JP4925263B2 - Polyhydroxyether resin having allyl group in side chain, method for producing the same, and resin composition thereof - Google Patents

Description

The present invention relates to a novel functional polyhydroxy ether resin having an allyl group in a side chain which can be used in a wide range of fields such as paints, electronic materials, adhesives, photosensitive materials, inks, and a method for producing the same, and a resin composition thereof. It is to provide.
More specifically, the present invention provides a functional polyhydroxy ether resin having an allyl group in a side chain that can be cross-linked by an active energy source such as heat or light, a production method thereof, and a resin composition thereof.

A polyhydroxy ether obtained by a reaction condensate of a dihydric phenol and epichlorohydrin or an addition polymerization reaction of a dihydric phenol and a divalent glycidyl ether is generally referred to as “phenoxy resin”, and its adhesiveness, Features such as electrical insulation, toughness of coating film and film, low oxygen gas permeability, primer paint, can paint, self-bonding electric wire, magnetic material binder, film adhesive, copper foil with adhesive, printing It is used for applications such as circuit boards and various polymer alloys.
However, such phenoxy resins are themselves thermoplastic resins and do not crosslink. Conventionally, when a polyhydroxy ether resin (hereinafter abbreviated as PHE) is crosslinked, a secondary hydroxyl group present in the pendant is used and crosslinked with an isocyanate compound or a blocked isocyanate compound. Furthermore, a method is adopted in which a condensation reaction is performed at the time of baking with a butylated resol (phenol) resin, a methylolated melamine resin, or the like. In addition, a method in which a low molecular weight epoxy resin is used in combination with the crosslinked structure of the epoxy resin is employed.

An attempt to modify the secondary hydroxyl group of the PHE pendant is disclosed in Patent Document 1. Accordingly, the Pendant secondary hydroxyl group of PHE is reacted with monoisocyanate, which is a reaction product of diisocyanate and 2-hydroxy acrylate, to obtain radiation curable PHE having an α-β unsaturated bond in the side chain. However, this method has problems such as difficulty in temperature and moisture management, and a long time for production.
In Patent Document 2, a glycidyl methacrylate (hereinafter abbreviated as GMA) is added to a secondary hydroxyl group of a PHE pendant to obtain a photosensitive resin having an α-β unsaturated bond in the side chain. However, in this method, since PHE is dissolved in excess GMA and subjected to addition reaction, and then the polymer is precipitated in a large amount of methanol, a stable addition rate of GMA cannot be obtained. There was a problem that handling property was poor and unsuitable for industrialization, and that the basic unit of expensive GMA was poor and the cost was high.
On the other hand, in Patent Document 3, after adding ethylene oxide, propylene oxide or the like to the secondary hydroxyl group of PHE, polybasic acid anhydride is further added, and further reacted with GMA, as a component of the photosensitive resin composition. Yes. This method has problems such as a long manufacturing process, a small number of functional groups, and poor curability, so that it cannot be used alone.

In Patent Document 4, a polybasic acid anhydride is added to PHE, and then GMA is added to obtain a photosensitive resin having an α-β unsaturated bond in the side chain. And the photosensitive resin composition and photosensitive element which use this resin as a component are obtained. However, since the number of functional groups is small and the curability is poor, there is a problem that it cannot be used alone.
In addition, when a group having a highly reactive α-β unsaturated bond is introduced into a polymer resin having a number average molecular weight of 10,000 or more such as PHE, the number of functional groups to be introduced is improved in order to improve curability. If the amount is increased, gel particles are generated, the functional groups react with each other to increase the viscosity remarkably, or in an extreme case, gelation occurs during the reaction. Therefore, there has been a problem that a technique such as reducing the functional group concentration or increasing the polymerization inhibitor more than usual or blowing air during the reaction has been required. As a result, the photosensitivity by itself is insufficient, and there is a problem that a large amount of low-molecular polyfunctional photosensitive resin must be used in combination.
JP-A-1-2902022 JP 59-53534 A JP-A-5-281733 WO2004 / 006235

  As a result of intensive studies to solve the above problems, the present inventors have caused generation of gel particles, significant increase in viscosity, and gelation without blowing a polymerization inhibitor or air during the reaction. And has a high number of functional groups, good storage stability, toughness, good film-forming properties, good substrate adhesion and durability, and can be crosslinked by heat or light The present inventors have found a functional polyhydroxy ether and have completed the present invention.

  A polyhydroxy ether resin having an allyl group in the side chain represented by the general formula (1), wherein the main chain polyhydroxy ether has a number average molecular weight of 1,000 or more and 200,000 or less. Hydroxy ether resin.

（式中、R₁は多塩基酸無水物残基、Ｒ_２はアリル基含有グリシジル化合物残基、Mは2価フェノール残基であり、同一でも異なっていてもよく、ｌ、ｍ、ｎは整数であって、ｍは０の場合があっても良い。ｐは１〜３の整数である。）
即ち、本発明は、主鎖ポリマーであるＰＨＥの数平均分子量が１，０００〜２００，０００で分子内に２級水酸基を有するポリヒドロキシエーテル樹脂（ａ）と多塩基酸無水物（ｂ）の反応に基づく半エステル化変性ポリヒドロキシエーテル樹脂（Ａ）を得る。次に、半エステル化変性ポリヒドロキシエーテル樹脂（Ａ）中のカルボキシル基とアリル基含有グリシジル化合物（ｃ）を反応せしめて側鎖にアリル基を有するポリヒドロキシエーテル（Ｂ）を得る。
本発明における主鎖ポリマーの数平均分子量が１，０００〜２００，０００で分子内に２級水酸基を有するポリヒドロキシエーテル（ａ）は２価フェノール類とエピクロルヒドリン（以下ＥＣＨと略記）の縮合反応によって製造されるか、２価フェノール類と２価グリシジルエーテル類との付加反応により製造されるＰＨＥである。主鎖の数平均分子量が小さいとフイルム形成能が無く、塗膜の強靭性に欠け、あまり数平均分子量が大きすぎると溶剤に溶解したときの溶解性の悪化や、粘度が高くなり取り扱いづらい。好ましい数平均分子量は１，０００〜２００，０００、より好ましくは２，０００〜１００，０００、更に好ましくは４，０００〜６０，０００である。尚、本発明の数平均分子量は標準ポリスチレンを標準物質として、ゲル浸透クロマトグラフィー（ＧＰＣ）に依って測定された数平均分子量を言う。

(In the formula, R ₁ is a polybasic acid anhydride residue, R ₂ is an allyl group-containing glycidyl compound residue, M is a divalent phenol residue, which may be the same or different, and l, m and n are (It may be an integer and m may be 0. p is an integer of 1 to 3.)
That is, the present invention relates to a polyhydroxy ether resin (a) having a number average molecular weight of PHE as a main chain polymer of 1,000 to 200,000 and having a secondary hydroxyl group in the molecule and a polybasic acid anhydride (b). A half-esterified modified polyhydroxyether resin (A) based on the reaction is obtained. Next, the carboxyl group in the half-esterified modified polyhydroxy ether resin (A) is reacted with the allyl group-containing glycidyl compound (c) to obtain a polyhydroxy ether (B) having an allyl group in the side chain.
The polyhydroxy ether (a) having a number average molecular weight of 1,000 to 200,000 in the present invention and having a secondary hydroxyl group in the molecule is obtained by a condensation reaction of a dihydric phenol and epichlorohydrin (hereinafter abbreviated as ECH). PHE produced by addition reaction of dihydric phenols and divalent glycidyl ethers. If the number average molecular weight of the main chain is small, there is no film-forming ability and the toughness of the coating film is lacking. If the number average molecular weight is too large, the solubility when dissolved in a solvent is deteriorated and the viscosity becomes high and difficult to handle. The number average molecular weight is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, and still more preferably 4,000 to 60,000. The number average molecular weight of the present invention refers to the number average molecular weight measured by gel permeation chromatography (GPC) using standard polystyrene as a standard substance.

  PHE (a) which is a main chain polymer in the present invention is represented by the general formula (2).

  Here, M represents a divalent phenol residue. The dihydric phenol constituting PHE may be a homopolymer composed of one kind, or may be a random copolymer or a block copolymer composed of two or more kinds of dihydric phenols. Furthermore, long-chain branching or short-chain branching within the range not impairing the object of the present invention may be used.

  Specific examples of dihydric phenols used in the present invention include dihydric mononuclear phenols such as hydroquinone, resorcin, catechol, 2,5-ditertiarybutyl hydroquinone, bisphenol A (hereinafter abbreviated as BPA), bisphenol. Divalent polynuclear bisphenols such as F (hereinafter abbreviated as BPF), bisphenol B, bisphenol E, bisphenol K, bisphenol S (hereinafter abbreviated as BPS), 3,3 ′, 5,5′-tetramethylbisphenol F, 1, Naphthalenediols such as 4-naphthalenediol and 1,6-naphthalenediol, halogenated bisphenols such as tetrabromobisphenol A (hereinafter abbreviated as TBBA), tetrachlorobisphenol A and hexafluorobisphenol A, 4,4′-biphenol , 3, 3 ', 5, Biphenols such as' -tetramethylbiphenol, bisphenols having a ring such as bisphenol fluorin, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 1,4-benzoquinone or 1,4 -Examples include, but are not limited to, phosphorus-containing dihydric phenols (hereinafter abbreviated as HCA-HQ and HCA-NQ) represented by formula (3) and formula (4), which are addition reactions of naphthoquinone. It is not something.

ＨＣＡ−ＨＱ

HCA-HQ

ＨＣＡ−ＮＱ

HCA-NQ

  Specific examples of divalent glycidyl ethers that can be used in the present invention are not particularly limited as long as they are diglycidyl ethers obtained by the condensation reaction of divalent phenols and ECH shown in paragraph No. 0010. Those having a high (epoxy) group purity are preferred. Specific commercially available products include “Epototo YD-8125”, “Epototo YD-127”, “Epototo YD-128”, “Epototo YD-134”, “Epototo YD-011”, “Epototo YD” manufactured by Toto Kasei Co., Ltd. -012 "," Epototo YD-013 "," Epototo YD-014 "," Epototo YD-901 "," Epototo YD-902 "," Epototo YD-903 "," Epototo YD-904 ", etc. Different BPA type diglycidyl ethers, TBBA type diglycidyl ethers such as “Epototo YDB-400”, “Epototo YDB-460”, BPF type diglycidyl such as “Epototo YDF-170”, “Epototo YDF-8170” Ethers of 2,5-ditertiarybutyl hydroquinone type Pototo YDC-1312 ", 3,3 ', 5,5'-tetramethyl bisphenol F type" EPOTOHTO YSLV-80XY "bisphenol full oleic type" EPOTOHTO ESF-300 ", etc. can be exemplified.

Specific commercial products of PHE (a), which is the main chain polymer used in the present invention, include BPA type PHE “Phenototo YP-40”, “Phenototo YP-50”, “Phenototo YP” manufactured by Tohto Kasei Co., Ltd. -50S ", BPA / BPF copolymer type PHE" Phenothoto YP-70 ", TBBA type PHE" Phenothoto YPB-40 "," Phenothoto YPB-43 ", Phosphorus-containing PHE" Phenothoto ERF-001 ", Bisphenol A sulfone type “phenotote YOS-007” and the like can be exemplified.
Examples of the polybasic acid anhydride (b) used in the present invention include maleic anhydride, citraconic anhydride, itaconic anhydride, chlorendic anhydride, succinic anhydride, alkenyl succinic anhydride, hexahydrophthalic anhydride, and methylhexahydroanhydride. Examples include phthalic acid, tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, polyadipic anhydride, polyazeline anhydride, phthalic anhydride, trimellitic anhydride, maleic anhydride adduct of methylcyclopentadiene, etc. be able to. Two or more types of acid anhydrides can be used in combination.

  The allyl group-containing glycidyl compound (c) used in the present invention may be any compound having an allyl group and a glycidyl (epoxy group) in the molecule, and allyl glycidyl ether, diallyl monoglycidyl isocyanuric acid is obtained by the following scheme. (Alkyl) monophenols and allyl chloride obtained in the presence of an alkali metal hydroxide, and allylated phenol obtained by Claisen rearrangement under heating, and further presence of epichlorohydrin and alkali metal hydroxide Mention may be made of compounds obtained by glycidyl etherification below.

Here, MeOH represents an alkali metal hydroxide.
Allylation of such phenols can be easily obtained by referring to the descriptions in JP-A-53-134099 and JP-A-58-159436. JP-A-5-065239 and JP-A-5-0665240 disclose a method for producing allylated phenols in high yield by Claisen rearrangement. USP-2,910,455 and JP-A-11-279257 disclose a method for producing an epoxy resin from an allylated polyphenol compound. Furthermore, Japanese Patent Application Laid-Open No. 2000-191572 discloses a method using diallyl carbonate as a method for producing an allylated phenol. Any method can be used for producing the allylated phenyl glycidyl ether of the present invention, but the glycidyl group may be monofunctional, and a plurality of allyl groups may be contained. Thus, the phenol source may be monophenol with unalkylated or multiple substituted alkyl groups. Examples of the phenol source include phenol, cresols, xylenols, p-tert-butylphenol, octylphenol, nonylphenol and the like.
Further, it does not prevent the combined use of an α-β unsaturated glycidyl compound such as glycidyl methacrylate within the range not exceeding the intention of the present invention for the purpose of promoting the initiation of the photosensitive initial reaction.

  The polyhydroxy ether resin having an allyl group in the side chain of the present invention does not generate gel particles or the like in the production stage, and the composition is excellent in good photocurability and thermosetting and adhesive strength. It is an effective resin for paints, adhesives, electronic materials, etc.

Hereinafter, it demonstrates along the embodiment of this invention sequentially. The addition reaction of the polybasic acid anhydride (b) to the secondary hydroxyl group of PHE (a), which is the main chain polymer, which is the first stage of the present invention will be described.
This reaction is carried out in the presence of a non-reactive solvent. Preferred solvents include ketones such as acetone, methyl ethyl ketone, cyclohexanone and isophorone, cyclic ethers such as 1,4-dioxane and tetrahydrofuran, linear ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, ethyl acetate and butyl acetate. An aprotic solvent such as dimethyl sulfoxide, dimethylformamide and N-methylpyrrolidone, and an aromatic hydrocarbon such as toluene and xylene. These solvents may be used alone or in combination.
Further, in order to avoid side reactions of polybasic acid anhydrides, it is necessary to reduce the amount of water in the solvent used and the PHE used as much as possible. Therefore, PHE is used after being dried at about 70 to 80 ° C. for 24 hours or more in advance or dehydrated after being dissolved in a solvent to achieve the object.
Such an addition reaction proceeds even without a catalyst, but it is desirable to use a catalyst in order to complete the addition reaction in a short time. Catalysts that can be used include tertiary amines such as triethylamine, N, N′-dimethylpiperazine, and benzyldimethylamine, quaternary ammonium salts thereof, and alkylimidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole. Furthermore, phosphines such as triphenylphosphine and tricyclophosphine, and quaternary phosphonium salts thereof can be used. The amount of these catalysts used is 10 to 10,000 ppm, more preferably 100 to 8,000 ppm, still more preferably 500 to 7,000 ppm, based on the total solid content.

  In such an addition reaction, PHE is dissolved in the presence of a solvent that does not affect the reaction, and then the polybasic acid anhydride is added in a batch or dividedly to react. The reaction temperature is 50 to 150 ° C, preferably 90 to 150 ° C, more preferably 100 to 130 ° C. The addition reaction can be traced by measuring the absorption spectrum of the polybasic acid anhydride by FT-IR, and the completion of the reaction can be easily determined by the disappearance. Sequentially, a solvent is added so that the concentration of the reaction product is in the range of 20 to 60% by weight, more preferably 30 to 50% by weight. The reaction time may normally be about 2 to 20 hours, and can be adjusted by the amount of catalyst, reaction temperature, and solid content concentration.

In the present invention, the addition ratio of PHE (a) and polybasic acid anhydride (b) is 0.1 to 0.9 mol, more preferably 0.2 to 0.7 mol, relative to 1 mol of the hydroxyl group of (a). Mol, more preferably 0.3 to 0.6 mol. If the addition ratio is small, the curability is inferior, and if the addition ratio is too large, the cured product is hard and lacks toughness. Since the number of functional groups is not determined only by the addition ratio, but varies depending on the number of bases of anhydride and the number of allyl groups of the allyl group-containing glycidyl compound, various resin designs are possible.
The reaction of the carboxyl group and the allyl group-containing glycidyl compound (c) in the half-esterified modified polyhydroxy ether resin (A), which is the second stage of the present invention, is a ring-opening addition reaction of the carboxyl group and the glycidyl group. Although this reaction proceeds even without catalyst, it is more preferable to use a catalyst. As a preferred catalyst, the catalyst described in paragraph 0019 can be used. That is, the same catalyst can be used for the first stage half-esterification and the second stage catalyst. If the first stage catalyst activity remains, no additional addition is required for this reaction. Of course, it does not prevent you from adding if necessary.

Since the allyl group-containing glycidyl compound (c) is relatively stable during the reaction, the polymerization is prevented by bubbling a small amount of air to prevent polymerization, such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, phenothiazine, etc. Although it is not necessary to use a polymerization inhibitor, it does not prevent its use.
Such an addition reaction may be carried out at a temperature of 50 to 150 ° C, preferably 60 to 130 ° C, more preferably 60 to 120 ° C. The tracking of the reaction can be easily determined by confirming the disappearance of the epoxy group by FT-IR and by the disappearance of the peak of the allyl group-containing glycidyl compound (c) by HPLC or GPC measurement.
The addition ratio of the allyl group-containing glycidyl compound (c) to the carboxyl group in the half-esterified modified polyhydroxy ether resin (A) may be such that (c) is 0.5 mol or more per mol of the carboxyl group, Although an excess mole may be used, it is not preferable because the excess portion is unreacted and the cured material properties are hard and the tendency to become brittle becomes strong. On the other hand, if it is 0.5 mol or less, the allyl group content decreases, the properties of the half-esterified modified polyhydroxy ether resin (A) become strong, and the effects of the present invention cannot be exhibited.
In the final resin (B) obtained in the present invention, a secondary hydroxyl group and an allyl group are mixed in the pendant, but the addition molar ratio of (c) is between 0.5 and 1.0 mol. In the final resin (B), free carboxyl groups are present. Whether a free carboxyl group is required should be determined by purpose and use. In the case of making aqueous using a carboxyl group, in the case of imparting alkali aqueous solubility such as a resist, or in the case where adhesion to a metal is required, it is preferable that a free carboxyl group exists. In addition, it should not exist in applications where water resistance, chemical resistance, electrolytic corrosion, etc. are a concern.

The resin composition of the present invention will be described. In particular, in order to obtain a thermosetting resin composition, it is necessary to blend a radical polymerization initiator as an essential component. As radical polymerization initiators, ethyl methyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, isobutyryl peroxide, lauroyl peroxide, benzoyl peroxide, cumene hydroperoxide, di-tert-butyl Examples thereof include peroxides and peroxides such as tert-butyl-α-cumyl peroxide. The usage-amount of a radical polymerization initiator is 0.1-10 weight part with respect to 100 weight part of polyhydroxy ether resin (B) which has an allyl group in the side chain of this invention, Preferably it is 1-5 weight part.
As the thermosetting resin composition, other thermosetting monomers and oligomers can be added and used, but the final resin (B) obtained in the present invention is contained at least 5% by weight, preferably 20% by weight or more. It is desirable to do. Specific examples of monomers that can be used in combination include diallyl phthalate, allyl glycidyl ether, triallyl isocyanate, acrylates, etc. Specific examples of oligomers include diallyl phthalate resin, unsaturated polyester resin, acrylic ester oligomer, epoxy acrylate resin, etc. be able to.

  In order to make the resin composition of the present invention particularly a photosensitive resin composition, it is necessary to blend a photocuring initiator as an essential component. Specific examples of such a photocuring initiator include acetophenone, benzophenone, 4,4′-bisdimethylaminobenzophenone, benzoin butyl ether, benzophenone such as 2-dimethoxy-2-phenylacetophenone and derivatives thereof, thioxanthone, and 2,4-dimethyl. Thioxanthone such as thioxanthone and 2,4-diisopropylthioxanthone and derivatives thereof, methylbenzoylformate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one (Ciba Specialty Chemicals) It is preferable to select a compound having an absorption wavelength in the ultraviolet rays of an exposure machine to be used. The amount of these photocuring initiators used is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the polyhydroxy ether resin (B) having an allyl group in the side chain of the present invention. is there. These can be used alone or in combination of two or more. Furthermore, photosensitizers such as tertiary amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, 4-dimethylaminobenzoate, triethylamine, triethanolamine, etc. It can be used alone or in combination of two or more.

When using polyhydroxy ether resin (B) which has an allyl group in the side chain of this invention as a photosensitive resin composition, a photopolymerizable unsaturated monomer can be added and used. The addition of monomer has a function of controlling fluidity and tackiness. Examples of photopolymerizable unsaturated monomers include (meth) acrylic acid, hydroxyethyl (meth) acrylate, hydroxyl (meth) acrylate, methyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, Examples include ethylene glycol (meth) acrylate, trimethylolpropane (meth) acrylate and the like.
In the resin composition using the polyhydroxyether resin (B) having an allyl group in the side chain of the present invention, a solvent, a pigment, a dye, a colorant, a flame retardant, an antifoaming agent, a wetting agent, Dispersants, rust inhibitors, antistatic agents, surface treatment agents, thermoplastic resins, elastomers, acrylic acid monomers, acrylic acid oligomers, epoxy acrylates, silane coupling agents, inorganic fillers, fiber reinforcements, etc. It is possible to mix.

The photosensitive resin composition using the polyhydroxy ether resin (B) having an allyl group in the side chain of the present invention can be cured by irradiation with energy rays such as visible light, ultraviolet rays, X-rays and electron beams. Curing by irradiation with energy rays such as visible light, ultraviolet rays, X-rays, and electron beams can be performed by a conventional method. For example, in the case of irradiating ultraviolet rays, an ultraviolet generator such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, or an ultraviolet light emitting laser may be used.
The resin composition of the present invention is used as a printing ink material for UV or thermosetting ink, metal printing such as tinplate and aluminum, label printing and business form printing. Solder mask for printed wiring board, marking ink, copper foil with adhesive, dry film resist, film adhesive for semiconductor chip and wiring board, multilayer circuit board by additive method, motor coil insulation impregnation varnish, Electric field applications such as self-bonding insulated electric wire varnish, wood furniture, plywood and other clear coatings, paper surface glazing, plastic hard coats and other coatings, optical lens adhesives, optical fiber adhesives, It can be used for adhesives such as a film-like adhesive (heat, photocrosslinking type), a laminate having a low oxygen permeability as a crosslinked film, and a food packaging material as a coating agent.
Examples and comparative examples

  Hereinafter, the present invention will be specifically described based on synthesis examples, examples, and comparative examples. In addition, this invention is not limited only to an Example.

Synthesis example 1 (40% MeHHPA addition)
PHE obtained from BPA and ECH, specifically phenototoy YP-50S (manufactured by Toto Kasei Co., Ltd., number average molecular weight 15,000, hydroxyl group equivalent 284 g / eq) in a vacuum desiccator maintained at 70 ° C. for 24 hours After drying, 213 g (hydroxyl group 0.75 mol) and 320 g of diethylene glycol dimethyl ether (hereinafter abbreviated as MDM) (solid content concentration 40%) dehydrated in advance are added to a 1-liter separable flask, and the mixture is stirred at about 50 ° C. Warmed to dissolve completely. Next, 50.4 g (0.30 mol) of methylhexahydrophthalic anhydride (MeHHPA anhydride equivalent weight 168 g / eq) and 0.26 g (1,000 ppm / total solid) of triphenylphosphine (hereinafter abbreviated as TPP) as a catalyst. The reaction was completed at 110 ° C. for 7 hours to complete the addition reaction. 75 g of methyl ethyl ketone (hereinafter abbreviated as MEK) was added to obtain a modified polyhydroxy ether resin solution (A1). The properties of this resin are shown in Table 1.

Synthesis example 2 (30% TMA addition)
It is the same except that instead of MeHHPA in Synthesis Example 1, trimellitic anhydride (TMA, anhydride equivalent = 192 g / eq) 43.2 g (0.225 mol), TPP 0.26 g, and MEK 64.3 g were used. To obtain a modified polyhydroxy ether resin solution (A2). The properties of this resin are shown in Table 1.

Synthesis example 3 (50% THPA addition)
PHE which is a copolymer of bisphenol A diglycidyl ether and bisphenol F, specifically, phenotoate YP-70 (manufactured by Toto Kasei Co., Ltd., number average molecular weight 10,000, hydroxyl group equivalent 270 g / eq, 216 g) 0.80 mol) and 324 g of MDM were added and dissolved by stirring at 50 ° C. This was charged with 60.8 g (0.40 mol) of tetrahydroxyphthalic anhydride (THPA, acid anhydride equivalent of 152 g / eq) and 0.14 g of 2-ethyl-4-methylimidazole as a catalyst, and the temperature was increased to 110 ° C. with stirring. The temperature gradually increased. After stirring for 7 hours while maintaining the reaction temperature of 105 ° C to 125 ° C, 91 g of MEK was added to obtain a modified polyhydroxy ether resin solution (A3). The properties of this resin are shown in Table 1.

Synthesis Example 4 (Allyl group-containing glycidyl compound from alkylphenol)
To a 1-liter flask equipped with a stirrer, 108 g (1 mol) of orthocresol, 229.5 g (3 mol) of allyl chloride, 200 g of n-butanol and 75 g of toluene were added, and 137 g (1%) of a 49% aqueous solution of caustic potash was controlled at 75 to 82 ° C. 2 mol) was added dropwise over 4 hours. During this time, water generated by reflux was separated and removed. Further, the mixture was aged at 75 to 88 ° C. for 3 hours. After cooling to room temperature, suction filtration was performed to remove byproduct potassium chloride. Unreacted substances and the solvent were removed from the filtrate at 120 to 130 ° C. under a reduced pressure of 5 torr. 10 g of N, N′-dimethylacetamide was added as a rearrangement accelerator, and Claisen rearrangement was performed at 200 ° C. ± 5 ° C. for 6 hours under a nitrogen stream. A pale yellow liquid o-allylated cresol was obtained. This was dissolved in 62.5 g (5 mol) of ECH, and 81.6 g (1 mol) of a 49% aqueous sodium hydroxide solution was added dropwise at 45 to 55 ° C. over 4 hours. During this period, water generated under a reduced pressure reflux of 140 to 160 torr was separated and removed. After maintaining the same temperature for 1 hour, ECH was recovered at 120 ° C. under reduced pressure of 5 torr. 370 g of methyl isobutyl ketone and 230 g of water were added to dissolve and remove the salt. After washing twice with the same amount of water, the pH was adjusted to 6.0 to 6.5 with dilute phosphoric acid, suction filtered, and dried under reduced pressure at 130 ° C. and 5 torr for 30 minutes. (Abbreviation) 195 g was obtained. This product had an epoxy equivalent of 208.2 g / eq and an iodine value of 167.4 I / 100 g.

Example 1 (AGE equimolar addition to a carboxylic acid group)
In a 500 ml separable flask, 250 g of the modified polyhydroxy ether resin solution (A1) obtained in Synthesis Example 1 (0.114 mol of carboxyl group), 13 g of allyl glycidyl ether (AGE manufactured by NOF Corporation) (epoxy group 0.114) Mol), 0.011 g of TPP and 13 g of MDM were added as catalysts, reacted at 100 ° C. for 5 hours, added with 0.11 g of TPP, and further reacted for 5 hours to react with the polyhydroxy ether resin having an allyl group in the side chain of the present invention ( B1) was obtained. The solid content was adjusted to about 30 wt% with MEK. Table 2 shows the properties of this resin.

Example 2 (0.6 mol addition of AGE to carboxylic acid group)
250 g (carboxyl group 0.114 mol), AGE 7.8 g (epoxy group 0.068 mol), and MDM 8 g obtained in Synthesis Example 1 were added in the same manner as in Example 1 except that 250 g (carboxyl group 0.114 mol) was obtained. A polyhydroxy ether resin (B2) having an allyl group in the side chain of the present invention was obtained. Table 2 shows the properties of this resin.

Example 3 (0.5 mol addition of AGE to carboxylic acid group)
250 g (carboxyl group 0.167 mol), AGE 9.59 g (epoxy group 0.084 mol), and MDM 20 g obtained in Synthesis Example 2 were added in the same manner as in Example 1 except for 250 g (A2) of the modified polyhydroxypolyether resin solution (A2). A polyhydroxy ether resin (B3) having an allyl group in the side chain of the present invention was obtained. Table 2 shows the properties of this resin.

Example 4 (ACGE equimolar addition to a carboxylic acid group)
250 g (carboxyl group 0.222 mol) of the modified polyhydroxypolyether resin solution (A2) obtained in Synthesis Example 2, 46.2 g of ACGE (epoxy group 0.222) produced in Synthesis Example 4, MDM 47 g, and TPP 0 .014 g was added and reacted at 80 ° C. for 5 hours, and then 0.014 g of TPP was added and reacted for another 5 hours. Finally, the solid content was adjusted to about 30 wt% with MEK to obtain a polyhydroxy ether resin (B4) having an allyl group in the side chain of the present invention. Table 2 shows the properties of this resin.

Comparative Example 1 (GMA equimolar addition to carboxylic acid group)
250 g of modified polyhydroxy ether resin solution (A2) obtained in Synthesis Example 2 (carboxyl group 0.222 mol), 31.5 g of glycidyl methacrylate (Nippon Yushi Co., Ltd. GMA) (epoxy group 0.222 mol), MDM 32 g And 19 mg of hydroquinone monomethyl ether were added, reacted for 5 hours at 95 ° C. while blowing air, added 0.013 g of TPP and further reacted for 5 hours to produce an α-β unsaturated group-containing half-esterified modified polyhydroxy ether ( B5) was obtained, but the viscosity was significantly increased. Table 2 shows the properties of this resin.

Example 5 (photosensitive resin composition)
200 g of polyhydroxy ether (B3) having an allyl group in the side chain obtained in Example 3, 57.1 g of cresol novolac epoxy acrylate (EA-7120 / PGMAC Shin-Nakamura Chemical Co., Ltd., solid content 70%) 57.1 g photopolymerization As an initiator, 5 g of Irgacure 907 was diluted with MEK to a solid content concentration of 20%. This solution was applied onto a PET film using a bar coater and dried with a hot air dryer at 40 ° C. A 15 micron transparent film was obtained. When this film was exposed with a UV irradiation apparatus (HMW-590 manufactured by Oak Seisakusho Co., Ltd.) at an exposure amount of 500 J / cm ² and further heated at 160 ° C. for 30 minutes, a tough and flexible crosslinked film that did not dissolve in MEK was obtained. Obtained.

Example 6 and Comparative Example 2 (thermosetting resin composition)
100 parts of polyhydroxy ether (B1 to B4) having an allyl group in the side chain obtained in Examples 1 to 4 (solid content: 30%), di-tert-butyl peroxide (manufactured by NOF Corporation) as a peroxide Perbutyl D) 1.2 parts, MEK 50 g, and cyclohexanone 50 g were added and mixed uniformly. This was applied to a PET film using a bar coater, dried with a hot air dryer at 80 ° C., and peeled to obtain a transparent heat-bonding film having a film thickness of about 10 to 15 microns.
The five transparent heat-bonding films were sandwiched between two previously degreased 25 mm × 150 mm × 1 mm mild steel plates and cured with a hot press at 180 ° C. for 5 minutes. For comparison, a PHE (phenototo YP-50S (BPA-type PHE manufactured by Toto Kasei Co., Ltd.)) having no allyl group in the side chain was prepared without adding a peroxide to obtain an adhesion test piece. The results of measuring the adhesive strength at 25 ° C. and 100 ° C. are shown in Table 3.

  The polyhydroxy ether resin having an allyl group in the side chain of the present invention does not generate gel particles or the like in the production stage, and the composition is excellent in good photocurability and thermosetting and adhesive strength. It is an effective resin for paints, adhesives, electronic materials, etc.

Each gel permeation chromatograph (GPC) chart of the main chain PHE used in Synthesis Example 2 Gel permeation chromatograph (GPC) chart of polyhydroxy ether (B3) having an allyl group in the side chain of Example 3 FT-IR spectrum of main chain PHE used in Synthesis Example 2 FT-IR spectrum of polyhydroxy ether (B3) having an allyl group in the side chain of Example 3

Claims (10)

A polyhydroxy ether resin having an allyl group in the side chain represented by the general formula (1), wherein the main chain polyhydroxy ether has a number average molecular weight of 1,000 or more and 200,000 or less. Hydroxy ether resin.

(In the formula, R ₁ is a polybasic acid anhydride residue, R ₂ is an allyl group-containing glycidyl compound residue, M is a divalent phenol residue, which may be the same or different, and l, m and n are (It may be an integer and m may be 0. p is an integer of 1 to 3.) A polyhydroxy ether whose main chain polyhydroxy ether is selected from bisphenol A type, bisphenol F type, bisphenol A / bisphenol F copolymer type, tetrabromobisphenol A type, bisphenol sulfone type, biphenyl type, and phosphorus-containing dihydric phenol type 2. The polyhydroxy ether resin according to claim 1, wherein 2. The polyhydroxy ether resin according to claim 1, wherein the polybasic acid anhydride is trimellitic acid anhydride, and the allyl group-containing glycidyl compound is allyl glycidyl ether. The polyhydroxy ether resin according to any one of claims 1 to 3, wherein the allyl group-containing glycidyl compound is a glycidyl ether of an allylated (alkyl) monophenol. 0.1 to 0 with respect to 1 mol of hydroxyl group of the polyhydroxy ether resin obtained by either the condensation reaction of dihydric phenol and epichlorohydrin or the addition polymerization reaction of dihydric phenol and divalent glycidyl compound. The side chain according to claim 1, comprising adding a polybasic acid anhydride within a range of 9.9 moles, and reacting a carboxyl group produced thereafter with 0.5 mole or more of an allyl group-containing glycidyl compound. A method for producing a polyhydroxy ether resin having an allyl group. A polyhydroxy ether whose main chain polyhydroxy ether is selected from bisphenol A type, bisphenol F type, bisphenol A / bisphenol F copolymer type, tetrabromobisphenol A type, bisphenol sulfone type, biphenyl type, and phosphorus-containing dihydric phenol type The method for producing a polyhydroxy ether resin according to claim 5. The method for producing a polyhydroxy ether resin according to claim 5, wherein the polybasic acid anhydride is trimellitic acid anhydride and the allyl group-containing glycidyl compound is allyl glycidyl ether. The method for producing a polyhydroxy ether resin according to any one of claims 5 to 7, wherein the allyl group-containing glycidyl compound is a glycidyl ether of an allylated (alkyl) monophenol. 2. A resin composition comprising at least 5% by weight or more of a polyhydroxy ether resin having an allyl group in a side chain according to claim 1. 2. A heat-sensitive material obtained from a resin composition comprising at least 5% by weight or more of a polyhydroxy ether resin having an allyl group in the side chain according to claim 1, and containing an organic peroxide or a photopolymerization initiator. Or a photosensitive resin film.

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