JP2003147036A - Binder composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a binder composition suitable for obtaining molded form having practically sufficient mechanical strengths and heat resistance and freed from problems of safety and odor, to provide a molding compound composition containing the binder composition, and to provide the molded form obtained by molding the molding compound composition. SOLUTION: This binder composition comprises polystyrene powder [(A) component], unsaturated polyester powder [(B) component] and/or unsaturated polyester-polyamide powder[(C) component]. The molding compound composition comprises the binder composition and a fibrous base material [(E) component]. The molded form is obtained by molding the molding compound 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 binder composition used when molding a molding material that is preferably used, a molding material composition containing the binder composition, and a 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 molded body suitably used for a heat insulating material, a soundproofing material, a sound deadening plate for an air conditioner, a glass mat, etc. used in a building, an aircraft, a vehicle, a ship, etc., a fiber and a phenol resin / Those containing an amine-based curing agent as a base are used (Japanese Patent Laid-Open No. 7-1666).
No. However, the phenol resin produces formaldehyde during the reaction and when decomposed, and the amine-based curing agent has a problem of odor.

A molding material composition comprising a radical generator and a composition comprising an amorphous unsaturated polyester and an ethylenically unsaturated group-containing monomer compatible with the unsaturated polyester is also known. It is (special fair 2-31
090 publication). However, ethylenically unsaturated group-containing monomers such as styrene which are compatible with unsaturated polyesters all act as a cross-linking agent, so that the strength of the molded article is improved, but the odor and safety of the monomer There's a problem.

[0004]

SUMMARY OF THE INVENTION The present invention provides a binder composition suitable for obtaining a molded product having practically sufficient strength and heat resistance and having improved safety and odor problems, and the binder. An object of the present invention is to provide a molding material composition containing the composition, and a molded article obtained by molding the molding material composition.

[0005]

In the present invention, since a powder of a resin that does not generate formaldehyde is used, safety and odor are improved, and a polystyrene resin and an unsaturated polyester resin or an unsaturated polyester polyamide resin are used in combination. According to the above, the obtained molded product has sufficient strength and heat resistance. That is, the gist of the present invention is (1) polystyrene powder [(A) component], unsaturated polyester powder [(B) component] and / or unsaturated polyester polyamide powder [(C) component], If necessary, a binder composition containing a powdery radical generator [(D) component], (2) the binder composition described in (1) above, and a fiber base material [(E) component]. The present invention also relates to a molding material composition contained therein, and (3) a molded article obtained by molding the molding material composition according to (2) above.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a binder composition in which a polystyrene powder and an unsaturated polyester powder and / or an unsaturated polyester polyamide powder are optionally blended with a powdery radical generator is used. As a result, the problem of formaldehyde generation and odor can be improved, and an inexpensive molded article having practically sufficient strength can be obtained. Further, in the present invention, by using the above-mentioned various components as a powder, a solvent is not required, and there is no problem of safety of an organic solvent or a problem of requiring a drying time when water is used as a solvent.

The polystyrene as the component (A) is a radical, anion, cation or Ziegler (Ziegl).
er) may be polymerized by any of the mechanisms,
General industrial products having a molecular weight of 100,000 to 400,000 can be used. Further, expanded polystyrene obtained by expanding the polystyrene, and used expanded polystyrene waste such as packing material, cushioning material or tray processed may be washed and crushed before use. In particular, the use of used expanded polystyrene has an advantage that resources can be effectively utilized. The polystyrene content may be less than 10% and may be modified with other copolymerization monomers such as (meth) acrylic acid ester and butadiene.

The unsaturated polyester as the component (B) 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 contains a known divalent or higher valent alcohol component, divalent or higher carboxylic acid, carboxylic acid anhydride, carboxylic acid component such as carboxylic acid ester, and a radically polymerizable unsaturated group. Monomers are used. In the present invention, the radical-polymerizable unsaturated group-containing monomer is an essential component when the alcohol component and the carboxylic acid component used have no radical-polymerizable unsaturated bond.

The dihydric alcohol component is an alkylene (having 2 to 4 carbon atoms) oxide adduct of bisphenol A (average addition mole number of 1 to 10), ethylene glycol, propylene glycol, 1,6-hexanediol, 1 ,.
4-butanediol, bisphenol A, hydrogenated bisphenol A and the like can be mentioned, and preferably, alkylene (having 2 to 4 carbon atoms) oxide adduct of bisphenol A (average addition mole number 1 to 10), ethylene glycol,
1,4-butanediol and hydrogenated bisphenol A
Is. The alkylene oxide is preferably ethylene oxide or propylene oxide. Also, 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.

As the divalent carboxylic acid component, various dicarboxylic acids, succinic acid substituted with an alkyl group or an alkenyl group having 1 to 20 carbon atoms, anhydrides and alkyls of these acids (having 1 to 12 carbon atoms). ) Ester and the like,
Preferably, maleic acid, fumaric acid, terephthalic acid and succinic acid substituted with an alkenyl group having 2 to 20 carbon atoms,
Specifically, octenyl succinic anhydride, dodecenyl succinic anhydride and the like.

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, citraconic acid and the like, and fumaric acid and maleic anhydride are preferable.

The unsaturated polyester polyamide as the component (C) is not particularly limited as long as it is a polyester polyamide having a radical-polymerizable unsaturated bond, and the unsaturated polyester polyamide used as the unsaturated polyester in the component (B) is used. It is obtained by further using an amine-based monomer as a monomer. Examples of the amine-based monomer include various known polyamines, aminocarboxylic acids, aminoalcohols, lactams, and the like. Preferred specific examples include meta-xylenediamine, ethylenediamine, hexamethylenediamine, xylylenediamine and ε-caprolactam. Can be mentioned.

The unsaturated polyester as the component (B) and the unsaturated polyester polyamide as the component (C) 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 content of at least one radical-polymerizable unsaturated group-containing monomer is preferably 5% by weight or more, more preferably 10% by weight or more, among all the constituent monomers, It is preferable to use the one obtained by using 20 to 65% by weight.
In addition, the above-mentioned constituent monomers may be appropriately used to make 100% by weight.

These components (B) and (C) can be used as a mixture of one or more kinds. Further, in the present invention, the component (B) alone, the component (C) alone, or the combination of the component (B) and the component (C) may be used.

The unsaturated polyester as the component (B) and the unsaturated polyester polyamide as the component (C) are each a mixture of the above monomers, preferably in a nitrogen atmosphere.
It is obtained by reacting at 0 to 250 ° C. and, if necessary, under reduced pressure for 5 to 20 hours. The unsaturated polyester as the component (B) and the unsaturated polyester polyamide as the component (C) 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 softening point of the component (B) or the component (C) is preferably 80 ° C. or higher, more preferably 80 to 160 ° C., from the viewpoint of meltability during molding and storage stability of the molding material composition. . The softening point is a Koka type flow tester (manufactured by Shimadzu Corporation), load 196N, orifice diameter 1
mm, orifice length 1 mm, measured at a temperature rising condition of 3 ° C./min.

The component (B) or the component (C) may be either crystalline or non-crystalline.

The component (A) and the component (B) or the component (C) react by heating and are cured. Although the reaction mechanism is not clear, when the unsaturated bond of the component (B) or the component (C) causes a crosslinking reaction by heating,
Styrene oligomer component in component (A) elutes (B)
It is considered that it reacts with the component or the component (C). Then, it is considered that the portion derived from the styrene oligomer component of the crosslinked polymer generated as a result of the reaction enhances the compatibility with polystyrene and expresses sufficient strength. From the viewpoint of accelerating this reaction, it is preferable to add a powdery radical generator [component (D)] if necessary. Examples of the component (D) include peroxide-based, persulfide-based, and azo-based radical generators. From the viewpoint of safety of suppressing foaming at the time of heating / pressurizing, peroxide type and persulfide type are preferably used. Preferred specific examples include benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, dicumyl peroxide, 1,3-di (2-isopropylperoxyisopropyl) benzene, sodium persulfate and the like. When the radical generator is in a liquid state, a powder of the radical generator supported on a carrier such as silica or calcium carbonate can be used as the component (D). The half-life of the component (D) is preferably 7 days or longer at 40 ° C in consideration of the storage stability of the binder composition, and within 10 minutes at 250 ° C due to the molding time. Is desirable.

If necessary, a curing aid such as diallyl phthalate or triallyl phthalate, a releasing agent such as fatty acid amide wax, synthetic wax, latex or fatty acid metal salt, a flame retardant such as halogen-based or phosphorus-based flame retardant, A known additive such as a lubricant such as silica or an inorganic filler such as talc, calcium carbonate or aluminum hydroxide may be added and used.

The content of each component in the binder composition of the present invention is not particularly limited as long as the strength of the obtained molded body is practically sufficient. For example, when compounded with a fiber base material and cured, "the strength of the molded body is practically sufficient" means
Bending strength at room temperature based on JIS K 6911 is preferably 100 kg / cm ² or more, more preferably 120 kg.
/ Cm ² or more.

Specifically, the component (A) and the component (B) and / or the component (C) in the binder composition (however, when the component (B) and the component (C) are used in combination, the total amount is The weight ratio of 1) means 1: from the viewpoint of the strength of the molded body.
It is preferably 99 to 99: 1, more preferably 1: 9 to
It is 9: 1, more preferably 3: 7 to 9: 1, and particularly preferably 5: 5 to 9: 1.

The content of the component (A) is preferably 1 to 99 in the binder composition from the viewpoint of the strength of the molded product.
%, More preferably 10 to 90% by weight, more preferably 30 to 90% by weight, particularly preferably 50 to 90% by weight.

The content of the component (B) and / or the component (C) (however, when the component (B) and the component (C) are used in combination means the total amount) is the strength and heat resistance of the molded article. From the viewpoint of, in the binder composition, preferably 1 to 99% by weight, more preferably 10 to 90% by weight, more preferably 10 to 70% by weight, particularly preferably 10 to 50% by weight.
Is.

The content of the component (D) in the binder composition is preferably 0.1 to 30% by weight, more preferably 0.1 to 2 from the viewpoint of the molding speed and the strength of the molded product.
It is 0% by weight.

The average particle size of the components (A), (B) and (C) is preferably 1 to 5 from the viewpoint of the strength of the molded product.
The thickness is 00 μm, more preferably 10 to 300 μm.
The average particle size of component (D) is preferably 0.1-5.
The thickness is 00 μm, more preferably 1 to 400 μm.

The content of additives such as catalysts, curing aids, release agents and inorganic fillers in the binder composition is not particularly limited as long as the desired effect can be exhibited.

The binder composition of the present invention has the above-mentioned (A).
Obtained by mixing the component and the component (B) and / or the component (C), and if necessary, the component (D) with a household mixer, a Henschel mixer, a fluidized bed, a V-blender, a Nauta mixer, etc. You can

The binder composition of the present invention obtained as described above and the fiber base material (component (E)) are formulated to obtain a molding material composition. The component (E) is not particularly limited, and inorganic fibers such as glass fibers, synthetic fibers, organic fibers such as natural fibers can be used. Cotton, among others,
Organic fibers such as hemp, hair, silk, nylon, etc.
It is preferable from the viewpoint of heat insulation. Moreover, you may mix and use an inorganic fiber and an organic fiber. The component (E) may be used in the form of non-woven fabric or woven fabric, or may be used in the form of threads.

The content of the component (E) in the molding material composition is preferably 30 to 99% by weight, and particularly preferably 50 to 90% by weight from the viewpoint of elasticity and strength of the molded product. Further, the content of the binder composition in the molding material composition is preferably 1 to 70% by weight, and particularly 10 from the viewpoint of the strength of the molded body.
-50% by weight is preferred.

As a method for prescribing the binder composition and the component (E), for example, when the component (E) is understood,
Examples include adding a binder composition.

The method of 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.

Since the molded product thus obtained has practically sufficient strength and its heat resistance is also good, structural members typified by automobile interior materials, buildings, aircraft, vehicles and ships. It is preferably used as a heat insulating material, a soundproofing material, a sound deadening plate for an air conditioner, a glass mat, etc. The heat resistance is measured by the method described in Examples below.

[0035]

EXAMPLES Production Example 1 [Production of unsaturated polyester] 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, ethylene glycol 527 g (8.5 mol), fumaric acid 2366
g (20.4 mol), dibutyltin oxide 16 g and hydroquinone 0.6 g under nitrogen atmosphere at 160 ° C.
And reacted 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 having a softening point of 106 ° C. The resin is referred to as resin 1.

Production Example 2 [Production of Unsaturated Polyester Polyamide] Bisphenol A-propylene oxide (average addition mole number: 2.1) 700 g (2 mole) of adduct, 217 g (3.5 mole) of ethylene glycol, hydrogenated bisphenol A 840 g (3.5 mol), 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, 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 resin obtained has a softening point of 110.
It was an unsaturated polyester polyamide at ℃. The resin is referred to as resin 2.

Production Example 3 [Production of Unsaturated Polyester] Bisphenol A-propylene oxide (average addition mole number: 2.1) 700 g (2 mole) of adduct, 200 g (2.04 mole) of maleic anhydride, and hydroquinone 0 0.4 g was made to react at 160 degreeC under nitrogen atmosphere 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 having a softening point of 93 ° C.
The resin is referred to as resin 3.

Examples 1 to 3 and Comparative Examples 1 and 2 Polystyrene [(A) component] was washed with pelletized polystyrene (trade name "Stylon 666R", manufactured by Asahi Kasei Corporation) or expanded polystyrene used as a packing material. , And ground with a coffee mill and used as powder having a particle size of 30 to 200 μm. Polystyrene A-1,
Polystyrene A-2. Resins 1, 2, and 3 obtained in the above Production Example were pulverized with a coffee mill as [(B) component or (C) component] to obtain 30 to 200 μm.
Used as a powder with a particle size of m. Further, as the radical generator [(D) component] (average particle size 300 μm),
Using 3-di (2-isopropylperoxyisopropyl) benzene, the components were mixed in the composition shown in Table 1 to prepare a binder composition.

[0039]

[Table 1]

Test Examples 1 to 3 and Comparative Test Examples 1 to 2 The binder compositions of Examples 1 to 3 and Comparative Examples 1 and 2 were mixed with cotton and hemp (1: 1) as a fiber base material (component (E)). The defibrated lint-like material was formulated to obtain a molding material composition. Next, this molding material composition is sandwiched between mirror-finished stainless steel plates and placed in a heat and pressure molding machine at 210 ° C. for 15 kgf.
/ Cm ² (147 N / cm ² ) at a contact pressure of 2 minutes under heat and pressure to obtain a molded plate having a thickness of 6 mm, a length of 20 cm and a width of 5 cm. By these operations, there was no monomer odor or irritating odor.

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 2. In all cases, no irritating odor was found during the 120 ° C heat resistance evaluation. Also, put the molded body in a desiccator,
After 24 hours, when the gas in the desiccator was sucked using a formalin gas detection tube, no formalin was detected.

Regarding the room temperature bending strength test, JIS
Based on K 6911. The 120 ° C heat resistance evaluation was performed by leaving a molded plate having a diameter of 15 mm and a columnar handle with a weight of 20 g at the center for 2 hours on a flat plate in an oven at 120 ° C, and then taking it out, and based on the following evaluation criteria. It was judged.

Evaluation Criteria A: There is no warpage. ◯: When the center was placed on the ground, the warpage was less than 1 mm. Δ: When the center is set on the ground, the warpage is 1 mm or more, 2.
It was less than 5 mm. X: When the center was placed on the ground, the warpage was 2.5 mm or more.

[0044]

[Table 2]

From the results shown in Table 2, the molded plates obtained by using the binder compositions of Examples 1 to 3 are all Comparative Example 1.
It can be seen that it has practically sufficient strength and heat resistance as compared with the molded plate obtained by using the binder composition of Nos.

[0046]

Industrial Applicability According to the present invention, an inexpensive molded product having practically sufficient strength and heat resistance, improved safety and odor problems, and a binder composition suitable for obtaining such a molded product, An excellent effect is obtained that a molding material composition is obtained.

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Claims (5)

[Claims] 1. A binder composition containing polystyrene powder [component (A)] and unsaturated polyester powder [component (B)] and / or unsaturated polyester polyamide powder [component (C)]. 2. The binder composition according to claim 1, which further contains a powdery radical generator [component (D)]. 3. The binder composition according to claim 1, wherein the weight ratio of the component (A) to the component (B) and / or the component (C) is 1:99 to 99: 1. 4. A molding material composition containing the binder composition according to claim 1 and a fiber base material [component (E)]. 5. A molded product obtained by molding the molding material composition according to claim 4.