JP2021138792A - Resin composition, molding material and molding thereof - Google Patents

Abstract

To provide a resin composition that reduces a styrene odor of a molding material and can provide a molding having excellent mechanical strength and leaving no smell.SOLUTION: A resin composition contains a resin component (A) containing an unsaturated polyester resin (a1) and a styrene (a2), a terpene flavor component (B), an ester compound (C) with a boiling point of 55-150°C, and a polymerization initiator (D). The content of the terpene flavor component (B) is 0.1-4 mass% of the resin component (A) and is 0.15-20 mass% of the styrene (a2). A mass ratio between the terpene flavor component (B) and the ester compound (C), (B/C), is 98/2-50/50.SELECTED DRAWING: None

Description

The present invention relates to a resin composition, a molding material, and a molded product thereof.

The sheet molding compound (hereinafter, may be abbreviated as "SMC") is kneaded with a thermosetting resin mainly composed of an unsaturated polyester resin and a vinyl ester resin, an inorganic filler, a thickener, a curing agent and the like. It is a sheet-like molding material in which a paste (compound) is impregnated with fibers and is B-staged through an aging process. A molded product can be obtained by heating and pressure molding this SMC. Such molded products have characteristics such as excellent durability, water resistance, and mechanical strength, and are widely used as housing materials such as bathtubs, water storage tanks, septic tanks, pipe lining materials, electrical parts, and vehicle materials. It is used.

Styrene is used as a diluting solvent and reactive monomer in unsaturated polyester resin and vinyl ester resin, which are the main agents, but there is a problem that styrene volatilizes during kneading and molding, and its odor deteriorates the working environment. There is. As a countermeasure against this odor, a method of substituting a part or all of styrene of an unsaturated polyester resin or a vinyl ester resin with another reactive monomer has been proposed (see, for example, Patent Document 1). However, this method has a problem that the odor due to styrene or other reactive monomers remains to some extent and the cost is significantly higher than that when styrene is used.

Japanese Unexamined Patent Publication No. 2005-97523

An object to be solved by the present invention is to provide a resin composition capable of reducing the styrene odor of a molding material, having excellent mechanical strength, and obtaining a molded product having no odor residue.

The present inventors have found that a resin composition containing a specific resin component, a fragrance, an ester compound, and a polymerization initiator in a specific mass ratio solves the above-mentioned problems, and has completed the present invention.

That is, a resin component (A) containing an unsaturated polyester resin (a1) and styrene (a2), a terpene-based fragrance component (B), an ester compound (C) having a boiling point of 55 to 150 ° C., and a polymerization initiator (D). In the resin composition contained, the content of the terpene-based fragrance component (B) is 0.1 to 4% by mass of the resin component (A), and 0.15 to 20 of the styrene (a2). The present invention relates to a resin composition, which is by mass% and has a mass ratio (B / C) of the sterene-based fragrance component (B) to the ester compound (C) of 98/2 to 50/50.

The resin composition of the present invention reduces the styrene odor of the molding material, has excellent mechanical strength, and can obtain a molded product having no odor residue. It can be suitably used for housing equipment members such as bathroom members and wash bowls, sports members, light vehicle members, building civil engineering members such as pipe lining materials, and housings for OA equipment and the like.

The resin composition of the present invention comprises a resin component (A) containing an unsaturated polyester resin (a1) and styrene (a2), a terpene-based fragrance component (B), an ester compound (C) having a boiling point of 55 to 150 ° C., and polymerization. A resin composition containing an initiator (D), wherein the content of the terpene-based fragrance (B) is 0.1 to 4% by mass of the resin component (A), and the content of the styrene (a2). It is 0.15 to 20% by mass, and the mass ratio (B / C) of the sterene-based fragrance component (B) to the ester compound (C) is 98/2 to 50/50.

The resin component (A) of the present invention contains an unsaturated polyester resin (a1) and styrene (a2) as essential components, but other thermosetting resins other than the unsaturated polyester resin (a1) (a1). It can contain a3), other polymerizable unsaturated monomer (a4) other than the styrene (a2), a low shrinkage agent (a5), and the like.

Since the unsaturated polyester resin (a1) in the resin component (A) has a high viscosity, it is preferable to dilute it with styrene (a2) before mixing it with other components, and the non-volatile content is 30 to 30 to. It is preferably used as an 80% by mass styrene solution. The unsaturated polyester resin (a1) can be used alone or in combination of two or more.

The unsaturated polyester resin (a1) in the resin component (A) is preferably 20 to 60% by mass because it is easy to form SMC and has excellent curability during high-temperature molding. If it is less than 20% by mass, the curability may be lowered, and if it is more than 60% by mass, the curing shrinkage may be large and the dimensional accuracy of the molded product may be deteriorated.

The styrene (a2) in the resin component (A) is easy to form SMC, has excellent curability during high-temperature molding, and more effectively obtains the odor effect of the present invention. Therefore, it is 20 to 60. Mass% is preferred.

Examples of the other thermosetting resin (a3) include vinyl ester resin, vinyl urethane resin, acrylic resin, epoxy resin, phenol resin, melamine resin, furan resin, etc., which are mixed with unsaturated polyester resin. Vinyl ester resins are preferable because they are easy to use and have equivalent molding workability. These thermosetting resins (a3) can be used alone or in combination of two or more.

When the vinyl ester resin is used, it is preferably diluted with styrene (a2) or other polymerizable unsaturated monomer (a4) before being mixed with other components because of its high viscosity. , It is preferable to use it as a solution having a non-volatile content of 30 to 80% by mass. The vinyl ester resin may be used alone or in combination of two or more.

Examples of the other polymerizable unsaturated monomer (a4) include (meth) acrylics such as methyl (meth) acrylate, butyl (meth) acrylate, phenoxyethyl (meth) acrylate, and benzyl (meth) acrylate. In addition to the acid ester monomer, vinyl monomers such as vinyl toluene, vinyl acetate, chlorostyrene, α-methylstyrene, tert-butylstyrene, and vinylbenzene can be mentioned. These polymerizable unsaturated monomers (a4) can be used alone or in combination of two or more.

In the present invention, the notation of "(meth) acrylic acid" represents either or both of "acrylic acid" and "methacrylic acid".

Examples of the low shrinkage agent (a5) include nylon resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin, polypropylene resin, polyethylene resin, polystyrene resin, acrylic resin, and a resin obtained by modifying these by copolymerization or the like. Examples thereof include thermoplastic resins such as. Among these, styrene resin, styrene-acrylic acid copolymer, styrene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene copolymer such as styrene-olefin copolymer, poly (meth) acrylic acid ester Is preferable. These hyposhrinkling agents may be used alone or in combination of two or more.

The low shrinkage agent (a5) in the resin component (A) is preferably 5 to 40% by mass because the heat compression moldability and the appearance of the obtained molded product are further improved.

Examples of the terpene-based fragrance component (B) include limonene, myrcene, linalool, simene, α-terpinene, γ-terpinene, terpinene, α-ferandrene, osimen, cineol, pinen, fencon, citral, citronellal, β-. Citronerol, nerol, geraniol, terpineol, timol, menthol, menthol, carbachlor, carvone, hinokithiol, lambagerol, ionone, carbeol, dihydrocarbeol, berbenone, camphor, farnesole, nerolidol, notecaton, valensen, or these However, a compound having a boiling point of 55 to 200 ° C. is preferable because the styrene odor can be more effectively reduced and the odor residue of the molded product can be suppressed. If the boiling point is 55 ° C. or lower, it may volatilize during the aging process and the expected odor effect may not be obtained.

The content of the terpene-based fragrance component (B) is 0.1 to 4% by mass of the resin component (A), but the styrene odor is more effective while maintaining the excellent mechanical strength of the molded product. 0.2 to 3% by mass is preferable because it can be reduced to.

The content of the terpene-based fragrance component (B) is 0.15 to 20% by mass of the styrene (a2), but the styrene odor is more effective while maintaining the excellent mechanical strength of the molded product. 0.3 to 15% by mass is preferable because it can be reduced.

Examples of the ester compound (C) having a boiling point of 55 to 150 ° C. include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and propyl propionate. Examples thereof include butyl propionate, methyl butyrate, ethyl butyrate, and propyl butyrate, but ester compounds having a boiling point of 75 to 150 ° C. are preferable because the styrene odor can be reduced more effectively. Since the ester compound itself has fragrance, it can be expected to interact with terpene-based fragrances, and since the ester compound promotes volatilization of the fragrance component in the composition, it is more fragile than using the fragrance component alone. The odor effect is improved.

The mass ratio (B / C) of the terpene-based fragrance component (B) to the ester compound (C) is 98/2 to 50/50, but the terpene-based fragrance component (B / C) based on the ester compound (C) 95/5 to 70/30 is preferable because the balance between the volatilization promoting effect of B) and the odor effect of the styrene odor due to the ester-based fragrance component (B) is further improved.

The resin composition of the present invention may contain a fragrance component other than the terpene-based fragrance component (B) and an ester compound other than the ester compound (C) as long as the effects of the present invention are not impaired.

The polymerization initiator (D) is not particularly limited, but an organic peroxide is preferable, and for example, a diacyl peroxide compound, a peroxy ester compound, a hydroperoxide compound, a ketone peroxide compound, an alkyl perester compound, and a per carbonate are used. Examples thereof include compounds, which can be appropriately selected according to the molding conditions. These polymerization initiators can be used alone or in combination of two or more. These polymerization initiators are preferably contained in an amount of 0.4 to 4 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin (a1).

The resin composition of the present invention may contain other than the resin component (A), the terpene-based fragrance component (B), the ester compound (C), and the polymerization initiator (D). For example, fillers, thickeners, polymerization inhibitors, curing accelerators, low shrinkage agents, mold release agents, thickeners, pigments, antioxidants, plasticizers, flame retardants, antibacterial agents, UV stabilizers, reinforcing materials. , Photocuring agent and the like can be contained.

The filler includes an inorganic compound and an organic compound, and can be used to adjust physical properties such as strength of a molded product. These fillers may be used alone or in combination of two or more.

Examples of the inorganic compound include aluminum hydroxide, calcium carbonate, magnesium carbonate, barium sulfate, mica, talc, kaolin, clay, celite, asbestos, burlite, baryta, silica, silica sand, dolomite limestone, gypsum, and fine aluminum powder. , Hollow balloon, alumina, glass powder, cold water stone, zirconium oxide, antimony trioxide, titanium oxide, molybdenum dioxide, iron powder and the like.

Examples of the organic compound include natural polysaccharide powders such as cellulose and chitin, synthetic resin powders, and the like, and synthetic resin powders are composed of hard resins, soft rubbers, elastomers, polymers (copolymers), and the like. Particles having a multi-layer structure such as organic powder or core-shell type can be used. Specific examples thereof include particles made of butadiene rubber and / or acrylic rubber, urethane rubber, silicon rubber and the like, polyimide resin powder, fluororesin powder, phenol resin powder and the like.

Examples of the thickener include metal oxides such as magnesium oxide, magnesium hydroxide, calcium oxide and calcium hydroxide, metal hydroxides and isocyanate compounds, and the film peeling property and the touch property are used. Magnesium oxide is preferable because the balance between the handleability of the molding material and the moldability is further improved. These thickeners may be used alone or in combination of two or more.

The molding material of the present invention contains the above-mentioned resin composition and reinforcing fibers (E).

Examples of the reinforcing fiber (E) include organic fibers such as glass fiber, carbon fiber, silicon carbide fiber, alumina fiber, boron fiber, metal fiber, aramid fiber, vinylon fiber, and tetron fiber, but the price is higher. Glass fiber or carbon fiber is preferable because a molded product having high strength and high elasticity can be obtained. These reinforcing fibers (E) can be used alone or in combination of two or more.

The length of the reinforcing fiber (E) is preferably in the range of 3 to 60 mm from the viewpoint of the cut property of the fiber itself and the impregnation property with the resin component (A). Further, reinforcing fibers having different lengths may be mixed.

The content of the reinforcing fiber (E) in the molding material of the present invention is preferably in the range of 10 to 60% by mass, preferably in the range of 15 to 45% by mass, because the mechanical strength of the obtained molded product is further improved. More preferable.

The fiber-reinforced molding material of the present invention is preferably SMC or a bulk molding compound (hereinafter, may be abbreviated as "BMC") from the viewpoint of excellent productivity and moldability having design diversity. ..

As a method for producing the SMC, a mixer such as a normal mixer, an intermixer, a planetary mixer, a roll, a kneader, or an extruder is used to obtain the resin component (A), the terpene-based fragrance component (B), and the above. Each component such as the ester compound (C) and the polymerization initiator (D) is mixed and dispersed, and the obtained resin composition is applied to the carrier films placed on the upper and lower sides so as to have a uniform thickness. The reinforcing fibers (E) are sandwiched between the resin compositions on the carrier films installed above and below, and then the whole is passed between the impregnating rolls, and pressure is applied to impregnate the reinforcing fibers (E) with the resin composition. After that, a method of winding it into a roll or folding it into a zigzag fold can be mentioned. Further, it is preferable to carry out aging at a temperature of 25 to 55 ° C. after this. As the carrier film, a polyethylene film, a polypropylene film, a polyethylene-polypropylene laminate film, polyethylene terephthalate, nylon or the like can be used.

As the method for producing the BMC, the resin component (A), the above, using a mixer such as a normal mixer, an intermixer, a planetary mixer, a roll, a kneader, an extruder, etc. Each component such as the terpene-based fragrance component (B), the ester compound (C), and the polymerization initiator (D) is mixed and dispersed, and the reinforcing fiber (E) is mixed and dispersed in the obtained resin composition. There is a method of making it. Further, it is preferable to ripen at a temperature of 25 to 55 ° C. like SMC.

The molded product of the present invention can be obtained from the above-mentioned molding material, but from the viewpoint of excellent productivity and excellent design diversity, heat compression molding of SMC or BMC is preferable as the molding method.

In the heat compression molding, for example, a predetermined amount of a molding material such as SMC or BMC is weighed, put into a mold heated to 80 to 180 ° C. in advance, molded by a compression molding machine, and the molding material is applied. A manufacturing method is used in which a molding material is cured by molding and holding a molding pressure of 0.1 to 30 MPa, and then the molded product is taken out to obtain a molded product. As specific molding conditions, molding conditions in which the molding pressure of 1 to 10 MPa is maintained in the mold at a mold temperature of 100 to 160 ° C. for 1 to 2 minutes per 1 mm of the thickness of the molded product is preferable, and the productivity is high. It is more preferable that the molding condition keeps the molding pressure of 1 to 10 MPa for 30 to 150 seconds per 1 mm of the thickness of the molded product at the mold temperature of 120 to 160 ° C.

The resin composition of the present invention reduces the styrene odor of the molding material, has excellent mechanical strength, and can obtain a molded product having no odor residue. It can be suitably used for housing equipment members such as bathroom members and wash bowls, sports members, light vehicle members, building civil engineering members such as pipe lining materials, and housings for OA equipment and the like.

Hereinafter, the present invention will be described in more detail with reference to specific examples.

(Example 1: Production and evaluation of resin composition (1))
Unsaturated polyester resin solution (1) (“Sandoma PS-293” manufactured by DIC Material Co., Ltd .; a mixture of 60 parts by mass of unsaturated polyester resin and 40 parts by mass of styrene) 80 parts by mass, polystyrene resin solution (1) (DIC material) "Sandoma PS-957" manufactured by Sandoma Co., Ltd .; 20 parts by mass of polystyrene resin (mixture of 35 parts by mass of polystyrene resin and 65 parts by mass of styrene), 120 parts by mass of aluminum hydroxide, polymerization initiator ("Trigonox BPIC-75" manufactured by Chemical Nurion Co., Ltd. ”; Hereinafter, it is abbreviated as“ polymerization initiator (D-1) ”.) 1.2 parts by mass of limonene, 0.2 parts by mass of ethyl acetate, and 0.52 parts by mass of magnesium oxide are dissolved. The resin composition (1) was obtained.

[Manufacturing of SMC]
Two sheets of the resin composition (1) obtained above coated on a PP film were prepared, and one sheet of glass fiber (CPIC "ECT56BT") cut into 1 inch was uniformly formed so as to be 27% by mass. The resin composition of No. 1 is dropped onto a film coated with the above resin composition, sandwiched between another film coated with the resin composition to impregnate the glass fiber with the resin, and then aged at 45 ° C. for 24 hours to SMC (1). Got

[Evaluation of odor]
In a windless room at 23 ° C. RH 50%, with the carrier film of SMC (1) obtained above peeled off, the odor was sensorimetrically judged from a distance of 20 cm between the sample and the face of the judge, and the following criteria were used. The odor was evaluated by.
○: No styrene odor △: Styrene odor ×: Styrene odor

[Manufacturing of molded products]
The SMC (1) obtained above was peeled from the PP film, cut into 280 mm × 280 mm, placed in the center of a 300 mm × 300 mm flat plate mold heated at 145 ° C. for the upper mold and 130 ° C. for the lower mold, and added. Press molding was performed at a pressure of 10 MPa and a pressurization time of 6 minutes to obtain a flat plate-shaped molded product (1) having a thickness of 4 mm.

[Evaluation of residual odor]
In a windless room at 23 ° C. RH 50%, the odor residue of the molded product (1) after 30 minutes of molding is sensorimetrically judged from a distance where the face of the sample and the judge is 20 cm, and the odor residue is evaluated according to the following criteria. bottom.
〇: No odor residue (odorless)
×: There is a residual odor

[Measurement of bending strength and flexural modulus]
In accordance with JIS K7171, the molded product (1) obtained above was subjected to a three-point bending test using "Autograph AG-I" manufactured by Shimadzu Corporation, and the bending strength and flexural modulus were measured. ..
Specimen size: 15 mm x 100 mm, distance between fulcrums: 16 x thickness mm, test speed: 2.0 mm / min

[Measurement of tensile strength and tensile modulus]
In accordance with JIS K7164, the molded product (1) obtained above was subjected to a tensile test using "Autograph AG-I" manufactured by Shimadzu Corporation, and the tensile strength and tensile elastic modulus were measured.
Specimen size: 25 mm x 200 mm without strip-shaped tabs, distance between marked lines: 50 mm, distance between grippers: 100 mm, test speed: 10 mm / min

(Example 2: Production and evaluation of resin composition (2))
The operation is the same as in Example 1 except that 0.8 parts by mass of limonene and 0.2 parts by mass of ethyl acetate used in Example 1 are changed to 0.95 parts by mass of limonene and 0.05 parts by mass of ethyl acetate. As a result, the resin composition (2), SMC (2) and molded product (2) were prepared and evaluated in various ways.

(Example 3: Production and evaluation of resin composition (3))
80 parts by mass of the unsaturated polyester resin solution (1) used in Example 1, 40 parts by mass of the unsaturated polyester resin solution (1) and the vinyl ester resin solution (1) (“VP-801” manufactured by DIC Material Co., Ltd.”; A mixture of 70 parts by mass of vinyl ester resin and 30 parts by mass of phenoxyethyl methacrylate) was changed to 40 parts by mass, and 0.8 parts by mass of limonene and 0.2 parts by mass of ethyl acetate were changed to 0.4 parts by mass of limonene and ethyl acetate. The resin composition (3), SMC (3) and molded product (3) were prepared and evaluated in various ways by operating in the same manner as in Example 1 except that the content was changed to 0.1 part by mass.

(Example 4: Preparation and evaluation of resin composition (4))
The operation is the same as in Example 1 except that 0.8 parts by mass of limonene and 0.2 parts by mass of ethyl acetate used in Example 1 are changed to 0.65 parts by mass of limonene and 0.35 parts by mass of ethyl acetate. As a result, the resin composition (4), SMC (4) and molded product (4) were prepared and evaluated in various ways.

(Example 5: Preparation and evaluation of resin composition (5))
The resin composition (5), SMC (5) and molded product (5) were prepared and evaluated in the same manner as in Example 1 except that the limonene used in Example 1 was changed to geraniol. Was done.

(Comparative Example 1: Production and Evaluation of Resin Composition (R1))
The resin composition (R1), SMC (R1) and molded product (R1) were prepared by operating in the same manner as in Example 1 except that limonene and ethyl acetate used in Example 1 were not added. Various evaluations were performed.

(Comparative Example 2: Preparation and Evaluation of Resin Composition (R2))
The resin composition (R2), SMC (R2) and molded product (R2) were prepared by operating in the same manner as in Example 1 except that limonene and ethyl acetate used in Example 3 were not added. Various evaluations were performed.

(Comparative Example 3: Preparation and Evaluation of Resin Composition (R3))
The operation is the same as in Example 1 except that 0.8 parts by mass of limonene and 0.2 parts by mass of ethyl acetate used in Example 1 are changed to 0.4 parts by mass of limonene and 0.6 parts by mass of ethyl acetate. As a result, a resin composition (R3), SMC (R3) and a molded product (R3) were prepared and evaluated in various ways.

(Comparative Example 4: Preparation and Evaluation of Resin Composition (R4))
By operating in the same manner as in Example 1, 0.8 parts by mass of limonene and 0.2 parts by mass of ethyl acetate used in Example 1 were changed to 1 part by mass of ethyl acetate without adding limonene. A resin composition (R4), SMC (R4) and a molded product (R4) were prepared and evaluated in various ways.

(Comparative Example 5: Preparation and Evaluation of Resin Composition (R5))
By changing the 0.8 parts by mass of limonene and 0.2 parts by mass of ethyl acetate used in Example 1 to 1 part by mass of limonene and operating in the same manner as in Example 1 except that ethyl acetate was not added. , Resin composition (R5), SMC (R5) and molded product (R5) were prepared and evaluated in various ways.

(Comparative Example 6: Preparation and Evaluation of Resin Composition (R6))
By changing the 0.8 parts by mass of limonene and 0.2 parts by mass of ethyl acetate used in Example 1 to 5 parts by mass of limonene and operating in the same manner as in Example 1 except that ethyl acetate was not added. , Resin composition (R6), SMC (R6) and molded product (R6) were prepared and evaluated in various ways.

The evaluation results of the resin compositions (1) to (5) and (R1) to (R6) obtained above are shown in Table 1 or 2.

The SMCs obtained from the resin compositions (1) to (5) of Examples 1 to 5 have no styrene odor, the molded product has no residual odor, and is excellent in bending strength, flexural modulus, tensile strength and tensile modulus. Was confirmed.

On the other hand, Comparative Examples 1 and 2 are examples in which the terpene-based fragrance component (B) and the ester compound (C) having a boiling point of 55 to 150 ° C. are not contained, but the reduction of the styrene odor of SMC was insufficient.

Comparative Example 3 is an example in which the mass ratio (B / C) deviates from 98/2 to 50/50, but the reduction of the styrene odor of SMC was insufficient.

Comparative Example 4 is an example in which the terpene-based fragrance component (B) is not contained, but the reduction of the styrene odor of SMC was insufficient.

Comparative Example 5 is an example in which the ester compound (C) having a boiling point of 55 to 150 ° C. is not contained, but the reduction of the styrene odor of SMC was insufficient.

Comparative Example 6 is an example in which the amount of the terpene-based fragrance component (B) is large and the ester compound (C) having a boiling point of 55 to 150 ° C. is not contained. The mechanical properties of Ester were inadequate.

Claims (4)

It contains a resin component (A) containing an unsaturated polyester resin (a1) and styrene (a2), a terpene-based fragrance component (B), an ester compound (C) having a boiling point of 55 to 150 ° C., and a polymerization initiator (D). In the resin composition, the content of the terpene-based fragrance component (B) is 0.1 to 4% by mass of the resin component (A) and 0.15 to 20% by mass of the styrene (a2). The resin composition is characterized in that the mass ratio (B / C) of the sterene-based fragrance component (B) to the ester compound (C) is 98/2 to 50/50. The resin composition according to claim 1, wherein the terpene-based fragrance component (B) has a boiling point of 55 to 200 ° C. A molding material containing the resin composition according to claim 1 or 2 and a reinforcing fiber (E). A molded product obtained from the molding material according to claim 3.