JP4403295B2 - Resin composition for molding and molding material - Google Patents

Description

  The present invention relates to a molding resin composition having excellent mechanical strength and a molding material containing the molding resin composition.

  Conventionally, as a molding material, for example, a molding composition containing a resin composition such as a phenol resin and a filler and, if necessary, a fibrous material, and the like, specifically, for example, phenol resin and wollastonite, There is a phenol resin molding material containing natural organic fibers, graphite, and powdered silica (for example, see Patent Document 1). However, the phenol resin molding material has a drawback that sufficient mechanical strength cannot be obtained.

Japanese Patent Laid-Open No. 9-194485

  An object of the present invention is to provide a resin composition for molding materials having excellent mechanical strength and a molding material containing the resin composition for molding materials.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a novolac type phenol resin (A) having an ortho / para ratio of less than 2 and a melting point of 80 to 120 ° C. and an ammonia resol type phenol resin. And the phenol core bonding functional group of the ammonia resol type phenol resin has a ratio of methylene bond, methylol bond, nitrogen-containing bond, and dimethylene ether bond, respectively, 10 to 30 mol%, 30 to 50 mol%, It is a molding resin composition containing 20 to 40 mol%, 2 to 10 mol% of a solid resol type phenol resin (B), and is defined in ISO-8619 of the molding resin composition. It has been found that a molding material having excellent mechanical strength can be obtained by using a molding resin composition having a flow distance of 50 to 100 mm. The has been completed.

That is, the present invention relates to a novolak type phenol resin (A) having an ortho / para ratio of less than 2 and a melting point of 80 to 120 ° C. , an ammonia resol type phenol resin, and the ammonia resol type phenol resin. The phenol nucleus-bonding functional group has a methylene bond, a methylol bond, a nitrogen-containing bond, and a dimethylene ether bond in proportions of 10 to 30 mol%, 30 to 50 mol%, 20 to 40 mol%, and 2 to 10 mol%, respectively. A molding resin composition comprising a solid resol type phenolic resin (B), wherein the flow distance specified in ISO-8619 of the molding resin composition is 50 to 100 mm. A resin composition is provided.

  The present invention also provides a molding material comprising the molding resin composition and a filler.

  The molding material containing the molding resin composition according to the present invention is excellent in mechanical strength and suitable for molding material applications.

  The novolac type phenol resin (A) used in the present invention needs to have an ortho / para ratio of less than 2. The ortho / para ratio is a ratio of a novolac type phenol resin in which phenolic compounds are linked at the ortho position or para position to those bonded at the ortho position and those bonded at the para position ([ortho Position bond] / [para position bond]). The ortho / para ratio is preferably 0.5 to 1.9, more preferably 1.0 to 1.5.

  Examples of the novolak type phenol resin (A) used in the present invention include those obtained by reacting phenols and aldehydes as raw materials in the presence of a catalyst. Examples of the phenols include phenols; alkylphenols such as cresol, xylenol, ethylphenol, butylphenol and octylphenol; polyhydric phenols such as resorcin and catechol; halogenated phenols, phenylphenols and aminophenols. These phenols are not limited to one type in use, and two or more types can be used in combination.

  Examples of the aldehydes include formaldehyde such as formaldehyde, paraformaldehyde, and trioxane; acetaldehyde and the like. These aldehydes are not limited to only one type, and two or more types can be used in combination.

  Examples of the catalyst include oxalic acid, sulfuric acid, paratoluenesulfonic acid, and the like. These catalysts are not limited to one type in use, and two or more types can be used in combination. The amount of the catalyst added is not particularly limited, but is preferably 0.05 to 5 parts by weight, and preferably 0.1 to 3.0 parts by weight with respect to 100 parts by weight of phenols. Particularly preferred.

  The melting point (ring and ball method) of the novolak type phenol resin (A) used in the present invention is particularly limited if the flow distance specified in ISO-8619 of the molding resin composition of the present invention is selected to be 50 to 100 mm. Although it is not a thing, 80-120 degreeC is preferable, for example, and 90-110 degreeC is more preferable.

  Examples of the solid resol type phenolic resin (B) used in the present invention include those obtained by reacting phenols and aldehydes as raw materials in the presence of a catalyst. The phenols are not particularly limited. For example, phenols; alkylphenols such as bisphenol A, bisphenol F, cresol, xylenol, ethylphenol, butylphenol, octylphenol; polyhydric phenols such as resorcin, catechol; Phenol, phenylphenol, aminophenol and the like can be mentioned. These phenols are not limited to one type in use, and two or more types can be used in combination.

  Examples of the aldehydes include formaldehyde such as formaldehyde, paraformaldehyde, and trioxane; acetaldehyde and the like. These aldehydes are not limited to only one type, and two or more types can be used in combination.

Examples of the catalyst include ammonia and the like . These catalysts are not limited to one type in use, and two or more types can be used in combination. The amount of the catalyst added is not particularly limited, but is preferably 0.05 to 5 parts by weight, particularly preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the phenols.

  The melting point of the solid resol type phenol resin (B) (ring and ball method) is not particularly limited if the flow distance specified in ISO-8619 of the molding resin composition of the present invention is selected to be 50 to 100 mm. Although it is not, it is preferable that it is 60-85 degreeC. The number average molecular weight of the solid resol type phenol resin (B) is preferably 500 to 1,000. The weight average molecular weight of the solid resol type phenol resin (B) is particularly preferably 1500 to 2500. The number average molecular weight and weight average molecular weight can be determined by gel permeation chromatography (GPC).

  The solid resol type phenol resin (B) is preferably a solid ammonia resol type phenol resin. This solid ammonia resol type phenol resin can be obtained, for example, by using ammonia as a catalyst in the method for producing the resol type phenol resin.

In the solid ammonia resole type phenolic resin, the phenol core bond functional group has a methylene bond, a methylol bond, a nitrogen-containing bond, and a dimethylene ether bond ratio of 10 to 30 mol%, 30 to 50 mol%, and 20 to 40, respectively. It is especially preferable that it is mol% and 2-10 mol%. In addition, the said phenol nucleus coupling | bonding functional group can be calculated | required by < ¹³ > C-NMR.

  The molding resin composition of the present invention contains the novolak type phenol resin (A) and the solid resol type phenol resin (B), and the flow distance specified in ISO-8619 needs to be 50 to 100 mm. It is. When the flow distance (hereinafter referred to as “flow”) defined in ISO-8619 is less than 50 mm, the resin flow is not sufficient and the strength of the molding material is lowered, which is not preferable. On the other hand, if the flow exceeds 100 mm, the resin fluidity is not sufficient when the resin is cured, and the strength of the molding material is lowered, which is not preferable. The molding resin composition preferably has a flow distance specified by ISO-8619 of 55 to 95 mm.

  The flow distance defined in ISO-8619 is measured by the following method. That is, 0.5 g of the powdered resin composition is used as a tablet having a diameter of 12.5 mm and a height of 4.8 mm. The tablet is placed on a glass plate and heated in an oven at 125 ° C. for 3 minutes, and then the temperature is maintained. The glass plate is tilted at 60 degrees, the distance through which the resin flows after 20 minutes is measured, and the distance (unit: mm) is defined as the flow distance.

  The blending ratio of the novolac type phenol resin (A) and the solid resol type phenol resin (B) is not particularly limited as long as the flow is in a range of 50 to 100 mm. The solid content weight ratio of the resin (A) to the solid resol type phenol resin (B) is [novolak type phenol resin (A)] / [resole type phenol resin (B)] = 9/1 to 6/4. However, a sufficient flow during resin curing can be obtained, which is preferable.

  Polyisocyanates represented by MDI (diphenylmethane diisocyanate) and TDI (toluene diisocyanate) can also be added as a crosslinking agent to the molding resin composition of the present invention. In particular, when a polyisocyanate is used in combination with a novolac type phenolic resin and a resol type phenolic resin, the curing proceeds rapidly, so that the flow at the time of curing of the resin is not sufficiently obtained and the strength is not expressed. When the polyisocyanates of the novolak type phenol resin (A) and the resol type phenol resin (B) are used in combination, sufficient resin flow is obtained without rapid progress of curing, and the molding has strength. Since a body is obtained, it is preferable.

  Moreover, you may add additives, such as crosslinking agents, such as an epoxy, or intensity | strength imparting agents, such as a silane coupling agent, polyvinyl alcohol, and surfactant, to this invention.

  The molding material of the present invention can be obtained by adding a filler to the molding resin composition. As the filler, various materials can be used, and examples thereof include magnesium oxide, zinc oxide, silica, calcium carbonate, talc, clay, graphite, shirasu balloon, phenol balloon, etc., which can be used alone or in combination. is there. The amount of the filler added is preferably 3 to 1500 parts by weight with respect to 100 parts by weight of the solid content of the molding resin composition.

  A fibrous substance can be further added to the molding material. As the fibrous material, various materials can be used. For example, inorganic fibers such as glass fiber, carbon fiber, ceramic fiber, and stainless steel fiber; natural fibers such as cotton and hemp; synthetic organic materials such as polyester and polyamide A fiber etc. are mention | raise | lifted and you may use individually and together. The shape of the fiber base material is not limited at all, and it may be a short fiber, a yarn, a mat, or a sheet. The amount of the fibrous substance added is preferably 50 to 1000 parts by weight with respect to 100 parts by weight of the solid content of the molding resin composition.

The molding material of the present invention can be molded by heating, but the mixing method and molding method are not particularly limited. For example, the compound can be put in a mold and molded at 150 to 200 ° C. at a pressure of 5 to 10 kg / cm ² to obtain a molded product.

The present invention will be specifically described below with reference to examples. In the examples, “part” and “%” are based on weight unless otherwise specified.

Example 1
940 g of phenol and 532.5 g of 40% aqueous formaldehyde solution were added to a four-necked 2 liter flask equipped with a stirrer, condenser, thermometer and dropping funnel, and stirring was started. As a catalyst, 4.7 g of oxalic acid dihydrate was added, and the temperature was raised to the reflux temperature. After reacting by refluxing for 6 hours, the temperature was raised to 170 ° C. while distillation was started to remove water. After partially removing free phenol by reducing the pressure at 170 ° C., it was taken out from the reaction vessel to obtain a solid novolac type phenol resin (A1) having a softening point (ring ball method) of 93 ° C. ^The ortho / para ratio was 1.2 from ¹³ C-NMR. Next, 18 parts of the solid novolac type phenol resin (A1), solid ammonia resole type phenol resin (B1) (melting point 70 ° C., number average molecular weight 787, weight average molecular weight 2182, phenol nucleus-binding functional group methylene bond 21%, methylol Bonding 43%, nitrogen bonding 30%, dimethylene ether bonding 6%) 2 parts, Shirasu 80 parts, calcium carbonate 20 parts was sufficiently uniformly mixed with a mixer to obtain a molding resin composition of the present invention. This was put into a 25 cm × 25 cm mold, dried at 120 ° C. for 30 minutes, and then molded by hot pressing at 180 ° C. for 30 minutes and a thickness of 7 mm to obtain the molding material of the present invention. The bending strength and bending elastic modulus of the obtained molding material were measured. The obtained results are shown in Table 1. The flow (ISO-8619) of the molding resin composition was 70 mm.

Example 2
8 parts of the solid novolak type phenol resin (A1) obtained in Example 1, solid ammonia resol type phenol resin (B2) (melting point 64 ° C., number average molecular weight 596, weight average molecular weight 1701, phenol methylene bond functional group methylene bond) 29%, methylol bond 46%, nitrogen bond 22%, dimethylene ether bond 3%) 2 parts, shirasu 80 parts and calcium carbonate 20 parts were sufficiently mixed with a mixer to obtain a resin composition for molding. Thereafter, this was put in a 25 cm × 25 cm mold, dried at 120 ° C. for 30 minutes, and then molded by hot pressing at 180 ° C. for 30 minutes and a thickness of 7 mm to obtain a molding material. The bending strength and bending elastic modulus of the obtained molding material were measured. The obtained results are shown in Table 1. The flow (ISO-8619) of the molding resin composition was 94 mm.

Comparative Example 1
A solid novolac type phenol resin (A2) was obtained in the same manner as in Example 1 except that 435 g of 40% formaldehyde aqueous solution was used. The softening point (ring and ball method) of the solid novolac type phenol resin (A2) was 78 ° C., and the ortho / para ratio was 1.1 from ¹³ C-NMR. Next, 8 parts of the solid novolac type phenol resin (A2), solid ammonia resole type phenol resin (B2) (melting point 70 ° C., number average molecular weight 787, weight average molecular weight 2182, phenol nucleus-bonded functional group methylene bond 21%, 2 parts of methylol bond, 30% nitrogen bond, 6% dimethylene ether bond), 80 parts of shirasu, and 20 parts of calcium carbonate were sufficiently uniformly mixed with a mixer to obtain a comparative molding resin composition. . This was put into a 25 cm × 25 cm mold, dried at 120 ° C. for 30 minutes, and then molded by hot pressing at 180 ° C. for 30 minutes and a thickness of 7 mm to obtain a comparative molding material. The bending strength and bending elastic modulus of the obtained comparative molding material were measured. The obtained results are shown in Table 1. The flow of the molding resin composition (ISO-8619) was 110 mm.

Comparative Example 2
8 parts of solid novolac type phenol resin (A1) obtained in Example 1, solid resol type phenol resin (B3) (melting point 64 ° C., number average molecular weight, weight average molecular weight 1701, phenol nucleus-binding functional group methylene bond 28%, Methylol bond 72%) 2 parts, Shirasu 80 parts and calcium carbonate 20 parts were sufficiently uniformly mixed with a mixer to obtain a comparative molding resin composition. This was put in a 25 cm × 25 cm mold, dried at 120 ° C. for 30 minutes, and then molded by hot pressing at 180 ° C. for 30 minutes and a thickness of 7 mm to obtain a comparative molding material. The bending strength and bending elastic modulus of the obtained molding material were measured. The obtained results are shown in Table 1. The flow (ISO-8619) of the molding resin composition was 115 mm.

Claims (6)

The novolak type phenol resin (A) having an ortho / para ratio of less than 2 and a melting point of 80 to 120 ° C. , and an ammonia resol type phenol resin, wherein the phenol core binding functional group of the ammonia resol type phenol resin is , Methylene bond, methylol bond, nitrogen-containing bond, and dimethylene ether bond ratios of 10 to 30 mol%, 30 to 50 mol%, 20 to 40 mol%, and 2 to 10 mol%, respectively, A molding resin composition comprising (B), wherein the molding resin composition has a flow distance defined by ISO-8619 of 50 to 100 mm. 2. The molding resin composition according to claim 1, wherein the ortho / para ratio of the novolac type phenolic resin (A) is 1 to 1.5, and the flow distance is 55 to 95 mm. The molding resin composition according to claim 2, wherein the solid resol type phenolic resin (B) has a melting point of 60 to 85 ° C, a number average molecular weight of 500 to 1000, and a weight average molecular weight of 1500 to 2500. Furthermore, the resin composition for shaping | molding of any one of Claims 1-3 containing polyisocyanate. A molding material comprising the molding resin composition according to any one of claims 1 to 4 and a filler. Furthermore, the molding material of Claim 5 containing a fibrous substance.