JP2019156980A - Thermosetting resin composition, method for producing thermosetting resin composition, sheet molding compound, and molding - Google Patents

Abstract

To provide a thermosetting resin composition having excellent impregnating and thickening properties.SOLUTION: A thermosetting resin composition has a thermosetting resin, at least one thickener selected from the group consisting of a metal oxide thickener and a metal hydroxide thickener, and a W/O surfactant.SELECTED DRAWING: None

Description

  The present invention relates to a thermosetting resin composition, a method for producing a thermosetting resin composition, a sheet molding compound, and a molded article, and more specifically, a thermosetting resin composition that can be used as a material for a sheet molding compound. The present invention relates to a method for producing the thermosetting resin composition, a sheet molding compound including the thermosetting resin composition, and a molded article including a cured product of the sheet molding compound.

  Fiber reinforced plastic (hereinafter referred to as “FRP”) is a molding material having excellent mechanical properties, electrical properties, water resistance, corrosion resistance, etc., and is manufactured by blending reinforcing fibers with a composition containing a resin component. The As such an FRP, a sheet molding compound (hereinafter referred to as “SMC”) is known. SMC is usually produced by impregnating glass fibers with a resin composition containing components such as an unsaturated polyester resin and a filler.

  Various additives are added to the resin composition used for producing SMC as necessary. For example, Patent Document 1 discloses that a compound used for a molding material for heat compression molding contains a thickener or the like.

  The thickener is used to impart viscosity to the resin composition by being combined with moisture, and when producing SMC, even if the viscosity is lowered so that the glass fiber is satisfactorily impregnated with the resin composition. In addition, during storage after impregnation, the SMC is thickened to a viscosity suitable for molding by being combined with moisture of the resin composition or moisture in the outside air.

JP-A-2005-42044

  However, if the amount of water in the resin composition increases due to seasonal factors, the resin composition may thicken and the viscosity becomes too high. If the viscosity of the resin composition before impregnating the glass fiber is too high, poor impregnation of the glass fiber is likely to occur, and the SMC may not be satisfactorily formed. In order to impart appropriate impregnation properties and thickening to the resin composition, it is necessary to control the water content of the resin composition.

  An object of the present invention is to provide a thermosetting resin composition having good impregnation properties and thickening, a method for producing the thermosetting resin composition, a sheet molding compound containing the thermosetting resin composition, and the thermosetting It is providing the molded article containing the hardened | cured material of an adhesive resin composition.

  The thermosetting resin composition according to an embodiment of the present invention is at least one thickener selected from the group consisting of a thermosetting resin, a metal oxide thickener, and a metal hydroxide thickener. And a W / O type surfactant.

  The manufacturing method of the thermosetting resin composition which concerns on one Embodiment of this invention is a manufacturing method of the said thermosetting resin composition, Comprising: The said thermosetting resin, the said thickener, and the said W / O And a mold surfactant.

  The sheet molding compound which concerns on one Embodiment of this invention contains the said thermosetting resin composition and glass fiber.

  A molded product according to an embodiment of the present invention includes a cured product of the sheet molding compound.

  According to the present invention, a thermosetting resin composition having good impregnation properties and thickening, a method for producing the thermosetting resin composition, a sheet molding compound containing the thermosetting resin composition, and a sheet molding compound It is possible to obtain a molded product containing the cured product.

  A mode for carrying out the present invention will be described.

  The thermosetting resin composition according to this embodiment includes a thermosetting resin, at least one thickener selected from the group consisting of a metal oxide thickener and a metal hydroxide thickener, and W / O type surfactant.

  The thermosetting resin composition contains at least one thickener selected from the group consisting of a metal oxide thickener and a metal hydroxide thickener, and a W / O type surfactant. Therefore, it has good impregnation properties and thickening properties. Therefore, when a sheet molding compound is produced by impregnating glass fibers with a thermosetting resin composition, the viscosity of the thermosetting resin composition does not become too high and the thermosetting resin composition is satisfactorily impregnated. It can suppress that an unimpregnated part arises in glass fiber. This is considered to be because the W / O type surfactant forms micelles in the thermosetting resin composition. The moisture contained in the thermosetting resin composition is taken into these micelles, and the amount of moisture associated with the thickener can be controlled. Further, as described later, when the thermosetting resin composition contains an unsaturated polyester resin as a thermosetting resin, since the unsaturated polyester resin has hydrophobicity, by using a W / O type surfactant, In particular, micelles are easily formed in the thermosetting resin composition.

  The thermosetting resin composition has thermosetting properties. Therefore, the thermosetting resin composition can be cured by heating the thermosetting resin composition. For example, as described above, a glass fiber is impregnated with a thermosetting resin composition, a sheet molding compound is produced, the sheet molding compound is molded by heating and pressing, and the thermosetting resin composition in the sheet molding compound is formed. Can be cured to obtain a molded product. The thermosetting property of the thermosetting resin composition is imparted by containing a thermosetting resin.

  The thermosetting resin is not particularly limited as long as it is a thermosetting resin. The thermosetting resin preferably contains an unsaturated polyester resin. The unsaturated polyester resin includes an unsaturated or saturated polycarboxylic acid such as aliphatic unsaturated polycarboxylic acid, aliphatic saturated polycarboxylic acid, and aromatic polycarboxylic acid, and an organic polyol such as diol, triol, and tetraol. Obtained by the condensation reaction of

  Examples of aliphatic unsaturated polycarboxylic acids include (anhydrous) maleic acid and fumaric acid. Examples of aliphatic saturated carboxylic acids include sepacic acid, (anhydrous) succinic acid, and adipic acid. Examples of aromatic polycarboxylic acids include (anhydrous) phthalic acid, isophthalic acid, and terephthalic acid. As unsaturated or saturated polycarboxylic acid, 1 type may be used independently and 2 or more types may be mixed and used for it.

  Examples of organic polyols include aliphatic polyols and aromatic polyols. Examples of aliphatic polyols include ethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, triethylene glycol, neopentyl glycol, hexamethylene glycol, trimethylene glycol, glycerin, and hydrogenated bisphenol A. Examples of aromatic polyols include bisphenol A and bisphenol S. As an organic polyol, 1 type may be used independently and 2 or more types may be mixed and used.

  As the thermosetting resin, only an unsaturated polyester resin may be used, or an unsaturated polyester resin and a resin other than the unsaturated polyester resin may be used in combination. As the thermosetting resin, one type of thermosetting resin other than the unsaturated porester resin may be used alone, or two or more types of resins other than the unsaturated polyester resin may be used in combination.

  The thermosetting resin composition may contain a polymerizable monomer. The polymerizable monomer can be used as a mixture with a thermosetting resin. As the polymerizable monomer, an unsaturated monomer capable of crosslinking with a thermosetting resin such as an unsaturated polyester resin can be used. Examples of unsaturated monomers include styrene, vinyl toluene, vinyl acetate, diallyl phthalate, triallyl cyanurate, acrylate esters, methyl acrylate, methacrylate esters, methyl methacrylate, and ethyl methacrylate. As a polymerizable monomer, 1 type may be used independently and 2 or more types may be mixed and used for it.

  When the thermosetting resin composition contains a polymerizable monomer, the content of the polymerizable monomer is 15 parts by mass or more with respect to 100 parts by mass in total of the thermosetting resin and the polymerizable monomer. It is preferable that it is 80 mass parts or less.

  The thermosetting resin composition contains at least one thickener selected from the group consisting of a metal oxide thickener and a metal hydroxide thickener. The thickener imparts thickening to the thermosetting resin composition. Examples of metal oxide thickeners include magnesium oxide and calcium oxide. Examples of metal hydroxide thickeners include magnesium hydroxide and calcium hydroxide. As the thickener, one kind may be used alone, or two or more kinds may be mixed and used. Moreover, the thermosetting resin composition may contain a thickener other than the metal oxide thickener and the metal hydroxide thickener.

  Content of the at least 1 sort (s) of thickener selected from the group which consists of a metal oxide thickener and a metal hydroxide thickener is 0.3 mass with respect to 100 mass parts of thermosetting resin compositions. It is preferably from 5 parts to 5 parts by weight, more preferably from 0.5 parts by weight to 2 parts by weight.

  The thermosetting resin composition contains a W / O type surfactant. The W / O type surfactant is a water-in-oil type surfactant. The W / O-type surfactant forms micelles in the thermosetting resin composition, and incorporates moisture contained in the thermosetting resin composition into the micelles. Can control the amount of water. Therefore, it can suppress that the water | moisture content more than necessary is combined with a thickener, and can prevent that the viscosity of a thermosetting resin composition becomes high too much before making glass fiber etc. impregnate. In particular, when the thermosetting resin contains an unsaturated polyester resin, the unsaturated polyester resin has hydrophobicity. Therefore, by using a W / O type surfactant, micelles are particularly generated in the thermosetting resin composition. It becomes easier to form.

  The thermosetting resin composition may contain only the W / O type surfactant, and contains both the W / O type surfactant and a surfactant other than the W / O type surfactant. May be. That is, the thermosetting resin composition may contain both a W / O type surfactant and an O / W type (oil-in-water type) surfactant. However, from the viewpoint of efficiently controlling the amount of water in the thermosetting resin composition, the thermosetting resin composition preferably contains only a W / O type surfactant.

  The content of the W / O type surfactant is preferably 0.01 parts by mass or more and 0.1 parts by mass or less, and 0.02 parts by mass or more and 0 parts by mass with respect to 100 parts by mass of the thermosetting resin composition. More preferably, the amount is 0.05 parts by mass or less.

  The W / O type surfactant preferably has an HLB value of 1 or more and 7 or less. The HLB value is a value indicating a balance between hydrophilicity and lipophilicity of the surfactant. When the HLB value of the W / O type surfactant is 7 or less, the ratio of hydrophilic groups to lipophilic groups in the W / O type surfactant is sufficiently small, and the W / O type surfactant has W / O in the thermosetting resin composition. O-type surfactants tend to form micelles.

  As a W / O type surfactant, a W / O type surfactant having an HLB value of 1 or more and 7 or less may be used alone, or two or more types of W / O type surfactants having different HLB values may be used. An agent may be used in combination. Further, a W / O type surfactant having an HLB value of 1 to 7 and a W / O type surfactant having no HLB value of 1 to 7 may be used in combination. However, from the viewpoint of efficiently controlling the amount of water in the thermosetting resin composition, it is preferable to use only a W / O type surfactant having an HLB value of 1 or more and 7 or less.

  The W / O type surfactant is preferably a nonionic surfactant. By using a nonionic surfactant, ions such as alkali metal ions are not generated in the thermosetting resin composition. Therefore, the thermosetting resin after impregnating the glass fiber or the like with the thermosetting resin composition The thickening of the composition is less likely to be inhibited. Therefore, the thermosetting resin composition can have better impregnation properties and thickening properties. As the W / O type surfactant, only a nonionic surfactant may be used, or a nonionic surfactant and an ionic surfactant may be used in combination. However, as described above, it is preferable to use only a nonionic surfactant as the W / O type surfactant from the viewpoint of imparting good impregnation property and thickening to the thermosetting resin composition.

  Examples of nonionic surfactants include glycerin fatty acid esters such as acyl glycerin, glycerin (mono-di-tri) alkanoate, aliphatic glycerin, and lipophilic mono-fatty acid glycerin; sorbitan (mono-di-tri) alkanoate , Fatty acid sorbitan, and sorbitan fatty acid esters such as (mono-di-tri) alkanoyl sorbitan; sucrose fatty acid esters such as acyl sucrose and sugar (fatty acid) ester; alkyl polyoxyethylene ether, alcohol polyethylene glycol ether, polyoxy Ethylene alkyl, polyethylene glycol alkyl ether, alkyl polyethylene glycol ether, alkyl polyethoxyethanol, alkyl polyglycol ether, and polyoxyethylene alkyl ether Polyoxylene alkyl ethers such as Ter; alkylphenyl polyoxyethylene ether, polyoxyethylene alkylphenyl ether, polyoxyethylene alkylphenyl, polyethylene glycol alkylphenyl ether, alkylphenol polyethylene glycol ether, alkylphenyl polyethoxyethanol, alkylphenyl polyethylene glycol Ethers and polyoxyethylene alkylphenyl ethers such as polyoxyethylene alkylphenyl ether; polyoxyethylene polyoxypropylene, polyoxyethylene polyoxypropylene glycol ether, polypropylene glycol polyethylene glycol ether, and polyoxyalkylene block polymers Oxyethylene Lioxypropylene glycols; fatty acid polyethylene glycols such as acyl polyethylene glycol, polyethylene glycol fatty acid ester, fatty acid polyoxyethylene glycol ester, polyethylene glycol fatty acid ester, polyoxyethylene alkanoate, and alkylcarbonyloxypolyoxyethylene; acyl polyoxy Ethylene sorbitan, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan (mono-di-tri) alkanoate, polyoxyethylene hexitan fatty acid ester, sorbitan fatty acid ester polyethylene ethylene glycol, and polyoxyethylene sorbitan (mono-di-tri) Fatty acid polyoxyethylene sorbitans such as fatty acid esters; and alkanol fats Fatty acid amides, alkanolamides, alkanolalkanamides, and fatty acid alkanolamides such as alkylolamides. As a nonionic surfactant, 1 type may be used independently, and 2 or more types may be mixed and used for it.

  The thermosetting resin composition may contain additives such as a curing agent, a polymerization inhibitor, a low shrinkage agent, an inorganic filler, and an internal release agent, if necessary.

  As the curing agent, for example, a high temperature curing catalyst for producing a sheet molding compound at a high temperature of 100 ° C. or higher and a pressure can be used. Examples of high temperature curing catalysts include methyl ethyl ketone peroxide, t-butyl peroxy 2-ethyl hexanate, benzoyl peroxide, di-t-butyl peroxy 3,3,5 trimethylcyclohexane, t-butyl peroxybenzoate, Dicumyl peroxide and t-butyl hydroperoxide are included.

As the polymerization inhibitor, for example, a quinone polymerization inhibitor can be used. Examples of the quinone polymerization inhibitor include p-benzoquinone, t-butyl p-benzoquinone, naphthoquinone, phenanthraquinone, tolquinone, 2,5-diphenyl-p-benzoquinone, 2,5-diacetoxy p-benzoquino, 2, Low shrinkage agents including 5-dicaproxy p-benzoquinone and 2,5-diasiloxy p-benzoquinone are used to reduce cure shrinkage of thermosetting resins. As the low shrinkage agent, for example, a thermoplastic resin can be used. Examples of the thermoplastic resin used as the low shrinkage agent include polystyrene, polyethylene, polymethyl methacrylate, saturated polyester, polyvinyl acetate, polystyrene, polyvinyl acetate copolymer, and polystyrene-modified copolymer. When the thermosetting resin composition contains a low shrinkage agent, the content of the low shrinkage agent is 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass in total of the thermosetting resin and the polymerizable monomer. It is preferable that

  Examples of inorganic fillers include calcium carbonate, aluminum hydroxide, silica, and alumina. When the thermosetting resin composition contains an inorganic filler, the content of the inorganic filler is 100 parts by mass with respect to a total of 100 parts by mass of the thermosetting resin, the polymerizable monomer, and the low shrinkage agent. The amount is preferably 250 parts by mass or less. When the content of the inorganic filler is 100 parts by mass or more, when the glass fiber is impregnated with the thermosetting resin composition, it can be uniformly impregnated with the glass fiber, and the strength variation of the produced molded product is varied. Can be reduced. In addition, when the content of the inorganic filler is 300 parts by mass or less, an increase in the viscosity of the thermosetting resin composition before impregnating the glass fiber or the like is suppressed, and the glass fiber is impregnated with the thermosetting resin composition. In this case, the glass fiber can be satisfactorily impregnated, and the strength of the molded product to be produced can be further increased.

The inorganic filler is preferably surface-treated with a fatty acid, a coupling agent, or the like. In this case, even when a fine inorganic filler is used, aggregation and oil absorption can be made difficult to occur. As the fatty acid, one represented by the general formula C _n H _m COOH can be used (n and m are integers of 1 or more), and either saturated fatty acid or unsaturated fatty acid may be used. Examples of saturated fatty acids include butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid. Examples of unsaturated fatty acids are α-linolenic acid, stearidonic acid, eicosapentaenoic acid, docosahexaenoic acid, linoleic acid, γ-linolenic acid, dihomo-γ-linolenic acid, arachidonic acid, oleic acid, elaidic acid, erucic acid, nerbon acid Contains acid. As the coupling agent, a silane coupling agent represented by the general formula R—Si (OR ′) 3 can be used. Here, R is a functional group such as an aminopropyl group, a glycidoxy group, a methacryloxy group, an N-phenylaminopropyl group, a mercato group, or a vinyl group. R ′ is a methyl group or an ethyl group.

  An example of an internal mold release agent includes stearic acid.

  In addition to the additives described above, the thermosetting resin composition may contain a curing catalyst and a polymerization inhibitor for adjusting the curing conditions of the thermosetting resin. Moreover, the thermosetting resin composition may contain a colorant and other organic and inorganic additives as necessary.

  The thermosetting resin composition of this embodiment is manufactured by mixing the raw material of a thermosetting resin composition. That is, the method for producing a thermosetting resin composition includes a step of mixing a thermosetting resin, a thickener, and a W / O type surfactant. The order in which the raw materials are mixed is not particularly limited, and a thermosetting resin composition may be obtained by stirring and mixing a thermosetting resin, a thickener, a W / O type surfactant, and other additives at a time. Good. Moreover, after stirring and mixing components other than the thickener in the raw material first, the thermosetting resin composition may be obtained by adding and mixing the thickener.

  The thermosetting resin composition thus obtained can be used for production of a sheet molding compound. The sheet molding compound can be produced by impregnating a reinforcing fiber with a thermosetting resin composition. The impregnation operation when producing the sheet molding compound can be performed by a generally used impregnation machine. In addition, after impregnating the thermosetting resin composition into the reinforcing fiber, the thermosetting resin composition is thickened by heating and storing at room temperature to 60 ° C. as necessary, and the sheet molding compound. You may improve the handleability.

  Examples of reinforcing fibers include glass fibers, carbon fibers, metal fibers, vinylon fibers, aramid fibers, and polyester fibers.

  As the reinforcing fiber, glass fiber is preferably used. That is, it is preferable that the sheet molding compound according to the present embodiment includes a thermosetting resin composition and glass fibers.

  The compounding amount of the reinforcing fiber in the sheet molding compound is preferably adjusted so that the amount of the reinforcing fiber is 1% by mass or more and 50% by mass or less in the molded product produced using the sheet molding compound. It is more preferable to adjust so that it may become mass%-40 mass%.

  A molded product can be obtained by heating and pressurizing the sheet molding compound and molding it into a desired shape. That is, the molded product according to the present embodiment includes a cured product of the sheet molding compound. The cured product of the sheet molding compound means a state in which the thermosetting resin composition impregnated in the reinforcing fiber is completely cured.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.

(1) Preparation of thermosetting resin composition Components other than the thickener shown in the “Composition” column of Table 1 below are stirred and mixed in the amounts shown in the “Composition” column of Table 1 to obtain a paste-like mixture Got. Then, the thickener was added in the quantity shown in the "composition" column of Table 1, and the thermosetting resin composition of Examples 1-2 and Comparative Examples 1-3 was obtained.

Details of the components shown in the “Composition” column of Table 1 are as follows.
Unsaturated polyester resin: Showa Denko Co., Ltd., product number M-580.
Polymerizable monomer: Styrene, Mitsubishi Chemical Corporation, CAS (100-42-5) compliant styrene monomer.
Thickener: Magnesium oxide, manufactured by Kyowa Chemical Co., Ltd., product name Kyowamag # 40.
W / O type surfactant A: Sorbitan fatty acid ester, manufactured by Kao Corporation, HLB value 3.7.
W / O type surfactant B: polyoxyethylene alkyl ether, manufactured by Kao Corporation, HLB value 6.3.
Surfactant A: polyoxyethylene alkyl ether, manufactured by Takemoto Yushi Co., Ltd.
Surfactant B: polyoxyalkylene derivative, manufactured by Kao Corporation.
-Surfactant C: Alkyl sulfate ester, manufactured by Kao Corporation.
-Low shrinkage agent: polystyrene, manufactured by PS Japan Ltd., product name GPPS.
Curing agent: t-butyl peroxybenzoate, manufactured by NOF Corporation, product name perbutyl Z.
Polymerization inhibitor: p-benzoquinone, manufactured by Wako Pure Chemical Industries, Ltd.
Inorganic filler: calcium carbonate, manufactured by Shiraishi Kogyo Co., Ltd., product name Whiten SB Blue.
Release agent: Zinc stearate, manufactured by Kawamura Chemical Co., Ltd.

(2) Preparation of sheet molding compound Two polypropylene films were prepared, and the thermosetting resin compositions of Examples 1-2 and Comparative Examples 1-3 were applied to each of them. A reinforcing fiber material obtained by cutting glass roving (manufactured by Nittobo Co., Ltd., product number RS-480PB-549) into a certain size was sprayed on the thermosetting resin composition applied on one film. . On top of that, the surface of the other film coated with the thermosetting resin composition was put together to obtain a laminate. The laminate was impregnated using an impregnation machine, and sheet molding compounds of Examples 1-2 and Comparative Examples 1-3 were obtained. The fiber reinforcing material was dispersed on the thermosetting resin composition so that the content of the fiber reinforcing material in the sheet molding compound was the amount shown in the “glass fiber” column of Table 1 below.

(3) Evaluation test (3-1) Viscosity The viscosity of the thermosetting resin composition after 30 minutes from the preparation of the thermosetting resin compositions of Examples 1-2 and Comparative Examples 1-3, Measurement was performed using a B-type viscometer. The measurement results are shown in the “Viscosity” column of Table 1 below.

(3-2) Impregnation The impregnation state of the thermosetting resin composition to the reinforcing fiber material in the sheet molding compounds of Examples 1-2 and Comparative Examples 1-3 was visually evaluated according to the following evaluation criteria. The results are shown in the column “Impregnability” in Table 1 below. A: The reinforcing fiber material is well impregnated with the thermosetting resin composition.
B: A part of the fiber reinforcing material is not impregnated with the thermosetting resin composition.
C: The fiber reinforcing material has many portions that are not impregnated with the thermosetting resin composition.

(3-3) Stickiness After producing the sheet molding compounds of Examples 1 and 2 and Comparative Examples 1 to 3, the sheet molding compounds were stored at 40 ° C. for 48 hours, and the stickiness of the sheet molding compounds was confirmed by touch. It was evaluated according to the evaluation criteria. The results are shown in the “stickiness” column of Table 1 below.
A: There was no stickiness of the sheet molding compound.
B: There was stickiness of the sheet molding compound.

Claims (6)

A thermosetting resin;
At least one thickener selected from the group consisting of metal oxide thickeners and metal hydroxide thickeners;
W / O type surfactant,
Containing a thermosetting resin composition. The W / O type surfactant has an HLB value of 1 or more and 7 or less.
The thermosetting resin composition according to claim 1. The W / O type surfactant is a nonionic surfactant.
The thermosetting resin composition according to claim 1 or 2. It is a manufacturing method of the thermosetting resin composition given in any 1 paragraph of Claims 1-3,
Including a step of mixing the thermosetting resin, the thickener, and the W / O surfactant.
A method for producing a thermosetting resin composition. The thermosetting resin composition according to any one of claims 1 to 3,
Glass fiber,
Including seat molding compounds. A cured product of the sheet molding compound according to claim 5,
Molding.