JP2009096758A - Method for producing curable resin component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for easily producing a colorless curable resin component from an epoxy compound and (meth)acrylic acid anhydride, having extremely low hydroxyl value and low hygroscopicity and usable for forming a cured product having excellent durability such as heat resistance, chemical resistance and scratch resistance and excellent insulation properties and mechanical strength. <P>SOLUTION: The method for producing a curable resin component comprises the ring-opening addition reaction of 0.1-1.0 mol equivalent of (meth)acrylic acid anhydride to 1.0 mol equivalent of the epoxy group in an epoxy compound selected from an epoxy-containing fluorine compound, an epoxy-containing copolymer compound, and an epoxy resin having an aromatic ring group, an alicyclic group, a straight- or branched-chain alkyl group or alkylene group in the presence of a metal-containing compound catalyst. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention produces a curable resin component used as a raw material for molding materials, low dielectric members, and low water absorbing members by ring-opening addition of (meth) acrylic anhydride to a compound containing an epoxy group. It is about how to do.

  Forms products such as home appliances and precision instruments, electronic and optical components, functional coating materials, etc., and exhibits excellent electrical insulation, chemical resistance, and strong mechanical strength A curable resin component is used as a component of the composition forming the surface.

  A curable resin component, particularly an epoxy resin, is used as a resin component of a surface coating composition for printed circuit boards and as a resin component of a sealant composition for electronic components. Among them, the curable unsaturated resin component obtained by reacting an epoxy resin with (meth) acrylic acid is cured by light irradiation, so that it requires excellent processability such as fine patterning. It is widely used as a resin component of the composition.

  Generally, such a curable unsaturated resin component obtained by reacting (meth) acrylic acid and an epoxy resin has a high hydroxyl value because it has many hydroxyl groups in the molecule. The film formed by curing this resin component has high water absorption, coating properties such as mechanical strength, durability such as heat resistance, insulation, chemical resistance and scratch resistance, and sealing performance. It was insufficient.

  As a composition for improving coating characteristics and the like using a curable unsaturated resin component having a reduced hydroxyl value, for example, Patent Document 1 reacts with an epoxy resin and (meth) acrylic anhydride to obtain a double bond equivalent. 200-500, an unsaturated resin containing a (meth) acryloyl group having an ester value of 100-300 and a hydroxyl value of 130 or less, preferably 20-130, an ethylenically unsaturated monomer, and a radical polymerization initiator The curable resin composition containing these is disclosed.

  Such a curable unsaturated resin component containing a (meth) acryloyl group still remains considerably even when the hydroxyl group is reduced, and it is colored or contains a large amount of oligomers and by-products having an undesired molecular weight. It is mixed in. For this reason, the film-like cured product obtained by curing it is not completely colorless and transparent, and still has sufficient coating properties, durability, and sealability required to satisfy the added value of the final product. I can't say that.

  As final products require higher added value such as durability, it is desirable to further improve the curable resin component and improve the coating properties, durability, and sealability of the cured product. ing.

JP 2004-346315 A

  The present invention has been made to solve the above problems, and is obtained from an epoxy compound and (meth) acrylic anhydride, has a very low hydroxyl value, low water absorption, heat resistance, chemical resistance, An object of the present invention is to provide a method for easily producing an uncolored curable resin component, which is used to form a cured product excellent in durability such as scratch resistance, insulation, and mechanical strength.

  The method for producing a curable resin component according to claim 1, which is made to achieve the above object, includes an epoxy group-containing fluoro compound, an epoxy group-containing copolymer compound, an aromatic ring group, and an alicyclic group. In addition, 0.1 mole equivalent of (meth) acrylic anhydride with respect to 1.0 molar equivalent of epoxy group in any epoxy compound selected from epoxy resins containing linear or branched alkyl groups or alkylene groups. ˜1.0 molar equivalent is characterized by ring-opening addition in the presence of a metal-containing compound catalyst.

  The method for producing a curable resin component according to claim 2 is the method according to claim 1, wherein the metal-containing compound catalyst is a metal alkoxide.

  The method for producing a curable resin component according to claim 3 is the method according to claim 2, wherein the metal alkoxide is titanium or zirconium, and the alkoxide group is a straight chain having 1 to 18 carbon atoms. It is derived from a saturated, unsaturated alcohol in the form of a chain, a branched chain or a ring.

  The method for producing a curable resin component described in claim 4 is the method described in claim 1, characterized in that the metal-containing compound catalyst coexists with a promoter containing an acid.

  The method for producing a curable resin component according to claim 5 is the method according to claim 1, wherein the epoxy compound is a linear, branched or cyclic perfluoroalkyl group, a partial fluoroalkyl group, It is the said epoxy group containing fluoro compound containing the perfluoroalkylene group and / or the partial fluoroalkylene group, It is characterized by the above-mentioned.

から選ばれるエポキシ基含有基、
−Ｒｆ−は、-ＣＨ₂-(ＣＦ₂)_m-(ＣＨ₂)_n-(ｍ＝１〜２０、ｎ＝０〜１の整数)、-ＣＨ₂-(ＣＦ₂)_p-Ｃ[-(ＣＦ₂)_q-Ｆ][-(ＣＦ₂)_r-Ｆ]-ＣＨ₂-(ｐ＝１〜１０、ｑ＝０〜２２、ｒ＝１〜２２の整数)、又は-ＣＨ₂-(ＣＦ₂)_s-(-Ｏ-Ｃ_tＦ_2t)_u-Ｏ-(ＣＦ₂)_v-(ＣＨ₂)_w-(ｓ＝１〜３、ｔ＝１〜４、ｕ＝１〜１００、ｖ＝０〜３、ｗ＝０〜１の整数)、
−Ｂは、該Ａ−と同一若しくは異なる前記エポキシ基含有基、-Ｃ_yＦ_2y+1若しくは-ＯＣＨ₂-Ｃ_yＦ_2y+1（ｙ＝１〜２２の整数）、又は-Ｃ_zＦ_2z-1若しくは-ＯＣＨ₂-Ｃ_zＦ_2z-1（ｚ＝３〜２０の整数）である。）
で表されることを特徴とする。 The method for producing a curable resin component according to claim 6 is the method according to claim 5, wherein the epoxy group-containing fluoro compound is represented by the following chemical formula (I):
A-Rf-B (I)
(In the chemical formula (I), A-

An epoxy group-containing group selected from
—Rf— represents —CH ₂ — (CF ₂ ) _m — (CH ₂ ) _n — (m = 1 to 20, n = 0 to 1), —CH ₂ — (CF ₂ ) _p —C [— (CF ₂ ) _q —F] [— (CF ₂ ) _r —F] —CH ₂ — (p = 1 to 10, q = 0 to 22, r = 1 to 22), or —CH ₂ — ( _{CF 2) s - (- O} -C t F 2t) u -O- (CF 2) v - (CH 2) w - (s = 1~3, t = 1~4, u = 1~100, v = 0 to 3, w = 0 to 1 integer),
-B is the A- identical or different the epoxy group-containing group, -C _y F _{2y + 1} or _{-OCH 2 -C y F 2y + 1} (y = 1~22 integer), or -C _z F _2z-1 or a _{-OCH 2 -C z F 2z-1} (z = 3~20 integer). )
It is represented by.

  The method for producing a curable resin component according to claim 7 is the method according to claim 1, wherein the epoxy compound is obtained by copolymerization of an epoxy group-containing unsaturated monomer and an epoxy group-free unsaturated monomer. It is an epoxy group-containing copolymer compound.

から選ばれるエポキシ基含有基及び（メタ）アクリロイル基を含有する前記エポキシ基含有不飽和モノマーと、直鎖状、分岐鎖状若しくは環状の脂肪族基、パーフルオロアルキル基又はパーシャルフルオロアルキル基、及び（メタ）アクリロイル基を含有する前記エポキシ基非含有モノマーとの共重合体であって、そのエポキシ基一つあたりの分子量を１００〜１００００とすることを特徴とする。 The method for producing a curable resin component according to claim 8 is the method according to claim 7, wherein the epoxy group-containing copolymer compound is:

An epoxy group-containing unsaturated monomer containing an epoxy group-containing group and a (meth) acryloyl group selected from: a linear, branched or cyclic aliphatic group, a perfluoroalkyl group or a partial fluoroalkyl group; and It is a copolymer with the said epoxy group non-containing monomer containing a (meth) acryloyl group, Comprising: The molecular weight per the epoxy group shall be 100-10000, It is characterized by the above-mentioned.

  The method for producing a curable resin component according to claim 9 is the method according to claim 1, wherein the epoxy compound is the aromatic ring group, alicyclic group, linear or branched alkyl group, or An epoxy resin containing an alkylene group, wherein the molecular weight per epoxy group is 100 to 10,000.

  The method for producing a curable resin component according to claim 10 is the method according to claim 9, wherein the epoxy resin is phenyl glycidyl ether, bisphenol A diglycidyl ether, phenol novolac type epoxy resin, cresol novolac type epoxy. An epoxy compound containing an aromatic ring group selected from a resin, naphthalenediol epoxy resin, biphenol epoxy resin, bisfluorene type epoxy resin, trisphenylol methane epoxy resin, tetrakisphenylol ethane epoxy resin, phenol dicyclopentadiene novolac epoxy resin; Epoxy resin containing the alicyclic group selected from those saturated products and tricyclodecane skeleton-containing epoxy resin; alkylene diglycidyl ether, trimethylolpropane triglycine Be any of the epoxy resins containing the linear or branched alkylene group selected from the ether, characterized in that the molecular weight per one its epoxy groups with 100 to 10,000.

  The manufacturing method of the hardened | cured material of Claim 11 contains this curable resin component manufactured by the manufacturing method of the curable resin component in any one of Claims 1-10, and contains curable resin composition It is characterized in that an article is prepared and applied or molded and cured.

  According to the method for producing a curable resin component of the present invention, one molecule of (meth) acrylic anhydride is ring-opened and added by exactly an equivalent amount to one epoxy group to form two (meth) acrylic acid ester groups. Is.

  Not only methacrylic anhydride, which has a relatively large steric hindrance and is less likely to cause side reactions, but also acrylic acid anhydrides, which are less likely to cause side reactions due to small steric hindrance and are liable to be colored or by-products, When the ring-opening addition is performed to obtain a curable resin component, the curable resin component has a very low hydroxyl value because the hydroxyl peak is hardly recognized by infrared absorption spectroscopy, and the curable resin component is Not colored.

  This component is used as a prepolymer contained in the curable resin composition. Therefore, when a composition containing the same is cured, an uncolored cured product having low water absorption and excellent heat resistance, insulation, chemical resistance, scratch resistance, and mechanical strength is formed.

Preferred form for carrying out the invention

  Hereinafter, although the preferable form for implementation of this invention is demonstrated in detail, the scope of the present invention is not limited to these forms.

  A preferred embodiment of the method for producing a curable resin component of the present invention is a metal which is a metal-containing compound catalyst with respect to 1.0 molar equivalent of an epoxy group of bisphenol A diglycidyl ether as an epoxy resin containing a plurality of aromatic ring groups. In the presence of an alkoxide, 1.0 molar equivalent of (meth) acrylic anhydride is added, and the reaction is carried out at 60 to 120 ° C. in the absence of a solvent. Ring-opening addition is performed to obtain a curable resin component.

The metal alkoxide is represented by, for example, M-OR (M is a metal atom, and OR is an alkoxide group). Specifically, titanium and zirconium are exemplified as the metal atom: M, and the alkoxide group: OR is derived from a linear, branched, or cyclic, saturated or unsaturated alcohol having 1 to 4 carbon atoms. An alkoxide group is mentioned. More specifically, metal alkoxides include tetra-n-butyl titanate (Ti [O (CH ₂ ) ₃ CH ₃ ] ₄ ), tetraisopropyl titanate (Ti [OCH ₂ (CH ₃ ) ₂ ] ₄ ), butyl titanate dimer. ([(BuO) ₃ Ti—O—Ti (OBu) ₃ ]) and tetra n-butoxyzirconium (Zr [O (CH ₂ ) ₃ CH ₃ ] ₄ ).

  It is preferable to use 0.1 to 5% by weight of a metal-containing compound catalyst with respect to the epoxy compound and the (meth) acrylic anhydride. A cocatalyst that is an acid may be used in an amount of 0.01 to 2% by weight together with the metal-containing compound catalyst. Examples of the co-catalyst include light ester P-2M (manufactured by Kyoeisha Chemical Co., Ltd .; trade name) which is di- (2-methacryloyloxyethyl) -phosphate that can be copolymerized with the curable resin component.

  The metal-containing compound catalyst may remain in the obtained curable resin component, or may be removed by a post-treatment using an adsorbent having an acid and / or alkali adsorption action. Examples of the adsorbent include adsorbents containing one or more selected from magnesium oxide, aluminum oxide, and silicon dioxide. More specifically, KYOWARD (Kyowa Chemical Industry Co., Ltd .; trade name) is mentioned.

  The obtained curable resin component has a very low hydroxyl value. Under the reaction conditions, 1 mole equivalent of epoxy group of epoxy resin and 1 mole equivalent of (meth) acrylic anhydride react to cleave and add (meth) acrylic anhydride, This is because 2 mole equivalent of (meth) acrylic acid ester is formed. In addition, since the epoxy resin does not have a hydroxyl group, the epoxy group and the (meth) acrylic anhydride are directly reacted with each other in an equivalent amount, and hardly cause a side reaction that generates a hydroxyl group. It is.

  When reacting a hydroxyl group-containing epoxy resin with (meth) acrylic anhydride, when mixing a hydroxyl group-free epoxy resin with (meth) acrylic acid and (meth) acrylic anhydride, or patenting When the epoxy resin and (meth) acrylic anhydride are reacted as described in Document 1, a hydroxyl value of about several tens or more remains.

  An example in which (1.0) molar equivalent of (meth) acrylic anhydride was used with respect to 1.0 molar equivalent of an epoxy group was shown. Good. For example, when 0.5 molar equivalent of (meth) acrylic anhydride is used with respect to 1.0 molar equivalent of an epoxy group, 0.5 molar equivalent of an epoxy group is hardly generated without causing a side reaction that generates a hydroxyl group. The contained (meth) acrylate is obtained. Such a partially acrylated epoxy resin is usually obtained by reacting with 0.5 molar equivalent of (meth) acrylic acid, for example, with respect to 1.0 molar equivalent of epoxy group, but is equivalent to (meth) acrylic acid. An amount of hydroxyl groups is formed. Therefore, since the (meth) acrylic equivalent is low and it contains a hydroxyl group, it is difficult to design for expressing the required performance, and the storage stability also deteriorates. On the other hand, since the partial (meth) acrylated epoxy resin obtained by the method of the present invention can provide a sufficient (meth) acrylic equivalent, it can be designed to express the required performance and has a hydroxyl value of Since it is extremely small, the storage stability is improved.

  Although the example which manufactured the curable resin component from the epoxy resin containing several aromatic ring groups and (meth) acrylic anhydride was shown, it replaced with such an epoxy resin, and several other aromatic ring groups were shown. An epoxy resin containing a single aromatic ring group, an epoxy group-containing fluoro compound, an epoxy group-containing copolymer compound, a plurality of alicyclic groups, and / or a linear or branched alkylene group An epoxy resin may be used.

  The epoxy group-containing fluoro compound is preferably A-Rf-B represented by the formula (I).

のようなエポキシ基含有基が挙げられる。 A- constituting the epoxy group-containing fluoro compound is a terminal epoxy group such as a glycidyl ether group, a group containing an epoxy group on an alicyclic ring such as an epoxycyclohexyl group, more specifically,

An epoxy group-containing group such as

—Rf— constituting the epoxy group-containing fluoro compound is —CH ₂ — (CF ₂ ) _m — (CH ₂ ) _n — (each integer of m = 1 to 20, n = 0 to 1), more specifically For example, when n ≠ 0, 2,2-difluoropropanediol, 2,2,3,3-tetrafluorobutanediol, 2,2,3,3,4,4, -hexafluoropentanediol, 2, 2,3,3,4,4,5,5-octafluorohexanediol, 2,2,3,3,4,4,5,5,6,6-decafluoroheptanediol, 2,2,3, 3,4,4,5,5,6,6,7,7-dodecafluorooctanediol, 2,2,3,3,4,4,5,5,6,6,7,7,8,8 -Dehydration of either tetradecafluorononanediol and 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-heptadecafluorodecanediol Elementary residues;
_{-CH 2 - (CF 2) p} -C [- (CF 2) q -F] [- (CH 2) r -F] -CH 2 - (p = 1~10, q = 0~22, r = An integer of 1 to 22), more specifically 2-fluoro-2-perfluorooctyl-1,3-propanediol, 2-fluoro-2-perfluoroisooctyl-1,3-propanediol, and 2 Any dehydrogenated residue of -fluoro-2-perfluoro (4-ethyl-hexyl) -2-hydroxymethyl-1-methanol;
_{-CH 2 - (CF 2) s} - (- O-C t F 2t) u -O- (CF 2) v - (CH 2) w - (s = 1~3, t = 1~4, u = 1 to 100, v = 0 to 3, w = 0 to 1), more specifically 2,2,4,4-tetrafluorodiethylene glycol, 2,2,4,4,5,5,7 , 7-octafluorotriethylene glycol, 2,2,4,4,5,5,7,7,8,8,10,10-dodecafluorotetraethylene glycol, 2,2,4,4,5,5 , 7,7,8,8,10,10,11,11,13,13-heptadecafluoropentaethylene glycol, 2,2,4,4,5,5,7,7,8,8,10, 10,11,11,13,13,14,14,16,16-icosadecafluorohexaethylene glycol, 2,2,4,4,5,5,7,7,8,8,10,10, 11,11,13,13,14,14,16,16,17,17,19,19-tetracosafluoroheptaethylene glycol, 2,2,4,4,5,5,7,7,8,8 , 10,10,11,11,13,13,14,14,16,16,17,17,19,19,20,20,22,22-octacosafluorooctaethylene glycol, 2,2,4, 4,5,5,7,7,8,8,10,10,11,11,13,13,14,14,16,16,17,17,19,19,20,20,22,22, twenty three , 23,25,25-Dotriacontafluorononaethylene glycol, 2,4,4-trifluoro-2,5-di (trifluoromethyl) diethylene glycol, 2,4,4,5,7,7-hexafluoro -2,5,8-tri (trifluoromethyl) triethylene glycol, 2,4,4,5,7,7,8,10,10-nonafluoro-2,5,8,11-tetra (trifluoromethyl) ) Tetraethylene glycol, 2,4,4,5,7,7,8,10,10,11,13,13-dodecafluoro-2,5,8,11,14-penta (trifluoromethyl) pentaethylene Glycol, 2,4,4,5,7,7,8,10,10,11,13,13,14,16,16,17-pentadecafluoro-2,5,8,11,14,17- Hexa (trifluoromethyl) hexaethylene glycol, 2,4,4,5,7,7,8,10,10,11,13,13,14,16,16,17,19,19,20-octadeca Fluoro-2,5,8,11,14,17,20-hepta (trifluoromethyl) heptaethylene glycol, 2,4,4,5,7,7,8,10,10,11,13,13 , 14,16,16,17,19,19,20,22,22,23-docosafluoro-2,5,8,11,14, 17,20,23-octa (trifluoromethyl) octaethylene glycol, 2,4,4,5,7,7,8,10,10,11,13,13,14,16,16,17,19, 19,20,22,22,23,25,25,26-tetracosafluoro-2,5,8,11,14,17,20,23,26-nona (trifluoromethyl) nonaethylene glycol, 2, 2,3,3,4,4,6,6,7,7,8,8-dodecafluoroditetramethylene glycol 2,2,3,3,4,4,6,6,7,7,8, 8,9,9,11,11,12,12,13,13-icosafluorotritetramethylene glycol, 2,2,3,3,4,4,6,6,7,7,8,8, 9,9,11,11,12,12,13,13,14,14,16,16,17,17,18,18-octacosafluorotetratetramethylene glycol, 2,2-bis (4-hydroxy- Decafluorocyclohexyl) -1,3-hexafluoropropane, 2,2-bis (4-hydroxymethyl-decafluorocyclohexyl) -1,3-hexafluoropropane, 2,2-bis [4-oxy (1,1 -Difluoroethoxy) -decafluorocyclohexyl] -1,3-hexafluoropro Emissions, and 2,2-bis [4- oxy (1-perfluoromethyl-1-fluoroethoxy) - decafluoro cyclohexyl] either dehydrogenation residue of 1,3-hexafluoropropane;
Is mentioned.

-B constituting the epoxy group-containing fluoro compound is the same or different from the A-;
-C _y F _{2y + 1} or _{-OCH 2 -C y F 2y + 1} (y = 1~22 integer), more specifically, as _{-OCH 2 -C y F 2y + 1} , for example perfluoro methanol Perfluoroethylmethanol, perfluoropropylmethanol, perfluorobutylmethanol, perfluoropentylmethanol, perfluorohexylmethanol, perfluorooctylmethanol, perfluorononylmethanol, perfluorodecylmethanol, perfluoroundecylmethanol, perfluorododecyl Methanol, perfluorotridecyl methanol, perfluoro tetradecyl methanol, perfluoro pentadecyl methanol, perfluoro hexadecyl methanol, perfluoro heptadecyl methanol, perfluoro octadecyl methanol, perfluoro Any dehydrogenation residue of Le Oro nonadecyl methanol, perfluoro icosyl methanol or perfluoro f Nico sills methanol;
-C _z F _2z-1 or _{-OCH 2 -C z F 2z-1} (z = 3~20 integer), more specifically, as -C _z F _2z-1, perfluoro cyclohexyl group also - as _{OCH 2 -C z F 2z-1} , 1- undecafluorocyclohexyl cyclohexyl methanol or 2-fluoro-2-undecafluorocyclohexylmethyl cyclohexyl ethanol, dehydration of 2,2,3-trifluoro-3- undecafluorocyclohexylmethyl cyclohexyl propanol An elementary residue is mentioned.

-Rf-B _{is, (C y F 2y + 1} ) - time _{(CF 2 CF 2 -O-) u} -CF 2 CH 2 O- (y, u are as defined above) which is, more specifically, 2-perfluoromethoxy-2,2-difluoroethanol, 2-perfluoroethoxy-2,2-difluoroethanol, 2-perfluorobutoxy-2,2-difluoroethanol, 2-perfluorooctoxy-2,2 -Difluoroethanol, 5-perfluoromethoxy-4,4,5,5-tetrafluoroethoxy-2,2-difluoroethanol, 5-perfluorobutoxy-4,4,5,5-tetrafluoroethoxy-2,2 -Difluoroethanol, 5-perfluorooctoxy-4,4,5,5-tetrafluoroethoxy-2,2-difluoroethanol, 8-perfluoromethoxy-7,7,8,8-tetrafluoroethoxy-4, 4,5,5-tetrafluoroethoxy-2,2-difluoroethanol, 8-perfluorooctoxy-7,7,8,8-tetrafluor Ethoxy-4,4,5,5-tetrafluoroethoxy-2,2-difluoroethanol, 11-perfluoromethoxy-10,10,11,11-tetrafluoroethoxy-7,7,8,8-tetrafluoroethoxy -4,4,5,5-tetrafluoroethoxy-2,2-difluoroethanol or 11-perfluorooctoxy-10,10,11,11-tetrafluoroethoxy-7,7,8,8-tetrafluoro Examples include dehydrogenated residues of ethoxy-4,4,5,5-tetrafluoroethoxy-2,2-difluoroethanol. Perfluorodecanediol diglycidyl which is fluorite FE-16 (manufactured by Kyoeisha Chemical Co., Ltd .; trade name) may be used.

  These epoxy group-containing fluoro compounds may be used alone or in combination.

  The epoxy group-containing copolymer compound may have a fluoro group, an epoxy group-containing unsaturated monomer having an epoxy group-containing group as described above and an unsaturated group such as a (meth) acryloyl group, and linear Or a copolymer with the epoxy group-free monomer containing an unsaturated group such as a branched or cyclic alkyl group, a perfluoroalkyl group or a partial fluoroalkyl group, and a (meth) acryloyl group. Good. More specifically, such an epoxy group-containing copolymer compound is a copolymer of a (meth) acrylic acid ester containing an epoxy group-containing group as described above and a (meth) acrylic acid ester not containing an epoxy group. A polymer is mentioned.

  The epoxy group-containing unsaturated monomer constituting the epoxy group-containing copolymer compound has an alkyl group having 2 to 10 carbon atoms such as glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate. Glycidyloxyalkyl (meth) acrylate; 3,4-epoxycyclohexylmethoxyalkyl (meth) acrylate having an alkyl group having 2 to 10 carbon atoms; in place of these alkyl having 2 to 10 carbon atoms, 2 carbon atoms Examples include those containing a polyalkylene glycol (repeat unit; 2 to 20) skeleton having -4 alkylene groups.

  The epoxy group-free unsaturated monomer constituting the epoxy group-containing copolymer compound is an ester of a linear, branched or cyclic aliphatic alcohol and (meth) acrylic acid having 1 to 18 carbon atoms such as methyl ( (Meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) Acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, (phenoxyphenyl) benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyalkyl having an alkyl group having 2 to 4 carbon atoms (Me ) Acrylate, naphthalene (meth) acrylate, tricyclodecane (meth) acrylate, adamantyl (meth) acrylate. Acrylic acid ester containing perfluoroalkyl group or partial fluoroalkyl group, for example perfluoromethanol, perfluoroethylmethanol, perfluoropropylmethanol, perfluorobutylmethanol, perfluoropentylmethanol, perfluorohexylmethanol, perfluorooctylmethanol Perfluorononylmethanol, perfluorodecylmethanol, perfluoroundecylmethanol, perfluorododecylmethanol, perfluorotridecylmethanol, perfluorotetradecylmethanol, perfluoropentadecylmethanol, perfluorohexadecylmethanol, perfluoroheptadecyl Methanol, perfluorooctadecylmethanol, perfluorononadecylme Nord, perfluoroicosyl methanol, or perfluoro henicosyl methanol, 1-undecafluorocyclohexyl methanol, or 2-fluoro-2-undecafluorocyclohexyl ethanol, 2,2,3-trifluoro-3-undeca It may be an ester of fluorocyclohexylpropanol and (meth) acrylic acid.

The epoxy resin has an epoxy group-containing group such as a glycidyl group, and more specifically, an epoxy compound containing a single aromatic ring group such as phenyl glycidyl ether;
Bisphenol A diglycidyl ether such as jER827 (manufactured by Japan Epoxy Resin Co., Ltd .; jER is a registered trademark of the same company), cresol novolac epoxy resin such as EOCN-104S (manufactured by Nippon Kayaku Co., Ltd .; trade name), naphthalenediol epoxy Epoxy compounds containing a plurality of aromatic ring groups such as resins, biphenol epoxy resins, bisfluorene type epoxy resins, trisphenylol methane epoxy resins, tetrakisphenylol ethane epoxy resins, phenol dicyclopentadiene novolac epoxy resins;
Epoxy resins containing a plurality of the alicyclic groups saturated by hydrogenation, such as decahydronaphthalene epoxy resin hydrogenated naphthalenediol epoxy resin, epoxy resin containing tricyclodecane skeleton;
An epoxy resin containing the linear or branched alkylene group selected from alkylene diglycidyl ether such as diglycidyl ether of hexanediol, trimethylolpropane triglycidyl ether;
Examples of α-olefin monoepoxide and epoxidized polybutadiene such as Epolide PB3300 and AOE X24 (both manufactured by Daicel Chemical Industries, Ltd .; trade name), linear, branched or cyclic unsaturated fat And an epoxy compound obtained by epoxidizing a double bond of a group hydrocarbon.

  The (meth) acrylic anhydride may be an acrylic anhydride, methacrylic anhydride, a mixed acid anhydride of acrylic acid / methacrylic acid, they may be used alone, or a plurality of them in any ratio It may be used as a mixture.

  Epoxy group-containing fluoro compounds, epoxy group-containing copolymer compounds, and epoxy resins have low boiling points when the molecular weight per epoxy group is less than 100 to 10,000, and the production efficiency and ease of production of curable resin components are poor. On the other hand, if it is larger than this range, the content of (meth) acryloyl group is reduced, resulting in a decrease in reactivity during curing, physical properties such as insufficient hardness and scratch resistance of the resulting cured product. I will wake you up. Furthermore, even if the epoxy group-containing copolymer compound or epoxy resin contains a fluorine group, if the content is smaller than this range, the fluorine content is extremely reduced. As a result, the water resistance, oil resistance, and optical properties inherent in the fluorine group are reduced. Characteristics such as characteristics cannot be expressed.

  The composition containing this curable resin component is used to form a cured product. Such a composition contains 10 to 99 parts by weight of a curable resin component, 0.5 to 15 parts by weight of a polymerization initiator, and 0.1 to 70 parts by weight of an additive as necessary.

  As a polymerization initiator, a general initiator that decomposes by light irradiation to generate radicals, such as benzyl, benzoin isobutyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin ethyl ether, 2,2-diethoxyacetophenone 2,2-dibutoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-isopropyl-α-hydroxyisobutylphenone, α-hydroxy Examples include but are not limited to isobutylphenone, 1-hydroxycyclohexyl phenyl ketone, 2-methylthioxanthone, and the like. These may be used alone or in combination of two or more. As the polymerization initiator, a peroxide that generates a radical by heat may be used.

  The composition is suitably an organic or inorganic filler such as acrylic resin or silica sol, various additives such as sensitizers, antioxidants, light stabilizers, ultraviolet absorbers, fine particle metal oxides, leveling agents, and other additional functions. Additives for expression may be added.

  When this composition is cured in the form of a film by irradiation with active energy rays such as heat, infrared rays, ultraviolet rays, and electron beams, or cured in a mold, a cured product is obtained.

  Below, the example manufactured with the manufacturing method of the curable resin component to which this invention is applied is shown in an Example, and the example manufactured with the manufacturing method of the curable resin component to which this invention is not applied is shown in a comparative example.

Example 1
154 g (1 mole amount) of Epiol P (Nippon Yushi Co., Ltd .; trade name, epoxy equivalent 154), which is phenylglycidyl ether (PGE), in a flask equipped with a stirrer, thermometer, condenser, and dropping funnel, polymerization prohibited 0.140 g (500 ppm) of methoquinone, 0.140 g (500 ppm) of 2,6-di-t-butyl-4-methylphenol, 0.014 g (500 ppm) of thiodiphenylamine, and a metal-containing compound as a catalyst. 2.80 g (1% by weight) of a certain tetra n-butyl titanate was charged, and the temperature was raised to 120 ° C. From the dropping funnel, 126 g (1 mol) of acrylic anhydride was added dropwise over 1 to 2 hours, and the mixture was reacted at 120 ° C. for 11 hours after completion of the addition. It was confirmed that the acid value was 5 or less by the measurement method based on JIS K0070 and the epoxy equivalent was 7000 g / equivalent or more by the measurement method based on JIS K7236. The reaction end point was determined. After cooling to around 60 ° C., the product was taken out of the flask to obtain a curable resin component composed of desired PGE and acrylic anhydride. The purity of the curable resin component was measured by gel permeation chromatography (GPC). The results are shown in Table 1.

(Examples 2 to 4 and Comparative Examples 1 to 3)
A curable resin component was obtained in the same manner as in Example 1 except that the catalyst and the reaction time were changed to the conditions shown in Table 1. The purity of the curable resin component was measured by gel permeation chromatography (GPC). The results are summarized in Table 1.

  As is apparent from Table 1, according to the production method using the metal-containing compound catalyst containing a metal which is a Lewis acid as in Examples, a curable resin component having a high purity of about 86 to 88% is obtained. It was. In this curable resin component, no peak of hydroxyl group was observed by infrared absorption spectroscopy. On the other hand, according to the production method using the quaternary ammonium salt as in the comparative example and the metal-free compound catalyst which is an amine or phosphine which is a Lewis base, the curable resin component is only obtained with low purity. .

(Example 6)
To a flask equipped with a stirrer, a thermometer, and a cooling tube, a bisphenol A type epoxy resin (BisA diglycidyl) jER827 (manufactured by Japan Epoxy Resin Co., Ltd .; trade name, epoxy equivalent 180, purity 85-88%) (BISAEP) 180 g, 126 g of acrylic anhydride, 0.153 g of 2,6-di-t-butyl-4-methylphenol as a polymerization inhibitor, and ORGATICS ZA-65 (Matsumoto Fine Chemical Co., Ltd.) which is tetra n-butoxyzirconium as a catalyst Product: 3.06 g (1 wt%) of product name) and 0.918 g of light ester P-2M (manufactured by Kyoeisha Chemical Co., Ltd .; product name) as a co-catalyst, heated to 85 ° C., then 85 ° C. For 19 hours. It was confirmed that the acid value by the measuring method based on JIS K0070 was 5 or less, and the epoxy equivalent by the measuring method based on JIS K7236 was 7000 g / equivalent or more, and the reaction was terminated. After cooling to around 60 ° C., the product was taken out from the flask to obtain a desired curable resin component consisting of BISAEP and acrylic anhydride. The purity of the curable resin component was measured by gel permeation chromatography (GPC). The results are shown in Table 2.

(Examples 5 and 7 to 11)
Instead of the bisphenol A type epoxy resin jER827 of Example 6, phenylglycidyl ether, 9,9′-bis (4-hydroxyphenyl) fluorene (epoxy equivalent 256, purity 85 to 88%), EOCN which is a novolac type epoxy resin -104S (Nippon Kayaku Co., Ltd .; trade name, epoxy equivalent 216), Fluorite FE-16 (Kyoeisha Chemical Co., Ltd .; trade name, epoxy equivalent 355) which is perfluorodecanediol diglycidyl was used. A curable resin component was obtained in the same manner as in Example 1 except that the catalyst / co-catalyst as shown in Table 2 was used for reaction for a predetermined reaction time. The purity of the curable resin component was measured by gel permeation chromatography (GPC). The results are summarized in Table 2.

  As is apparent from Table 2, when the epoxy compound was phenyl glycidyl ether, the purity of Example 5 using a cocatalyst was improved as compared with Example 4 using no cocatalyst. Further, when the epoxy compound is BisA-diglycidyl or bisfluorene type epoxy resin, the purity is 85 to 88%, and the purity of the curable resin component is substantially the same. The reaction is considered to have progressed almost quantitatively. In addition, when an epoxy compound is a novolak type epoxy resin, since the molecular weight distribution has a considerable width | variety, the purity measurement by GCP measurement cannot be performed.

  In addition, when the infrared absorption spectrum (IR) measurement of the curable resin component obtained in the Example was carried out, the peak based on a hydroxyl group was hardly recognized. Further, when the presence or absence of coloring was visually observed, almost no coloring was observed, and in particular, no coloring was observed when tetra-n-butoxyzirconium and an acid promoter were used.

Example 12
In a flask equipped with a stirrer, a thermometer, and a cooling tube, 50 parts by weight of a curable resin component that is an adduct of acrylic anhydride to the bisfluorene type epoxy resin obtained in Example 14, and propylene glycol as a solvent 50 parts by weight of monomethyl ether acetate, 5 to 1 parts by weight of KYOWARD # 100 (manufactured by Kyowa Chemical Industry Co., Ltd .; trade name) as described in Table 3, and 1 to 5 parts by weight of water are mixed. Stir at 80 ° C. for 1 hour. After 1 hour, the mixture was cooled to 60 ° C. or lower, the catalyst and keyword were removed by filtration, and the curable resin component was purified. To 100 parts by weight of the solid content of the curable resin component, 3 parts by weight of Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd .; trade name) as a photopolymerization initiator is added and dissolved to obtain a curable resin composition. Prepared. The composition was applied on an aluminum dish and cured by irradiating with an ultraviolet ray so that the energy dose was 600 mJ / cm ² using a high-pressure mercury lamp to obtain a film-like cured product. About the hardened | cured material, the amount of residual zirconium was quantified by the fluorescent X ray analysis. As a blank, except that the catalyst is not removed, a composition is prepared using a curable resin component that is an adduct of acrylic anhydride to the bisfluorene type epoxy resin of Example 14, After curing, X-ray fluorescence analysis was performed to determine the amount of zirconium remaining. The results are shown in Table 3.

  The curable resin component may remain containing the metal-containing compound catalyst, but the catalyst can be removed by a catalyst removal treatment using an adsorbent. When the catalyst removal treatment is performed using water together with the adsorbent, the catalyst can be removed below the detection limit.

(Example 13)
In a flask equipped with a stirrer, thermometer, and condenser, 180 g of bisphenol A type epoxy resin jer827 (manufactured by Japan Epoxy Resin Co., Ltd .; epoxy equivalent 180) (BISAEP), 63 g of acrylic anhydride, 2, as a polymerization inhibitor 0.122 g of 6-di-t-butyl-4-methylphenol, 2.43 g (1 wt%) of ORGATIZ ZA-65 (manufactured by Matsumoto Fine Chemical Co., Ltd .; trade name) which is tetra n-butoxyzirconium as a catalyst, 0.729 g of light ester P-2M (manufactured by Kyoeisha Chemical Co., Ltd .; trade name) was charged as a catalyst, and the temperature was raised to 85 ° C., followed by reaction at 85 ° C. for 10 hours. After confirming that the acid value by the measuring method based on JIS K0070 was 5 or less, the reaction was terminated. After cooling to around 60 ° C., the product was taken out from the reaction vessel to obtain the desired curable resin component. The obtained resin was stored at 5 ° C., room temperature, and 40 ° C. for a long time, and the molecular weight distribution was followed by GPC. The results are shown in Table 4.

  As is apparent from Table 4, the partial addition product of acrylic anhydride to the bisphenol A type epoxy resin is a partial addition to the main component of the epoxy resin that occupies about 85% of the epoxy resin. It was stable. In addition, a dimer or higher impurity oligomer occupying about 15% of the remainder in the epoxy resin is also partially added. A compound in which a part of the epoxy group of the epoxy resin is (meth) acrylated is very useful as a raw material for a resin for forming a protective film for a resist or an interlayer insulating film for a printed circuit board. Conventional partial (meth) acrylate compounds of epoxy resins have poor temporal stability and are decomposed. In contrast, the partial addition of acrylic anhydride to the bisphenol A type epoxy resin obtained in this example was very stable.

(Example 14)
In a flask equipped with a stirrer, a thermometer, and a condenser tube, 216 g of novolac type epoxy resin EOCN-104S (manufactured by Nippon Kayaku Co., Ltd .; epoxy equivalent 216), 63 g of acrylic anhydride, 2,6-as a polymerization inhibitor 0.140 g of di-t-butyl-4-methylphenol, 2.79 g (1 wt%) of ORGATIX ZA-65 (manufactured by Matsumoto Fine Chemical Co., Ltd .; trade name) which is tetra-n-butoxyzirconium as a catalyst, as a promoter 0.837 g of light ester P-2M (manufactured by Kyoeisha Chemical Co., Ltd .; trade name) was charged, and the temperature was raised to 85 ° C., followed by reaction at 85 ° C. for 10 hours. After confirming that the acid value by the measuring method based on JIS K0070 was 5 or less, the reaction was terminated. After cooling to around 60 ° C., the product was taken out from the reaction vessel to obtain the desired curable resin component. The obtained resin was stored at a predetermined temperature, and the molecular weight distribution of the number average molecular weight and the weight average molecular weight was traced by GPC. The results are shown in Table 5.

  As is clear from Table 5, since the number average molecular weight and the weight average molecular weight hardly changed after long-term storage, the curable resin component was stable over time.

  Next, acrylic acid (AA) was used in place of the curable resin component obtained in Examples 5, 6, 9 and 10 and acrylic acid anhydride (AAH) in Examples 5 and 6 for comparison. A cured product was prepared from a composition prepared using each of the curable resin components obtained in the same manner as in Examples 5 and 6 except for the above.

(Preparation Examples 1 to 4 for cured products, Preparation Comparative Examples 1 to 2 for cured products)
100 parts by weight of the curable resin components (PGE-AAH, jER827-AAH, BFL-AAH, EOCN-104S-AAH) of Examples 5, 6, 9 and 10 and Irgacure 184 (Ciba Specialty) which is a photopolymerization initiator 5 parts by weight of Chemicals Co., Ltd. (trade name) were kneaded to prepare a composition. It is coated on a glass plate and an aluminum pan, covered with a release PET film, and cured by irradiating it with ultraviolet rays so that the energy dose is 600 mJ / cm ² using a high-pressure mercury lamp to obtain a film-like cured product. It was. Moreover, about what contains a solvent, after drying with an 80 degreeC dryer, it covers with a release PET film, By irradiating ultraviolet rays so that an energy dose may be 600 mJ / cm < ² > using a high pressure mercury lamp, Cured to prepare a film-like cured product of the cured product preparation example. Similarly, the hardened | cured material of hardened | cured material preparation comparative example was prepared from curable resin component (PGE-AA, jER827-AA) using acrylic acid (AA).

  Next, the following physicochemical analysis was performed about the obtained hardened | cured material.

(Water absorption rate)
The sample obtained by the above curing method was adjusted to a length of 20 mm, a width of 20 mm, and a thickness of 0.5 mm. The weight of the sample was measured and immersed in water at 60 ° C. for 24 hours. The weight was immediately measured, and the water absorption was calculated according to the following formula.
Water absorption rate (%) = [(weight after water absorption) − (weight before water absorption) / (weight before water absorption)] × 100
The results are shown in Table 6.
(Pencil hardness)

  Pencil hardness is measured with a weight of 1 kg based on JISK5600 for the coating film cured to 10 μm on a 100 μm PET substrate by the above-mentioned curing method, and is indicated by the hardness of the hardest pencil without scratches. It was. The results are shown in Table 6.

(Dielectric constant, dielectric loss tangent)
The sample obtained by the above curing method was measured using a coaxial resonator type dielectric constant measuring device ADMS01O (manufactured by AE Japan Co., Ltd .; trade name) under the condition of a frequency of 1 GHz. ) And dielectric loss tangent (tan δ). The results are shown in Table 6.

(Steel wool resistance)
About the coating film obtained by the same method as the said hardness measurement, the coating-film surface state after 10 reciprocations with steel wool (No. 0000) with a load of 200 g / cm < ² > was observed. Evaluation was made in 5 stages, with 5 being no scratch, 4 being 1 to 10 scratches, 3 being about a dozen scratches, 2 being innumerable scratches, and 1 being whitening or film peeling. The results are shown in Table 6.

  As is apparent from Table 6, the cured product obtained by curing the curable resin component of the example to which the present invention was applied had high hardness, low dielectric constant / dielectric loss tangent, and low water absorption. On the other hand, the curable resin component of the comparative example, to which the present invention was not applied, exhibited a hardness lower than that of the example, had a high dielectric constant / dielectric loss tangent, and high water absorption.

  The curable resin component obtained by the production method of the present invention is used as a raw material for molding materials, low dielectric members, low water absorption members, etc. for products such as home appliances, precision equipment and electronic parts, and as a sealant. It is useful as a raw material for surface coating agents.

Claims (11)

  Epoxy in any epoxy compound selected from epoxy resins containing an epoxy group-containing fluoro compound, an epoxy group-containing copolymer compound, an aromatic ring group, an alicyclic group, a linear or branched alkyl group or an alkylene group A curable resin component characterized by ring-opening addition of 0.1 to 1.0 molar equivalent of (meth) acrylic anhydride in the presence of a metal-containing compound catalyst with respect to 1.0 molar equivalent of a group Manufacturing method.   The method for producing a curable resin component according to claim 1, wherein the metal-containing compound catalyst is a metal alkoxide.   The metal alkoxide is characterized in that the metal is titanium or zirconium, and the alkoxide group is derived from a linear, branched or cyclic, saturated or unsaturated alcohol having 1 to 18 carbon atoms. The manufacturing method of the curable resin component of Claim 2.   The method for producing a curable resin component according to claim 1, wherein the metal-containing compound catalyst coexists with a co-catalyst containing an acid.   The epoxy compound is an epoxy group-containing fluoro compound containing a linear, branched or cyclic perfluoroalkyl group, partial fluoroalkyl group, perfluoroalkylene group and / or partial fluoroalkylene group. The method for producing a curable resin component according to claim 1. The epoxy group-containing fluoro compound is represented by the following chemical formula (I)
A-Rf-B (I)
(In the chemical formula (I), A-

An epoxy group-containing group selected from
—Rf— represents —CH ₂ — (CF ₂ ) _m — (CH ₂ ) _n — (m = 1 to 20, n = 0 to 1), —CH ₂ — (CF ₂ ) _p —C [— (CF ₂ ) _q —F] [— (CF ₂ ) _r —F] —CH ₂ — (p = 1 to 10, q = 0 to 22, r = 1 to 22), or —CH ₂ — ( _{CF 2) s - (- O} -C t F 2t) u -O- (CF 2) v - (CH 2) w - (s = 1~3, t = 1~4, u = 1~100, v = 0 to 3, w = 0 to 1 integer),
-B is the A- identical or different the epoxy group-containing group, -C _y F _{2y + 1} or _{-OCH 2 -C y F 2y + 1} (y = 1~22 integer), or -C _z F _2z-1 or a _{-OCH 2 -C z F 2z-1} (z = 3~20 integer). )
It is represented by these. The manufacturing method of the curable resin component of Claim 5 characterized by the above-mentioned.   The said epoxy compound is the said epoxy group containing copolymer compound by copolymerization of an epoxy group containing unsaturated monomer and an epoxy group non-containing unsaturated monomer, The manufacture of the curable resin component of Claim 1 characterized by the above-mentioned. Method. The epoxy group-containing copolymer compound is

An epoxy group-containing unsaturated monomer containing an epoxy group-containing group and a (meth) acryloyl group selected from: a linear, branched or cyclic aliphatic group, a perfluoroalkyl group or a partial fluoroalkyl group; and It is a copolymer with the said epoxy group non-containing monomer containing a (meth) acryloyl group, Comprising: The molecular weight per the epoxy group shall be 100-10000, Curability of Claim 7 characterized by the above-mentioned. A method for producing a resin component.   The epoxy compound is the epoxy resin containing the aromatic ring group, alicyclic group, linear or branched alkyl group or alkylene group, and the molecular weight per epoxy group is 100 to 10,000. The manufacturing method of the curable resin component of Claim 1 characterized by the above-mentioned.   The epoxy resin is phenyl glycidyl ether, bisphenol A diglycidyl ether, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthalenediol epoxy resin, biphenol epoxy resin, bisfluorene type epoxy resin, trisphenylol methane epoxy resin, tetrakis Epoxy compound containing an aromatic ring group selected from phenylolethane epoxy resin, phenol dicyclopentadiene novolac epoxy resin; a saturated product thereof, and an epoxy resin containing the alicyclic group selected from tricyclodecane skeleton-containing epoxy resin A linear or branched alkylene group selected from alkylene diglycidyl ether and trimethylolpropane triglycidyl ether; Be any of carboxy resin, a manufacturing method of the curable resin component according to claim 9, characterized in that the molecular weight per one its epoxy groups with 100 to 10,000.   A curable resin composition is prepared by containing the curable resin component produced by the method for producing a curable resin component according to any one of claims 1 to 10, and applied or molded. A method for producing a cured product, characterized by curing.