JP5397361B2 - Manufacturing method of prepreg - Google Patents

Description

  The present invention relates to a method for producing a prepreg.

  Lignin, which is contained in about 30% by mass in a general wood component, is a substance that is abundantly biosynthesized after cellulose. This lignin is generally a three-dimensional crosslinked polymer composed of three different phenylpropenol moieties. However, since its chemical structure is extremely complex, an effective utilization method has not been established. However, since the chemical structure contains abundant aromatic rings, phenolic hydroxyl groups, and alcoholic hydroxyl groups, a resin raw material can be considered as one of effective utilization methods of lignin (see, for example, Patent Document 1). When a functional group for crosslinking such as an epoxy group is introduced into lignin as the resin raw material, an alcoholic hydroxyl group having low reactivity in lignin inhibits the introduction of the functional group. According to the report by Tsujioka et al., The molar ratio of the phenolic hydroxyl group to the alcoholic hydroxyl group is about 0.8: 1.0 to 1.5: 1.0 (see, for example, Non-Patent Document 1). In addition, when a functional group for crosslinking such as an epoxy group is introduced into lignin, the alcoholic hydroxyl group is inferior in reactivity, so that it is necessary to introduce a phenol compound in advance. Hasegawa et al. Are studying epoxidation of lignophenol, but there is a problem that the introduction rate of epoxy groups is reduced to around 20% even though phenolic hydroxyl groups are increased (for example, non-patent documents). 2). Therefore, when these lignophenols and epoxidized products thereof are applied to substrate applications, there is a problem that the heat resistance of the prepreg and the substrate is inferior.

JP 2004-238539 A

K. Mikame, M.M. Funaoka, Polym. J. et al. , 38, 585-591, 2006J . Kadota, K .; Hasegawa, M.M. Funoka Journal of Network Polymer. Japan, 27, 118-125, 2006

  This invention is made | formed in view of this condition, and provides the method of manufacturing reliably the prepreg which is excellent in heat resistance compared with the case where the conventional lignophenol is used.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have used a resin composition containing a lignin compound having a phenolic hydroxyl group or other reactive group in a specific ratio and a crosslinking agent. In addition to finding out that a prepreg capable of realizing excellent heat resistance and physical properties can be obtained, a method for reliably producing such a prepreg has been found, and the present invention has been completed.

Such an object is achieved by the present inventions (1) to (6) below.
(1) A process for producing a prepreg the resin composition obtained by impregnating a substrate comprising a a lignin compound crosslinking agent,
A decomposition step in which biomass is placed in the presence of water, and these are stirred and decomposed under high temperature and pressure;
An immersion step of immersing the insoluble matter in the processed product obtained by the decomposition step in a solvent in which lignin is soluble;
A distillation step for distilling off the solvent in which the lignin is soluble from the soluble matter in the treated product obtained by the immersion step;
A crosslinking agent mixing step of mixing the processed product obtained by the distillation step and a crosslinking agent;
An impregnation step of impregnating a base material with the processed product obtained by the crosslinking agent mixing step,
The said lignin compound is a manufacturing method of the prepreg characterized by including a phenolic hydroxyl group and alcoholic hydroxyl group by the molar ratio of 9: 1-8: 2.
(2) A process for producing a prepreg the resin composition obtained by impregnating a base material containing a lignin derivative obtained by introducing a reactive group into the phenolic hydroxyl group of lignin compound and a crosslinking agent,
A decomposition step in which biomass is placed in the presence of water, and these are stirred and decomposed under high temperature and pressure;
An immersion step of immersing the insoluble matter in the processed product obtained by the decomposition step in a solvent in which lignin is soluble;
A distillation step for distilling off the solvent in which the lignin is soluble from the soluble matter in the treated product obtained by the immersion step;
A reactive group introducing step of mixing the treated product obtained by the distillation step and the compound containing the reactive group;
A crosslinking agent mixing step of mixing the processed product obtained by the reactive group introduction step and a crosslinking agent;
An impregnation step of impregnating a base material with the processed product obtained by the crosslinking agent mixing step,
The said lignin compound is a manufacturing method of the prepreg characterized by including a phenolic hydroxyl group and alcoholic hydroxyl group by the molar ratio of 9: 1-8: 2.
(3) The manufacturing method of the prepreg as described in said (2) whose said reactive group is an epoxy group.
(4) The method for producing a prepreg according to any one of (1) to (3), wherein the resin composition further includes a filler.
(5) In the total amount of the lignin compound and the crosslinking agent, the resin composition has a lignin compound content of 40 to 95% by mass and a crosslinking agent content of 5 to 60% by mass (1) to (1) to (4) The manufacturing method of the prepreg in any one of.
(6) The method for producing a prepreg according to any one of (1) to (5), wherein a temperature in the decomposition treatment is 150 to 400 ° C., and a pressure in the decomposition treatment is 1.0 to 40 MPa.

  ADVANTAGE OF THE INVENTION According to this invention, the method of manufacturing reliably the prepreg excellent in heat resistance can be provided. Moreover, the board | substrate which hardened | cured the prepreg obtained by this invention is excellent in heat resistance.

  The present invention is a method for producing a prepreg in which a base material is impregnated with a resin composition containing a lignin compound and a crosslinking agent, the molar ratio of phenolic hydroxyl groups and alcoholic hydroxyl groups obtained by decomposing biomass. Or a lignin compound having a ratio of 9: 1 to 8: 2 (hereinafter sometimes referred to as a lignin degradation product) and a lignin derivative in which a reactive group is introduced into the phenolic hydroxyl group of the lignin compound or Two types are used. According to the present invention, a prepreg excellent in heat resistance can be reliably produced, and a substrate obtained by curing the prepreg can be provided.

  Examples of the structure having a phenolic hydroxyl group in the lignin compound include a phenol structure, a guaiacol structure, and a 2,6-dimethoxyphenol structure.

The lignin degradation product in the lignin compound used in the present invention is obtained by decomposing biomass, and has a phenolic hydroxyl group and an alcoholic hydroxyl group in a molar ratio of 9: 1 to 8: 2.
Further, the lignin derivative having a reactive group other than the phenolic hydroxyl group in the lignin compound includes a reactive group such as an epoxy group, a vinyl group, an ethynyl group, a maleimide group, a cyanate group and an isocyanate group, which will be described later. Was introduced.
Since the lignin compound including the lignin derivative has a number of cross-linked sites, when it is used for a prepreg, it has excellent properties such as heat resistance.
Among the above, as the lignin compound used in the present invention, a lignin degradation product obtained by decomposing biomass is preferable in terms of reactivity and ease of handling.

  Examples of the biomass include plants containing lignin and processed products of the plants. Examples of the plant include broad-leaved trees such as beech, birch and oak, conifers such as cedar, pine, and oak, and gramineous plants such as bamboo and rice straw. Examples of the shape of biomass used in the present invention include blocks, chips, and powders.

The lignin degradation product in the lignin compound used in the present invention can be obtained by decomposing the biomass by high-temperature and high-pressure treatment in the presence of a solvent.
As a specific example of a method for producing a lignin compound, first, the biomass is adjusted to a certain size, and then, together with a solvent, optionally a catalyst, put in a pressure vessel with a stirrer and a heating device, The biomass is decomposed while being heated and pressurized (decomposition step). Next, the content of the pressure vessel is filtered to remove the filtrate, and the water-insoluble matter is washed with water and separated. Next, the water-insoluble matter is immersed in a solvent in which the lignin compound is soluble (for example, acetone) (immersion step), the lignin compound is extracted into acetone, and the acetone is distilled off (distillation step). Thus, a lignin compound can be obtained as a lignin degradation product.

  As a magnitude | size of the biomass in the said decomposition | disassembly process, about 100 micrometers-1 cm are preferable, and 200 micrometers-500 micrometers are more preferable. At this time, the shape of the biomass may be any of a block shape, a chip shape, a powder shape and the like as described above.

  Examples of the solvent in the decomposition treatment include water, alcohols such as methanol and ethanol, phenols such as phenol and cresol, ketones, ethers, and the like, and it is particularly preferable to use water. As a usage-amount of a solvent, although it is so preferable that it is used in large quantities with respect to biomass, about 2 mass times-10 mass times of biomass mass are preferable, and about 3 mass times-5 mass times are more preferable. Moreover, when accelerating | stimulating decomposition | disassembly of biomass, you may add inorganic bases, such as sodium carbonate, as a catalyst.

  As conditions for processing the biomass at high temperature and high pressure, the processing temperature is usually preferably from 150 ° C to 400 ° C, more preferably from 200 ° C to 380 ° C. The treatment temperature can be used outside the above range, but the molecular weight of the lignin compound can be controlled by the treatment temperature, and tends to be a low molecular weight body when treated at a high temperature and a high molecular weight body when treated at a low temperature.

As processing time in the said process, 0 minute-480 minutes are preferable normally, More preferably, it is 30 minutes-120 minutes. Although the treatment time can be used outside the above range, the phenolic hydroxyl group equivalent of the lignin compound can be controlled by the treatment time, the phenolic hydroxyl group equivalent tends to increase with short-time treatment, and tends to decrease with long-time treatment. . The processing time is a time from when the temperature in the pressure vessel reaches a predetermined temperature until cooling is started (heating is finished).
The pressure in the high-pressure treatment is preferably 1.0 MPa to 40 MPa, more preferably 1.5 MPa to 25 MPa. The pressure can be used even outside the above range, but by treating at a higher pressure, an effect equivalent to that obtained when the treatment is performed for a long time can be obtained.

By treating the biomass under the conditions within the above range, the number average molecular weight is in the preferred range of about 300 to 2,000, and furthermore, it is a preferred phenolic hydroxyl group equivalent of 100 to 200 as the lignin compound in the present invention. It becomes easy to control to the phenolic hydroxyl group equivalent of a grade.
In the specific example of the production method, the phenolic hydroxyl group equivalent and the molecular weight can be controlled independently. For example, the phenolic hydroxyl group equivalent (mainly phenolic hydroxyl group) is obtained by short-time treatment regardless of the treatment temperature. A large product of about 200 is obtained, and a small phenolic hydroxyl group equivalent is obtained by saturation at about 100 by long-time treatment.

  The lignin degradation product obtained by the production method exemplified above has a phenolic hydroxyl group and an alcoholic hydroxyl group in a molar ratio of 9: 1 to 8: 2.

  The lignin degradation product preferably has a polystyrene-equivalent number average molecular weight of 300 to 2,000 as measured by gel permeation chromatography. Although it can be used outside the above range, if it is smaller than 300, monofunctional monomers and oligomers exist as lignin decomposition products, and when cured, the crosslink density may decrease and heat resistance may be poor. If it is larger than 2,000, the softening point of the lignin decomposition product becomes too high, which may cause the problem of difficulty in molding. The same applies to the number average molecular weight of lignin derivatives.

  Moreover, the lignin derivative in the lignin compound used in the present invention is obtained by introducing a reactive group other than a phenolic hydroxyl group into the lignin decomposition product, has a useful reactivity as a resin raw material, and obtains a high crosslinking density. Can do.

  The reactive group of the lignin derivative is a reactive group, the reactive group is self-reactive, and two or more identical reactive groups can react with each other, or other functional group As long as they can react with each other, and examples thereof include carbon-carbon unsaturated bond groups such as epoxy groups, vinyl groups, and ethynyl groups, maleimide groups, cyanate groups, and isocyanate groups. It is not limited to. Among these, an epoxy group is preferable because the cured product has high dimensional stability, water resistance, chemical resistance, and electrical insulation.

  As a method for producing the lignin derivative, a person skilled in the art can generally use a known method in which a reactive group is bonded to a phenolic hydroxyl group via a covalent bond. Can be selected. As a specific example, it can be obtained by introducing the reactive group into the phenolic hydroxyl group of the lignin degradation product obtained above.

Although the specific example of the introduction method (reactive group introduction | transduction process) of a reactive group is shown below, it is not limited to these.
When an epoxy group is introduced as a reactive group, for example, the lignin decomposition product obtained above is obtained by dissolving in epichlorohydrin and reacting with a base catalyst such as sodium hydroxide under reflux under reduced pressure. .

  When a vinyl group is introduced as a reactive group, for example, a halogen compound containing a vinyl group such as allyl halide and vinylbenzyl halide and the lignin decomposition product obtained above are dissolved in a solvent and heated. It can be obtained by reacting using a base catalyst such as sodium hydroxide.

  As the crosslinking agent used in the present invention, any one capable of reacting with the phenolic hydroxyl group or phenol nucleus of the lignin compound or having a functional group that reacts with the reactive group of the lignin compound (lignin derivative) having a reactive group. There is no particular limitation.

  As a crosslinking agent in the case of using a lignin degradation product as a lignin compound, for phenolic hydroxyl groups contained in the lignin compound, epoxy resins such as orthocresol novolac epoxy resin and bisphenol A type epoxy resin; hexamethylene diisocyanate and toluene diisocyanate Urethane resins such as formaldehyde, acetaldehyde and paraformaldehyde; aldehyde sources such as polyoxymethylene; hexamethylenetetramine; resol type phenol resins; Examples of the aromatic ring contained in the compound include compounds capable of crosslinking by electrophilic substitution reaction.

  The resol type phenol resin is not particularly limited, but may include an oil-modified resol type phenol resin. Examples of the oil-modified resol type phenol resin include a dry oil-modified resol type phenol resin modified with a drying oil such as paulownia oil, linseed oil, safflower oil, and walnut oil; Examples include semi-drying oil-modified resol type phenol resin. Among these, when considering punchability in a prepreg or a substrate, tung oil-modified resol type phenol resin is preferable.

  Moreover, as a crosslinking agent in the case of using the lignin compound (lignin derivative) which has a reactive group, what is necessary is just a crosslinking agent which reacts with this reactive group, or has a self-crosslinking reactive group.

  As a crosslinking agent in the case of using a lignin compound having an epoxy group as a lignin derivative, a general curing agent for an epoxy resin may be used. For example, a phenol resin such as a novolac-type phenol resin; a lignin having a phenolic hydroxyl group Compounds; amine compounds such as diethylenetriamine, m-xylylenediamine and N-aminoethylpiperazine; acid anhydrides such as phthalic anhydride, succinic anhydride and maleic anhydride; dicyandiamide, guanidines, 2-methylimidazole; An anionic curing agent of epoxy resin such as ethyl-4-methylimidazole can be used. In the self-crosslinking of the epoxy group, for example, imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole; anionic polymerization initiators such as 1,8-diazabicyclo (5,4,0) undecene-7 And cationic polymerization initiators such as sulfonium salts such as triphenylsulfonium hexafluorophosphate and diphenylsulfonium tetrafluoroborate, and diazonium salts such as phenyldiazonium hexafluorophosphate and phenyldiazonium tetrafluoroborate. Among these, a lignin compound is preferable in terms of reactivity.

  As a crosslinking agent in the case of using a lignin compound having an isocyanate group as a lignin derivative, a general curing agent for isocyanate resin may be used, for example, phenol resin, lignin decomposition product, polyvinyl alcohol, polyamine compound, and the like. Can be mentioned.

  As a crosslinking agent when a lignin compound having a vinyl group is used as the lignin derivative, a general vinyl group-containing compound polymerization initiator may be used. For example, anionic polymerization initiators such as butyl lithium and sodium ethoxide And radical polymerization initiators such as azobisisobutyronitrile (AIBN) and benzoyl peroxide (BPO).

  As a lignin derivative, a crosslinking agent in the case of using a lignin compound having an ethynyl group may be a polymerization catalyst of a general ethynyl group-containing compound, such as molybdenum pentachloride, tungsten pentachloride and norbornadiene rhodium chloride dimer. Can be mentioned.

  As a lignin derivative, the crosslinking agent in the case of using a lignin compound having a maleimide group may be a general polymerization initiator of a maleimide group-containing compound, such as a peroxide such as BPO and the anionic polymerization initiator. And so on.

  As the lignin derivative, the crosslinking agent in the case of using a lignin compound having a cyanate group may be a general polymerization catalyst of a cyanate group-containing compound, and examples thereof include metal catalysts such as cobalt naphthenate. .

  The resin composition used in the present invention contains a lignin compound and a crosslinking agent, and is obtained by mixing these components (crosslinking agent mixing step). Moreover, a lignin compound has a phenolic hydroxyl group obtained by decomposing biomass and an alcoholic hydroxyl group in a molar ratio of 9: 1 to 8: 2, and a reactive group to the phenolic hydroxyl group of the lignin compound. 1 type or 2 types chosen from the lignin derivative which introduce | transduced can be used, and each 1 type, or 2 or more types can be used in the said lignin compound and lignin derivative.

  As content of the lignin compound and a crosslinking agent in a resin composition, it is preferable to use 40-95 mass% of lignin compounds in the total amount of a lignin compound and a crosslinking agent, and it is more preferable to use 50-90 mass%. Moreover, it is preferable to use 5-60 mass% of crosslinking agents, and it is more preferable to use 10-50 mass%.

  The resin composition used in the present invention may optionally contain a filler in addition to the lignin compound and the crosslinking agent. Examples of the filler include inorganic fillers such as fused silica, crystalline silica, clay, alumina, mica and glass fiber, and organic fillers such as wood powder, pulp, pulverized cloth, and thermosetting resin cured powder. One or more of these can be used, but is not limited thereto. Among these, inorganic fillers are effective in improving flame retardancy.

  As content of the filler in the said lignin resin composition, 10-900 mass parts is preferable with respect to 100 mass parts of total amounts of a lignin compound and a crosslinking agent, and 20-500 mass parts is more preferable.

  In addition to the above components, various additives such as a colorant, an antioxidant, a reducing agent, and an ultraviolet opaque agent can be optionally added within the range not impairing the object of the present invention. These may be used alone or in combination of two or more.

In the production of prepreg, an organic solvent can be used when the resin composition is used as a varnish. The organic solvent is not particularly limited as long as it is compatible with the lignin compound and the crosslinking agent. Specific examples include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, propylene glycol methyl ether and its acetate, toluene, xylene, dimethylformamide, and the like. These may be used alone or in combination of two or more. It is also possible to do.
In the varnish, the amount of the organic solvent used is preferably 20 to 400 parts by mass, more preferably 50 to 200 parts by mass with respect to 100 parts by mass of the lignin resin composition.

  The prepreg obtained by the present invention is obtained by impregnating a base material with the above resin composition.

  As the base material used in the present invention, glass fiber base materials such as glass woven fabric and glass non-woven fabric, paper materials such as kraft paper and linter paper, woven fabric such as synthetic fibers such as aramid fiber, polyester fiber and acrylic fiber, Examples include organic synthetic fiber base materials composed of non-woven fabrics, woven fabrics such as metal fibers, carbon fibers and mineral fibers, inorganic fiber base materials composed of non-woven fabrics, and mats thereof. May be used.

  The prepreg obtained by the present invention can be produced by drying the impregnated substrate after impregnating the resin composition (impregnation step). At this time, the resin composition can be usually used as a varnish using an organic solvent, but may also be used as a powder.

A usual method can be used as a method of impregnating the substrate with the resin composition. For example, a method of immersing the substrate in a resin varnish and impregnating, a method of applying with various coaters, a spraying method by spraying and the like can be mentioned.
In the prepreg obtained by drying, the organic solvent used for the varnish is preferably volatilized by 80% by mass or more.

The drying conditions for producing the prepreg are usually a drying temperature of about 80 to 180 ° C., and the drying time can be freely selected according to the desired prepreg characteristics in consideration of the gelation time of the varnish.
Although the manufacturing conditions of the said prepreg were demonstrated, it is not limited to these.

  According to the present invention, the resin impregnation rate is represented by the ratio of the total mass of the lignin compound and the crosslinking agent with respect to the total mass of the prepreg, and is preferably 30 to 80% by mass, more preferably 40 to 70% by mass. preferable. The resin content can be appropriately determined according to the performance of the target prepreg and the thickness of the insulating layer in the substrate obtained by laminating the prepreg. Moreover, it is preferable that the amount of impregnations of a varnish shall be 35-70 mass% of varnish solid content with respect to the total amount of a varnish solid content and a base material.

  The substrate obtained by the present invention is obtained by curing a laminate obtained by laminating one or two or more of the prepregs.

The manufacturing method of the board | substrate obtained by this invention is as follows.
The prepreg in the present invention or a laminate obtained by laminating a plurality of the prepregs is usually at a temperature in the range of 150 to 280 ° C, preferably in the range of 180 ° C to 250 ° C, and usually in the range of 0.5 to 20 MPa, preferably in the range of 1 to 8 MPa. Thus, by pressing and molding while heating, a single-layer substrate and a substrate that is a laminate obtained from the laminate can be produced.
Moreover, in the said manufacturing process, a metal-clad laminated board can be manufactured by laminating | stacking metal foil on the one surface or both surfaces of the said prepreg or a laminated body as needed, and heat-pressing and shape | molding it. By using a metal foil as a metal-clad laminate, circuit processing can be applied to the metal layer to obtain a printed circuit board.

  As the metal foil used in the present invention, a copper foil or an aluminum foil is generally used. However, a metal foil having a thickness of 5 to 200 μm which is usually used for a laminate can be used. Also, nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead, lead-tin alloy, etc. are used as intermediate layers, and a 0.5-15 μm copper layer and a 10-300 μm copper layer are provided on both sides. Alternatively, a three-layer composite foil or a two-layer composite foil in which aluminum and a copper foil are combined can be used.

  The laminated board is preferably used for, for example, a printed wiring board, a mother board, and a semiconductor plastic package on which a semiconductor chip is mounted.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these at all.

Example 1
[Production of lignin degradation product varnish]
15 g of Somune bamboo powder (60 mesh under) and 80 g of pure water were introduced into a 300 ml autoclave, and the contents were treated at 1.6 MPa and 200 ° C. for 120 minutes while stirring at 300 rpm to decompose the Somune bamboo. Subsequently, 10.0 g of water-insoluble parts were separated by filtering the decomposition product and washing with pure water. The water-insoluble part was immersed in 200 ml of acetone for 8 hours and then filtered to collect the acetone-soluble part. Subsequently, acetone was distilled off from the acetone-soluble part, followed by drying to obtain 3.2 g of a lignin decomposition product (A). Next, the lignin degradation product (A) obtained by repeating the above-described production process of the lignin degradation product was diluted with methanol to obtain 330 g of a lignin degradation product (A) varnish having a resin content of 50% by mass.

From the result of ¹ H-NMR measurement of the lignin degradation product (A) obtained above, the peak of the aromatic group was 7-8 ppm, the aromatic ring was 3.5-8 ppm, the methoxy group was near 3.5-4 ppm, and 0.5-3 ppm. It was confirmed that it was a lignin degradation product.

  The OH equivalent of the lignin degradation product obtained above was determined by the following method. In a stoppered Erlenmeyer flask, 4.0 g of a mixed solution of acetic anhydride / pyridine (1/3 volume ratio) and 1.0 g of the lignin decomposition product obtained above were dissolved. After maintaining this solution at 60 ° C. for 3 hours, 1 ml of pure water was added. When the solution thus obtained was titrated with a 0.1 mol / L NaOH aqueous solution with pH = 10 as an end point, the OH equivalent of the lignin decomposition product (A) was 118.

The molar ratio of phenolic OH groups and alcoholic OH groups in the lignin degradation product obtained above (hereinafter referred to as P / A ratio) was determined by the following method. The lignin degradation product (A) 1.0 g obtained above was acetylated using 4.0 g of acetic anhydride / pyridine (1/3 volume ratio) mixed solution. From this reaction solution, unreacted acetic anhydride and pyridine were distilled off, and the acetylated lignin decomposition product (A) obtained by drying was measured by ¹ H-NMR. From the integral ratio of protons derived from acetyl groups (derived from acetyl groups bonded to phenolic OH groups: 2.2 to 2.6 ppm, derived from acetyl groups bonded to alcoholic OH groups: 1.6 to 2.2 ppm), mol When the ratio was determined, the P / A ratio was 8.9: 1.1.

  Further, the molecular weight of the lignin degradation product (A) obtained above was measured by gel permeation chromatography in terms of polystyrene using tetrahydrofuran as an eluent. The number average molecular weight (Mn) = 1000, molecular weight distribution (Mw / Mn ) = 2.02.

[Production of resol-type phenolic resin]
A mixture consisting of 240 g of phenol, 240 g of 37% by weight formaldehyde aqueous solution and 4.8 g of triethylamine was reacted at 60 ° C. for 2 hours in a 300 mL three-necked flask equipped with a stirrer and a condenser, and then concentrated under reduced pressure. To obtain 670 g of a resol type phenol resin varnish having a resin content of 50% by mass.

[Adjustment of resin varnish for substrate impregnation]
33 parts by mass of the lignin degradation product (A) varnish obtained above and 67 parts by mass of a resol type phenolic resin varnish were mixed to obtain 1000 g of a resin varnish for impregnating a substrate.

[Manufacture of prepreg and laminate]
Next, the varnish for impregnating the base material obtained above was applied to kraft paper (basis weight 135 g / m ² ) with a dip coater so that the resin content was 55% by mass (ratio to the whole prepreg). And dried at 160 ° C. for 5 minutes to obtain a prepreg. Eight prepregs and both front and back sides of the copper foil with adhesive (FSM Nippon Electrolytic Co., Ltd., thickness 18 μm) are overlaid, heat-pressed at 200 ° C., 5 MPa, 10 minutes, thickness 1.6 mm A laminate was obtained.

  About solder heat resistance, after performing a moisture absorption treatment for 2 hours with boiling using the laminate obtained above according to JIS-C6481, abnormal appearance after floating in a solder bath at 260 ° C. for 180 seconds The presence or absence of was investigated. Those that were not visually inspected were regarded as having no abnormality.

Example 2
[Manufacture of tung oil-modified resol type phenol resin]
115 g of phenol and 72 g of paulownia oil were reacted at 95 ° C. for 2 hours in the presence of paratoluenesulfonic acid, and 47 g of paraformaldehyde, 2.2 g of hexamethylenetetramine and 2000 g of toluene were further added, and the reaction was performed at 90 ° C. for 2 hours. The mixture was concentrated under reduced pressure and diluted with a mixed solvent of toluene and methanol to obtain 420 g of tung oil-modified resol type phenol resin varnish having a resin content of 50% by mass.

  In the resin varnish for substrate impregnation in Example 1, 33 parts by mass of the lignin decomposition product (A) varnish and 67 parts by mass of the resol type phenol resin varnish, 42 parts by mass of the lignin decomposition product (A) varnish, and the resol type phenol resin varnish A laminated board was obtained in the same manner as in Example 1 except that 16 parts by mass and 42 parts by mass of the tung oil-modified resol type phenol resin varnish obtained above were used.

Example 3
[Production of lignin derivative varnish having an epoxy group]
Into a 100 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel, 1.2 g of the lignin degradation product (A) obtained in the same manner as in Example 1 and 100.0 g of epichlorohydrin were introduced. While refluxing under a reduced pressure of 100 mmHg, 2.0 g of a 20 mass% NaOH aqueous solution was added dropwise over 30 minutes. Thereafter, the reaction mixture was obtained by maintaining the reduced-pressure reflux state for 90 minutes. In the reaction mixture, the insoluble part was removed by filtration, and the epichlorohydrin soluble part was isolated. Epichlorohydrin was distilled off from this epichlorohydrin soluble part and dried to obtain 0.8 g of lignin derivative (D) (epoxidized lignin).

When the structure of the lignin derivative (D) having an epoxy group obtained above was confirmed by ¹ H-NMR, it was found to be 2.7, 2.9, 3.3, 3.5, 3 in addition to the peak of the lignin derivative. A peak derived from an epoxy group was observed at .9 ppm.

The molecular weight of the lignin derivative (D) having an epoxy group was Mn = 950 and Mw / Mn = 3.67 as measured by gel permeation chromatography in terms of polystyrene.
The epoxy equivalent of the lignin derivative (D) having an epoxy group was 390 as measured by ¹ H-NMR.

  The lignin derivative (D) having an epoxy group obtained by repeating the operation for producing the lignin derivative was diluted with methanol to obtain 790 g of a lignin derivative (D) varnish having a resin content of 50% by mass.

[Manufacture of novolac-type phenolic resin varnish]
A novolac-type phenol resin (softening point: 105 ° C., hydroxyl group equivalent: 104) was diluted with methanol to obtain a novolac-type phenol resin varnish having a resin content of 50% by mass.

  In the resin varnish for impregnating the paper base material in Example 1, 33 parts by mass of the lignin decomposition product (A) varnish and 67 parts by mass of the resol type phenol resin varnish were used to obtain the lignin derivative (D) varnish having the epoxy group obtained above. A laminate was obtained in the same manner as in Example 1, except that 79 parts by mass and 21 parts by mass of the novolac type phenolic resin varnish obtained above were added with 2 parts by mass of 2-methylimidazole.

Example 4
In the resin varnish for substrate impregnation in Example 1, 33 parts by mass of the lignin degradation product (A) varnish and 67 parts by mass of the resol type phenolic resin varnish were obtained in the same manner as in Example 3 to obtain a lignin derivative having an epoxy group. (D) 77 mass parts of varnish, lignin decomposition product (A) Except having added 2 mass parts of 2-methylimidazole to 23 mass parts of varnish, it carried out similarly to Example 1, and obtained the laminated board.

Example 5
In the resin varnish for substrate impregnation in Example 1, 33 parts by mass of the lignin degradation product (A) varnish and 67 parts by mass of the resol type phenolic resin varnish were obtained in the same manner as in Example 3 to obtain a lignin derivative having an epoxy group. (D) A laminate was obtained in the same manner as in Example 1 except that 98 parts by mass of varnish and 2 parts by mass of 2-methylimidazole were added.

Example 6
In Example 1, it carried out like Example 1 except having changed processing temperature 200 ° C in manufacture of a lignin decomposition product into 300 ° C, and obtained 3.6 g of lignin decomposition products (B). The lignin degradation product (B) obtained here was evaluated in the same manner as in Example 1. As a result, the hydroxyl equivalent weight = 171, P / A ratio = 8.5: 1.5, softening point 88 ° C., Mn = 570 Mw / Mn = 1.24.

  The lignin decomposition product (B) obtained by repeating the production of the above lignin decomposition product was diluted with methanol to obtain 330 g of a lignin decomposition product (B) varnish having a resin content of 50% by mass.

  In the resin varnish for base material impregnation in Example 1, 33 parts by mass of the lignin decomposition product (A) varnish was changed to 33 parts by mass of the lignin decomposition product (B) varnish obtained above, and was the same as Example 1. To obtain a laminate.

Example 7
In the resin varnish for substrate impregnation in Example 2, except that 42 parts by mass of the lignin decomposition product (A) varnish was changed to 42 parts by mass of the lignin decomposition product (B) varnish obtained in the same manner as in Example 6, A laminate was obtained in the same manner as in Example 2.

Example 8
In the production of the lignin derivative of Example 3, 1.2 g of the lignin degradation product (A) was changed to 1.2 g of the lignin degradation product (B) obtained in the same manner as in Example 6, and the same as in Example 3. Then, 0.9 g of a lignin derivative (E) having an epoxy group was obtained. When the lignin derivative (E) having an epoxy group obtained here was evaluated in the same manner as in Example 3, the molecular weight was measured by gel permeation chromatography in terms of polystyrene. Mn = 750, Mw / Mn = It was 2.89.
The epoxy equivalent of the lignin derivative (E) having an epoxy group was 540 as measured by ¹ H-NMR.

  The lignin derivative (E) having an epoxy group obtained by repeating the production of the lignin derivative was diluted with methanol to obtain 840 g of a lignin derivative (E) varnish having a resin content of 50% by mass.

  In Example 1, the resin varnish for impregnating the base material was 84 parts by mass of the lignin derivative (E) varnish obtained above, 16 parts by mass of the novolak type phenol resin varnish obtained in the same manner as in Example 3, and 2-methyl A laminate was obtained in the same manner as in Example 1 except that 2 parts by mass of imidazole were mixed.

Example 9
In Example 1, the resin varnish for impregnating the base material was 76 parts by mass of the lignin derivative (E) varnish having an epoxy group obtained in the same manner as in Example 8, and the lignin decomposition product obtained in the same manner as in Example 6 ( B) A laminate was obtained in the same manner as in Example 1 except that 24 parts by mass of varnish and 2 parts by mass of 2-methylimidazole were mixed.

Example 10
In Example 1, the resin varnish for base impregnation was mixed with 98 parts by mass of the lignin derivative (E) varnish having an epoxy group obtained in the same manner as in Example 8 and 2 parts by mass of 2-methylimidazole. Except for this, a laminate was obtained in the same manner as in Example 1.

Example 11
In Example 1, it carried out like Example 1 except having changed processing temperature 200 ° C in manufacture of a lignin decomposition product into 150 ° C, and obtained lignin decomposition product (C) 3.5g. The lignin degradation product (C) obtained here was evaluated in the same manner as in Example 1. As a result, hydroxyl equivalent = 122, P / A ratio = 8.1: 1.9, softening point 121 ° C, Mn = 1800 Mw / Mn = 1.82.

  The lignin degradation product (C) obtained by repeating the production of the lignin degradation product was diluted with methanol to obtain 330 g of a lignin degradation product (C) varnish having a resin content of 50% by mass.

  In Example 1, the resin varnish for substrate impregnation was the same as in Example 1 except that 33 parts by mass of the lignin decomposition product (A) varnish was changed to 33 parts by mass of the lignin decomposition product (C) varnish obtained above. To obtain a laminate.

Example 12
In the resin varnish for impregnating the base material in Example 2, Example 2 except that 33 parts by mass of the lignin decomposition product (A) varnish was changed to 33 parts by mass of (C) varnish obtained in the same manner as Example 11. In the same manner as above, a laminate was obtained.

Example 13
In the production of the lignin derivative of Example 3, 1.2 g of the lignin degradation product (A) was changed to 1.2 g of the lignin degradation product (C) obtained in the same manner as in Example 11, and the same as in Example 3. To obtain 0.7 g of a lignin derivative (F) having an epoxy group. When the lignin derivative (F) having an epoxy group obtained here was evaluated in the same manner as in Example 3, the molecular weight was measured by gel permeation chromatography in terms of polystyrene. Mn = 2000, Mw / Mn = 3.47.
The epoxy equivalent of the lignin derivative (F) having an epoxy group was 620 as measured by ¹ H-NMR.

  The lignin derivative having an epoxy group (F) obtained by repeating the production of the lignin derivative was diluted with methanol to obtain 860 g of a lignin derivative (F) varnish having a resin content of 50% by mass.

  In Example 1, the resin varnish for impregnating the base material was 96 parts by mass of the lignin derivative (F) varnish obtained above, 14 parts by mass of the novolac-type phenol resin varnish obtained in the same manner as in Example 3, and 2-methyl A laminate was obtained in the same manner as in Example 1 except that 2 parts by mass of imidazole were mixed.

Example 14
In Example 1, the resin varnish for impregnating the base material was 84 parts by mass of the lignin derivative (F) varnish having an epoxy group obtained in the same manner as in Example 13, and the lignin decomposition product (C ) A laminate was obtained in the same manner as in Example 1 except that 16 parts by mass of varnish and 2 parts by mass of 2-methylimidazole were mixed.

Example 15
In Example 1, the resin varnish for substrate impregnation was mixed with 98 parts by mass of the lignin derivative (F) varnish having an epoxy group obtained in the same manner as in Example 13 and 2 parts by mass of 2-methylimidazole. Except for this, a laminate was obtained in the same manner as in Example 1.

Example 16
100 g of lignin decomposition product (A), 300 mL of acetone, 5 g of potassium carbonate, and 100 g of allyl bromide obtained by repeating the operation of Example 1 were introduced into a 1 L three-necked flask equipped with a stirrer and a condenser, and heated at reflux for 3 hours. The solvent was removed from the reaction mixture and the residue was dissolved in ethyl acetate. The organic phase was washed with 2% by mass hydrochloric acid and pure water, dried over magnesium sulfate, reprecipitated in 1 L of hexane, and dried to obtain 88 g of a lignin derivative (G) having a vinyl group.

The structure of the lignin derivative (G) having a vinyl group obtained above was confirmed by ¹ H-NMR. In addition to the peak of the lignin derivative, 6.1, 5.4, 5.3, 4.7 ppm were allylated. A peak derived from the group was observed. From the integration ratio with pyridine added as an internal standard, the vinyl group equivalent was 512 g / mol.
The molecular weight, molecular weight distribution, and softening point of the lignin derivative (G) having a vinyl group were evaluated in the same manner as in Example 1, and were Mn = 1150, Mw / Mn = 2.86, and 93 ° C., respectively.

The lignin derivative (G) having a vinyl group obtained by repeating the operation for producing the lignin derivative was diluted with methanol to obtain 990 g of a lignin derivative (G) varnish having a resin content of 50% by mass.
In Example 1, except that the resin varnish for impregnating the base material was prepared by adding 1 part by mass of azobisisobutyronitrile to 99 parts by mass of the lignin derivative (G) varnish obtained in the same manner as described above. In the same manner as in Example 1, a laminate was obtained.

Example 17
Methanol was added to crushed fused silica powder (average particle size 10 μm) to obtain 330 g of fused silica varnish adjusted to 50 mass%.
In Example 1, the resin varnish for impregnating the base material was 22 parts by mass of the lignin decomposition product (A) varnish obtained in the same manner as in Example 1, and the resol type phenolic resin varnish obtained in the same manner as in Example 1 was 45 mass. A laminate was obtained in the same manner as in Example 1 except that 33 parts by mass of the fused silica varnish obtained above was mixed.

Comparative Example 1
According to Non-Patent Document 1 (K. Mikame, M. Funaka, Polym. J., 38, 585-591, 2006), a lignophenol derivative was synthesized by the following method. Take 10 g of Somune bamboo powder in a 500 ml beaker, add acetone solution of p-cresol (containing 3 mol times phenol derivative per lignin constituent unit), stir with a glass rod and let stand for 24 hours. Thereafter, acetone was completely distilled off to obtain p-cresol sorption wood flour. To this bamboo flour, 100 ml of 72 mass% sulfuric acid was added and stirred vigorously at 30 ° C. for 1 hour, and then the mixture was poured into a large excess of water, the insoluble fraction was collected, deacidified, and dried. A lignophenol derivative was obtained. When this lignophenol derivative was evaluated in the same manner as in Example 1, Mn = 3600, OH equivalent = 143 g / eq, and P / A ratio = 5.8: 4.2.
This lignophenol derivative was diluted with methanol to obtain a lignophenol derivative varnish having a resin content of 50% by mass.
In Example 1, the base material impregnation varnish was prepared by mixing 37 parts by mass of the lignophenol derivative varnish obtained above and 63 parts by mass of the resol type phenol resin varnish obtained in the same manner as in Example 1. Except for this, a laminate was obtained in the same manner as in Example 1.

Comparative Example 2
According to Non-Patent Document 2 (Kadota, K. Hasegawa, M. Funoka Journal of Network Polymer. Japan, 27, 118-125, 2006), the lignophenol derivative obtained in Comparative Example 1 was epoxidized by the following method. . Into a 100 ml three-necked flask equipped with a stirrer, a cooler and a dropping funnel, 1.4 g of the lignophenol derivative obtained in Comparative Example 1 and 100.0 g of epichlorohydrin were introduced and refluxed to 100 mmHg under reduced pressure. 1.0 g of 20% NaOH aqueous solution was added dropwise over 30 minutes. Thereafter, the vacuum reflux state was maintained for 90 minutes. The insoluble part was filtered off from the reaction mixture, and epichlorohydrin was distilled off from the epichlorohydrin soluble part and dried to obtain 1.3 g of an epoxidized lignophenol secondary derivative. The obtained lignophenol secondary derivative having an epoxy group was evaluated in the same manner as in Example 3. As a result, Mn = 2400 and the epoxy equivalent was 790.
This lignophenol secondary derivative having an epoxy group was diluted with methanol to obtain a lignophenol secondary derivative varnish having an epoxy group with a resin content of 50% by mass.
In Example 1, except that the base material impregnation varnish was prepared by mixing 100 parts by mass of the lignophenol secondary derivative varnish having an epoxy group obtained above and 2 parts by mass of 2-methylimidazole. 1 to obtain a laminate.

  From Table 1, the board | substrate using the prepreg obtained by this invention was excellent in heat resistance compared with the comparative example.

Claims (6)

The resin composition comprising a lignin compound and crosslinking agent A method of manufacturing a prepreg obtained by impregnating a base material,
A decomposition step in which biomass is placed in the presence of water, and these are stirred and decomposed under high temperature and pressure;
An immersion step of immersing the insoluble matter in the processed product obtained by the decomposition step in a solvent in which lignin is soluble;
A distillation step for distilling off the solvent in which the lignin is soluble from the soluble matter in the treated product obtained by the immersion step;
A crosslinking agent mixing step of mixing the processed product obtained by the distillation step and a crosslinking agent;
An impregnation step of impregnating a base material with the processed product obtained by the crosslinking agent mixing step,
The said lignin compound is a manufacturing method of the prepreg characterized by including a phenolic hydroxyl group and alcoholic hydroxyl group by the molar ratio of 9: 1-8: 2. A method of manufacturing a prepreg the resin composition obtained by impregnating a base material containing a lignin derivative obtained by introducing a reactive group into the phenolic hydroxyl group of lignin compound and a crosslinking agent,
A decomposition step in which biomass is placed in the presence of water, and these are stirred and decomposed under high temperature and pressure;
An immersion step of immersing the insoluble matter in the processed product obtained by the decomposition step in a solvent in which lignin is soluble;
A distillation step for distilling off the solvent in which the lignin is soluble from the soluble matter in the treated product obtained by the immersion step;
A reactive group introducing step of mixing the treated product obtained by the distillation step and the compound containing the reactive group;
A crosslinking agent mixing step of mixing the processed product obtained by the reactive group introduction step and a crosslinking agent;
An impregnation step of impregnating a base material with the processed product obtained by the crosslinking agent mixing step,
The said lignin compound is a manufacturing method of the prepreg characterized by including a phenolic hydroxyl group and alcoholic hydroxyl group by the molar ratio of 9: 1-8: 2.   The method for producing a prepreg according to claim 2, wherein the reactive group is an epoxy group.   The method for producing a prepreg according to claim 1, wherein the resin composition further contains a filler.   5. The resin composition according to claim 1, wherein, in the total amount of the lignin compound and the crosslinking agent, the content of the lignin compound is 40 to 95 mass% and the content of the crosslinking agent is 5 to 60 mass%. The method for producing a prepreg according to 1. The method for producing a prepreg according to any one of claims 1 to 5, wherein a temperature in the decomposition treatment is 150 to 400 ° C, and a pressure in the decomposition treatment is 1.0 to 40 MPa.