JP2015063595A - High molecular weight epoxy resin, epoxy resin composition and cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high molecular weight epoxy resin suitable for an adhesive agent having high flexibility and high adhesiveness and excellent transparency, chemical resistance, compatibility and solubility and to provide an epoxy resin composition and a cured product using the same.SOLUTION: There is provided a high molecular weight epoxy resin having a Mw of 10000 to 300000 and an epoxy equivalent of 5000 to 30000 g/eq, which is obtained by reacting an ester skelton-containing aliphatic dicarboxylic acid (A) obtained from a diol compound (a1) having an Mn of 800 or more and an acid anhydride (a2) with a difunctional aromatic epoxy resin (B) in a molar ratio (A)/(B) of the carboxyl group of the ester skelton-containing aliphatic dicarboxylic acid (A) to the epoxy group of the difunctional aromatic epoxy resin (B) in the of range of 1/1.001 to 1/1.050.

Description

  The present invention relates to a high molecular weight epoxy resin having high flexibility, high adhesion, excellent transparency, chemical resistance, compatibility, and solubility, a high molecular weight epoxy resin composition using the high molecular weight epoxy resin, and It relates to a cured product.

  Epoxy resins are widely used in the fields of paint, civil engineering, adhesion, and electrical applications because they are excellent in heat resistance, adhesion, chemical resistance, water resistance, mechanical strength, electrical properties, and the like. For example, as an adhesive application, it is known that a secondary hydroxyl group generated when an epoxy group reacts contributes to adhesion, and is widely used. On the other hand, high molecular weight epoxy resins can be added to base resins for paints and film molding, flow regulators to adjust fluidity by adding to epoxy resin varnish, additives to improve toughness when cured. It is used.

  However, the cured epoxy resin has hard and brittle properties, and it has become difficult to meet the performance required for paints, electrical / electronic materials, adhesives, CFRP, etc., which have been required in recent years. There is a need for an epoxy resin imparted with flexibility.

  In order to improve such properties, for example, in Patent Documents 1 and 2, a siloxane skeleton is introduced into the epoxy resin. However, the flexibility is low, the compatibility with other materials is poor, and the handling is difficult. . In Patent Document 3, an oxetane skeleton is introduced into an epoxy resin, but this also has low flexibility and low adhesion. In Patent Document 4, an epoxy resin and a carboxylic acid are reacted to synthesize an ester type epoxy resin. However, since the molecular chain of the carboxylic acid used is short, flexibility is low. In Patent Document 5, flexibility is given by blending a rubber component with polyhydroxypolyether as a polymer material, but blending rubber may adversely affect physical properties such as electrical characteristics. It is mentioned as a drawback.

JP 2004-75769 A JP 2007-106852 A JP 2001-187814 A JP 2009-29933 A JP 2007-177054 A

  Accordingly, an object of the present invention is to provide a high molecular weight epoxy resin having high flexibility and high adhesiveness, and having excellent transparency, chemical resistance, compatibility, and solubility, a high molecular weight epoxy resin composition using the same, and curing. To provide things.

（式中、Ｚは炭素数４〜１２の２価の飽和環状脂肪族基を表し、縮環構造を有していても良い。ｑは平均の繰り返し数であり、５〜２５０を表す。Ｒ₁は式（２）で表される内部にエステル結合を有する炭素数２０以上の２価の基であり、Ｒ₂、Ｒ₃は炭素数２〜２０の２価の炭化水素基を表し、各々同一でも異なっていても良い。Ｅｓｔはエステル基を表し、ｎは平均の繰り返し数であり、１〜１００の数を表す。Ｙは、式（３）で表される２価の基であり、Ｘは芳香族基を表し、ｔは平均の繰り返し数であり、０〜１００のである。）

The present invention is a high molecular weight epoxy represented by the following general formula (1), having a weight average molecular weight of 10,000 to 300,000 and an epoxy equivalent of 5,000 to 30,000 g / eq. Resin.

(In the formula, Z represents a divalent saturated cycloaliphatic group having 4 to 12 carbon atoms, and may have a condensed ring structure. Q is an average number of repetitions and represents 5 to 250. R ₁ is a divalent group having 20 or more carbon atoms having an ester bond inside represented by the formula (2), R ₂ and R ₃ each represent a divalent hydrocarbon group having 2 to 20 carbon atoms, May be the same or different, Est represents an ester group, n is an average number of repetitions, and represents a number of 1 to 100. Y is a divalent group represented by Formula (3), X represents an aromatic group, t is the average number of repetitions, and is 0-100.)

In the general formula (1), it is preferable that either X is represented by the formula (4) or R ₁ is a divalent group represented by the formula (6).

（式中、Ｄは単結合、または、―ＣＨ₂―、−Ｃ（ＣＨ₃）₂−、−ＣＨ（ＣＨ₃）−、−Ｓ−、−ＳＯ₂−、−Ｏ−、−ＣＯ−、及び下記式（５）で表わされる基からなる群れから選ばれる２価の基であり、ＥおよびＧは、水素原子、炭素数１〜４のアルキル基、フェニル基のいずれかを表し、複数のＥおよびＧ各々同一でも異なっていても良い。）

(In the formula, D is a single bond, or —CH ₂ —, —C (CH ₃ ) ₂ —, —CH (CH ₃ ) —, —S—, —SO ₂ —, —O—, —CO—, And a divalent group selected from the group consisting of groups represented by the following formula (5), E and G each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, E and G may be the same or different.)

（式中、Ｒ₄は炭素数４〜１２の２価の炭化水素基を表し、各々同一でも異なっていても良い。ｍは平均の繰り返しであり、１〜５０の数を表す。Ｒ₂は式（２）と同意である。）

(In the formula, R ₄ represents a divalent hydrocarbon group having 4 to 12 carbon atoms, and each may be the same or different. M is an average repetition and represents a number of 1 to 50. R ₂ represents (It is in agreement with equation (2).)

（式中、ｋは平均の繰り返しであり、１〜２０の数を表す。Ｒ₄は式（６）と同意である。） More preferable R ₁ includes a divalent group represented by the formula (7).

(In the formula, k is an average repetition and represents a number of 1 to 20. R ₄ is the same as the formula (6).)

  The high molecular weight epoxy resin preferably has a glass transition point (Tg) of 0 ° C. or lower in the measurement by differential scanning calorimetry (DSC).

  Further, the present invention provides a diol compound (a1) having a number average molecular weight of 800 or more and an acid anhydride (a2) in a molar ratio (a1) / (a2) of 1/200 to 1 / 2.05. The ester skeleton-containing aliphatic dicarboxylic acid (A) and the bifunctional aromatic epoxy resin (B) obtained by the esterification reaction under the conditions to become the carboxyl group of the ester skeleton-containing aliphatic dicarboxylic acid (A) and the bifunctional It is a method for producing a high molecular weight epoxy resin, wherein the molar ratio (A) / (B) of the epoxy groups of the aromatic epoxy resin (B) is reacted at 1 / 1.001 to 1 / 1.050.

  It is preferable that the epoxy equivalent of the said bifunctional aromatic epoxy resin (B) is 170-1500 g / eq.

  Furthermore, the present invention is a high molecular weight epoxy resin composition comprising the above high molecular weight epoxy resin, and the above high molecular weight epoxy resin composition further comprising another epoxy resin, an epoxy resin curing agent and an additive. It is a thing. Moreover, it is an adhesive agent which consists of said high molecular weight epoxy resin composition.

  The high molecular weight epoxy resin of the present invention can have high flexibility. Furthermore, since this high molecular weight epoxy resin is excellent in adhesiveness, transparency, and chemical resistance, it is highly useful as an adhesive, an optical material, and a polymer actuator. Moreover, since it is excellent in compatibility with other materials and in organic solvents, it can be mixed with various materials, and there is an advantage that the performance can be easily controlled.

It is IR spectrum of the high molecular weight epoxy resin of this invention.

Hereinafter, embodiments of the present invention will be described in detail.
The high molecular weight epoxy resin of the present invention is represented by the general formula (1), has a weight average molecular weight (Mw) of 10,000 to 300,000, and an epoxy equivalent of 5,000 to 30,000 g / eq. . In formula (1), q is an average number of repetitions and represents 5-250.
Although there is no restriction | limiting in the manufacturing method of this high molecular weight epoxy resin, Preferably the diol compound (a1) which has an ester structure whose number average molecular weight (Mn) is 800 or more, and acid anhydride (a2) are molar ratio. An ester skeleton-containing aliphatic dicarboxylic acid (A) obtained by an esterification reaction under the condition that (a1) / (a2) is 1/200 to 1 / 2.05, and a bifunctional aromatic epoxy resin (B ), The molar ratio (A) / (B) between the carboxyl group of the ester skeleton-containing aliphatic dicarboxylic acid (A) and the epoxy group of the bifunctional aromatic epoxy resin (B) is 1 / 1.001 to 1/1. Obtained by reacting at 050. The high molecular weight epoxy resin obtained by the method for producing a high molecular weight epoxy resin of the present invention is not limited as long as it is a high molecular weight epoxy resin obtained by the method, but the high molecular weight epoxy resin of the present invention is preferred.

The diol compound (a1) is a polyester diol having an ester structure, and Mn is 800 or more. Polyester diols having a linear structure and Mn of 1000 to 10,000 are preferred. As such a polyester diol, Kuraray Polyols P-1010, P-2010, P-3010, etc. can be used.
Since the polyester diol gives R ₁ in the general formula (1), the details will be understood from the description of R ₁ described later. R ₁ is understood to be a residue that excludes two OH groups from the polyester diol.

R ₁ is a divalent hydrocarbon group having 20 or more carbon atoms having an ester bond inside represented by the above formula (2), and represents a structure having a molecular weight distribution. In formula (2), Est represents an ester group. There are two types of ester groups, -C (O) -O- and -OC (O)-, but either form may be used.

In formula (2), R ₂ and R ₃ represent a divalent hydrocarbon group having 2 to 20 carbon atoms, and may be the same or different. Examples of such a group include, but are not limited to, ethylene group, propylene group, butylene group, pentylene group, 3-methylpentylene group, hexylene group, octylene group, decylene group, dodecylene group, stearylene group, and the like. Not. Preferably, it is a C2-C12 alkylene group.

  In the formula (2), n is an average number of repetitions and represents a number of 1 to 100, preferably Mn in a state in which two OH groups are added to be 800 to 10,000. In this specification, the average number of repetitions means number average. And carbon number which comprises Formula (2) will be 20 or more. Preferred n is a number having more than 20 carbon atoms and a molecular weight (Mn) of the group represented by the formula (2) in the range of 1000 to 5000, more preferably in the range of 1000 to 3000.

  Among the structures represented by the formula (2), a preferable form capable of improving the effect of the present invention is a divalent polyester structure represented by the above formula (6) or the formula (7).

In the formula (6), R ₄ represents a divalent hydrocarbon group having 4 to 12 carbon atoms, and may be the same or different. Examples of the divalent hydrocarbon group include an ethylene group, a propylene group, a butylene group, a pentylene group, a 3-methylpentylene group, a hexylene group, an octylene group, a decylene group, and a dodecylene group. m is an average repetition, is a number of 1 to 50, and represents a number with 20 or more carbon atoms constituting the formula (6). Preferred m is the same as that described for n in the formula (2). R ₂ is the same as in formula (2).

In Formula (7), k is an average repetition, represents the number of 1-20, and represents the number from which the carbon number which comprises Formula (6) becomes 20 or more. R ₄ is the same as in formula (6).

  The acid anhydride (a2) is not particularly limited as long as it is an aliphatic dicarboxylic acid anhydride, but is preferably a saturated cyclic aliphatic dicarboxylic acid anhydride having 6 to 14 carbon atoms, for example, cyclobutane-1, 2-dicarboxylic acid anhydride, cyclopentane-1,2-dicarboxylic acid anhydride, cyclohexane-1,2-dicarboxylic acid anhydride, 3-methylcyclohexane-1,2-dicarboxylic acid anhydride, 4-methylcyclohexane-1 , 2-dicarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, and the like. However, it is not limited to these, It is used individually or in combination of 2 or more types. A preferred acid anhydride compound is cyclohexane-1,2-dicarboxylic acid anhydride from the viewpoint of ease of reaction operation.

  It is understood that the acid anhydride (a2) gives Z in the general formula (1). Z is understood to be a residue obtained by removing an acid anhydride group from an acid anhydride. Z represents a divalent saturated cycloaliphatic group having 4 to 12 carbon atoms which may have a condensed ring structure inside, and may have a substituent. Examples of Z include a cyclobutanylene group, a cyclopentylene group, a cyclohexylene group, a methylcyclohexylene group, a cycloheptylene group, a norbornylene group, a methylnorbornylene group, a decahydronaphthylene group, and a bicyclohexylene group. It is not limited to these. Preferred is a cyclohexylene group.

  The aliphatic dicarboxylic acid (A) can be obtained by a ring-opening esterification reaction of the diol compound (a1) and the acid anhydride (a2). By making the esterification reaction a condition that the molar ratio (a1) / (a2) is 1/200 to 1 / 2.05, the ester skeleton-containing aliphatic dicarboxylic acid (A) having a carboxy group at the terminal Can be obtained. It is also possible to control the molecular weight of the aliphatic dicarboxylic acid (A) by changing the molar ratio within the above range. It is understood that the aliphatic dicarboxylic acid (A) gives -OC-Z-COO-R1-OCO-Z-CO- in the general formula (1).

  In the ring-opening esterification reaction, the molar ratio (a1) / (a2) between (a1) and (a2) is 1/200 to 1 / 2.05, more preferably 1/200. 1 / 2.03. The reaction rate to the ester skeleton-containing aliphatic dicarboxylic acid (A) obtained by this reaction is preferably 95% or more. At this time, it is necessary that the acid anhydride is completely ring-opened and does not remain as an unreacted acid anhydride, and further it is necessary that the hydroxyl group-containing compound does not remain alone. The presence or absence of residual acid anhydrides can be confirmed using known methods such as acid value measurement and gas chromatography.

  The aliphatic dicarboxylic acid (A) and the bifunctional aromatic epoxy resin (B) have a molar ratio (A) / (B) of the epoxy group to the carboxyl group of 1 / 1.001 to 1 / 1.050. React with conditions. By using the bifunctional aromatic epoxy resin (B) in excess of the theoretical amount, both ends can be converted into epoxy groups, and the degree of polymerization can be controlled by controlling the molar ratio within the above range.

  In this reaction, by setting the molar ratio of the carboxyl group of (A) to the epoxy group of (B) within the above range, preferably 1 / 1.005 to 1 / 1.030, an epoxy group is introduced at the terminal, and the hue Will be better. Moreover, the epoxy equivalent of the high molecular weight epoxy resin obtained shall be 5000-30000 g / eq. This is because when the epoxy equivalent exceeds 30000 g / eq, a carboxyl group tends to remain at the end, and conversely, when the epoxy equivalent is less than 5000 g / eq, the molecular weight is 10,000 or less even if the ends are all epoxy groups. turn into. The epoxy equivalent is more preferably 8000 to 25000 g / eq.

It is understood that the bifunctional aromatic epoxy resin (B) gives Y in the general formula (1). Y is represented by Formula (3). In the formula (3), t is an average number of repetitions and represents a number of 0 to 100, and X is understood to be a residue obtained by removing two epoxy groups from the bifunctional aromatic epoxy resin (B), preferably It is represented by Formula (4). In the formula (4), D is a single bond or a divalent group described later. Examples of the divalent group include —CH ₂ —, —C (CH ₃ ) ₂ —, —CH (CH ₃ ) —, —S—, —SO ₂ —, —O—, —CO—, or the formula (5 ) Represented by a divalent group. In the formulas (4) and (5), E and G each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and a plurality of E or a plurality of G may be the same or different. good.

  The bifunctional aromatic epoxy resin (B) is preferably a bifunctional aromatic epoxy resin obtained by glycidyl etherification of a bifunctional aromatic phenol. Preferred bifunctional aromatic phenols and bifunctional aromatic epoxy resins obtained therefrom include bisphenol A (BPA), bisphenol F, bisphenol S, 4,4′-biphenol, tetramethylbisphenol A, dimethylbisphenol A, and tetramethyl. Bisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S, dimethyl bisphenol S, biphenyl, tetramethylbiphenyl tetramethyl-4,4′-biphenol, dimethyl-4,4′-biphenol, 1- (4-hydroxyphenyl) -2 -[4- (1,1-bis- (4-hydroxyphenyl) ethyl) phenyl] propane, 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidene- Screw (3-methyl) -6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, 1,1-di-4-hydroxyphenylfluorene and other bifunctional aromatic phenols, and bifunctional aromatic epoxy resins obtained therefrom. . These may be used alone or in combination of two or more. More preferable bifunctional aromatic epoxy resins include BPA epoxy resins from the viewpoint of ease of reaction operation. Further, the epoxy equivalent of the bifunctional aromatic epoxy resin (B) is preferably 170 to 1500 g / eq. If the epoxy equivalent is 170 g / eq or less, it is difficult to produce a film of the resulting polymer epoxy resin. Conversely, if the epoxy equivalent is 1500 g / eq or more, the viscosity is too high, making synthesis and blending difficult. Cheap. More preferably, it is 500-1200 g / eq.

  The molecular weight of the high molecular weight epoxy resin of the present invention is 10,000 to 300,000. If the molecular weight is 10,000 or less, the film properties are deteriorated. Conversely, if the molecular weight is 300,000 or more, the viscosity becomes too high and handling becomes difficult. More preferably, it is 20000 to 200000.

  Next, the epoxy resin composition of the present invention will be described. The epoxy resin composition of the present invention includes a composition containing the high molecular weight epoxy resin of the present invention, another epoxy resin compatible with the high molecular weight epoxy resin of the present invention, an epoxy resin curing agent and an additive. And a composition. Since the former composition does not require a curing agent, when the curing agent is not blended, it can be used as a thermoplastic resin in the same manner as the phenoxy resin. When a curing agent is blended or the latter composition is a resin that can be thermally cured.

  The high molecular weight epoxy resin of the present invention can be blended with various known resins as long as they are compatible. For example, other epoxy resins, phenoxy resins, acrylic resins, and the like can be given. Preferably, the following compounds may be mentioned, but the present invention is not limited thereto. For example, as an epoxy resin, phenol novolak type, orthocresol novolak type, cresol novolak type, dicyclopentadiene type, biphenyl type, fluorene bisphenol type, triazine type, naphthol type, naphthalenediol type, triphenylmethane type, tetraphenyl type, Examples thereof include epoxy resins such as bisphenol A type, bisphenol F type, bisphenol AD type, bisphenol S type, and trimethylolmethane type. Examples of the phenoxy resin include bisphenol A type, bisphenol A / F type, bisphenol F type, bisphenol S type, bisphenol A / S type, cardo skeleton type and the like. Examples of the acrylic resin include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) Acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol te La (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate, etc. (meth) resins obtained by polymerizing acrylic acid esters. These compounds can be used alone or in combination of two or more thereof. These resins are unreacted even if they are compatible with the high molecular weight epoxy resin of the present invention. At this time, in order to obtain high flexibility, it is preferable that the ratio of the high molecular weight epoxy resin of the present invention is larger than various resins to be blended.

  The high molecular weight epoxy resin of the present invention can be blended and cured with various other known epoxy resins, epoxy resin curing agents, and additives as long as they are compatible. For example, other epoxy resins include phenol novolac, orthocresol novolak, cresol novolak, dicyclopentadiene, biphenyl, fluorene bisphenol, triazine, naphthol, naphthalenediol, triphenylmethane, tetraphenyl Examples include, but are not limited to, epoxy resins such as phenyl type, bisphenol A type, bisphenol F type, bisphenol AD type, bisphenol S type, and trimethylolmethane type. These compounds can be used alone or in combination of two or more thereof.

  When the epoxy resin composition containing the high molecular weight epoxy resin of the present invention is cured, it can be cured by heat or light. The cured product of the present invention is obtained by curing this epoxy resin composition.

  Accordingly, examples of the curing agent include amine curing agents, imidazole curing agents, phenol curing agents, acid anhydride curing agents, and ultraviolet curing agents. Preferably, the following compounds may be mentioned, but the present invention is not limited thereto. For example, organic amine compounds, dicyandiamide and derivatives thereof, imidazoles and derivatives thereof such as 2-methylimidazole and 2-ethyl-4-methylimidazole, bisphenol A, bisphenol F, brominated bisphenol A, naphthalenediol, 4,4′- Dihydric phenol compounds such as biphenol, novolak resin or aralkyl phenol resin obtained by condensation reaction of phenol or naphthols with formaldehyde or xylylene glycols, succinic anhydride, maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride Acid anhydrides such as methylated hexahydrophthalic anhydride, nadic anhydride, hydrogenated nadic anhydride, trimellitic anhydride, pyromellitic anhydride, hydrazide compounds such as adipic hydrazide, Benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin-iso-propyl ether, α-methylbenzoin, α-hydroxyisobutylphenone, benzophenone, p-methylbenzophenone, p-chlorobenzophenone, p-diethylaminobenzophenone, etc. Benzophenones, acetophenone, 9,10-anthraquinone, 1-chloroanthraquinone, anthraquinones such as 2-chloroanthraquinone, sulfur-containing compounds such as diphenyldisulfide, tetramethylthiuram disulfide, etc. can be applied, if necessary Two or more types may be used.

  Furthermore, examples of the additive include a curing accelerator, a dispersant, a filler, and an antioxidant. Preferably, the following compounds may be mentioned, but the present invention is not limited thereto. Examples of the curing accelerator include tertiary amines and salts thereof, imidazoles and salts thereof, organic phosphine compounds and salts thereof, and organic metal salts such as zinc octylate and tin octylate. The above may be used. Examples of the dispersant include a cationic polymer dispersant, an anionic polymer dispersant, a nonionic polymer dispersant, a pigment derivative dispersant (dispersion aid), and the like. Examples of the filler include polyethylene powder, polypropylene powder, quartz, silica, silicate, calcium carbonate, magnesium carbonate, gypsum, bentonite, fluorite, titanium dioxide, carbon black, graphite, iron oxide, aluminum powder, iron powder. , Talc, mica, kaolin clay and the like. Antioxidants include 2,6-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-tert-butyl-p-ethylphenol, stearyl-β- (3,5-di-tert- Monophenols such as butyl-4--4-hydroxyphenyl) propionate, 2,2-methylenebis (4-methyl-6-tert-butylphenol), 2,2-methylenebis (4-ethyl-6-tert-butylphenol), Bisphenols such as 4,4′-thiobis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3 , 5-Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) Polymer, phenols such as tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 9,10-dihydro-9-oxa-10-phosphaphenanthrene -10-oxide, 10- (3,5-di-tert-butyl 4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10 Oxaphosphaphenanthrene oxides such as dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, dilauryl 3,3′-dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-dilauryl 3 , 3'-thiodipropionate, distearyl 3,3'-dilauryl 3 , 3'-thiodipropionate, pentaerythrityl tetrakis (3-lauryl thiopropionate), and other ester skeleton-containing thioether compound-based antioxidants. Two or more of these antioxidants may be used as necessary.

  The high molecular weight epoxy resin of the present invention can be used as an adhesive regardless of the presence or absence of a curing agent. When used as an adhesive, no solvent or a predetermined solvent, for example, amide solvents such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N-methyl-2-pyrrolidone (NMP), 1- Mixing one or more of ether solvents such as methoxy-2-propanol, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and cyclopentanone, and aromatic solvents such as toluene and xylene It may be used after it is dissolved or dispersed in a varnish to form it, and the components constituting the composition do not necessarily have to be dissolved in the solvent as long as they are uniformly dispersed in the solvent.

  When used as a varnish, the varnish may be applied on a base film as a support material and dried to form a film adhesive, or the varnish may be applied on a substrate and dried. You may form a base material with a film adhesive by. Here, as for the film support before curing in the film-like adhesive or the substrate with the film-like adhesive, the higher the solvent residual rate, the better the film support property, but when the solvent residual rate is too high The film-like adhesive or the equipment with the film-like adhesive may be tacked or foamed when cured. Therefore, the solvent residual ratio is preferably 5% by weight or less. Moreover, about the said film adhesive and copper foil with a film adhesive, after apply | coating the epoxy resin composition of this invention which does not contain a solvent on the base film as a support material in a heat-melting state, it is made to cool. May be obtained.

  Next, the present invention will be specifically described based on examples, but the present invention is not limited to the following examples unless it exceeds the gist. In the following synthesis examples, examples and comparative examples, “parts” represents “parts by weight”. In addition, Examples 1-10 show the example of resin itself (thermoplastic resin), Examples 11-13 show the example of the resin composition containing resin of Example 2. FIG.

In the present invention, the following analysis method and measurement method were used.
Epoxy equivalent: The method described in JIS K-7236.

-Total chlorine amount: The method described in JIS K-7243-3.

・ Molecular weight measurement: Calculated by a polystyrene calibration curve using gel permeation chromatography (HLC-8320GPC, manufactured by Tosoh Corporation, elution solvent: tetrahydrofuran, flow rate: 1 ml / min, column temperature: 40 ° C., detection: RI detector). The area ratio (area%) of the elution distribution occupied by the molecular weight of the monomer component in the total molecular weight distribution to be eluted was determined.

Water absorption rate: A method according to JIS C6481 5.14. The weight change before and after immersing a molded substrate with a width of 50 mm in distilled water at 23 ° C. for 24 hours was calculated.

-Breaking elongation: The obtained resin was formed into a film by pressing and cut into a width of 10 mm and a length of 50 mm. For measurement, an autograph EZ-S manufactured by Shimadzu Corporation was used, and the breaking elongation and the maximum point stress of the test piece were measured with a measurement length of 30 mm. The pulling speed at this time was 1 mm / min.

-Differential scanning calorimetry (DSC): The obtained resin film was punched, laminated, and packed in aluminum capsules as measurement samples. The measurement temperature range was -70 to 150 ° C. The heating rate was 10 ° C./min. The measurement was performed for 2 cycles, and from the DSC chart obtained in the second cycle, the extrapolated glass transition start temperature (Tig) was defined as Tg (DSC) of the high molecular weight epoxy resin.

Thermogravimetry: The measurement was carried out using a differential thermogravimetry apparatus under a nitrogen stream at a heating rate of 10 ° C./min. The temperature at the time of 1 wt% weight reduction, the temperature at the time of 5 wt% weight reduction, and the decomposition start temperature were determined.

-Chemical resistance: The method described in JIS A1454. 10% NaOH and 10% HCl were used as chemicals, the immersion time was 24 hours, and the change in weight after immersion was measured.

-Refractive index: The refractive index of the obtained film was measured using the Abbe refractometer.

Adhesive strength: The method described in JIS K-6850. A SUS347 test piece was coated with a varnish and dried at 150 ° C. for 1 hour, and a sample having a thickness of 10 μm was measured.

Example 1
In a reactor equipped with a stirrer, a thermometer, a nitrogen blowing tube, and a cooling tube, 38.4 parts of hexahydrophthalic anhydride (HHPA) as an acid anhydride (a2) and polyester diol (P-2010) as a diol compound (a1) ) A mixture of 250.0 parts and 32.0 parts of xylene was reacted at 120 ° C. for 3 hours with stirring in a nitrogen gas atmosphere to obtain an ester skeleton-containing dicarboxylic acid, and then a bifunctional BPA type epoxy resin (YD- 014) 238.2 parts of xylene, 40.9 parts of xylene, and 0.06 part of n-butyltriphenylphosphonium bromide (TPP-BB) as a catalyst were added and stirred at 165 ° C. for 4 hours to give Mw 100,000, epoxy equivalent of 9 , 000 g / eq high molecular weight epoxy resin (ER1) was obtained. The IR spectrum of ER1 is shown in FIG.

Examples 2-10
Using the apparatus used in Example 1, synthesis was performed under the same conditions and operations as in Example 1 at the ratios shown in Tables 1 and 2, to obtain high molecular weight epoxy resins (ER2 to 10), respectively. The molecular weight and epoxy equivalent of the obtained resin are also shown in Tables 1 and 2, respectively. The number of the raw material indicates the blending amount (part). The high molecular weight epoxy resin obtained in Example 2 is referred to as ER2, and the same shall apply hereinafter.

The raw materials used are shown below.
(a1) component
P-2010: Polyester diol, Kuraray Polyols P-2010 manufactured by Kuraray Co., Ltd., Mn2,000, alcoholic hydroxyl group equivalent of 1000 g / mol, average carbon number of about 100
P-1010: Same as above, Mn1,000
P-3010: Same as above, Mn3,000
(a2) component
HHPA: Hexahydrophthalic anhydride, Shin Nippon Rika Co., Ltd. Rikacid HH, acid anhydride equivalent 185g / eq
MH-700: Hexahydrophthalic anhydride / methylhexahydrophthalic acid, Ricacid MH-700, acid anhydride equivalent 163g / eq
HNA-100: Methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride / bicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, Ricacid HNA-100, acid anhydride equivalent 185 g / eq
YD-014: Solid bisphenol A type epoxy resin, YD-014 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 950g / eq, softening point 96 ° C, 150 ° C melt viscosity 6500mPa · s
(B) component
YD-128: Liquid bisphenol type epoxy resin Epoxy equivalent 188g / eq
YDF-2004: Solid bisphenol F type epoxy resin Epoxy equivalent 950g / eq
(Catalyst etc.)
TPP-BB: n-butyltriphenylphosphonium bromide
TPP-EI: Ethyltriphenylphosphonium iodide
TEAB: Tetraammonium bromide

Example 11
8.0 parts of the high molecular weight epoxy resin (ER2) obtained in Example 2 and 8.0 parts of YP-50S (bisphenol A-type phenoxy resin, average molecular weight 50000; manufactured by Nippon Kayaku Epoxy Co., Ltd.) are added to MEK (methyl ethyl ketone) 24 The varnish obtained by dissolving in 0.0 part was dried in a vacuum oven at 150 ° C. for 3 hours to obtain a high molecular weight epoxy resin composition (ERC1).

Examples 12 and 13
In the same manner as in Example 11, blending was performed under the same conditions and operations as in Synthesis Example 1 at the ratios shown in Table 3, to obtain resin compositions (ERC2, 3), respectively.

Comparative Examples 1 and 2
In a flask equipped with a stirrer, thermometer, nitrogen gas inlet tube, and reflux condenser, 210 parts of methyl ethyl ketone, 95.9 parts of YD-8125 (manufactured by Tohto Kasei Co., Ltd., bisphenol A type n = 0 epoxy resin), 35 terephthalic acid .3 parts, 8.8 parts of isophthalic acid and 0.5 part of NN′-dimethylbenzylamine were allowed to react at 80 ° C. to give an ester type epoxy resin having an Mw of 13,000 and an epoxy equivalent of 4,000 g / eq (EER1 ) Was synthesized.

  About EER1 obtained by the comparative example 1, and YP-50S (comparative example 2), the test similar to Examples 1-10 was done.

  The measurement results of the resins or resin compositions of Examples 1 to 13 and Comparative Examples 1 and 2 are shown in Tables 4 to 6.

  As shown in Tables 4 to 6, it was found that the high molecular weight epoxy resin of the present invention and products such as molded products obtained therefrom maintained high adhesive strength while having high elongation at break and low elasticity. It was. On the other hand, Comparative Examples 1 and 2 had high adhesive strength but low elongation at break and high elasticity.

Example 14
14.4 parts of high molecular weight epoxy resin (ER2) obtained in Example 2 and 1.6 parts of YP-128 (liquid epoxy resin, epoxy equivalent 188 g / eq) and dicyandiamide (DICY, active hydrogen equivalent 21 g / eq.) 0.3 part was mix | blended and this was melt | dissolved in 24.0 parts of MEK, and it was set as the resin varnish. This varnish was dried and cured in a vacuum oven at 150 ° C. for 3 hours to obtain a cured product of high molecular weight epoxy resin.

Regarding the physical properties of the obtained cured product, the water absorption was 0.6% and the chemical resistance was also good. The elongation at break was 300%, the maximum point stress was 10 N / mm ² , the glass transition point was 45 ° C., and the adhesive strength was 16.2 MPa. Thus, it was found that when the high molecular weight epoxy resin of the present invention was used as a cured product, the water absorption was low, the elongation at break was high, and the adhesive strength was strong.

Claims (11)

A high molecular weight epoxy resin represented by the following general formula (1), having a weight average molecular weight of 10,000 to 300,000 and an epoxy equivalent of 5,000 to 30,000 g / eq.

(In the formula, Z represents a divalent saturated cycloaliphatic group having 4 to 12 carbon atoms, and may have a condensed ring structure. Q is an average number of repetitions and represents 5 to 250. R ₁ is a divalent group having 20 or more carbon atoms having an ester bond inside represented by the formula (2), R ₂ and R ₃ each represent a divalent hydrocarbon group having 2 to 20 carbon atoms, May be the same or different, Est represents an ester group, n is an average number of repetitions, and represents a number of 1 to 100. Y is a divalent group represented by Formula (3), X represents an aromatic group, t is the average number of repetitions, and is a number from 0 to 100.)

The high molecular weight epoxy resin according to claim 1, wherein X is an aromatic group represented by the formula (4).

(In the formula, D is a single bond, or —CH ₂ —, —C (CH ₃ ) ₂ —, —CH (CH ₃ ) —, —S—, —SO ₂ —, —O—, —CO—, And a divalent group selected from the group consisting of groups represented by the following formula (5), E and G each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, E and G may be the same or different from each other.)

The high molecular weight epoxy resin according to claim 1 or 2, wherein R ₁ is a divalent group represented by the formula (6).

(In the formula, R ₄ represents a divalent hydrocarbon group having 4 to 12 carbon atoms, and each may be the same or different. M is an average repetition and represents a number of 1 to 50. R ₂ represents (It is in agreement with equation (2).) The high molecular weight epoxy resin according to claim 3, wherein R ₁ is a divalent group represented by the formula (7).

(In the formula, k is an average repetition and represents a number of 1 to 20. R ₄ is the same as the formula (6).)   The high molecular weight epoxy resin according to any one of claims 1 to 4, wherein a glass transition point (Tg) in measurement by differential scanning calorimetry (DSC) is 0 ° C or lower.   The molar ratio (a1) / (a2) of the diol compound (a1) having an ester structure having a number average molecular weight of 800 or more and the acid anhydride (a2) is 1/200 to 1 / 2.05. The ester skeleton-containing aliphatic dicarboxylic acid (A) and the bifunctional aromatic epoxy resin (B) obtained by esterification reaction under the conditions, the carboxyl group of the ester skeleton-containing aliphatic dicarboxylic acid (A) and the bifunctional aromatic A process for producing a high molecular weight epoxy resin, comprising reacting the epoxy group (B) at a molar ratio (A) / (B) of 1 / 1.001 to 1 / 1.050.   The epoxy equivalent of bifunctional aromatic epoxy resin (B) is 170-1500 g / eq, The manufacturing method of the high molecular weight epoxy resin of Claim 6 characterized by the above-mentioned.   A high molecular weight epoxy resin composition comprising the high molecular weight epoxy resin according to claim 1.   The high molecular weight epoxy resin composition according to claim 8, further comprising another epoxy resin compatible with the high molecular weight epoxy resin, an epoxy resin curing agent, and an additive.   An adhesive comprising the high molecular weight epoxy resin composition according to claim 8.   A cured product obtained by curing the high molecular weight epoxy resin composition according to claim 9.

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