JPS6024809B2 - New resin composition for laminates - Google Patents

Description

[Detailed description of the invention] The present invention relates to a novel resin composition for laminates.

More specifically, liquid conjugated diolefin polymer has Q,3-
Esterified product B (hereinafter referred to as esterified product B) obtained by reacting an alcohol having 1 to 27 carbon atoms to adduct A (hereinafter referred to as adduct A) to which an unsaturated dicarboxylic acid or its anhydride is added. is reacted with one or more types of phenols in the presence of an acidic catalyst to form composition C.
(hereinafter referred to as composition C) and further reacts formaldehyde with composition C in the presence of a basic catalyst to obtain a new resin composition for laminates (hereinafter referred to as LB modified resol). Involved. The laminate produced using the resin composition of the present invention has excellent machinability, chemical resistance, and hardenability, and has conventionally used drying oil-modified phenolic resin (hereinafter referred to as drying oil-modified resol). ) has physical properties equivalent to or better than
It is also characterized by being manufactured at low cost. Although phenolic resins generally have excellent properties such as water resistance, heat resistance, and electrical properties, they are hard and brittle, and cannot be used alone, so they are used in combination with various base materials.

In the case of laminates, a number of substrates such as paper, cotton cloth, asbelt paper, asbelt cloth, glass cloth are impregnated with uncured phenol resin, dried, stacked together, and heated and pressed to form a sheet. It is molded and widely used as an electrical insulating material. Among them, the thickness is 0.8~ for light electrical equipment.
Paper phenol laminates of about 3.2 sides and copper-clad laminates for printed wiring boards are often used. In the latter case, the resistance,
When inserting parts such as diodes and capacitors using an automatic insertion machine, punching workability at room temperature is required to improve punching dimensional accuracy, and in order to withstand the impact during processing, materials such as vegetable oil, alkylphenol, and polyether are used. Modified with a modifier to give flexibility. Currently, tung oil is a typical modifier, but because it is a natural product and most of the products in Japan are imported, the market fluctuates significantly and is expensive, making it difficult to provide a stable supply. Therefore, there is a strong demand for a synthetic drying oil to replace tung oil. The present invention relates to a resin composition for laminates that meets these demands, and includes a compound A in which a q,8-unsaturated dicarboxylic acid or a hot water thereof is added to a liquid conjugated diolefin polymer, and a compound A having 1 carbon atom is added to a liquid conjugated diolefin polymer. The esterified product B obtained by reacting the alcohol of ~27 is reacted with one or more phenols in place of tung oil, which is used to impart coagulability to the secondary phenolic resin laminate. It is characterized by the fact that it is used in a variety of ways.

In addition, the conventionally known method for synthesizing an adduct of a conjugated diolefin polymer and phenol is as follows: Samurai Sekisho 48-208
90, Japanese Patent Publication No. 50-161493, Special Publication No. 47-3922
There are 0, etc.

Further, a method for producing a resol resin by reacting a conjugated diolefin polymer and a phenol adduct with formalin is disclosed in Tokusekki Sho 48-79895, JP 50-10928, Samurai Kosho 47-43312, and the like. The resol resin obtained in this way becomes non-uniform and tends to foam when cured with one whistle and zero competition. This is because the conjugated diolefin polymer lacks ester groups and carboxyl groups, so it lacks lacquer properties. However, the present invention is characterized in that such drawbacks can be eliminated and flexibility can also be maintained. The conjugated diolefin polymer used in the present invention is a conjugated diolefin homopolymer or copolymer or a derivative thereof, and one type or a mixture of two or more types may be used.

Homopolymers of conjugated diolefins include polybutadiene, polyisoprene, poly1,3-pentadiene, dicyclobentadiene polymer, polychloroprene, 2,3
-dimethylbutadiene polymer, etc. The conjugated diolefin copolymer is a copolymer of a conjugated diolefin and a conjugated diolefin or a copolymerizable monomer.

Copolymerizable monomers include Q-olefin, aromatic substituted vinyl monomers, acrylic acid and its derivatives, methacrylic acid and its derivatives, acetylene and its derivatives,
acrylonitrile, methacrylonitrile, pinyl acetate,
Contains vinyl chloride, vinylidene chloride, etc. Conjugated diolefin copolymers include binary copolymers, ternary copolymers,
Original copolymers, quinary copolymers, etc. are included. Q-olefins include ethylene, propylene, butene-1, isobutylene, bentene-1, hexene-1, octene-1, thecene-1, dode-1cene-1, octadecene-1
However, copolymers of conjugated diolefin and Q-olefin include copolymers of two or more of these, such as butadiene-ethylene copolymer, butadiene-propylene copolymer, butadiene-propylene copolymer, Isobutylene copolymer, ptadiene-butene-1 copolymer, butadiene-isoprene-isobutylene copolymer, butadiene-octene-1 copolymer, inprene-propylene copolymer, isoprene-isobutylene copolymer Polymers such as 1,3-pentadiene-isobutylene copolymer, 1,3-bentadiene-butene-1 copolymer, cyclobentadiene-isobutylene copolymer, and the like.

Examples of aromatic substituted vinyl monomers include styrene, Q-methylstyrene, p-chlorostyrene, p-oxystyrene, and vinyltoluene. Copolymers of these and conjugated diolefins include, but are not limited to, butadiene-styrene copolymers, isoprene-styrene copolymers, vinyltoluene-styrene copolymers, etc. . Furthermore, examples of acetylene or its derivatives include acetylene, methylacetylene, and phenyl acetylene, while examples of copolymers with conjugated diolefin include butadiene-acetylene copolymer, butadiene-methylacetylene copolymer, and isoprene-phenyl copolymer. Examples include acetylene copolymers. Acrylic acid or methacrylic acid and their respective derivatives include acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate,
2-ethylhexyl acrylate, hydroxyethyl acrylate, glycidyl acrylate, aminoethyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, n-
Examples include octyl methacrylate, hydroxyethyl methacrylate, glycidyl methacrylate, and aminoethyl methacrylate. Examples of polymers with conjugated diolefin include butadiene-acrylic acid copolymer, butadiene-methyl acrylate copolymer, butadiene-glycidyl acrylate copolymer, isoprene-ethyl acrylate copolymer, and isoprene-ethyl acrylate copolymer. Examples include hydroxyethyl methacrylate copolymer, isoprene-ethyl methacrylate copolymer, 1,3-bentadiene-methyl acrylate copolymer, and cyclobentadiene-ethyl methacrylate copolymer. Copolymers of conjugated diolefin and acrylonitrile or methacrylonitrile include butadiene-acronitrile copolymers,
These include butadiene-methacrylonitrile copolymer, isoprene-acrylonitrile copolymer, isopreso-methacrylonitrile copolymer, 1,3-bentadiene-acrylonitrile copolymer, butadiene-styrene-acrylonitrile copolymer. The copolymerization ratio of each monomer in these copolymers is 30 mol% or less.

Examples of the 0,B-unsaturated dicarboxylic acid or its anhydride, which is another raw material for producing the adduct A used in the present invention, include maleic acid, maleic anhydride, fumaric acid,
Examples include itaconic acid and citraconic acid.

The adduct A used in the present invention is a mixture of a liquid conjugated diolefin polymer and a Q,8-unsaturated dicarboxylic acid or its anhydride in an inert gas atmosphere without a catalyst at 150%
It can be easily obtained by heating to ~250 qo.

The content of Q,8-unsaturated dicarboxylic acid or its anhydride in the adduct A used in the present invention is 3 to 5% by weight.
is appropriate.

Among its performance, the LB modified resol produced using adduct A with a content less than 3% by weight has the following properties:
Uniform solubility in solvents and uniformity during curing, which are necessary when impregnating base materials such as paper, cotton cloth, asveld paper, asveld cloth, and glass cloth, with LB modified resol are insufficient; The viscosity increases too much to be practical.

The alcohols used in the esterification reaction of the present invention are alcohols having 1 to 27 carbon atoms, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, in-propyl alcohol, n-butyl alcohol, isobutyl alcohol, sec. -butyl alcohol, rt-butyl alcohol, n-amyl alcohol, SeC-amyl alcohol, diethyl methanol, isoamyl alcohol, ten-amyl alcohol, te
n-butylmethanol, methylisopropylmethanol, n-hexyl alcohol, methylimbutylcarbinol, methylamylcarbinol, n-hef. Chyl alcohol, methyl-n-amyl carbinol, n-octyl alcohol, caprylic alcohol, 2-ethyl-n-
Hexyl alcohol, inoctyl alcohol, n-nonyl alcohol, n-decyl alcohol, n-undecyl alcohol, n-dodecyl alcohol, n-tridecyl alcohol, n-tetradedecyl alcohol, n-tetradedecyl alcohol, - Saturated/hydric alcohols such as bentade'ole alcohol, cetinoreal alcohol, stearyl alcohol, n-nonadecyl alcohol, behenyl alcohol and cyclohexanol, allyl alcohol, propargyl alcohol, crotyl alcohol, oleyl alcohol, elaidil alcohol, unsaturated monohydric alcohols such as linoleyl alcohol and geraniol;
Aromatic alcohols such as benzyl alcohol, 8-phenylethyl alcohol and hydrocinnamyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether , diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, furfuryl alcohol and tetrafuryl alcohol, or a mixture of two or more thereof can be used. In addition, dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, propanediol, and butanediol can also be used in systems where the viscosity increases only to an extent that does not cause problems when used in the reaction product. .

For liquid conjugated diolefin polymer, the esterification reaction of 8-unsaturated dicarboxylic acid or its anhydride adduct and alcohol is carried out when the alcohol/Q,8-unsaturated dicarboxylic anhydride is in a 1/1 molar ratio. , half-esterification can be carried out using a small amount of amines as a catalyst.

When the molar ratio of alcohol/Q,8-unsaturated dicarboxylic acid anhydride is 1/1 or more, in the esterification reaction, a slightly excess amount of alcohol than the calculated amount is used, and an inorganic acid such as sulfuric acid or hydrochloric acid or para-toluene sulfone is used. This can be carried out by a known method in which the reaction is carried out in the presence of a catalyst such as an organic acid such as an acid while extracting the generated water from the system. In this case, a reaction solvent may be used. In the present invention, esterified product B
and one or more types of phenols. Composition C
1 to 100 parts by weight, preferably 5 to 30 parts by weight of one or more phenols based on the weight part of the esterified product BIO, and also 0. It is desirable to add the esterified product B all at once, preferably in portions, to the mixture with one or more types of acidic catalyst in an amount of 1 part by weight to 1 part by weight.

In this case, if the amount of one or more phenols is less than 1 part by weight per part by weight of the esterified product BIOO, L
When processing a B-modified resol into a laminate, the curing speed of the LB-modified resol is insufficient, and the chemical resistance required for a laminate is poor. Moreover, on the other hand, one or two or more phenols are added to 10 parts by weight of the esterified product BIO.
If the amount exceeds 0 parts by weight, the Tsunezumi punching workability of the obtained laminate will deteriorate.

Phenols in the present invention include phenol, cresol, xylenol, and n-f. Alkylphenols such as ropinolephenol, impropylphenol, n-butylphenol, /f-laterbutylphenol, and nonylphenol, and monohydric or polyhydric phenols such as resorcinol, hydroquinone, tritecol, and saligen are used. Acidic catalysts include key acids such as sulfuric acid and hydrochloric acid, sulfonic acids such as para-toluene sulfonic acid, Lewis acids such as aluminum chloride, ferric chloride, and boron trichloride, and Lewis acids such as boron trichloride phe/fer complexes. Included are acidic compounds and combinations of two or more thereof.

The concentration of the catalyst can be arbitrarily selected within the range of 0.01 part by weight to 1 part by weight based on the weight part of the polymer 10. Furthermore, when producing Composition C by reacting esterified product B with one or more phenols, the two may be mixed together and reacted; Cyclization occurs due to the intramolecular reaction of the double bonds contained, which may lead to deterioration in the performance of the laminate produced from the LB modified resol in the present invention, especially in terms of specularity. Alternatively, it is desirable to add esterified product B to two or more phenols in portions.

Here, the phrase "add in portions" means that the phenol and acidic catalyst are not mixed into the mixture all at once, but are added continuously over a certain period of time, or in portions discontinuously. It refers to a purposeful mixing operation that is divided into several batches at certain time intervals.

However, there are no particular limitations on the addition time or addition interval. These are determined by the relationship between the molecular weight and chemical structure of adduct A, the quantitative ratio of esterified product B and phenol, the acidic catalyst, and the reaction temperature. The reaction temperature is not particularly limited, but is preferably between 4 and 0 to 170°C. In the present invention, when formaldehyde is reacted with composition C, in the presence of a basic catalyst, formalin or paraformaldehyde is 0.8 hol in terms of formaldehyde based on the total amount of phenols used to produce composition C. In the following, the methylolization is not sufficient, and the performance of the laminate produced from the obtained L-modified resol is poor, especially the curing properties and solvent resistance.
If the amount is more than 1 mol, the rate of methylolization is extremely high, making it difficult to control the reaction, which is unsuitable for practical use.

Furthermore, the basic catalyst used in the present invention is ammonia,
These include amines such as hexamethylenetetramine, trimethylolamine, ethylenediamine, dimethylamine, diethylamine, and triethylamine, and hydroxides such as sodium hydroxide, potassium hydroxide, and barium hydroxide. 1 or 2 of
It is possible to use combinations of more than one species.

The concentration of the catalyst can be arbitrarily selected within the range of 0.001 to 0.5 mol based on the total amount of phenol used to produce composition C. Other reaction conditions are not particularly limited, but the reaction temperature is preferably 6 pi~120 qo.
The reaction is carried out for 0 to 180 minutes, followed by dehydration under reduced pressure.
The method for manufacturing a laminate using the resin composition for laminates of the present invention is directly adapted to the conventional method, and the varnish that dissolves the resin composition for laminates of the present invention is applied to paper, cotton cloth, asbestos, etc. Impregnate a material such as paper, asbestos cloth, glass cloth, etc. and dry it to make a prepure, or first impregnate the aforementioned material with a predetermined amount of water-soluble phenolic resin and/or amine-modified phenolic resin and dry it. , soaking the resin of the present invention in a predetermined amount and drying it to make prepurek;
Next, the desired laminate is obtained by laminating the required number of sheets and molding them by hot pressing.

Examples are shown below, but the present invention is not limited to the following examples.

Examples Various resol type resins used in Examples were prepared as follows.

'1) Production of Adduct A ■ Production of Adduct A-1 A 500' 3-meter flask equipped with a stirrer, a thermometer and a three-way cock for an inert gas seal had a viscosity of 102 centipoise at 30 qo, as measured by a vapor pressure permeometer. Measured number average molecular weight: 1000, orthogonal value (Wiss method) 4
63, liquid polybutadiene 340% and maleic anhydride 60% having physical properties of 56% cis-1,4 structure, 33% trans-1,4 structure, and 11% vinyl structure were charged, and after purging the inside of the vessel with nitrogen gas, 19 with gas pressure applied
Adduct A-1 was obtained by reacting at 0°C for 4 hours.

(2) Production of adduct A-2 In the same manner as in the production of adduct A-1 in the above example, 320 g of liquid polybutadiene and 80 g of maleic anhydride were charged.
Adduct A-2 was obtained.

■ Manufacture of esterified product 8 ■ Manufacture of esterified product B-1 45 ml of ethyl cellosolve of adduct A-1300 obtained in the above example was poured into a 300 ml tube equipped with a stirrer, a thermometer, and an inert gas blowing pipe. Put it in a shout 4-ro flask, 11
After half-esterification by heating at 000 to 12,500 °C for 3 hours, 48 °C of n-amyl alcohol, 10 °C of xylene as a solvent, and 0.6 °C of a 50% aqueous sulfuric acid solution as a catalyst were added, and water was heated at 130 °C to 145 °C for 3 hours. While extracting the ester, the esterification reaction was carried out until the acid value of the reaction solution (subtracting the value due to sulfuric acid content) became 20 or less.

After the reaction was completed, ester compound B-1 was obtained by concentrating under reduced pressure to remove excess alcohol and low-boiling components.
(2) Production of esterified compound B-2 In the same manner as in the production of esterified compound B-1 in the above example, 60 mL of ethyl cellosolve was added to adduct A-2300, and after half-esterification, 64 mL of n-amyl alcohol and the solvent were added. xylene as catalyst, 50% sulfuric acid aqueous solution as catalyst
．． 65 was added thereto, reacted, and concentrated under reduced pressure to obtain ester compound B-2.

'3' Production of composition C Esterified products B-1 and 8-2 obtained in the above examples
were reacted under the conditions shown in Table 1 to form compositions C-1 to C.
-5 was obtained.

Table 1' 4) Manufacture of LB modified resol varnish 75 days of isopropanol and 50 days of 37% formalin were added to each of the compositions C-1 to C-5 obtained in the above examples for 75 days, Triethylamine 1 as a catalyst
3 quartz was added, and the mixture was reacted at 80 qo for 2 hours to form a resol.

After the reaction solution was subjected to dehydration under reduced pressure, a mixed solvent of methanol and toluene was added to prepare a solution having a non-volatile content of 6% by weight. 100% of the varnish thus obtained
% cotton cylinder paper and heated and dried at 130 qo for 5 minutes, the dry resin amount was 5% of the base material for resin-impregnated laminates.
The content was adjusted to 0% by weight.

One sheet of adhesive-coated steel foil was stacked on top of the required number of resin-impregnated base materials and thermocompression bonded at a temperature of 160 qo and a pressure of 100 k9/m for 6 nights to form a laminate with a thickness of 1.6.
Table 2 shows the various performances of the obtained laminate.

The laminates obtained from compositions C-1 to C-5 were A
- Indicated by E. Table-2 Note 1) 25 x 25. Flower specimens were heated to 260°C and 2°C.
Float the copper side down on a melt hunter and measure the time required for blistering to occur (Note 2) 25 x 25
A test piece of the product is immersed in boiling trichlorene for 10 minutes, and the presence or absence of any abnormality in appearance is determined.

Claims (1)

[Scope of Claims] 1. Esterified product B obtained by reacting and esterifying adduct A, which is a liquid conjugated diolefin polymer with α,β-unsaturated dicarboxylic acid or its anhydride, with an alcohol having 1 to 27 carbon atoms. to obtain a composition C which is subjected to an addition reaction with one or more types of phenols in the presence of an acidic catalyst,
Furthermore, formaldehyde was added to Composition C in the presence of a basic catalyst.
A novel resin composition for laminates obtained by reacting with. 2 Liquid conjugated diolefin polymer has a number average molecular weight of 150
10,000 centipoise and a viscosity of 2 to 30,000 centipoise at 30°C. 3. The novel resin composition for a laminate according to claim 1, wherein the content of the α,β-unsaturated dicarboxylic acid or its anhydride in the adduct A is 3 to 50% by weight. 3. When producing composition C from esterified product B and one or more types of phenols, 10 to 1000 parts by weight, preferably 50 to 500 parts by weight, per 100 parts by weight of esterified product B. one or more types of phenols of 0.01
The novel method according to claim 1, characterized in that the esterified product B is added all at once, preferably in portions, to a mixture with one or more types of acidic catalyst in an amount of from 10 parts by weight to 10 parts by weight. Resin composition for laminates. 5 When formaldehyde is reacted with composition C, in the presence of a basic catalyst, 0 in terms of formaldehyde based on the total amount of phenols used to produce composition C.
．． The novel resin composition for laminates according to claim 1, characterized in that formalin or paraformaldehyde in an amount corresponding to 6 to 3.0 moles is reacted with composition C.