JP6935081B2 - Trioxazoline compound, cross-linking agent and resin composition - Google Patents

Description

The present invention relates to new avian oxazoline compound. Further, regarding the cross-linking agent and a resin composition using the previous SL tri oxazoline compound.

Conventionally, many coating agents, inks, films, adhesives, adhesives and the like containing a carboxyl group in a synthetic resin have been used. Then, a cross-linking agent capable of reacting with this carboxyl group is added to improve the characteristics. Examples of the cross-linking agent include epoxy compounds, melamine compounds, metal salts, organic metal compounds, aziridine compounds, isocyanate compounds, carbodiimide compounds, and oxazoline compounds. However, the epoxy compound needs to be heated to a high temperature of 120 ° C. or higher at the time of curing, and the problem of outgas such as formalin cannot be eliminated with the melamine resin. Since metal salts and organometallic compounds are reversible reactions, hydrolysis or dissociation of chemical bonds due to other factors is likely to occur, resulting in poor chemical resistance. Aziridine compounds have a problem with monomer toxicity and tend to be rarely used today. Isocyanate compounds and carbodiimide compounds alone are organic and have different crosslink densities, and are inferior in heat resistance and solvent resistance. The oxazoline compound is catalyst-free and reacts at a relatively low temperature (around 100 ° C.), has good storage stability even after mixing, has low toxicity, has excellent film adhesiveness, water resistance, and corrosion resistance. It has features.

As a conventional cross-linking agent for an oxazoline compound, many compounds having two oxazoline groups in the molecule are known (Patent Document 1). Further, as a trifunctional or higher functional compound, a polymer polymer obtained by copolymerizing an addition-polymerizable oxazoline group-containing monomer with another monomer is known (Patent Document 2). However, none of these oxazoline compounds had a low crosslink density and sufficiently high hardness and heat resistance.

Japanese Unexamined Patent Publication No. 2012-126877 Japanese Unexamined Patent Publication No. 2016-188264

The present invention has been made in view of the above circumstances, and imparts unprecedented hardness and heat resistance as well as reactivity, stability, low toxicity, adhesiveness, water resistance, corrosion resistance, etc. of conventional oxazoline compounds. The purpose is to obtain a novel oxazoline compound useful as a cross-linking agent. Particularly coating made of synthetic resin containing a carboxyl group, the ink, film, adhesive, and, an adhesive, and to provide an optimal Application Benefits oxazoline compound as a wide range of applications of the cross-linking agent.

式中Ｙは、中心核であり、トリアジン、Ｂ、Ｐ＝Ｏ、およびＳｉ−ＣＨ _３ からなる群より選ばれるいずれかである。式中Ｘ_２は（Ｒ−Ｏ−）ｎで表され、ｎは０か１であり、Ｒは炭素数が１から４の範囲内である直鎖若しくは分枝アルキレン基である。 In order to solve the above problems, tri oxazoline compound of the present invention are tri-oxazoline compound represented by the following Symbol Formula.

Wherein Y is a central core, triazines, either to B, selected from the group consisting of P = O, and Si-CH _3. In the formula, X ₂ is represented by (RO−) n, n is 0 or 1, and R is a linear or branched alkylene group having a carbon number in the range of 1 to 4.

Crosslinking agent of the present invention contains a tri-oxazoline compound before Symbol present invention.

In addition, the resin composition of the present invention contains the above-mentioned cross-linking agent of the present invention.

Since the oxazoline compound, which is the raw material of the present invention, is a small molecule compound, it has good compatibility with a wide range of resins. Then, the trioxazoline compound of the present invention can be easily trifunctionalized to obtain the trioxazoline compound of the present invention. Before SL tri oxazoline compound can be obtained a small amount also can be firmly crosslinked with various resins having a carboxyl group in compounding, the resin composition, such as excellent heat resistance coatings.

FIG. 1 shows the TOFMS measurement results of the trioxazoline compound obtained in Synthesis Example 5.

式中Ｘは、ＨまたはＲ−ＯＨで表され、Ｒは炭素数が１から４の範囲内である直鎖若しくは分枝アルキレン基である。上記は、ベンゼン環のオルソ位、メタ位、パラ位のいずれかにオキサゾリン環を有しているオキサゾリン化合物である。 Hereinafter, preferred embodiments of the present invention will be described in detail. The oxazoline compound which is the raw material of the present invention is an oxazoline compound represented by the following chemical formula.

In the formula, X is represented by H or R-OH, and R is a linear or branched alkylene group having 1 to 4 carbon atoms. The above is an oxazoline compound having an oxazoline ring at any of the ortho-position, meta-position, and para-position of the benzene ring.

In the above chemical formula, examples of the oxazoline compound in which X is H include 4-hydroxyphenyloxazoline (para position) and 2-hydroxyphenyloxazoline (ortho position), which are represented by the following structural formulas.

In the above chemical formula, _{examples of the oxazoline compound in which X is CH 2} CH _2- OH are 4- (2-hydroxyethoxy) phenyloxazoline (para position) and 2- (2-hydroxyethoxy) phenyloxazoline (ortho position). These are represented by the following structural formulas.

式中Ｙは、中心核である。式中Ｘ_２は（Ｒ−Ｏ−）ｎで表され、ｎは０か１であり、Ｒは炭素数が１から４の範囲内である直鎖若しくは分枝アルキレン基である。上記は、ベンゼン環のオルソ位、メタ位、パラ位のいずれかにオキサゾリン環を有しているトリオキサゾリン化合物である。 The trioxazoline compound of the present invention is a trioxazoline compound represented by the following chemical formula, which is trifunctionalized by binding the oxazoline compound to the central nucleus.

In the formula, Y is the core. In the formula, X ₂ is represented by (RO−) n, n is 0 or 1, and R is a linear or branched alkylene group having a carbon number in the range of 1 to 4. The above is a trioxazoline compound having an oxazoline ring at any of the ortho-position, meta-position, and para-position of the benzene ring.

The central core of the trioxazoline compounding portion is preferably any one selected from the group consisting of triazine, boron, phosphorus, and organosilicon.

An example of the trioxazoline compound whose core is triazine is a compound represented by the following structural formula.

An example of the trioxazoline compound having a boron core is a compound represented by the following structural formula.

As an example of the trioxazoline compound whose core is phosphorus, a compound represented by the following structural formula can be mentioned.

An example of the trioxazoline compound having an organosilicon core is a compound represented by the following structural formula.

The synthetic resin having a carboxyl group to which the oxazoline compound or the trioxazoline compound of the present invention can be blended as a cross-linking agent is not particularly limited, and conventionally known ones can be used. For example, in thermoplastic resins, polyvinyl chloride, polyvinylidene chloride, polyolefin, polycarbonate, polystyrene, (meth) acrylic resin, polyamide, polyester, ABS resin, polyurethane resin, vinyl chloride-vinylidene chloride-acrylonitrile copolymer, AS resin, etc. Examples thereof include vinyl chloride resin, polyvinylidene ether, polysulfone, polyether sulfone, PEK, PEEK, liquid crystal plastic and the like. Examples of the thermosetting resin include phenol resin, urea resin, melamine resin, unsaturated polyester, silicone resin, alkyd resin, and epoxy resin. Of these, (meth) acrylic resin, polyurethane resin, epoxy resin, polyester resin and the like are preferable.

The (meth) acrylic resin having a carboxyl group is not particularly limited, and examples thereof include a (meth) acrylic resin obtained by copolymerizing a radically polymerizable unsaturated monomer containing a carboxyl group with another ethylenically unsaturated monomer. be able to.

Examples of the radically polymerizable unsaturated monomer having a carboxyl group include (meth) acrylic acid, maleic acid, and itaconic acid. Other ethylenically unsaturated monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, Acrylate esters such as stearyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and lauryl (meth) acrylate can be mentioned as the main monomer. Other copolymerizable monomers include styrene-based monomers such as styrene, vinyltoluene, 2-methylstyrene, t-butylstyrene, and chlorostyrene; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and 4-hydroxybutyl ( Hydroxyl group-containing monomers such as meta) acrylate and caprolactone-modified (meth) acrylate; (meth) acrylonitrile; N-substituted (meth) acrylic monomers such as N-methylol (meth) acrylamide and N-butoxy (meth) acrylamide; glycidyl (meth) ) An epoxy group-containing monomer such as acrylate; a vinyl ester monomer such as vinyl acetate and vinyl propionate; an α-olefin monomer such as ethylene and propylene can be mentioned. Further, the polymerization is synthesized by solution polymerization in an organic solvent, emulsion polymerization in water, suspension polymerization and the like.

The carboxyl group-containing polyester resin is obtained by an ester bond forming reaction using a polyhydric alcohol, a polyvalent carboxylic acid, or the like as a raw material, and also contains an alkyd resin.

A polyhydric alcohol is a compound having two or more hydroxyl groups in one molecule. Examples of the polyhydric alcohol include pentaerythritol, which is a tetrafunctional raw material, triols such as trimethylolpropane and hexanetriol, and diols such as propylene glycol, neopentyl glycol, butylene glycol, and the like. A polyvalent carboxylic acid is a compound having two or more carboxyl groups in one molecule. Examples of the polyvalent carboxylic acid include aromatic dicarboxylic acids such as phthalic acid and isophthalic acid; aliphatic dicarboxylic acids such as adipic acid, azelaic acid and tetrahydrophthalic acid; and tricarboxylic acids such as trimellitic acid.

The carboxyl group-containing polyurethane resin is a resin obtained by reacting a diisocyanate compound with a diol containing various polyol components such as acrylic, polyester, polyether, and polycarbonate, and examples thereof include resins having a urethane bond. Among the above urethane resins, a resin containing a carboxyl group is preferably used, and the introduction of the carboxyl group is carried out by modifying a part or all of the hydroxyl groups derived from the raw material into a carboxyl group with an acid anhydride or the like, or in one molecule. A case where a compound having a hydroxyl group and a carboxyl group is used as a diol component can be mentioned. As the diol having a carboxyl group, for example, dimethylolpropionic acid and the like can be mentioned as suitable. Examples of the diisocyanate compound include 2,4-toluene diisocyanate (2,4-TDI), diphenylmethane-4,4'-diisocyanate (4,4'-MDI), isophorone diisocyanate (IPDI), and hexamethylene diisocyanate (HDI). ), Etc. can be mentioned.

Examples of the carboxyl group-containing epoxy resin include resins having a resin skeleton obtained by the reaction of bisphenol and epichlorohydrin. Among the above epoxy resins, a resin containing a carboxyl group is preferably used, and as a method for introducing the carboxyl group, a part or all of the hydroxyl group derived from the raw material is modified to a carboxyl group with an acid anhydride, or a molecule. A compound having a carboxyl group inside may be used as a raw material component. Examples of the bisphenol include bisphenols A and F. In addition, those obtained by chain-extending these with an appropriate chain extender can be mentioned.

In addition, the curable resin composition according to the present invention may be used in combination with other cross-linking agents, if necessary. Other cross-linking agents are not particularly limited, and for example, oxazoline compounds other than the oxazoline compounds according to the present invention, metal salts, organic metal compounds, melamine resins, phenol resins, polyepoxy resins, polyaziridine resins, polyisocyanate resins, etc. Examples thereof include polycarbodiimide resins and unsaturated compounds, and a plurality of cross-linking agents can be used in combination.

The blending amount of the oxazoline compound of the present invention or the trioxazoline compound of the present invention as a cross-linking agent is preferably 3 to 30 parts by weight with respect to 100 parts by weight of the resin. Further, from the viewpoint of heat resistance of the cured resin, 5 to 30 parts by weight is more preferable. From the viewpoint of adhesion, 5 to 20 parts by weight is most preferable.

The oxazoline compound of the present invention or the trioxazoline compound of the present invention can be suitably applied to a wide range of applications in which a synthetic resin is used as a cross-linking agent, such as a coating agent, an ink, a film, and an adhesive. The base material to be coated with these is not particularly limited, and examples thereof include glass, metal plate, wood plate, plastic material, and paper.

Hereinafter, the present invention will be described in detail based on Examples, but the present invention is not limited to these Examples, and any modification can be made within the scope of the technical idea of the present invention.

Ｄｅａｎ−ｓｔａｒｋ装置をつけた５００ｍＬの３ツ口フラスコに、４−ヒドロキシ安息香酸メチル（２１０．６ｇ、１．３８ｍｏｌ）を秤りとり、エタノールアミン（１２７．０ｇ、２．０８ｍｏｌ）を加え、１３０℃で２時間攪拌した。反応混合物を９０℃まで放冷し、減圧下（ダイヤフラムポンプ）で過剰のエタノールアミンを留去した。反応混合物（アミドアルコール）は精製せずに次の反応に用いた。 [Synthesis Example 1]
(Synthesis of amide field)

Methyl 4-hydroxybenzoate (210.6 g, 1.38 mol) was weighed in a 500 mL three-necked flask equipped with a Dean-Stark apparatus, ethanolamine (127.0 g, 2.08 mol) was added, and 130 The mixture was stirred at ° C. for 2 hours. The reaction mixture was allowed to cool to 90 ° C., and excess ethanolamine was distilled off under reduced pressure (diaphragm pump). The reaction mixture (amide alcohol) was used in the next reaction without purification.

２Ｌセパラブルフラスコに反応混合物（アミドアルコール）を移しかえ、ジグリム（ｄｉｇｌｙｍｅ、ジエチレングリコールジメチルエーテル）７３０ｇを加えて、スラリー状にした。氷水浴下、塩化チオニル（２１８．０ｇ、１．８３ｍｏｌ）を滴下した。滴下後、室温にて３０分間攪拌した。生じた沈殿を濾過、テトラヒドロフラン（ＴＨＦ）で洗浄した。濾取した固体を７００ｍＬのＴＨＦに懸濁させて、濾過し、塩酸塩を得た。塩酸塩を水１０００ｍＬに溶解し、４８％ＮａＯＨ水溶液で中和した、析出した固体を濾過、水で洗浄した後、乾燥して４−ヒドロキシフェニルオキサゾリン（１３７．８ｇ、６１％）を得た。 (Circulation)

The reaction mixture (amide alcohol) was transferred to a 2 L separable flask, and 730 g of diglyme (diethylene glycol dimethyl ether) was added to form a slurry. Thionyl chloride (218.0 g, 1.83 mol) was added dropwise under an ice water bath. After the dropping, the mixture was stirred at room temperature for 30 minutes. The resulting precipitate was filtered and washed with tetrahydrofuran (THF). The collected solid was suspended in 700 mL of THF and filtered to obtain hydrochloride. The hydrochloride salt was dissolved in 1000 mL of water, neutralized with a 48% aqueous NaOH solution, and the precipitated solid was filtered, washed with water, and dried to obtain 4-hydroxyphenyloxazoline (137.8 g, 61%).

Instrumental analysis of 4-hydroxyphenyloxazoline:
1H NMR (400MHz, CDCl ₃ ), δ7.80 (dd, J = 8.7, 2.0Hz, 2H), 6.81 (dd, J = 8.7, 2.0Hz, 2H), 4.43 (T, J = 9.6Hz, 2H), 4.05 (t, J = 9.6Hz, 2H)

Ｄｅａｎ−ｓｔａｒｋ装置をつけた１Ｌ４ツ口フラスコに、２−ヒドロキシ安息香酸メチル（２９３．６ｇ、１．９３ｍｏｌ）を秤りとり、エタノールアミン（１７６．８ｇ、２．８９ｍｏｌ）を加え、１３０℃で２時間攪拌した。反応混合物を１２６−１３０℃、減圧下（６００Ｐａ）で過剰のエタノールアミンを留去した。反応混合物（アミドアルコール）は精製せずに次の反応に用いた。 [Synthesis Example 2]
(Synthesis of amide field)

Methyl 2-hydroxybenzoate (293.6 g, 1.93 mol) was weighed in a 1 L 4-neck flask equipped with a Dean-Stark apparatus, ethanolamine (176.8 g, 2.89 mol) was added, and the temperature was 130 ° C. Stirred for 2 hours. Excess ethanolamine was distilled off from the reaction mixture at 126-130 ° C. under reduced pressure (600 Pa). The reaction mixture (amide alcohol) was used in the next reaction without purification.

３Ｌセパラブルフラスコに反応混合物（アミドアルコール）を移しかえ、ＴＨＦ９００ｍＬに溶解した。氷水浴下、塩化チオニル（３２２．４０ｇ、２．５７ｍｏｌ）を滴下した（内温６−１４℃）。滴下後、室温にて１５時間攪拌した。生じた沈殿を濾過、ＴＨＦ（２５０ｍＬ×２）で洗浄し、塩酸塩を得た。塩酸塩を水１０００ｍＬに溶解し、４８％ＮａＯＨ水溶液で中和した、析出した固体を濾過、水で洗浄した後、乾燥して２−ヒドロキシフェニルオキサゾリン（２８５．６ｇ、９２％）を得た。 (Circulation)

The reaction mixture (amide alcohol) was transferred to a 3 L separable flask and dissolved in 900 mL of THF. Thionyl chloride (322.40 g, 2.57 mol) was added dropwise under an ice water bath (internal temperature 6-14 ° C.). After the dropping, the mixture was stirred at room temperature for 15 hours. The resulting precipitate was filtered and washed with THF (250 mL x 2) to give hydrochloride. The hydrochloride salt was dissolved in 1000 mL of water, neutralized with a 48% aqueous NaOH solution, and the precipitated solid was filtered, washed with water, and dried to obtain 2-hydroxyphenyloxazoline (285.6 g, 92%).

Instrumental analysis of 2-hydroxyphenyloxazoline:
1H NMR (400MHz, CDCl ₃ ), δ12.2 (br s, 1H), 7.64 (d, J = 7.8Hz, 1H), 7.36 (dd, J = 7.8, 7.8Hz, 1H), 7.00 (d, J = 7.8Hz, 1H), 6.84 (dd, J = 7.8, 7.8Hz, 1H), 4.41 (t, J = 9.5Hz, 2H) ), 4.09 (t, J = 9.5Hz, 2H)

２００ｍＬの２ツ口フラスコに、合成例１で得られた４−ヒドロキシフェニルオキサゾリン（３２ｇ、１９６ｍｍｏｌ）、炭酸エチレン（６０ｇ、６８１ｍｍｏｌ）、テトラメチルアンモニウムクロリド（２００ｍｇ、１．８２ｍｍｏｌ）、炭酸カリウム（１ｇ、７．２ｍｍｏｌ）を秤りとり、１３０℃で４時間攪拌した。反応混合物を室温まで放冷し、メタノール（２５０ｍＬ）と水とを加え、析出した固体を濾過し、粗生成物を３０ｇ得た。前記粗生成物をメタノールに溶解し、不溶物を取り除き、再結晶（メタノール−酢酸エチル）により、第一晶（１３．５ｇ、３３％）、第二晶（８．３ｇ、２０％）の４−（２−ヒドロキシエトキシ）フェニルオキサゾリンを得た。 [Synthesis Example 3]

4-Hydroxyphenyloxazoline (32 g, 196 mmol), ethylene carbonate (60 g, 681 mmol), tetramethylammonium chloride (200 mg, 1.82 mmol), potassium carbonate (1 g) obtained in Synthesis Example 1 in a 200 mL two-necked flask. , 7.2 mmol) was weighed and stirred at 130 ° C. for 4 hours. The reaction mixture was allowed to cool to room temperature, methanol (250 mL) and water were added, and the precipitated solid was filtered to obtain 30 g of a crude product. The crude product was dissolved in methanol, the insoluble material was removed, and recrystallization (methanol-ethyl acetate) resulted in 4 of the first crystal (13.5 g, 33%) and the second crystal (8.3 g, 20%). -(2-Hydroxyethoxy) phenyloxazoline was obtained.

Instrumental analysis of 4- (2-hydroxyethoxy) phenyloxazoline 1H NMR (400MHz, CDCl ₃ ), δ7.89 (d, J = 8.6Hz, 2H), 6.93 (d, J = 8.6Hz, 2H), 4.41 (t, J = 9.4Hz, 2H), 4.13 (t, J = 4.6Hz, 2H), 4.04 (t, J = 9.4Hz, 2H), 3. 98 (m, 2H)

１００ｍＬの４ツ口フラスコに、合成例２で得られた２−ヒドロキシフェニルオキサゾリン（２０．４ｇ、１２５ｍｍｏｌ）、炭酸エチレン（１２．２ｇ、１３８ｍｍｏｌ）、炭酸カリウム（２２９ｍｇ、１．６６ｍｍｏｌ）を秤りとり、１４５℃で５時間攪拌した。反応混合物を室温まで放冷し、メチルイソブチルケトン（５０ｍＬ）を加えた。水（２０ｍＬ）、飽和食塩水（５ｍＬ）でそれぞれ２回洗浄し、硫酸ナトリウムで乾燥後、減圧蒸留（７２〜７７Ｐａ、１４６〜１５７℃）で精製し、２−（２−ヒドロキシエトキシ）フェニルオキサゾリン（１０．５ｇ、４０％）を得た。 [Synthesis Example 4]

2-Hydroxyphenyloxazoline (20.4 g, 125 mmol), ethylene carbonate (12.2 g, 138 mmol) and potassium carbonate (229 mg, 1.66 mmol) obtained in Synthesis Example 2 were weighed in a 100 mL four-necked flask. The mixture was stirred at 145 ° C. for 5 hours. The reaction mixture was allowed to cool to room temperature and methyl isobutyl ketone (50 mL) was added. Wash twice with water (20 mL) and saturated brine (5 mL), dry over sodium sulfate, purify by vacuum distillation (72-77 Pa, 146-157 ° C.), and 2- (2-hydroxyethoxy) phenyloxazoline. (10.5 g, 40%) was obtained.

Instrumental analysis of 2- (2-hydroxyethoxy) phenyloxazoline:
1H NMR (400MHz, CDCl ₃ ), δ7.75 (dd, J = 7.8, 1.8Hz, 1H), 7.40 (ddd, J = 7.8, 7.8, 1.8Hz, 1H) , 7.04 (dd, J = 7.8, 7.8Hz, 1H), 7.01 (d, J = 7.8Hz, 1H), 6.4 (br s, 1H), 4.31 (t) , J = 9.4Hz, 2H), 4.23 (t, J = 4.4Hz, 2H), 4.06 (t, J = 9.4Hz, 2H), 3.81 (t, J = 4. 4Hz, 2H)

２Ｌのセパラブルフラスコに、塩化シアヌルを４６．７５ｇ（２５３．５ｍｍｏｌ）、トリエチルアミンを２．５６ｍＬ秤りとり、ジクロロメタン６１５ｇに溶解した。合成例１で得られた４―ヒドロキシフェニルオキサゾリン（１２７ｇ、７７８ｍｍｏｌ）、４８％水酸化ナトリウム水溶液（６６．３ｇ、７９６ｍｍｏｌ）、水５００ｍＬの溶液を１時間かけて室温にて滴下した。滴下後、１０時間室温で攪拌し、水相を取り除き、水２００ｍＬを加え、有機相を分離した。有機相を濃縮し、得られた固体をメタノール６６５ｍＬ、酢酸エチル５５０ｍＬで順に懸濁させ、ろ過し、上記化学式のトリオキサゾリン化合物（１０９ｇ、７６％）を得た。 [Synthesis Example 5]
(3 functionalization)

In a 2 L separable flask, 46.75 g (253.5 mmol) of cyanuric chloride and 2.56 mL of triethylamine were weighed and dissolved in 615 g of dichloromethane. A solution of 4-hydroxyphenyloxazoline (127 g, 778 mmol) obtained in Synthesis Example 1, a 48% aqueous sodium hydroxide solution (66.3 g, 796 mmol), and 500 mL of water was added dropwise at room temperature over 1 hour. After the dropping, the mixture was stirred at room temperature for 10 hours, the aqueous phase was removed, 200 mL of water was added, and the organic phase was separated. The organic phase was concentrated, and the obtained solid was suspended in 665 mL of methanol and 550 mL of ethyl acetate in this order and filtered to obtain a trioxazoline compound (109 g, 76%) having the above chemical formula.

Instrumental analysis of trioxazoline compounds:
1H NMR (400MHz, CDCl ₃ ), δ7.95 (d, J = 8.7Hz, 6H), 7.19 (d, J = 8.7Hz, 6H), 4.44 (t, J = 9.5Hz) , 6H), 4.06 (t, J = 9.5Hz, 6H)

In addition, the TOFMS (Time of Flight Mass Spectrometry) measurement result of the obtained trioxazoline compound is shown in FIG. The measurement was performed using a flight time mass spectrometer (AXIMA-CFRplus) manufactured by Shimadzu Corporation. As a result of the measurement, it was confirmed that the molecular weight was 564.

[Production Example 1] (Synthesis of Acrylic Resin A)
After charging 40.0 g of butyl acetate into a 0.3 L 4-port flask equipped with a thermometer, a stirrer, a reflux cooler, a dropping funnel and a nitrogen gas introduction tube, the temperature was raised to 140 ° C., and 10 parts by weight of methacrylic acid was added. 2 parts by weight of 2-hydroxyethyl methacrylate, 20 parts by weight of methyl methacrylate, 20 parts by weight of styrene, 20 parts by weight of ethyl acrylate, 28 parts by weight of butyl acrylate, 0.3 parts by weight of t-butylperoxy-2-ethylhexanoate. The mixture was added dropwise over 5 hours and polymerized to obtain an acrylic resin A having a solid content of 70%. The acid value of the obtained acrylic resin (solid content) was 65 mg / KOHg (see Table 1).

[Manufacturing Example 2] (Synthesis of Acrylic Resin B)
After charging 40.0 g of butyl acetate into a 0.3 L 4-port flask equipped with a thermometer, a stirrer, a reflux cooler, a dropping funnel and a nitrogen gas introduction tube, the temperature was raised to 140 ° C., and 5 parts by weight of methacrylic acid was added. 10 parts by weight of 2-hydroxyethyl methacrylate, 10 parts by weight of methyl methacrylate, 25 parts by weight of styrene, 30 parts by weight of ethyl acrylate, 20 parts by weight of butyl acrylate, 0.3 parts by weight of t-butylperoxy-2-ethylhexanoate. The mixture was added dropwise over 5 hours and polymerized to obtain an acrylic resin B having a solid content of 70%. The acid value of the obtained acrylic resin (solid content) was 32 mg / KOHg (see Table 1).

[Production Example 3] (Synthesis of Acrylic Resin C)
After charging 40.0 g of butyl cellosolve into a 0.3 L 4-port flask equipped with a thermometer, a stirrer, a reflux cooler, a dropping funnel and a nitrogen gas introduction tube, the temperature was raised to 140 ° C., and 10 parts by weight of methacrylic acid, 2 -Hydroxyethyl methacrylate 2 parts by weight, methyl methacrylate 20 parts by weight, styrene 20 parts by weight, ethyl acrylate 20 parts by weight, butyl acrylate 28 parts by weight, α-methylstyrene dimer (chain transfer agent) 3 parts by weight, t-butylperoxy 0.3 part by weight of -2-ethylhexanoate was added dropwise over 5 hours and polymerized to obtain an acrylic resin C having a solid content of 70%. The acid value of the obtained acrylic resin (solid content) was 65 mg / KOHg (see Table 1).

[Example 1]
To 20 g of the acrylic resin A obtained in Production Example 1, 4.2 g of the trioxazoline compound obtained in Synthesis Example 5 and 12.2 g of dimethylacetamide were added to formulate a coating material having a solid content of 50%.

[Example 2]
To 20 g of the acrylic resin A obtained in Production Example 1, 2.8 g of the trioxazoline compound obtained in Synthesis Example 5 and 10.8 g of dimethylacetamide were added to blend a coating material having a solid content of 50%.

[Example 3]
To 20 g of the acrylic resin A obtained in Production Example 1, 1.4 g of the trioxazoline compound obtained in Synthesis Example 5 and 9.4 g of dimethylacetamide were added to blend a coating material having a solid content of 50%.

[Example 4]
To 20 g of the acrylic resin B obtained in Production Example 2, 1.4 g of the trioxazoline compound obtained in Synthesis Example 5 and 3.5 g of a melamine resin (Symel 325, solid content 80%, manufactured by Nippon Cytec Industry Co., Ltd.) and dimethylacetamide. 11.5 g was added to formulate a paint having a solid content of 50%.

[Comparative Example 1]
The paint was blended in the same manner as in Example 2 except that 2.8 g of 1,3-bis (2-oxazoline-2-yl) benzene, which is a dioxazoline compound, was used instead of the trioxazoline compound of Example 2. ..

[Comparative Example 2]
Add 7.2 g of an oxazoline group-containing polymer (Epocross WS-500, solid content 39%, manufactured by Nippon Shokubai Co., Ltd.) and 6.4 g of butyl cellosolve to 20 g of the acrylic resin C obtained in Production Example 3 to prepare a coating material having a solid content of 50%. Formulated.

(Creation of test board)
The paints prepared in Examples 1 to 4 and Comparative Examples 1 and 2 are applied to an aluminum plate (A-5052P test piece, manufactured by standard test piece) having a thickness of 0.26 mm and 10 cm × 14 cm, and a film after drying by a roll coating method. A test plate was prepared by applying the coating so as to have a thickness of 7 μm and heat-treating at 170 ° C. for 10 minutes.

(Pencil hardness)
The coating film of the obtained test plate was subjected to a pencil scratch test specified in JIS K 5600-5-4: 1999. The results are shown in Table 2.

(Adhesion test)
The coating film of the test plate is cross-cut as specified in JIS K 5600-5-6: 1999, and Nichiban Co., Ltd. cellophane tape (registered trademark) is attached to the cross-cut portion, and this is applied at 90 degrees to the coated plate. It peeled off rapidly in the direction, and the condition of the coated surface was visually confirmed and evaluated based on the following evaluation criteria. The results are shown in Table 2.
In A, there is no peeling of the coating film.
In B, the peeling of the coating film is less than 20%.
In C, the peeling of the coating film is 20% or more and less than 80%.
In D, the peeling of the coating film is 80% or more.

(Water resistance test / appearance)
After immersing the obtained test plate in hot water at 125 ° C. for 30 minutes in an autoclave, the occurrence of blister (blister) and the degree of whitening of the coating film were visually evaluated according to the following criteria. The results are shown in Table 2.
In A, no blister or whitening was observed on the coating film.
In B, blister and whitening are hardly observed in the coating film.
In C, blister and whitening coating surface abnormality are observed in the coating film.
In D, at least one coating surface abnormality such as blister and whitening is remarkable in the coating film.

(Water resistance test / pencil hardness)
The obtained test plate was immersed in hot water at 125 ° C. for 30 minutes in an autoclave, and then a pencil scratch test was performed in the same manner as described above. The results are shown in Table 2.

(Water resistance test / adhesion test)
The obtained test plate was immersed in hot water at 125 ° C. for 30 minutes in an autoclave, and then an adhesion test was conducted in the same manner as described above. The results are shown in Table 2.

As is clear from the above results, the trioxazoline compound of the present invention obtained by trifunctionalizing the oxazoline compound of the present invention can improve its coating performance by adding it to a resin having a carboxyl group. Therefore, it can be suitably used for paints, surface treatment agents, coating agents, adhesives, sealing materials and the like.

Claims (3)

Tri oxazoline compound represented by the following Symbol Formula.

Wherein Y is a central core, triazines, either to B, selected from the group consisting of P = O, and Si-CH _3. In the formula, X ₂ is represented by (RO−) n, n is 0 or 1, and R is a linear or branched alkylene group having a carbon number in the range of 1 to 4. Crosslinking agents containing Application Benefits oxazoline compound of claim 1. A resin composition containing the cross-linking agent according to claim 2.

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