JP2002105160A - Phenolic compound, thermosetting resin composition and cured material of the same composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To synthesize a phenolic compound which is a raw material of new various plastics (a polycarbonate, PEEK, PPO, polysulfon, etc.), or a raw material of additives and thermosetting resins (an epoxy resin, a cyanate resin, an acrylic resin, etc.), and provide useful materials as insulating materials for electronic parts (highly reliable semiconductor-sealing material, etc.), laminated boards (a printed circuit board, build up base plate, etc.), various composite materials to begin with a CFRP, adhesives, coating materials, etc., by using the phenolic compound as the resin composition or plastics for exhibiting its excellent low water-absorption and flame retardant property in its cured materials or plastics. SOLUTION: This phenolic compound is synthesized as a polycondensate of a compound expressed by the formula (1) with formaldehyde, and used as a plastic raw material, an additive for plastic and a constituting component of a thermosetting composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to various plastic (polycarbonate, PEEK, PPO, polysulfone, etc.) additives, thermosetting resin (epoxy resin, cyanate resin, acrylate resin, etc.) raw materials, or highly reliable semiconductor encapsulation. Insulation materials for electrical and electronic parts, including various composite materials such as laminated boards (printed wiring boards) and CFRP (carbon fiber reinforced plastic), adhesives, paints,
Ingredients such as molding materials, polyhydric phenol compounds useful as various industrial intermediates, and insulating materials for electric and electronic parts including highly reliable semiconductor encapsulations containing these compounds, and laminates (printed Wiring board, build-up board)
The present invention relates to a thermosetting resin composition useful for various composite materials including CFRP (carbon fiber reinforced plastic), optical materials, adhesives, paints, and the like, and a cured product thereof.

[0002]

2. Description of the Related Art Phenol compounds include thermoplastic plastic additives (antioxidants, etc.), thermosetting resin raw materials,
Or insulating materials for electric / electronic parts, structural materials, adhesives,
It is widely used in the field of components such as paints. Further, in making the organic polymer material flame-retardant, a phosphorus-based or halogen-based organic flame retardant, aluminum hydroxide, antimony trioxide or the like is mainly used in combination as required. In particular, bromine-based flame retardants and antimony trioxide are often used in electrical and electronic parts such as semiconductors that require high reliability.

However, it has recently been pointed out that halogen-based flame retardants contribute to the generation of toxic substances such as dioxin by improper treatment after disposal, and antimony trioxide is also considered to have toxicity. In addition, most of the phosphorus-based flame retardants that are generally used are phosphate esters, and when used in highly reliable electrical and electronic components, when used in highly reliable electric and electronic components, water resistance and phosphoric acid generated by hydrolysis cause the formation of electronic circuits. Corrosion is a concern. Therefore, a flame-retardant polymer material that does not contain halogen or antimony and has a structure that does not easily cause hydrolysis or the like in a phosphorus system is required, but it cannot be said that it is still sufficient.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to novel plastics (polycarbonate, PEEK, PP).
O, polysulfone, etc.) Additives and phenol compounds which are the raw materials of thermosetting resins (epoxy resins, cyanate resins, acrylate resins, etc.) are synthesized, and these are used in the resin composition to give excellent cured products. By exhibiting low water absorption and flame retardancy, various composites including insulating materials for electric and electronic parts (highly reliable semiconductor sealing materials, etc.) and laminated boards (printed wiring boards, build-up boards, etc.) and CFRP Provide useful materials for materials, adhesives, paints, etc.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems and completed the present invention. That is, the present invention provides:

Embedded image A phenol compound which is a polycondensate of a compound represented by the formula (1), formaldehyde and a phenol, (2) a compound represented by the formula (1) and a compound represented by the formula (2):

Embedded image (In formula (2), a plurality of Rs independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group.
n shows the integer of 2-3, and m shows the integer of 1-5. )
A phenol compound which is a polycondensate with the compound represented by the formula (3):

Embedded image (In formula (3), a plurality of Rs independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group.
n shows the integer of 2-3, and m shows the integer of 1-5. )
A phenolic compound of the above (1) or (2), (4) a thermosetting resin composition containing the phenolic compound according to any one of the above (1) to (3),
(5) the thermosetting resin composition of (4), which does not contain halogen; (6) a cured product of the thermosetting resin composition of (4) or (5); 6) A cured product, and (8) a flame-retardant thermoplastic containing the phenol compound according to any one of (1) to (3).

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The phenolic compound of the present invention is obtained by polycondensing a compound of the formula (1) with formaldehyde and a monovalent phenol, and is a monovalent compound having two or more phosphorus atoms in one molecule. (Structure having one phenolic hydroxyl group) is preferred. More preferably, the polymethylol compound represented by the formula (2) is synthesized, and is synthesized by dehydration condensation of the methylol group with the compound of the formula (1).

Hereinafter, a method for producing the phenolic compound of the present invention using the compound of the formula (2), which is a preferred embodiment of the present invention, will be described. The polymethylol represented by the formula (2) can be obtained by a conventionally known method, for example, a method of reacting phenols with formaldehyde usually in the presence of an alkali catalyst, or an aromatic polyaldehyde compound having a hydroxy group. A method of reducing the aldehyde group of the above may be employed. Specific examples of the alkali catalyst that can be used here include sodium hydroxide, potassium hydroxide,
Lithium hydroxide, magnesium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, sodium methoxide, sodium ethoxide, potassium tert-butoxide, triethylamine, trioctylamine, tetramethylethylenediamine, N, N-dimethylethanolamine, N, N
-Diethylmethanolamine, N, N-dibutylethanolamine and the like, but are not limited thereto.

Specific examples of phenols that can be used in producing the compound of the formula (2) include phenol, cresol, alkyl-substituted phenols such as ethylphenol, butylphenol and octylphenol, and aromatic compounds such as phenylphenol and cumylphenol. Examples include substituted phenols, alkoxy-substituted phenols such as methoxyphenol and ethoxyphenol, naphthols and alkyl-substituted naphthols. Incidentally, these phenols can be used as a mixture of two or more kinds. It can also be used in one-batch polycondensation of the compound of formula (1) with formaldehyde and phenols.

The dehydration-condensation reaction between the compound of the formula (1) and the compound of the formula (2) usually proceeds without a catalyst by heating in a solvent solution if necessary. Specific examples of the solvent that can be used include:
Toluene, xylene, dioxane, dimethylformamide, dimethylsulfoxide, methanol, ethanol,
Isopropanol, ethylene glycol, ethers,
Phenols and the like. Ketone solvents such as acetone and methyl ethyl ketone are not suitable for use because they themselves react with the compound of formula (1).

The reaction between the compound of the formula (1) and the compound of the formula (2) is a dehydration reaction, and the compound of the formula (1) easily generates phosphoric acid when reacted with water. It is preferred to discharge to The reaction temperature and time vary depending on the solvent used and the reactivity of the methylol group of the compound of the formula (2), but are usually 50 to 200 ° C, preferably 70 ° C to
In the range of 180 ° C., usually for 5 to 100 hours, preferably 6
-30 hours.

Hereinafter, the thermosetting resin composition of the present invention will be described. The thermosetting resin composition of the present invention contains the phenol compound of the present invention. Other components include an epoxy resin and / or a cyanate ester resin and / or a maleimide compound and / or a resol resin and / or a curing agent thereof, and the phenol compound of the present invention accounts for 3% by weight of the total resin. The above is preferable, and particularly preferable is 5% by weight or more.

Examples of the curing agent for other resins that can be used in combination with the phenol compound of the present invention include amine compounds,
Acid anhydride compounds, amide compounds, phenol compounds and the like can be mentioned. Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, phthalic anhydride, and trianhydride. Merritic acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, With droxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Polycondensates, phenols and various diene compounds (dicyclopentadiene, terpenes,
Vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene,
Polymers with divinyl biphenyl, diisopropenyl biphenyl, butadiene, isoprene, etc., polycondensates with phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanol (Benzenedimethanol, α, α, α ′, α′-benzenedimethanol, biphenyldimethanol, α, α, α ′,
α′-biphenyldimethanol), polycondensates of phenols with aromatic dichloromethyls (α, α′-dichloroxylene, bischloromethylbiphenyl, etc.) Condensate,
And modified products thereof, imidazo - Le, BF 3 _- amine complex, guanidine derivatives, never the like dicyandiamide and the like is not limited thereto. When the thermosetting resin composition contains an epoxy resin, the epoxy resin is used in a ratio of 0.5 to 1.5 equivalents per 1 equivalent of the curing agent, and when the thermosetting resin composition contains a cyanate ester resin, the curing agent is used. Agent: cyanate ester resin (weight ratio) = 20:80
80:20, and when a maleimide compound is contained, curing agent: maleimide compound (weight ratio) = 2
It is preferable to use each in a ratio of 0:80 to 80:20.

Specific examples of epoxy resins that can be used in the thermosetting resin composition of the present invention include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols and various aldehydes (formaldehyde, Polycondensates with acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc .; phenols and various diene compounds (dicyclopentadiene, terpenes, Vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisoprope Le biphenyl, butadiene, polymers of isoprene, etc.), phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone,
Polycondensates with acetophenone, benzophenone, etc., phenols and aromatic dimethanols (benzenedimethanol, α, α, α ′, α′-benzenedimethanol, biphenyldimethanol, α, α, α ′, α) Polycondensate with phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensation with bisphenols and various aldehydes Glycidyl ether-based epoxy resins, alicyclic epoxy resins, glycidylamine-based epoxy resins, glycidyl ester-based epoxy resins, etc. obtained by glycidyl etherification of products, alcohols, etc. It is not something to be done. These may be used alone or in combination of two or more.

When the thermosetting resin composition of the present invention contains an epoxy resin, if necessary, a composition generally used as a curing accelerator for the epoxy resin may be contained.
Specific examples of the curing accelerator that can be used include imidazole compounds such as 2-methylimidazole and 2-ethylimidazole, boron trifluoride complex, triphenylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine and triphenyl. Borane, phosphorus-based compounds such as tetraphenylphosphonium / tetraphenylborate, tertiary amine compounds, and the like can be used. To 10 parts by weight.

Specific examples of the cyanate ester resin that can be used in the thermosetting resin composition of the present invention include dicyanatobenzene, tricyanatobenzene, dicyanatonaphthalene, dicyanatobiphenyl, and 2,2′-.
Bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl) methane, bis (3,5-dimethyl-4-cyanatophenyl) methane, 2,2′-bis (3,5-dimethyl-4-cia) 2,2'-bis (4-cyanatophenyl) ethane, 2,2'-bis (4-cyanatophenyl) hexafluoropropane, bis (4-cyanatophenyl) sulfone, bis (4 -Cyanatophenyl) thioether,
Phenol novolak cyanate and phenol / dicyclopentadiene cocondensate in which a hydroxyl group is converted to a cyanate group are exemplified, but not limited thereto. These may be used alone or in combination of two or more.

When the thermosetting resin composition of the present invention contains a cyanate ester resin, zinc naphthenate, cobalt naphthenate, and the like are used in order to trim a cyanate group to form a sym-triazine ring, if necessary. A catalyst such as copper naphthenate, lead naphthenate, zinc octylate, tin octylate, lead acetylacetonate, dibutyltin maleate and the like can also be contained. The catalyst is used in an amount of 0.0001 to 0.001 parts by weight per 100 parts by weight of the resin component in the thermosetting resin composition.
10 parts by weight, preferably 0.00015 to 0.0015
Use in proportions by weight. These may be used alone or in combination of two or more.

The maleimide compound which can be used in the thermosetting resin composition of the present invention is not particularly limited as long as it has a maleimide group, and can be obtained by subjecting a compound having a secondary amine and maleic anhydride to a condensation / dehydration reaction. And phenylmaleimide, hydroxyphenylmaleimide, N, N′-ethylenebismaleimide, N, N′-hexamethylenebismaleimide, N, N′-phenylenebismaleimide,
4,4′-bismaleimidodiphenylmethane, 4,4 ′
-Bismaleimide diphenylpropane, 4,4'-bismaleimide diphenyl sulfone, maleimide resin obtained by condensation dehydration of maleic anhydride and amino group of aniline / aldehyde polycondensate, aniline / aromatic dimethanol polycondensate Examples thereof include a maleimide resin obtained by condensation dehydration of an amino group and maleic anhydride, but are not limited thereto. These may be used alone or in combination of two or more.

When a maleimide compound is contained in the thermosetting resin composition of the present invention, the curing accelerator may be a curing accelerator for an epoxy resin or a cyanate ester resin, or a radical polymerization initiator such as an organic peroxide or an azo compound. May be used. In this case, the curing accelerator or the polymerization initiator is used in an amount of usually 0.01 to 10 parts by weight based on 100 parts by weight of the resin component in the thermosetting resin composition. These may be used alone or in combination of two or more.

When the thermosetting resin composition of the present invention contains the epoxy resin or maleimide compound of the present invention, it can be cured by light by using a photoradical initiator or a photocationic initiator. Becomes

Further, the thermosetting resin composition of the present invention may contain various additives as required. Specific examples of additives that can be used include polybutadiene and modified products thereof, modified acrylonitrile copolymer, indene resin, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, silicone gel, silicone oil, silica, alumina, Calcium carbonate, quartz powder, aluminum powder, graphite, talc, clay, iron oxide, titanium oxide, aluminum nitride,
Inorganic filler such as asbestos, mica, glass powder, glass fiber, glass non-woven fabric or carbon fiber, surface treatment agent for filler such as silane coupling agent, release agent, coloring of carbon black, phthalocyanine blue, phthalocyanine green, etc. And flame retardants such as brominated epoxy resins.

When a flame-retardant resin cured product containing no halogen is obtained, no bromine-based or chlorine-based compound is added to the composition, and only the phenolic compound of the present invention or another phosphorus-based flame retardant or nitrogen is used. Flame retardancy is exhibited by using a compound containing the same in combination.

The thermosetting resin composition of the present invention can be obtained by uniformly mixing the above-mentioned components at the above-mentioned ratio. Mixing may be carried out, if necessary, at a temperature of 20
It can be performed by heating and melting at a temperature as high as about 100 ° C.

The components of the thermosetting resin composition can be mixed by uniformly dispersing or dissolving the components in a solvent or the like. The solvent in this case is not particularly limited, but specific examples that can be used include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, dioxane, methyl cellosolve, and dimethylformamide. These solvents are usually used in an amount of 5 to 100 parts by weight of the resin component.
300 parts by weight, preferably 10 to 150 parts by weight are used.

The cured product of the present invention can be obtained by treating the above-mentioned thermosetting resin composition at room temperature to 250 ° C. for 30 seconds to 50 hours. Alternatively, the components of the thermosetting resin composition may be uniformly dispersed or dissolved in a solvent or the like, and after removing the solvent, the composition may be cured under the above-described conditions. or,
When the resin composition contains a photoradical initiator, a photocationic initiator, or the like, the resin composition can be cured mainly by irradiating ultraviolet rays. Thereafter, it is preferable to perform a heat treatment under the above conditions.

Further, flame retardancy can be imparted by adding the phenol compound of the present invention to a thermoplastic. When the polyhydric phenol compound of the present invention is used for this purpose, it may be used alone or in combination with other flame retardants and flame retardant auxiliaries. Other flame retardants include generally used phosphorus-based flame retardants (mainly phosphate esters),
Organic flame retardants such as halogen-based flame retardants and nitrogen-based compounds,
Inorganic flame retardants such as red phosphorus flame retardants, antimony trioxide, and aluminum hydroxide are exemplified. However,
Considering recent environmental issues, it is preferable not to use halogen-based flame retardants or antimony trioxide. The amount of the phenolic compound of the present invention used in the thermoplastic plastic of the present invention varies depending on the amount of other flame retardants and flame retardant aids used and the type of plastic, but is usually calculated by the phosphorus content in the plastic. 0.1 to 15% by weight, preferably 0.3 to 10% by weight.

[0026]

The present invention will be described in more detail with reference to the following examples. Note that the present invention is not limited to these examples. In Examples, the melt viscosity and softening point were measured under the following conditions. 1) Melt viscosity Melt viscosity in cone plate method at 200 ° C Measurement machine: cone plate (ICI) high temperature viscometer (RESE)
ARCH EQUIPMENT (LONDON) LTD. : 4 (measurement range: 0 to 40 poise) Sample amount: 0.100 ± 0.005 (g) 2) Softening point According to ASTM D1763

Synthesis Example 1 108 parts by weight of p-cresol, paraformaldehyde 6
5.2 parts by weight, 80 parts by weight of water and 12 parts by weight of sodium hydroxide were charged into a reaction vessel, heated and stirred, and reacted at 50 ° C. for 5 hours. After completion of the reaction, 230 parts by weight of water was charged and neutralized with hydrochloric acid, and the crystals were filtered and dried to obtain 147 parts by weight of a polymethylol body of p-cresol (M1).

Example 1 A reaction vessel was charged with 21.6 parts by weight of the compound of the formula (1), 9.2 parts by weight of the compound (M1) obtained in Synthesis Example (1), and 20 parts by weight of xylene. Stir, 140-15
The reaction was performed at 0 ° C. for 20 hours. At that time, the xylene and the produced water distilled off by azeotropic distillation were cooled and separated, and then the reaction was carried out while returning only the organic layer xylene into the system.
After completion of the reaction, xylene is distilled off under heating and reduced pressure to obtain the following formula (4)

[0029]

Embedded image Was obtained as a compound (P1). The obtained phenol compound (P1) had a softening point of 142 ° C. and a melt viscosity of 0.32 Pa · s.

Example 2 A mixture prepared at the ratios shown in Table 1 was kneaded with a biaxial roll, pulverized and tableted, and a resin molded product was prepared by transfer molding.
Cured at 0 ° C. for 8 hours.

The results of measuring the physical properties of the cured product thus obtained are shown in Table 1. In addition, the measurement of the physical property value was performed by the following method. -Moisture absorption: Weight increase rate (%) after leaving a disk-shaped test specimen of 5 cm in diameter x 4 mm in thickness at 121 ° C / 100% RH for 24 hours-Flame retardancy: Compliant with UL-94

[0032]

[Table 1]

In the table, ECN: o-cresol novolak epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: EOCN-1020, epoxy equivalent: 199 g / eq, softening point: 63 ° C.) PN: phenol novolak (Meiwa Kasei Co., Ltd.) H-1, hydroxyl equivalent 105 g / eq, softening point 84 ° C.) TPP: triphenylphosphine

[0034]

The phenolic compound of the present invention is used as a raw material for various resins, and the thermosetting resin containing the phenolic compound has excellent moisture resistance (determined from its low moisture absorption) and flame retardancy in the cured product. It is used in insulating materials for electric and electronic parts (such as highly reliable semiconductor encapsulation materials) and laminates (such as printed wiring boards) and various composite materials such as CFRP, adhesives, and paints. Extremely useful. In addition, by using the phenolic compound of the present invention in a plastic as a part of a raw material or an additive, flame retardancy can be exhibited without using halogen or the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 23/31

Claims (8)

[Claims] (1) Formula (1) A phenol compound which is a polycondensate of a compound represented by the formula (1), formaldehyde and a monovalent phenol. 2. A compound represented by the formula (1) and a compound represented by the formula (2): (In formula (2), a plurality of Rs independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group.
n shows the integer of 2-3, and m shows the integer of 1-5. )
A phenol compound which is a polycondensation product with a compound represented by the formula: (3) Formula (3) (In formula (3), a plurality of Rs independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group.
n shows the integer of 2-3, and m shows the integer of 1-5. )
The phenol compound according to claim 1 or 2, which is represented by the formula: 4. A thermosetting resin composition containing the phenol compound according to claim 1. 5. The thermosetting resin composition according to claim 4, which contains no halogen. 6. A cured product of the thermosetting resin composition according to claim 4. 7. The cured product according to claim 6, which has flame retardancy. 8. A flame-retardant thermoplastic containing the phenolic compound according to claim 1.