3
Adeka Resin EP-4100E was put in an aluminum pan, and 0.10 equivalent of the anionic polymerization initiator shown in Table 3 was added to Adeka Resin EP-4100E. This was heated to 120 ° C. on a hot plate, and the time until gelation (curing time) was examined. The results are shown in Table 3.

  From Table 3, the polymerizable composition of the present application containing the compound represented by the general formula (I) as an anionic polymerization initiator has high curability, but other anionic polymerization initiators have low curability. it is obvious.

[Example 4-1 and Comparative Examples 4-1 to 4-2] Measurement of reaction rate in polymerizable composition A nitrogen flow (20 mL / min) was performed on a vacuum-degassed 50 mL three-necked flask to obtain glycidyl phenyl ether and o. -Equimolar amount of cresol was added and stirred at 5 ° C. Thereto was added dropwise a THF solution of 0.01 anion of the anionic polymerization initiator shown in Table 4 with respect to glycidyl phenyl ether. After stirring for 10 minutes, heating and stirring were performed at 75 ° C. Sampling was performed every hour and ¹ H-NMR measurement was performed. ^The reaction rate was determined from the integral ratio of ¹ H-NMR (the integral ratio of 3.90 ppm of glycidyl phenyl ether and 4.43 ppm of hydrogen substituted for the tertiary carbon of the product). The results are shown in Table 4.

  From Table 4, the polymerizable composition of the present application containing the compound represented by the general formula (I) as an anionic polymerization initiator is highly reactive, but the other polymerizable compositions containing the anionic polymerization initiator are It is clear that the reactivity is low.

From Tables 1 to 4, it is clear that the polymerizable composition of the present invention has high reactivity, the molecular weight of the polymer is high, the molecular weight distribution is narrow, the coloring is small, and the curability is high.

Claims (7)

  An anionic polymerization initiator containing at least one ionic phosphide compound. The anionic polymerization initiator according to claim 1, wherein the ionic phosphide compound is represented by the following general formula (I).

Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. , M ^{n +} represents an alkali metal ion, an alkaline earth metal ion, another metal ion or an organic ion exhibiting a cationic property, and n is a number of 1 to 5.)   A polymerizable composition comprising the anionic polymerization initiator (A) according to claim 1 or 2 and an anionic polymerizable organic substance (B).   The polymerizable composition according to claim 3, wherein the anionic polymerizable organic substance (B) contains a monofunctional epoxy compound or a polyfunctional epoxy compound.   The manufacturing method of the polymer which polymerizes the polymeric composition of Claim 3 or 4 by heating.   A polymer of the polymerizable composition according to claim 3 or 4. The polymer of Claim 6 which has a structure represented by the following general formula (IV).

(In the formula, Y represents a hydroxyl group or —PR ¹¹ R ¹² , and R ¹¹ and R ¹² are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Or an arylalkyl group having 7 to 20 carbon atoms, α is a polymer chain, and β is a hydrogen atom or a polymerization termination terminal group.