TW201628861A - Impregnated plate, laminate, and resin composition - Google Patents

Abstract

An impregnated plate includes a substrate and a resin composition impregnated in a substrate, wherein the resin composition contains a reaction product of lignin, phenols, and aldehydes.

Description

Impregnated board, laminated board and resin composition

The present invention relates to an impregnated sheet, a laminated board, and a resin composition, and more particularly to an impregnated sheet, a laminated sheet formed by laminating the impregnated sheet, and a resin composition used in the production of the impregnated sheet.

An impregnation plate formed by impregnating a resin component with a base material such as paper, and a laminated plate formed by laminating a plurality of layers of the impregnation plate are widely used as a support substrate of a wired circuit board such as an electrical machine component.

For such impregnated sheets and laminates, various physical properties such as heat resistance, mechanical strength, and electrical insulation are required. Here, in order to satisfy the above characteristics, it is reviewed using a resol type phenol resin or the like for the resin component.

More specifically, for example, it is proposed to react a phenol or a vegetable oil compound such as vernonia oil under an acidic catalyst, and then react with formaldehyde under an alkaline catalyst to obtain a A laminated plate obtained by laminating a phenolic phenol resin composition, impregnating and drying it on a fibrous sheet substrate, and laminating it (see Patent Document 1).

In addition, for example, a paper base material phenol resin laminated board obtained by heating and pressurizing a metal foil on a prepreg obtained by impregnating a phenol resin varnish with a paper base material is proposed (see Patent Document 2).

Furthermore, proposals have made phenolic aldehydes in dry oils, for example under acidic catalysts. A pre-dip obtained by adding a phenol resin and then reacting the aldehyde under a base catalyst to obtain a dry oil-modified resol phenol resin, which is then impregnated into a paper substrate, and a laminate thereof (Refer to Patent Document 3).

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. Hei 7-224134

Patent Document 2: Japanese Patent Laid-Open Publication No. 2004-244565

Patent Document 3: Japanese Patent Laid-Open No. 2011-122009

On the other hand, such impregnated sheets and laminated sheets are required to have various physical properties for use, such as electrical insulating properties, workability, heat resistance, mechanical strength, and water resistance (moisture resistance).

An object of the present invention is to provide an impregnated sheet excellent in various physical properties for use, a laminated board formed by laminating the impregnated sheet, and a resin composition used in the production of the impregnated sheet.

The present invention [1] includes an impregnated sheet comprising: a substrate and a resin composition impregnated into the substrate; and the resin composition contains a reaction product of lignin, a phenol, and an aldehyde.

The immersion plate according to the above [1], wherein the lignin is lignin modified with acetic acid.

Furthermore, the present invention [3] contains the impregnation as described in [1] or [2] above. In the plate, the amount of the lignin to be added is 5 parts by mass or more and 300 parts by mass or less based on 100 parts by mass of the phenol.

The impregnated sheet according to any one of the above [1], wherein the amount of the aldehyde is compared with the phenolic hydroxyl group of the lignin and the phenol. The total amount of phenolic hydroxyl groups is 100 moles, and is 50 moles or more and 500 moles or less.

The impregnation plate according to any one of the above-mentioned [1], wherein the resin composition is present in an amount of 1 part by mass or more based on 100 parts by mass of the phenol. 50 parts by mass or less of the basic catalyst contains a reaction product which is reacted with the above lignin, the above phenol, and the above aldehyde.

The method of manufacturing the impregnated sheet according to any one of the above [1] to [4], wherein the resin composition is 100 parts by mass relative to the phenol. The reaction product containing the lignin, the phenol, and the aldehyde described above is contained in an alkaline catalyst having 1 part by mass or more and 50 parts by mass or less.

Furthermore, the present invention [6] includes a laminated board which is a laminated board which is laminated by a plurality of plate-like members, wherein at least one of the above-mentioned plate-shaped members is the one described in any one of the above [1] to [5]. Impregnated board.

Further, the present invention [7] contains a resin composition containing a reaction product of lignin, a phenol, and an aldehyde.

The impregnated sheet, the laminated board and the resin composition of the present invention can be improved in various physical properties.

1‧‧‧ laminate

2‧‧‧impregnated board

3‧‧‧ reinforcing plate

Fig. 1 is a view showing an embodiment of a laminated board of the present invention, showing a state in which the impregnated sheet is singular.

Fig. 2 is a view showing another embodiment of the laminated board of the present invention, showing a state in which the impregnated sheets are plural.

The impregnated sheet of the present invention comprises a prepreg comprising a substrate and a resin composition impregnated in the substrate, in other words, the impregnated sheet of the present invention comprises: a substrate, and a resin impregnated in the substrate The composition is preferably composed of a substrate and a resin composition impregnated into the substrate. That is, it is a base material impregnated with a resin composition.

The substrate is not particularly limited, and examples thereof include papers such as kraft paper, short lint paper, and melamine paper, and cotton cloth, glass fiber cloth, glass fiber non-woven fabric, melamine cloth, and glass fiber felt (glass). Fiber mat), glass fiber yarn bundle cloth, etc. These base materials may be used alone or in combination of two or more.

The base material is preferably paper, cotton cloth or glass cloth.

Further, the thickness of the substrate is not particularly limited, and the purpose and use of the substrate are appropriately set.

The resin composition contains a reaction product of lignin, a phenol, and an aldehyde, and is preferably composed of a reaction product of lignin, a phenol, and an aldehyde.

Lignin is a polymer composed of basic skeletons such as guaiacyl lignin (G type), syringyl lignin (S type), and p-hydroxyphenyl lignin (H type). A phenolic compound is contained in all plants. Industrial natural lignin which is taken out industrially, for example, when a pulp is produced from a plant material by a soda method, a sulfurous acid method, a sulfate method, or the like, in the discharged waste liquid (black liquor) Contains alkali lignin, sulfite lignin, sulfate lignin (kraft Lignin) and so on.

Specific examples of the lignin include lignin derived from woody plants and lignin derived from herbaceous plants.

The lignin system derived from the woody plant is, for example, a coniferous lignin contained in a conifer (for example, cedar), for example, a broad-leaved tree lignin contained in a broad-leaved tree. Such lignin derived from woody plants does not contain lignin with H-type as the basic skeleton. For example, coniferous lignin adopts G-type as basic skeleton, and broad-leaved lignin adopts G-type and S-type as basic. skeleton.

The lignin derived from the herbaceous plant may, for example, be a grass lignin contained in a gramineous plant (wheat straw, rice straw, maize, bamboo, etc.). Such a lignin derived from a herbaceous plant has all of the H-type, G-type, and S-type as a basic skeleton.

These lignin systems may be used alone or in combination of two or more.

The lignin is preferably a lignin derived from a herbaceous plant, and more preferably a lignin derived from a herbaceous plant derived from corn stover (the stalk, stem, leaf, etc.) of corn stalk.

Further, from the viewpoint of reactivity, lignin preferably contains an H-type basic skeleton in a ratio of preferably 9% by mass or more, more preferably 14% by mass or more.

Further, lignin is preferably modified with a carboxylic acid. That is, it is preferred to use lignin which has been modified with a carboxylic acid (hereinafter referred to as a carboxylic acid-modified lignin).

In the carboxylic acid-modified lignin, for example, a carboxylic acid having one carboxyl group (hereinafter referred to as a monofunctional carboxylic acid) may be mentioned, and specific examples thereof include a saturated aliphatic monofunctional carboxylic acid. An unsaturated aliphatic monofunctional carboxylic acid, an aromatic monofunctional carboxylic acid or the like.

Examples of the saturated aliphatic monofunctional carboxylic acid include acetic acid, propionic acid, butyric acid, and lauric acid.

Examples of the unsaturated aliphatic monofunctional carboxylic acid include acrylic acid, methacrylic acid, and linoleic acid.

Examples of the aromatic monofunctional carboxylic acid include benzoic acid, 2-phenoxybenzoic acid, and 4-methylbenzoic acid.

These carboxylic acids may be used alone or in combination of two or more.

The carboxylic acid is preferably a saturated aliphatic monofunctional carboxylic acid, and more preferably acetic acid (in other words, lignin is a lignin modified with acetic acid). When the above carboxylic acid is used, the carboxylic acid-modified lignin can be easily obtained, and the obtained carboxylic acid-modified lignin is as described later, and has high solubility in an organic solvent and a low melting temperature (100 to 200 ° C). It is also excellent in handling properties.

Further, the carboxylic acid system can be adjusted to be an aqueous solution. In this case, the concentration of the aqueous carboxylic acid solution is not particularly limited and can be appropriately set.

The method for producing the carboxylic acid-modified lignin is not particularly limited, and can be a known method.

Specifically, for example, a plant material (for example, a conifer, a broad-leaved tree, a grassy plant, etc.) to be a raw material of lignin is extracted with a carboxylic acid (preferably acetic acid), whereby a carboxylic acid can be obtained in the form of a pulp waste liquid. Lignin.

The leaching method is not particularly limited. For example, a plant material which is a raw material of lignin is mixed with a carboxylic acid and an inorganic acid (for example, hydrochloric acid, sulfuric acid, etc.) to carry out a reaction.

The ratio of the carboxylic acid to the plant material is 100 parts by mass, and the carboxylic acid (100% conversion) is, for example, 500 parts by mass or more, preferably 900 parts by mass or more, and for example, 30,000 parts by mass or less. Good for 15000 parts by mass under.

In addition, the ratio of the inorganic acid to the plant material is 100 parts by mass, and the inorganic acid (100% conversion) is, for example, 0.01 parts by mass or more, preferably 0.05 parts by mass or more, and is, for example, 10 parts by mass. Hereinafter, it is preferably 5 parts by mass or less.

Further, the reaction conditions are, for example, 30 ° C or higher, preferably 50 ° C or higher, and for example, 400 ° C or lower, preferably 250 ° C or lower. Further, the reaction time is, for example, 0.5 hours or longer, preferably 1 hour or longer, and is, for example, 20 hours or shorter, preferably 10 hours or shorter.

By such leaching, the carboxylic acid-modified lignin can be obtained in the form of a pulp waste liquid while obtaining the pulp.

Next, when this method is carried out, the pulp is separated by a known separation method such as filtration, and the filtrate (pulp waste liquid) is recovered, and if necessary, the unreacted carboxylic acid is further subjected to a known method such as a rotary evaporator or a vacuum distillation. Remove (distillate). Then, a large amount of excess water is added to precipitate the carboxylic acid-modified lignin, and by filtration, the carboxylic acid-modified lignin is recovered as a solid portion.

Further, the method for obtaining the carboxylic acid-modified lignin is not limited to the above, and for example, a lignin (hereinafter referred to as unmodified lignin) which has not been modified with a carboxylic acid is reacted with a carboxylic acid, whereby a carboxylic acid can also be obtained. Carboxylic acid modified lignin.

In such a method, the unmodified lignin is preferably a powdery unmodified lignin.

The average particle diameter of the powdery unmodified lignin is, for example, 0.1 μm or more, preferably 5 μm or more, and is, for example, 1000 μm or less, or preferably 500 μm or less.

When the average particle diameter is within the above range, aggregation of unmodified lignin can be suppressed, and unmodified lignin can be favorably dispersed with respect to the carboxylic acid.

Further, the powdery unmodified lignin can be obtained by drying and pulverizing the bulk unmodified lignin by a known method, and a commercially available product can also be used.

A method of reacting unmodified lignin with a carboxylic acid, for example, mixing unmodified lignin with a carboxylic acid and a mineral acid (for example, hydrochloric acid, sulfuric acid, etc.) and reacting.

The blending ratio of the carboxylic acid is, for example, 100 parts by mass or more, preferably 500 parts by mass or more, and preferably 15,000 parts by mass or less, and preferably 15,000 parts by mass or less, based on 100 parts by mass of the unmodified lignin. 10,000 parts by mass or less.

In addition, the blending ratio of the inorganic acid is 100 parts by mass or less, and the inorganic acid (in terms of 100%) is, for example, 0.01 parts by mass or more, preferably 0.05 parts by mass or more, and is, for example, 10 parts by mass or less. It is preferably 5 parts by mass or less.

Further, the reaction conditions are, for example, 30 ° C or higher, preferably 50 ° C or higher, and for example, 400 ° C or lower, preferably 250 ° C or lower. Further, the reaction time is, for example, 0.5 hours or longer, preferably 1 hour or longer, and is, for example, 20 hours or shorter, preferably 10 hours or shorter.

Such a carboxylic acid-modified lignin is excellent in handleability.

That is, lignin which has not been modified with a carboxylic acid has a low solubility in an organic solvent and does not melt, and thus has poor handleability depending on the application.

On the other hand, lignin modified by the use of a carboxylic acid as described above, due to a polar organic solvent (for example: acetone, methanol, phenol, tetrahydrofuran, acetonitrile, N-methylpyrrolidone, N,N-dimethylmethyl) The solubility of decylamine, N,N-dimethylacetamide, dimethyl hydrazine, hexamethylphosphoniumamine, etc. is high, and it can be melted at a relatively low melting temperature (about 100 to 200 ° C). Therefore, it has excellent handling properties.

Therefore, a carboxylic acid-modified lignin can also be used as a solution of the above organic solvent. In this case, the carboxylic acid-modified lignin concentration in the solution is, for example, 10% by mass or more, preferably 30% by mass or more.

Further, the average particle diameter of the carboxylic acid-modified lignin is, for example, 0.1 μm or more, preferably 5 μm or more, and is, for example, 2 cm or less, preferably 1 cm or less.

Further, the phenolic hydroxyl equivalent of lignin (preferably carboxylic acid-modified lignin) is, for example, 100 g/eq or more, preferably 300 g/eq or more, and is, for example, 1700 g/eq or less, preferably 1350 g/ Below eq.

Further, the phenolic hydroxyl equivalent is determined according to the examples described later.

Phenolic phenols and derivatives thereof (phenolic modified substances), such as phenols, and, for example, o-cresol, p-cresol, p-tert-butylphenol, p-phenylphenol, p-cumylphenol, p-nonyl a bifunctional phenol derivative such as phenol, 2,4- or 2,6-xylenol; a trifunctional phenol derivative such as m-cresol, resorcin, or 3,5-xylenol; for example: double A tetrafunctional phenol derivative such as phenol A or dihydroxydiphenylmethane. Further, the phenol derivative may, for example, be a halogen-substituted halogenated phenol such as chlorine or bromine; for example, a modified phenol (such as tung oil-modified phenol) modified with a fatty acid-containing fat or oil (such as tung oil). These phenols may be used alone or in combination of two or more. Further, when a phenol derivative (phenolic modified substance) is used, the timing of upgrading the phenol is not particularly limited, and the lignin, the phenol, and the aldehyde are reacted before, after, or at the same time as the reaction. can.

Phenols are preferred as phenols.

Examples of the aldehydes include formaldehyde, polyoxymethylene, acetaldehyde, benzaldehyde, and trisole. ,four (tetraoxane) and so on. Further, a part of the aldehyde may be substituted by furfural, decyl alcohol or the like. These aldehydes may be used alone or in combination of two or more.

The aldehyde is preferably a formaldehyde or a polyoxymethylene.

Further, an aldehyde system can be used as, for example, an aqueous solution. In this case, the concentration of the aldehyde is, for example, 10% by mass or more, preferably 20% by mass or more, and is, for example, 80% by mass or less, preferably 70% by mass or less.

Further, when lignin (preferably carboxylic acid-modified lignin), phenols, and aldehydes are reacted, these are blended and heated.

The blending ratio is, for example, 4% by mass or more, preferably 6% by mass or more, and is, for example, 60% by mass or less, preferably 50% by mass or less, based on the total amount of the lignin, the phenol, and the aldehyde. . Further, the phenol type is, for example, 20% by mass or more, preferably 25% by mass or more, and is, for example, 80% by mass or less, preferably 70% by mass or less. Further, the aldehyde is, for example, 15% by mass or more, preferably 20% by mass or more, and is, for example, 50% by mass or less, preferably 40% by mass or less.

In addition, the amount of the lignin to be added is, for example, 5 parts by mass or more, preferably 10 parts by mass or more, and preferably 300 parts by mass or less, preferably 200 parts by mass, based on 100 parts by mass of the phenol. the following.

Further, the amount of the aldehyde is 100 mol per mol of the phenolic hydroxyl group of the lignin and the phenolic hydroxyl group of the phenol, and is, for example, 50 mol or more, preferably 100 mol or more, and is, for example, 500. Below Moher, preferably below 400 Mo.

When the blending ratio of each component is within the above range, various physical properties for the intended use can be improved.

Further, a basic catalyst is added to the reaction.

Examples of the basic catalyst include oxides and/or hydroxides of alkaline earth metals such as magnesium oxide, calcium oxide, magnesium hydroxide, and calcium hydroxide; or, for example, dimethylamine, triethylamine, butylamine, and An aliphatic amine such as butylamine, tributylamine, diethylenetriamine or dicyandiamide; or an aromatic aliphatic amine such as N,N-dimethylbenzylamine; an aromatic such as aniline or 1,5-naphthalenediamine; Amine; ammonia; others may be exemplified by a naphthenic acid of a divalent metal, a hydroxide of a divalent metal, or the like. These alkaline catalysts may be used alone or in combination of two or more.

In addition, the ratio of the basic catalyst to be blended is appropriately set in accordance with the type of the basic catalyst, the type of the phenol, the type of the aldehyde, and the like.

The alkaline catalyst is preferably a hydroxide of an alkaline earth metal or an aliphatic amine. From the viewpoint of improvement in mechanical strength, an alkaline earth metal is more preferable, and from the viewpoint of improvement in heat resistance, it is more preferable. A fatty amine can be mentioned.

The blending ratio of the basic catalyst varies depending on the reaction conditions of the lignin, the phenols, and the aldehyde, the type of the catalyst, the desired physical properties, and the like, and is, for example, 1 part by mass or more based on 100 parts by mass of the phenol. It is preferably 1.5 parts by mass or more, and is, for example, 50 parts by mass or less, preferably 40 parts by mass or less.

If the blending ratio of the alkaline catalyst is within the above range, various physical properties of the impregnated sheet can be improved.

For example, when the heat resistance, the mechanical strength, the water resistance (moisture resistance), and the like are improved, the proportion of the basic catalyst is, for example, 7 parts by mass or more, preferably 10 parts by mass, per 100 parts by mass of the phenol. The above is, for example, 50 parts by mass or less, preferably 40 parts by mass or less.

When the blending ratio of the basic catalyst is within the above range, when the lignin is modified by using acetic acid or the like to cause the alkaline catalyst to be consumed, sufficient alkaline catalyst can be secured, and thus lignin, Phenols and aldehydes are excellent in reactivity. As a result, by using the obtained resin composition, an impregnated sheet excellent in heat resistance, mechanical strength, and water resistance (water resistance) can be obtained. In addition, when the blending ratio of the basic catalyst is within the above range, the obtained resin composition is well dissolved in an organic solvent such as methanol, and thus the workability in varnish preparation and the like described later can be improved.

In addition, when the electrical insulating property and the workability are improved, for example, the blending ratio of the basic catalyst is, for example, 1 part by mass or more, preferably 1.5 parts by mass or more, based on 100 parts by mass of the phenol, and for example, It is 7 parts by mass or more, preferably 5 parts by mass or less.

When the blending ratio of the basic catalyst is within the above range, the reaction rates of lignin, phenols, and aldehydes are controlled, and as a result, electrical insulation (low dielectric constant) can be obtained by using the obtained resin composition. ) and impregnated sheets excellent in processability.

Further, the addition timing of the basic catalyst is not particularly limited, and may be added to at least one of lignin, phenols, and aldehydes, or may be added simultaneously with lignin, phenols, and aldehydes. In addition, it can also be added after lignin, phenols and aldehydes are formulated.

The reaction conditions in the reaction of the lignin, the phenol, and the aldehyde are appropriately set in accordance with the type and amount of the basic catalyst, and the reaction temperature is, for example, 50 ° C or higher, preferably 60 ° C or higher, and is, for example, 140 ° C or less, preferably 120 ° C or less. Further, the reaction time is, for example, 0.5 hours or longer, preferably 1 hour or longer, and is, for example, 10 hours or shorter, preferably 8 hours or shorter.

Thereby, a reaction product of lignin, a phenol, and an aldehyde can be obtained. More specifically, a resol type phenol resin can be obtained by a reaction of a phenol with an aldehyde under an alkaline catalyst, and the novolak type phenol resin is modified with lignin. Hereinafter, the obtained product may be referred to as a lignin-containing resol type phenol resin.

Further, as described above, the reaction of the lignin, the phenol, and the aldehyde can be carried out by uniformly arranging the above components, and the above components can be sequentially reacted from the viewpoint of improving the heat resistance. Further, when the above components are reacted in order to carry out the reaction, the mixing ratio of the lignin, the phenol, and the aldehyde is the same as the case where the respective components are uniformly reacted.

More specifically, when the above components are sequentially mixed and reacted, first, lignin and a phenol are reacted under an acid catalyst.

Examples of the acid catalyst include organic acids, inorganic acids, and the like.

Examples of the organic acid system include sulfonic acid compounds such as methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, cumenesulfonic acid, dinonylnaphthalenesulfonic acid, and dinonylnaphthalene disulfonic acid; For example: trimethyl phosphate, triethyl phosphate, monobutyl phosphate, dibutyl phosphate, tributyl phosphate, trioctyl phosphate, etc., having a carbon number of 1 to 18 alkyl groups; for example: formic acid, Acetic acid, oxalic acid, etc.

Examples of the inorganic acid system include phosphoric acid, hydrochloric acid, sulfuric acid, and nitric acid.

These acid catalysts may be used alone or in combination of two or more.

The acid catalyst is preferably an organic acid, and more preferably an oxalic acid.

The acid catalyst is, for example, 0.1 parts by mass or more, preferably 0.3 parts by mass or more, and is, for example, 20 parts by mass or less, preferably 15 parts by mass or less, based on 100 parts by mass of the phenol.

Further, the reaction conditions in the reaction are, for example, 50 ° C or higher, preferably 80 ° C or higher, and preferably 200 ° C or lower, preferably 180 ° C or lower, under an inert atmosphere and atmospheric pressure. Further, the reaction time is, for example, 1 hour or longer, preferably 2 hours or longer, and is, for example, 20 hours or shorter, preferably 15 hours or shorter.

Next, in this method, the reaction product (and unreacted lignin and/or phenol) obtained in accordance with the above, and an aldehyde are reacted under the above basic catalyst.

The reaction conditions in the reaction are, for example, 50 ° C or higher, preferably 60 ° C or higher, and for example, 140 ° C or lower, preferably 120 ° C or lower. Further, the reaction time is, for example, 0.5 hours or longer, preferably 1 hour or longer, and is, for example, 10 hours or shorter, preferably 8 hours or shorter.

Even in this method, a lignin-containing resol type phenol resin can be obtained in the form of a reaction product of lignin, a phenol, and an aldehyde.

From the viewpoint of various physical properties, particularly the improvement of water resistance, it is preferred to carry out the reaction by blending the above components.

In the above reaction, when the alkaline catalyst is a hydroxide of an alkaline earth metal or the like, it is neutralized by an acid as needed.

The acid is not particularly limited, and is appropriately selected in accordance with the type of the alkaline catalyst. Specific examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid. Further, the amount of the acid to be added is not particularly limited, and is appropriately set in accordance with the amount of addition of the alkaline catalyst.

Further, in this method, the obtained lignin-containing novolac type phenol resin is dried by a known method as needed.

Further, the resin composition may contain a phenol resin curing agent as needed.

The phenol resin hardener is not particularly limited, and a known hardener can be used. Specific examples thereof include hexamethylenetetramine, methylol melamine, methylol urea, and phenolic phenol.

These phenol resin hardeners can be used individually or in combination of 2 or more types.

The blending ratio of the phenol resin hardener is appropriately set in accordance with the purpose and use.

Further, the resin composition may further contain an additive.

The additive may be a known additive added to the resin composition, for example, a flame retardant (phosphorus compound, halogen compound, amine resin, etc.), a hardening accelerator, a filler, a colorant, a plasticizer, a stabilizer, and a mold release. A reagent (such as a metal soap such as zinc stearate).

These additives may be used alone or in combination of two or more. The content of the additive is within a range that does not inhibit the excellent effects of the present invention, and is appropriately set in accordance with the purpose and use.

Further, the additive may be added to at least one of lignin, phenols, and aldehydes in advance, or may be added simultaneously in the preparation of lignin, phenols, and aldehydes, or in lignin, The phenols and the aldehydes are added after being blended, and may be directly added to the reaction products.

Since the resin composition obtained in this manner contains a reaction product of lignin, phenols, and aldehydes, an impregnation plate and a laminate having various physical properties for the intended use can be obtained. Further, when lignin is used as a lignin modified with a carboxylic acid, the resin composition is excellent in handleability, and thus the resin composition can be easily obtained with ease of handling.

Further, such a resin composition is also encompassed within the scope of the invention.

Further, when the impregnation plate is obtained using the resin composition, for example, first, a varnish of the resin composition is prepared, the obtained varnish is impregnated into the substrate, and dried.

The varnish of the resin composition can be obtained by dissolving and/or diluting the above resin composition in an organic solvent.

Examples of the organic solvent include acetone, methyl ethyl ketone, methanol, phenol, tetrahydrofuran, acetonitrile, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and the like. A polar organic solvent such as sulfonium or hexamethylphosphoniumamine. These organic solvents may be used alone or in combination of two or more.

Further, when the reaction product of lignin, phenol, and aldehyde is obtained as a solution and/or a dispersion medium of an organic solvent, the organic solvent may be used as an organic solvent as a varnish.

The solid content concentration in the resin composition varnish is, for example, 10% by mass. The above is preferably 20% by mass or more, and is, for example, 80% by mass or less, preferably 70% by mass or less.

The method of impregnating the obtained varnish into the substrate is not particularly limited, and examples thereof include a method of applying a varnish to a substrate by using a known coating device such as various coaters and sprayers; for example, impregnating the substrate The method in varnish, etc. Preferably, the substrate is immersed in a varnish.

The impregnation ratio (resin impregnation rate) of the varnish to the substrate is, for example, 10% or more based on the total mass of the substrate and the resin composition (solid content) after drying, and the resin composition (solid content) in the varnish is, for example, 10% or more. It is preferably 20% or more, and is, for example, 90% or less, preferably 80% or less.

The drying conditions are not particularly limited, and the drying temperature is, for example, 30 ° C or higher, preferably 40 ° C or higher, and is, for example, 80 ° C or lower, preferably 60 ° C or lower. Further, the drying time is, for example, 1 hour or longer, preferably 2 hours or longer, and is, for example, 100 hours or shorter, preferably 80 hours or shorter.

Thereby, an impregnation plate can be obtained.

Further, the thickness of the impregnation plate is not particularly limited, and the purpose and use are appropriately set.

According to the impregnated sheet obtained as described above, since the above resin composition is used, excellent physical properties can be obtained. Therefore, the above impregnated sheet is suitable for the manufacture of laminated sheets.

The laminated board of the present invention is formed by laminating a plurality of (two or more) plate-like members, and at least one of the plate-shaped members uses the above-mentioned impregnated sheet.

More specifically, as shown in FIG. 1, the laminated board 1 is provided with a singular (1 piece) impregnated sheet 2 as a plate-like member, and a laminate on at least one surface thereof. It is a reinforcing plate 3 (described later) of a plate-shaped member. Moreover, in this case, the reinforcing plate 3 (described later) (refer to the two-dot chain line) may be provided on the other side surface of the impregnation plate 2.

Further, for example, as shown in FIG. 2, the laminated board 1 may be provided with the impregnation board 2 which has a plurality of layers (for example, four sheets) laminated as a plate-shaped member. Further, in this case, the outermost side surface and/or the other side surface of the laminated impregnation plate 2 (that is, the surface on the uppermost side of the paper surface of FIG. 2 and/or the surface on the lowermost side of the paper surface) may be provided as a plate. Reinforcing plate 3 (described later) of the member (see two-point chain line).

Further, although not shown, when the plurality of impregnated sheets 2 are laminated, the reinforcing sheets 3 may be interposed between the impregnated sheets 2.

Examples of the reinforcing plate 3 include a metal foil such as copper and/or an alloy thereof, aluminum, and/or an alloy thereof. These reinforcing plates may be used alone or in combination of two or more.

Further, the thickness of the reinforcing plate 3 is not particularly limited, and is appropriately set in accordance with the purpose and use.

Such a laminated board 1 is obtained by laminating a singular or plural impregnation plate 2 and, if necessary, a reinforcing plate 3, which is provided by a known method, by heating and pressurization.

The heating condition is, for example, 100 ° C or higher, preferably 120 ° C or higher, and is, for example, 250 ° C or lower, preferably 220 ° C or lower. Further, the pressure is, for example, 1 MPa or more, preferably 2 MPa or more, and is, for example, 50 MPa or less, preferably 40 MPa or less.

Thereby, the laminated board 1 can be obtained.

Further, the obtained laminated board 1 can be hardened by heat treatment as needed.

In this case, the heat treatment conditions are, for example, a heating temperature of 100 ° C or higher. It is preferably 120 ° C or higher, and is, for example, 250 ° C or lower, preferably 220 ° C or lower. Further, the heating time is, for example, 0.5 hours or longer, preferably 1 hour or longer, and is, for example, 10 hours or shorter, preferably 8 hours or shorter.

Further, the heat treatment may be a one-stage treatment or a multi-stage (two or more stages) treatment.

Further, since the laminated board 1 obtained as described above is provided with the impregnated sheet 2 using the above resin composition, various physical properties can be obtained.

Therefore, the laminated board 1 and the impregnated sheet 2 can be widely used in various industrial fields, and more specifically, they are applied as a supporting substrate of a wired circuit board such as a switchboard, a transformer, or an electric machine component such as a vehicle. Further, the laminated plate 1 and the impregnated plate 2 are also used as a jig material for bearings and gears, and other insulating plates, insulating supports, insulating spacers, switchboards, circuit breakers, transformers, vehicles, etc., as needed. Electrical, mechanical parts, etc.

[Examples]

Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited by the following examples. In addition, in the following description, "parts" and "%" are quality standards unless otherwise stated. In addition, the specific numerical values, such as a ratio (content ratio), a physical property value, and a parameter used by the following description are replaced with the compounding ratio (content ratio), physical property value, and The parameters include the upper limit (the value defined by "below" or "not full") or the lower limit (the value defined by "above" and "exceed").

<Manufacture of acetic acid modified lignin> [Manufacturing Example 1]

100 parts by mass of corn stover was mixed with 1000 parts by mass of 95% by mass of acetic acid and 3 parts by mass of sulfuric acid, and the reaction was carried out under reflux for 4 hours. After the reaction, filtration was carried out to remove the pulp, and the pulp waste liquid was recovered. Next, the acetic acid in the pulp waste liquid was removed by a rotary evaporator, and the mixture was concentrated until the volume became 1/10. Then, 10 times (mass-based) water of the concentrate was added, and filtration was carried out to obtain a solid portion. Acetic acid modified lignin.

The phenolic hydroxyl equivalent of the obtained acetic acid modified lignin was 435.9 g/eq.

Further, the phenolic hydroxyl equivalent is determined by the following method.

Specifically, first, 10 mg of the acetic acid-modified lignin sample was dissolved in 10 mL of 2-methoxyethanol/water (1/1, w/w) to prepare a seed sample.

Next, 1 mL of the seed sample was diluted to 10 mL with 2-methoxyethanol/water (1/1, w/w) to prepare Sample 1.

Further, 1 mL of the seed sample was diluted to 10 mL with a 2-methoxyethanol/2N aqueous sodium hydroxide solution (1/1, w/w) to prepare a sample 2.

Then, the obtained two kinds of samples (sample 1 and sample 2) were supplied for the measurement of the absorbance shown below.

More specifically, first, 2-methoxyethanol/water (1/1, w/w) was placed in the front and rear tanks, and the baseline was taken, and then the sample 1 was attached to the reference side, and the sample 2 was installed. On the sample side, the absorption (absorbance) at 296 nm and 366 nm was measured.

Further, the absorption (absorbance) at 296 nm was caused by the structure of the following formula (1), and the molar absorption coefficient of the relevant phenolic hydroxyl group concentration was 4,100 L/(mol ‧ cm).

Further, the absorption (absorbance) at 366 nm was caused by the structure of the following formula (2), and the molar absorption coefficient of the relevant phenolic hydroxyl group concentration was 37,250 L/(mol ‧ cm).

Then, the phenolic hydroxyl group concentration in the sample was determined from the absorption (absorbance) at the above two wavelengths and the molar absorptivity, and converted into a phenolic hydroxyl equivalent.

<<Electrical insulation and processing improvement>> <Modulation of Resin Composition> [Example 1]

141 g (1.5 mol) of phenol (manufactured by Nacalai Tesque Co., Ltd.) was charged at a temperature of 40 ° C in a four-necked 1-liter separable flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel.

Next, 42.3 g of acetic acid-modified lignin obtained in Production Example 1 (corresponding to 30 g of phenol 100 g) was added and stirred at 40 °C.

Next, 186 g (2.3 mol) of 37% formalin (formaldehyde aqueous solution (manufactured by Nacalai Tesque)) was added.

Further, the amount of formaldehyde was 144 mols based on the total amount of the phenolic hydroxyl group of the acetic acid-modified lignin and the phenolic hydroxyl group of the phenol of 100 mol.

In addition, 2% by mass (141 × 0.02 = 2.8 g) of phenol was added to triethylamine (manufactured by Nacalai Tesque Co., Ltd.) as an alkaline catalyst, and the mixture was stirred to obtain a homogeneous product.

Next, the temperature was slowly raised to (about 1 hour) at 80 ° C, and the reaction was carried out at 80 ° C for 3 hours. Then, water or the like is removed by an evaporator, and by drying under reduced pressure, a lignin-containing resol type phenol resin is obtained as a reaction product. will It serves as a resin composition.

[Embodiment 2]

The ratio of the blending ratio of acetic acid-modified lignin was changed to 70.5 g (corresponding to 50 g of phenol 100 g), and the blending ratio of 37% of fumarin (formaldehyde aqueous solution) was changed to 189.2 g (2.33 mol). A lignin-containing resol type phenol resin was obtained in the same manner as in Example 1. This was used as a resin composition.

Further, the amount of formaldehyde blended was 140 mols based on the total amount of the phenolic hydroxyl group of the acetic acid-modified lignin and the phenolic hydroxyl group of the phenol of 100 mol.

[Example 3]

In addition to changing the blending ratio of acetic acid-modified lignin to 141 g (100 g equivalent to 100 g of phenol), and changing the blending ratio of 37% formalin (formaldehyde aqueous solution) to 195 g (2.41 mol), the rest are In Example 1, a lignin-containing resol type phenol resin was obtained in the same manner. This was used as a resin composition.

Further, the amount of formaldehyde added was 132 mols based on the total amount of the phenolic hydroxyl group of the acetic acid-modified lignin and the phenolic hydroxyl group of the phenol of 100 mol.

[Example 4]

A lignin-containing novolak-type phenol resin was obtained in the same manner as in Example 3 except that the blending ratio of 37% of the formalin (formaldehyde aqueous solution) was changed to 390.8 g (4.82 mol). This was used as a resin composition.

Further, the amount of formaldehyde was 364 mols based on the total amount of the phenolic hydroxyl group of the acetic acid-modified lignin and the phenolic hydroxyl group of the phenol of 100 mol.

[Example 5]

A lignin-containing novolak-type phenol resin was obtained in the same manner as in Example 2 except that the blending ratio of 37% of the formalin (formaldehyde aqueous solution) was changed to 377.8 g (4.66 mol). This was used as a resin composition.

Further, the amount of formaldehyde was 331 mols based on the total amount of the phenolic hydroxyl group of the acetic acid-modified lignin and the phenolic hydroxyl group of the phenol of 100 mol.

[Comparative Example 1]

141 g (1.5 mol) of phenol (manufactured by Nacalai Tesque Co., Ltd.) was charged at a temperature of 40 ° C in a four-necked 1-liter separable flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel.

Then, 186 g (2.3 mol (about 1.5 times of phenol)) of 37% of the sulphate (formaldehyde aqueous solution (manufactured by Nacalai Tesque Co., Ltd.)) was added, and phenol was added to triethylamine (manufactured by Nacalai Tesque Co., Ltd.) as a basic catalyst. 2% by mass (141 × 0.02 = 2.8 g), and stirred to make a uniform.

Next, the temperature was slowly raised to (about 1 hour) at 80 ° C, and the reaction was carried out at 80 ° C for 3 hours. Then, water or the like is removed by an evaporator, and by drying under reduced pressure, a resol type phenol resin is obtained as a reaction product. This was used as a resin composition.

<Evaluation of Resin Composition and Setting of Hardening Temperature>

The resin compositions obtained in the respective examples and comparative examples were analyzed by differential scanning calorimetry (DSC). The result is that any resin composition is observed due to hardening A fever spike that should be caused.

More specifically, the heat-generating peak of the resin composition of each of the examples was about 200 to 220 ° C, and the heat-generating peak of the resin composition of the comparative example was about 160 to 170 ° C.

From the results of the above, the curing temperature of the resin composition of each example was set to 200 ° C, and the curing temperature of the resin composition of the comparative example was set to 160 ° C.

<Manufacture of laminates> [Embodiment 6]

The resin composition obtained in Example 1 was dissolved in tetrahydrofuran to prepare a varnish (solid content: 50% by mass).

Next, the obtained varnish is impregnated into the paper base in such a manner that the resin impregnation rate (the mass of the resin composition (solid content) is 50% with respect to the total mass of the dried substrate and the resin composition (solid content)) In the material (made by Oji Paper Co., Ltd.). Then, drying was carried out at 40 ° C for 48 hours to obtain an impregnation plate.

Then, the obtained impregnated sheet was superposed on four sheets, and subjected to heating and press molding at 200 ° C and 10 MPa for 30 minutes to obtain a laminated sheet having a thickness of about 1 mm.

Further, the obtained laminated plate was heated at 160 ° C for 1 hour, then heated at 180 ° C for 1 hour, and further heated at 200 ° C for 2 hours, thereby performing a hardening treatment.

[Embodiment 7]

An impregnation plate and a laminate were produced in the same manner as in Example 6 except that the resin composition obtained in Example 2 was used, and the obtained laminate was subjected to a hardening treatment.

[Embodiment 8]

An impregnation plate and a laminate were produced in the same manner as in Example 6 except that the resin composition obtained in Example 3 was used, and the obtained laminate was subjected to a hardening treatment.

[Embodiment 9]

An impregnation plate and a laminate were produced in the same manner as in Example 6 except that the resin composition obtained in Example 4 was used, and the obtained laminate was subjected to a hardening treatment.

[Embodiment 10]

An impregnation plate and a laminate were produced in the same manner as in Example 6 except that the resin composition obtained in Example 5 was used, and the obtained laminate was subjected to a hardening treatment.

[Comparative Example 2]

An impregnated sheet and a laminated sheet were produced in the same manner as in Example 6 except that the resin composition obtained in Comparative Example 1 was used, and the heating temperature at the time of forming the laminated sheet was changed from 200 ° C to 160 ° C, and the obtained laminated sheet was obtained. Hardening treatment is applied.

<Evaluation of laminates>

The physical properties of the laminated sheets obtained in the respective examples and comparative examples were evaluated. The evaluation method is as follows.

(1) Dielectric rate

For the dielectric constant of the laminate obtained in each of the examples and the comparative examples, the impedance was used. The analyzer E4991A (manufactured by Agilent Technologies, Inc.) was measured at a frequency of 1 GHz. The results are shown in Table 1.

Further, the dielectric constant was measured before and after the laminate was subjected to the hardening treatment.

(2) Punching processability

In the laminated sheets obtained in each of the examples and the comparative examples, punching was performed by using a punching hole diameter of 6 mm, and the peripheral state of the formed holes was visually observed to evaluate the presence or absence of interlayer peeling. The results are shown in Table 2.

In addition, the criteria for determining the punching workability are as follows: ASTM D617 "Punching Quality of Phenolic Laminate Sheets" (the method for testing the punching performance of a phenolic laminate).

◎: Thoroughly punching and obtaining a beautiful cut surface.

X: Punching was not performed thoroughly, and a large defect or crack of 2 mm or more was present around the hole.

△: Punching was not performed thoroughly, and a small defect or crack of less than 2 mm was present around the hole.

<<Improvement of heat resistance, mechanical properties and water resistance (moisture resistance)>> [Example 11]

In a four-port, 1 L separation flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel, 169.2 g (1.8 mol) of phenol (manufactured by Nacalai Tesque Co., Ltd.) was charged at a temperature of 40 °C.

Next, 84.6 g of acetic acid-modified lignin obtained in Production Example 1 (corresponding to 50 g of phenol 100 g) was added and stirred at 40 °C.

Next, 466 g (5.7 mol) of 37% formalin (formaldehyde aqueous solution (manufactured by Nacalai Tesque)) was added.

Further, the amount of formaldehyde was 286 mols based on the total amount of the phenolic hydroxyl group of the acetic acid-modified lignin and the phenolic hydroxyl group of the phenol of 100 mol.

In addition, 2% by mass (169.2 × 0.02 = 3.38 g) of phenol and 16% by mass (84.6 × 0.16 = 13.54 g) of lignin were added to triethylamine (manufactured by Nacalai Tesque Co., Ltd.) as a basic catalyst. 16.9 g and stir to make a homogeneous mass.

Next, the temperature was gradually raised to (over 1 hour) at 95 ° C, and the reaction was carried out at 95 ° C for 2 hours. Then, water or the like is removed by an evaporator, and by drying under reduced pressure, a lignin-containing resol type phenol resin is obtained as a reaction product. This was used as a resin composition.

[Embodiment 12]

In a four-port, 1 L separation flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel, 169.2 g (1.8 mol) of phenol (manufactured by Nacalai Tesque Co., Ltd.) was charged at a temperature of 40 °C.

Next, 84.6 g of acetic acid-modified lignin obtained in Production Example 1 (corresponding to 50 g of phenol 100 g) was added and stirred at 40 °C.

Then, 370.7 g (3.8 mol) of 37% formalin (formaldehyde aqueous solution (manufactured by Nacalai Tesque Co., Ltd.)) was added.

Further, the amount of formaldehyde was 191 mols based on the total amount of the phenolic hydroxyl group of the acetic acid-modified lignin and the phenolic hydroxyl group of the phenol of 100 mol.

In addition, 2% by mass (169.2 × 0.02 = 3.38 g) of phenol and 16% by mass (84.6 × 0.16 = 13.54 g) of lignin were added to triethylamine (manufactured by Nacalai Tesque Co., Ltd.) as a basic catalyst. 16.9 g and stir to make a homogeneous mass.

Next, the temperature was gradually raised to (over 1 hour) at 95 ° C, and the reaction was carried out at 95 ° C for 2 hours. Then, water or the like is removed by an evaporator, and by drying under reduced pressure, a lignin-containing resol type phenol resin is obtained as a reaction product. This was used as a resin composition.

[Example 13]

A phenol (Nacalai Tesque) 100 g (1.1 mol) was charged at a temperature of 40 ° C in a four-port, 1-liter separable flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel.

Next, 100 g of acetic acid-modified lignin obtained in Production Example 1 (corresponding to 100 g of phenol 100 g) was added and stirred at 40 °C.

Next, 376.5 g (3.4 mol) of 37% formalin (formaldehyde aqueous solution (manufactured by Nacalai Tesque Co., Ltd.)) was added.

Further, the amount of formaldehyde was 263 mols based on the total amount of the phenolic hydroxyl group of the acetic acid-modified lignin and the phenolic hydroxyl group of the phenol of 100 mol.

Further, 18% by mass (100×0.02=2 g) of phenol and 16% by mass (100×0.16=16 g) of lignin were added to triethylamine (manufactured by Nacalai Tesque Co., Ltd.) as a basic catalyst, and the total amount was 18 g. And stir to make a uniform.

Next, the temperature was slowly raised to (about 1 hour) at 95 ° C, and the reaction was carried out at 95 ° C for 3 hours. Then, water or the like is removed by an evaporator, and by drying under reduced pressure, a lignin-containing resol type phenol resin is obtained as a reaction product. This was used as a resin composition.

[Embodiment 14]

In a four-port, 1 L separation flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel, 75 g (0.8 mol) of phenol (manufactured by Nacalai Tesque Co., Ltd.) was charged at a temperature of 40 °C.

Next, 150 g of acetic acid-modified lignin obtained in Production Example 1 (corresponding to 200 g of phenol 100 g) was added and stirred at 40 °C.

Next, 220 g (2.7 mol) of 37% formalin (formaldehyde aqueous solution (manufactured by Nacalai Tesque)) was added.

Further, the amount of formaldehyde was 236 mols based on the total amount of the phenolic hydroxyl group of the acetic acid-modified lignin and the phenolic hydroxyl group of the phenol of 100 mol.

Further, 2% by mass (75 × 0.02 = 1.5 g) of phenol and 16 mass of lignin were added to triethylamine (manufactured by Nacalai Tesque Co., Ltd.) as an alkaline catalyst. A total of 26 g of % (150 × 0.16 = 24 g) was stirred and made into a homogeneous mass.

Next, the temperature was gradually raised to (over 1 hour) at 95 ° C, and the reaction was carried out at 95 ° C for 2 hours. Then, water or the like is removed by an evaporator, and by drying under reduced pressure, a lignin-containing resol type phenol resin is obtained as a reaction product. This was used as a resin composition.

[Example 15]

A phenol (Nacalai Tesque) 100 g (1.1 mol) was charged at a temperature of 40 ° C in a four-port, 1-liter separable flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel.

Next, 100 g of acetic acid-modified lignin obtained in Production Example 1 (corresponding to 100 g of phenol 100 g) was added and stirred at 40 °C.

Next, 376.5 g (3.4 mol) of 37% formalin (formaldehyde aqueous solution (manufactured by Nacalai Tesque Co., Ltd.)) was added.

Further, the amount of formaldehyde was 263 mols based on the total amount of the phenolic hydroxyl group of the acetic acid-modified lignin and the phenolic hydroxyl group of the phenol of 100 mol.

Further, to the 95% magnesium hydroxide (manufactured by Nacalai Tesque Co., Ltd.) as an alkaline catalyst, 2.5% by mass (100 × 0.025 = 2.5 g) of phenol and 4.6% by mass of lignin (100 × 0.046 = 4.6 g) were added. The total amount of 7.1 g was divided by 7.5 g after 0.95, and stirred to make a homogeneous product.

Next, the temperature was slowly raised to (about 1 hour) at 80 ° C, and the reaction was carried out at 80 ° C for 3 hours. Then, after neutralizing treatment with phosphoric acid, water or the like is removed by an evaporator, and by drying under reduced pressure, a lignin-containing resol type phenol resin is obtained as a reaction product. This was used as a resin composition.

[Example 16]

A phenol (Nacalai Tesque) 100 g (1.1 mol) was charged at a temperature of 40 ° C in a four-port, 1-liter separable flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel.

Next, 100 g of acetic acid-modified lignin obtained in Production Example 1 (corresponding to 100 g of phenol 100 g) was added and stirred at 40 °C.

Next, 376.5 g (3.4 mol) of 37% formalin (formaldehyde aqueous solution (manufactured by Nacalai Tesque Co., Ltd.)) was added.

Further, the amount of formaldehyde was 263 mols based on the total amount of the phenolic hydroxyl group of the acetic acid-modified lignin and the phenolic hydroxyl group of the phenol of 100 mol.

Further, to the 95% magnesium hydroxide (manufactured by Nacalai Tesque Co., Ltd.) as an alkaline catalyst, 2.5% by mass (100 × 0.025 = 2.5 g) of phenol and 4.6% by mass of lignin (100 × 0.046 = 4.6 g) were added. The total amount of 7.1 g was divided by 7.5 g after 0.95, and stirred to make a homogeneous product.

Next, the temperature was slowly raised to (about 1 hour) at 80 ° C, and the reaction was carried out at 80 ° C for 3 hours. Then, water or the like is removed by an evaporator, and by drying under reduced pressure, a lignin-containing resol type phenol resin is obtained as a reaction product. This was used as a resin composition.

[Example 17]

A phenol (Nacalai Tesque) 100 g (1.1 mol) was charged at a temperature of 40 ° C in a four-port, 1-liter separable flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel.

Next, 100 g of acetic acid-modified lignin obtained in Production Example 1 (corresponding to 100 g of phenol 100 g) was added and stirred at 40 °C.

Next, 376.5 g (3.4 mol) of 37% formalin (formaldehyde aqueous solution (manufactured by Nacalai Tesque Co., Ltd.)) was added.

Further, the amount of formaldehyde was 263 mols based on the total amount of the phenolic hydroxyl group of the acetic acid-modified lignin and the phenolic hydroxyl group of the phenol of 100 mol.

Further, 3.3% by mass of phenol (100×0.033=3.3 g) and 5.9 mass% of lignin (100×0.059=5.9 g) were added to 95% calcium hydroxide (manufactured by Nacalai Tesque Co., Ltd.) as an alkaline catalyst. The total amount of 9.2 g was divided by 9.7 g after 0.95, and stirred to prepare a homogeneous product.

Next, the temperature was slowly raised to (about 1 hour) at 80 ° C, and the reaction was carried out at 80 ° C for 3 hours. Then, water or the like is removed by an evaporator, and by drying under reduced pressure, a lignin-containing resol type phenol resin is obtained as a reaction product. This was used as a resin composition.

[Embodiment 18]

A phenol (manufactured by Nacalai Tesque Co., Ltd.) (100 g (1.1 mol)) was charged at a temperature of 40 ° C in a four-port, 1-liter, separable flask equipped with a water suction tube, a thermometer, and a stirrer.

Next, 200 g of acetic acid-modified lignin obtained in Production Example 1 (corresponding to 200 g of phenol 100 g) and 10.15 g (0.11 mol) of oxalic acid as an acid catalyst were added. Then, the temperature was raised to 130 ° C, and the reaction was carried out for 2.5 hours under a nitrogen atmosphere. Thereby, phenol-modified lignin is obtained.

Then, the phenol-modified lignin was cooled to 80 ° C, and 37% of formalin (formaldehyde aqueous solution (Nacalai Tesque) 293.3 g (3.6 mol) was added.

Further, the amount of formaldehyde was 236 mols based on the total amount of the phenolic hydroxyl group of the acetic acid-modified lignin and the phenolic hydroxyl group of the phenol of 100 mol.

In addition, 2% by mass (100 × 0.02 = 2.0 g) of phenol and 16% by mass (200 × 0.16 = 32 g) of lignin were added to triethylamine (manufactured by Nacalai Tesque Co., Ltd.) as a basic catalyst, and the total amount was 34 g. And stir to make a uniform.

Next, a reflux condenser was attached to the flask, and the temperature was slowly raised to (about 1 hour) at 80 ° C, and the reaction was carried out at 80 ° C for 4 hours. Then, water or the like is removed by an evaporator, and by drying under reduced pressure, a lignin-containing resol type phenol resin is obtained as a reaction product. This was used as a resin composition.

<Evaluation of Resin Composition and Setting of Hardening Temperature>

The resin compositions obtained in the respective examples and comparative examples were analyzed by differential scanning calorimetry (DSC). As a result, a heat generation peak due to the hardening reaction was observed in any of the resin compositions.

More specifically, the heat-generating peak of the resin composition of each of the examples was about 150 to 190 ° C, and the heat-generating peak of the resin composition of the comparative example was about 160 to 170 ° C.

As a result of the above, the curing temperature of the resin composition of each Example was set to 160 ° C, and the curing temperature of the resin composition of the comparative example was also set to 160 ° C.

<Manufacture of laminates> (not subjected to heat hardening treatment) [Embodiment 19]

The resin composition obtained in Example 1 was dissolved in methanol to prepare a varnish (solid The form is 50% by mass).

Next, the obtained varnish is impregnated into the paper base in such a manner that the resin impregnation rate (the mass of the resin composition (solid content) is 50% with respect to the total mass of the dried substrate and the resin composition (solid content)) In the material (made by Oji Paper Co., Ltd.). Then, drying was carried out at 40 ° C for 48 hours to obtain an impregnation plate.

Next, the obtained impregnated sheets were superposed on four sheets, and subjected to heating and press molding at 160 ° C and 10 MPa for 30 minutes to obtain a laminate having a thickness of about 1 mm.

[Example 20]

An impregnation plate and a laminate were produced in the same manner as in Example 19 except that the resin composition obtained in Example 12 was used.

[Example 21]

An impregnation plate and a laminate were produced in the same manner as in Example 19 except that the resin composition obtained in Example 13 was used.

[Example 22]

An impregnation plate and a laminate were produced in the same manner as in Example 19 except that the resin composition obtained in Example 14 was used.

[Example 23]

An impregnation plate and a laminate were produced in the same manner as in Example 19 except that the resin composition obtained in Example 15 was used.

[Example 24]

An impregnation plate and a laminate were produced in the same manner as in Example 19 except that the resin composition obtained in Example 16 was used.

[Example 25]

An impregnation plate and a laminate were produced in the same manner as in Example 19 except that the resin composition obtained in Example 17 was used.

[Example 26]

An impregnation plate and a laminate were produced in the same manner as in Example 19 except that the resin composition obtained in Example 18 was used.

[Comparative Example 3]

Using the resin composition obtained in Comparative Example 1, an impregnation plate and a laminate were produced in the same manner as in Example 19.

(There is a heat hardening treatment) [Example 27]

The laminated sheet obtained in Example 19 was heated at 160 ° C for 1 hour, then heated at 180 ° C for 1 hour, and further heated at 200 ° C for 2 hours to carry out a hardening treatment.

[Example 28]

The laminate obtained in Example 20 was heated at 160 ° C for 1 hour, followed by 180 The mixture was heated at ° C for 1 hour and further heated at 200 ° C for 2 hours to carry out a hardening treatment.

[Example 29]

The laminated sheet obtained in Example 21 was heated at 160 ° C for 1 hour, then heated at 180 ° C for 1 hour, and further heated at 200 ° C for 2 hours to carry out a hardening treatment.

[Example 30]

The laminated plate obtained in Example 22 was heated at 160 ° C for 1 hour, then heated at 180 ° C for 1 hour, and further heated at 200 ° C for 2 hours to carry out a hardening treatment.

[Example 31]

The laminate obtained in Example 23 was heated at 160 ° C for 1 hour, then heated at 180 ° C for 1 hour, and further heated at 200 ° C for 2 hours to carry out a hardening treatment.

[Example 32]

The laminated sheet obtained in Example 24 was heated at 160 ° C for 1 hour, then heated at 180 ° C for 1 hour, and further heated at 200 ° C for 2 hours to carry out a hardening treatment.

[Example 33]

The laminate obtained in Example 25 was heated at 160 ° C for 1 hour, then heated at 180 ° C for 1 hour, and further heated at 200 ° C for 2 hours to carry out a hardening treatment.

[Example 34]

The laminate obtained in Example 26 was heated at 160 ° C for 1 hour, then heated at 180 ° C for 1 hour, and further heated at 200 ° C for 2 hours to carry out a hardening treatment.

[Comparative Example 4]

The laminate obtained in Comparative Example 3 was heated at 160 ° C for 1 hour, then heated at 180 ° C for 1 hour, and further heated at 200 ° C for 2 hours to carry out a hardening treatment.

<Evaluation of laminates>

The physical properties of the laminated sheets obtained in the respective examples and comparative examples were evaluated. The evaluation method is as follows.

(1) Glass transition temperature (Tg)

The solid dynamic viscoelasticity (stretching mode) (frequency 1 Hz, temperature rising rate 2 ° C/min) was measured using a Rheogel-E4000 (manufactured by UBM). Then, the peak temperature of the obtained tan δ curve was taken as the glass transition temperature (Tg). The results are shown in Tables 3 and 4.

(2) bending strength

According to JIS K6911 (1995 edition), the bending strength was measured at a chuck speed of 1 mm/min and a span of 50 mm. The results are shown in Tables 3 and 4.

(3) Water absorption rate

The initial mass (dry mass) of the molded article was measured, and then the molded article was immersed in distilled water of 23 ° C for 24 hours, and then the mass (water absorption mass) and the amount of increase were measured, and the water absorption ratio was determined by the following formula. The results are shown in Tables 3 and 4.

Water absorption (% by mass) = 100 × mass increase after immersion in distilled water / dry quality

(4) Volume resistivity (electrical insulation)

The volume resistivity (Ω‧ cm) was measured using HP4339A (manufactured by Agilent Technologies) in accordance with JIS K6911 (1995 edition).

As a result, each of the examples and the comparative examples exhibited a volume resistivity of 1.0 × 10 ¹³ (Ω·cm), and satisfies the physical properties required for, for example, a support substrate of a wired circuit board.

It is to be understood that the above-described embodiments are merely illustrative of the invention, and are not intended to be limiting. Variations of the invention that are apparent to those skilled in the art are intended to be included within the scope of the appended claims.

(industrial availability)

The impregnated sheet, the laminated board, and the resin composition of the present invention can be widely used in various industrial fields such as a support substrate of a wiring circuit board of electrical machinery parts such as a switchboard, a transformer, and a vehicle.

1‧‧‧ laminate

2‧‧‧impregnated board

3‧‧‧ reinforcing plate

Claims (7)

An impregnated sheet comprising: a substrate and a resin composition impregnated into the substrate; and the resin composition contains a reaction product of lignin, phenol, and aldehyde. The impregnated sheet of claim 1, wherein the lignin is lignin modified with acetic acid. The impregnated sheet according to claim 1, wherein the amount of the lignin to be added is 5 parts by mass or more and 300 parts by mass or less based on 100 parts by mass of the phenol. The impregnated sheet according to claim 1, wherein the amount of the aldehyde is 50 mol or more and 500 mol or less relative to the total amount of the phenolic hydroxyl group of the lignin and the phenolic hydroxyl group of the phenol. . The impregnated sheet according to claim 1, wherein the resin composition contains the lignin, the phenol, and the phenolic compound in an amount of 1 part by mass or more and 50 parts by mass or less based on 100 parts by mass of the phenol. And a reaction product in which the aldehyde is reacted. A laminated board, which is a laminated board laminated with a plurality of plate-like members; characterized in that at least one of the above-mentioned plate-shaped members is the impregnated sheet of claim 1. A resin composition characterized by comprising a reaction product of lignin, a phenol, and an aldehyde.