Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/24—Di-epoxy compounds carbocyclic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

• the present invention relates to a phenoxy resin having excellent heat resistance, dielectric properties and folding resistance. Further, the present invention relates to a resin composition containing the phenoxy resin and a curing agent, a cured product having excellent heat resistance, dielectric properties and folding resistance, and a laminated board for an electric / electronic circuit made of the resin composition. ..
• Epoxy resin is widely used in fields such as paints, civil engineering, adhesives, and electrical materials because it has excellent heat resistance, adhesiveness, chemical resistance, water resistance, mechanical strength, and electrical properties. Then, the film-forming property is imparted by increasing the molecular weight by various methods.
• the high molecular weight epoxy resin is called a phenoxy resin.
• bisphenol A type phenoxy resin is mainly used as a base resin for paint varnish, a base resin for film molding, and is added to epoxy resin varnish to adjust fluidity, improve toughness and adhesiveness when made into a cured product. Used for improvement purposes. Further, those having a phosphorus atom or a bromine atom in the skeleton are used as a flame retardant to be blended in an epoxy resin composition or a thermoplastic resin.
• Phenoxy resin which is used as an electrical material such as laminated boards for electric and electronic circuits, is required to have heat resistance, dielectric properties, and folding resistance.
• Patent Document 1 discloses a phenoxy resin having excellent heat resistance obtained by reacting a bulky bisphenol compound with a bifunctional epoxy resin. However, although this method can impart excellent heat resistance to the phenoxy resin, there is a problem that the dielectric property is not improved.
• An object of the present invention is to provide a phenoxy resin having excellent heat resistance, dielectric properties and folding resistance. Another object of the present invention is to cure a resin composition containing the same to provide a cured product having excellent heat resistance, dielectric properties and folding resistance.
• the present inventor has diligently studied a phenoxy resin and found that a phenoxy resin having a specific structure is excellent in heat resistance, dielectric properties and folding resistance, and a resin containing the same.
• the present invention has been completed by finding that the cured product obtained by curing the composition is excellent in heat resistance, dielectric properties and folding resistance.
• the present invention is a phenoxy resin represented by the following formula (1) and having a weight average molecular weight of 10,000 to 200,000.
• X is a divalent group containing a dioxy group represented by the following formulas (2) and (3) independently
• Y is a hydrogen atom and a hydrocarbon group having 1 to 20 carbon atoms, respectively. It is an acyl group or a glycidyl group having.
• Z is an acyl group or a hydrogen atom having a hydrocarbon group having 1 to 20 carbon atoms, and 5 mol% or more is the above acyl group.
• n is the average value of the number of repetitions, which is 15 or more and 500 or less.
• R independently has an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and 7 to 13 carbon atoms.
• I is an integer of 0 to 4
• j is an integer of 0 to 6.
• the present invention is a resin composition containing the above-mentioned phenoxy resin and a curing agent.
• the resin composition may contain 0.1 to 100 parts by mass of the curing agent as a solid content with respect to 100 parts by mass of the solid content of the phenoxy resin.
• the resin composition contains the above-mentioned phenoxy resin, an epoxy resin, and a curing agent, and the mass ratio of the solid content of the phenoxy resin and the epoxy resin can be 99/1 to 1/99.
• This resin composition may contain 0.1 to 100 parts by mass of a curing agent as a solid content with respect to a total of 100 parts by mass of the solid content of the phenoxy resin and the epoxy resin.
• Examples of the curing agent to be blended in the above resin composition include acrylic acid ester resins, melanin resins, urea resins, phenol resins, acid anhydride compounds, amine compounds, imidazole compounds, amide compounds, and cationic polymerization initiators. There is at least one selected from the group consisting of organic phosphines, polyisocyanate compounds, blocked isocyanate compounds, and active ester-based curing agents.
• the present invention is a cured product obtained by curing the above resin composition. Further, the present invention is a laminated board for an electric / electronic circuit using the above resin composition.
• the present invention is a method for producing the above-mentioned phenoxy resin, which comprises reacting a bifunctional epoxy resin represented by the following formula (7) with a compound represented by the following formula (8).
• X 1 is a divalent group containing a dioxy group independently represented by the above formula (2) or the formula (3), and is included in X 1 of the formulas (7) and (8) as a whole.
• Z 1 is an acyl group or a hydrogen atom having a hydrocarbon group having 1 to 20 carbon atoms, and 5 mol% or more is the above acyl group.
• the compound represented by the formula (8) is a mixture of two or more selected from a compound in which both of Z 1 are acyl groups, a compound in which one is an acyl group, and a compound in which both are hydrogen atoms. You may. m is the average value of the number of repetitions and is 0 or more and 6 or less.
• the present invention is characterized in that the acyl group of the acylating agent is reacted in an amount of 0.05 mol or more and 2.0 mol or less with 1 mol of the alcoholic hydroxyl group of the phenoxy resin represented by the following formula (12).
• This is the method for producing the above-mentioned phenoxy resin.
• X 2 is a divalent group containing a dioxy group represented by the above formulas (2) and (3) independently
• Y 2 is a hydrogen atom or a glycidyl group independently.
• n is the average value of the number of repetitions, which is 15 or more and 500 or less.
• a phenoxy resin having excellent heat resistance, dielectric properties and folding resistance. Further, a resin composition using this phenoxy resin can provide a cured product having excellent heat resistance, dielectric properties and folding resistance.
• the phenoxy resin of the present invention is a phenoxy resin having a weight average molecular weight (Mw) of 10,000 to 200,000 represented by the above formula (1), and has a benzene skeleton represented by the above formula (2) and a formula. It has a naphthalene skeleton represented by (3), and further has a structure in which a part or all of hydrogen atoms in a hydroxyl group are substituted with an acyl group (Z).
• Mw is smaller than 10,000, the film-forming property and the mechanical property (particularly the folding resistance) may be deteriorated, which is not preferable.
• Mw is larger than 200,000, the compatibility may decrease, which may make it difficult to handle the resin, which is not preferable.
• the Mw is preferably 15,000 to 160,000, more preferably 20,000 to 120,000, still more preferably 20,000 to 120,000.
• the Mw of the phenoxy resin can be measured by the gel permeation chromatography method (GPC method) described in Examples.
• the phenoxy resin of the present invention has a structure in which a hydrogen atom in a hydroxyl group is substituted with an acyl group, so that the polarity is low and an effect of excellent dielectric properties can be obtained. In addition, low hygroscopicity and solvent solubility are improved.
• the phenoxy resin of the present invention can be advantageously obtained by the production method of the present invention.
• the phenoxy resin obtained by the production method of the present invention is sometimes referred to as "phenoxy resin of the present invention”
• the cured product obtained by curing the resin composition of the present invention is referred to as "cured product of the present invention”.
• the method for producing a phenoxy resin of the present invention may be referred to as "the method for producing the phenoxy resin of the present invention".
• X is a divalent group containing a dioxy group independently represented by the above formulas (2) and (3).
• the groups represented by the formulas (2) and (3) are called dioxy groups because they have oxygen atoms at both ends.
• the divalent group is any of the above formulas (2), (3) or other divalent groups, but is represented by the formulas (2) and (3) as a whole. Contains dioxy groups.
• the molar ratio of dioxy groups represented by the formulas (2) and (3) (formula 2 / formula 3) is preferably 1/9 to 9/1, more preferably 2/8 to 8/2, and 3 /. 7 to 7/3 is more preferable, and 4/6 to 6/4 is particularly preferable.
• the dioxy group represented by the formulas (2) and (3) is preferably 1 mol% or more, more preferably 10 mol% or more, still more preferably 30 mol% or more, based on the total number of moles of X. , 50 mol% or more is particularly preferable. If it is out of this range, heat resistance, folding resistance and deterioration may occur.
• Examples of the divalent group other than the above dioxy group include a divalent group represented by —O—Ar—O—, and Ar is a hydroxyl group from a bifunctional phenol compound which may be used in combination, which will be described later. Residues and the like excluding two are mentioned.
• R independently has an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and 7 to 13 carbon atoms, respectively. It is a group arbitrarily selected from an aralkyl group, an aryloxy group having 6 to 12 carbon atoms, an aralkyloxy group having 7 to 13 carbon atoms, an alkoxy group having 2 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.
• the alkyl group having 1 to 12 carbon atoms may be linear, branched or cyclic, and may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group or a sec-butyl group.
• n-pentyl group isopentyl group, neopentyl group, t-pentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, n-heptyl group, cycloheptyl group, methylcyclohexyl group, n- Octyl group, cyclooctyl group, n-nonyl group, 3,3,5-trimethylcyclohexyl group, n-decyl group, cyclodecyl group, n-undecyl group, n-dodecyl group, cyclododecyl group, benzyl group, methylbenzyl group , Dimethylbenzyl group, trimethylbenzyl group, naphthylmethyl group, phenethyl group, 2-phenylisopropyl group and the like.
• the alkoxy group having 1 to 12 carbon atoms may be linear, branched or cyclic, and may be, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group or a sec-butoxy group.
• Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, an ethylphenyl group, a styryl group, a xsilyl group, an n-propylphenyl group and an isopropylphenyl group. , Mesityl group, ethynylphenyl group, naphthyl group, vinyl naphthyl group and the like, but are not limited thereto.
• Examples of the aralkyl group having 7 to 13 carbon atoms include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, an ethylphenyl group, a styryl group, a xsilyl group, an n-propylphenyl group and an isopropylphenyl group. , Mesityl group, ethynylphenyl group, naphthyl group, vinyl naphthyl group and the like, but are not limited thereto.
• Examples of the aryloxy group having 6 to 12 carbon atoms include a phenoxy group, an o-tolyloxy group, an m-tolyloxy group, a p-tolyloxy group, an ethylphenoxy group, a styryloxy group, a xylyloxy group, an n-propylphenoxy group and isopropyl.
• Examples thereof include, but are not limited to, a phenoxy group, a mesityloxy group, an ethynylphenoxy group, a naphthyloxy group, a vinylnaphthyloxy group and the like.
• Examples of the aralkyloxy group having 7 to 13 carbon atoms include a benzyloxy group, a methylbenzyloxy group, a dimethylbenzyloxy group, a trimethylbenzyloxy group, a phenethyloxy group, a 1-phenylethyloxy group, and a 2-phenylisopropyloxy group. , Naftylmethyloxy group and the like, but are not limited thereto.
• alkenyl group having 2 to 12 carbon atoms examples include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-methylvinyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, and 1,3.
• -Butadienyl group, cyclohexenyl group, cyclohexadienyl group, cinnamyl group, naphthylvinyl group and the like can be mentioned, but the present invention is not limited thereto.
• alkynyl group having 2 to 12 carbon atoms examples include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 3-butanyl group, a 1,3-butanjienyl group and a phenylethynyl group.
• Groups, naphthylethynyl groups and the like can be mentioned, but are not limited thereto.
• R a hydrogen atom and an alkyl group having 1 to 4 carbon atoms are preferable, and a hydrogen atom and a methyl group are more particularly preferable. This is because if the substituent is large, the heat resistance may decrease.
• R is a hydrogen atom means that i or j is 0. i is an integer of 0 to 4 and j is an integer of 0 to 6, but preferably i is an integer of 0 to 2 and j is an integer of 0 to 2.
• Y is independently a hydrogen atom, an acyl group having a hydrocarbon group having 1 to 20 carbon atoms, or a glycidyl group.
• Y is a hydrogen atom, a hydroxyl group is given to the end, when it is an acyl group, an ester group is given to the end, and when it is a glycidyl group, an epoxy group is given to the end, so the ratio is controlled according to the application. That is good.
• the hydrocarbon group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms, and examples thereof include the groups exemplified above. .. Among these, an acyl group having a hydrocarbon group having 1 to 7 carbon atoms is more preferable, an acetyl group, a propanoyl group, a butanoyl group, a benzoyl group and a methylbenzoyl group are more preferable, and an acetyl group and a benzoyl group are particularly preferable.
• the acetyl group is understood to be an acyl group having a hydrocarbon group having 1 carbon atom.
• Z is an acyl group or a hydrogen atom having a hydrocarbon group having 1 to 20 carbon atoms. More than 5 mol% of Z is an acyl group and the rest is a hydrogen atom. 10 mol% or more, preferably 50 mol% or more, more preferably 70 mol% or more of Z is an acyl group. The upper limit is preferably 100 mol%, but it may be substantially 95 mol%.
• the acyl group having a hydrocarbon group having 1 to 20 carbon atoms is the same as that exemplified in Y above, and the preferred acyl group is also the same.
• the phenoxy resin of the present invention does not contain a secondary hydroxyl group, and the dielectric properties and moisture resistance can be further improved.
• the phenoxy resin of the present invention does not significantly affect other physical properties such as moisture resistance. It is also possible to intentionally allow an appropriate amount of secondary hydroxyl groups to be present therein.
• n is the number of repetitions and is an average value.
• the range of the value is 15 or more and 500 or less. From the viewpoint of moldability and handleability, it is preferably 17 or more and 400 or less, and more preferably 20 or more and 300 or less.
• the n number can be calculated from the number average molecular weight (Mn) obtained by the GPC method.
• the epoxy equivalent of the phenoxy resin of the present invention is not particularly limited, but is 2,000 to 50,000 g / eq.
• the range of is preferable. Within this range, the phenoxy resin of the present invention is itself involved in the curing reaction and can be incorporated into the crosslinked structure.
• the phenoxy resin of the present invention is obtained by acylating a part or all of the secondary hydroxyl groups and can be obtained by various methods.
• a preferable manufacturing method for example, there are the following manufacturing methods.
• a manufacturing method (A) A phenoxy resin represented by the above formula (12) (sometimes referred to as a phenoxy resin (a) to distinguish it from the phenoxy resin of the present invention), an acid anhydride of an organic acid, and an organic acid.
• an acid component acylating agent
• a manufacturing method (B) The phenoxy resin obtained by the production methods (A) and (B) is the phenoxy resin of the present invention and is represented by the same formula (1).
• the production method (A) is a method of reacting the bifunctional epoxy resin represented by the formula (7) with the compound represented by the formula (8).
• G is a glycyl group
• m is the number of repetitions
• the average value thereof is 0 or more and 6 or less.
• 5 mol% or more of Z 1 is an acyl group having a hydrocarbon group having 1 to 20 carbon atoms, and the rest is a hydrogen atom.
• the compound represented by the formula (8) is selected from a compound in which both of Z 1 are acyl groups, a compound in which one is an acyl group and the other is a hydrogen atom, and a compound in which both are hydrogen atoms.
• the diester compound may be a compound in which both Z 1 are acyl groups or a compound (mixture) in which the main component (50% or more) is the compound.
• X 1 in equations (7) and (8) is selected to give X in equation (1). Therefore, X 1 in the formulas (7) and (8) contains a dioxy group represented by the formulas (2) and / or the formula (3) in any of the formulas (7) and (8) as a whole. It contains a dioxy group represented by the formula (2) and the formula (3). For example, a dioxy group represented one of X 1 of the formula (7) or (8) in equation (2), and include a dioxy group represented by the formula (3) on the other, the equation (7 ) Or only one X 1 of the formula (8) may contain a dioxy group represented by the formula (2) and the formula (3) and may not be contained in the other, but the former is preferable.
• the phenoxy resin of the present invention always contains dioxy groups represented by the formulas (2) and (3), and as long as these are satisfied, the dioxy groups of the formulas (2) and (3) can be used.
• the raw material bifunctional epoxy resin and / or the compound represented by the formula (8) may be contained in any of the ester compounds, and the ratio thereof is not limited. Further, when X 1 in the above formula (7) or (8) does not include the chemical structures of the formulas (2) and (3), another divalent group should be introduced into X 1. Can be done.
• the bifunctional epoxy resin used in the production method (A) of the present invention is an epoxy resin represented by the above formula (7), and for example, a bifunctional phenol compound represented by the following formula (14) and epihalohydrin.
• epichlorohydrin include epichlorohydrin and epibromohydrin.
• alkali metal compound include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide and potassium hydroxide, alkali metal salts such as sodium carbonate, sodium bicarbonate, sodium chloride, lithium chloride and potassium chloride, and the like.
• alkali metal alkoxides such as sodium methoxydo and sodium ethoxydo
• alkali metal salts of organic acids such as sodium acetate and sodium stearate
• alkali metal phenoxide sodium hydride, lithium hydride and the like.
• the reaction between the bifunctional phenol compound and epihalohydrin to obtain the raw material epoxy resin is 0.80 to 1.20 times mol, preferably 0.85 to 1.05 times the functional group in the bifunctional phenol compound.
• a molar alkali metal compound is used. If it is less than this, the amount of residual hydrolyzable chlorine increases, which is not preferable.
• the alkali metal compound it is used in an aqueous solution, an alcohol solution or a solid state.
• an excess amount of epihalohydrin is used for the bifunctional phenol compound.
• 1.5 to 15 times mol of epihalohydrin is used with respect to 1 mol of functional groups in the bifunctional phenol compound, preferably 2 to 10 times mol, more preferably 5 to 8 times mol. If it is more than this, the production efficiency is lowered, and if it is less than this, the amount of high molecular weight epoxy resin produced increases, which makes it unsuitable as a raw material for phenoxy resin.
• the epoxidation reaction is usually carried out at a temperature of 120 ° C. or lower. During the reaction, if the temperature is high, the amount of so-called poorly hydrolyzable chlorine increases, making it difficult to achieve high purity.
• the temperature is preferably 100 ° C. or lower, more preferably 85 ° C. or lower.
• X 1 is the same as X 1 in the formula (7) or (8).
• the diester compound used in the production method (A) of the present invention is, for example, a bifunctional phenol compound represented by the above formula (14), which is an acid anhydride of an organic acid, a halide of an organic acid, or an organic compound. It is obtained by acylation by a condensation reaction with an acid.
• the phenoxy resin of the present invention does not contain a secondary hydroxyl group, and the dielectric properties and moisture resistance can be further improved. Further, for example, when finely adjusting the adhesiveness to a metal, by using an epoxy resin having an appropriate number of m, the phenoxy resin of the present invention does not significantly affect other physical properties such as moisture resistance. It is also possible to intentionally allow an appropriate amount of secondary hydroxyl group to be present therein.
• the bifunctional epoxy resin or diester compound used in the production method (A) has a chemical structure represented by the above formulas (2) and (3), which is X in the above formulas (7) and (8). it preferably contains 1 to 100 mol% relative to 1 total moles. From the viewpoint of sufficiently exhibiting the folding resistance and dielectric properties resulting from the chemical structures represented by the formulas (2) and (3), the chemical structures represented by the formulas (2) and (3) are more preferable. Is 10 mol% or more, more preferably 30 mol% or more, and particularly preferably 50 mol% or more.
• the amount of the bifunctional epoxy resin and the diester compound used is preferably 0.8 to 1.0 equivalents of the ester group with respect to 1 equivalent of the epoxy group. This equivalent ratio is preferable because it facilitates the progress of increasing the molecular weight in the state of having an epoxy group at the end of the molecule. It is also possible to replace a part of the diester compound with a bifunctional phenol compound represented by the above formula (14). As a result, as described above, the physical properties can be finely adjusted by intentionally allowing an appropriate amount of secondary hydroxyl groups to be present in the phenoxy resin of the present invention. In the production method (A), a polymerization reaction and a transesterification reaction occur to increase Mw to produce a phenoxy resin, and at the same time, a part of the aquatic group of the phenoxy resin is esterified.
• a catalyst may be used, and the catalyst may be any compound having a catalytic ability to promote the reaction between the epoxy group and the ester group.
• the catalyst may be any compound having a catalytic ability to promote the reaction between the epoxy group and the ester group.
• tertiary amines, cyclic amines, imidazoles, organic phosphorus compounds, quaternary ammonium salts and the like can be mentioned. Further, these catalysts may be used alone or in combination of two or more.
• tertiary amine examples include triethylamine, tri-n-propylamine, tri-n-butylamine, triethanolamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol and the like. , Not limited to these.
• cyclic amines examples include 1,4-diazabicyclo [2,2,2] octane (DABCO), 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), 1,5-diazabicyclo [ 4,3,0] Nonen-5 (DBN), N-methylmorpholin, pyridine, N, N-dimethylaminopyridine (DMAP) and the like, but are not limited thereto.
• imidazoles examples include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2- Examples include, but are not limited to, phenylimidazole and the like.
• organophosphorus compound examples include tri-n-propylphosphine, tri-n-butylphosphine, diphenylmethylphosphine, triphenylphosphine, triphenylphosphine, tricyclohexinephosphine, tri (t-butyl) phosphine, and the like.
• Hosphines such as tris (p-methoxyphenyl) phosphine, paramethylphosphine, 1,2-bis (dimethylphosphine) ethane, 1,4-bis (diphenylphosphine) butane, tetramethylphosphonium bromide, tetramethylphosphonium.
• Iodide tetramethylphosphonium hydroxide, tetrabutylphosphonium hydroxide, trimethylcyclohexylphosphonium chloride, trimethylcyclohexylphosphonium bromide, trimethylbenzylphosphonium chloride, trimethylbenzylphosphonium bromide, tetraphenylphosphonium bromide, triphenylmethylphosphonium bromide, triphenylmethylphosphonium Examples thereof include, but are not limited to, iodido, triphenylethylphosphonium chloride, triphenylethylphosphonium bromide, triphenylethylphosphonium iodide, triphenylbenzylphosphonium chloride, and phosphonium salts such as triphenylbenzylphosphonium bromide.
• Examples of the quaternary ammonium salt include tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium hydroxide, triethylmethylammonium chloride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium bromide, and tetra.
• Examples thereof include propylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium hydroxide, benzyltributylammonium chloride, phenyltrimethylammonium chloride and the like. However, it is not limited to these.
• the amount of the catalyst used is usually 0.001 to 1% by mass in the reaction solid content, but when these compounds are used as catalysts, these catalysts remain as residues in the obtained phenoxy resin, and the printed wiring is printed.
• the nitrogen content in the phenoxy resin is preferably 0.5% by mass or less, preferably 0.3% by mass or less, because it may deteriorate the insulating properties of the plate or shorten the pot life of the composition. More preferred.
• the phosphorus content in the phenoxy resin is preferably 0.5% by mass or less, more preferably 0.3% by mass.
• a solvent for reaction may be used, and the solvent may be any solvent as long as it dissolves the phenoxy resin.
• aromatic solvents, ketone solvents, amide solvents, glycol ether solvents, ester solvents and the like can be mentioned. Further, these solvents may be used alone or in combination of two or more.
• aromatic solvent examples include benzene, toluene, xylene and the like.
• ketone solvent examples include acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclohexanone, acetylacetone, dioxane, diisobutyl ketone, isophorone, methylcyclohexanone, acetophenone and the like. Be done.
• amide solvent examples include formamide, N-methylformamide, N, N-dimethylformamide (DMF), acetamide, N-methylacetamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone and the like. Be done.
• glycol ether-based solvent examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoalkyl ethers, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol mono-n-butyl ether.
• Ethylene glycol dialkyl ethers such as propylene glycol monomethyl ether
• propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol mono-n-butyl ether, ethylene glycol dimethyl ether and ethylene glycol diethyl ether.
• Ethethylene glycol dialkyl ethers such as ethylene glycol dibutyl ether, polyethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, and triethylene glycol dibutyl ether, Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, and propylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, and tripropylene glycol diethyl ether, Polypropylene glycol dialkyl ethers such as tripropylene glycol dibutyl ether, ethylene glycol monoalkyl ether acetates such as
• glycol monoalkyl ether acetates examples include glycol monoalkyl ether acetates and propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether acetate.
• ester solvent examples include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, benzyl acetate, ethyl propionate, ethyl butyrate, butyl butyrate, valerolactone, butyrolactone and the like. And so on.
• solvents examples include dimethylsulfoxide, sulfolane, ⁇ -butyrolactone, N-methyl-2-pyrrolidone and the like.
• the solid content concentration at the time of reaction is preferably 35 to 95% by mass. Further, when a highly viscous product is generated during the reaction, an additional solvent can be added to continue the reaction. After completion of the reaction, the solvent can be removed or added as needed.
• the reaction temperature should be within the temperature range where the catalyst used does not decompose. If the reaction temperature is too high, the catalyst may decompose and the reaction may stop, or the phenoxy resin produced may deteriorate. If the reaction temperature is too low, the reaction may not proceed sufficiently and the target molecular weight may not be reached. Therefore, the reaction temperature is preferably 50 to 230 ° C, more preferably 120 to 200 ° C.
• the reaction time is usually 1 to 12 hours, preferably 3 to 10 hours. When a low boiling point solvent such as acetone or methyl ethyl ketone is used, the reaction temperature can be secured by carrying out the reaction under high pressure using an autoclave. When it is necessary to remove the heat of reaction, it is usually carried out by the evaporation / condensation / reflux method of the solvent used by the heat of reaction, the indirect cooling method, or a combination thereof.
• the manufacturing method (B) of the present invention will be described.
• the acylating agent is reacted with the phenoxy resin represented by the formula (12) and 1 mol of the alcoholic hydroxyl group of the phenoxy resin when the acyl group is 0.05 mol or more and 2.0 mol or less.
• This is a method for obtaining a phenoxy resin represented by the formula (1) having a weight average molecular weight of 10,000 to 200,000, that is, the phenoxy resin of the present invention.
• Raw phenoxy resin (a) comprises dioxy group represented by the above formula in X 2 in the formula (12) (2) and (3) as essential.
• This phenoxy resin (a) can be obtained by a conventionally known method.
• a bifunctional phenol compound having a structure represented by the above formula (2) (sometimes referred to as a bifunctional phenol compound (a)) and a bifunctional phenol compound having a structure represented by the above formula (3) (may be referred to as a bifunctional phenol compound (a)).
• a method for producing a bifunctional phenol compound that requires "bifunctional phenol compound (b)") and epihalohydrin in the presence of an alkali metal compound hereinafter referred to as a one-step method).
• the bifunctional epoxy resin and the bifunctional phenol compound is catalyzed by the bifunctional epoxy resin and the bifunctional phenol compound having the structures represented by the above formulas (2) and (3).
• Examples thereof include a method of producing by reacting in the presence (hereinafter, referred to as a two-step method).
• the phenoxy resin (a) may be obtained by any production method, but it is generally preferable to use the two-step method because the two-step method is easier to obtain the phenoxy resin than the one-step method. ..
• the weight average molecular weight and epoxy equivalent of the phenoxy resin (a) are determined by the molar ratio of epihalohydrin and the bifunctional phenol compound charged in the one-step method, and the charged molar ratio of the bifunctional epoxy resin and the bifunctional phenol compound in the two-step method. By making appropriate adjustments, it is possible to manufacture a product in the desired range.
• the bifunctional phenol compound (a) and the bifunctional phenol compound (b) are indispensable.
• the bifunctional phenol compound (a) include catechol, resorcin, and hydroquinone. Further, these may be substituted with a substituent having no adverse effect such as an alkyl group or an aryl group.
• the bifunctional phenol compound (b) include 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and the like. .. Further, these may be substituted with a substituent having no adverse effect such as an alkyl group or an aryl group.
• bifunctional phenol compounds may be used in combination as long as the object of the present invention is not impaired.
• the bifunctional phenol compound that may be used in combination include bisphenols such as bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol E, bisphenol C, bisphenol acetophenone, bisphenol fluoride, dihydroxybiphenyl ether, and dihydroxybiphenyl thioether.
• examples thereof include biphenols such as 4,4'-biphenol and 2,4'-biphenol, and 1,1-bi-2-naphthol.
• a plurality of these bifunctional phenol compounds may be used in combination.
• the one-step method In the case of the one-step method, 0.985 to 1.015 mol of epihalohydrin, preferably 0.99 to 1.012 mol, and more preferably 0.995 to 1.01 mol with respect to 1 mol of the bifunctional phenol compound.
• the phenoxy resin (a) can be obtained by reacting in a non-reactive solvent in the presence of an alkali metal compound so that epihalohydrin is consumed and the weight average molecular weight is 10,000 or more. .. After completion of the reaction, it is necessary to remove the by-produced salt by filtration or washing with water.
• the alkali metal compound include the same alkali metal compounds used in the production of the bifunctional epoxy resin represented by the above formula (7) used in the production method (A) of the present invention.
• the molar ratio of the bifunctional phenol compound (a) used as a raw material to the bifunctional phenol compound (b) is preferably 1/9 to 9/1, more preferably 2/8 to 8/2, and 3/7 to 3/7. 7/3 is more preferable, and 4/6 to 6/4 is particularly preferable.
• the total number of moles of the bifunctional phenol compound (a) and the bifunctional phenol compound (b) is preferably 1 mol% or more, more preferably 20 mol% or more, and 50 mol% in all the bifunctional phenol compounds. The above is more preferable, and 75 mol% or more is particularly preferable. If it is out of this range, the heat resistance, folding resistance, and deterioration of the phenoxy resin of the present invention may occur.
• the reaction temperature is usually preferably 20 to 200 ° C., more preferably 30 to 170 ° C., even more preferably 40 to 150 ° C., and particularly preferably 50 to 100 ° C. in the case of a reaction under normal pressure.
• 20 to 100 ° C. is preferable, 30 to 90 ° C. is more preferable, and 35 to 80 ° C. is further preferable. If the reaction temperature is within this range, side reactions are unlikely to occur and the reaction can easily proceed.
• the reaction pressure is usually normal pressure. When it is necessary to remove the heat of reaction, it is usually carried out by the evaporation / condensation / reflux method of the solvent used, the indirect cooling method, or a combination thereof by the heat of reaction.
• alcohols such as ethanol, isopropyl alcohol, and butyl alcohol can be used in addition to the reaction solvent exemplified in the production method (A) of the present invention. Only one type may be used, or two or more types may be used in combination.
• the two-step method As the bifunctional epoxy resin used as the raw material epoxy resin of the two-step method, the same as the bifunctional epoxy resin represented by the above formula (7) used in the production method (A) of the present invention is used.
• the bifunctional epoxy resin represented by the above formula (7) is preferable, but other bifunctional epoxy resins may be used in combination as long as the object of the present invention is not impaired. ..
• the bifunctional epoxy resin that can be used together include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol acetophenone type epoxy resin, diphenyl sulfide type epoxy resin, and diphenyl ether type epoxy resin.
• examples thereof include resins, biphenol type epoxy resins, diphenyldicyclopentadiene type epoxy resins, alkylene glycol type epoxy resins, and aliphatic cyclic epoxy resins. These epoxy resins may be substituted with a substituent having no adverse effect such as an alkyl group or an aryl group. A plurality of types of these epoxy resins may be used in combination.
• any compound can be used as long as it can use a catalyst and has a catalytic ability to promote the reaction between the epoxy group and the phenolic hydroxyl group.
• the same as the catalyst exemplified in the production method (A) of the present invention can be mentioned.
• an alkali metal compound used in the production of the bifunctional epoxy resin represented by the above formula (7) can also be used.
• These catalysts may be used alone or in combination of two or more. Further, the amount used is the same as the amount used exemplified in the production method (A) of the present invention.
• a solvent may be used, and any solvent may be used as long as it dissolves a phenoxy resin and does not adversely affect the reaction.
• any solvent may be used as long as it dissolves a phenoxy resin and does not adversely affect the reaction.
• the same solvent as that exemplified in the production method (A) of the present invention is exemplified. These solvents may be used alone or in combination of two or more.
• the amount of the solvent to be used can be appropriately selected according to the reaction conditions, but for example, in the case of the two-step method, the solid content concentration is preferably 35 to 95% by mass. If a highly viscous product is produced during the reaction, a solvent can be added during the reaction to continue the reaction. After completion of the reaction, the solvent can be removed by distillation or the like, if necessary, or can be further added.
• the reaction temperature should be within the temperature range where the catalyst used does not decompose. If the reaction temperature is too high, the catalyst may decompose and the reaction may stop, or the phenoxy resin produced may deteriorate. If the reaction temperature is too low, the reaction may not proceed sufficiently and the target molecular weight may not be reached. Therefore, the reaction temperature is preferably 50 to 230 ° C, more preferably 100 to 210 ° C, and even more preferably 120 to 200 ° C.
• the reaction time is usually 1 to 12 hours, preferably 3 to 10 hours. When a low boiling point solvent such as acetone or methyl ethyl ketone is used, the reaction temperature can be secured by carrying out the reaction under high pressure using an autoclave. When it is necessary to remove the heat of reaction, it is usually carried out by the evaporation / condensation / reflux method of the solvent used by the heat of reaction, the indirect cooling method, or a combination thereof.
• the phenoxy resin of the present invention can be obtained by acylating the hydroxyl group in the phenoxy resin (a) represented by the above formula (12) thus obtained. Acylation may be performed not only by direct esterification but also by a method such as transesterification.
• Examples of the acid component used for the acylation include acetic acid, propionic acid, butyric acid, isobutyric acid, pentanoic acid, octanoic acid, capric acid, lauric acid, stearic acid, oleic acid, benzoic acid, and t-butyl benzoic acid.
• Organic acids such as hexahydrobenzoic acid, phenoxyacetic acid, acrylic acid, and methacrylic acid, acid anhydrides of organic acids, halides of organic acids, esterified products of organic acids, and the like can be used.
• an acid anhydride represented by the following formula (13) is preferable.
• Z 2 is an acyl group having a hydrocarbon group having 1 to 20 carbon atoms.
• Examples of the acid anhydride of the organic acid include acetic anhydride, benzoic acid anhydride, phenoxyacetic anhydride and the like.
• Examples of the esterified product of the organic acid include methyl acetate, ethyl acetate, butyl acetate, methyl benzoate, ethyl benzoate and the like.
• Examples of the halide of the organic acid include chloride, benzoic acid chloride, phenoxyacetic acid chloride and the like.
• Compounds used for esterification include halides of organic acids such as chloride, benzoic acid chloride, and phenoxyacetic acid chloride, acid halides such as acetic anhydride, benzoic acid anhydride, and phenoxyacetic acid anhydride, and acid anhydride of organic acids.
• Acid anhydrides such as acetic anhydride and benzoic acid anhydride are more preferable in the sense that they are preferable, do not require washing with water after esterification, and avoid mixing of halogen, which is disliked in electrical material applications.
• the phenoxy resin (a) is reacted with an acid component such as the organic acid used for esterifying the hydroxyl group of the phenoxy resin (a), an acid anhydride of the organic acid, a halide of the organic acid, or an esterified product of the organic acid.
• the charging ratio may be the same as the target esterification ratio, or if the reactivity is low, the above acid component is excessively charged with respect to the hydroxyl group and reacted to the target esterification ratio, and then not yet.
• the acid component of the reaction may be removed.
• the amount of the acylating agent used for the raw material phenoxy resin (a) is such that the acyl group of the acylating agent is 0.05 mol or more and 2.0 mol with respect to 1 mol of the alcoholic hydroxyl group of the phenoxy resin (a).
• it is preferably 0.1 to 1.0 mol, more preferably 0.2 to 0.8 mol.
• the acylating agent is an acid anhydride represented by the formula (13), it is understood that the acylating agent has 2 mol of an acyl group with respect to 1 mol of the acylating agent.
• acid catalysts such as paratoluenesulfonic acid and phosphoric acid and metal catalysts such as tetraisopropyl titanate, tetrabutyl titanate, dibutyltin oxide, dioctyltin oxide and zinc chloride. It can be carried out while dehydrating using a catalyst. Usually, it is preferably carried out at 100 to 250 ° C. in a nitrogen atmosphere, and more preferably 130 to 230 ° C.
• an acid halide or acid anhydride is used for esterification
• a method of filtering the salt after neutralization using a basic compound, or washing with water after neutralization using a basic compound Any of the method, the method of washing with water without neutralization, and the method of removing by distillation or adsorption may be used, or may be used in combination.
• the phenoxy resin (a) is esterified by ester exchange, it is usually carried out under a nitrogen atmosphere, for example, dibutyltin oxide, dioctyltin oxide, stanoxane catalyst, tetraisopropyl titanate, tetrabutyl titanate, lead acetate, zinc acetate, antimony trioxide. It is desirable to carry out the process while dealcoholizing using an organic metal catalyst such as, an acid catalyst such as hydrochloric acid, sulfuric acid, phosphoric acid or sulfonic acid, or a known esterification catalyst such as a basic catalyst such as lithium hydroxide or sodium hydroxide.
• an organic metal catalyst such as, an acid catalyst such as hydrochloric acid, sulfuric acid, phosphoric acid or sulfonic acid, or a known esterification catalyst such as a basic catalyst such as lithium hydroxide or sodium hydroxide.
• a solvent for reaction may be used, and the solvent may be any solvent as long as it dissolves a phenoxy resin.
• the solvent exemplified in the production method (A) of the present invention can be mentioned.
• These solvents may be the same as those used in the preparation of the phenoxy resin (a), or may be different. Further, only one type may be used, or two or more types may be used in combination.
• the resin composition of the present invention is a resin composition containing at least the phenoxy resin of the present invention and a curing agent. Further, various additives such as an epoxy resin, an inorganic filler, a coupling agent, and an antioxidant can be appropriately added to the resin composition of the present invention, if necessary.
• the resin composition of the present invention provides a cured product that sufficiently satisfies various physical properties required for various uses.
• a curing agent can be blended with the phenoxy resin of the present invention to obtain a resin composition.
• the curing agent refers to a substance that contributes to a cross-linking reaction and / or a chain length extension reaction with a phenoxy resin.
• a curing accelerator even if it is usually called a "curing accelerator", if it is a substance that contributes to the cross-linking reaction and / or the chain length extension reaction of the phenoxy resin, it is regarded as a curing agent.
• the content of the curing agent in the resin composition of the present invention is preferably 0.1 to 100 parts by mass in terms of solid content with respect to 100 parts by mass in solid content of the phenoxy resin of the present invention. Further, it is more preferably 80 parts by mass or less, and further preferably 60 parts by mass or less.
• the weight ratio of the solid content of the phenoxy resin of the present invention to the epoxy resin is 99/1 to 1/99.
• the "solid content” means a component excluding the solvent, and includes not only solid phenoxy resin and epoxy resin but also semi-solid and viscous liquid substances.
• the "resin component” means the total of the phenoxy resin of the present invention and the epoxy resin described later.
• the curing agent used in the resin composition of the present invention is not particularly limited, and any generally known epoxy resin curing agent can be used. From the viewpoint of increasing heat resistance, phenol-based curing agents, amide-based curing agents, imidazoles, active ester-based curing agents and the like can be mentioned. These curable agents may be used alone or in combination of two or more.
• phenolic curing agent examples include bisphenol A, bisphenol F, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, 1,4-bis (4-hydroxyphenoxy) benzene, and 1,3-bis ( 4-Hydroxyphenoxy) benzene, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylketone, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, phenol novolac, bisphenol A novolac, o-cresol novolac, m-cresol novolac, p-cresol novolac , Xylenol novolac, poly-p-hydroxystyrene, hydroquinone
• amide-based curing agent examples include dicyandiamide and its derivatives, polyamide resins, and the like.
• imidazoles examples include 2-phenylimidazole, 2-ethyl-4 (5) -methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole.
• 1-Cyanoethyl-2-undecylimidazole 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimerite, 1-cyanoethyl-2-phenylimidazolium trimerite, 2,4- Diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl -S-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4 , 5-Dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxy
• the active ester-based curing agent has two or more ester groups with high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds in one molecule.
• Compounds are preferable, and among them, phenol esters obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group are more preferable.
• Specific examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
• aromatic compounds having a phenolic hydroxyl group examples include catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucin, and benzenetriol. Examples thereof include dicyclopentadienyldiphenol and phenol novolac.
• the resin composition of the present invention can contain an epoxy resin.
• the epoxy resin preferably has two or more epoxy groups in the molecule, and more preferably an epoxy resin having three or more epoxy groups. Examples thereof include polyglycidyl ether compounds, polyglycidyl amine compounds, polyglycidyl ester compounds, alicyclic epoxy compounds, and other modified epoxy resins. These epoxy resins may be used alone, two or more kinds of epoxy resins of the same system may be used in combination, or epoxy resins of different systems may be used in combination.
• polyglycidyl ether compound examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, bisphenol Z type epoxy resin, bisphenol fluorene type epoxy resin, and diphenyl sulfide type epoxy resin.
• Diphenyl ether type epoxy resin Diphenyl ether type epoxy resin, naphthalene type epoxy resin, hydroquinone type epoxy resin, resorcinol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alkyl novolac type epoxy resin, styrated phenol novolac type epoxy resin, bisphenol novolac type Epoxy resin, naphthol novolac type epoxy resin, phenol aralkyl type epoxy resin, ⁇ -naphthol aralkyl type epoxy resin, naphthalenediol aralkyl type epoxy resin, ⁇ -naphthol aralkyl type epoxy resin, biphenyl aralkyl phenol type epoxy resin, biphenyl type epoxy resin, Various epoxy resins such as triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, alkylene glycol type epoxy resin, and aliphatic cyclic epoxy resin can be used.
• polyglycidylamine compound examples include diaminodiphenylmethane type epoxy resin, metaxylene diamine type epoxy resin, 1,3-bisaminomethylcyclohexane type epoxy resin, isocyanurate type epoxy resin, aniline type epoxy resin, and hydantin type epoxy resin.
• Aminophenol type epoxy resin and the like can be mentioned.
• polyglycidyl ester compound examples include a dimer acid type epoxy resin, a hexahydrophthalic acid type epoxy resin, and a trimellitic acid type epoxy resin.
• alicyclic epoxy compound examples include aliphatic cyclic epoxy resins such as celloxide 2021 (manufactured by Daicel Chemical Industry Co., Ltd.).
• modified epoxy resins include, for example, urethane-modified epoxy resin, oxazolidone ring-containing epoxy resin, epoxy-modified polybutadiene rubber derivative, carboxyl group-terminated butadiene nitrile rubber (CTBN) -modified epoxy resin, and polyvinyl allene polyoxide (for example, divinylbenzene dioxide). , Trivinylnaphthalene trioxide, etc.), phenoxy resin, etc.
• CBN butadiene nitrile rubber
• the blending amount of the epoxy resin is preferably 1 to 99% by mass in all the components of the phenoxy resin and the epoxy resin as solids. It is more preferably 5 to 97% by mass, further preferably 10 to 95% by mass, still more preferably 10 to 90% by mass.
• the epoxy resin is within the above blending amount, heat resistance and mechanical strength can be improved when a cured product made of the resin composition of the present invention is prepared.
• the resin composition of the present invention may contain a solvent or a reactive diluent in order to appropriately adjust the viscosity of the resin composition at the time of handling at the time of forming the coating film.
• the solvent or the reactive diluent is used to ensure the handleability and workability in molding of the resin composition, and the amount used is not particularly limited.
• the word "solvent” and the above-mentioned word “solvent” are used separately according to their usage modes, but the same type or different ones may be used independently.
• Examples of the solvent that can be contained in the resin composition of the present invention include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate, ethers such as ethylene glycol monomethyl ether, N and N. -Includes amides such as dimethylformamide and N, N-dimethylacetamide, alcohols such as methanol and ethanol, alkanes such as hexane and cyclohexane, and aromatics such as toluene and xylene.
• the above-mentioned solvents may be used alone or in admixture of two or more in any combination and ratio.
• the reactive diluent examples include monofunctional glycidyl ethers such as allyl glycidyl ether, bifunctional glycidyl ethers such as propylene glycol diglycidyl ether, polyfunctional glycidyl ethers such as trimethylolpropane polyglycidyl ether, and glycidyl esters. , Glycidyl amines and the like.
• solvents or reactive diluents are preferably used in an amount of 90% by mass or less as a non-volatile content, and the appropriate type and amount to be used are appropriately selected depending on the application.
• a polar solvent having a boiling point of 160 ° C. or lower such as methyl ethyl ketone, acetone, or 1-methoxy-2-propanol, is preferable, and the amount used is preferably 40 to 80% by mass in terms of non-volatile content.
• ketones, acetic acid esters, carbitols, aromatic hydrocarbons, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like are preferably used, and the amount used is a non-volatile component. 30 to 60% by mass is preferable.
• a curing accelerator (excluding those contained in the “curing agent”) can be used in the resin composition of the present invention, if necessary.
• the curing accelerator include phosphorus compounds such as imidazoles, tertiary amines and phosphines, metal compounds, Lewis acids, amine complex salts and the like. These curing accelerators may be used alone or in combination of two or more.
• the amount of the curing accelerator to be blended may be appropriately selected according to the purpose of use, but 0.01 to 15 parts by mass is used as necessary with respect to 100 parts by mass of the epoxy resin component in the resin composition. 0.01 to 10 parts by mass is preferable, 0.05 to 8 parts by mass is more preferable, and 0.1 to 5 parts by mass is further preferable.
• the curing accelerator By using the curing accelerator, the curing temperature can be lowered and the curing time can be shortened.
• various known flame retardants can be used for the purpose of improving the flame retardancy of the obtained cured product as long as the reliability is not lowered.
• the flame retardants that can be used include halogen-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, and organic metal salt-based flame retardants. From the viewpoint of the environment, halogen-free flame retardants are preferable, and phosphorus-based flame retardants are particularly preferable.
• These flame retardants may be used alone, two or more kinds of flame retardants of the same system may be used in combination, or different flame retardants may be used in combination.
• the resin composition of the present invention may contain components other than those listed above (may be referred to as "other components" in the present invention) for the purpose of further improving its functionality. ..
• Such other components include fillers, thermoplastic resins, thermosetting resins, photocurable resins, UV inhibitors, antioxidants, coupling agents, plasticizers, fluxes, rock release agents, smoothing agents. , Colorants, pigments, dispersants, emulsifiers, low elastic agents, mold release agents, antifoaming agents, ion trapping agents and the like.
• the filler examples include molten silica, crystalline silica, alumina, silicon nitride, boron nitride, aluminum nitride, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, boehmite, talc, mica, clay, calcium carbonate, magnesium carbonate, and the like.
• Inorganic fillers such as barium carbonate, zinc oxide, titanium oxide, magnesium oxide, magnesium silicate, calcium silicate, zirconium silicate, barium sulfate, carbon, carbon fiber, glass fiber, alumina fiber, silica alumina fiber, silicon dioxide
• fibrous fillers such as fibers, polyester fibers, cellulose fibers, aramid fibers, and ceramic fibers, and fine particle rubber.
• thermoplastic resin other than the phenoxy resin of the present invention may be used in combination with the resin composition of the present invention.
• the thermoplastic resin include phenoxy resins other than the present invention, polyurethane resins, polyester resins, polyethylene resins, polypropylene resins, polystyrene resins, ABS resins, AS resins, vinyl chloride resins, polyvinyl acetate resins, and polymethyl methacrylate resins.
• a phenoxy resin other than the present invention is preferable from the viewpoint of compatibility, and a polyphenylene ether resin or a modified polyphenylene ether resin is preferable from the viewpoint of low dielectric property.
• Other components include organic pigments such as quinacridone, azo, and phthalocyanine, inorganic pigments such as titanium oxide, metal foil pigments, and rust preventive pigments, and ultraviolet absorption such as hindered amines, benzotriazoles, and benzophenones.
• Agents antioxidants such as hindered phenol, phosphorus, sulfur, and hydrazide, release agents such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, leveling agents, rheology control agents, and pigment dispersion.
• Additives such as agents, anti-pigment agents, antifoaming agents and the like can be mentioned.
• the blending amount of these other components is preferably in the range of 0.01 to 20% by mass with respect to the total solid content in the resin composition.
• the resin composition of the present invention is obtained by uniformly mixing each of the above components.
• a resin composition containing a phenoxy resin, a curing agent, and various components if necessary can be easily made into a cured product by a method similar to a conventionally known method.
• This cured product has an excellent balance of low hygroscopicity, dielectric properties, heat resistance, adhesion and the like, and exhibits good cured physical properties.
• the term "curing" as used herein means that the resin composition is intentionally cured by heat and / or light, and the degree of curing may be controlled according to desired physical properties and applications. The degree of progress may be completely cured or semi-cured, and is not particularly limited, but the reaction rate of the curing reaction between the epoxy group and the curing agent is usually 5 to 95%.
• the resin composition of the present invention can be cured by the same method as the known epoxy resin composition to obtain a cured product.
• a method for obtaining a cured product the same method as that of a known epoxy resin composition can be adopted, such as casting, injection, potting, dipping, drip coating, transfer molding, compression molding, resin sheet, resin, etc.
• a method such as forming a laminated plate by laminating in the form of a copper foil with an epoxy, a prepreg, or the like and curing by heating and pressure is preferably used.
• the curing temperature at that time is usually in the range of 80 to 300 ° C., and the curing time is usually about 10 to 360 minutes.
• This heating is preferably performed by a two-step treatment of a primary heating at 80 to 180 ° C. for 10 to 90 minutes and a secondary heating at 120 to 200 ° C. for 60 to 150 minutes, and the glass transition temperature (Tg) is high.
• Tg glass transition temperature
• the curing reaction of the resin composition is usually allowed to the extent that the shape can be maintained by heating or the like.
• the resin composition contains a solvent, most of the solvent is usually removed by a method such as heating, depressurization, or air drying, but 5% by mass or less of the solvent remains in the resin semi-cured product. May be good.
• the prepreg obtained by using the resin composition of the present invention will be described.
• the sheet-like base material inorganic fibers such as glass and woven fabrics or non-woven fabrics of organic fibers such as polyamine, polyacrylic, polyimide, Kevlar, and cellulose such as polyester can be used, but are limited thereto. is not it.
• the method for producing a prepreg from the resin composition and the base material of the present invention is not particularly limited, and for example, the above base material is impregnated by immersing the above base material in a resin varnish whose viscosity is adjusted with a solvent.
• the resin component is semi-cured (B-staged) and obtained by heating and drying.
• the resin component can be heat-dried at 100 to 200 ° C. for 1 to 40 minutes.
• the amount of resin in the prepreg is preferably 30 to 80% by mass of the resin content.
• a method of manufacturing a laminated board using a prepreg or an insulating adhesive sheet will be described.
• a laminated board using a prepreg one or a plurality of prepregs are laminated, metal foils are arranged on one side or both sides to form a laminate, and the laminate is heated and pressurized to integrate the laminate. do.
• the metal foil a single metal leaf such as copper, aluminum, brass, nickel or the like, an alloy, or a composite metal leaf can be used.
• As a condition for heating and pressurizing the laminate it is sufficient to appropriately adjust and heat and pressurize under the condition that the resin composition is cured. However, if the pressure of pressurization is too low, air bubbles remain inside the obtained laminate.
• the temperature can be set to 160 to 220 ° C.
• the pressure can be set to 49.0 to 490.3 N / cm 2 (5 to 50 kgf / cm 2 ), and the heating time can be set to 40 to 240 minutes.
• a multilayer plate can be produced by using the single-layer laminated plate thus obtained as an inner layer material.
• a circuit is formed on the laminated board by an additive method, a subtractive method, or the like, and the formed circuit surface is treated with an acid solution and blackened to obtain an inner layer material.
• An insulating layer is formed on one side or both side of the circuit forming surface of the inner layer material with a prepreg or an insulating adhesive sheet, and a conductor layer is formed on the surface of the insulating layer to form a multilayer plate.
• the insulating adhesive sheet is arranged on the circuit forming surface of a plurality of inner layer materials to form a laminate.
• an insulating adhesive sheet is arranged between the circuit forming surface of the inner layer material and the metal foil to form a laminate. Then, by heating and pressurizing this laminate and integrally molding it, a cured product of the insulating adhesive sheet is formed as an insulating layer, and a multi-layered inner layer material is formed.
• the inner layer material and the metal foil which is the conductor layer are formed as an insulating layer by forming a cured product of the insulating adhesive sheet.
• the same metal leaf as that used for the laminated board used as the inner layer material can be used. Further, the heat and pressure molding can be performed under the same conditions as the molding of the inner layer material.
• the resin composition is applied to the laminated board to form an insulating layer
• the circuit-forming surface resin of the outermost layer of the inner layer material is applied to the above resin composition to a thickness of preferably 5 to 100 ⁇ m, and then 100 to 200. It is heated and dried at ° C. for 1 to 90 minutes to form a sheet. It is formed by a method generally called a casting method. It is desirable to form the thickness after drying to 5 to 80 ⁇ m.
• a printed wiring board can be formed by further forming a via hole or a circuit on the surface of the multilayer laminated board thus formed by an additive method or a constructive method. Further, by repeating the above-mentioned construction method using this printed wiring board as an inner layer material, a multi-layer laminated board can be further formed.
• the insulating layer is formed by the prepreg
• one or a plurality of prepregs are arranged on the circuit forming surface of the inner layer material, and a metal foil is further arranged on the outside to form the laminate. ..
• a cured product of the prepreg is formed as an insulating layer, and a metal foil on the outside thereof is formed as a conductor layer.
• the metal foil the same metal leaf as that used for the laminated board used as the inner layer material can also be used. Further, the heat and pressure molding can be performed under the same conditions as the molding of the inner layer material.
• a printed wiring board can be formed by further forming a via hole or a circuit on the surface of the multilayer laminated board thus formed by an additive method or a subtractive method. Further, by repeating the above method using this printed wiring board as an inner layer material, a multi-layer board can be further formed.
• the cured product obtained from the resin composition of the present invention and the laminated board for electric / electronic circuits have excellent flame retardancy and heat resistance.
• Weight average molecular weight (Mw) and number average molecular weight (Mn) Obtained by GPC measurement. Specifically, a main body HLC8320GPC (manufactured by Tosoh Corporation) equipped with columns (TSKgel SuperH-H, SuperH2000, SuperHM-H, SuperHM-H, and above, manufactured by Tosoh Corporation) in series is used, and the column temperature is set. The temperature was set to 40 ° C. A DMF (20 mM lithium bromide-containing product) was used as the eluent, the flow rate was 0.3 mL / min, and a differential refractive index detector was used as the detector.
• Mw Weight average molecular weight
• Mn number average molecular weight
• Epoxy equivalent The measurement was performed in accordance with JIS K 7236 standard. Specifically, a potentiometric titrator was used, cyclohexanone was used as a solvent, a brominated tetraethylammonium acetic acid solution was added, and a 0.1 mol / L perchloric acid-acetic acid solution was used. For the solvent-diluted product (resin varnish), the numerical value as a solid content conversion value was calculated from the non-volatile content.
• Non-volatile content Measured according to JIS K 7235 standard. The drying temperature was 200 ° C. and the drying time was 60 minutes.
• Tg Glass transition temperature
• IPC-TM-650 2.4.25 Glass transition temperature
• c standard a sample having a thickness of 4 mm and a diameter of 3 mm was subjected to a temperature rise condition of 10 ° C./min using a differential scanning calorimetry device EXSTAR6000 DSC6200 (manufactured by SII Nanotechnology Co., Ltd.).
• EXSTAR6000 DSC6200 manufactured by SII Nanotechnology Co., Ltd.
• Tmg midpoint glass transition temperature
• Dielectric characteristics It was evaluated by the dielectric loss tangent when measured at 1 GHz by the cavity resonator perturbation method. Specifically, using a PNA network analyzer N5230A (manufactured by Agilent Technologies Co., Ltd.) and a cavity resonator CP431 (manufactured by Kanto Electronics Applied Development Co., Ltd.), the width is set in a measurement environment at room temperature of 23 ° C. and humidity of 50% RH. The measurement was performed using a test piece of 1.5 mm ⁇ length 80 mm ⁇ thickness 150 ⁇ m.
• A1 Hydroquinone type epoxy resin (manufactured by Nittetsu Chemical & Materials Co., Ltd., ZX-1027, epoxy equivalent 131, m ⁇ 0.18)
• A2 Resorcin type epoxy resin (manufactured by Sigma-Aldrich, epoxy equivalent 127, m ⁇ 0.14)
• A3 2,5-Di-t-butylhydroquinone type epoxy resin (manufactured by Nittetsu Chemical & Materials Co., Ltd., Epototo YDC-1213, epoxy equivalent 175, m ⁇ 0.05)
• A4 Naphthalene type epoxy resin (manufactured by DIC Corporation, Epicron HP4032D, epoxy equivalent 142, m ⁇ 0.07)
• A5 Bisphenol A type liquid epoxy resin (manufactured by Nittetsu Chemical & Materials Co., Ltd., Epototo YD-128, epoxy equivalent 186)
• m has the same meaning as m in the above formula
• E1 Acetic anhydride (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)
• E2 Benzoic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.)
• [Curing agent] H1 Phenol novolac resin (manufactured by Aica Kogyo Co., Ltd., Shonor BRG-5575, hydroxyl group equivalent 105)
• Example 1 In a glass reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas introduction device, a cooling tube, and a dropping device, 100 parts of A1, 89 parts of B1 and 47 parts of S1 as a reaction solvent were charged at room temperature, and nitrogen was charged. The temperature was raised to 130 ° C. while flowing and stirring the gas, 0.2 part of D1 was added as a catalyst, the temperature was raised to 145 ° C., and the reaction was carried out at the same temperature for 7 hours. A phenoxy resin varnish (R1) having a non-volatile content of 40% was obtained by diluting and mixing using 47 parts of S1 and 189 parts of S2 as a diluting solvent.
• R1 phenoxy resin varnish
• Example 2 to 8 Comparative Examples 1 to 3 According to the charged amount (part) of each raw material shown in Tables 1 and 2, the same operation as in Example 1 was carried out to obtain a phenoxy resin varnish.
• the molar ratio in the table represents the molar ratio of the bifunctional epoxy resin to the diester compound and the bifunctional phenol compound, and the varnish represents the phenoxy resin varnish.
• Example 10 100 parts (40 parts in terms of solid content) of the phenoxy resin varnish (RH3) obtained in Comparative Example 3 and 600 parts of S1 were blended, the temperature was raised to 100 ° C., and 5 parts of E1 was added to carry out a reaction for 4 hours. ..
• the obtained resin varnish was added to methanol, the precipitated insoluble matter was filtered off, and the filtrate was dried in a vacuum dryer at 150 ° C. and 0.4 kPa (3 torr) for 1 hour to obtain a phenoxy resin. ..
• To the obtained phenoxy resin 21 parts of S1 and 42 parts of S2 were added and uniformly dissolved to obtain a phenoxy resin varnish (R10) having a non-volatile content of 40%.
• Example 11 The same operation as in Example 10 was carried out except that E1 was 23 parts, S1 of the diluting solvent was 25 parts, and S2 was 49 parts, to obtain a phenoxy resin varnish (R11).
• Example 12 The same operation as in Example 10 was carried out except that 51 parts of E2 was used instead of E1, 31 parts of S1 of the diluting solvent and 62 parts of S2 were used to obtain a phenoxy resin varnish (R12).
• the resin varnishes R1 to R12 and RH1 to RH3 obtained in Examples 1 to 12 and Comparative Examples 1 to 3 were applied to an iron plate so that the film thickness after drying was 100 ⁇ m and 150 ⁇ m, and the temperature was changed to 150 ° C. using a dryer. It was dried for 1 hour to obtain a resin film. Epoxy equivalent and Mw were measured with a phenoxy resin varnish, and Tg, dielectric properties, and folding resistance were measured with a resin film. The results are shown in Table 3.
• formula (2) content rate is the content rate (mol%) of the structure of formula (2) in all X in formula (1)
• “formula (3) content rate” is the formula ( The content rate (mol%) of the structure of the formula (3) in the total X in 1) is represented by the content rate (mol%) of the structure of the formula (3)
• the "acyllation rate” represents the content rate (mol%) of the acyl group in the total Z.
• An example using the resin varnishes RH1 to RH3 is a comparative example.
• a resin composition was obtained by blending 2.5 parts of H1 as a curing agent in a 50% MEK solution and 0.6 parts of C2 as a curing accelerator in a 20% MEK solution. Further, these were applied to an iron plate so that the film thickness after drying was 100 and 150 ⁇ m, and dried at 150 ° C. for 1 hour using a dryer to obtain a film-like cured product. Tg, dielectric properties, and folding resistance were measured, respectively. The results are shown in Table 4.
• the phenoxy resin of the present invention shown in Examples 1 to 12 is excellent in heat resistance, dielectric properties, and folding resistance. Further, as can be seen from Table 4, the cured product made of the resin composition of the present invention is also excellent in heat resistance, dielectric properties, and folding resistance.
• the phenoxy resin and resin composition of the present invention can be applied to various fields such as adhesives, paints, building materials for civil engineering, and insulating materials for electrical and electronic parts. It is useful as a material, sealing material, etc.
• the phenoxy resin of the present invention and the resin composition containing the same can be used for multilayer printed wiring substrates, laminated boards for electric / electronic circuits such as capacitors, film-like adhesives, adhesives such as liquid adhesives, semiconductor encapsulants, and underfills. It can be suitably used as a material, an interchip fill material for 3D-LSI, an insulating sheet, a prepreg, a heat radiating substrate, and the like.

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