JP2003313373A - Molding composition - Google Patents

Abstract

(57) Abstract: A molding material composition and a molding material suitable for obtaining a mat-like molded body having practically sufficient strength and heat resistance, and having improved safety and odor problems. To provide a molded article obtained by molding a composition. A fiber substrate (component (A)), polyethylene (component (B)) and / or polypropylene ((C))
Component], unsaturated polyester [Component (D)] and / or unsaturated polyester polyamide [Component (E)], and a radical generator [Component (F)], and the molding material. A molded article obtained by molding the composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a structural member represented by an automobile interior material, a heat insulating material used in a building, an aircraft, a vehicle, a ship, etc., a soundproofing material, a sound deadening plate for an air conditioner, a glass mat and the like. The present invention relates to a molding material composition that is preferably used and a mat-like molded article obtained by molding the molding material composition.

[0002]

2. Description of the Related Art Structural members typified by automobile interior materials,
As a mat-like molded body suitably used for a building, an aircraft, a vehicle, a heat insulating material used in a ship, a soundproofing material, a sound deadening plate for an air conditioner, a glass mat, etc., since a resin as a continuous phase is unnecessary, A composition containing no ethylenically unsaturated group-containing monomer such as styrene, for example, a composition containing fibers and a phenol resin / amine-based curing agent as a base in order to maintain sufficient strength is used. JP-A-57-55962, JP-A-7-1166, etc.). However, phenolic resin produces formaldehyde during reaction and decomposition, which is problematic in terms of safety.
Amine curing agents have a problem in terms of odor.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a molding material composition suitable for obtaining a mat-like molded article having practically sufficient strength and heat resistance, and having improved safety and odor problems. And it aims at providing the molded object obtained by shape | molding such a molding material composition.

[0004]

The summary of the present invention is as follows.
(1) Fiber substrate [component (A)], polyethylene [(B)
Component] and / or polypropylene [(C) component], unsaturated polyester [(D) component] and / or unsaturated polyester polyamide [(E) component], and radical generator [(F) component] And (2) a molded article obtained by molding the molding material composition according to (1) above.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION As described above, the molding material composition of the present invention comprises a fiber substrate [component (A)], polyethylene [component (B)] and / or polypropylene [(C)].
Component], unsaturated polyester [(D) component] and / or unsaturated polyester polyamide [(E) component], and radical generator [(F) component], and a styrene derivative, (meth) It does not substantially contain an ethylenically unsaturated group-containing monomer such as an acrylic ester.

The molding material composition of the present invention uses the component (B) and / or the component (C), the component (D) and / or the component (E) in addition to the component (A) and the component (F). In order to obtain a mat-like molded article which is inexpensive and has practically sufficient strength and heat resistance, the problem of formaldehyde generation and odor is improved by molding such a molding material composition. You can

The fiber base material of component (A) is not particularly limited, and inorganic fibers such as glass fibers, synthetic fibers, and organic fibers such as natural fibers can be used. Cotton, among others,
Organic fibers such as hemp, wool, silk and nylon are preferable from the viewpoint of flexibility and heat insulation of the molded plate. Moreover, you may mix and use an inorganic fiber and an organic fiber. The component (A) is a non-woven fabric,
It may be used in the form of a woven fabric or in the form of a thread.

As the polyethylene as the component (B), known low density polyethylene, linear low density polyethylene, and high density polyethylene can be used. Above all, a high-density type having a high heat distortion temperature is preferable from the viewpoint of heat resistance of the molded product.

As the polypropylene as the component (C), polypropylene for general molding can be used.

The unsaturated polyester as the component (D) is not particularly limited as long as it is a polyester having a radical-polymerizable unsaturated bond. The raw material monomer is not particularly limited, and examples thereof include known divalent or higher alcohol components, divalent or higher carboxylic acids, carboxylic acid anhydrides, carboxylic acid components such as carboxylic acid esters, and radically polymerizable unsaturated groups. A containing monomer is used. The radical-polymerizable unsaturated group-containing monomer is an essential component when the alcohol component, carboxylic acid component, etc. used do not have a radical-polymerizable unsaturated bond.

As the dihydric alcohol component, alkylene (C2-4) oxide adduct of bisphenol A (average number of moles added 1-10), ethylene glycol,
Propylene glycol, 1,6-hexanediol,
1,4-butanediol, bisphenol A, hydrogenated bisphenol A and the like can be mentioned, and preferably, an alkylene (C2-4) oxide adduct of bisphenol A (average addition mole number 1-10), ethylene glycol,
It is 1,4-butanediol. The alkylene oxide in the alkylene oxide adduct is preferably ethylene oxide or propylene oxide. Further, two or more kinds of alkylene oxides may be added.

Examples of the trihydric or higher alcohol component include sorbitol, 1,4-sorbitan, pentaerythritol, glycerin, and trimethylolpropane, and glycerin and trimethylolpropane are preferable.

Examples of the divalent carboxylic acid component include various dicarboxylic acids, anhydrides of these acids and alkyl (C1-12) esters, and preferably maleic acid, fumaric acid and itaconic acid. , Terephthalic acid and adipic acid.

As the trivalent or higher carboxylic acid component, 1,
2,4-benzenetricarboxylic acid (trimellitic acid), its acid anhydride, alkyl (C1-12) ester, etc. are mentioned.

Examples of the radical-polymerizable unsaturated group-containing monomer include fumaric acid, maleic acid, maleic anhydride, itaconic acid and the like, and fumaric acid and maleic anhydride are preferable.

The unsaturated polyester polyamide as the component (E) is not particularly limited as long as it is a polyester polyamide having a radical-polymerizable unsaturated bond, and its raw material monomer is the unsaturated polyester polyamide as the component (D). Further, an amine-based monomer is used as the monomer used in the saturated polyester. Examples of the amine-based monomer include various known polyamines, aminocarboxylic acids, aminoalcohols, lactams, and the like. Preferred specific examples include metaxylenediamine, ethylenediamine, hexamethylenediamine,
Examples include xylylenediamine and ε-caprolactam.

The unsaturated polyester as the component (D) and the unsaturated polyester polyamide as the component (E) having such a constitution have good moldability and a uniform molded product can be obtained. The molded product at room temperature and high temperature. From the viewpoint of further improving the strength of the above, the content of at least one radically polymerizable unsaturated group-containing monomer is preferably 20
It is desirable to use a resin obtained by using at least 30% by weight, more preferably at least 30% by weight, and even more preferably from 35 to 50% by weight. It should be noted that the above-mentioned raw material monomer is appropriately used for the remainder of the constituent monomers of these resins, and may be 100% by weight.

The component (D) or the component (E) may be composed of a single unsaturated polyester or an unsaturated polyester polyamide, or may be a mixture of two or more kinds.

The unsaturated polyester as the component (D) and the unsaturated polyester polyamide as the component (E) can be produced by a known method. For example, a mixture of the above-mentioned monomers is preferably in a nitrogen atmosphere at 150 to 250 ° C. In 5
It is obtained by reacting for 20 hours. The unsaturated polyester as the component (D) and the unsaturated polyester polyamide as the component (E) may be either linear or non-linear polymers. In addition, a monohydric alcohol component or a carboxylic acid component may be used to adjust the molecular weight, and a commonly used esterification catalyst such as dibutyltin oxide may be used to accelerate the reaction.

The component (D) and the component (E) may be crystalline or non-crystalline. Among them, those having crystallinity have a main melting point of 90 ° C. or more and 160 ° C. or less by the tangential method at the time of DSC measurement under a temperature rising condition of 10 ° C./min from the viewpoint of the strength of the molded body Melt viscosity at a temperature 20 ° C higher than the melting point is 100 Pa · s
The following is preferable. The melt viscosity is measured by an ordinary method using a Koka type flow tester (manufactured by Shimadzu Corporation) or a rheometer (manufactured by Rheometrics).

When the component (D) or the component (E) is amorphous, the softening point (° C.) of each resin is from the viewpoint of meltability during molding and storage stability of the molding material composition. It is preferably 80 ° C or higher, more preferably 80 to 130 ° C. In addition,
What is the softening point? Koka type flow tester (manufactured by Shimadzu Corporation)
Under a load of 196 N, an orifice diameter of 1 mm, an orifice length of 1 mm, and a temperature rising condition of 3 ° C./min.

Examples of the radical generator as the component (F) include peroxide type, persulfide type, and azo type. From the viewpoint of safety, it is preferably a peroxide type or a persulfide type. Preferred specific examples include benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, 1,3-di (2-isopropylperoxyisopropyl) benzene and sodium persulfate, and among them, 1,3-di ( 2-Isopropylperoxyisopropyl) benzene is preferred. The half-life of the component (F) is preferably 7 days or longer at 40 ° C. in consideration of the storage stability of the molding material composition, and within 10 minutes at 250 ° C. due to the molding time. Is desirable.

If desired, a curing aid such as diallyl phthalate prepolymer, a fatty acid amide wax, a synthetic wax, a latex, a releasing agent such as a fatty acid metal salt, calcium carbonate, aluminum hydroxide, magnesium hydroxide, magnesium oxide, Known additives such as talc, mica, silica, kaolin, clay, titanium oxide, alumina, zinc oxide, barium sulfate, and glass frit, and inorganic fillers such as fatty acids and those surface-treated with various coupling agents. The agent may be externally added and used.

The content of each component in the molding material composition of the present invention is not particularly limited as long as the molded product obtained has practically sufficient strength and heat resistance. Here, “practically sufficient strength” means that the room-temperature bending strength based on JIS-K6911 is preferably 100 kg / cm ² or more, and more preferably 120 kg / cm ² or more. Also,
"Practically sufficient heat resistance" means heat resistance to the extent that a judgment of "no warpage" can be obtained in the evaluation criteria in the 120 ° C heat resistance evaluation described in the examples below.

The content of each component in the molding material composition of the present invention is preferably 29 to 94% by weight, more preferably 50 to 90% by weight of the component (A) from the viewpoint of elasticity and strength of the resulting molded article. % By weight of the component (B) and /
Alternatively, the component (C) is preferably 5 to 65% by weight, more preferably 10 to 50% by weight, from the viewpoint of the price and heat resistance of the resulting molded article, and the component (D) and / or the component (E). Is preferably 0.5 to 35% by weight, more preferably 3 to 20% by weight from the viewpoint of the strength of the molded body, and the component (F) is preferably 0.05 from the viewpoint of the strength of the molded body. -30% by weight, more preferably 0.1-2
It is 0% by weight. Here, the definition of the content of the component (B) and the component (C) means the total amount when both are used in combination. The same applies to the component (D) and the component (E).

Further, the contents of the catalyst, the crosslinking agent, the curing aid, the releasing agent, and other additives in the molding material composition exert their desired effects, and the desired object of the present invention is achieved. There is no particular limitation as long as it is within the range.

The molding material composition of the present invention can be prepared by a conventional method, for example, by using the above-mentioned component (B) and / or component (C) and component (D) and / or component (E) and component (F) for household use. It can be obtained by mixing a mixture of a mixer, a Henschel mixer, a fluidized bed, etc. with the component (A).

The method for molding the molding material composition of the present invention to obtain the molded article of the present invention is not particularly limited, and known methods such as compression molding, lamination molding, injection molding and extrusion molding are used. be able to. Further, such a molding material composition may be preheated or heated before being used for molding.

The molded product thus obtained is in the form of a mat, has sufficient strength for practical use, and has good heat resistance, so that it can be used for structural members such as automobile interior materials and for construction. It is preferably used as a heat insulating material, a sound insulating material, a sound deadening plate for an air conditioner, a glass mat, and the like used for objects, aircraft, vehicles, ships and the like.

[0030]

EXAMPLES Resin Production Example 1 2275 g (6.5 mol) of bisphenol A-propylene oxide (average addition mole number: 2.1) adduct, 1200 g (5 mole) of hydrogenated bisphenol A, 527 g (8.5 mole) of ethylene glycol. ), Fumaric acid 2366
g (20.4 mol), 16 g of dibutyltin oxide and 0.6 g of hydroquinone under a nitrogen atmosphere.
The reaction was carried out at 0 ° C for 4 hours. Then, the temperature was raised to 200 ° C., and the reaction was carried out at normal pressure for 1 hour, and further under reduced pressure of 9.33 kPa for 1 hour. The obtained resin was an unsaturated polyester resin having a softening point of 106 ° C. The resin is referred to as resin 1.

Resin Production Example 2 1300 g (4 moles) of bisphenol A-ethylene oxide (average addition mole number: 2.1) adduct, 960 g (4 moles) of hydrogenated bisphenol A, 540 g (6 moles) of 1,4-butanediol. Fumaric acid 1650 g (1
(4.3 mol) and 0.4 g of hydroquinone were reacted at 160 ° C. for 4 hours under a nitrogen atmosphere. Then 200 ℃
After the temperature was raised to 1, the reaction was carried out under normal pressure for 1 hour, and further under reduced pressure of 9.33 kPa for 1 hour. The obtained resin has a softening point of 10
It was an unsaturated polyester resin at 8 ° C. The resin is referred to as resin 2.

Resin Production Example 3 Bisphenol A-propylene oxide (average number of moles added: 2.1) 700 g (2 moles) of adduct, 217 g (3.5 moles) of ethylene glycol, 840 g (3.5 moles) of hydrogenated bisphenol A. , Metaxylene diamine 136 g (1 mol), maleic anhydride 1009 g (1
0.3 mol) and 0.4 g of hydroquinone were reacted at 160 ° C. for 4 hours under a nitrogen atmosphere. Then 200 ℃
After the temperature was raised to 1, the reaction was carried out under normal pressure for 1 hour, and further under reduced pressure of 9.33 kPa for 1 hour. The obtained resin has a softening point of 11
It was an unsaturated polyester polyamide resin at 0 ° C. The resin is referred to as resin 3.

Examples 1 to 3 and Comparative Examples 1 to 2 Resins 1 to 3 obtained in the above resin production examples were crushed and used as powders having a particle size of 30 to 200 μm. Further, polyethylene [(B) component] and polypropylene [(C) component] were also used as powders having a particle size of 10 to 300 μm. A cotton thread-like material was used as the fiber base material [component (A)], and 1,3-di (2-isopropylperoxyisopropyl) benzene was used as the radical generator [component (F)]. Each component was mixed with the composition shown in Table 1 to prepare a molding material composition. Then, the molding material composition is sandwiched between mirror-finished stainless steel plates, and the temperature is set to 190 ° C.
15 kgf / cm ² (147
N / cm ² ) with a contact pressure of 1 minute by heat and pressure molding,
A molded plate having a thickness of 6 mm and a length of 20 cm and a width of 5 cm was obtained.

[0034]

[Table 1]

Each molded plate was subjected to a room temperature bending strength test and a 120 ° C. heat resistance evaluation. The results are shown in Table 1. In addition, neither molded plate had an irritating odor when evaluated at 120 ° C. heat resistance. The molded product was placed in a desiccator, and after 24 hours, the gas in the desiccator was sucked using a formalin gas detector tube, but no formalin was detected.

The room temperature bending strength test is JIS K-6.
911. 120 ° C heat resistance evaluation is 120
A molding plate having a weight of 20 g on its center was left for 2 hours in an oven at 0 ° C. and then taken out and judged based on the following evaluation criteria.

Evaluation Criteria A: There is no warpage. ◯: When the center was placed on the ground, the warpage was less than 1 mm. △: When the center is set on the ground, the warpage is 1 mm or more and 2.5
It was less than mm. X: When the center was placed on the ground, the warpage was 2.5 mm or more.

From the results shown in Table 1, it is found that the molded plates obtained in Examples 1 to 3 have practically sufficient strength and heat resistance as compared with the molded plates obtained in Comparative Examples 1 and 2. Recognize.

[0039]

INDUSTRIAL APPLICABILITY According to the present invention, a molding material composition suitable for obtaining a mat-like molded product which has practically sufficient strength and heat resistance, has improved safety and odor problems, and is inexpensive And the excellent effect that such a molded body is obtained is exhibited.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4F072 AA04 AA05 AA07 AB03 AD38                       AD44 AE02 AH05 AH24 AJ04                       AK05 AK14 AL02 AL11                 4J002 AB01Y AD03Y BB03W BB12W                       CF22X CL00Y CL08X DG037                       DL006 EK037 EK047 FA04Y                       FA046 FD016 FD157 GL00                       GN00

Claims (3)

[Claims] 1. A fiber base material [component (A)], polyethylene [component (B)] and / or polypropylene [(C)].
Component], unsaturated polyester [(D) component] and / or unsaturated polyester polyamide [(E) component], and radical generator [(F) component]. 2. The component (A) in the molding material composition is from 29 to 29.
94% by weight, component (B) and / or component (C) is 5
The molding material composition according to claim 1, wherein the component (D) and / or the component (E) is 0.5 to 35% by weight, and the component (F) is 0.05 to 30% by weight. 3. A molded product obtained by molding the molding material composition according to claim 1.