JP3458557B2 - Thermosetting resin composition, laminate using the same, and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a heat-effective resin composition for obtaining a paper base-impregnated composite having excellent flame retardancy and processability, and particularly excellent in electrical properties, punching processability and flame retardancy. The present invention relates to a thermosetting resin composition for obtaining a paper base laminate and a method for producing the laminate.

[0002]

2. Description of the Related Art Conventionally, a printed circuit wiring board paper base material phenol resin laminated board is obtained by impregnating and drying a phenol resin varnish on kraft paper or linter paper, laminating the impregnated paper, and adding copper foil to one or both sides. Is molded and manufactured.

Further, the laminated plate used for such an insulating material uses various flame-retardant formulations because there is a strong demand for flame-retardant. As a method of flame retardation, there are cases where an addition type flame retardant in which a halogen or phosphorus compound is added to a resin is used and a case where a reaction type flame retardant chemically bonded to the resin is used. The latter is preferred to prevent the decrease of Epoxy compounds having halogen substituents are often used as such reactive flame retardants, but they have the drawback that the punching processability deteriorates when a large amount of such compounds is used.

[0004]

DISCLOSURE OF THE INVENTION The present invention is intended to solve the above-mentioned problems, and is intended to obtain a paper base laminate having excellent electrical characteristics, punching workability and flame retardancy. The present invention relates to a curable resin composition, a laminated board and a method for producing the same.

[0005]

Means for Solving the Problems As a result of intensive studies in view of the above circumstances, the present inventors have found that a phenol resin using a resol resin as a resin used for coating and impregnation and an acidic catalyst composed of a basic catalyst or an organic acid. The inventors have found that the above problems can be solved by using a novolak type phenolic resin composed of a co-condensate of a compound having a triazine ring and the like, and have completed the present invention.

That is, the present invention relates to a resol resin (A)
And a basic catalyst or an acidic catalyst composed of an organic acid as a catalyst, which is a condensate obtained by subjecting a compound having a triazine ring and an aldehyde to a condensation reaction, wherein the unreacted aldehyde It is composed of a novolac type phenol resin (B) characterized in that it does not contain a class and does not contain a methylol group, and preferably the resole resin (A) is a low molecular weight resole resin (a) and a drying oil-modified resole resin (b). ) And a thermosetting resin composition. Furthermore, in the method for producing a laminated sheet by coating and impregnating a paper base material with a phenol resin in a two-stage impregnation method and drying and laminating the obtained laminated material, a low-impregnation resin is used as the first step. A molecular weight resol resin (a) is used, and a drying oil-modified resol resin (b) is used in the second step, and a condensate of a phenol, a compound having a triazine ring, and an aldehyde is used, and unreacted in the condensate. The present invention relates to a method for producing a laminate, which comprises using a novolac type phenol resin (B) containing no aldehydes and containing no methylol group.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The resole resin (A) of the present invention is
It is a low molecular weight condensation resin obtained by reacting phenols such as phenol, cresol, butylphenol, nonylphenol, xylenol, resorcin, and aldehydes such as formaldehyde in the presence of a basic catalyst. It may be a dry oil-modified resin using phenols modified with a dry oil such as castor oil, linseed oil and tall oil. Furthermore, it is a low molecular weight condensation resin obtained by reacting melamine, guanamine, etc. and aldehydes, such as formaldehyde, in the presence of a basic catalyst. Some or all of their methylol groups are converted with lower alcohols such as methanol and butanol. It may be etherified. These resins are not limited to one kind in use, and two or more kinds can be used in combination, but from the viewpoint of achieving both impregnating property and punching property, a low molecular weight resole resin and a drying oil-modified resole are used. It is preferable to use a resin together.

Here, as the basic catalyst, ammonia,
An amine catalyst such as ethylenediamine or triethylamine, or a metal hydroxide is used. The above-mentioned phenols for obtaining the phenol resin (B) of the present invention is not particularly limited, and examples thereof include phenol, alkylphenols such as cresol, xylenol, ethylphenol, butylphenol, nonylphenol and octylphenol, bisphenol A, Examples thereof include polyphenols such as bisphenol F, bisphenol S, resorcin, and catechol, halogenated phenols, phenylphenols, and aminophenols. In addition, these phenols are not limited to one kind in use, and two or more kinds can be used in combination.

Further, the compound containing a triazine ring for obtaining the phenol resin of the present invention is not particularly limited, but the following general formula (I) and / or general formula (I)
The compound represented by I) is preferred.

[0010]

[Chemical 3]

(Wherein R ₁ , R ₂ and R ₃ represent any of an amino group, an alkyl group, a phenyl group, a hydroxyl group, a hydroxylalkyl group, an acid group, an unsaturated group, a cyano group and a halogen atom. )

[0012]

[Chemical 4]

(In the formula, R ₄ , R ₅ and R ₆ represent any one of a hydrogen atom, an alkyl group, a phenyl group, a hydroxyl group, a hydroxylalkyl group, an acid group, an unsaturated group, a cyano group and a halogen atom. In the general formula (I), it is preferable that at least one of R ₁ , R ₂ and R ₃ is an amino group.

As the compound represented by the general formula (I),
Specific examples include melamine, guanamine derivatives such as acetoguanamine and benzoguanamine, cyanuric acid, and cyanuric acid derivatives such as methylcyanurate, ethylcyanurate, acetylcyanurate, and cyanuric chloride. Among these, guanamine derivatives such as melamine, acetoguanamine, and benzoguanamine in which any two or three of R ₁ , R ₂ and R ₃ are amino groups are more preferable.

Further, in the general formula (II), it is preferable that at least one of R ₄ , R ₅ and R ₆ is a hydrogen atom.
Specific examples of the compound represented by the general formula (II) include isocyanuric acid, methyl isocyanurate, ethyl isocyanurate, allyl isocyanurate, 2-hydroxyethyl isocyanurate, 2-carboxyethyl isocyanurate, and chlorinated isocyanuric acid. Isocyanuric acid derivatives and the like. Among these, R ₄ ,
Most preferred is isocyanuric acid in which all of R ₅ and R ₆ are hydrogen atoms. Further, cyanuric acid which is a compound represented by the general formula (I) which is a tautomer is also a preferable compound.

These compounds are not limited to one kind in use, and two or more kinds can be used in combination. The aldehyde for obtaining the phenol resin of the present invention is not particularly limited, but formaldehyde is preferable from the viewpoint of easy handling. The formaldehyde includes, but is not limited to, formalin, paraformaldehyde and the like as typical sources.

The phenol resin of the present invention is characterized by containing no unreacted aldehydes and substantially containing no methylol group. By containing no unreacted aldehydes and substantially not containing a methylol group, compatibility with a dry oil-modified resole resin or the like is improved, and it is possible to uniformly impart a flame retardant effect to a laminate.

A typical production method for obtaining the phenol resin of the present invention will be described below. First, the above-mentioned phenols, aldehydes and a compound having a triazine ring are reacted with each other under an acidic catalyst composed of a basic or organic acid. At this time, the pH of the system is not particularly limited, but since many compounds containing a triazine ring are easily dissolved in a basic solution, it is preferable to react under a basic catalyst. Preference is given to using amines. Also, the reaction order of each raw material is not particularly limited, and even if a compound having a triazine ring is first reacted with a phenol or an aldehyde, then a compound having a triazine ring is reacted with an aldehyde and then the phenol is reacted. The raw materials may be added, or all the raw materials may be added at the same time and reacted. At this time, the molar ratio of the aldehydes to the phenols is not particularly limited, but can be 0.
2-1.5 are preferable and 0.4-0.8 are more preferable. The weight ratio of the compound having a triazine ring to the phenols is not particularly limited, but 10 to 10
98: 90-2 is preferable, and 50-95: 50-5 is more preferable. When the weight ratio of the phenols is 10% by weight or less, it becomes difficult to make it into a resin, and when it is 98% by weight or more, a sufficient flame retarding effect cannot be obtained, which is not preferable.

As the basic catalyst, for example, hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide and barium hydroxide, and oxides thereof, ammonia, primary to tertiary amines, Hexamethylenetetramine, sodium carbonate and the like can be mentioned. Oxalic acid, acetic acid, etc. are mentioned as an acidic catalyst which consists of organic acids.

Since the phenol resin of the present invention is used especially for laminated plates for electric and electronic materials, it is not preferable that inorganic substances such as metals remain as a catalyst residue. Therefore, amines are used as the basic catalyst. Preference is given to using.

From the viewpoint of reaction control, the reaction can be carried out in the presence of various solvents. At this time, the solvent is not particularly limited, for example, acetone, methyl ethyl ketone,
Toluene, xylene, methyl isobutyl ketone, ethyl acetate, ethylene glycol monomethyl ether, N, N
-Dimethylformamide, methanol, ethanol and the like. These solvents can be used alone or as a mixed solvent of two or more kinds as appropriate.

Next, if necessary, neutralization and washing with water are performed to remove impurities such as salts. However, it is not necessary when amines are used as the catalyst. After completion of the reaction, unreacted aldehydes, phenols, solvents and the like are removed by ordinary methods such as atmospheric distillation and vacuum distillation. At this time, in order to obtain a resin composition which is substantially free of unreacted aldehydes and methylol groups, which is a characteristic of the resin composition of the present invention, heat treatment at 120 ° C. or higher is required. It is difficult to substantially eliminate the methylol group by heat treatment at 120 ° C. or lower. Further, if the temperature is 120 ° C. or higher, the methylol group can be eliminated by taking sufficient time, but it is preferable to perform heat treatment at a higher temperature, preferably 150 ° C. or higher for efficient elimination. . At this time, at high temperature, it is preferable to distill with heating according to the usual method for obtaining a novolac resin.

The mixing ratio of the resole resin (A) and the phenol resin (B) of the present invention is not particularly limited, but the solid content weight ratio is A: B = 100: 5 to 50. Preferably.

Other thermosetting resins may be used in the thermosetting resin composition of the present invention, if necessary. Examples of other thermosetting resins include epoxy resins, unsaturated polyester resins, and thermosetting acrylic resins, but epoxy resins are preferable from the viewpoint of punching workability, and the epoxy resin in this case is, for example, bisphenol A. Type epoxy resin, polyphenol type epoxy resin, aliphatic epoxy resin, aromatic ester type epoxy resin, cycloaliphatic ester type epoxy resin, aliphatic ester type epoxy resin, ether ester type epoxy resin, and epoxidized soybean oil. Examples thereof include glycidyl epoxy resins and halogen-substituted products thereof such as bromine or chlorine, and brominated epoxy resins are more preferable from the viewpoint of flame retardancy. There is no problem even if these epoxy resins are used alone or as a mixture of several kinds.

If desired, various additives, flame retardants, fillers, etc. may be added to the thermosetting resin composition of the present invention. The laminated plate of the present invention is obtained by dissolving the thermosetting resin composition obtained as described above in an organic solvent as necessary to form a varnish, and then kraft paper, linter paper, glass cloth, glass non-woven cloth, polyester cloth. It can be obtained by coating and impregnating a paper base material such as aramid fiber cloth or canvas, and drying to laminate-mold the laminated material.

At this time, the mixing procedure and mixing ratio of the resol resin (A) and the phenol resin (B) composed of a phenol and a compound having a triazine ring are not particularly limited, but two-step impregnation is performed. With a method of applying and impregnating with a phenol resin, a low molecular weight resole resin is used as the first stage impregnation resin, and a drying oil-modified resole resin as the second stage impregnation resin, and a phenol and a triazine ring It is preferable to use a phenol resin composed of a compound.

The thermosetting resin composition of the present invention can be used not only for laminated plate applications but also for paper base composites such as oil or air filters, battery separators, adhesive paper and paper tubes.

[0028]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples. Hereinafter, "%" means "% by weight" and "part" means "part by weight".

[Synthesis Example 1] (Synthesis Example of Phenol Resin) 94 parts of phenol and 9.4 parts of benzoguanamine were added to 41.
51 parts of 5% formalin and 0.47 part of oxalic acid were added, and the temperature was gradually raised to 100 ° C while paying attention to heat generation.
After reacting at 100 ° C for 5 hours, the temperature was raised to 180 ° C over 2 hours while removing water under normal pressure, and then unreacted phenol was removed under reduced pressure to remove phenol having a softening point of 103 ° C. A resin was obtained.

Hereinafter, this resin is abbreviated as "N1". The weight ratio of the phenols to the compound having a triazine ring, the amount of unreacted formaldehyde, the presence or absence of a methylol group, and the amount of unreacted phenol monomer in the obtained resin were determined as follows. <Weight ratio of phenol to triazine ring-containing compound (benzoguanamine)> 180 ° C, the phenol content in the effluent removed outside the reaction system under reduced pressure was calculated by gas chromatography, and subtracted from the number of charged phenol parts in the resin. Of the amount of phenol present. The amount of benzoguanamine to be charged was included in the resin as it was. The ratio of the two was defined as the existence ratio. Column: 30% Celite 545 Carnauba wax 2m x
3 mmφ Column temperature: 170 ° C. Inlet temperature: 230 ° C. Detector: FID Carrier gas: N ₂ gas 1.0 kg / cm ² Measurement method: internal standard method <unreacted formaldehyde> About 5 g of composition finely pulverized in 50 g of distilled water Was added and kept at room temperature for 24 hours. It was set on a pH meter and adjusted to pH = 4.0 by adding N / 10 hydrochloric acid aqueous solution. PH to this
= 50% 7% hydroxylamine aqueous solution adjusted to 4.0
ml was added, and the mixture was sealed with aluminum foil or the like and left for 30 minutes. Then, it is set on a pH meter and titrated with 1N sodium hydroxide solution until neutralization to pH = 4.0. The amount of free formaldehyde was determined by the following formula.

[0031]

[Chemical 1] A: 1N sodium hydroxide solution amount required for titration (ml) F: 1N sodium hydroxide solution factor required for titration S: Sample (finely pulverized resin) amount (g) <Presence or absence of methylol group> C13 -Methylol groups present in the resin were measured using NMR. Apparatus: JEOL Ltd. GSX270 Proton: 270MHz Measurement solvent: Heavy methanol or heavy acetone Reference substance: Tetramethylsilane Measurement conditions Pulse condition: 45 ° × 4000 times Pulse interval: 2 seconds Appear at 60 to 70 ppm of the obtained chart , A peak that can be clearly distinguished from noise was used for the determination. The case where a peak was observed was defined as “Yes”, and the case where it was not observed was defined as “No”. <Amount of Unreacted Phenol Monomer> The phenol monomer content in the resin was measured under the same measurement conditions as in the gas chromatography described above. The amounts of the components thus obtained are summarized in Table 1.

Synthesis Example 2 (Synthesis Example of Phenol Resin) To 94 parts of phenol, 29 parts of 41.5% formalin, 19 parts of melamine, and 0.47 part of triethylamine were added and reacted at 100 ° C. for 3 hours. While removing water under normal pressure, the temperature is raised to 120 ° C, and while maintaining the temperature, 2
Reacted for hours. 180 ℃ while removing water under normal pressure
Up to 2 hours, and then unreacted phenol was removed under reduced pressure to obtain a phenol resin having a softening point of 123 ° C. The weight ratio of phenol and melamine, the amount of unreacted formaldehyde, the presence or absence of methylol groups, and the amount of unreacted phenol monomer were determined, and the results are summarized in Table 1.

Hereinafter, this resin is abbreviated as "N2". [Synthesis Example 3] (Synthesis example of phenol resin) 36 parts of 41.5% formalin and 0.47 part of triethylamine were added to 94 parts of phenol, and the mixture was reacted at 80 ° C for 3 hours. Next, 14 parts of melamine and 14 parts of benzoguanamine were added and reacted for another 2 hours. Synthesis Example 2 below
A phenol resin having a softening point of 130 ° C. was obtained by reacting in the same manner as in (1). The weight ratio of phenol to melamine and benzoguanamine, the amount of unreacted formaldehyde, the presence or absence of a methylol group, and the amount of unreacted phenol monomer were determined in the same manner as in Synthesis Example 1, and the results are summarized in Table 1.

Hereinafter, this resin is abbreviated as "N3". [Synthesis Example 4] (Synthesis Example of Phenol Resin) 94 parts of phenol, 9.4 parts of cyanuric acid, 43 parts of 41.5% formalin, and 0.47 part of trimethylamine were added to prepare 1
The reaction was carried out at 00 ° C for 4 hours. Next, the temperature was raised to 120 ° C. while removing water under normal pressure, and the reaction was carried out for 2 hours while maintaining the temperature. 180 while removing water under normal pressure
The temperature was raised to 0 ° C over 2 hours, unreacted phenol was removed under reduced pressure, and a phenol resin having a softening point of 107 ° C was obtained. The weight ratio of phenol and cyanuric acid, the amount of unreacted formaldehyde, the presence or absence of methylol groups, and the amount of unreacted phenol monomer were determined, and the results are summarized in Table 1.

Hereinafter, this resin is abbreviated as "N4".

[0036]

[Table 1] [Synthesis Example 5] (Synthesis Example of Resol Resin) 94 parts of phenol, 87 parts of 41.5% formalin and 1.9 parts of trimethylamine were added, and the mixture was reacted at 60 ° C. for 2 hours. Next, the water was removed under reduced pressure, and methanol / water = 70
It was diluted with a mixed solvent of / 30 to obtain a low molecular weight resol resin varnish having a resin content of 50%.

Hereinafter, this resin varnish is abbreviated as "W1". [Synthesis Example 6] (Synthesis Example of Resol Resin) 94 parts of phenol, 60 parts of tung oil, and 0.5 part of paratoluenesulfonic acid were added and reacted at 80 ° C. for 3 hours. Next, 60 parts of toluene and 2 g of triethanolamine were added to dilute and neutralize, then 40 parts of paraformaldehyde and 2.4 parts of 25% aqueous ammonia were added and reacted at 90 ° C. for 4 hours. After adding 12 parts of a brominated epoxy resin (Epiclone 153 [manufactured by Dainippon Ink and Chemicals, Inc.]) and 12 parts of triphenyl phosphate, methanol / toluene = 50.
It was diluted with a mixed solvent of / 50 to obtain a tung oil-modified resin varnish having a resin content of 50%.

Hereinafter, this resin varnish is abbreviated as "W2". [Examples 1 to 4 and Comparative Example 1] W1, W2 and N1 to N4 were mixed and dissolved in accordance with the ratios shown in Table 2 to form a uniform solution, which was then coated and impregnated on kraft paper of 135 g / m ^2. Then, it was dried to obtain a prepreg having a resin content of 52 to 55%. 8 sheets of this are laminated, 160 ℃, 80kg / c
Thermoforming was performed at m ² for 60 minutes to obtain a laminated plate having a thickness of 1.6 mm.

Example 5 and Comparative Example 2 W1 of 135
A g / m ² kraft paper was applied and impregnated and dried to obtain a treated substrate having a resin content of 10 to 12%. Then, according to the ratio shown in Table 2, W2 and N1-
N4 was previously mixed and dissolved to form a uniform solution, which was then impregnated and dried to obtain a prepreg having a resin content of 55 to 58%. 8 sheets of this are laminated, 160 ℃, 80kg
/ Cm ² for 60 minutes to form a laminated sheet having a thickness of 1.6 mm.

The properties obtained for these laminates are shown in Table 2. The test method is JIS water absorption and insulation resistance.
Performed according to C6481 and the punching workability is ASTM
According to D-617.

[0041]

[Table 2]

[0042]

The laminated board using the thermosetting resin composition of the present invention has excellent electrical characteristics, flame retardancy and punching workability.

─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP 59-157126 (JP, A) JP 59-157152 (JP, A) JP 8-311142 (JP, A) JP 58- 152045 (JP, A) JP 61-236834 (JP, A) JP 61-236833 (JP, A) JP 52-52992 (JP, A) JP 9-124896 (JP, A) JP 8-253559 (JP, A) JP 61-238829 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 61/00-61/34 C08G 14/00 -14/14 WPI / L (QUESTEL) CA (STN) REGISTRY (STN)

Claims (10)

(57) [Claims] 1. A condensate obtained by subjecting a phenol compound, a compound having a triazine ring and an aldehyde to a condensation reaction by using a resole resin (A) and an acidic catalyst composed of a basic catalyst or an organic acid as a catalyst. A thermosetting resin composition comprising a novolac type phenol resin (B) containing no unreacted aldehydes and containing no methylol group in the condensate. 2. The novolac type phenolic resin (B), wherein the compound having a triazine ring is a compound represented by the general formula (I) and / or a compound represented by the general formula (II). Item 1. The composition according to Item 1. [Chemical 1] (In the formula, R ₁ , R ₂ , and R ₃ are each an amino group, an alkyl group,
Represents any of a phenyl group, a hydroxyl group, a hydroxylalkyl group, an acid group, an unsaturated group, a cyano group and a halogen atom. (In the formula, R ₄ , R ₅ , and R ₆ are each a hydrogen atom, an alkyl group,
Represents one of a phenyl group, a hydroxyl group, a hydroxylalkyl group, an acid group, an unsaturated group, a cyano group, and a halogen atom) 3. The composition according to claim 1, wherein in the general formula (I), at least one of R ₁ , R ₂ and R ₃ is an amino group. 4. The composition according to claim 3, wherein in the general formula (I), any _{two of} R ₁ , R ₂ and R ₃ are amino groups. 5. The composition according to claim 3, wherein R ₁ , R ₂ and R _{3 in the} general formula (I) are amino groups. 6. R ₄ , R ₅ and R _{6 in the} general formula (II).
Is hydrogen, The composition of any one of Claims 1-5 characterized by the above-mentioned. 7. The composition according to claim 1, wherein the resole resin (A) comprises a mixture of a low molecular weight resole resin (a) and a drying oil-modified resole resin (b). 8. The ratio of the resole resin (A) to the phenol resin (B) is A: B = 100: 5 in terms of solid content weight ratio.
The composition according to any one of claims 1 to 7, wherein the composition is -50. 9. A laminated board obtained by molding a laminated material obtained by coating and impregnating a paper base material with the thermosetting resin composition according to claim 1 and drying. 10. A method for producing a laminated sheet by laminating a laminated material obtained by coating and impregnating a phenolic resin in a method of impregnating a paper base material in two steps, followed by impregnation in the first step. Low molecular weight resole resin (a)
And a dry oil-modified resole resin (b)
And a basic catalyst or an acidic catalyst composed of an organic acid as a catalyst, which is a condensate obtained by subjecting a compound having a triazine ring and an aldehyde to a condensation reaction, which is not reacted in the condensate. A method for producing a laminate, which comprises using a novolac type phenol resin (B) containing no aldehydes and containing no methylol group.